266391 (FP7-2010-GC ELECTROCHEMICAL- STORAGE) …...Detailed Raman studies not only support the...

7thFramework Programme

Project no: 266391 (FP7-2010-GC ELECTROCHEMICAL-

STORAGE) Project acronym: ElectroGraph Project title: Graphene-based Electrodes for Application in

Supercapacitors Funding Scheme: Collaborative Project

Patent and Literature Study

Date of preparation: November 2011 Start date of project: 1st June 2011 Duration: 36 Months (3 years) Project coordinator name: Urszula Kosidlo Project coordinator organisation name: Fraunhofer Institute for Manufacturing Engineer and Automation, Fraunhofer IPA Fraunhofer-Gesellschaft zur Förderung der Angewandten Forschung E.V

Patent and Literature Study – November 2011 Page 1 of 75

TABLE OF CONTENT

Executive Summary

1 Introduction ............................................................................................................ 3

2 Selected Scientific Articles ..................................................................................... 5

3 Selected Patents .................................................................................................... 23

3.1 Graphene – Electrochemical Method .................................................................. 23

3.2 Graphene – CVD Method ..................................................................................... 31

3.3 Graphene – Electrode Material ............................................................................. 39

3.4 Graphene – Supercapacitor/Ultracapacitor ......................................................... 62

4 Conclusions .......................................................................................................... 74


Executive Summary

The area of graphene supercapacitors is the fast moving field and the keyword graphene search has revealed increase for 41% of number of patents when supercapacitor was used as an additional keyword and increase for 53% when electrochemical method was used as an additional keyword in a period from May 2011 to November 2011. The majority of patent applications are coming from the US (39%) followed by China (23%), Japan (19%), South Korea (12%), Germany (5%) and Australia (2%). The graphene is the youngest child in the carbon nanomaterials family and the most patents are related to synthesis. Even those that do have supercapacitor word in their abstract are in most cases patents about synthesis with reference to supercapacitor applications.


1. Introduction

A graphene is carbon structure of hexagonally arranged sp2 bonded carbon atoms in a plane, an isolated atomic plane of graphite. The Nobel Prize in Physics for 2010 was awarded to Andre Geim and Konstantin Novoselov "for groundbreaking experiments regarding the two-dimensional material graphene.

Fig. 1 Graphene C62H20 - A 'flake' of graphite with hydrogen used to terminate the dangling bonds (This image has been used with permission from Dr Chris Ewels. ©Chris Ewels)

The ElectroGraph project (EC FP7 Grant Agreement No. 266391) Graphene-based Electrodes for Application in Supercapacitors is focused on use of graphene as material for electrodes in supercapacitor electrochemical devices. Therefore the objective of this report is to present information related to graphene production and supercapacitor applications. Both production methods of graphene sheets (CVD and electrochemical) that are being developed in the ElectroGraph project are considered in this report. The aim of this report is to be a database catalogue for the ElectroGraph project partners. The knowledge database is created using existing knowledge of patents and scientific publications from partners. The database creation will be strengthening knowledge transfer between partners in the early stage of the project and initiate fresh ideas for patent and scientific publication at the beginning of the project. Abstracts of selected scientific articles and patents are presented in the report. The abstracts of selected scientific papers related to the ElectroGraph project are presented in the section 2 of this report and abstracts of the patents related to the ElectroGraph project are presented in the section 3 of this report. In order to make assessment about the patent landscape for graphene production methods and use as an electrode material in supercapacitors four search keywords group were prepared. These keywords groups are: 1) Graphene & Electrochemical Method, 2) Graphene & CVD Method, 3) Graphene & Electrode Material, 4) Graphene & Supercapacitor. An additional keyword search has been performed when in the last group a keyword supercapacitor was replaced by a word ultracapacitor that has been used in the US. Both words were also tested in a search engine as a singular (supercapacitor, ultracapacitor) and plural (supercapacitors, ultracapacitors). Use of keywords super-capacitor or ultra-capacitor did not reveal any patents.


The European Patent Office espacenet worldwide database was searched for these keywords in the title and patent abstract. Some patents are selected, discussed and their abstracts presented in the report as an illustration and inspiration for development of intellectual property. It is important to notify that sometimes the keyword patent search does not reflect the try patent situation and that some patents could be missed.


2. Selected Scientific Articles The abstracts of selected scientific articles related to the ElectroGraph project are presented in this section.

A1. Carbon-Based Supercapacitors Produced by Activation of Graphene Yanwu Zhu,

1 Shanthi Murali,

1 Meryl D. Stoller,

1 K. J. Ganesh,

1 Weiwei Cai,

1 Paulo J.

Ferreira,1 Adam Pirkle,

2 Robert M. Wallace,

2 Katie A. Cychosz,

3 Matthias Thommes,

3 Dong

Su,4 Eric A. Stach,

4 Rodney S. Ruoff

1

1Department of Mechanical Engineering and Materials Science and Engineering Program, University of Texas at Austin, One University Station C2200, Austin, TX 78712, USA. 2Department of Materials Science and Engineering, University of Texas at Dallas, 800 West Campbell Road, Richardson, TX 75080, USA. 3Quantachrome Instruments, 1900 Corporate Drive, Boynton Beach, FL 33426, USA. 4Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY 11973, USA.

Supercapacitors, also called ultracapacitors or electrochemical capacitors, store electrical charge on high-surface-area conducting materials. Their widespread use is limited by their low energy storage density and relatively high effective series resistance. Using chemical activation of exfoliated graphite oxide, we synthesized a porous carbon with a Brunauer-Emmett-Teller surface area of up to 3100 square meters per gram, a high electrical conductivity, and a low oxygen and hydrogen content. This sp2-bonded carbon has a continuous three-dimensional network of highly curved, atom-thick walls that form primarily 0.6- to 5-nanometer-width pores. Two-electrode supercapacitor cells constructed with this carbon yielded high values of gravimetric capacitance and energy density with organic and ionic liquid electrolytes. The processes used to make this carbon are readily scalable to industrial levels. Corresponding Author: [email protected] SCIENCE Vol 332 (2011), 24: 1537-1541 A2. Synthesis of Graphene and Its Applications: A Review Wonbong Choi,

1, Indranil Lahiri,

1 Raghunandan Seelaboyina,

1 and Yong Soo Kang

2

1Nanomaterials and Devices Laboratory, Florida International University, Miami, Florida, USA 2Department of Energy Engineering, Hanyang University, Seoul, Korea

Graphene, one-atom-thick planar sheet of carbon atoms densely packed in a honeycomb crystal lattice, has grabbed appreciable attention due to its exceptional electronic and optoelectronic properties. The reported properties and applications of this two-dimensional form of carbon structure have opened up new opportunities for the future devices and systems. Although graphene is known as one of the best electronic materials, synthesizing single sheet of graphene has been less explored.


This review article aims to present an overview of the advancement of research in graphene, in the area of synthesis, properties and applications, such as field emission, sensors, electronics, and energy. Wherever applicable, the limitations of present knowledgebase and future research directions have also been highlighted. Corresponding author: [email protected] Critical Reviews in Solid State and Materials Sciences, 35:52–71, 2010 A3. Monolithic self-sustaining nanographene sheet grown using plasma-enhanced chemical vapor deposition Wakana Takeuchi,

1, Keigo Takeda

1, Mineo Hiramatsu

2, Yutaka Tokuda

3, Hiroyuki Kano

4,

Shigeru Kimura5, Osami Sakata

5, Hiroo Tajiri

5, and Masaru Hori

1

1 Department of Electrical Engineering and Computer Science, Nagoya University, Chikusa, Nagoya 468-8603, Japan 2 Department of Electrical and Electronic Engineering, Meijo University, Tempaku, Nagoya 468-8502, Japan 3 Department of Electrical and Electronics Engineering, Aichi Institute of Technology, Yakusa, Toyota 470-0392, Japan 4NU Eco-Engineering Co., Ltd., Kurozasa, Miyoshi, Nishikamo 470-0201, Japan 5 Japan Synchrotron Radiation Research Institute (JASRI)/SPring-8, Kouto, Sayo 679-5198, Japan

We have fabricated carbon nanowalls (CNWs) composed of monolithic self-sustaining nanographene sheets standing vertically on a Si substrate, using plasma-enhanced chemical vapour deposition with a C2F6/H2 mixture. The crystallinity, evaluated by Raman spectroscopy and synchrotron X-ray surface diffraction, and the electrical properties of the CNWs were improved by introducing O2 gas into the source gas mixture during the CNW growth process. The temperature dependence of the resistivity of the CNW films exhibited semiconductor behavior. Corresponding author: e-mail [email protected] Phys. Status Solidi A 207, No. 1, 139–143 (2010) A4. Exploring the fundamental effects of deposition time on the microstructure of graphene nanoflakes by Raman scattering and X-ray diffraction Navneet Soin,

a Susanta Sinha Roy,

a Christopher O’Kane,

a James A. D. McLaughlin,

a Teck H.

Lim b and Crispin J. D. Hetherington

b

aNanotechnology and Integrated Bio-Engineering Centre, School of Engineering, University of Ulster, Newtownabbey, BT37 0QB, UK. bDepartment of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK

A systematic study is reported of the growth of vertically aligned few layered graphene (FLG) nanoflakes on Si (100) substrates by microwave plasma enhanced chemical vapour deposition (MPECVD) method. Asymmetric grazing incident angle X-ray diffraction (GIAXRD) studies revealed a structural transformation, from nanocrystalline graphite layers to FLG, with the increase of growth time. As the


growth time increased we observed a preferred vertical orientation of FLGs accompanied by a sharp decrease in the d002 spacing. Transmission electron microscopy shows these structures have highly graphitized edge planes which terminate in a few layers (1–3) of graphene sheets. Detailed Raman studies not only support the structural transformation but also confirm that the process occurs via the sudden release of stress in nanocrystalline turbostratic graphite films. Graphical plot of all major Raman parameters (such as G peak position, ID/IG value, FWHM of D, G, and G0 peaks) vs. Growth time shows a well defined trend. Using the graphical plots a tentative trajectory of the Raman parameters is proposed, which can be very useful in understanding structural transformation during growth process. Finally, a possible growth mechanism of FLGs is presented. Corresponding author: [email protected] CrystEngComm, 2011, 13, 312

A5. Cationic surfactant mediated exfoliation of graphite into graphene flakes Sajini Vadukumpully, Jinu Paul, Suresh Valiyaveettil Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore

A simple and effective method for the preparation of a few layered graphene nanoflakes directly from graphite has been successfully demonstrated. Mild ultrasonication of highly ordered pyrolytic graphite, in presence of a cationic surfactant cetyltrimethylammonium bromide and acetic acid yielded graphene nanoflakes, which formed a stable colloidal suspension in organic solvent such as N,N-dimethyl formamide. Scanning and transmission electron microscopic analyses showed that the dispersed phase consist of mainly few layered graphene nanoflakes. Average thickness of the flakes was found to be 1.18 nm. Energy dispersive X-ray analysis indicated the absence of graphene oxide. Field emission measurements for the nanoflakes showed a turn on voltage of 7.5 V/lm and emission current densities of 0.15 mA/cm2. Corresponding author: [email protected] Carbon 47 (2009) 3288-3294. A6. Direct exfoliation of natural graphite into micrometre size few layers graphene sheets using ionic liquids Xiqing Wang,

a Pasquale F. Fulvio,

a Gary A. Baker,

a Gabriel M. Veith,

b Raymond R. Unocic,

b

Shannon M. Mahurin,a Miaofang Chib and Sheng Dai*

a

a Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA. b Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

Stable high-concentration suspensions (up to 0.95 mg mL-1) of non-oxidized few layer graphene (FLG), five or less sheets, with micrometre-long edges were obtained


via direct exfoliation of natural graphite flakes in ionic liquids, such as 1-butyl-3-methylimidazolium bis(trifluoro-methane-sulfonyl)imide ([Bmim]-[Tf2N]), by tip ultrasonication. Graphene is a nanometre-thick two-dimensional (2D) material composed by hexagonal carbon lattice with delocalized p electrons. The unique electronic, thermal, and mechanical properties of graphene have brought great interest to this material. The properties of graphene sheets can be greatly affected by the number of layers, their stacking sequence, lateral area, and the degree of surface reduction or oxidation. Corresponding author: [email protected] Chem. Commun., 2010, 46, 4487–4489 A7. Dispersion of graphene sheets in ionic liquid [bmim][PF6] stabilized by an ionic liquid polymer Xiaosi Zhou, Tianbin Wu, Kunlun Ding, Baoji Hu, Minqiang Hou and Buxing Han* Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

Dispersion of graphene sheets in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was successfully achieved with the aid of a polymerized ionic liquid (PIL). Graphene, a one atom thick and two-dimensional honeycomb lattice, has attracted enormous attention in recent years from both the experimental and theoretical scientific communities because of its unique mechanical, electronic, and thermal properties. This special nanostructure has great potential applications in many technological fields, such as nanocomposites, nanoelectronics, and biosensors. Different methods, such as mechanical exfoliation, thermal expansion, epitaxial growth, and chemical vapour deposition has been developed for preparing graphene. Recently, many attempts to produce graphene sheets in a large quantity via chemical reduction of dispersed graphite oxide have been reported. Corresponding author: [email protected] Chem. Commun., 2010, 46, 386–388 A8. Environmentally friendly approaches toward the mass production of processable graphene from graphite oxide J. I. Paredes,* S. Villar-Rodil, M. J. Fernandez-Merino, L. Guardia, A. Martınez-Alonso and J. M. D. Tascon Instituto Nacional del Carbon, CSIC, Apartado 73, 33080, Oviedo, Spain

Graphene has attracted a great deal of scientific interest in later years owing to its unique properties, with many prospective applications being actively investigated at present. However, the actual implementation of graphene in technological uses will depend critically on the development of appropriate methodologies for its mass production. In this regard, one of the most promising approaches is based on the exfoliation and reduction of graphite oxide. Graphenes derived from graphite oxide can be prepared at low cost and high throughput, can be further processed in a


number of solvents, and are chemically versatile, among other attractive features. In an environment-conscious world, the availability of green approaches toward graphene production would also constitute an added advantage. During the last year, different environmentally friendly methods for the production of graphene from graphite oxide have emerged, which we highlight here. These are based on solvothermal and electrochemical processes, as well as on the use of green reductants. Several open questions and possible future directions for this research topic are also discussed. Corresponding author: [email protected] J. Mater. Chem., 2011, 21, 298–306 A9. High-Yield Synthesis of Few-Layer Graphene Flakes through Electrochemical Expansion of Graphite in Propylene Carbonate Electrolyte Junzhong Wang, Kiran Kumar Manga, Qiaoliang Bao, and Kian Ping Loh* Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543

High-yield production of few-layer grapheme flakes from graphite is important for the scalable synthesis and industrial application of graphene. However, high-yield exfoliation of graphite to form graphene sheets without using any oxidation process or super-strong acid is challenging. Here we demonstrate a solution route inspired by the lithium rechargeable battery for the high-yield (>70%) exfoliation of graphite into highly conductive few-layer graphene flakes (average thickness <5 layers). A negative graphite electrode can be electrochemically charged and expanded in an electrolyte of Li salts and organic solvents under high current density and exfoliated efficiently into few-layer graphene sheets with the aid of sonication. The dispersible graphene can be ink-brushed to form highly conformal coatings of conductive films (15 ohm/square at a graphene loading of <1 mg/cm2) on commercial paper. Corresponding Author: [email protected] J. Am. Chem. Soc. 2011, 133, 8888–8891 A10. One-Step Ionic-Liquid-Assisted Electrochemical Synthesis of Ionic-Liquid-Functionalized Graphene Sheets Directly from Graphite** Na Liu

1, Fang Luo,

1* Haoxi Wu

1, Yinghui Liu

2, Chao Zhang

2, and Ji Chen

2

1College of Chemistry, Northeast Normal University, Changchun 130024 (P.R. China) 2Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (P.R. China)

Graphite, inexpensive and available in large quantities, unfortunately does not readily exfoliate to yield individual grapheme sheets. Here a mild, one-step electrochemical approach for the preparation of ionic-liquid-functionalized graphite sheets with the assistance of an ionic liquid and water is presented. These ionic-liquid-treated graphite sheets can be exfoliated into functionalized graphene nanosheets that can


not only be individuated and homogeneously distributed into polar aprotic solvents, but also need not be further deoxidized. Different types of ionic liquids and different ratios of the ionic liquid to water can influence the properties of the grapheme nanosheets. Graphene nanosheet/polystyrene composites synthesized by a liquid-phase blend route exhibit a percolation threshold of 0.1 vol % for room temperature electrical conductivity, and, at only 4.19 vol %, this composite has a conductivity of 13.84 S m�1, which is 3–15 times that of polystyrene composites filled with single-walled carbon nanotubes. Corresponding Author: [email protected] Adv. Funct. Mater. 2008, 18, 1518–1525 A11. GENERAL PROPERTIES OF IONIC LIQUIDS AS ELECTROLYTES FOR CARBON-BASED DOUBLE LAYER CAPACITORS A. Lewandowski and M. Galinski Faculty of Chemical Technology, Poznan University of Technology,PL-60 965 Poznan, Poland

Activated carbons have been used for a long time in many industrial applications. One of the recent applications is using activated carbon as an active electrode material in double-layer capacitors (DLC). Electrochemical capacitors, based on the capacity of the double layer formed at the carbon/electrolyte interface, have received considerable attention as they can be used as high power-density energy-storage devices. Batteries have high energy density, but they suffer from low power density and low cyclability (usually <1000). On the other hand, electrochemical capacitors offer an order of magnitude higher power density and at least two orders of magnitude higher number of charge-discharge cycles (~100 000). However, the energy density is an order of magnitude lower in comparison to that characteristic for batteries. There are a number of electrochemical capacitor potential applications, but it seems that they are being investigated mainly for hybrid vehicles as a short-term power accumulator and supply. Therefore, the DLC research aims to develop an energy-storage device having energy density close to that typical of batteries and the power characteristic typical of capacitors. This goal can be obtained by optimisation of carbon materials as well as electrolyte. Carbon materials, for the use in double-layer capacitors, have been developed in various systems: powders, fabrics, tissues or aerogels. It is possible to obtain activated carbons of high specific surface area at the level of 2500 m2/g. Similarly, many aqueous and organic liquid solutions of electrolytes as well as a limited number of polymer electrolytes have been developed for the use in carbon-based electrochemical capacitors. Corresponding author: [email protected] I.V. Barsukov et al. (eds.), New Carbon Based Materials for Electrochemical Energy Storage Systems, 73–83.© 2006 Springer.


