ETRI. IG Kim, JH Sul, BN Kim, SH Kang, YS Yang, IK You

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1 ETRI IG Kim, JH Sul, BN Kim, SH Kang, YS Yang, IK You

2 Seoul Daejeon

3 Contents Introduction to supercapacitors Graphene oxide and reduction process ETRI IPL system Sample preparation and characterization CV measurement of supercapacitor cell Summary

4 Energy storage devices U.S. Department of Energy; BCC Research 2015

5 Typical properties : Capacitors, SCs, Batteries Capacitor EDLC Battery Capacitance Up to 2.2 mf ,000 F n.a. Energy density < 0.1 Wh/kg 1-30 Wh/kg Wh/kg Power density kw/kg kw/kg < 1 kw/kg Charge / discharge time s s >300 s Cycle-life Typical life time 30 years years 5 years Efficiency >95 % > 90 % % BCC Research, 2015

6 Power density vs. energy density R. Kotz and M. Carlen, Electrochimica Acta, 1999

7 Capacitors Electrostatical charge storage CC = QQ VV = εεaa dd 11 CC = 11 CC SS + 11 CC dddddddd L.L. Zhang and X.S. Zhao, 2009 Electrochemical charge storage Electrochemical and electrostatical charge storage C. Zhong et al. Chem. Soc. Rev. 44, 7484 (2015)

8 Supercapacitors M.S. Halper and J.C. Ellenbogen, MITRE, 2006

9 Applications of supercapacitor flexible, micro, chip, pouch, wire, transparent, etc. Wearable devices - printed supercapacitors - knitted supercapacitors ; textile energy storage Knitted supercapacitor Graphene based biosupercapacitor - implantable medical device ; cardiac pacemaker, gastric/bladder stimulator - peak power assist for insulin pump L. Kou, et al. Nat. Commun Flexible supercapacitor In-plane supercapacitor M. El-Kady, et al. Nat. Commu & 2013 Biosupercapacitor pacemakers I. Mosa & M. El-Kady, 2017

10 Graphene supercapacitor charger : 5 minutes charger (Zap&Go) Graphene supercapacitor engine starter : SkelStart Trucks, boats, yachts mining equipment agricultural machinery etc

Limited surface area Flake Graphene (graphene oxide) - Mass production - Less expensive - Large surface

11 Graphene materials for supercapacitor electrode Graphene - Large surface area 2600 m 2 /g (theoretical) - High electrical conductivity 10 6 S/cm [Hummers, 1958] CVD Graphene - High quality - Expensive - Limited surface area Flake Graphene (graphene oxide) - Mass production - Less expensive - Large surface area in limited space Need reduction! Oxygen containing group removal J. Kotakoski, et al. Nano Lett. 2015

12 Identification of functional groups carboxyl group epoxy bridge carbonyl group hydroxyl group Zhi An et al. Northwestern Univ.

13 GO reduction recover graphene properties UV IR, mid-ir Visible Photo Reduction Photoreduction of GO by flash light Thermal Chemical Electrical Cote et al Wong and Pumera, RSC Adv. 2, 6068 (2012)

Pros & cons of Xe IPL process for GO photoreduction PROs Ultrafast

pulse width of millisecond) Layer-selective (substrate protective,

conditions, various gas atmosphere Continuous process (ex.

14 Pros & cons of Xe IPL process for GO photoreduction PROs Ultrafast sintering (ex. pulse width of millisecond) Layer-selective (substrate protective, absorbance contrast) Large area in film form / patterning Ambient conditions, various gas atmosphere Continuous process (ex. Roll-to-roll process) Toxic chemical free Y. Tu, et al. APL, 2015 CONs Difficult process control (narrow working window) Explosive reaction (out gasing of H 2 O, CO 2, CO) 10cm 10cm

15 ETRI Xe IPL (Intense pulsed light) system

16 ETRI Xe IPL (Intense pulsed light) system Xe lamp Reaction chamber N 2 Vacuum heating

17 GO film process GO 1g/DI water 40ml mixture Peel off from PET freestanding GO films Ultrasonic, Sonication 15cm 3-axis rotator, mixing 20cm GO slurry Bar coating of GO on PET - thickness of dried GO film 10μm

18 GO photoreduction using Xe IPL before irradiation GO after irradiation PrGO *PrGO : photoreduced GO

19 SEM images of GO & photoreduced GO (PrGO) GO 11um PrGO 1000um

20 FT-IR spectroscopy of GO & PrGO transmittance (arb. unit) OH - GO PrGO C=O, -COOH C=C O-C=O C-H C-O epoxy wavenumber (cm -1 )

21 XPS of GO & PrGO C : O=68 : 32 C : O=96 : 4 GO C 1s XPS PrGO C 1s XPS Sum C ev C-O ev C=O ev O-C=O ev Sum C ev C-O ev C=O ev O-C=O ev binding energy (ev) binding energy (ev) GO O 1s XPS PrGO O 1s XPS binding energy (ev) binding energy (ev)

