1. Redox-Active Polymers for Energy Storage Nanoarchitectonics
Jeonghun Kim, Jung Ho Kim, Katsuhiko Ariga 
Joule 
Volume 1, Issue 4, Pages (December 2017)
DOI: /j.joule
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3. Figure 1
Schematic Illustration of Synthetic Route of Redox-Active Polymers and Application to Energy Storage Systems
The redox-active polymers are synthesized through organic synthetic methods including polymerization from various organic materials and applied to energy storage systems in the form of rechargeable batteries and supercapacitors. (i) CO2 utilization by plants for photosynthesis; (ii) CO2 reduction by catalytic reaction.
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4. Figure 2
Classification and Chemical Structure of Representative Redox-Active Polymers and Redox-Active Functional Groups
Conductive polymer: PANI, polyaniline; PEDOT, poly(3,4-ethylenedioxythiophene); PPy, polypyrrole; PEDOT:PSS, poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate). Other polymers: PA, polyacetylene; PI, poly(indole); P-p-P, poly(p-phenylene); Poly(S-r-DIB) copolymer, poly(styrene-r-1,3-diisopropenylbenzene).
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5. Figure 3 Lithium n-Doped Polyaniline for Rechargeable Battery
(A) Diagram showing the different possible protonation and degrees of oxidation of polyaniline; the circles represent the canonical forms that can be represented with four aniline repeating unit formulas.
(B) The formulas and reactions of some of the polyaniline states shown in the diagrams, including some of the new deprotonated-lithiated states (right).
(C) Extension in 3D of (A) with an axis to include the possible lithium p-doped states.
(D) Cyclic voltammetry (5 mV s−1) plot of a LiEB electrode in ethylene carbonate (EC)/dimethyl carbonate (DMC) with 1 M LiPF6 before (red) and after (blue) the conversion to ELi by deprotonation.
(E) UV/Vis-NIR spectroelectrochemistry plots of different absorption spectra of ELi film.
(F) Galvanostatic charge and discharge curves of ELi electrode between 4.3 and 2.5 V.
Reprinted with permission from Jiménez et al.80 Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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6. Figure 4
Click Chemistry-Based Redox-Active Polymer Gels and CNT Hybrid Composite
(A–C) Redox-active polymer gel. (A) One-step synthesis for the formation of the PTMPM-containing networks. (B) Specific capacity versus cycle number for PBIB-P(TMPM23-r-AzPMA2)-PMA (DP23, in red) and PBIB-P(TMPM5-r-AzPMA2)-PMA (DP5, in blue) electrodes (half-cell with lithium). (C) The rate performance of PBIB-P(TMPM23-r-AzPMA2)-PMA (DP23, in red) and PBIB-P(TMPM5-r-AzPMA2)-PMA (DP5, in blue). Reprinted with permission from Boujioui et al.89 Copyright 2017, Royal Society of Chemistry.
(D–F) Redox-active polymer/carbon nanotube hybrid material. (D) Grafting of PTMA on MWCNTs by click chemistry. (E) Illustration of prepared hybrid material with conductive network. (F) Charge-discharge curves of the MWCNT-g-PTMA60 electrode at various C rates (EC/DEC 1:1 by volume; 1 M LiPF6). Reprinted with permission from Ernould et al.90 Copyright 2017, Royal Society of Chemistry.
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7. Figure 5
Redox-Active Poly(Ionic Liquid) for Energy Storage Applications
(A) Anion exchange reaction proposed for the synthesis of redox-active poly(ionic liquid)s. The mother starting poly(ionic liquid) is PDADMA at center.
(B) Different applications of redox-active poly(ionic liquid)s, including the active material in lithium batteries, the electrocatalyst for the oxygen reduction reaction, and redox electrolytes in organic redox-flow batteries.
(C) Cyclic voltammetry of PDADMA-100AQ at 5 mV s−1. Inset: redox mechanism of PDADMA-100AQ.
(D) Hydrodynamic voltammetry results of the ORR at various rotation rates for PDADMA-100AQ in the oxygen-saturated electrolyte.
(E) Voltage difference representation of a redox-flow battery made of poly(ionic liquid) electrolytes based on anthraquinone (blue) and TEMPO (red) units. Reprinted with permission from Hernández et al.97 Copyright 2017, Royal Society of Chemistry.
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8. Figure 6 The Impact of the Molecular Weight of Redox-Active Polymer
(A) Synthesis of TMPM via the transesterification reaction and its polymerization via single electron transfer-living radical polymerization (SET-LRP) followed by oxidation to give PTMA.
(B) Comparison of number of radicals per repeating unit in PTMA determined by EPR (red), UV-Vis (green), and magnetic susceptibility (blue).
(C and D) Molecular weight dependence of cell performance. (C) Capacity retention over 300 cycles at a current density of 1 C. (D) Rate performance of PTMA483 and PTMA703, both with 25 wt.% PTMA loading.
Reprinted with permission from Zhang et al.108 Copyright 2017, Royal Society of Chemistry.