A12. Graphene photonics and optoelectronics F. Bonaccorso, Z. Sun, T. Hasan and A. C. Ferrari* Department of Engineering, University of Cambridge, Cambridge CB3 0FA, UK.

The richness of optical and electronic properties of graphene attracts enormous interest. Graphene has high mobility and optical transparency, in addition to flexibility, robustness and environmental stability. So far, the main focus has been on fundamental physics and electronic devices. However, we believe its true potential lies in photonics and optoelectronics, where the combination of its unique optical and electronic properties can be fully exploited, even in the absence of a bandgap, and the linear dispersion of the Dirac electrons enables ultrawideband tunability. The rise of graphene in photonics and optoelectronics is shown by several recent results, ranging from solar cells and light-emitting devices to touch screens, photodetectors and ultrafast lasers. Here we review the state-of-the-art in this emerging field. Corresponding Author: [email protected] NATURE PHOTONICS VOL 4, 2010, 611-622 A13. Properties of graphene inks stabilized by different functional groups DiWei

1, Hongwei Li

1, Dongxue Han

2, Qixian Zhang

2, Li Niu

2, Huafeng Yang

2, Chris Bower

1,

Piers Andrew1 and Tapani Ryhanen

1

1 Nokia Research Centre, Broers Building, 21 JJ Thomson Avenue, Cambridge CB3 0FA, UK

2 State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun City 130022, Jilin Province, People’s Republic of China

Different graphene inks have been synthesized by chemical methods. These uniform dispersions were stabilized by various functional groups such as room temperature ionic liquid, polyaniline, polyelectrolyte (poly[2,5-bis(3-sulfonatopropoxy)-1,4 ethynylphenylene-alt-1,4-ethynylphenylene] sodium salt) and poly(styrenesulfonate) (PSS). The dispersions can be easily cast into high-quality, free-standing films but with very different physiochemical properties such as surface tension and adhesion. SEM and AFM methods have been applied to have a detailed study of the properties of the inks. It is found that graphenes modified by p-type polyaniline show the highest surface tension. Diverse surface adhesive properties to the substrate are also found with various functional groups. The different viscoelasticities of graphene inks were related to the microscopic structure of their coating layer and subsequently related to the configuration, chemistry and molecular dimensions of the modifying molecules to establish the property–structure relationship. Modifications of graphene inks made from chemical reduction cannot only enable cost-effective processing for printable electronics but also extend the applications into, for example, self-assembly of graphene via bottom-up nano-architecture and surface energy engineering of the graphenes. To fabricate useful devices, understanding the surface properties of graphene inks is very important. It is the first paper of this kind to study the surface tension and adhesion of graphene influenced by different functional groups. Corresponding Authors: [email protected] and [email protected] Nanotechnology 22 (2011) 245702


A14. High concentration few-layer graphene sheets obtained by liquid phase exfoliation of graphite in ionic liquid Daniele Nuvoli,

a Luca Valentini,

b Valeria Alzari,

a Sergio Scognamillo,

a Silvia Bittolo Bon,

b

Massimo Piccinini,c Javier Illescas

d and Alberto Mariani*

a

aDipartimento di Chimica, Universita di Sassari, and local INSTM Unit, Via Vienna 2, 07100 Sassari, Italy. bDipartimento di Ingegneria Civile ed Ambientale, Universita di Perugia and local INSTM Unit, Strada di Pentima 4, 05100 Terni, Italy. cPorto Conte Ricerche S.r.l., SP 55 km 8.400 Loc. Tramariglio, 07041 Alghero (SS), Italy. dInstituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior S/N, Ciudad Universitaria, C.P. 04510 Mexico D.F.

In the present work, the use of a commercial ionic liquid as a convenient solvent medium for graphite exfoliation in mild and easy conditions without any chemical modification is presented. To confirm the presence of few layer graphene, its dispersion, which exhibits Tyndall effect, was characterized by Raman and UV spectroscopies, and atomic force and field emission electron microscopies. It is noteworthy that, by gravimetric analysis, a graphene concentration as high as 5.33 mg/ml was determined, which is the highest value reported so far in any solvent. Corresponding Author: [email protected]; J. Mater. Chem., 2011, 21, 3428 A15. High-Performance Supercapacitors Based on Poly(ionic liquid)-Modified Graphene Electrodes Tae Young Kim,† Hyun Wook Lee,† Meryl Stoller,‡ Daniel R. Dreyer,§ Christopher W. Bielawski,§ Rodney S. Ruoff,‡,* and Kwang S. Suh†,* †Department of Materials Science and Engineering, Korea University, 5-1 Anam-dong Seongbuk-gu, Seoul 136-713, South Korea, ‡Department of Mechanical Engineering and the Texas Materials Institute, The University of Texas at Austin, One University Station C2200, Austin, Texas 78712, United States, and §Department of Chemistry and Biochemistry, The University of Texas at Austin, One University Station A5300, Austin, Texas 78712, United States

We report a high-performance supercapacitor incorporating a poly(ionic liquid)-modified reduced graphene oxide (PIL:RG-O) electrode and an ionic liquid (IL) electrolyte (specifically, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide or EMIM-NTf2). PIL:RG-O provides enhanced compatibility with the IL electrolyte, thereby increasing the effective electrode surface area accessible to electrolyte ions. The supercapacitor assembled with PIL:RG-O electrode and EMIM-NTf2 electrolyte showed a stable electrochemical response up to 3.5 V operating voltage and was capable of yielding a maximum energy density of 6.5 W · h/kg with a power density of 2.4 kW/ kg. These results demonstrate the potential of the PIL:RG-O material as an electrode in high-performance supercapacitors.

Corresponding Authors: [email protected], and [email protected]

ACSNano VOL.5, NO. 1 436-442 (2010)


A16. Ionic liquids for hybrid supercapacitors Andrea Balducci

a,b, Ugo Bardi

c, Stefano Caporali

c, Marina Mastragostino

a, *Francesca Soavi

a

a UCI – Scienze Chimiche Radiochimiche e Metallurgiche, Universita di Bologna, Via San Donato 14, 40127 Bologna, Italy b CIRIMAT, UMR CNRS 5085, 118 Route de Narbonne, 31062 Toulouse Cedex, France

c Dipartimento di Chimica, Universita di Firenze, Via della Lastruccia 3, 50019 Sesto F.no, Italy

The use of ionic liquids based on 1-buthyl-3-methyl-imidazolium as electrolytes in an activated carbon//poly(3-methylthiophene) hybrid supercapacitor was investigated. Preliminary results of the electrochemical characterization of electrodes sized for practical use in the supercapacitor and of a laboratory scale cell are reported and compared to those with propylene carbonate-tetraethylammonium tetrafluoroborate as electrolyte. The interest in supercapacitors has increased enormously in recent years mainly for electric vehicles, in which the supercapacitors operating in parallel with batteries and fuel cells are expected to provide power peaks during acceleration, especially with fuel cells which have lower performance power than batteries. Given this application, the focus of interest is on supercapacitors with relatively high specific energy and operating at temperatures of at least 60 oC. Corresponding Author: [email protected]

Electrochemistry Communications 6 (2004) 566–570 A17. Exfoliation of graphite D. D. L. CHUNG Department of Mechanical and Aerospace Engineering, State University of New York, Buffalo, New York 14260, USA

The exfoliation of graphite is a phase transition involving the vaporization of the intercalate in the graphite. Exfoliated graphite is an expanded graphite with a low density. This paper reviews the process of the exfoliation of graphite and the exfoliated graphite material. It surveys the applications of exfoliated graphite, covers both reversible and irreversible exfoliation and reviews the methods and mechanism of exfoliation. Other topics include the structure and properties of exfoliated graphite, graphite foils, exfoliated carbon fibres and composites. JOURNAL OF MATERIALS SCIENCE 22 (1987) 4190 4198 A18. Solvothermal-Assisted Exfoliation Process to Produce Graphene with High Yield and High Quality Wen Qian

1, Rui Hao

1, Yanglong Hou

1, Yuan Tian

2, Chengmin Shen

2, Hongjun Gao

2, and

Xuelei Liang3

1 Department of Advanced Materials and Nanotechnology, College of Engineering, Peking University, Beijing 100871, China


2 Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

3 Key Laboratory for the Physics and Chemistry of Nanodevices and Department of Electronics, Peking University, Beijing 100871, China

Monolayer and bilayer graphene sheets have been produced by a solvothermal-assisted exfoliation process in a highly polar organic solvent, acetonitrile, using expanded graphite (EG) as the starting material. It is proposed that the dipole-induced dipole interactions between graphene and acetonitrile facilitate the exfoliation and dispersion of graphene. The facile and effective solvothermal-assisted exfoliation process raises the low yield of graphene reported in previous syntheses to 10 wt% 12 wt%. By means of centrifugation at 2000 rpm for 90 min, monolayer and bilayer graphene were separated effectively without the need to add a stabilizer or modifier. Electron diffraction and Raman spectroscopy indicate that the resulting graphene sheets are high quality products without any significant structural defects. Corresponding Author: [email protected]

Nano Res (2009) 2: 706 7120

A19. Ultrathin Planar Graphene Supercapacitors Jung Joon Yoo,

1,2, Kaushik Balakrishnan,

1, Jingsong Huang,

3, Vincent Meunier,

3, Bobby G.

Sumpter,3, Anchal Srivastava,

1,4 Michelle Conway,

1 Arava Leela Mohana Reddy,

1 Jin Yu,

2

Robert Vajtai,1 and Pulickel M. Ajayan,

1

1 Department of Mechanical Engineering and Materials Science, Rice University, Houston, Texas, United States 2 Department of Material Science and Engineering, KAIST, Daejeon, Republic of Korea 3 Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States 4 Department of Physics, Banaras Hindu University, Varanasi, India

With the advent of atomically thin and flat layers of conducting materials such as graphene, new designs for thin film energy storage devices with good performance have become possible. Here, we report an “in-plane” fabrication approach for ultrathin supercapacitors based on electrodes comprised of pristine graphene and multilayer reduced graphene oxide. The in-plane design is straightforward to implement and exploits efficiently the surface of each graphene layer for energy storage. The open architecture and the effect of graphene edges enable even the thinnest of devices, made from as grown 1-2 graphene layers, to reach specific capacities up to 80 µFcm-2, while much higher (394 µFcm-2) specific capacities are observed multilayer reduced graphene oxide electrodes. The performances of devices with pristine as well as thicker graphene-based structures are examined using a combination of experiments and model calculations. The demonstrated all solid-state supercapacitors provide a prototype for a broad range of thin-film based energy storage devices. Corresponding Authors: [email protected] and [email protected] Nano Lett. 2011, 11, 1423–1427


A20. Patterning Vertically Oriented Graphene Sheets for Nanodevice Applications Kehan Yu, Pengxiang Wang, Ganhua Lu, Ke-Hung Chen, Zheng Bo, and Junhong Chen Department of Mechanical Engineering, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, United States

Graphene has attracted growing interest in the past few years. Growing vertically oriented graphene sheets with a designed pattern is practically attractive for device applications based on graphene. Here we report a patterned synthesis of vertical graphene nanosheets using plasma-enhanced chemical vapor deposition. Both experimental and modeling results suggest that the electric field distribution above the substrate material plays a key role in the grapheme coverage. Vertical graphene patterns can thus be designed through artificially designing the surface electric field distribution. A field-effect transistor (FET) sensor device has been demonstrated for detection of low-concentration gases using vertically patterned grapheme sheets bridging a metal electrode gap. Corresponding Author: [email protected] J. Phys. Chem. Lett. 2011, 2, 537–542 A21. A mechanism for carbon nanosheet formation Mingyao Zhu

a,b, Jianjun Wang

b, Brian C. Holloway

b,c, R.A. Outlaw

b, Xin Zhao

b,

Kun Hou b, V. Shutthanandan

d, Dennis M. Manos

a,b

a Physics Department, College of William and Mary, Williamsburg, VA 23187-8795, United States b Applied Science Department, College of William and Mary, Williamsburg, VA 23187-8795,

United States c Luna nanoWorks Division, Luna Innovations, 521 Bridge Street, Danville, VA 24543, United States d Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland, WA 99352, United States

The growth, structure and properties of a two-dimensional carbon nanostructure–carbon nanosheet produced by radio frequency plasma enhanced chemical vapor deposition have been investigated. The effects of deposition parameters on the structure and properties of carbon nanosheets were also investigated. A growth model has been described proposing that atomically thin graphene sheets result from a balance between deposition through surface diffusion and etching by atomic hydrogen, and that the observed vertical orientation of these sheets results from the interaction of the plasma electric field with their anisotropic polarizability. Corresponding author: [email protected] Carbon 45 (2007) 2229–2234


A22. Hexagonal Single Crystal Domains of Few-Layer Graphene on Copper Foils Alex W. Robertson and Jamie H. Warner Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, United Kingdom

Hexagonal-shaped single crystal domains of few layer graphene (FLG) are synthesized on copper foils using atmospheric pressure chemical vapor deposition with a high methane flow. Scanning electron microscopy reveals that the graphene domains have a hexagonal shape and are randomly orientated on the copper foil. However, the sites of grapheme nucleation exhibit some correlation by forming linear rows. Transmission electron microscopy is used to examine the folded edges of individual domains and reveals they are few-layer graphene consisting of approximately 5-10 layers in the central region and thinning out toward the edges of the domain. Selected area electron diffraction of individual isolated domains reveals they are single crystals with AB Bernal stacking and free from the intrinsic rotational stacking faults that are associated with turbostratic graphite. We study the time-dependent growth dynamics of the domains and show that the final continuous FLG film is polycrystalline, consisting of randomly connected single crystal domains. Corresponding author: [email protected] Nano Lett. 2011, 11, 1182–1189 A23. Transfer of Large-Area Graphene Films for High-Performance Transparent Conductive Electrodes Xuesong Li,† Yanwu Zhu,† Weiwei Cai,† Mark Borysiak,‡ Boyang Han,† David Chen,† Richard D. Piner,† Luigi Colombo,§ and Rodney S. Ruoff † Department of Mechanical Engineering and the Texas Materials Institute, The University of Texas at Austin. ‡ 2009 NNIN REU Intern at The University of Texas at Austin. § Texas Instruments Incorporated.

Graphene, a two-dimensional monolayer of sp2-bonded carbon atoms, has been attracting great interest due to its unique transport properties. One of the promising applications of graphene is as a transparent conductive electrode owing to its high optical transmittance and conductivity. In this paper, we report on an improved transfer process of large-area graphene grown on Cu foils by chemical vapor deposition. The transferred graphene films have high electrical conductivity and high optical transmittance that make them suitable for transparent conductive electrode applications. The improved transfer processes will also be of great value for the fabrication of electronic devices such as field effect transistor and bilayer pseudospin field effect transistor devices. Corresponding authors: [email protected] and [email protected] NANO LETTERS 2009 Vol. 9, No. 12: 4359-4363.


A24. Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition Qingkai Yu

1,2, Luis A. Jauregui

3, WeiWu

1, Robert Colby

4, Jifa Tian

5, Zhihua Su

6, Helin Cao

5,

Zhihong Liu6, Deepak Pandey

5, DongguangWei

7, Ting Fung Chung

5, Peng Peng

1, Nathan P.

Guisinger8, Eric A. Stach

4,9, Jiming Bao

6, Shin-Shem Pei

1 and Yong P. Chen

10

1Center for Advanced Materials and Department of Electrical and Computer Engineering, University of Houston, Houston, Texas 77204, USA 2Ingram School of Engineering, and Materials Science, Engineering and Commercialization Program, Texas State University, San Marcos, Texas 78666,USA 3Birck Nanotechnology Center and School of Electrical and Computer Engineering, Purdue University,West Lafayette, Indiana 47907, USA 4Birck Nanotechnology Center and School of Materials Engineering, Purdue University,West Lafayette, Indiana 47907, USA 5Birck Nanotechnology Center and Department of Physics, Purdue University, West Lafayette, Indiana 47907, USA 6Department of Electrical and Computer Engineering, University of Houston, Houston, Texas 77204, USA 7Carl Zeiss SMT, Inc., One CorporationWay, Peabody, Massachusetts 01960, USA,

8Argonne

National Laboratory, Argonne, Illinois 60439, USA 9Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, USA 10Birck Nanotechnology Center and Department of Physics and School of Electrical and

Computer Engineering, Purdue University, West Lafayette, Indiana 47907, USA.

