Supplementary Information. Indole-Based Conjugated Macromolecule as Redox- Mediated Electrolyte for Ultrahigh Power Supercapacitor

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Electronic Supplementary Material (ESI) for Energy & Environmental Science. This journal is The Royal Society of Chemistry 2017 Supplementary Information Indole-Based Conjugated Macromolecule as Redox- Mediated Electrolyte for Ultrahigh Power Supercapacitor Ting Xiong a,b,, Wee Siang Vincent Lee a,, Li Chen c, Teck Leong Tan d, Xiaolei Huang *a, Junmin Xue * a a National University of Singapore, Department of Materials Science and Engineering, Singapore 117573. b Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, Singapore 117546. c Department of Chemistry, Tianjin University, Tianjin 300072, People s Republic of China d Institute of High Performance Computing, A*STAR, 1 Fusionopolis Way, #16-16 Connexis, Singapore 138632 * To whom correspondence should be addressed. E-mail: msexuejm@nus.edu.sg (Junmin Xue), msehx@nus.edu.sg (Xiaolei Huang), Tel./fax +65 65164655.

Fig. S1 CV curves of the obtained porous honeycomb-like using dopamine with different concentration as the redox-active additive at scan rate of 25 mv s -1. Inspired by this, we firstly studied dopamine as a redox additive in supercapacitor. By using the prepared porous honeycomb-like (labeled as PHC) as the electrode material, we tested the capacitive performance of the redox-active electrolyte using a two-electrode configuration. As shown in Fig. S1, PHC showed excellent rectangle-like cyclic voltammetry curves in 0.5 M H 2 SO 4 in the potential range of 0 1.4 V. The addition of dopamine into 0.5 M H 2 SO 4 solution caused increases in capacitance, and the capacitance increased gradually with the concentration of dopamine from 0.01 M to 0.05 M (certain amount of dopamine chloride was dissolved into 50 ml of 0.5 M H 2 SO 4 to obtain 0.01 mol L -1 (M), 0.025 M, and 0.05 M dopamine solution, which were labeled as RE0.01M, RE0.025M and RE0.05M, respectively). Notably, strong peaks related to the redox reaction of phenolic hydroxyl group/quinoid yl group (equation (1)) were observed, which contributed to the pseudocapacitance. Among the three redox electrolytes, the cyclic voltammetry curves of the porous honeycomb-like in RE0.025M electrolyte was much rectangle-like, suggesting that the optimal concentration of dopamine was 0.025M.

Fig. S2 The transformation process of RE0.025M to BRE0.025M in the three electrode at scan rate of 1000 mv s -1. Fig. S3 a) The size distribution of the molecules in BRE0.025M electrolytes; b) The Raman spectrum of PC.

Fig. S4 The cyclic voltammetry (CV) curves of the porous honeycomb-like with step-wise potential increment of 0.2 V from an initial potential window of 0.8 V to a final potential window of 1.8V in BRE0.025M electrolyte at scan rate of 25 mv s - 1. Fig. S5 Three electrodes test to investigate the individual contribution of negative and positive electrodes in the BRE0.025M electrolyte.

Fig. S6 SEM image of PC. Fig. S7 Electrochemical characterization of AC and PC using BRE0.025M electrolyte. (a),(b), CV curves; (c) rate performance at different current densities; (d) Ragone plot.

Fig. S8 Dynamic electrolyte contact angle measurements for the bare paper, porous honeycomb-like (PHC), activated (AC) and another porous (PC) in the RE0.025M and BRE0.025M electrolytes.

Table S1. Comparison of the supercapacitor performance parameters for redox supercapacitors and our present work. Active material Electrolytes Potential window Capacitance Max Energy density Max Power density Capacitance retention Ref. Activated Fe(CN) 6 3 / Fe(CN) 6 4 in 1M Na 2 SO 4 0 2 V 364.6 mf cm 2 18.9 Wh kg 1 11.5 kw kg 1 80% after 7000 cycles 1 Activated (KOH activated) N/Ofunctionalized nanoporous 0.38 M Hydroquinone in 1 M H 2 SO 4 0 1 V 901 Fg -1 18 Wh kg 1 12 kw kg -1 65%after 4000 cycle Pyrocatechol in 1 M H 2 SO 4 0 1 V 368.7 F g -1 124.4 29.9 Wh kg -1 kw kg -1 2 96.4% after 5000 cycles 3 /1, 4- dihydroxyanthr aquinone nanosheets Hydroquinone 0 1 V 239 F g in 1M H 2 SO -1 21.1 Wh kg -1 5.0 kw kg -1 91.6 % after 4 5000 cycles Anthraquinone- 2-sulfonic acid 95.2 % after 0 1.8 V 75 F sodium and KI g 1 33.8 Wh kg 1 10 kw kg 1 5000 cycles in 1M KNO 3 Hierarchical α- MnO 2 tube-ontube arrays 1.0 M Na 2 SO 4 0 0.8 V 213 F g 1 20.8 Wh kg 1 3.2 kw kg 1 6 phosphate ion functionalized 6.0 M KOH 0 1.5 V 229 F g Co 3 O 1 71.58 4 Wh kg 1 24 kw kg 1 95% after 2000 cycles 7 4 5 Mn 3 O 4 embedded on 1 M Na 2 SO 4 0 0.8 V 195 F g 1 4.3 Wh kg -1 52 kw kg -1 59% after 60h 8 Fe(CN) 6 3 modified Carbon Porous honeycomblike 1 M Na 2 SO 4 0 1.8 V indole-based conjugated macromolecula r in 0.5 M H 2 SO 4 15 W 1h kg 15 1 W h kg 15 Wh kg -1 79.1 kw kg 1 100% after 20000 cycles 0 1.4 V 550 F g -1 31.6 Wh kg -1 153 kw kg -1 97.1% after 20000 cycles 9 this work

Table S2. Comparison of the supercapacitor performance parameters for EDLC supercapacitors and our present work. Active material Electrolytes 3D porous RGO films 1.0 M H 2 SO 4 0 1 V Potential window Capacitance Max Energy density 3D Casting Cellular Graphene Films Ultrahigh- Power- Density Supercapaci tors Freeze- for of Max Power density 284.2 F g -1 9.9 Wh kg 1 282 kw kg 1 Capacitance retention 97.6% after 10000 cycles Ref. 10 3D Few-Layer Graphene-like Carbon porous foam electrode with multiscale pore network 6 M KOH 0 1 V 219 F g -1 8 Wh kg -1 199.7 kw kg -1 LiOH-PVA 0 1 V 315.2 F g -1 10.4 Wh kg 1 250 kw kg -1 99% after 20000 cycles 11 97.6 % after 10000 cycles 12 Nitrogen-doped mesoporous 0.5 M H 2 SO 4 0 1.2 V 855 F g 1 39.5 42.5 Wh kg 1 kw kg 1 313 1F g 82 % after 50000 cycles 13 N-Doped nanocages 6 M KOH 0 1 V 313 F g 1 10.9 Wh k 1 22.2 kw kg -1 98% after 50000 cycles 14 Graphene films 6 M KOH 0 1 V 178 F g 1 ~6 Wh kg 1 112.6 kw kg -1 Porous honeycomblike indole-based conjugated macromolecu lar in 0.5 M H 2 SO 4 95 % after 2000 cycles 0 1.4 V 550 F g -1 31.6 Wh kg 1 153 kw kg -1 97.1% after 20000 cycles 15 this work

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