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Mechanical and Mechatronics Systems Research Laboratories
Industrial Technology Research Institute (ITRI)
Taiwan, ROC
Graphene Task ForceProject Manager Dr. Kun-Ping Huang
High-Voltage Electrical Double-Layer Capacitors
K. P. Huang / [email protected]
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GrapheneBackground
High specific surface ratio (2630 m2/g)
High specific capacitor (530 F/g)
High electron transport (200, 000 cm2 V−1 s−1)
http://physicsworld.com/cws/article/news/2012/mar/20/laser-writer-makes-graphene-supercapacitors
http://energyeducation.ca/encyclopedia/Supercapacitor
K. P. Huang
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GraphenePatent Analysis of Energy Storage
Graphene supercapacitor can provide high power density (>2k W/h)
Supercapacitor has longer cycle life (>10, 000 cycles)
LIB36%
Spercapacitor
26%
Solar Cell24%
Fuel Cell9%
Others5%
0
200
400
600
800
1000
1200
2008 2009 2010 2011 2012 2013 2014 2015 2016
Spercapacitor
30%
Energy Storage Patent Analysis Trend Chart of Supercapacitor Patent
11,852 patents 30% annual growth
K. P. Huang
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GrapheneLIB and Spercapacitor
Start Uphill Downhill(Charge)
Start/Stop
http://www.ecmag.com/section/your-business/tesla-gives-ev-battery-industry-jolt
Working Voltage ~2.8V
Volume ?
Electric Car
K. P. Huang
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MP CVDBottom-Up Synthesis
MWGenerator
Ionization > 40%Plasma Density > 1E14 ion/cm3
Microwave Plasma enhanced Chemical Vapor Deposition
Reaction Area
ArCH4N2
K. P. Huang
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Graphene NanowallsGrowth and Doping
NGNW growth through Plasma
N DopingGrowthK. P. Huang
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Bottom-Up SynthesisGraphene Allotrope
< 100 torr
Graphene Nanowall
> 100 torr
Graphene Powder
K. P. Huang
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SupercapacitorPowder vs GNW
Chen, J., Bo, Z., & Lu, G. (2015). Vertically-Oriented Graphene. Springer International Publishing Switzerland, DOI, 10, 978-3.
K. P. Huang
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GNW with few edge and regular distribution and it provide these inner face between active material and electrolyte.without oxidation reaction or HER. Cell voltage raise to 4V.
Graphene powder with a lot reactive edge and random distribution. The reaction (oxidation or HER) is easy happen between the electrolyte and active material. Cell voltage can’t higher than 2.8V.
SupercapacitorPowder vs GNW
K. P. Huang
Naoi, K. (2010). ‘Nanohybrid capacitor’: the next generation electrochemical capacitors. Fuel cells, 10(5), 825-833.
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10Kun-Ping Huang
Gas evolution from an EDLC cell upon over-voltage application.
Reduce the electrode activity to electrolyte/the interface reactions
Naoi, K. (2010). ‘Nanohybrid capacitor’: the next generation electrochemical capacitors. Fuel cells, 10(5), 825-833.
SupercapacitorEdge Reaction
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11Kun-Ping Huang
SupercapacitorPowder vs GNW
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Graphene NanowallsChemical Analysis
Nano Lett. 2016, 16, 5719−5727
Raman XPS
K. P. Huang
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13Nano Lett. 2016, 16, 5719−5727
sp2 93%
< 5 layers
Graphene NanowallsLP HRTEM
TEM EELS
C60
K. P. Huang
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Positive Negative
SupercapacitorGNW
HER
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Positive Negative
SupercapacitorNGNW
Oxidation
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50 mV s-1
(a) CV curves and (b) constant-i charge-discharge curves of an N-graphene//LQ graphene ASC in 1 M TEABF4/PC with a cell voltage of 2.5, 3.0, 3.5, 4.0 V at 50 mV/s or 2 A/g.
N-graphene (-)//GNW (+) is a 4V EDLC
0.5 A g-1
SupercapacitorGNW-NGNW
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(c) The charge-discharge curves of an N-GNW (-)//GNW (+) ASC in 1 M TEABF4/PC with a cell voltage of 4.0 V at 0.3, 0.5, 1, 2, 3, and 5 A/g. (d) The C.E. and cell capacitance retention vs. charge-discharge current density for symmetric and asymmetric designs.
SupercapacitorGNW-NGNW
(d)
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18Kun-Ping Huang
After 10000 cycles,
efficiency and retention are
still maintain 93% and 100%
respectively.
SupercapacitorCycle Life Test
4 V @ 2 A g−1
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Conclusions
• MP CVD can grow and dope graphene at the same time.
• GNW Oxygen free inhibit oxidation reaction Be positive electrode 1.43V
• NGNW nitrogen inhibit HER reaction Be negative electrode -2.57V
• Asymmetric electrodes can accomplish 4V electrical double-layer capacitors.
(Energy Density is 53 Wh/kg; Power Density is 8k W/kg)
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20Kun-Ping Huang
Acknowledgements
Ministry of Economic Affairs: G301AR3200
Funding
Graphene Task Force
Collaboration
Prof. C. S. Kou Prof. C. C. Hu
Dr. C. C. Chang Miss Y. W. Chi Mr. H. F. Wang Mr. J. C. Ho
Consultant
Team Members
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21黃昆平
Thanks for your attention!