The strong interest in graphene has motivated the scalable production of high-quality graphene and graphene devices. As the large-scale graphene films synthesized so far are typically polycrystalline, it is important to characterize and control grain boundaries, generally believed to degrade graphene quality. Here we study single-crystal graphene grains synthesized by ambient chemical vapour deposition on polycrystalline Cu, and show how individual boundaries between coalescing grains affect graphene’s electronic properties. The graphene grains show no definite epitaxial relationship with the Cu substrate, and can cross Cu grain boundaries. The edges of these grains are found to be predominantly parallel to zigzag directions. We show that grain boundaries give a significant Raman ‘D’ peak, impede electrical transport, and induce prominent weak localization indicative of intervalley scattering in graphene. Finally, we demonstrate an approach using pre-patterned growth seeds to control graphene nucleation, opening a route towards scalable fabrication of single-crystal graphene devices without grain boundaries. Corresponding authors: [email protected] and [email protected]. NATURE MATERIALS, 2011, VOL 10: 443-449. A25. Preparation of Novel 3D Graphene Networks for Supercapacitor Applications Xiehong Cao

1, Yumeng Shi

1, Wenhui Shi

1,2, Gang Lu

1, Xiao Huang

1,

Qingyu Yan 1,2,3

, Qichun Zhang1 and Hua Zhang

1

1School of Materials Science and Engineering Nanyang Technological University 50 Nanyang Avenue, Singapore 639798, Singapore 2Energy Research Institute Nanyang Technological University637459, Singapore 3TUM CREATE Centre for Electromobility Nanyang Technological University 637459, Singapore


Graphene, a 2D sp 2 -hybridized carbon sheet with one-atom thickness, has attracted increasing attention in recent years because of its unique structure and special properties. Its high theoretical surface area (2630m2g − 1) and high electrical conductivity make it an attractive material for applications in energy-storage systems. The supercapacitor is considered as a promising candidate for energy storage due to its high power performance, long life cycle, and low maintenance cost. Pseudocapacitive materials, such as transition metal oxides, are being explored for use in supercapacitors with a large specific capacitance and high energy density. However, pseudocapacitors often suffer from the low rate capability and poor stability, because the active materials are usually insulating or semiconducting, which hinders the fast electron transport required for high charge/discharge rates. Corresponding author: [email protected] Small 2011, Vol 7, No. 22, 3163-3168 A26. Graphene-Based Ultracapacitors Meryl D. Stoller, Sungjin Park, Yanwu Zhu, Jinho An, and Rodney S. Ruoff Department of Mechanical Engineering and Texas Materials Institute, University of Texas at Austin, One University Station C2200, Austin, Texas, 78712-0292

The surface area of a single graphene sheet is 2630 m2/g, substantially higher than values derived from BET surface area measurements of activated carbons used in current electrochemical double layer capacitors. Our group has pioneered a new carbon material that we call chemically modified graphene (CMG). CMG materials are made from 1-atom thick sheets of carbon, functionalized as needed, and here we demonstrate in an ultracapacitor cell their performance. Specific capacitances of 135 and 99 F/g in aqueous and organic electrolytes, respectively, have been measured. In addition, high electrical conductivity gives these materials consistently good performance over a wide range of voltage scan rates. These encouraging results illustrate the exciting potential for high performance, electrical energy storage devices based on this new class of carbon material. Corresponding author: [email protected] NANO LETTERS, 2008, Vol. 8, No. 10: 3498-3502 A27. Graphene-based materials in electrochemistry Da Chen,

ab Longhua Tanga and Jinghong Li*

a

a Department of Chemistry, Key Lab of Bioorganic Phosphorus Chemistry & Chemical Biology, Tsinghua University, Beijing 100084, China. b College of Materials Science & Engineering, China Jiliang University, Hangzhou 310018, China

Graphene, as the fundamental 2D carbon structure with exceptionally high crystal and electronic quality, has emerged as a rapidly rising star in the field of material science. Its sudden discovery in 2004 led to an explosion of interest in the study of


graphene with respect to its unique physical, chemical, and mechanical properties, opening up a new research area for materials science and condensed-matter physics, and aiming for wide-ranging and diversified technological applications. In this critical review, we will describe recent advances in the development of graphene-based materials from the standpoint of electrochemistry. To begin with, electron transfer properties of graphene will be discussed, involving its unusual electronic structure, extraordinary electronic properties and fascinating electron transport. The next major section deals with the exciting progress related to graphene-based materials in electrochemistry since 2004, including electrochemical sensing, electrochemoluminescence, electrocatalysis, electrochemical energy conversion and FET devices. Finally, prospects and further developments in this exciting field of graphene-based materials are also suggested (224 references). Corresponding author: [email protected] Chem. Soc. Rev., 2010, 39, 3157–3180 A28. Graphene-based nanomaterials for energy storage Martin Pumera Division of Chemistry & Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371

There is enormous interest in the use of graphene-based materials for energy storage. This article discusses the progress that has been accomplished in the development of chemical, electrochemical, and electrical energy storage systems using graphene. We summarize the theoretical and experimental work on graphene-based hydrogen storage systems, lithium batteries, and supercapacitors. Even though the research on the use of graphene for energy storage began very recently, the explosive growth of the research conducted in this area makes this minireview timely. Corresponding author: [email protected] Energy Environ. Sci., 2011, 4, 668–674 A29. Interfacial capacitance of single layer grapheme Meryl D. Stoller, Carl W. Magnuson, Yanwu Zhu, Shanthi Murali, Ji Won Suk, Richard Piner and Rodney S. Ruoff* Dept of Mechanical Engineering and the Materials Science and Engineering Program, The University of Texas, Austin 1 University Station, C2200, Austin, TX 78712-0292.

The interfacial capacitance of large area, single layer graphene was directly measured with electrolyte accessing both sides of the graphene sheet. PMMA and photoresist patterns were used as supports to suspend the CVD grown graphene in electrolyte during electrochemical testing. Both one and two sides of single layer graphene films were measured and compared. The results show that the area normalized charge that can be stored simultaneously on both sides is significantly


lower than could be stored on just one side of single layer graphene, consistent with charge storage having a quantum capacitance component. These measurements are also consistent with the specific capacitance of graphene materials as previously measured in supercapacitor cells and provide a basis for the further understanding and development of graphene based materials for electrical energy storage. Corresponding author: [email protected] Energy Environ. Sci., 2011, 4, 4685 A30. Multilayer graphene nanoribbons exhibit larger capacitance than their few-layer and single-layer graphene counterparts Madeline Shuhua Goh, Martin Pumera Division of Chemistry & Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore

This article demonstrates that it is not always beneficial to exfoliate graphitic structures to single-layer graphene to achieve maximum electrochemical performance. Using electrochemical impedance spectroscopy, we show that multilayer graphene nanoribbons with cross sections of 100×100 nm provide larger capacitance (15.6 F/g) than do few-layer graphene nanoribbons (14.9 F/g) and far larger capacitance than single-layer graphene nanoribbons (10.9 F/g) with the same cross section. Graphene is currently in the forefront of electrochemical research. It is making a significant impact in development of enhanced electrochemical sensors and energy storage devices. Graphene is a single-atom-thick sheet of sp2 hybridized carbon with large lateral dimension; there are varieties of graphene-derived materials. These include graphenes with more than one layer, such as double and few-layer (3–9 layers) or multilayer (10 or more layers) grapheme structures. The graphene family also includes graphene structures that are dimensionally limited along the basal plane of the graphene sheets, in x–y axes, from a few to hundred nanometers, thus creating grapheme nanoribbons, which can also have a single- (G-SL), few- (G-FL), or multilayer (G-ML) structure (see Fig. 1). Graphene nanostructures are projected to play significant roles in energy storage devices. The electrochemical capacitance of graphene nanostructures has a direct and very important relevance to their energy storage capacity. It has been demonstrated that the electrochemical capacitance of graphitic nanomaterials such as nanotubes and nanofibers directly depends on the number of available graphene edge planes. Significant efforts are being put into the exfoliation of graphene to create single-layer graphene sheets. However, we wish to show here that single-layer graphene structures do not always provide an electrochemical advantage and that multilayered structures provide higher capacitance than do single-layer sheets. Corresponding author: [email protected] or [email protected] Electrochemistry Communications 12 (2010) 1375–1377


A31. Partially reduced graphite oxide for supercapacitor electrodes: Effect of grapheme layer spacing and huge specific capacitance M.M. Hantel

a, T. Kaspar

b, R. Nesper

b, A. Wokaun

a, R. Kötz

a

a General Energy Research Department, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland b Laboratory of Inorganic Chemistry, ETH Zürich, CH-8092 Zürich, Switzerland

Partially reduced graphite oxide (GOpr) prepared from natural as well as synthetic graphite was used as electrode material for supercapacitors in 1 M Et4NBF4 in acetonitrile electrolyte. As a function of the degree of reduction of graphite oxide (GO) the graphite layer distance was varied between 0.46 and 0.33 nm. The initial specific capacitance of all samples was negligibly small around the open circuit potential, which was in agreement with the small BET surface area of the reduced GO powder of around 5 m2/g. During the first potential cycle, however, electrochemical activation resulted in a specific capacitance of up to 220 F/g for samples with a graphene layer distance of 0.44 nm. The potential for anodic and cathodic electrochemical activation was found to be a function of the GO layer distance. Dilatometrie investigations showed a significant swelling and shrinking of the samples. Corresponding author: [email protected] Electrochemistry Communications 13 (2011) 90–92 A32. Preparation of functionalized graphene sheets by a low-temperature thermal exfoliation approach and their electrochemical supercapacitive behaviours Qinglai Du, Mingbo Zheng, Lifeng Zhang, Yongwen Wang, Jinhua Chen, Luping Xue, Weijie Dai, Guangbin Ji, Jieming Cao Nanomaterials Research Institute, College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Yudao Street 29, Nanjing 210016, China

Two kinds of functionalized graphene sheets were produced by thermal exfoliation of graphite oxide. The first kind of functionalized graphene sheets was obtained by thermal exfoliation of graphite oxide at low temperature in air. The second kind was prepared by carbonization of the first kind of functionalized graphene sheets at higher temperature in N2. Scanning electron microscopy images show that both two kinds of samples possess nanoporous structures. The results of N2 adsorption–desorption analysis indicate that both of two kinds of samples have high BET surface areas. Moreover, the second kind of functionalized graphene sheets has a relatively higher BET surface area. The results of electrochemical tests is as follows: the specific capacitance values of the first kind of functionalized graphene sheets in aqueous KOH electrolyte are about 230 F g−1; the specific capacitance values of the second kind of functionalized graphene sheets with higher BET surface areas are only about 100 F g−1; however, compared with the first kind of functionalized graphene sheets, the second kind has a higher capacitance retention at large current density because of its good conductive behaviors; furthermore, in nonaqueous EC/DEC electrolyte, the specific capacitance values of the first kind sample and the second kind sample are about 73 F g−1 and 36 F g−1, respectively.


Corresponding author: [email protected] Electrochimica Acta 55 (2010) 3897–3903 A33. True Performance Metrics in Electrochemical Energy Storage Y. Gogotsi

1 and P. Simon

2

1Department of Materials Science and Engineering and A. J. Drexel Nanotechnology Institute,

Drexel University, Philadelphia, PA 19104, USA. 2Université Paul Sabatier–Toulouse III, CIRIMAT UMR-CNRS 5085, 118 Route de

Narbonne,31062 Toulouse, France

Exceptional performance claims for electrodes used in batteries and electrochemical capacitors often fail to hold up when all device components are included. A dramatic expansion of research in the area of electrochemical energy storage (EES) during the past decade has been driven by the demand for EES in handheld electronic devices, transportation, and storage of renewable energy for the power grid. However, the outstanding properties reported for new electrode materials may not necessarily be applicable to performance of electrochemical capacitors (ECs). These devices, also called supercapacitors or ultracapacitors, store charge with ions from solution at charged porous electrodes. Unlike batteries, which store large amounts of energy but deliver it slowly, ECs can deliver energy faster (develop high power), but only for a short time. However, recent work has claimed energy densities for ECs approaching or even exceeding that of batteries. We show that even when some metrics seem to support these claims, actual device performance may be rather mediocre. We will focus here on ECs, but these considerations also apply to lithium (Li) −ion batteries. Corresponding authors: [email protected]; [email protected] SCIENCE 334 (2011) 917-918


3. Selected Patents

3.1. Graphene – Electrochemical Method

The keyword graphene search has revealed 20 patents when electrochemical method was used as an additional keyword. Selected abstracts and claims of some selected patents are presented below.

P1. Method for preparing novel high-performance composite nanometer material modified electrode

Page bookmark CN 101792137 (A) - Method for preparing novel high-performance composite nanometer material modified electrode

Publication date:

2010-08-04

Inventor(s): DANMING CHAO; LILI CUI; JIN E; XIAOFENG LU; CE WANG +

Applicant(s): UNIV JILIN +

Classification: - international: C01B31/04; C01C3/14

- European:

Application number:

CN20101030844 20100120

Priority number(s):

CN20101030844 20100120

View INPADOC patent family

View list of citing documents

Abstract of CN 101792137 (A)

The invention belongs to the technology for preparing a graphene and prussian blue composite nanometer sheet material modified electrode and particularly relates to a method for preparing the graphene and prussian blue composite nanometer sheet material modified electrode by utilizing a simple wet chemical method. The method has the advantages of simple operation, low cost, large specific surface area of the prepared material, good dispersibility and the like. The invention uses graphite, ferric chloride, potassium ferricyanate and potassium chloride as the raw materials and adopts the wet chemical method to prepare a graphene/prussian blue composite nanometer sheet. The invention utilizes the reduction performance of the graphene sheet so as to directionally load prussian blue on the surface of the graphene sheet. An H2O2 electrochemical sensor with better response recovery, high sensitivity and low detection limit can be prepared by the method. The method has the advantages of simple operation, low cost, high performance, easy popularization and the like and can meet the wide application in the fields of chemistry, clinical medicine, biomedicine and the like.


P2. Green and fast electrochemical preparation method for graphene

Page bookmark CN 101634032 (A) - Green and fast electrochemical preparation method for graphene

Publication date: 2010-01-27

Inventor(s): XINGHUA XIA; HUILIN GUO; XIANFEI WANG +

Applicant(s): UNIV NANJING +

Classification: - international: C25B1/00

- European:

Application number:

CN20091184202 20090814

Priority number(s):

CN20091184202 20090814




The invention relates to an electrochemical preparation method for graphene, comprising the following steps: taking chemical and electrochemical stability metal and alloy or nonmetal conductor materials as a cathode and an anode, under the condition of stirring, the temperature of 5 below zero DEG C to 90 DEG C and a constant voltage of negative 1.5 V to 10.0negative V, electrolytic reduction is carried out on oxidation state graphene solution for 1min to 10h, to form high-quality graphene on the surface of a cathode electrode; or coating the oxidation state graphene solution on the surface of cathode materials in a dripping way to obtain the grapheme by reducing, and the grapheme is used for applications of modifying the electrode as biosense, and the like. In the method for preparing the graphene, an oxygen-containing functional group on oxidation state graphene is utilized to be reduced by obtaining electrons on the cathode. Except needing one electrochemical workstation, the invention does not need any other special equipment, therefore, the invention has simple manufacture method, easy control of a reaction process, low cost, no pollution, high quality of the prepared graphene, and easy popularization and use of the preparation technology.

P3. ULTRACAPACITORS AND METHODS OF MAKING AND USING

Page bookmark WO 2009134707 (A2) - ULTRACAPACITORS AND METHODS OF MAKING AND USING

Publication date:

2009-11-05

Inventor(s): RUOFF RODNEY S [US]; STOLLER MERYL [US] +

Applicant(s): UNIV TEXAS [US]; RUOFF RODNEY S [US]; STOLLER MERYL [US] +

Classification: - international: H01G9/042; H01G9/058

- European: H01G9/058; Y02E60/13

Application number:

WO2009US41768 20090427

Priority US20080048196P 20080427


number(s):



Also published as:

• WO 2009134707 (A3) • US 2010035093 (A1)

Cited documents:

US7150840 (B2) US2002141140 (A1) US2002098135 (A1) US2007212538 (A1) View all

Abstract of WO 2009134707 (A2)

An electrochemical device comprising a chemically modified graphene material is disclosed. An ultracapacitor comprising a chemically modified graphene material is disclosed, along either with a method of making an ultracapacitor, the method comprising forming two electrodes, wherein at least one of the two electrodes comprises a graphene material, and positioning each of the two electrodes such that each is in contact with an opposing side of a separator and a current collector.

P4. Electrochemical method of producing nano-scaled graphene platelets

Page bookmark US 2009026086 (A1) - Electrochemical method of producing nano-scaled graphene platelets


Inventor(s): ZHAMU ARUNA [US]; JANG JOAN [US]; JANG BOR Z [US] +

Applicant(s):

Classification:

international: C25B1/00

European: B82Y30/00; C01B31/00D; C01B31/02B; C01B31/04

Application number:

US20070881388 20070727

Priority number(s):

US20070881388 20070727



Abstract of US 2009026086 (A1)

A method of producing nano-scaled graphene platelets with an average thickness smaller than 30 nm from a layered graphite material. The method comprises (a) forming a carboxylic acid-intercalated graphite compound by an electrochemical reaction which uses a carboxylic acid as both an electrolyte and an intercalate source, the layered graphite material as an anode material, and a metal or graphite as a cathode material, and wherein a current is imposed upon the cathode and the anode at a current density for a duration of time sufficient for effecting the electrochemical reaction; (b) exposing the intercalated graphite compound to a thermal shock to produce exfoliated graphite; and (c) subjecting the exfoliated


graphite to a mechanical shearing treatment to produce the nano-scaled graphene platelets. Preferred carboxylic acids are formic acid and acetic acid. The exfoliation step in the instant invention does not involve the evolution of undesirable species, such as NOx and SOx, which are common by-products of exfoliating conventional sulfuric or nitric acid-intercalated graphite compounds. The nano-scaled platelets are candidate reinforcement fillers for polymer nanocomposites. Nano-scaled graphene platelets are much lower-cost alternatives to carbon nano-tubes or carbon nano-fibers.

