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Improving the cycling stability of lithium-ion batteries with a dry-processed cathode via the synergistic effect of carboxymethyl cellulose and siloxane

通过羧甲基纤维素和硅氧烷的协同作用提升锂离子电池干法正极的循环稳定性

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Abstract

The solvent-free dry process for fabricating battery electrodes has received widespread attention owing to its low cost and environmental friendliness. However, the conventional polytetrafluoroethylene (PTFE) used as a binder in the preparation of dry-processed electrodes results in insufficient adhesion, limiting their practical industrial applications. Herein, we reported an industrially viable dry process for producing lithium-ion batteries using the combination of carboxymethyl cellulose (CMC) and siloxane as the binder composite. The synergistic effect of CMC and siloxane enhanced the adhesive performance of the electrode, thereby improving the mechanical strength and electrochemical performance of the developed dry-processed electrode. Half cells based on aluminum-doped lithium manganese oxide (LMA) dry-processed electrodes with CMC and siloxane (LMA/CS) exhibited a capacity retention of 79.8% after 200 cycles at 1 C. Furthermore, LMA/CS∥lithium titanate oxide full cells with a high mass loading of 20.6 mg cm−2 demonstrated an excellent capacity retention of 89.2% after 1000 cycles, which is considerably higher than that of cells based on slurry-processed electrodes prepared with a polyvinylidene fluoride binder and conventional dry-processed electrodes prepared using a PTFE binder.

摘要

近年来, 无溶剂干法电极制备工艺由于其低成本和低污染等优 点在锂电池领域获得了广泛关注. 然而, 现有干法制备工艺中采用的聚 四氟乙烯(PTFE)粘结剂存在粘附力和循环稳定性不足等缺点, 限制了 其实际工业化应用. 我们通过引入羧甲基纤维素(CMC)和硅氧烷作为 粘结剂复合材料, 发展了一种与现有工业化生产兼容的锂离子电池干 法电极制备工艺. CMC和硅氧烷的协同作用增强了电极活性材料的粘 附性能, 实现了干法电极膜片机械强度和电化学性能的大幅提升. 基于 这种干法电极工艺制备的铝掺杂锰酸锂(LMA/CS)半电池在1 C下循环 200圈后展示出79.8%的保持率. 进一步地, 制备的高负载(20.6 mg cm−2) 锰酸锂-钛酸锂全电池(LMA/CS∥LTO)实现了1000圈的超长稳定循环, 容量保持率高达89.2%, 超过现有基于PTFE粘结剂干法工艺和传统湿 法工艺的电池性能.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (52090034), the Ministry of Science and Technology of China (2020YFA0711500), and the Higher Education Discipline Innovation Project (111 Project B12015).

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Authors and Affiliations

  1. The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China

    Minghan Ni  (倪铭韩), Yang Zhao  (赵阳), Nuo Xu  (许诺), Yanfeng Ma  (马延风), Chenxi Li  (李晨曦), Hongtao Zhang  (张洪涛) & Yongsheng Chen  (陈永胜)

  2. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, China

    Yongsheng Chen  (陈永胜)

  3. Renewable Energy Conversion and Storage Center (RECAST), Nankai University, Tianjin, 300071, China

    Minghan Ni  (倪铭韩), Yang Zhao  (赵阳), Nuo Xu  (许诺), Yanfeng Ma  (马延风), Chenxi Li  (李晨曦), Hongtao Zhang  (张洪涛) & Yongsheng Chen  (陈永胜)

  4. Tianjin Plan Nano Co., Ltd, Tianjin, 300071, China

    Mengxin Kong  (孔萌昕)

Authors
  1. Minghan Ni  (倪铭韩)
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  2. Yang Zhao  (赵阳)
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  3. Nuo Xu  (许诺)
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  4. Mengxin Kong  (孔萌昕)
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  5. Yanfeng Ma  (马延风)
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  6. Chenxi Li  (李晨曦)
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  7. Hongtao Zhang  (张洪涛)
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  8. Yongsheng Chen  (陈永胜)
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Contributions

Author contributions Zhang H conceived and designed the research; Ni M fabricated the electrodes and assembled the cells; Ni M, Zhao Y and Xu N conducted the characterizations and analyses with support from Kong M, Ma Y and Li C; Ni M and Zhang H wrote the paper with support from Chen Y; Chen Y and Zhang H coordinated the study. All authors contributed to the general discussion.

Corresponding author

Correspondence to Hongtao Zhang  (张洪涛).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Minghan Ni received her BS degree in materials science and engineering from China University of Geoscience (Beijing). Currently, she is pursuing her Master’s degree at Nankai University under the guidance of Prof. Yongsheng Chen. Her research is primarily focused on improving the electrochemical performances and mechanical properties of dry-processed LIBs.

Hongtao Zhang received his PhD degree from the Institute of Chemistry, Chinese Academy of Sciences in 2012. He joined Prof. Yongsheng Chen’s group at Nankai University in 2014. He worked as a visiting scholar at the University of California, Los Angeles from 2018 to 2019. His current research primarily centers on polymer solid electrolytes and high-performance lithium metal batteries.

Yongsheng Chen graduated from the University of Victoria with a PhD degree in chemistry in 1997 and then joined the University of Kentucky and the University of California, Los Angeles for postdoctoral reseach from 1997 to 1999. Since 2003, he has been a chair professor at Nankai University. His main research interests include (i) carbon-based nanomaterials, including carbon nanotubes and grapheme, (ii) organic and polymeric functional materials, and (iii) energy devices including organic photovoltaics and supercapacitors.

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40843_2023_2673_MOESM1_ESM.pdf

Improving the cycling stability of lithium-ion batteries with a dry-processed cathode via the synergistic effect of carboxymethyl cellulose and siloxane

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Ni, M., Zhao, Y., Xu, N. et al. Improving the cycling stability of lithium-ion batteries with a dry-processed cathode via the synergistic effect of carboxymethyl cellulose and siloxane. Sci. China Mater. 67, 76–84 (2024). https://doi.org/10.1007/s40843-023-2673-6

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  • DOI: https://doi.org/10.1007/s40843-023-2673-6

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