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Flexible polytriphenylamine-based cathodes with reinforced energy-storage capacity for high-performance sodium-ion batteries

原位聚合法构筑柔性聚三苯胺正极材料助力高性能 钠离子电池

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Abstract

Owing to the excellent redox reversibility and structural diversity, polytriphenylamine (PTPAn) has been regarded as one of the promising cathode candidates for sodium-ion batteries. However, it still suffers from the bulk aggregation and low operating capacity in practical applications. Assisted by the in-situ polymerization, leaf-like PTPAn nanosheets are uniformly introduced on the surface of carbon nanofibers (CNFs) to form the free-standing CNF@PTPAn composite electrodes. Interestingly, the formation mechanism of the leaf-on-branch structure of CNF@PTPAn composites is systematically explored, confirming that the controlling of oxidation rate and growth degree plays crucial roles in tuning the morphology and active material content of the composite electrodes. Supported by the capacity-cutting analysis, the effective coupling between the active PTPAn and conductive CNFs can provide fast electron/ion-shuttling channels and deepen the electrochemical reaction process. At 50 mA g−1, the capacity of the optimized CNF@PTPAn composite can reach 105 mA h g−1, with a stable rate capability of 78 mA h g−1 even at 400 mA g−1 after 500 cycles in a half cell. The detailed kinetic analysis confirms that the ion-storage behaviors in the low-voltage region can be tailored for the improved capacitive contribution and diffusion coefficients. Meanwhile, the flexible CNF-based full cell with CNF@PTPAn as the cathode and CNFs as the anode exhibits a high energy density of 60 W h kg−1 at 938 W kg−1. Based on this, the rational design is expected to provide more possibilities to obtain advanced freestanding electrode systems.

摘要

聚三苯胺(PTPAn)因具有优异的氧化还原可逆性和结构多样性, 被认为是极有前景的钠离子电池正极材料之一. 然而, 在实际应用中, 大块体的PTPAn材料仍存在团聚和工作容量低的问题. 本文通过原位 聚合法将树叶状的PTPAn纳米片均匀地生长在碳纳米纤维(CNFs)表 面, 构建了一种自支撑的CNF@PTPAn复合电极. 本文还系统探索了 CNF@PTPAn复合材料中枝叶结构的形成机理, 证实了原位反应的氧 化速率和生长程度对调控复合电极的形貌及其活性物质含量起了关键 作用. 通过截止容量分析发现, PTPAn活性材料与导电CNFs之间的高 效复合可以提供快速的电子/离子传输通道, 有助于增强电极的深度电 化学反应过程. 由优化后的CNF@PTPAn复合材料所组装的钠离子半 电池具有高比容量和稳定的倍率性能. 在50 mA g−1的电流密度下可达 105 mAh g−1, 甚至在400 mAg−1的高电流密度下循环500圈后仍能保持 78 mAh g−1的比容量. 动力学分析证明, 通过调控材料在低电压区域的 离子存储行为, 可以有效提升其电容主导的容量贡献和扩散系数. 同时, 以CNF@PTPAn为正极和CNFs为负极组装的柔性CNF基全电池, 在 938Wkg−1功率密度下表现出60Wh kg−1的高能量密度. 基于此, 该设 计有望为获得先进的自支撑电极体系提供更多的可能性.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (22075042), the Natural Science Foundation of Shanghai (20ZR1401400 and 18ZR1401600), the Shanghai Scientific and Technological Innovation Project (18JC1410600), the Fundamental Research Funds for the Central Universities and DHU Distinguished Young Professor Program (LZB2021002).

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Authors and Affiliations

  1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Innovation Center for Textile Science and Technology, Donghua University, Shanghai, 201620, China

    Lulu Mo  (莫璐璐), Gangyong Zhou  (周刚勇), Yue-E Miao  (缪月娥) & Tianxi Liu  (刘天西)

  2. Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, China

    Tianxi Liu  (刘天西)

  3. School of Minerals Processing and Bioengineering, Central South University, Changsha, 410083, China

    Peng Ge  (葛鹏)

Authors
  1. Lulu Mo  (莫璐璐)
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  2. Gangyong Zhou  (周刚勇)
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Contributions

Mo L, Zhou G and Miao Y conceived the idea. Mo L performed the experiments, analyzed the data and wrote the manuscript. Zhou G performed partial experiments and tests. Ge P contributed to the schematic diagrams partly and guided the manuscript. Miao Y contributed to the theoretical analysis, supervision and editing. Liu T contributed to the supervision and editing. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Peng Ge  (葛鹏), Yue-E Miao  (缪月娥) or Tianxi Liu  (刘天西).

Additional information

Lulu Mo received her Master’s degree in Chemistry from Henan University of Technology in 2017. Currently, she is a PhD candidate under the supervision of Prof. Tianxi Liu at the College of Materials Science and Engineering, Donghua University. Her research focuses on the design and synthesis of novel carbon nanofiber composites for lithium/sodium ion batteries.

Peng Ge is an associate professor at the School of Minerals Processing and Bioengineering, Central South University. He received his PhD at the Central South University in 2019. His research interests are the development of new materials derived from mineral chemistry and their applications in electrochemical energy storage and conversion.

Yue-E Miao received her BS degree from the Southeast University in 2010 and PhD degree from Fudan University in 2015. She is now an associate professor at the College of Materials Science and Engineering, Donghua University. Her research interests mainly focus on high-performance organic fiber electrodes/separators, carbon nanofiber composites, as well as their applications in electrochemical energy storage devices (such as Li/Na-ion batteries and Li-S batteries).

Tianxi Liu obtained his BS degree from Henan University (1992) and PhD degree from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (1998). He is currently a full professor at the College of Materials Science and Engineering, Donghua University. His main research interests include polymer nanocomposites, organic/inorganic hybrid materials, nanofibers and their composites, and advanced energy materials for energy conversion and storage.

Conflict of interest

The authors declare that they have no conflict of interest.

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Flexible polytriphenylamine-based cathodes with reinforced energy-storage capacity for high-performance sodium-ion batteries

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Mo, L., Zhou, G., Ge, P. et al. Flexible polytriphenylamine-based cathodes with reinforced energy-storage capacity for high-performance sodium-ion batteries. Sci. China Mater. 65, 32–42 (2022). https://doi.org/10.1007/s40843-021-1718-2

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