P5. METHOD FOR ENCAPSULATING METALS AND METAL OXIDES WITH GRAPHENE AND USE OF SAID MATERIALS

Page bookmark WO 2011141486 (A1) - METHOD FOR ENCAPSULATING METALS AND METAL OXIDES WITH GRAPHENE AND USE OF SAID MATERIALS

Publication date:

2011-11-17

Inventor(s): IVANOVICI SORIN [DE]; YANG SHUBIN [DE]; FENG XINLANG [DE]; MUELLEN KLAUS [DE] +

Applicant(s): BASF SE [DE]; MAX PLANCK GESELLSCHAFT [DE]; IVANOVICI SORIN [DE]; YANG SHUBIN [DE]; FENG XINLANG [DE]; MUELLEN KLAUS [DE] +

Classification: - international: C01G51/04; C09C3/08; H01M4/525

- European: C01G51/04; C09C3/08

Application number:

WO2011EP57563 20110510

Priority number(s):

EP20100162807 20100514



Cited documents:

XP055002990 (A) View all



The invention relates to a method for coating nanoparticles with graphene, comprising the steps: (a) providing a suspension, comprising a suspension medium and nanoparticles having a positive surface charge; (b) adding graphene oxide particles to the suspension from step (a), wherein the graphene oxide particles deposit on the nanoparticles; and (c) converting the graphene oxide particles deposited on the nanoparticles into graphene, nanoparticles coated with graphene, containing at least one metal, a metalloid, a metal compound and/or a metalloid compound. The invention further relates to the use of said graphene-coated nanoparticles in electrochemical cells and super capacitors, and to super capacitors and electrochemical cells containing said nanoparticles.

P6. CONDUCTIVE GRAPHENE POLYMER BINDER FOR ELECTROCHEMICAL CELL ELECTRODES

Page bookmark WO 2011079238 (A1) - CONDUCTIVE GRAPHENE POLYMER BINDER FOR ELECTROCHEMICAL CELL ELECTRODES

Publication date:

2011-06-30

Inventor(s): ZHAMU ARUNA [US]; JANG BOR Z [US] +

Applicant(s): ZHAMU ARUNA [US]; JANG BOR Z [US] +

Classification:

international: H01M4/131; H01M4/139; H01M4/62

European: H01G9/058; H01M4/131; H01M4/139; H01M4/62B; H01M4/62C2; Y02E60/12B

Application number:

WO2010US61949 20101223

Priority number(s):

US20090655172 20091224



Also published as:

• US 2011159372 (A1)

Cited documents:

WO2009061685 (A1) WO2009085015 (A1) US2009092747 (A1) View all


The present invention provides an electrically conductive electrode comprising particles of an electroactive material and a conductive graphene polymer binder that bonds multiple particles of the electroactive material together, wherein the binder is in an amount of from 0.01% to 90% by weight based on the total electrode weight. Also provided are (a) a precursor solution or suspension to the graphene polymer binder for the electrode; (b) a paste containing electroactive particles and a graphene polymer dispersed in a liquid; (c) a method of producing the electrode from the precursor paste; and (d) an electrochemical cell (a battery or supercapacitor) containing such an electrode.


P7. Graphene/titanium dioxide lithium ion battery cathode material and preparation method

Page bookmark CN 101937985 (A) - Graphene/titanium dioxide lithium ion battery cathode material and preparation method


Inventor(s): LIZHEN FAN; HUACHAO TAO; YUCHUAN FENG; LIGONG CHEN +

Applicant(s): UNIV BEIJING SCIENCE & TECH; HEBEI SHANXIN TAIRUI BATTERY TECHNOLOGY CO LTD +

Classification: - international: H01M4/13; H01M4/139

- European: Y02E60/12B

Application number:

CN20101256906 20100819

Priority number(s):

CN20101256906 20100819




The invention discloses a graphene/titanium dioxide lithium ion battery cathode material and a preparation method, and belongs to the field of electrochemistry and new energy materials. The method comprises the following steps of: oxidizing graphite powder into graphite oxide by using concentrated sulfuric acid or potassium permanganate as an oxidant, peeling the graphite oxide to form graphene oxide by adopting an ultrasonic peeling method, mixing the graphite oxide and a titanium source, preparing a graphite oxide/titanium dioxide composite material by liquid phase reaction, and then reducing the graphite oxide/titanium dioxide composite material into the graphene/titanium dioxide composite material by adopting liquid phase reduction. Electrochemical tests show that the graphene/titanium dioxide composite material prepared by the method has high specific capacity and cyclical stability, and is an ideal lithium ion battery cathode material. The material has relatively high specific capacity and cyclical stability, and can exert respective advantages of graphene and titanium dioxide. The preparation method is relatively simple, has low cost, and is suitable for industrialized production.

P8. Preparation method of polypyrrole/ graphene composite material

Page bookmark CN 101882480 (A) - Preparation method of polypyrrole/ graphene composite material


Inventor(s): DACHENG ZHANG; YANWEI MA; XIONG ZHANG; YAO CHEN; PENG YU +

Applicant(s): INST OF ELECTRICIAN CHINESE ACADEMY OF SCIENCES +

Classification: - international: H01B1/04; H01B1/12; H01B13/00; H01G9/042

- European: Y02E60/13

Application number:

CN20101209772 20100618

Priority number(s): CN20101209772 20100618





The invention relates to a preparation method of polypyrrole/ graphene composite material, comprising the steps of: reducing graphite oxide by hydrazine hydrate, washing the reduction product by deionized water, and obtaining graphene colloid which is evenly dispersed; mixing the graphene colloid and pyrrole monomer according to a certain proportion, carrying out ultrasonic dispersion, and then stirring under the condition of ice bath; slowly dripping FeCl3 hydrochloric acid solution into reactant, and leading the reactant to react under the condition of ice bath after dripping; and finally, washing and drying after the reaction, and obtaining the polypyrrole/ graphene composite material powder. The invention has simple technique condition and low cost, and the polypyrrole in the prepared composite material is evenly covered by graphene. Furthermore, the polypyrrole/ graphene composite material can be taken as super-capacitor, and has high conductivity and good electrochemical performance.

P9. Preparation method of lithium titanate-graphene combination electrode material

Page bookmark CN 101877405 (A) - Preparation method of lithium titanate-graphene combination electrode material


Inventor(s): HAIHUI WANG; BINGBING TIAN; PEICHAO LIAN +

Applicant(s): UNIV SOUTH CHINA TECH +


- European: Y02E60/12B

Application number:

CN20101156850 20100420

Priority number(s):

CN20101156850 20100420




The invention relates to a preparation method of lithium titanate-graphene combination electrode material, belonging to the field of electrochemical power source; in the invention, the lithium titanate and graphite oxide are mixed and are prepared into titanate-graphene combination electrode material by heating under inert atmosphere; in the synthesized lithium titanate-graphene combination electrode material, metallic lithium is used as the cathode for preparing a battery, and the first charging and discharging capacity exceeds 186mAh/g when 10C charging and discharging is carried out; after 100 circles of the charging and discharging are carried out, the discharging capacity is higher than 116mAh/g. the method in the invention has low cost, and simple and flexible preparation procedures, and is suitable for industrial large-scale production. High multiplying power of the prepared titanate-graphene combination electrode material has good performance, and the combination electrode material has high specific capacity and can be widely applied to lithium ion batteries of various kinds of portable electronic equipment and various electric motors.


P10. Method for preparing graphene-based flexible super capacitor and electrode material thereof

Page bookmark CN 101894679 (A) - Method for preparing graphene-based flexible super capacitor and electrode material thereof


Inventor(s): HUIMING CHENG; FENG LI; DAWEI WANG; WENCAI REN; ZHONGSHUAI WU +

Applicant(s): INST METAL RES CHINESE ACAD SC +

Classification: - international: C25D9/02; C25D9/04; H01G9/058; H01G9/155


Application number:

CN20091011632 20090520

Priority number(s):

CN20091011632 20090520



Also published as:

• CN 101894679 (B)


The invention relates to a method for preparing a graphene-based flexible super capacitor and an electrode material. The method comprises the following steps of: (1) filtering graphene aqueous dispersion with different concentrations through a filter film to form a film-shaped product, drying the filter film and the film-shaped product and stripping the film-shaped product from the filter film so as to obtain a graphene thin film; (2) taking the graphene thin film as an electrode material, taking sulfuric acid and aqueous solution of conducting polymer or transition metal oxide as electrolyte solution respectively, and depositing the conducting polymer or the transition metal oxide on the surface of the graphene thin film by adopting constant potential electrochemical deposition so as to prepare a grapheme-based composite thin film; and (3) taking the grapheme-based composite thin film as an electrode material, taking the sulfuric acid or saline solution as electrolyte solution, taking flexible plastics as packaging materials, and assembling into an electrochemical capacitor.; Through the method, the super capacitor which has higher weight capacity and volume capacity and has a flexible structure is obtained, and the application of the super capacitor can be further expanded in the fields of energy and electronic devices.


3.2 Graphene – CVD Method

The keyword graphene search has revealed 8 patents when CVD was used as an additional keyword and 6 patents of these 8 when CVD method was used as an additional keyword. Selected abstracts and claims of some selected patents are presented below.

P11. MANUFACTURING METHOD FOR TRANSPARENT CONDUCTIVE CARBON FILM, AND TRANSPARENT CONDUCTIVE CARBON FILM

Page bookmark

WO 2011115197 (A1) - MANUFACTURING METHOD FOR TRANSPARENT CONDUCTIVE CARBON FILM, AND TRANSPARENT CONDUCTIVE CARBON FILM

Publication date:

2011-09-22

Inventor(s): KIM JAEHO [JP]; ISHIHARA MASATOU [JP]; KOGA YOSHINORI [JP]; TSUGAWA KAZUO [JP]; HASEGAWA MASATAKA [JP]; IIJIMA SUMIO [JP]; YAMADA TAKATOSHI [JP] +

Applicant(s):

NAT INST OF ADVANCED IND SCIEN [JP]; KIM JAEHO [JP]; ISHIHARA MASATOU [JP]; KOGA YOSHINORI [JP]; TSUGAWA KAZUO [JP]; HASEGAWA MASATAKA [JP]; IIJIMA SUMIO [JP]; YAMADA TAKATOSHI [JP] +

Classification: - international: C23C16/26; C23C16/511; C23C16/54; H01B13/00

- European:

Application number:

WO2011JP56352 20110317

Priority number(s):

JP20110041749 20110228; JP20110009616 20110120; JP20100200901 20100908; JP20100060055 20100317



Cited documents:

JP2009143799 (A) JP2008010683 (A) JP6216039 (A) WO2005103326 (A1) View all


The disclosed method for the formation of a transparent conductive carbon film solves the problems of high temperature processing and long processing times, which are issues in graphene film deposition by thermal CVD, and uses a crystalline carbon film formed at lower temperatures and in less time using a graphene film. The disclosed method is characterised in that: the substrate temperature is set to 500 DEG C or less; the pressure is set to 50 Pa or less; and a transparent conductive carbon film is deposited on the substrate surface of a copper or aluminium thin film by a microwave surface-wave plasma CVD process under a gas atmosphere in which an oxidation inhibitor for inhibiting the oxidation of the substrate surface is added to a mixed gas comprising a carbon-containing gas and an inert gas as an additive gas.


P12. CARBON FILM LAMINATE

Page bookmark WO 2011105530 (A1) - CARBON FILM LAMINATE

Publication date:

2011-09-01

Inventor(s): HASEGAWA MASATAKA [JP]; ISHIHARA MASATOU [JP]; KOGA YOSHINORI [JP]; KIM JAEHO [JP]; TSUGAWA KAZUO [JP]; IIJIMA SUMIO [JP] +

Applicant(s): NAT INST OF ADVANCED IND SCIEN [JP]; HASEGAWA MASATAKA [JP]; ISHIHARA MASATOU [JP]; KOGA YOSHINORI [JP]; KIM JAEHO [JP]; TSUGAWA KAZUO [JP]; IIJIMA SUMIO [JP] +


- European:

Application number:

WO2011JP54243 20110225

Priority number(s):

JP20100041419 20100226



Cited documents:

JP2009143799 (A) WO2011025045 (A1) View all


Disclosed is a carbon film laminate in which a graphene having a larger crystal size is deposited. The carbon film laminate has solved the problem of conventional graphene film formation by thermal CVD that uses a copper film as a substrate, namely the problem of small crystal size. Specifically disclosed is a carbon film laminate which comprises: a sapphire (0001) single crystal substrate having a surface that is composed of a terrace surface, which is flat on the atomic level, and an atomic layer step; a copper (111) single crystal thin film that is epitaxially grown on the substrate; and a graphene that is deposited on the copper (111) single crystal thin film. In this laminate, a graphene having a large crystal size can be formed.

P13. PROCESS FOR PRODUCING MONOATOMIC FILM

Page bookmark WO 2009119641 (A1) - PROCESS FOR PRODUCING MONOATOMIC FILM


Inventor(s): OSHIMA CHUHEI [JP] +

Applicant(s): UNIV WASEDA [JP]; OSHIMA CHUHEI [JP] +


Classification:

international: B82B3/00; C01B31/04; C23C16/01

European: C01B31/04; C23C16/02B; C23C16/26; C23C16/34B; C30B25/02; C30B29/02

Application number:

WO2009JP55905 20090325

Priority number(s):

JP20080079582 20080326




In a surface of a substrate comprising a chemically dissoluble metal or metal compound, a surface of a single crystal of the metal or metal compound is formed in which atoms constituting the metal or metal compound have been regularly arranged. This surface of the single crystal is used as a template, and a monoatomic film is formed on the single-crystal surface by the chemical vapor deposition (CVD) method in which a raw-material gas is brought into contact with the single-crystal surface. After the monoatomic film has been formed on the single-crystal surface of the substrate, this substrate is chemically dissolved away, whereby the monoatomic film is isolated. According to this process, a monoatomic film having a thickness corresponding to one atom, such as a graphene film or h-BN film, can be stably produced with satisfactory reproducibility. A monoatomic film having a far larger area than conventional ones and having satisfactory quality can be produced.

P14. CVD-GROWN GRAPHITE NANORIBBONS

Page bookmark

WO 2009151659 (A2) - CVD-GROWN GRAPHITE NANORIBBONS

Publication date:

2009-12-17

Inventor(s):

CAMPOS-DELGADO JESSICA [MX]; DRESSELHAUS MILDRED S [US]; ENDO MORINOBU [JP]; GRACIA-ESPINO EDGAR E [MX]; JIA XIAOTING [US]; ROMO-HERRERA JOSE MANUEL [MX]; TERRONES HUMBERTO [MX]; TERRONES MAURICIO [MX] +

Applicant(s):

MASSACHUSETTS INST TECHNOLOGY [US]; CAMPOS-DELGADO JESSICA [MX]; DRESSELHAUS MILDRED S [US]; ENDO MORINOBU [JP]; GRACIA-ESPINO EDGAR E [MX]; JIA XIAOTING [US]; ROMO-HERRERA JOSE MANUEL [MX]; TERRONES HUMBERTO [MX]; TERRONES MAURICIO [MX] +

Classification: - international: B82B1/00; B82B3/00


- European: B82Y30/00; C01B31/02B; D01F9/127

Application number:

WO2009US35644 20090302

Priority number(s):

US20080042544 20080305



Also published as:

• WO 2009151659 (A3)

• US 2009226361 (A1)

Cited documents:

US6586093 (B1) View all


The nanoribbon structure includes a plurality of thin graphite ribbons having long and highly crystalline structure. A voltage is applied across the length of the thin graphite ribbons to cause current flow so as to increase crystallinity as well as establishing interplanar stacking order and well-defined graphene edges of the thin graphite ribbons.

P15. GRAPHENE HYBRID MATERIAL AND METHOD FOR PREPARING THE SAME USING CHEMICAL VAPOR DEPOSITION

Page bookmark KR 20090017454 (A) - GRAPHENE HYBRID MATERIAL AND METHOD FOR PREPARING THE SAME USING CHEMICAL VAPOR DEPOSITION

Publication date:

2009-02-18

Inventor(s): LEE JAE KAP [KR]; LEE SEUNG CHEOL [KR]; JOHN PHILLIP [GB]; LEE WOOK SEONG [KR]; LEE JEON KOOK [KR] +

Applicant(s): KOREA INST SCI & TECH [KR] +

Classification:

international: C01B31/00; C01B31/04; C30B29/36

European: B82Y15/00; B82Y30/00; C01B31/04H2D; C23C16/01; C23C16/26; C30B25/02; C30B29/02; C30B29/04

Application number:

KR20080080167 20080814

Priority KR20070081989 20070814


number(s):



Also published as:

• KR 101019029 (B1)

• US 2009047520 (A1)

• US 7776445 (B2)

Abstract of KR 20090017454 (A)

A grapheme hybrid material in which grapheme is epitaxially grown to form a predetermined angle to the surface of a matrix using chemical vapor deposition is provided, a method for preparing the same is provided, a method of preparing grapheme to a large diameter of 8 inches or more is provided, and a method of obtaining a grapheme/matrix hybrid material and a carbon nanomaterial/diamond film hybrid material at the same time and obtaining a CVD diamond film and grapheme successively is provided. A grapheme hybrid material comprises: a matrix having a cut lattice plane on the surface thereof; and grapheme epitaxially grown along the cut lattice plane of the matrix surface.; A method for preparing a grapheme hybrid material comprises epitaxially growing the graphene along the cut lattice plane of the matrix surface while forming a predetermined angle to the matrix by a chemical vapor deposition method of contacting reaction gas comprising hydrogen and carbon components with a matrix having a cut lattice plane on the surface thereof such that graphene is capable of being epitaxially grown on the cut lattice plane.