22 Raman spectroscopy of GO & PrGO D intensity (arb. unit) PrGO GO G I D /I G ~1.9 I D /I G ~1.2 2D Raman shift (cm -1 )

23 Cyclic Characterization voltammetryof supercapacitor cell CYCLIC VOLTAMMETRY MEASUREMENT Cell Dry Room (22 ) Electrolyte Test method Ionic liquid electrolyte (20 mole% [EMIM][TFSI]/ACN) Coin cell (2 electrode system) Ф14mm coin cell

Cyclic Characterization voltammetry of supercapacitor cell 400 CYCLIC VOLTAMMETRY MEASUREMENT Cell Assembly @ Dry Room (22 )

200 100 0-100 0.5 V/s 0.1 V/s 0.05 V/s 0.01 V/s 1000V, 10ms pulse x2 Ф14mm coin cell capacitance (F/g) -200 400 300 200 100 0-100 0.

24 Cyclic Characterization voltammetry of supercapacitor cell 400 CYCLIC VOLTAMMETRY MEASUREMENT Cell Dry Room (22 ) Electrolyte Test method Ionic liquid electrolyte (20 mole% [EMIM][TFSI]/ACN) Coin cell (2 electrode system) capacitance (F/g) V/s 0.1 V/s 0.05 V/s 0.01 V/s 1000V, 10ms pulse x2 Ф14mm coin cell capacitance (F/g) voltage (V) 0.5 V/s 1200V, 10ms pulse x2 0.1 V/s 0.05 V/s 0.01 V/s voltage (V)

25 Cyclic Characterization voltammetry of supercapacitor cell 400 CYCLIC VOLTAMMETRY MEASUREMENT Cell Dry Room (22 ) Electrolyte Test method Ionic liquid electrolyte (20 mole% [EMIM][TFSI]/ACN) Coin cell (2 electrode system) capacitance (F/g) V/s 0.1 V/s 0.05 V/s 0.01 V/s 1000V, 10ms pulse x2 specific capacitance (F/g) V 10ms x2 irradiated 1200V 10ms x2 irradiated scan rate (V/s) capacitance (F/g) voltage (V) 0.5 V/s 1200V, 10ms pulse x2 0.1 V/s 0.05 V/s 0.01 V/s voltage (V)

26 Cyclic Characterization voltammetryof supercapacitor cell 250 scan rate 0.01V/s capacitance (F/g) V, atm C sp ~61F/g 1200V, N 2 C sp ~38F/g voltage (V) At N 2 atmosphere, photoreduction time becomes much shorter, less energy for GO reduction.

27 Summary Preliminary results of photoreduction of GO by ETRI IPL system were presented. The specific capacitances of the supercapacitors with the xenon IPL photoreduced GO electrode were presented. The GO photoreduction condition using the Xe IPL system will be optimized. We would like to acknowledge the financial support from the R&D Convergence Program of MSIP (Ministry of Science, ICT and Future Planning) and NST (National Research Council of Science & Technology) of Republic of Korea (Grant CAP ETRI)

28 Thank you!

29 Photo-reduction time (ms) mH 90Ω/sg 70Ω/sg Photoreduction process window of GO on Al 32mH 2.4kΩ/sq 762Ω/sg 1.1kΩ/sq 674Ω/sg 200Ω/sg 880Ω/sq 597Ω/sg 568Ω/sg 1.3kΩ/sq 620Ω/sg 315Ω/sg 2.1kΩ/sq 683Ω/sg 2.6kΩ/sg 1063Ω/sg 80Ω/sg 2.1kΩ/sg 1.3kΩ/sg 16mH 6.2kΩ/sg 264Ω/sg 1016Ω/sg 9kΩ/sg 12mH Applied voltage to Xe-lamp (V)

30 K. Jost et al. J. Mat. Chem. A (2015) Basic schematics for an (a) all carbon EDLC (left), (b) a pseudocapacitor (MnO 2 depicted center) and (c) a lithium ion battery (right). All devices have an active material (e.g., carbon, MnO 2, LiCoO 2 ), a current collector, a separating membrane and electrolyte, (e.g., Na 2 SO 4, or LiPF 6 solutions)

31 IDTechEx, 2016

32 IDTechEx, 2016

33 IDTechEx, 2016

34 IDTechEx, 2016

35 Application timeline of graphene Source: IDTechEx (2016)

36 Price of GO & GRAPHENE SUPERMARKET, NY Material Qty Price Unit price Single layer graphene oxide High porosity reduced graphene oxide 1g $300 $300/g 0.5g $175 $350/g 0.5g $300 $600/g 0.35g $175 $700/g Price of rgo 2 x Price of GO

37 Price of GO & Abalonyx, Oslo Material Qty Price Unit price Graphene oxide Reduced graphene oxide 100g $350 $3.5/g 50g $200 $4/g 1kg ( 75L) $9,000 $9/g 0.2kg ( 15L) $2,000 $10/g Price of rgo 3 x Price of GO

Transparent and ultra-bendable all-solid-state supercapacitors without percolation problems

Electronic Supplementary Information: Transparent and ultra-bendable all-solid-state supercapacitors without percolation problems Inho Nam, Soomin Park, Gil-Pyo Kim, Junsu Park and Jongheop Yi* World Class