Supporting Information. High cycling stable supercapacitor through electrochemical. deposition of metal-organic frameworks/polypyrrole positive

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Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2018 Supporting Information High cycling stable supercapacitor through electrochemical deposition of metal-organic frameworks/polypyrrole positive Yaozhi Liu, Na Xu, Weichao Chen, Xinlong Wang*, Chunyi Sun, Zhongmin Su* National & Local United Engineering Laboratory for Power Battery, Northeast Normal University, Changchun, Jilin, 130024, P. R. China. Fig. S1. SEM images of (a) the CC/ZIF-67 and (b) CC/ZIF-67/PPy. Fig. S2 (a) Colour of carbon cloth (CC), CC/ZIF-67 and CC/ZIF-67/PPy. (b) Chronopotentiometric curves during pyrrole polymerization.

Fig. S3. XRD patterns of (a) the simulated ZIF-67, as-synthesized ZIF-67, CC/ZIF-67 and (b) CC and CC/PPy Fig. S4. FTIR spectrum of the CC, CC/PPy and CC/ZIF-67/PPy. Fig. S5 (a) CV curves at 100 mv s -1 of CC/ZIF-67/PPy, CC/ZIF-67 and CC/PPy. (b) GCD curves at 20 ma cm -2 of CC/ZIF-67/PPy, CC/ZIF-67 and CC/PPy.

Fig. S6. CV curves of (a) ZIF/PPy/20 (c) ZIF/PPy/30 (e) ZIF/PPy/40 at different scan rate. GCD curves of (b) ZIF/PPy/20 (d) ZIF/PPy/30 (f) ZIF/PPy/40 at different current density.

Fig. S7. Capacitance retention of (a) ZIF/PPy/10 (b) ZIF/PPy/20 (c) ZIF/PPy/30 (d) ZIF/PPy/40 with different current density from 1 to 20 ma cm -2 Table S1. The mass loading of ZIF/PPy/10, ZIF/PPy/20, ZIF/PPy/30 and ZIF/PPy/40. Type ZIF/PPy/10 ZIF/PPy/20 ZIF/PPy/30 ZIF/PPy/40 Mass loading (mg) 0.45 0.55 0.63 0.70 Table S2. Comparison of capacitance between ZIF/PPy/10 and other MOF-based s. Type Specific Electrolyte Scan rate Specific surface area (current capacitance (F Ref. (m 2 g -1 ) density) g -1 ) Ni-DMOF- 783 2M KOH 1 A g -1 552 1 ADC Co-MOF - 1M LiOH 0.6 A g -1 207 2 Co8-MOF-5 2900 0.1M TBATF6 10 ma g -1 0.3 3 Co-BPDC 138 0.5M LiOH 10 mv s -1 179 4 Ni 3 (HITP) 2 630 TEABF 4 50 mv s -1 111 5