P16. MANUFACTURING METHOD OF ELECTRON EMISSION ELEMENT AND DISPLAY DEVICE

Page bookmark JP 2008153021 (A) - MANUFACTURING METHOD OF ELECTRON EMISSION ELEMENT AND DISPLAY DEVICE


Inventor(s): YAMAGE MASASHI +

Applicant(s): TOSHIBA CORP +


Classification: - international: H01J1/304; H01J31/12; H01J9/02

- European:

Application number:

JP20060338696 20061215

Priority number(s):

JP20060338696 20061215



Abstract of JP 2008153021 (A)

PROBLEM TO BE SOLVED: To provide a manufacturing method of an electron emission substance capable of surely constituting an electron emission part with a required structure under a lower temperature condition, and a display device. ; SOLUTION: In the manufacturing method of the electron emission element containing a carbon material and shaped in a fibrous or tubular form forming graphite nanotube 21 with an end face 22a of a graphene sheet 22 exposed at a side part on a conductive catalyst layer 12 with conductivity, the conductive catalyst layer 12 is heated, mixture gas is guided in around the conductive catalyst layer 12, and plasma is generated to carry out CVD.

P17. METHOD FOR PRODUCING SINGLE CRYSTAL GRAPHITE FILM

Page bookmark JP 2008050228 (A) - METHOD FOR PRODUCING SINGLE CRYSTAL GRAPHITE FILM


Inventor(s): UMENO MASAYOSHI; PRAKASH R SOMANI +

Applicant(s): UMENO MASAYOSHI +


- European:

Application number:

JP20060229947 20060826

Priority number(s):

JP20060229947 20060826



Cited documents: JP10194888 (A) JP2179878 (A) JP63004069 (A) JP2007100151 (A) View all



PROBLEM TO BE SOLVED: To obtain a graphene stacked body having a thickness of ten to several tens of nanometers by a simple method. ; SOLUTION: In a single crystal graphite film deposition apparatus 100 shown in Fig.1, a CVD reaction vessel 1 constituted of a quartz tube is fixed horizontally, argon (Ar) gas as a carrier gas is introduced from a left side port 1L and discharged from a right side port 1R, a first area 10 is provided on the left side of the central part of the reaction vessel 1, a second area 20 is provided on the right side of the central part, and each of the areas is kept at a prescribed temperature by an independent heating device 15 or 25. In the first area 10, 0.1-1 g of camphor is arranged, and in the second area 20, three nickel (Ni) plates 21 each having a square with one side of 2 cm are provided. The first area 10 is heated up to 100[deg.]C to vaporize camphor, and a graphite film is deposited on the Ni plates 21, provided in the second area 20 where is kept at 700-900[deg.]C, by a CVD process.

P18. ELECTRON EMISSION ELECTRODE AND ITS MANUFACTURING METHOD

Page bookmark JP 2005108721 (A) - ELECTRON EMISSION ELECTRODE AND ITS MANUFACTURING METHOD


Inventor(s): NISHIMURA KAZUHITO; SASAOKA HIDENORI; KO MINAMI; O HIROOKI; HIRAKI HIROHISA +

Applicant(s): KOCHI PREFECTURE; KOCHI PREFECTURE SANGYO SHINKO; CASIO COMPUTER CO LTD +

Classification: - international: H01J1/304; H01J9/02; (IPC1-7): H01J1/304; H01J9/02

- European:

Application number:

JP20030342415 20030930

Priority number(s):

JP20030342415 20030930



Also published as:

• JP 4423496 (B2)


PROBLEM TO BE SOLVED: To provide an electron emission electrode which has high electron emission efficiency and is easy to be manufactured. ; SOLUTION: A substrate 11 is formed by fixing diamond particles of a particle size of 5-30 [mu]m on a base body 12. A petal-like carbon flake aggregate 14 in which carbon flakes are


connected in a random direction with respect to the substrate is formed by using gas containing carbon and hydrogen gas by a DC plasma CVD by keeping the temperature of the substrate 11 at 950-1,200[deg.]C. Each carbon flake is constituted of a graphene sheet of a height of 1 nm-500 nm and the interval between each flake at an outer side aperture is 3 [mu]m or less and the size of the petal-like carbon flake aggregate 14 is 5 [mu]m-30 [mu]m, and the interval between adjoining carbon flake aggregates is 1 D-10 D when the diameter of the flake aggregate is made D.


3.3. Graphene – electrode material

The keyword graphene search has revealed 73 patents when electrode material was used as an additional keyword. Selected abstracts and claims of some selected patents are presented below.

P19. Preparation method of electrode material graphene nanometer sheet and electrode sheet prepared therefrom

Page bookmark CN 101870466 (A) - Preparation method of electrode material graphene nanometer sheet and electrode sheet prepared therefrom


Inventor(s): XIAOHONG CHEN; HUAIHE SONG; SHENGNA ZHAO +

Applicant(s): UNIV BEIJING CHEMICAL +

Classification: - international: C01B31/04; H01G9/058

- European:

Application number:

CN20101178452 20100520

Priority number(s):

CN20101178452 20100520




The invention provides a preparation method of an electrode material graphene nanometer sheet and an electrode sheet of a super capacitor prepared from the material. An electrode of the super capacitor assembled by using the material has a stable specific capacity up to 164-210 F/g under the current density of 100 mA/g; and a capacity retention ratio is more than 85% when the current density is gradually increased to 2000 mA/g from 1000 mA/g. The preparation of the graphene nano sheet by using a ball milling method has the advantages of simple method, easy operation, high specific capacity, good cycle performance and the like.

P20. GRAPHENE COMPOSITE NANOFIBER AND PREPARATION METHOD THEREOF

Page bookmark US 2010317790 (A1) - GRAPHENE COMPOSITE NANOFIBER AND PREPARATION METHOD THEREOF

Publication date:

2010-12-16

Inventor(s): JANG SUNG-YEON [KR]; PARK HO SEOK [KR]; JO SEONG MU [KR]; KIM DONG YOUNG [KR]; HONG WON HI [KR]; LEE SANG YUP [KR]; PARK TAE JUNG [KR]; CHOI BONG GILL [KR] +

Applicant(s):

Classification: - international: B29C47/00; C08K3/04

- European:

Application number:

US20100712653 20100225

Priority KR20090018146 20090303


number(s):



Also published as:

• KR 20100099586 (A)


Disclosed are a graphene composite nanofiber and a preparation method thereof. The graphene composite nanofiber is produced by dispersing graphenes to at least one of a surface and inside of a polymer nanofiber or a carbon nanofiber having a diameter of 1~1000 nm, and the graphenes include at least one type of monolayer graphenes, and multilayer graphenes having a thickness of 10 nm or less. The graphene composite nanofiber can be applied to various industrial fields, e.g., a light emitting display, a micro resonator, a transistor, a sensor, a transparent electrode, a fuel cell, a solar cell, a secondary cell, and a composite material, owing to a unique structure and property of graphene.

P21. ELECTRODE MATERIAL AND CAPACITOR

Page bookmark WO 2010045888 (A1) - ELECTRODE MATERIAL AND CAPACITOR

Publication date:

2010-04-29

Inventor(s): CHEN YONGSHENG [CN]; HUANG YI [CN]; WANG YAN [CN]; MA YANFENG [CN] +

Applicant(s): UNIV NANKAI [CN]; TIANJIN PULAN NANO TECHNOLOGY [CN]; CHEN YONGSHENG [CN]; HUANG YI [CN]; WANG YAN [CN]; MA YANFENG [CN] +

Classification: - international: H01G9/042; H01G9/058; H01G9/155

- European: H01G9/042; H01G9/058; Y02E60/13

Application number:

WO2009CN74620 20091026

Priority number(s):

CN20081152470 20081024



Also published as:

• CN 101383231 (A)

• CN 101383231 (B)

Cited documents:

CN101383231 (A) CN1757085 (A) View all



An electrode material containing 0.5-50wt.% functionalized graphene material and a capacitor comprising the electrode material are provided. A method for preparing the functionalized graphene material is also provided. The method comprises the step of chemically reducing the soluble graphene material and the step of physically reducing the chemically reduced graphene material.

P22. NOVEL CAPACITORS AND CAPACITOR-LIKE DEVICES

Page bookmark US 2010084697 (A1) - NOVEL CAPACITORS AND CAPACITOR-LIKE DEVICES

Publication date:

2010-04-08

Inventor(s): KOPP THILO [DE]; MANNHART JOCHEN DIETER [DE] +

Applicant(s):

Classification:

international: H01G4/00; H01G4/008; H01L29/92

European: H01G4/008; H01G4/33; H01L21/02B3B4; H01L21/02B3C; H01L29/16G; H01L29/94; H01L41/047; H01L45/00B; H01L45/00B2

Application number:

US20090570090 20090930

Priority number(s):

US20090570090 20090930; US20080102174P 20081002; US20090152389P 20090213




A capacitor and capacitor-like device or any other device showing capacitive effects, including FETs, transmission lines, piezoelectric and ferroelectric devices, etc., with at least two electrodes, of which at least one electrode consists of or comprises a material or is generated as electron system, whose absolute value of the electronic charging energy as defined by the charging-induced change of Ekin+Eexc+Ecorr exceeds 10% of the charging-induced change of the Coulomb field energy of the capacitor according to E=Ecoul+Ekin+Eexc+Ecorr. Therein, E is the energy of a capacitor and Ecoul=Q2/2 Ccoul=Q2d/(2 [epsilon]0 [epsilon]x A), A is the area of the capacitor electrodes, d is the distance and [epsilon]0[epsilon]x the dielectric constant between them. Ecorr describes the correlation energy, Ekin the electronic kinetic energy and Eexc the exchange energy of the electrode material. Particularly in miniaturized devices, Ecoul is becoming so small that, by using certain materials or material combinations for the capacitor, Ekin, Eexc, and/or Ecorr provide significant contributions to E. Preferred are materials with strongly correlated electron systems


such as perovskites like La1-xSrxTiO3, YBa2Cu3O7-d, vanadates such as (V1-xAx)2O3 with A=Cr, Ti, materials with free electron gases of typically low densities such as Cs, Bi or Rb, or of materials the carrier density of which is reduced by diluting these materials in other materials with smaller carrier densities, metals like Fe, or Ni, materials with van-Hove singularities in the electronic density of states such as graphite or Bechgaard salts or even or 2D-electron gases generated by graphene or by heterostructures, such as the electron gases generated at LaAlO3/SrTiO3 or ZnO/(MgxZn1-x)O multilayers and more.

P23. A METHOD FOR MANUFACTURING GRAPHENE FILM, GRAPHENE FILM MANUFUCTURED BY THE SAME, ELECTRODE MATERIAL COMPRISING THE SAME

Page bookmark KR 20100136576 (A) - A METHOD FOR MANUFACTURING GRAPHENE FILM, GRAPHENE FILM MANUFUCTURED BY THE SAME, ELECTRODE MATERIAL COMPRISING THE SAME

Publication date:

2010-12-29

Inventor(s): SEO TAE SEOK [KR]; LIU FEI [CN] +

Applicant(s): KOREA ADVANCED INST SCI & TECH [KR] +

Classification: - international: C01B31/02; H01L31/042; H01M4/96


Application number:

KR20090054708 20090619

Priority number(s):

KR20090054708 20090619




PURPOSE: A grapheme film manufacturing method, a grapheme film manufactured thereby and an electrode material including the same are provided to dry the graphene oxide dispersed in the hydrophilic solvent thereby economically manufacturing the graphene film of large area by the reduction of the graphene oxide. CONSTITUTION: A surface of a graphene oxide is processed by a hydrophile property function group like a hydroxyl group or a carboxylic group. The graphene oxide is dispersed in hydrophile property solvent. The rotating and drying of the graphene oxide is performed. An acquired grapheme oxide film is converted to the graphene film through deoxidation process. The graphene film has low electrical resistance and the transparent property.

P24. Preparation method of negative electrode material of lithium ion battery

Page bookmark CN 101604750 (A) - Preparation method of negative electrode material of lithium ion battery


Inventor(s): XIAOWEI YANG [CN]; ZIFENG MA [CN]; YUSHI HE [CN]; DAWEI BAI [CN] +

Applicant(s): UNIV SHANGHAI JIAOTONG [CN] +



- European:

Application number:

CN20091054595 20090709

Priority number(s):

CN20091054595 20090709




The invention discloses a preparation method of negative electrode material of lithium ion battery; oxidation, ultrasonic dispersion, vacuum filtration, natural air drying are carried out on the crystalline flake graphite using sodium nitrate, potassium permanganate and concentrated sulfuric acid to obtain the lithium ion battery negative electrode material, namely, graphene film with an area of 0.1-100 cm and a thickness of 0.1-100 microns. The negative electrode material in the invention has the advantages of high conductivity, large reaction area, large free expansion space in charge and discharge and adaption to different environments with high charge and discharge rates and the like, thus realizing high cycling battery performance, high battery specific capacity and swift charge and discharge capabilities of batteries; the reversible specific capacity can maintain above 300mAh-g when charging and discharging with current of 100mAh-g.The preparation process of the negative electrode material of lithium ion battery is free of agglomerant, conductive agent and metal current collectors, thus simplifying production process greatly, reducing cost and being applicable to industrialized production.

P25. ELECTRODE MATERIAL, LITHIUM-ION BATTERY AND METHOD THEREOF

Page bookmark US 2010291438 (A1) - ELECTRODE MATERIAL, LITHIUM-ION BATTERY AND METHOD THEREOF


Inventor(s): AHN DONGJOON [US]; LEE MYONGJAI [US]; SHAH SANDEEP R [US] +

Applicant(s): PDC ENERGY LLC +

Classification: - international: C08L83/04; H01M4/58; H01M4/60

- European:

Application number:

US20090483631 20090612

Priority number(s):

US20090483631 20090612; US20090178719P 20090515




The invention provides an anode comprising a nanocomposite of graphene-oxide and a silicon-based polymer matrix. The anode exhibits a high energy density such as ~800 mAhg-1 reversible capacity, a superlative power density that exceeds 250 kW/kg, a good stability, and a robust resistance to failure, among others. The anodes can be widely used in a lithium-ion battery, an electric car, a hybrid electromotive car, a mobile phone, and a personal computer etc. The invention also provides a liquid


phase process and a solid-state process for making the nanocomposite, both involving in-situ reduction of the graphene-oxide during a pyrolysis procedure.

P26. Lithium ion battery adopting graphene as cathode material

Page bookmark CN 101572327 (A) - Lithium ion battery adopting graphene as cathode material


Inventor(s): QUANHONG YANG [CN]; WEI LV [CN]; YANBING HE [CN]; HUI SUN [CN] +

Applicant(s): UNIV TIANJIN [CN] +

Classification: - international: H01M10/36; H01M4/02; H01M4/04; H01M4/38

- European:

Application number:

CN20091069217 20090611

Priority number(s): CN20091069217 20090611




The invention provides a lithium ion battery adopting graphene as a cathode material. The lithium ion battery which is prepared by the low-temperature method and adopts the graphene material as the cathode material includes a metal casing, a plate electrode, electrolytic solution and a septum, wherein active substances used by the anode plate electrode are commonly used anode materials for the lithium ion battery and include lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickelate, a ternary lithium-nickelate-cobaltate-manganate material and the like; and the electrolytic solution is lithium hexaflourophosphate electrolytic solution used by the lithium ion battery. The cathode of the lithium ion battery adopting the graphene material as the cathode material is made of the graphene material. The first discharge capacity of the lithium ion battery adopting the graphene material as the cathode material can reach 400 to 800mAh/g, and the first charge discharge efficiency can reach 40 to 90 percent; and after 20 cycles, the discharge capacity of the lithium ion battery can still reach 380 to 450mAh/g. The lithium ion battery has the advantages of simple preparation process of the graphene material, easy operation and low cost; and the lithium ion battery adopting the graphene as the cathode material has high discharge capacity and favorable cycle performance.

P27. THIN FILM SOLAR CELL

Page bookmark KR 20090057205 (A) - THIN FILM SOLAR CELL


Inventor(s): LEE JEONG HO [KR] +

Applicant(s): LEE JEONG HO [KR] +

Classification: - international: H01L31/042


Application number: KR20090042871 20090516

Priority number(s): KR20090042871 20090516





A thin film solar cell is provided to improve electronics acquisition ability by depositing a grapheme on a semiconductor conjunction layer. In a thin film solar cell, a transparent insulating substrate is prepared (100), and an anti-reflective film is formed while the transparent electrode layer is formed (200). A semiconductor n-type layer of a solar battery is formed (400), and a graphene layer is formed due to deposition (500). The p-type layer of solar battery semiconductor is formed (600), and the rear side contact electrode is formed and the insulating material layer is formed (800).

