A n‐type and redox‐active radical polymer bearing galvinoxyl radicals, poly(galvinoxylstyrene), is utilized as an anode‐active material, which enabled, for the first time, the fabrication of a totally organic polymer‐ based rechargeable battery in conjunction with p‐type redox‐active radical polymer. This battery was characterized by its remarkably high power rate capability.

p-and n-Type bipolar organic polymers have attracted remarkable interest in the development of organic-based devices, such as organic light-emitting diodes, organic thin-fi lm transistors, and photovoltaics, because they allow the proper balance of hole-and electron-conduction and simplifi cation of device structure. [ 1 ] Bipolarity is mostly carried on separate donor and acceptor sites and a few exceptions are p-and n-doped polythiophenes. [ 2 ] Insuffi cient stability of the n-doped state has limited the exploration of bipolar redox-active polymers, which are even accompanied by counterion migration. Stoichiometric bipolar redox activity for charge storage (long term) is challenging, but here we achieved three redox states (n-doped, neutral, and p-doped states) via judicious molecular design of the organic polymers.Recently, we successfully utilized redox polymers bearing robust, redox-active radical pendant groups, such as 2,2,6,6-tetramethylpiperidinyl-oxy (TEMPO) (p-type) [ 3 ] and galvinoxyl (n-type), [ 4 ] as cathode-and anode-active materials, respectively, and demonstrated high power rate capability in a totally organic-based rechargeable battery. We also reported either p-or n-type redox activity of poly(nitroxylstyrene) switched with substituent electronic effects, [ 5 ] however, these radical polymers did not show any bipolar redox activity, which is even more challenging than n-type redox activity. [ 6 ] Here we focus on redox reactions of nitronylnitroxide ( Figure 1 a ), [ 7 ] stabilized by the conjugated structure of two NO sites and by tuning the electrolyte conditions and report for the fi rst time poly(nitronylnitroxylstyrene) as the bipolar (p-and n-dopable) electrode-active material. In this report, we construct two unprecedented battery confi gurations: a) a symmetric confi guration (poleless battery) composed of poly(nitronylnitroxylstyrene) 1 for both electrodes and b) a both n-type electrode confi guration ("rocking-chair-type") utilizing poly(nitronylnitroxylstyrene) 1 and poly(galvinoxylstyrene) 2 [ 4 ] as the anode-and the cathode-active materials, respectively. A poleless battery confi guration is curious in the interest of simplifying the battery confi guration, and a "rocking-chair-type" confi guration would be favored to tremendously reduce the electrolyte solution. We demonstrate the versatility and signifi cance of bipolar redoxactive radical polymers.Poly[4-(nitronylnitroxyl)styrene] 1 was synthesized via radical polymerization of the silyl-protected precursor monomer, followed by deprotection and chemical oxidation to generate the corresponding radical polymer ( M n = 52 000, M w / M n = 3.2, 0.96 unpaired electrons per monomer unit. The theoretical redox capacity, Q , of 1 (103 mAh g − 1 ) was calculated from the formula weight ( F w ) of the monomer repeating unit and the number of radicals in the repeating unit ( a ) using the following equation: Q = 96 485 × a /( F w × 3 600) (mAh g − 1 ). See Experimental Section and Supporting Information for details). The polymer soluti...