PANI- 73 3M KCl 10 mv s -1 371 (35 mf 6 ZIF67-CC cm -2 ) PANI- CNT@ZIF- 1194 3M KCl 10 mv s -1 0.58 7 67-CC ZIF-PPy-2 1168 1M Na 2 SO 4 0.5 A g -1 554 8 ZIF/PPy/10-6M KOH 1 ma cm -2 284.9 (180.7 mf cm -2 ) This work Table S3. Comparison of cycling stability between ZIF/PPy/10 and other supercapacitor s. Type Electrolyte Capacitance cycles Ref retention Ni-DMOF- 2M KOH 98% 16000 1 ADC MOFs-based Co-MOF 1M LiOH 98.5% 1000 2 supercapacitor Ni 3 (HITP) 2 TEABF 4 90% 10000 5 PANI- 3M KCl 80% 2000 7 material CNT@ZIF- 67-CC ZIF-PPy-2 1M Na 2 SO 4 90.7% 10000 8 Zn/Ni-MOF@PPy 3M KOH 78.8% 5000 9 Carbon-based F-GRF 6M KOH 109% 40000 10 supercapacitor PTAC-6 6M KOH 100% 10000 11 Mo-S2-rGo@PPyNTs 3M KCl 72% 10000 12 material a-sa/bc-700 6M KOH 93.8% 10000 13 Metal-based supercapacitor material NiO/C&S 3M KOH 115.9% 5000 14 Co foam@cpna 2M KOH 77.5% 20000 15 Au-PEDOT H3PO4/PVA PEDOT-Au 1 M H 3 PO 4 91.8% 20000 16 ZIF/PPy/10 6M KOH 100.7% 40000 This work 1. C. Qu, Y. Jiao, B. Zhao, D. Chen, R. Zou, K. S.Walton and M. Liu, Nickel-Based Pillared MOFs for High- Performance Supercapacitors: Design, Synthesis and Stability Study. Nano Energy, 2016, 26, 66-73. 2. D. Y. Lee, S. J. Yoon, N. K. Shrestha, S.-H. Lee, H. Ahn and S.-H. Han, Unusual Energy Storage and Charge Retention in Co-Based Metal Organic Frameworks. Micropor. Mesopor. Mater., 2012, 153, 163-165. 3. R. Díaz, M. G. Orcajo, J. A. Botas, G. Calleja and J. Palma, Co8-MOF-5 as Electrode for Supercapacitors. Mater. Lett., 2012, 68, 126-128. 4. D. Y. Lee, D. V. Shinde, E.-K. Kim, W. Lee, I.-W. Oh, N. K. Shrestha, J. K. Lee and S.-H. Han, Supercapacitive Property of Metal Organic Frameworks with Different Pore Dimensions and Morphology. Micropor. Mesopor. Mater. 2013, 171, 53-57. 5. D. Sheberla, J. C. Bachman, J. S. Elias, C.-J. Sun, Y. Shao-Horn and M. Dincă, Conductive MOF Electrodes for Stable Supercapacitors with High Areal Capacitance. Nature Mater. 2017, 16, 220-224. 6. L. Wang, X. Feng, L. Ren, Q. Piao, J. Zhong, Y. Wang, H. Li, Y. Chen, B. Wang, Flexible Solid-State Supercapacitor Based on a Metal Organic Framework Interwoven by Electrochemically-Deposited PANI. J. Am. Chem. Soc., 2015, 137, 4920-4923. 7. L. Wang, H. Yang, G. Pan, L. Miao, S. Chen and Y. Song, Polyaniline-Carbon Nanotubes@Zeolite Imidazolate Framework 67-Carbon Cloth Hierarchical Nanostructures for Supercapacitor Electrode. Electrochim. Acta, 2017, 240, 16-23. 8. X. T. Xu, J. Tang, H. Y. Qian, S. J. Qian, S. J. Hou, Y. S. Bando, M. S. A. Hossain, L. K. Pan and Y. Yamauchi, Three- Dimensional Networked Metal Organic Frameworks with Conductive Polypyrrole Tubes for Flexible Supercapacitors, Acs Appl. Mater. Interfaces, 2017, 9, 38737-38744.

9. Y. Jiao, G. Chen, D. Chen, J. Pei and Y. Y. Hu, Bimetal organic framework assisted polymerization of pyrrole involving air oxidant to prepare composite s for portable energy storage, J. Mater. Chem. A, 2017, 5, 23744-23752. 10. L. Sheng, J. Chang, L. Jiang, Z. Jiang, Z. Liu, T. Wei and Z. Fan, Multilayer-Folded Graphene Ribbon Film with Ultrahigh Areal Capacitance and High Rate Performance for Compressible Supercapacitors, Adv. Funct. Mater., 2018, 28, 1800597. 11. X. Su, S. Li, S. Jiang, Z. Peng, X. Guan and X. Zheng, Superior capacitive behavior of porous activated carbon tubes derived from biomass waste-cotonier strobili fibers, Advanced Powder Technology, 2018, 29, 2097-2107. 12. D. Sarmah and A. Kumar, Layer-by-layer self-assembly of ternary MoS2-rGO@PPyNTs nanocomposites for high performance supercapacitor, Synthetic Metals, 2018, 243, 75-89. 13. Q. Bai, Q. Xiong, C. Li, Y. Shen and H. Uyama, Hierarchical porous carbons from a sodium alginate/bacterial cellulose composite for high-performance supercapacitor s, Applied Surface Science, 2018, 455, 795-807. 14. F. Shi, J. Jiang, H. Xiao and X. Li, An extra-long-life supercapacitor based on NiO/C&S composite by decomposition of Ni-based coordination complex, Materials and Design, 2018, 153, 203-210. 15. Y. Dai, S. Zhu, C. Wang, Y. Cong, Y. Zeng, T. Jiang, H. Huang and X. Meng, In-situ fabrication of Co foam@co3o4 porous nanosheet arrays for high performance supercapacitors, Journal of Alloys and Compounds, 2018, 748, 291-297. 16. N. Wang, G. Han, H. Song, Y. Xiao, Y. Li, Y. Zhang and H. Wang, Integrated flexible supercapacitor based on poly (3, 4-ethylene dioxythiophene) deposited on Au/porous polypropylene film/au, Journal of Power Sources, 2018, 395, 228-236.