P28. ELECTRIC DOUBLE-LAYER CAPACITOR

Page bookmark KR 20090037980 (A) - ELECTRIC DOUBLE-LAYER CAPACITOR


Inventor(s): TAKEUCHI MAKOTO [JP]; MOGAMI AKINORI [JP]; KOIKE KATSUMI [JP] +

Applicant(s): ADVANCED CAPACITOR TECHNOLOGIE [JP] +

Classification: international:

H01G9/00; H01G9/02; H01G9/035; H01G9/038; H01G9/058; H01G9/155

European: H01G9/038; H01G9/155; Y02E60/13

Application number:

KR20097006471 20090327

Priority number(s):

JP20030057305 20030304; JP20030424911 20031222



Also published as:

• WO 2004079759 (A2)

• WO 2004079759 (A3)

• US 2006164790 (A1)

• US 7180725 (B2)

• KR 20070064685 (A)

• more


Present invention relates to an electric double-layer capacitor having positive and negative electrodes containing nonporous carbon as an electrode active material. In the nonporous carbon, multiple layers of graphene having an average interplanar spacing d 002 of 0.350 to 0.380 nm have been grown well. The positive and negative electrodes are impregnated with an electrolyte solution. The nonporous carbon is obtained by activating easily graphitizable carbon, which in turn is obtained by calcining needle coke or pitch made infusible. The electrolyte solution is either a liquid electrolyte having a planar molecular structure or an electrolyte solution consisting of a liquid electrolyte dissolved in an organic solvent.


P29. Grapheme-organic material layered assembling film and preparation method thereof

Page bookmark CN 101474899 (A) - Grapheme-organic material layered assembling film and preparation method thereof


Inventor(s): YONGSHENG CHEN [CN]; YANFENG MA [CN]; JIAJIE LIANG [CN] +

Applicant(s): UNIV NANKAI [CN] +

Classification: - international: B32B7/02

- European:

Application number:

CN20091067711 20090116

Priority number(s):

CN20091067711 20090116




The invention relates to a multilayer film material formed by graphene and inorganic material and a preparation method thereof. The preparation method comprises: using a graphene material and an inorganic material as raw materials, and superposing films layer by layer by common film preparation methods such as spin coating, spraying, dipping, chemically depositing and the like to form the film, wherein the thickness of each layer of the film can be controlled between 10 nanometers and 2 millimeters according to requirement. The multilayer film material and the preparation method have the characteristics that the multilayer film materials with different functions are prepared by utilizing higher strength and modulus, and superior electric, magnetic, mechanical and chemical properties of the graphene, and can be used as electromagnetic shielding and wave absorbing materials, catalytic materials, electrode materials, ceramic materials and the like to be applied to chemistry and chemical industry, biology and precision instruments, and manufacture of micro electrons, machinery and aviation and aerospace devices according to the selected different inorganic materials.

P30. HIGH-THROUGHPUT SOLUTION PROCESSING OF LARGE SCALE GRAPHENE AND DEVICE APPLICATIONS

Page bookmark WO 2009094277 (A2) - HIGH-THROUGHPUT SOLUTION PROCESSING OF LARGE SCALE GRAPHENE AND DEVICE APPLICATIONS

Publication date:

2009-07-30

Inventor(s): YANG YANG [US]; KANER RICHARD B [US]; TUNG CHUN-CHIH [US]; ALLEN MATTHEW J [US] +

Applicant(s): UNIV CALIFORNIA [US]; YANG YANG [US]; KANER RICHARD B [US]; TUNG CHUN-CHIH [US]; ALLEN MATTHEW J [US] +

Classification:

international: C25C1/16

European: B82Y10/00; C01B31/04; H01G9/058; H01M4/96; Y02E60/13; Y02E60/50

Application WO2009US31004 20090114


number:

Priority number(s):

US20080006447P 20080114; US20080071579P 20080507; US20080129698P 20080714



Also published as:

• WO 2009094277 (A3)

• US 2010273060 (A1)

Cited documents:

US2001031900 (A1) US2005266605 (A1) US2003098640 (A1) View all


A method of producing carbon macro-molecular structures includes dissolving a graphitic material in a solvent to provide a suspension of carbon-based macro-molecular structures in the solvent, and obtaining a plurality of the carbon macro-molecular structures from the suspension. The plurality of carbon macro-molecular structures obtained from the suspension each consists essentially of carbon. A material according to some embodiments of the current invention is produced according to the method of producing carbon macro-molecular structures. An electrical, electronic or electro-optic device includes material produced according to the methods of the current invention. A composite material according to some embodiments of the current invention has carbon macro-molecular structures produced according to methods of producing carbon macro-molecular structures according to some embodiments of the current invention. A hydrogen storage device according to some embodiments of the current invention has carbon macro-molecular structures produced according to methods of producing carbon macro-molecular structures according to some embodiments of the current invention. An electrode according to some embodiments of the current invention has carbon macro-molecular structures produced according to methods of producing carbon macro-molecular structures according to some embodiments of the current invention.

P31. Process for producing nano graphene reinforced composite particles for lithium battery electrodes

Page bookmark US 2010176337 (A1) - Process for producing nano graphene reinforced composite particles for lithium battery electrodes

Publication date:

2010-07-15

Inventor(s): ZHAMU ARUNA [US]; JANG BOR Z [US]; SHI JINJUN [US] +

Applicant(s):

Classification:

international: H01M4/88

European: H01M4/1391; H01M4/1395; H01M4/38; H01M4/485; H01M4/505; H01M4/525; H01M4/587; H01M4/58D; H01M4/62; H01M4/62C2

Application US20090319812 20090113


number:

Priority number(s):

US20090319812 20090113




A process for producing solid nanocomposite particles for lithium metal or lithium ion battery electrode applications is provided. In one preferred embodiment, the process comprises: (A) Preparing an electrode active material in a form of fine particles, rods, wires, fibers, or tubes with a dimension smaller than 1 [mu]m; (B) Preparing separated or isolated nano graphene platelets with a thickness less than 50 nm; (C) Dispersing the nano graphene platelets and the electrode active material in a precursor fluid medium to form a suspension wherein the fluid medium contains a precursor matrix material dispersed or dissolved therein; and (D) Converting the suspension to the solid nanocomposite particles, wherein the precursor matrix material is converted into a protective matrix material reinforced by the nano graphene platelets and the electrode active material is substantially dispersed in the protective matrix material. For a lithium ion battery anode application, the matrix material is preferably amorphous carbon, polymeric carbon, or meso-phase carbon. Such solid nanocomposite particles provide a high anode capacity and good cycling stability. For a cathode application, the resulting lithium metal or lithium ion battery exhibits an exceptionally high cycle life.

P32. Porous Electrically Conductive Carbon Material And Uses Thereof

Page bookmark US 2009269667 (A1) - Porous Electrically Conductive Carbon Material And Uses Thereof

Publication date:

2009-10-29

Inventor(s): ANTONIETTI MARKUS [DE]; SMARSLY BERND [DE]; ADELHELM PHILIPP [DE]; MAIER JOACHIM [DE]; HORE SARMIMALA [DE]; HU YONG-SHENG [DE]; GUO YU-GUO [DE] +

Applicant(s): MAX PLANCK GESELLSCHAFT [DE] +

Classification:

international: B32B3/26; H01M4/58; H01M10/36

European: C01B31/02; H01G9/058; H01M4/04; H01M4/583; H01M4/587; Y02E60/12B; Y02E60/13; Y02E60/52B2B

Application number:

US20070302769 20070525

Priority number(s):

EP20060011198 20060531; EP20060018886 20060908; EP20060019348 20060915; WO2007EP04698 20070525



Also published as:

• WO 2007137794 (A1)

• US 2010008021 (A1)


• KR 20090019870 (A)

• JP 2009538813 (T)

• WO 2007137795 (A1)

• more


This disclosure relates to a porous electrically conductive carbon material having interconnected pores in first and second size ranges from 10 mum to 100 nm and from less than 100 nm to 3 nm and a graphene structure and to diverse uses of the material such as an electrode in a lithium-ion battery and a catalyst support, e.g. for the oxidation of methanol in a fuel cell. The carbon material has been heat treated to effect conversion to non-graphitic carbon with the required degree of order at a temperature in the range from 600 DEG C. to 1000 DEG C. A lithium-ion battery and an electrode for a lithium-ion battery are also claimed.

P33. PLATINUM CLUSTER FOR ELECTRODE AND METHOD FOR PRODUCING THE SAME

Page bookmark JP 2010129385 (A) - PLATINUM CLUSTER FOR ELECTRODE AND METHOD FOR PRODUCING THE SAME


Inventor(s): HONMA ITARU; KAYAMA MASANORI; AKITA TOMOKI; OKAZAKI KAZUYUKI; NAKAMURA JUNJI; YU UNJU +

Applicant(s): NAT INST OF ADVANCED IND SCIEN; UNIV TSUKUBA +


C01B31/02; H01G9/058; H01M4/92; H01M4/96; B01J23/42; B01J23/46; H01M4/88

European:

Application number:

JP20080303041 20081127

Priority number(s):

JP20080303041 20081127





PROBLEM TO BE SOLVED: To provide a platinum cluster for an electrode, in which a platinum cluster of platinum fine particles of smaller size or, if possible, subnanometer size which is derived from a platinum solution is supported with a high dispersion degree, and to provide a method for producing the platinum cluster for an electrode. ; SOLUTION: The platinum cluster for electrode includes a platinum (Pt) particle supported by a carbon material including graphene, the size (particle size) of the platinum (Pt) particle being 1 nm or less. The method for producing the platinum cluster for electrode includes: mixing a platinum solution that is a precursor for composing the platinum particle with a carbon material including graphene or layered graphene in which a plurality of graphenes synthesized by a process for peeling a single atom layer graphite from the graphene are superposed; evaporating a solvent in the platinum solution; and performing thermal treatment at 300-500[deg.]C for 1-10 hours.

P34. SEMICONDUCTOR DEVICE HAVING CARBON FILM AND METHOD FOR MANUFACTURING THE SAME

Page bookmark JP 2010120819 (A) - SEMICONDUCTOR DEVICE HAVING CARBON FILM AND METHOD FOR MANUFACTURING THE SAME

Publication date:

2010-06-03

Inventor(s): HIURA HIDEFUMI; TADA TETSUYA; KANAYAMA TOSHIHIKO +

Applicant(s): NEC CORP; NAT INST OF ADVANCED IND SCIEN +


C01B31/04; H01L21/28; H01L21/314; H01L21/3205; H01L21/336; H01L23/52; H01L29/06; H01L29/786; B23K101/40; B23K26/08; B23K26/36

European:

Application number:

JP20080297003 20081120

Priority number(s):

JP20080297003 20081120




PROBLEM TO BE SOLVED: To provide a semiconductor device in which a graphene film, a graphite film or an amorphous carbon film, each of which has an optional shape and optional substrate, and has both of electric conductivity and transparency simultaneously, is formed by a highly versatile, low-cost and resource-saving method and to provide a method for manufacturing the semiconductor device. ; SOLUTION: The graphene film, the graphite film or the amorphous carbon film is formed on various substrates arranged to be opposed to various carbon material substrates or carbon material-applied substrates by irradiating the various carbon material substrates or carbon material-applied substrates with laser beam. Laser


beam bears an ablation action and a graphitization action simultaneously. The graphene film, graphite film or amorphous carbon film having the optional shape is formed on an optional substrate by relative scanning of the laser beam. The semiconductor device having a wiring, electrode or channel consisting of these carbon films is manufactured.

P35. Field effect transistor device with graphene as electrode and method for producing the same

Page bookmark CN 101404322 (A) - Field effect transistor device with graphene as electrode and method for producing the same

Publication date:

2009-04-08

Inventor(s): XUEFENG GUO [CN]; YANG CAO [CN]; LINGCHUN YANG [CN] +

Applicant(s): UNIV BEIJING [CN] +

Classification: - international: H01L51/05; H01L51/30; H01L51/40

- European:

Application number:

CN20081226315 20081112

Priority number(s):

CN20081226315 20081112



Also published as:

• CN 101404322 (B)


The invention provides a field effect transistor device by taking graphene as an electrode and a preparation method thereof. In the device, the material of a source region and a drain region is graphene; the materials of a channel region are various small organic molecules, high polymers and semiconducting polymer materials, such as polythiophene, pentacene, polycyclic aromatic hydrocarbon, perylene imide and the like; and the material of a gate region is highly doped conductive silicone. The device further comprises a gate dielectric layer the material of which is silicon dioxide, silicon nitride and various high-K dielectrics. The nano field effect transistor device can be n-typed, p-typed or amphoteric type, and the device realizes all functions of a macroscopic field effect transistor device at the nanometer level. The transistor device has very high application value in terms of ultrasensitive environmental stimuli response devices, ultrasensitive solar stimuli response devices and the like. In addition, in the fields of molecular electronics and nanometer, the transistor device plays an essential role of promoting the development of ultramicro photoelectric devices with various dimensions at molecular level.


P36. NANO GRAPHENE PLATELET-BASED COMPOSITE ANODE COMPOSITIONS FOR LITHIUM ION BATTERIES

Page bookmark WO 2009061685 (A1) - NANO GRAPHENE PLATELET-BASED COMPOSITE ANODE COMPOSITIONS FOR LITHIUM ION BATTERIES

Publication date:

2009-05-14



Classification:

international: H01M4/133; H01M4/134; H01M4/136; H01M4/139; H01M10/0525; H01M10/36

European: H01M4/133; H01M4/134; H01M4/136; H01M4/139; H01M4/38; Y02E60/12B

Application number:

WO2008US82183 20081103

Priority number(s):

US20070982672 20071105



Also published as:

• US 2009117467 (A1)

• US 7745047 (B2)

• KR 20100088667 (A)

• JP 2011503804 (T)

• CN 101849302 (A)

Cited documents:

DE102005011940 (A1) US2007158618 (A1) EP1777771 (A1) View all


Nano-scaled graphene platelet-based composite material composition for use as an electrode, particularly as an anode of a lithium ion battery. The composition comprises: (a) micron- or nanometer-scaled particles or coating which are capable of absorbing and desorbing lithium ions,- and (b) a plurality of nano- scaled graphene platelets (NGPs), wherein a platelet comprises a graphene sheet or a stack of graphene sheets having a platelet thickness less than 100 nm; wherein at least one of the particles or coating is physically attached or chemically bonded to at least one of the graphene platelets and the amount of platelets is in the range of 2% to 90% by weight and the amount of particles or coating in the range of 98% to 10% by weight. Also provided is a lithium secondary battery comprising such a negative electrode (anode). The battery exhibits an exceptional specific capacity, an excellent reversible capacity, and a long cycle life.


P37. SEMICONDUCTOR LIGHT EMITTING DEVICE AND METHOD FOR FABRICATING THE SAME

Page bookmark KR 20100042122 (A) - SEMICONDUCTOR LIGHT EMITTING DEVICE AND METHOD FOR FABRICATING THE SAME


Inventor(s): KIM JI HYUN [KR]; GO GUN WOO [KR] +

Applicant(s): UNIV KOREA RES & BUS FOUND [KR] +


- European:

Application number:

KR20080101261 20081015

Priority number(s):

KR20080101261 20081015




PURPOSE: A semiconductor light emitting device and a manufacturing method thereof are provided to improve luminous efficiency of the semiconductor light emitting device by forming an electrode using graphene. CONSTITUTION: A first electrode and a second electrode (107) are respectively formed on both sides of a p-n junction and a semiconductor material layer. At least one of first and second electrodes is made of grapheme. A semiconductor material layer is formed on a substrate (101) with a multilayer structure. The semiconductor material layer includes a lowermost n type semiconductor layer and an uppermost p type semiconductor layer.

P38. SINGLE CRYSTALLINE GRAPHENE SHEET AND PROCESS OF PREPARING THE SAME

Page bookmark US 2009155561 (A1) - SINGLE CRYSTALLINE GRAPHENE SHEET AND PROCESS OF PREPARING THE SAME


Inventor(s): CHOI JAE-YOUNG [KR]; SHIN HYEON-JIN [KR]; YOON SEON-MI [KR]; HAN JAI-YONG [KR] +

Applicant(s): SAMSUNG ELECTRONICS CO LTD [KR] +

Classification: - international: B32B9/00; C30B1/02; D01F9/12

- European: C01B31/04; C30B29/02

Application number:

US20080170014 20080709

Priority number(s):

KR20070132682 20071217



Also published as:

• KR 20090065206 (A)

• JP 2009143799 (A)

• CN 101462717 (A)



A single-crystal graphene sheet includes a polycyclic aromatic molecule wherein a plurality of carbon atoms are covalently bound to each other, the single-crystal graphene sheet comprising between about 1 layer to about 300 layers; and wherein a peak ratio of a Raman D band intensity to a Raman G band intensity is equal to or less than 0.2. Also described is a method for preparing a single-crystal graphene sheet, the method includes forming a catalyst layer, which includes a single-crystal graphitizing metal catalyst sheet; disposing a carbonaceous material on the catalyst layer; and heat-treating the catalyst layer and the carbonaceous material in at least one of an inert atmosphere and a reducing atmosphere. Also described is a transparent electrode including a single-crystal graphene sheet.

P39. High electrochemistry capacitance oxidization plumbago alkene, low-temperature preparation method and uses

Page bookmark CN 101367516 (A) - High electrochemistry capacitance oxidization plumbago alkene, low-temperature preparation method and uses


Inventor(s): QUANHONG YANG [CN]; WEI LU [CN]; HUI SUN [CN] +

Applicant(s): UNIV TIANJIN [CN] +


- European:

Application number:

CN20081151807 20080926

Priority number(s):

CN20081151807 20080926



Also published as:

• CN 101367516 (B)


The invention discloses a high electrochemical capacity graphene oxide, and a method for preparing the high electrochemical capacity graphene oxide, and the application thereof. The lamina thickness of the graphene oxide is 0.35 to 20 nm; the specific surface area is 200 to 800 square meters per gram, and the electrochemical specific capacity reaches 50 to 220 F/g. The present invention relates to the method that graphite oxide is heated to 150 to 600 DEG C and is maintained at the temperature for 0.5 to 20 hours in a high vacuum to get the graphene oxide. The material is applied to the electrode material of the super capacitor. The invention has the advantages of simple preparation process, low preparation temperature, easy operation and low energy consumption.


