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Thiourea-based polyimide/RGO composite cathode: A comprehensive study of storage mechanism with alkali metal ions

硫脲基聚酰亚胺/还原氧化石墨烯复合正极: 碱金属离子储存机理的综合研究

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Abstract

Although organic electrode materials have merits of abundant resources, diverse structures and environmental friendliness, their performance for electrochemical energy storage is far insufficient. In this work, a thiourea-based polyimide/reduced graphene oxide (PNTCSA/RGO) composite was synthesized via a condensation polymerization method. As a cathode material in lithium-ion batteries, excellent performance is demonstrated with high reversible capacity (144.2 mA h g−1), high discharge voltage (∼2.5 V), and long cycling life (over 2000 cycles at 500 mA g−1), which are comparable to those of other well documented in organic electrodes. Encouraging electrochemical performance is also demonstrated for sodium ion batteries (a cycling life of 800 cycles at 500 mA g−1), while poor performance is delivered in potassium ion batteries. Theoretical studies reveal that the active sites are carbonyl groups for all alkali ions but one inserted alkali metal ion is shared by two carbonyl groups from the two neighbor units. More importantly, K ions have stronger interaction with S atoms than Li/Na ions, which may lead to poor structure reversibility and account for the poor cycling performance. Our findings provide a fundamental understanding of polyimide based polymer electrodes and help to design and develop high performance organic electrode materials for alkali metal ion batteries.

摘要

尽管有机电极材料具有资源丰富、 结构多样及环境友好等 特点, 但是它们的电化学性能仍然不理想. 本文通过缩聚法合成了 一种硫脲基聚酰亚胺/还原氧化石墨烯复合物. 当其作为正极材料 应用于锂离子电池时, 展现出优异的电化学性能, 如高可逆比容量 (144.2 mA h g−1), 高放电电压(∼2.5 V)和长循环寿命(在500 mA g−1 电流密度下超过2000次), 可以和其他发展较好的无机正极材料相媲美. 当其作为正极材料应用于钠离子电池时, 也可获得较好的电化学性能(在500 mA g−1电流密度下循环寿命达800次), 但是作为钾离子电池正极材料时的性能较差. 理论计算表明羰基是和三种碱金属离子结合的活性位点, 且插入的金属离子被邻位的两个羰基共用. 更重要的是, 硫原子和钾之间的作用力要远远大于和锂/钠之间的作用力, 使得该聚合物在钾离子电池中表现出较差的可逆性和循环稳定性. 我们的发现不仅为聚酰亚胺基的聚合物电极的设计和开发提供了理论基础, 同时也为高性能的碱金属离子电池有机电极材料的设计和开发提供了帮助.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51672188 and 21703036).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Key Laboratory of Advanced Ceramics and Machining Technology (Ministry of Education), and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin, 300072, China

    Peixun Xiong  (熊佩勋), Zifeng Chen  (陈子峰), Chen Zhao  (赵晨), Jixing Yang  (杨继兴) & Yunhua Xu  (许运华)

  2. Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials, College of Chemistry, Fuzhou University, Fuzhou, 350108, China

    Huiming Yin  (尹慧敏) & Shuping Huang  (黄淑萍)

  3. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, China

    Yunhua Xu  (许运华)

Authors
  1. Peixun Xiong  (熊佩勋)
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  2. Huiming Yin  (尹慧敏)
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  3. Zifeng Chen  (陈子峰)
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  4. Chen Zhao  (赵晨)
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  5. Jixing Yang  (杨继兴)
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  6. Shuping Huang  (黄淑萍)
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  7. Yunhua Xu  (许运华)
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Contributions

Xiong P and Xu Y designed the project; Xiong P performed the main experiments; Yin H and Huang S conducted the theoretical calculation; Chen Z, Zhao C and Yang J helped with the experiments and analyses; Xiong P wrote the manuscript with support from Xu Y. All authors participated in the manuscript revision.

Corresponding authors

Correspondence to Shuping Huang  (黄淑萍) or Yunhua Xu  (许运华).

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The authors declare no conflict of interest.

Additional information

Peixun Xiong received his BSc and MSc degree from Fuzhou University in 2013 and 2016, respectively. He is now a PhD candidate under the supervision of Prof. Yunhua Xu at the School of Materials Science and Engineering, Tianjin University. His current research mainly focuses on the synthesis and characterization of nanomaterials for electrochemical energy storage devices.

Shuping Huang obtained her PhD degree in physical chemistry at Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences in 2008. She joined Prof. Ruiqin Zhang’s group as a research fellow in CityU. She was awarded JSPS fellowship and hosted by Prof. Kazunari Yoshizawa at Kyushu University in 2010–2012. She continued her postdoctoral research at University of South Dakota with Prof. Dmitri Kilin and at University of Minnesota with Prof. Donald Truhlar from 2013–2016. She is currently a professor at Fuzhou University. Her research is focused on energy materials.

Yunhua Xu is a professor at the School of Materials Science and Engineering, Tianjin University. He received his PhD degree in materials physics and chemistry from South China University of Technology in 2008. Prior to joining Tianjin University, he worked as a visiting student and postdoc at the University of California, Santa Barbara and assistant research scientist at the University of Maryland, College Park from 2006 to 2015. His research interests focus on electrochemical storage materials and devices.

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Xiong, P., Yin, H., Chen, Z. et al. Thiourea-based polyimide/RGO composite cathode: A comprehensive study of storage mechanism with alkali metal ions. Sci. China Mater. 63, 1929–1938 (2020). https://doi.org/10.1007/s40843-020-1375-2

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