Long-Life and High-Power Binder-Free Cathode Based on One-Step Synthesis of Radical Polymers with Multi-Pendant Groups
Long-Life and High-Power Binder-Free Cathode Based on One-Step Synthesis of Radical Polymers with Multi-Pendant Groups
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基于一步合成多侧基自由基聚合物的长寿命、高功率无粘结剂正极
DOI：
10.1002/marc.201800195
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发表时间：
2018
影响因子：
4.6
通讯作者：
Mai Kancheng
中科院分区：
文献类型：
--
作者：
Chen Yaoguang;Zhang Yangfan;Liu Xiu;Fan Xuliang;Bai Bing;Yang Kang;Liang Zhongxin;Zhang Zishou;Mai Kancheng
自由基聚合物在有机自由基电池中广泛应用的主要瓶颈是由于自由基聚合物溶解到电解质中导致的循环稳定性差以及多步合成策略的效率低。在此，通过一步酯化反应将4-羟基-2,2,6,6-四甲基哌啶基-1-氧基接枝到市售的聚(乙烯-alt-马来酸酐)上，设计并合成了一种带有多个侧基的耐电解质自由基聚合物(聚(乙烯-alt-TEMPO马来酸酯)(PETM))。有趣的是，PETM几乎不溶于碳酸乙烯酯/碳酸二甲酯/碳酸甲乙酯基电解液，溶解度极低，为0.59 mg·mL-1，但易溶于四氢呋喃和N-甲基吡咯烷酮。衍生的无粘合剂 PETM 阴极表现出近 100% 的接枝硝基氧自由基利用率 (88 mA h g-1) 和优异的倍率性能，在 10 C 至 40 C 范围内电容几乎不变。值得注意的是，PETM 阴极在 1000 次循环后保留了 94% 的初始容量，优于大多数报道的基于自由基聚合物的阴极。
The main bottlenecks for the widespread application of radical polymers in organic radical batteries are poor cycling stability, due to the dissolution of radical polymers into the electrolyte, and the low efficiency of multi‐step synthesis strategies. Herein, a kind of electrolyte‐resistant radical polymer bearing multi‐pendant groups (poly(ethylene‐alt‐TEMPO maleate) (PETM)) is designed and synthesized through a one‐step esterification reaction to graft 4‐hydroxy‐2,2,6,6‐teramethylpiperidinyl‐1‐oxy into the commercially available poly(ethylene‐alt‐maleic anhydride). Interestingly, PETM is hardly soluble in the ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate‐based electrolyte, showing an extremely low solubility of 0.59 mg mL–1, but is easily soluble in tetrahydrofuran and N‐Methyl pyrrolidone. The derived binder‐free PETM cathode exhibits nearly 100% utilization of the grafted nitroxide radicals (88 mA h g–1) and excellent rate capability with almost invariant capacitance from 10 C to 40 C. Significantly, the PETM cathodes retain 94% of the initial capacity after 1000 cycles, outperforming most reported radical polymer‐based cathodes.