P40. Graphene nanocomposites for electrochemical cell electrodes

Page bookmark US 2010021819 (A1) - Graphene nanocomposites for electrochemical cell electrodes


Inventor(s): ZHAMU ARUNA [US]; JANG BOR Z [US]; SHI JINJUN [US] +

Applicant(s):

Classification:

international: H01M4/58

European: H01G9/058; H01M10/0525; H01M4/133; H01M4/1393; H01M4/587; H01M4/62B; Y02E60/12B

Application number:

US20080220651 20080728

Priority number(s):

US20080220651 20080728




A composite composition for electrochemical cell electrode applications, the composition comprising multiple solid particles, wherein (a) a solid particle is composed of graphene platelets dispersed in or bonded by a first matrix or binder material, wherein the graphene platelets are not obtained from graphitization of the first binder or matrix material; (b) the graphene platelets have a length or width in the range of 10 nm to 10 mum; (c) the multiple solid particles are bonded by a second binder material; and (d) the first or second binder material is selected from a polymer, polymeric carbon, amorphous carbon, metal, glass, ceramic, oxide, organic material, or a combination thereof. For a lithium ion battery anode application, the first binder or matrix material is preferably amorphous carbon or polymeric carbon. Such a composite composition provides a high anode capacity and good cycling response. For a supercapacitor electrode application, the solid particles preferably have meso-scale pores therein to accommodate electrolyte.

P41. INDUCTOR AND METHOD OF OPERATING THE SAME

Page bookmark KR 20090106169 (A) - INDUCTOR AND METHOD OF OPERATING THE SAME

Publication date:

2009-10-08

Inventor(s): JEON DAE YOUNG [KR]; KIM DONG CHUL [KR]; SEO SUN AE [KR];


JUNG RAN JU [KR]; WOO YUN SUNG [KR]; CHUNG HYUN JONG [KR] +


Classification: - international: H01F27/00

- European: H01F17/00A

Application number:

KR20080031714 20080404

Priority number(s):

KR20080031714 20080404



Also published as:

• US 2009251267 (A1)


PURPOSE: An inductor and an operating method thereof are provided to secure uniformity and reproduction and prevent problem due to misalignment using graphene. CONSTITUTION: An inductor includes a conductive line (C1), a first electrode (E1), a second electrode (E2), and a first unit. The conductive line includes a first material whose electric resistance is changed according to the electric field. The first material includes a graphene. The first electrode and the second electrode are electrically connected to both sides of the conductive line. The first unit applies the electric field to the conductive line. The first unit is a conductor (100) separated from the conductive line.

P42. NANODEVICES FOR SPINTRONICS METHODS OF USING SAME

Page bookmark WO 2008130465 (A2) - NANODEVICES FOR SPINTRONICS METHODS OF USING SAME

Publication date:

2008-10-30

Inventor(s): ZALIZNYAK IGOR [US]; TSVELIK ALEXEI [US]; KHARZEEV DMITRI [US] +

Applicant(s): BROOKHAVEN SCIENCE ASS LLC [US]; ZALIZNYAK IGOR [US]; TSVELIK ALEXEI [US]; KHARZEEV DMITRI [US] +


- European: B82Y25/00; G11C11/16; H01F10/00C; H01F10/32H

Application number:

WO2008US02761 20080229

Priority number(s):

US20070892595P 20070302



Also published as:

• WO 2008130465 (A3)

• US 2010109712 (A1)


Cited documents:

US2006057743 (A1) WO0167469 (A1) US2005238565 (A1) US2006186433 (A1) View all


Graphene magnet multilayers (GMMs) are employed to facilitate development of spintronic devices. The GMMs can include a sheet of monolayer (ML) or few-layer (FL) graphene in contact with a magnetic material, such as a ferromagnetic (FM) or an antiferromagnetic material. Electrode terminals can be disposed on the GMMs to be in electrical contact with the graphene. A magnetic field effect is induced in the graphene sheet based on an exchange magnetic field resulting from a magnetization of the magnetic material which is in contact with graphene. Electrical characteristics of the graphene can be manipulated based on the magnetization of the magnetic material in the GMM.

P43. Organic field effect transistor and special source/drain electrode and preparation method thereof

Page bookmark CN 101442105 (A) - Organic field effect transistor and special source/drain electrode and preparation method thereof


Inventor(s): GUI YU [CN]; ZHONGAN DI [CN]; DACHENG WEI [CN]; YUNQI LIU [CN]; YUNLONG GUO [CN]; DAOBEN ZHU [CN] +

Applicant(s): CHINESE ACAD INST CHEMISTRY [CN] +

Classification: - international: H01L51/05; H01L51/30; H01L51/40

- European:

Application number:

CN20071177814 20071121

Priority number(s):

CN20071177814 20071121



Also published as:

• CN 101442105 (B)


The invention discloses an organic field effect transistor (FET), as well as a special source-drain electrode and a preparation method thereof. The organic FET with an electrode structure comprises a gate electrode, a dielectric layer, an organic semiconductor layer, a source electrode and a drain electrode, wherein the source electrode and the drain electrode are patterned Graphene electrodes. The method for preparing the patterned Graphene electrodes comprises the following steps: 1) a metal film is deposited on a substrate and is patterned; and 2) the substrate on which the patterned metal film is deposited is placed in a chemical vapor deposition system, and chemical vapor Graphene deposition is performed on the surface of a patterned metal electrode material, so as to obtain the patterned Graphene electrodes, wherein a carbon source used in chemical vapor deposition is methanol, ethanol, propanol, pentanol, benzene, toluene, xylene, methane and the like.


P44. Process for producing nano-scaled graphene platelet nanocomposite electrodes for supercapacitors

Page bookmark US 2009092747 (A1) - Process for producing nano-scaled graphene platelet nanocomposite electrodes for supercapacitors



Applicant(s): NANOTEK INSTRUMENTS, INC

Classification: - international: B05D5/12

- European: H01G9/058; Y02E60/13

Application number:

US20070906786 20071004

Priority number(s):

US20070906786 20071004



Also published as:

• US 7875219 (B2)


A process for producing meso-porous nanocomposite electrode comprising nano-scaled graphene platelets. The process comprises: (A) providing nano-scaled graphene platelets, wherein each of the platelets comprises a single graphene sheet or a stack of multiple graphene sheets, and the platelets have an average thickness no greater than 100 nm (preferably less than 5 nm and most preferably less than 2 nm in thickness); (B) combining a binder material, the graphene platelets, and a liquid to form a dispersion; (C) forming the dispersion into a desired shape and removing the liquid to produce a binder-platelet mixture; and (D) treating the binder material under a desired temperature or radiation environment to convert the binder-platelet mixture into a meso-porous nanocomposite electrode, wherein the platelets are bonded by the binder and the electrode has electrolyte-accessible pores characterized in that the nanocomposite has a surface area greater than about 100 m2/gm (preferably greater than 200 m2/gm, more preferably greater than 500 100 m2/gm, and most preferably greater than 1,000 m2/gm). A supercapacitor featuring such a nanocomposite exhibits an exceptionally high capacitance value.

P45. A Negative Electrode Active Material for an Electricity Storage Device and Method for Manufacturing the Same

Page bookmark EP 1903628 (A2) - A Negative Electrode Active Material for an Electricity Storage Device and Method for Manufacturing the Same

Publication date:

2008-03-26

Inventor(s): KOJIMA TASAKI KENJI [JP]; ANDO NOBUO [JP] +

Applicant(s): FUJI HEAVY IND LTD [JP] +

Classification: international: C04B35/83; C04B38/00; H01G9/058; H01M10/0525;


H01M12/00; H01M4/133; H01M4/58; H01M4/583; H01M4/587; H01G9/155

European: C04B35/83; C04B38/00C; H01G9/058; H01M4/133; H01M4/587; Y02E60/12B; Y02E60/12H; Y02E60/13

Application number:

EP20070115814 20070906

Priority number(s):

JP20060241105 20060906



Also published as:

• EP 1903628 (A3)

• US 2008220329 (A1)

• KR 20080022494 (A)

• JP 2008066053 (A)

• CN 101140986 (A)

Cited documents:

WO2005096333 (A1) JP2003346801 (A) US2003026755 (A1) JP2001135304 (A) View all

Abstract of EP 1903628 (A2)

The invention provides a negative electrode active material for an electricity storage device, which has considerably enhanced low-temperature characteristics, increased energy density, and increased output power. A negative electrode active material is made of a carbon composite containing carbon particles as a core and a fibrous carbon having a graphene structure, which is formed on the surfaces and/or the inside of the carbon particles, wherein the carbon composite has a volume of all mesopores within 0.005 to 1.0 cm 3 /g, and a volume of the mesopores each with a pore diameter ranging from 100 to 400 AA of not less than 25% of the volume of all mesopores.

P46. INFRARED RAYS EMITTING DEVICE USING GRAPHENE

Page bookmark KR 20090003526 (A) - INFRARED RAYS EMITTING DEVICE USING GRAPHENE


Inventor(s): JUNG RAN JU [KR]; SEO SUN AE [KR]; KIM DONG CHUL [KR]; LEE CHANG WON [KR]; CHUNG HYUN JONG [KR] +


Classification: - international:

- European:

Application number:

KR20070058575 20070614

Priority number(s):

KR20070058575 20070614





The infrared emitting diode of the nano size using graphene of two-dimensional layer material are provided to improve the luminous efficiency by making same the transition speed of hole and electrons. The infrared emitting diode comprises the light-emitting layer, and the gate electrode and the isolation layer. The light-emitting layer (120) comprises the light emission region (123), the source region (121) and drain region (122). The gate electrode (114) is formed in the light emission region. The insulating layer (112) isolates the gate electrode from the light-emitting layer. The light-emitting layer is formed with at least one among the group consisting of the graphene, boron nitride, cadmiumtellurium, molybdenum disulfide, niobium die selenide into selected a one.

P47. NANOCARBON COMPOSITE STRUCTURE HAVING RUTHENIUM OXIDE TRAPPED THEREIN

Page bookmark KR 20070030274 (A) - NANOCARBON COMPOSITE STRUCTURE HAVING RUTHENIUM OXIDE TRAPPED THEREIN


Inventor(s): NAOI KATSUHIKO [JP] +

Applicant(s): UNIV TOKYO AGRICULTURE [JP] +


B82B1/00; B82B3/00; C01B31/02; C01G55/00; H01G9/058

European: B82Y30/00; C01B31/02B; C01G55/00; H01G9/058

Application number:

KR20077000585 20070109

Priority number(s):

JP20040173452 20040611



Also published as:

• EP 1772428 (A1)

• EP 1772428 (A4)

• US 2008048153 (A1)

• US 7572542 (B2)

• WO 2005121022 (A1)

• more


A novel nanocarbon composite structure having ruthenium oxide trapped therein, wherein using Ketjen black, through a mechanochemical effect utilizing an ultracentrifugal reaction field, both the specific surface area of ruthenium oxide and the space of electrode material have been expanded so as to have nanoparticles of ruthenium oxide highly dispersed in a graphene layer. This nanocarbon composite structure having ruthenium oxide trapped therein exhibits high electrochemical activity, so that it is suitable for use as an electrical energy storing device, such as a large-capacity capacitor.


P48. CARBON THIN FILM, AND FIELD EMISSION ELECTRON SOURCE AND WORKING ELECTRODE USING THE SAME

Page bookmark JP 2005060146 (A) - CARBON THIN FILM, AND FIELD EMISSION ELECTRON SOURCE AND WORKING ELECTRODE USING THE SAME

Publication date:

2005-03-10

Inventor(s): IIJIMA RYUTA; URAYAMA MASAO; KYOTANI TAKASHI; OGAWA TOMONORI; TOMITA AKIRA +

Applicant(s): SHARP KK; KYOTANI TAKASHI +


C01B31/02; C23C16/26; H01J1/304; H01J9/02; (IPC1-7): C01B31/02; C23C16/26; H01J1/304; H01J9/02

European:

Application number:

JP20030290291 20030808

Priority number(s):

JP20030290291 20030808



Also published as:

• JP 4245438 (B2)


PROBLEM TO BE SOLVED: To provide a carbon thin film which has high activity and can be used for the electron source of an FED (Field Emission Display) and the working electrode of a biochip, and to provide a production method therefor. ; SOLUTION: A gaseous starting material comprising carbon is decomposed onto the surface of alumina 2 deposited by anodization, so that the carbon thin film 1 comprising graphene 1a is deposited. The edge part 1E of the graphene 1a is exposed in the main surface 1S of the carbon thin film 1.


3.4. Graphene – supercapacitor/ultracapacitor

The keyword graphene have 17 patents when supercapacitor was used as an additional keyword.

49. Flexible asymmetric electrochemical cells using nano graphene platelet as an electrode material

Page bookmark US 2011183180 (A1) - Flexible asymmetric electrochemical cells using nano graphene platelet as an electrode material


Inventor(s): YU ZHENNING [US]; SHI JINJUN [US]; LIU CHEN-GUANG [US]; JANG BOR Z [US]; ZHAMU ARUNA [US] +

Applicant(s):

Classification:

international: H01G9/00; H01M4/133

European: H01G9/058; H01G9/155; H01M16/00; H01M4/133; H01M4/583; H01M4/587

Application number:

US20100657579 20100125

Priority number(s):

US20100657579 20100125




A flexible, asymmetric electrochemical cell comprising: (A) A sheet of graphene paper as first electrode comprising nano graphene platelets having a platelet thickness less than 1 nm, wherein the first electrode has electrolyte-accessible pores; (B) A thin-film or paper-like first separator and electrolyte; and (C) A thin-film or paper-like second electrode which is different in composition than the first electrode; wherein the separator is sandwiched between the first and second electrode to form a flexible laminate configuration. The asymmetric supercapacitor cells with different NGP-based electrodes exhibit an exceptionally high capacitance, specific energy, and stable and long cycle life.


P50. Continuous process for producing spacer-modified nano Graphene electrodes for supercapacitors

Page bookmark US 2011165321 (A1) - Continuous process for producing spacer-modified nano Graphene electrodes for supercapacitors


Inventor(s): ZHAMU ARUNA [US]; YU ZENNING [US]; LIU CHEN-GUANG [US]; JANG BOR Z [US] +

Applicant(s):

Classification: - international: B05D5/12

- European: H01G9/058

Application number:

US20100655744 20100107

Priority number(s):

US20100655744 20100107




A specific embodiment of the present invention is a process for continuously producing a porous solid film of spacer-modified nano graphene platelets for supercapacitor electrode applications. This process comprises: (a) dissolving a precursor material in a solvent to form a precursor solution and dispersing multiple nano graphene platelets into the solution to form a suspension; (b) continuously delivering and forming the suspension into a layer of solid film composed of precursor material-coated graphene platelets overlapping one another, and removing the solvent from the solid film (e.g., analogous to a paper-making, mat-making, or web-making procedure); (c) continuously converting the precursor material into nodules bonded to surfaces of graphene platelets to form a porous solid film composed of spacer-modified graphene platelets; and (d) continuously collecting the porous solid film on a collector (e.g., a winding roller). The roll of porous solid film (mat, paper, or web) can then be cut into pieces for used as supercapacitor electrodes.


P51. CONDUCTIVE GRAPHENE POLYMER BINDER FOR ELECTROCHEMICAL CELL ELECTRODES

Page bookmark WO 2011079238 (A1) - CONDUCTIVE GRAPHENE POLYMER BINDER FOR ELECTROCHEMICAL CELL ELECTRODES

Publication date:

2011-06-30



Classification:

international: H01M4/131; H01M4/139; H01M4/62

European: H01G9/058; H01M4/131; H01M4/139; H01M4/62B; H01M4/62C2; Y02E60/12B

Application number:

WO2010US61949 20101223

Priority number(s):

US20090655172 20091224



Also published as:

• US 2011159372 (A1)

Cited documents:

WO2009061685 (A1) WO2009085015 (A1) US2009092747 (A1) View all


The present invention provides an electrically conductive electrode comprising particles of an electroactive material and a conductive graphene polymer binder that bonds multiple particles of the electroactive material together, wherein the binder is in an amount of from 0.01% to 90% by weight based on the total electrode weight. Also provided are (a) a precursor solution or suspension to the graphene polymer binder for the electrode; (b) a paste containing electroactive particles and a graphene polymer dispersed in a liquid; (c) a method of producing the electrode from the precursor paste; and (d) an electrochemical cell (a battery or supercapacitor) containing such an electrode. P52. Spacer-modified nano graphene electrodes for supercapacitors

Page bookmark US 2011157772 (A1) - Spacer-modified nano graphene electrodes for supercapacitors


Inventor(s): ZHAMU ARUNA [US]; YU ZENNING [US]; LIU CHEN-GUANG [US]; JANG BOR Z [US] +

Applicant(s):

Classification: - international: B32B3/10; C01B31/02; C25B11/12; H01G9/058

- European: H01G9/058

Application number:

US20090655247 20091228

Priority number(s):

US20090655247 20091228





A surface-modified nano graphene platelet (NGP), comprising: (a) a nano graphene platelet having a thickness smaller than 10 nm; and (b) discrete, non-continuous, and non-metallic bumps or nodules bonded to a surface of the graphene platelet to serve as a spacer. When multiple surface-modified NGP sheets are stacked together to form an electrode, large numbers of electrolyte-accessible pores are formed, enabling the formation of large amounts of double layer charges in a supercapacitor, which exhibits an exceptionally high specific capacitance.

