Download - Min Wei-2016 Symposium Poster

www.buffalo.edu

3D Printing Flexible Solid-State High-Energy-Density Graphene SupercapacitorMin Wei1, Feng Zhang2, Chi Zhou2 and Gang Wu1

1Department of Chemical and Biological Engineering, University at Buffalo, SUNY, Buffalo, New York 142602Department of Industrial System and Engineering, University at Buffalo, SUNY, Buffalo, New York 14260

Project Overview

++ +

---

-

--3D Printing Techniques Physical Characterization

Summary

Acknowledgement

Supercapacitor Electrochemical Studies

We thank the financial support from SMART Project from University at Buffalo in the strategic strength areas of Materials and Materials Innovation, Advanced Design and Manufacturing.

Background on Energy Storage Devices

Motivation

Approach

Objective

A wide utilization of liquid acidic electrolytes has been caused corrosive issues.

Develop advanced solid-state high-energy-density graphene supercapacitor by using the 3D printing technologies.

Preparation the novel 3D graphene and graphene oxide (GO) as the electrode and the solid-state electrolyte to fabricate flexible supercapacitors as a sandwich structure.

+++++

-----

+++

-- --+ ve ions- ve ions

Separator

Electrolyte

Current Collector

Porous Electrode Materials

Batteries• Chemical storage• Slow charging-discharging rate at low power density• Bulky and heavySupercapacitor• Surface charge storage• Long cycle life (100000 cycles)• Rapid charging-discharging rate at high power density and

high-frequency response on a small scale• Light weight, small thickness and good flexibility

Inkjet printing

Multi-nozzle

Heated bed Temperature Sensor

Heating

Synthesis

• Electrodes: Iron-based polyaniline-derived carbon material• Solid-State electrolyte: Graphene oxide

Materials

2.5g graphite powder + 57.5mL pure H2SO4

Add 1.25g NaNO3 Move to an ice bath and slowly add 7.5g KMnO4

in 1h

Move to water bath and keep 35 for ℃

2h

Slowly add 125mL of water and increase T to 90 for ℃

0.5h

Pour into 500mL of water and add H2O2 to stop the reaction

wash with 5% HCl and DI Water until pH = 6

Dry in vacuum oven for two days

STEP: 1 STEP: 2 STEP: 3

STEP: 6

STEP: 5STEP: 4

STEP: 8 STEP: 7

Stirred for 24h Stirred for 1h

Graphene Oxide (The Modified Hummer’s Method)

Iron-Based Polyaniline-Derived Carbon

FeCl3 added in 2M HCl

stir for 30 mins toallow full dissolution

Add aniline

stir for another 1h to get fully mixed

Add APS

stir for 4 hours toallow full polymerization

Add BP carbon

stir for 24 hours

Transfer solution to a beaker

Scratch off and grind the left materials

put sample in tube furnace for heat treatment

Heat treatment

Acid leaching to remove metal

Put in vacuum oven and then get dry carbon materials

(3D graphene)

start heating of 70 to ℃slowly evaporate the solvent

Heating Coils

N2 flow

in

N2 flow out

Alumina Tube

Boat with Samples

STEP: 1 STEP: 2 STEP: 3 STEP: 4 STEP: 5

STEP: 6

STEP: 7STEP: 8

TEM images for Fe-PANI-C samples showing highly porous and 3D morphology

UV test for Graphene Oxide

The optimized reaction conditions for graphene oxide and iron-based polyaniline-derived carbon was successfully found.Graphene Oxide Iron-Based Polyaniline-Derived Carbon

• Low amount of FeCl3

• High temperature of heat treatment• Low amount of graphite• Amount of KMnO4 (8.5g)• T=35 C at step 4∘• R=200rpm at step 4

GO

CV test for different amount of GO in alkaline solution

CV test for different temperatures (step 4) in alkaline solution

0.0 0.2 0.4 0.6 0.8 1.0

-0.25

-0.20

-0.15

-0.10

-0.05

0.00

0.05

0.10

-0.25

-0.20

-0.15

-0.10

-0.05

0.00

0.05

0.10

Curre

nt D

ensit

y(m

A/m

g)

Potential (V vs RHE)

GO8(1.5) GO8(2.0) GO8(2.5) GO8(3.0)

Test in 0.1M NaOH-20mv-200rpm

0.0 0.2 0.4 0.6 0.8 1.0-0.18-0.16-0.14-0.12-0.10-0.08-0.06-0.04-0.020.000.02

0.040.06

Cur

rent

Den

sity

(mA

/mg)


GO5 GO5(KMnO4)


CV test for different rate to add KMnO4 (step 3) in alkaline solution

0.0 0.2 0.4 0.6 0.8 1.0-0.10

-0.08

-0.06

-0.04

-0.02

0.00

0.02

0.04

Cur

rent

Den

sity

(mA

/mg)


GO2 GO4(200) GO4(360)


CV test for different rotation speeds of stir bar (step 3) in alkaline solution

0.0 0.2 0.4 0.6 0.8 1.0-10

-8

-6

-4

-2

0

2

4

6

Cur

rent

Den

sity

(mA

/mg)


7.5Fe-1HT900-80C-Mix Acid 10Fe-1HT900-80C-Mix Acid 15Fe-1HT900-80C-Mix Acid

Test in 1M KOH-20mv-200rpm

0.0 0.2 0.4 0.6 0.8 1.0

-12-10-8-6-4-202468

1012

Curre

nt D

ensit

y (m

A/m

g)


7.5 Fe-1HT900-Mix Acid 7.5 Fe-1HT1000-Mix-Acid 7.5 Fe-1HT1050-Mix-Acid 7.5 Fe-1HT1100-Mix-Acid

Test in 1M KOH-20mv-200rpm

Iron-Based Polyaniline-Derived Carbon

CV test for different amount of FeCl3in alkaline solution

CV test for different temperatures of heat treatment in alkaline solution