Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial...
Transcript of Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial...
![Page 1: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/1.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
1
Exploring the Interfacial Nanostructures of LiTFSI in Ionic Liquids on Different Substrates
Abhishek Lahiri, Timo Carstens, Natalia Borisenko, Andriy Borodin, Frank Endres
Institute of Electrochemistry, Clausthal University of Technology, Arnold-Sommerfeld-Str. 6, D-38678 Clausthal-Zellerfeld, Germany
![Page 2: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/2.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
2
Introduction
Ionic liquid Interface
Importance of understanding IL interface in electrochemistry
LiTFSI on Au(111) and on Electrodeposited Ge
Conclusions
Contents of the talk
![Page 3: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/3.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
3
Introduction
Ionic
Liquids
http://lem.ch.unito.it/didattica/infochimica/Liquidi%20Ionici/ApplicationsMap.html
![Page 4: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/4.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
4
Ionic Liquid Interface
Ionic liquids / electrode interface
Electric Double Layer Multilayer model
Aqueous electrolyte / electrode interface
(from Wikipedia)
RTIL / Electrode interfaces Layered structure; strong interaction;
![Page 5: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/5.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
5
Various experimental techniques to explorethe interface
HE X-ray reflectivity/SFA
Mezger et al, Science, 2008, 322, 424
Perkin, PCCP, 2012, 14, 5052-62
XPS/UPS
Lovelock et al, Chem Rev, 2010, 110, 5158-5190
SPM
Carstens et al, J. Phys. ChemC, 2014, 118, 10833-43
Elbourne et al, ACS Nano, 2015, 9, 7608-7620
Uhl et al, Beilstein J Nanotechnol, 2013, 4, 903-918
SFG/ Impedance spectroscopy
Baldelli, Acc. Chem. Res, 2008, 40, 421-431
Fabregat-Santiago et al, PCCP, 2011,13, 9083-9118
![Page 6: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/6.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
6
Importance of understanding the interface
N+N-
S
O O
S
O O
CF3F3C[Py1,4]TFSI
[EMIM]TFSIN-
S
O O
S
O O
CF3F3C
N+N
Pulletikurthi et al, J. Solid. State. Electrochem, 2013, 17, 2823-2832Endres et al. PCCP, 2010, 12, 1724-1732Lahiri et al, Angew. Chem. Int. Ed, 2015, 54, 11870-11874
[Py1,4]TFSI
The structure and dynamics of the interfaciallayer influence the electrochemical reactions, deposit morphology and material property.
![Page 7: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/7.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
7
Ionic liquids as battery electrolytes
MacFarlane et al, Energy. Environ. Sci. 2014, 7, 232-250
Armand et al, Nature Mater, 2009, 8, 621-629
![Page 8: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/8.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
8
LiTFSI in [Py1,4]TFSI (Raman Spectroscopy)
Lahiri et al, J. Phys. Chem. C, 2015, 119, 16734- 16742
Cis
Trans
![Page 9: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/9.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
9
Raman Spectroscopy (Quantitative analysis)
Coordination number N =
𝐴𝐼𝐼𝐼(𝐴𝑡𝑜𝑡𝑎𝑙)
x
N= 2
N= 1N= 0.53
[Li(TFSI)2]-
[Lim(TFSI)n](n-m)-
n/m < 2
[Lim(TFSI)n](n-m)-
n/m < 2
Pitawala et al, Faraday Discussion, 2012, 154, 71-80Lahiri et al, J. Phys. Chem. C, 2015, 119, 16734- 16742
![Page 10: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/10.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
10
Cyclic Voltammetry
Lahiri et al, J. Phys. Chem. C, 2015, 119, 16734- 16742
![Page 11: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/11.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
11
In situ AFM Principle
Schematic view of an AFM tip approaching a solid surface in the presence of ILand corresponding approach curves
Schematic diagram ot the vertical tip movement during the approach
A practical guide to AFM force spectroscopy and data anylsis, JPK Instruments – www.jpk.com
![Page 12: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/12.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
12
In situ AFM of [Py1,4]TFSI
Lahiri et al, J. Phys. Chem. C, 2015, 119, 16734- 16742Lauw et al, Langmuir, 2012, 28, 7374-7381
Au (111)
![Page 13: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/13.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