P53. Dispersible and conductive Nano Graphene Platelets

Page bookmark US 2010055458 (A1) - Dispersible and conductive Nano Graphene Platelets


Inventor(s): JANG BOR Z [US]; ZHAMU ARUNA [US] +

Applicant(s):

Classification: - international: B32B5/16; C01B31/04

- European: C01B31/04H2F2

Application number:

US20080231417 20080903

Priority number(s): US20080231417 20080903




The present invention provides a dispersible and electrically conductive nano graphene platelet (NGP) material comprising at least a single-layer or multiple-layer graphene sheet, wherein the NGP material has an oxygen content no greater than 25% by weight and no less than 5% by weight. This NGP material can be produced by: (a) preparing a pristine NGP material from a graphitic material; and (b) subjecting the pristine NGP material to an oxidation treatment. Alternatively, the production process may comprise: (A) preparing a graphite oxide (GO) from a laminar graphite material; (b) exposing the GO to a first temperature for a first period of time to obtain


exfoliated graphite; and (c) exposing the exfoliated graphite to a second temperature in a protective atmosphere for a second period of time. Conductive NGPs can find applications in transparent electrodes for solar cells or flat panel displays, additives for battery and supercapacitor electrodes, conductive nanocomposite for electromagnetic wave interference (EMI) shielding and static charge dissipation, etc.

P54. MESOPOROUS METAL OXIDE GRAPHENE NANOCOMPOSITE MATERIALS

Page bookmark CA 2733275 (A1) - MESOPOROUS METAL OXIDE GRAPHENE NANOCOMPOSITE MATERIALS


Inventor(s): JUN LIU [US]; AKSAY IIHAN A [US]; KOU RONG [US]; WANG DONGHAI [US] +

Applicant(s): BATTELLE MEMORIAL INSTITUTE [US] +


C01B31/02; C01B31/04; H01M10/00; H01M10/052; H01M10/36; H01M16/00

European: C01B31/04; H01G9/058; Y02E60/12B

Application number:

CA20092733275 20090909

Priority number(s):

US20080095421P 20080909; US20080099388P 20080923; US20090553527 20090903; WO2009US05085 20090909



Also published as:

• WO 2010030361 (A1)

Abstract of CA 2733275 (A1)

A nanocomposite material formed of graphene and a mesoporous metal oxide having a demonstrated specific capacity of more than 200 F/g with particular utility when employed in supercapacitor applications. A method for making these nanocomposite materials by first forming a mixture of graphene, a surfactant, and a metal oxide precursor, precipitating the metal oxide precursor with the surfactant from the mixture to form a mesoporous metal oxide. The mesoporous metal oxide is then deposited onto a surface of the graphene.

P55. MASS PRODUCTION OF PRISTINE NANO GRAPHENE MATERIALS

Page bookmark WO 2011014347 (A1) - MASS PRODUCTION OF PRISTINE NANO GRAPHENE MATERIALS




Classification: - international: B82B1/00; H01B1/00

- European:

Application number:

WO2010US41652 20100712

Priority number(s):

US20090460863 20090727




Also published as:

• US 2011017585 (A1)

Cited documents:

US2008048152 (A1) US2009235721 (A1) US2009117467 (A1) View all


The present invention provides a method of producing pristine or non-oxidized nano graphene platelets (NGPs) that are highly conductive. The method comprises: (a) providing a pristine graphitic material comprising at least a graphite crystallite having at least a graphene plane and an edge surface; (b) dispersing multiple particles of the pristine graphitic material in a liquid medium containing therein no surfactant to produce a suspension, wherein the multiple particles in the liquid have a concentration greater than 0.1 mg/mL and the liquid medium is characterized by having a surface tension that enables wetting of the liquid on a graphene plane exhibiting a contact angle less than 90 degrees; and (c) exposing the suspension to direct ultrasonication at a sufficient energy or intensity level for a sufficient length of time to produce the NGPs. Pristine NGPs can be used as a conductive additive in transparent electrodes for solar cells or flat panel displays (e.g., to replace expensive indium-tin oxide), battery and supercapacitor electrodes, and nanocomposites for electromagnetic wave interference (EMI) shielding, static charge dissipation, and fuel cell bipolar plate applications.

P56. Graphene/Ru nano-composite material for supercapacitor and preparation method thereof

Page bookmark CN 101714463 (A) - Graphene/Ru nano-composite material for supercapacitor and preparation method thereof


Inventor(s): KUN CHANG; WEIXIANG CHEN; HUI LI; LIN MA; JIE ZHAO +

Applicant(s): UNIV ZHEJIANG +

Classification: - international: H01G9/058

- European:

Application number:

CN20091155046 20091214

Priority number(s):

CN20091155046 20091214





The invention discloses a graphene/Ru nano-composite material for a supercapacitor. The mass fraction of Ru is between 10 and 50 percent, and the mass fraction of graphene is between 90 and 50 percent. A preparation method comprises the steps of: ultrasonically dispersing oxidized graphite nano-plates into liquid polylol, and then adding solution of ruthenium chloride and solution of sodium acetate into the liquid polylol, wherein in the mixture, the content of the oxidized graphite nano-plates is between 0.5 and 1.5g/L, the concentration of the ruthenium chloride is between 0.0008 and 0.006mol/L, and the concentration of the sodium acetate is between 0.003 and 0.013mol/L; and transferring the mixture into a microwave hydrothermal reaction kettle, performing a microwave heating reaction for 5 to 10 minutes, and then obtaining the graphene/Ru nano-composite material through filtration, washing and drying. The preparation method has the advantages of energy conservation, quickness, simple process and the like; and the graphene/Ru nano-composite material which is taken as an electrode material of an electrochemical supercapacitor has high specific capacitance.

P57. Process for producing dispersible Nano Graphene Platelets from oxidized graphite

Page bookmark US 2010055025 (A1) - Process for producing dispersible Nano Graphene Platelets from oxidized graphite



Applicant(s):


- European: C01B31/00D; C01B31/04; C01B31/04F

Application number:

US20080231413 20080903

Priority number(s):

US20080231413 20080903




The present invention provides a process for producing nano graphene platelets (NGPs) that are dispersible and conducting. The process comprises: (a) preparing a graphite intercalation compound (GIC) or graphite oxide (GO) from a laminar graphite material; (b) exposing the GIC or GO to a first temperature for a first period of time to obtain exfoliated graphite; and (c) exposing the exfoliated graphite to a second temperature in a protective atmosphere for a second period of time to obtain the desired dispersible nano graphene platelet with an oxygen content no greater than 25% by weight, preferably below 20% by weight, further preferably between 5% and 20% by weight. Conductive NGPs can find applications in transparent electrodes for solar cells or flat panel displays, additives for battery and supercapacitor electrodes, conductive nanocomposite for electromagnetic wave interference (EMI) shielding and static charge dissipation, etc.


P58. Process for producing dispersible and conductive Nano Graphene Platelets from non-oxidized graphitic materials

Page bookmark US 2010056819 (A1) - Process for producing dispersible and conductive Nano Graphene Platelets from non-oxidized graphitic materials



Applicant(s):


C01B31/02; C07C211/43; C07C25/00; C07C315/00; C07C33/00; C07C45/27; C07F7/08

European: B82Y30/00; C01B31/02B

Application number:

US20080231411 20080903

Priority number(s):

US20080231411 20080903




The present invention provides a process for producing nano graphene platelets (NGPs) that are both dispersible and electrically conducting. The process comprises: (a) preparing a pristine NGP material from a graphitic material; and (b) subjecting the pristine NGP material to an oxidation treatment to obtain the dispersible NGP material, wherein the NGP material has an oxygen content no greater than 25% by weight. Conductive NGPs can find applications in transparent electrodes for solar cells or flat panel displays, additives for battery and supercapacitor electrodes, conductive nanocomposite for electromagnetic wave interference (EMI) shielding and static charge dissipation, etc.

P59. Supercritical fluid process for producing nano graphene platelets

Page bookmark US 2010044646 (A1) - Supercritical fluid process for producing nano graphene platelets



Applicant(s):

Classification: - international: D01F9/12; H01B1/04

- European: C01B31/04

Application number:

US20080229493 20080825

Priority number(s): US20080229493 20080825





The present invention provides a process for producing pristine or non-oxidized nano graphene platelets (NGPs) that are highly conductive. The process comprises: (i) subjecting a graphitic material to a supercritical fluid at a first temperature and a first pressure for a first period of time in a pressure vessel and then (ii) rapidly depressurizing the fluid at a fluid release rate sufficient for effecting exfoliation of the graphitic material to obtain the NGP material. Conductive NGPs can be used as a conductive additive in transparent electrodes for solar cells or flat panel displays (e.g., to replace expensive indium-tin oxide), battery and supercapacitor electrodes, and nanocomposite for electromagnetic wave interference (EMI) shielding and static charge dissipation, etc.

P60. Supercapacitor using carbon nanosheets as electrode

Page bookmark US 2008232028 (A1) - Supercapacitor using carbon nanosheets as electrode


Inventor(s): ZHAO XIN [US] +

Applicant(s): COLLEGE OF WILLIAM & MARY +


- European: H01G9/058; H01G9/155; Y02E60/13

Application number:

US20070976574 20071025

Priority number(s): US20070976574 20071025; US20060855221P 20061030



Also published as: • US 7852612 (B2)


A supercapacitor comprising a first electrode, a second electrode, and a separator. The electrodes are created with carbon nanosheets in various configurations. The electrodes are impregnated with an electrolyte.


P62. Nano-scaled graphene plate nanocomposites for supercapacitor electrodes

Page bookmark US 7623340 (B1) - Nano-scaled graphene plate nanocomposites for supercapacitor electrodes


Inventor(s): SONG LULU [US]; ZHAMU ARUNA [US]; GUO JIUSHENG [US]; JANG BOR Z [US] +

Applicant(s): NANOTEK INSTR INC [US] +


- European: C01B31/04; H01G9/058; Y02E60/13

Application number:

US20060499861 20060807

Priority number(s):

US20060499861 20060807



Cited documents:

US5786555 (A) US2003030963 (A1) US2004033187 (A1) US2004262584 (A1) View all

Abstract of US 7623340 (B1)

A preferred embodiment of the present invention is a meso-porous nanocomposite material comprising: (A) nano-scaled graphene platelets, wherein each of the platelets comprises a sheet of graphite plane or multiple sheets of graphite plane, and the platelets have a thickness no greater than 100 nm (preferably smaller than 10 nm) and an average length, width, or diameter no greater than 10 mum (preferably smaller than 500 nm); and (B) an electrically conducting binder or matrix material attached or bonded to the platelets to form the nanocomposite material having liquid accessible pores, which provide a surface area greater than about 100 m2/gm, preferably greater than 500 m2/gm, and most preferably greater than 1000 m2/gm. Also disclosed is a capacitor that includes at least an electrode comprising such a meso-porous nanocomposite material. A supercapacitor featuring such a nanocomposite exhibits an exceptionally high capacitance value.

P63. PROCESS FOR THE PREPARATION OF GRAPHENE

Page bookmark US 2010303706 (A1) - PROCESS FOR THE PREPARATION OF GRAPHENE


Inventor(s): WALLACE GORDON GEORGE [AU]; LI DAN [AU] +

Applicant(s): UNIV WOLLONGONG +


- European: B82Y30/00; C01B31/02B

Application number:

US20080738758 20081017

Priority number(s): AU20070905796 20071019; WO2008AU01543 20081017




Also published as:

• WO 2009049375 (A1)

• JP 2011500488 (T)

• EP 2212248 (A1)

• AU 2008314512 (A1)


The present invention relates to a process for the preparation of graphene which can be used in the development of graphene paper or films, graphene-based composites and articles for nanoelectronics, nanocomposites, batteries, supercapacitors, hydrogen storage and bioapplications. This process comprises reducing purified exfoliated graphite oxide in the presence of a base.

The keyword graphene have revealed 3 patents when ultracapacitor was used as an additional keyword.

P64. EXFOLIATION OF GRAPHITE OXIDE IN PROPYLENE CARBONATE AND THERMAL REDUCTION OF RESULTING GRAPHENE OXIDE PLATELETS

Page bookmark WO 2011041663 (A2) - EXFOLIATION OF GRAPHITE OXIDE IN PROPYLENE CARBONATE AND THERMAL REDUCTION OF RESULTING GRAPHENE OXIDE PLATELETS

Publication date:

2011-04-07

Inventor(s): RUOFF RODNEY S [US]; STOLLER MERYL D [US]; ZHU YANWU [US] +

Applicant(s): UNIV TEXAS [US]; RUOFF RODNEY S [US]; STOLLER MERYL D [US]; ZHU YANWU [US] +

Classification: - international: B01J19/10; C01B31/02; C01B31/04; H01B1/24

- European:

Application number:

WO2010US51101 20101001

Priority number(s):

US20090248108P 20091002



Also published as:

• US 2011079748 (A1)


Disclosed are compositions and methods wherein graphite oxide was exfoliated and dispersed in propylene carbonate (PC) by bath sonication. Heating the graphene oxide suspensions at 150 DEG C significantly reduced the graphene oxide platelets; paper samples comprised of such reduced graphene oxide platelets had an electrical conductivity of 5230 S/m. By adding TEA BF4 to the reduced graphene oxide/PC slurry and making a 2-cell ultracapacitor, specific capacitance values of about 120 F/g were obtained.


P65. Ionic Liquids for Use in Ultracapacitor and Graphene-Based Ultracapacitor

Page bookmark US 2011080689 (A1) - Ionic Liquids for Use in Ultracapacitor and Graphene-Based Ultracapacitor

Publication date:

2011-04-07

Inventor(s): BIELAWSKI CHRISTOPHER W [US]; RUOFF RODNEY S [US]; AGNIHOTRI DILEEP K [US]; DREYER DANIEL R [US]; STOLLER MERYL D [US]; ZHU YANWU [US] +

Applicant(s):

Classification: - international: C01B31/00; H01G9/155

- European: H01G9/038; H01G9/058

Application number:

US20100875880 20100903

Priority number(s):

US20100875880 20100903; US20090240120P 20090904



Also published as:

• WO 2011029006 (A2)


One embodiment of the current disclosure provides an ultracapacitor including at least one graphene-based electrode, an electrolyte containing an ionic liquid, and a dielectric separator dividing the ultracapacitor into two chambers, each chamber containing an electrode and a portion of the electrolyte. In another embodiment, the graphene has been expanded by exposure to microwave radiation then chemically activated. Another embodiment of the current disclosure provides an electrochemical energy storage device containing such an ultracapacitor. Still other embodiments of the disclosure relate to ionic liquids, some of which may be suitable for use in an ultracapacitor, methods of synthesizing such liquids, and methods of designing such liquids. Further embodiments relate to methods of using ultracapacitors, for example in automobiles, power grids, high-temperature applications, and other applications.


4. Conclusions

The use of graphene in supercapacitor applications has had dramatic increase in number of patents in 2009, 2010 and 2011 showing very intense graphene related patent activity in the World, especially in the US, China, South Korea and Japan. The number of the patent applications has been increasing rapidly indicating that the area of graphene supercapacitors is the fast moving field. This could be illustrated by the increase of total number of patents shown in the same keyword combination search in a period on six month. From example, the keyword graphene search has revealed 12 patents when supercapacitor was used as an additional keyword in similar internal study at the Fraunhofer IPA in May 2011 and 17 patents in this study in November 2011 indicating 41% increase in number of patents in the six months. Also the keyword graphene search has revealed 13 patents when electrochemical method was used as an additional keyword in May 2011 and 20 patents in November 2011 showing increase of 53% in number of patents in the six months and indicating need for an update at least every six months. However, the keyword graphene search has revealed 3 patents when ultracapacitors was used as an additional keyword in May 2011 and also 3 same patents in November 2011 indicating the term supercapacitor might be overtaking use of the term ultracapacitor even in the US. The majority of patent applications are coming from the US (39%) followed by China (23%), Japan (19%), South Korea (12%), Germany (5%) and Australia (2%) (see Fig 2). The most patents are related to graphene synthesis and sometime only have a reference to an application such as supercapacitors. Many of carbon nanotube application development pioneers such as Prof Rodney Ruoff from University of Texas, US are now in graphene application development field and do have ultracapacitors related patents presented in this report (For example see abstract P3, P64, P65), Mildred Dresselhaus form MIT, US (P14) and Sumio Iijima from Japan (P12). Large corporations such as Samsung (P38, P41, P46), NEC (P34), Toshiba (P16), Casio (P18), Sharp (P48), Fuji (P45) and BASF (P5) and also well known research institutions such as Tsukuba in Japan (P33) and Max Planck in Germany (P5, P38) are involved. However, it is interesting to note that the small start-up company from Dayton in Ohio, US the NANOTECK INSTRUMENTS INC. (www.nanotekinstruments.com) and its founding scientists Bor Z Jang and Aruna Zhamu do have 17 patent applications in this report (P4, P6, P31, P36, P40, P44, P49, P50, P51, P52, P53, P55, P57, 58, P59, P60, P62). They are involved in innovative energy storage and conversion technologies such as fuel cells, solar cells, batteries and supercapacitors. They are also producing low cost nanomaterials, such as nanopowders and nano-scale graphene platelets that they are advertising as a low cost alternative to carbon nanotubes. In this area they have an early patent: B Z Jang and W C Huang “Nano-scale Graphene Plates”, US Patent No. 7071258 (07/04/2006).


Fig. 2 Percentage of graphene synthesis and electrode and supercapacitor application related patents in different contries. The majority of patent applications are coming from the US (39%) followed by China (23%), Japan (19%), South Korea (12%), Germany (5%) and Australia (2%).

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