Supporting Information

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1 Supporting Information Electrochemically Scalable Production of Fluorine Modified Graphene for Flexible and High-Energy Ionogel-based Micro-Supercapacitors Feng Zhou, Haibo Huang, Chuanhai Xiao,, Shuanghao Zheng,,, Xiaoyu Shi,,, Jieqiong Qin,, Qiang Fu,, Xinhe Bao,, Xinliang Feng,*,ǁ Klaus Müllen,*, and Zhong-Shuai Wu*, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian , China State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian , China University of Chinese Academy of Sciences, 19 A Yuquan Rd, Shijingshan District, Beijing, , China Department of Chemical Physics, University of Science and Technology of China 96 JinZhai Road, Hefei , P. R. China ǁ Center for Advancing Electronics Dresden (cfaed) & Department of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstra e 4, Dresden, Germany Max-Planck-Institut für Polymerforschung, Ackermannweg 10, Mainz, Germany S1

2 Calculation. The capacitance values were calculated from the discharge curves of CV and GCD according to the following equations (1) and (2): C 1 V f I( V dv v( V V ) ) Vi f i (1) I t C (2) V f V ) ( i Where ν is the scan rate, V f and V i are the potential limits of CV curve. I(V) is the voltammetry discharge current. Δt refers to the discharge time. Areal capacitance areal C electrode (F cm -2 ) and volumetric capacitance volumetric C electrode (F cm -3 ) of single electrode were calculated from the formula (3) and (4): C 4 C / A (3) areal electrode electrode C 4 C / V (4) volumetric electrode electrode Where A electrode and V electrode refer to the area and volume of two electrodes, respectively. Areal capacitance and volumetric capacitance of the devices were calculated based on area and volume of two electrodes according to the formula (5) and (6): C / areal device C Aelectrode (5) C / volumetric device C Velectrode (6) The volumetric energy density E (Wh cm -3 ) and power density P (W cm -3 ) of the device was obtained from the equations: 2 1 volumetric ( Vf Vi IR) E Cdevice (7) S2

3 E P 3600 (8) t where IR is Ohmic drop. Figure S1. SEM image of FG nanosheets obtained from NaBF 4 electrolyte. FG nanosheets on (a, b) silicon wafer and on (c, d) copper gauze. S3

4 Figure S2. SEM images of FG flakes on silicon wafer obtained from (a) NH 4 BF 4 and (b) KPF 6 electrolyte. Figure S3. Statistical distribution of lateral size of FG nanosheets. S4

5 Ratio (%) Figure S4. (a, b) TEM images of FG nanosheets obtained from NaBF 4 electrolyte Number of layers Figure S5. Statistical thickness analysis of FG nanosheets obtained by HRTEM measurement. S5

$Figure S6. X-ray diffraction spectra of FG (inset: X-ray diffraction spectra of graphite foil and FG).$ 48 Å; whereas, the peak of graphite appears at 26.5 with d-spacing of 3.36 Å. Figure S7.

48 Å; whereas, the peak of graphite appears at 26.5 with d-spacing of 3.36 Å. Figure S7.

6 Figure S6. X-ray diffraction spectra of FG (inset: X-ray diffraction spectra of graphite foil and FG). The diffraction peak (002) of FG appears at 26.3, with a interlayer d-spacing of 3.48 Å; whereas, the peak of graphite appears at 26.5 with d-spacing of 3.36 Å. Figure S7. 3D view of the surface of FG electrode on PET substrate, measured by Alpha step D-600. (a) 45 o counter-clockwise view, (b) top view, and (c) 45 o clockwise view. S6

(c) Cross-section SEM image of FG electrode on

7 Figure S8. (a) 2D pseudo-color view of the surface and (b) 3D cross-section view of FG electrode on PET substrate, measured by Alpha step D-600. (c) Cross-section SEM image of FG electrode on PET. Figure S9. The CV curves of FG-MSCs in EMIMBF 4 obtained at (a) 1~20 and (b) 50~1000 mv s -1. S7

8 Figure S10. GCD curves of FG-MSCs in EMIMBF 4 obtained at different current densities of 0.2 to 10 A cm -3. S8

against different materials films using the

9 Figure S11. Electrochemical impedance spectra of FG-MSCs, EG-MSCs, and HG-MSCs. Figure S12. Contact angle measurements of EMIMBF 4 against different materials films using the drop shape method. (a) 25.8 o for FG film, (b) 64.2 o for EG film, (c) 48.7 o for HG film. S9

with different thickness of 0.7, 1.3 and 2.6 μm, respectively. Figure S14.

