In-situ constructing porous N-doped carbon skeleton with rich defects from modified polyamide acid to boost the high performance of Na3V2(PO4)3 cathode for full sodium-ion batteries

材料科学 化学工程 兴奋剂 阴极 多孔性 聚酰胺 原位 离子 碳纤维 高分子化学 化学 复合材料 有机化学 物理化学 冶金 光电子学 复合数 工程类
作者
Jiahao Li,Xin Liu,Chao Wang,Li Guo,Yanjun Chen
出处
期刊:Journal of Colloid and Interface Science [Elsevier BV]
卷期号:656: 513-527
标识
DOI:10.1016/j.jcis.2023.11.134
摘要

Generally, the transport of electrons and Na+ is seriously constrained in Na3V2(PO4)3 (NVP) due to intense interactions of V-O and PO bonds. Besides, polyamide acid (PAA) is hardly used in the sol–gel route due to insolubility. This work develops a facile liquid synthesis strategy based on modified PAA, achieving in-situ construction of a porous N-doped carbon framework with rich defects to improve the kinetics of NVP. The addition of triethylamine (TEA) reacts with carboxyls in PAA to achieve acid-base neutralization, turning PAA into polyamide salts with good solubility. The special morphology construction mechanism of this unique system was observed by ex-situ scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). Specifically, PAA undergoes in-situ conversion into chain-like polyimide (PI) through a thermal polymerization mechanism during the pre-sintering process. Meanwhile, NVP precursors are evenly dispersed in the PI fibers, efficiently reducing the particle size. After the final treatment, the favorable porous carbon skeleton could be generated derived from the partial decomposition of PI, on which small active grains are in situ grown. The resulting N-doped carbon substrate contains rich defects, benefiting from the migration of Na+. Furthermore, the porous construction is conducive to alleviating the stress and strain generated by the high current impact, increasing the contact area between electrodes/electrolytes to improve the utilization efficiency of active substances. Comprehensively, the optimized samples exhibit a capacity of 82.1 mAh g−1 at 15C with a retention rate of 95.45 % after 350 cycles. It submits a capacity of 67.6 mAh g−1 at 90C and remains 52.2 mAh g−1 after 1500 cycles. Even in full cells, it reveals a value of 110.6 mAh g−1. This work guides the application of in-situ multiple modifications of polymers in electrode materials.
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