Min Wei-2016 Symposium Poster
1
www.buffalo.edu 3D Printing Flexible Solid-State High-Energy-Density Graphene Supercapacitor Min Wei 1 , Feng Zhang 2 , Chi Zhou 2 and Gang Wu 1 1 Department of Chemical and Biological Engineering, University at Buffalo, SUNY, Buffalo, New York 14260 2 Department 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 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 ion s - ve ion s Sepa rato r Elec trol yte Current Collect or Porous Electrode Materials Batteries • Chemical storage • Slow charging-discharging rate at low power density • Bulky and heavy Supercapacitor • 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 H 2 SO 4 Add 1.25g NaNO 3 Move to an ice bath and slowly add 7.5g KMnO 4 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 H 2 O 2 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: 5 STEP: 4 STEP: 8 STEP: 7 Stirred for 24h Stirred for 1h Graphene Oxide (The Modified Hummer’s Method) Iron-Based Polyaniline-Derived Carbon FeCl 3 added in 2M HCl stir for 30 mins to allow full dissolution Add aniline stir for another 1h to get fully mixed Add APS stir for 4 hours to allow 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 N 2 flo w in N 2 flow out Alumina Tube Boat with Samples STEP: 1 STEP: 2 STEP: 3 STEP: 4 STEP: 5 STEP: 6 STEP: 7 STEP: 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 Carbo • Low amount of FeCl 3 • High temperature of heat treatment • Low amount of graphite • Amount of KMnO 4 (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 CV test for different rate to add KMnO 4 (step 3) in alkaline solution CV test for different rotation speeds of stir bar (step 3) in alkaline solution Iron-Based Polyaniline-Derived Carbon CV test for different amount of FeCl 3 in alkaline solution CV test for different temperatures of heat treatment 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 .2 5 -0 .2 0 -0 .1 5 -0 .1 0 -0 .0 5 0.00 0.05 0.10 C urren t D ensity(m A/m g) P o ten tial(V vs R HE) G O 8(1.5) G O 8(2.0) G O 8(2.5) G O 8(3.0) T e st in 0 .1 M N aO H -20m v-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 .02 0.00 0.02 0.04 0.06 C urrentD ensity (m A/mg) Potential(V vs R HE) GO5 G O 5(K M nO 4) T estin 0.1M N aOH -20m v-200rpm 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 C urrent D ensity (m A /m g) P otential(V vs R HE) GO2 G O 4(200) G O 4(360) T estin 0.1M N aO H -20m v-200rpm 0 .0 0.2 0.4 0.6 0 .8 1 .0 -10 -8 -6 -4 -2 0 2 4 6 C urrent D ensity (m A /m g) Potential(V vs R HE) 7.5Fe-1H T 900-80C -M ix A cid 10Fe-1H T900-80C -M ix A cid 15Fe-1H T900-80C -M ix A cid T estin 1M K OH-20m v-200rpm 0.0 0.2 0.4 0.6 0.8 1.0 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 C urren t D e n sity (m A/m g) P ote ntial(V vs R HE) 7 .5 F e -1 H T 900-M ix A cid 7 .5 F e -1 H T 1000 -M ix-A cid 7 .5 F e -1 H T 1050 -M ix-A cid 7 .5 F e -1 H T 1100 -M ix-A cid T e st in 1 M KO H -20m v-200rpm
Transcript of 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)
Potential (V vs RHE)
GO5 GO5(KMnO4)
Test in 0.1M NaOH-20mv-200rpm
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)
Potential (V vs RHE)
GO2 GO4(200) GO4(360)
Test in 0.1M NaOH-20mv-200rpm
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)
Potential (V vs RHE)
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)
Potential (V vs RHE)
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