10 Figure S13. (a) Areal capacitance and (b) volumetric capacitance of FG-MSCs with different FG film thickness as a function of scan rate. MSC-07, MSC-13 and MSC-26 are referred to as the devices based on the FG films with different thickness of 0.7, 1.3 and 2.6 μm, respectively. Figure S14. Electrochemical impedance spectra of FG-MSCs with different thickness FG films of 0.7, 1.3 and 2.6 μm, respectively. And their corresponding microdevices are referred to as MSC-07, MSCs-13 and MSC-26. S10

11 Figure S15. The ionic conductivity of EMIMBF 4 ionogel electrolyte as a function of the content (wt%) of PVdF-HFP polymer. S11

(c) Areal capacitance and (d) volumetric capacitance of FG-MSCs as a function of scan rate.

12 Figure S16. Electrochemical characterization of FG-MSCs in gel electrolyte of PVA/H 2 SO 4. (a,b) The CVs obtained at different scan rates of (a) 1~10 and (b) 20~500 mv s -1. (c) Areal capacitance and (d) volumetric capacitance of FG-MSCs as a function of scan rate. (e) Ragone plot of FG-MSCs. and (f) cycling stability of FG-MSCs, for 5000 times obtained at 0.2 ma cm -2. S12

13 Table S1. Elemental analysis of FG, EG and HG from XPS. Element FG (at%) EG (at%) HG (at%) C O F S13

14 Table S2. Performance Comparison of FG-MSCs with carbon-based MSCs. MSCs Electrolyt e FG-MSCs EMIMBF 4 / PVDF-HF P C A a mf cm -2 a C V F cm -3 S14 P b W cm -3 E b mwh cm -3 Refs This work FG-MSCs EMIMBF This work EG-MSCs EMIMBF This work HG-MSCs EMIMBF This work MPG-MSC H 2 SO 4 /PV s A CDC-MSC TEABF s AC-MSCs H 2 SO VACNT-M SCs LWG -MSCs OLC-MSC s rgo/cnt- MSCs LSG-MSCs Li 2 SO GO/H 2 O c 0.43 c 5 TEABF M KCl BMIMNT F 2 /fumed silica IPC-MSCs TEABF VGNs-MS PYR 13 NTF Cs 2 C A : areal capacitance; C V volumetric capacitance; P: power density; E: energy density; MPG: methane plasma reduced graphene; CDC: carbide-derived carbon; AC: activated carbon; VACNT: vertically aligned carbon nanotubes; LWG: laser written graphene oxide film; OLC: onion-like carbon; rgo: reduced graphene oxide; CNT: carbon nanotube; LSG: laser-scribed graphene; IPC: inkjet-printed carbon; VGNs: vertical graphene nanosheets. TEABF 4 : Tetraethylammonium tetrafluoroborate;

15 BMIMNTF 2 : 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; PYR 13 NTF 2 : N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonylimide); a These values are calculated based on the volume of single electrode. b These values are calculated based on the whole device. c These values are calculated based on the thickness of the electrodes. S15

16 References (1) Wu, Z.-S.; Parvez, K.; Feng, X.; Muellen, K. Nat. Commun. 2013, 4, (2) Chmiola, J.; Largeot, C.; Taberna, P.-L.; Simon, P.; Gogotsi, Y. Science 2010, 328, 480. (3) Wei, L.; Nitta, N.; Yushin, G. ACS Nano 2013, 7, (4) Ghosh, A.; Viet Thong, L.; Bae, J. J.; Lee, Y. H. Sci. Rep. 2013, 3, (5) Gao, W.; Singh, N.; Song, L.; Liu, Z.; Reddy, A. L. M.; Ci, L.; Vajtai, R.; Zhang, Q.; Wei, B.; Ajayan, P. M. Nat. Nanotechnol. 2011, 6, 496. (6) Pech, D.; Brunet, M.; Durou, H.; Huang, P.; Mochalin, V.; Gogotsi, Y.; Taberna, P.-L.; Simon, P. Nat. Nanotechnol. 2010, 5, 651. (7) Beidaghi, M.; Wang, C. Adv. Funct. Mater. 2012, 22, (8) El-Kady, M. F.; Kaner, R. B. Nat. Commun. 2013, 4, (9) Pech, D.; Brunet, M.; Taberna, P.-L.; Simon, P.; Fabre, N.; Mesnilgrente, F.; Conedera, V.; Durou, H. J. Power Sources 2010, 195, (10) Aradilla, D.; Delaunay, M.; Sadki, S.; Gerard, J.-M.; Bidan, G. J. Mater. Chem. A 2015, 3, S16

Ionic Liquid Pre-intercalated MXene Films for Ionogel-based Flexible. Micro-Supercapacitors with High Volumetric Energy Density

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 2019 Ionic Liquid Pre-intercalated MXene Films for Ionogel-based Flexible Micro-Supercapacitors