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9. Figure 7 Redox-Active Groups on Conductive Polymer Backbone
(A and B) Redox-active polymer battery cathode based on PANI. (A) Molecular formula of poly(2,5-dihydroxy aniline), and the redox mechanism based on two electrons per monomer unit. (B) Capacity retention plots of the materials. Reprinted with permission from Vlad et al.113 Copyright 2015, Royal Society of Chemistry.
(C–E) π-Conjugated redox polymer. (C) Graphical illustration of material design and molecular structure of the non-conjugated P(NDI2OD-TET) and the π-conjugated P(NDI2OD-T2) (D) Capacity retention of Li cells at increased rates. (E) Reversibility of P(NDI2OD-T2) during repeated deep n-doping-undoping at 10 C (12 min per cycle). Reprinted with permission from Liang et al.114 Copyright 2015, American Chemical Society.
(F and G) PEDOT with redox-active group. (F) Synthesis of PEDOT-TEMPO. (G) Cell performance of LFP cathodes. Reprinted with permission from Casado et al.115 Copyright 2016, American Chemical Society.
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10. Figure 8 Redox-Active Colloids
(A) Synthesis of polyvinyl benzyl chloride- and viologen-based redox-active colloidal particles.
(B) Scanning electron microscopy images of redox-active colloidal particles.
(C) Cyclic voltammograms of materials in the dispersion phase.
(D) Charge/discharge performance of RAC 2 in bulk electrolysis on SGL GFA6 carbon electrode (0.1 M LiBF4 in acetonitrile). The theoretical capacity is 134 mAh L−1 (5 mM). Inset: visual changes are observed from the neutral (top) to the charged state (bottom).
Reprinted with permission from Montoto et al.138 Copyright 2016, American Chemical Society.
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11. Figure 9 Mesoporous Conductive Polymer Nanoarchitecture
(A–C) Electroactive mesoporous ProDOT-silica structures. (A) Synthesis of ProDOT-C6TE. (B) Synthesis of conductive mesoporous silica hybrid composite. (C) Galvanostatic charge/discharge curves of PSM-1. Reprinted with permission from Kim et al.140 Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
(D–H) Two-dimensional (2D) free-standing mesoporous conductive polymer nanoarchitecture. (D) Synthesis of 2D mesoporous conductive polymer nanosheets, including micelle formation, polymerization, and removal of micelles (scale bar, 100 nm). (E) Surface and (F) cross-sectional scanning electron microscopy images of graphene oxide (GO)-based 2D mesoporous PPy (mPPy) nanosheets from PS102-b-PEO114. (G) Electrochemical performance of 2D large-pore mesoporous nanosheets. (H) CV curve of nanosheets as electrode for on-chip all solid-state micro-supercapacitor at 100 V s−1 (inset: photograph of on-chip all solid-state micro-supercapacitor). Reprinted with permission from Liu et al.141 Copyright 2015, Nature Publishing Group.
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12. Figure 10 Redox-Active Covalent Organic Frameworks
(A) Chemical structure of TaPa-Py covalent organic framework (COF). Reprinted with permission from Khattak et al.151 Copyright 2016, Royal Society of Chemistry.
(B) Chemical structure of TpPa-(OH)2 COF. Reprinted with permission from Chandra et al.153 Copyright 2017, American Chemical Society.
(C) Chemical structure of TAT-CMP-1COF. Reprinted with permission from Li et al.154 Copyright 2017, Royal Society of Chemistry.
(D and E) Exfoliation of COFs into few-layer redox-active nanosheets. (D) Exfoliation of COFs by the ball-milling process. (E) Chemical structures of DAAQ-TFP-COF, DABQ-TFP-COF, and TEMPO-COF. Reprinted with permission from Wang et al.155 Copyright 2017, American Chemical Society.
(F) Synthesis of three-dimensionally interconnected sulfur-rich polymer. Reprinted with permission from Kim et al.156 Copyright 2015, Nature Publishing Group.
(G) Synthesis of a covalent triazine framework. Reprinted with permission from Talapaneni et al.157 Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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13. Figure 11 New Approaches to Redox-Active Polymers for Future ESSs
(A–C) The all-organic battery. (A) Structure of full cell using thianthrene- and TCAQ-based polymers. (B) Charging mechanism. (C) Galvanostatic charge-discharge profiles of the coin cells. Working electrode: poly(2-vinylthianthrene), PVDF, and Super P (40:5:55, m/m/m). Reference/counter electrode: poly(2-methacrylamide-TCAQ), PVDF, and Super P (40:5:55, m/m/m), with 1 M LiClO4, EC/DMC (3/7, v/v) at 1 C. Reprinted with permission from Wild et al.164 Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
(D–F) Aqueous zinc-organic polymer battery. (D) Redox reaction of synthesized polymer. (E) Capacity development during extended charge/discharge cycling of a zinc-polymer hybrid battery. (F) Charge/discharge curves of the zinc-organic hybrid battery at different charging/discharging speeds. Reprinted with permission from Häupler et al.165 Copyright 2016, Nature Publishing Group.
(G) Biopolymer-based redox-active polymer composite for ESSs. Cell structures of a supercapacitor (left) and Na battery (right) based on lignin/PEDOT composite. Reprinted with permission from Navarro-Suárez et al.166 Copyright 2017, Royal Society of Chemistry (left). Reprinted with permission from Casado et al.167 Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim (right).
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