Sun Zhonghui, Liu Huiling, Shu Meng, Lin Ziyu, Liu Bing, Li Yunliang, Li Jiabin, Yu Tiechen, Yao Hongyan, Zhu Shiyang, Guan Shaowei
Key Laboratory of High-Performance Plastics, Ministry of Education, National & Local Joint Engineering Laboratory for Synthesis Technology of High-Performance Polymer, Jilin University, Qianjin Street 2699, Changchun 130012, China.
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China.
ACS Appl Mater Interfaces. 2022 Aug 17;14(32):36700-36710. doi: 10.1021/acsami.2c09618. Epub 2022 Aug 8.
A novel hexaazatrinaphthylene-based (HATN) azo polymer (PAH) was synthesized from a newly designed tri-nitro compound trinitrodiquinoxalino[2,3-a:2',3'-]phenazine (HATNTN) through a Zn-induced reductive homocoupling reaction and used as a cathode material for lithium-ion batteries (LIBs). The integration of redox-active HATN units and azo linkages can improve the specific capacity, rate performance, and cycling stability of the PAH cathode. The control LIBs were assembled from HATNTN, in which HATNTN can be electrochemically reduced to an HATN-based azo polymer. Compared with the HATNTN cathode, the PAH cathode delivers higher specific capacities with much-improved cycling stability (97 mA h g capacity retention after 1500 cycles at 500 mA g, which is around 28 times that of the HATNTN cathode) and considerably better rate performance (118 mA h g at 2000 mA g, which is around 90 times that of the HATNTN cathode), simultaneously. This work provides a chemical polymerization strategy to construct extended π-conjugated azo polymers with multiple redox centers from nitro compounds for developing high-performance LIBs.
一种新型的基于六氮杂三萘嵌苯（HATN）的偶氮聚合物（PAH）由新设计的三硝基化合物三硝基二喹喔啉并[2,3 - a:2',3'-]吩嗪（HATNTN）通过锌诱导的还原均偶联反应合成，并用作锂离子电池（LIBs）的阴极材料。氧化还原活性HATN单元和偶氮键的整合可以提高PAH阴极的比容量、倍率性能和循环稳定性。对照LIBs由HATNTN组装而成，其中HATNTN可被电化学还原为基于HATN的偶氮聚合物。与HATNTN阴极相比，PAH阴极具有更高的比容量，同时循环稳定性得到显著改善（在500 mA g下1500次循环后容量保持率为97 mA h g，约为HATNTN阴极的28倍），倍率性能也明显更好（在2000 mA g下为118 mA h g，约为HATNTN阴极的90倍）。这项工作提供了一种化学聚合策略，用于从硝基化合物构建具有多个氧化还原中心的扩展π共轭偶氮聚合物，以开发高性能LIBs。