13
In situ AFM of 0.1M LiTFSI in [Py1,4]TFSI
0.5 nm
LiTFSI
~ 0.2 nm
[Li(TFSI)2]-
![Page 14: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/14.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
14
In situ AFM of LiTFSI in [Py1,4]TFSI at -1.0 V (Different Concentrations)
0.1 M 0.5 M 1.0 M
![Page 15: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/15.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
15
1M LiTFSI-[Py1,4]TFSI on Electrodeposited Ge
N= 0.53
Lahiri et al, Phys.Chem.Chem.Phys, 2015, 17, 11161-11164
N= 0.75
![Page 16: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/16.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
16
Cyclic Voltammetry of 0.5 M LiTFSI-[Py1,4]TFSI on electrodeposited Ge
Ge deposit
After Cycling
![Page 17: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/17.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
17
Charge-Discharge Cycle and AFM
60 µA
![Page 18: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/18.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
18
XPS (Ge and F)
![Page 19: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/19.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
19
XPS (C and Li)
![Page 20: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/20.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
20
XPS (O and S)
![Page 21: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/21.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
21
IR and Raman of electrolyte
![Page 22: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/22.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
22
1M LiTFSI in [Py1,4]FSI
[Py1,4]TFSI
Lahiri et al, Phys.Chem.Chem.Phys, 2015, 17, 11161-11164
![Page 23: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/23.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
23
Raman of 1M LiTFSI in [Py1,4]FSI
CN= 0.71CN= 0.7
![Page 24: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/24.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
24
The interfacial nanostructure of LiTFSI in [Py1,4]TFSI and[Py1,4]FSI on Au(111) and on Ge was evaluated.
Multilayered nanostructure was observed for both [Py1,4]TFSIand [Py1,4]FSI on Au(111)
On addition of LiTFSI in [Py1,4]TFSI, the [Py1,4]+ cation wasreplaced by Li+ ion on the Au(111) surface. However, onaddition of LiTFSI in [Py1,4]FSI, a decrease in rupture force isnoted.
With increase in concentration of LiTFSI in [Py1,4]TFSI, thenumber of interfacial layers decreased.
At -1.0 V, for 1M LiTFSI-[Py1,4]TFSI, an underpotentialdeposition of Li might have taken place as no prominentinterfacial layers could be oberved.
Conclusions
![Page 25: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/25.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
25
On electrodeposited Ge, Li intercalation and deintercalationprocesses took place.
AFM analysis of LiTFSI in [Py1,4]TFSI showed that the SEIlayer is inhomogeneous and changes during the first charge-discharge cycles. However, the SEI layer was found to bestable after 10 charge-discharge cycles.
From IR spectroscopic analysis, it was shown that both thecation and anion is affected during the charge-dischargecycles
From Raman and AFM analyses it was shown that > 0.5 MLiTFSI- [Py1,4]TFSI is not ideal as an electrolyte for LIBs.
Conclusions
![Page 26: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/26.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
26
AcknowledgementProf. Dr. Frank Endres Dr. Timo Carstens Dr. Natalia Borisenko Dr. Andriy Borodin
Workgroup of Prof Endres
Financial Support
DFG
BMBF
![Page 27: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/27.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
27
Symposium on Material Synthesis in Ionic liquids and Interfacial
Processes
April 13-15th
2016, Goslar, Germany
Organising Team
Natalia Borisenko ([email protected])
Abhishek Lahiri ([email protected])
• Material Synthesis in Ionic Liquids
• Electrochemistry in Ionic Liquids
• Interfacial Processes in Ionic Liquids
![Page 28: Exploring the Interfacial Nanostructures of LiTFSI in ... · Exploring the Interfacial Nanostructures of LiTFSI in Ionic ... Chem Rev, 2010, 110, ... TFSI showed that the SEI](https://reader034.fdocuments.us/reader034/viewer/2022051601/5adf478d7f8b9ab4688becd2/html5/thumbnails/28.jpg)
Institute of Electrochemistry, Clausthal University of Technology, Germany (www.iec.tu-clausthal.de)
28
Thank you for your attention