稳定导电网络结构的C-SnO<sub>2</sub>/MWCNTs复合材料用于锂浆料电池

引用本文: 杨博文, 王瑞, 辛本舰, 刘丽丽, 牛志强. 稳定导电网络结构的C-SnO₂/MWCNTs复合材料用于锂浆料电池[J]. 物理化学学报, 2025, 41(2): 100015. doi: 10.3866/PKU.WHXB202310024 shu

Citation: Bowen Yang, Rui Wang, Benjian Xin, Lili Liu, Zhiqiang Niu. C-SnO₂/MWCNTs Composite with Stable Conductive Network for Lithium-based Semi-Solid Flow Batteries[J]. Acta Physico-Chimica Sinica, 2025, 41(2): 100015. doi: 10.3866/PKU.WHXB202310024 shu

稳定导电网络结构的C-SnO₂/MWCNTs复合材料用于锂浆料电池

杨博文 ^1, ,
王瑞 ^2, ,
辛本舰 ^1, ,
刘丽丽 ^{1,
,} ,
牛志强 ^{2,
,}

1.
天津理工大学材料科学与工程学院, 天津市光电显示材料与器件重点实验室, 天津 300384;
2.
南开大学化学学院, 先进能源材料化学教育部重点实验室, 物质绿色创造与制造海河实验室, 天津 300071

通讯作者: 刘丽丽, E-mail: lililiuhappy@163.com; 牛志强, E-mail: zqniu@nankai.edu.cn

基金项目:
国家重点研发计划(2019YFA0705601)和国家自然科学基金(51972231)资助项目

摘要: 锂浆料电池(LSSFBs)具有应用于大规模储能系统的潜力。然而，LSSFBs的电化学性能受限于活性材料本征导电性差以及活性材料与导电添加剂之间的不稳定接触。本文设计了碳包覆的二氧化锡/多壁碳纳米管(C-SnO₂/MWCNTs)复合材料作为LSSFBs负极材料。在该复合材料中，SnO₂纳米颗粒均匀分布在(MWCNTs)表面，同时SnO₂颗粒外表进行碳包覆。纳米尺寸赋予SnO₂更多反应活性位点。此外，碳纳米管和碳包覆层共同构建稳定的导电网络。这种导电网络有效改善SnO₂的电子转移动力学，并抑制其在充/放电过程中的体积膨胀，从而提高倍率和循环性能。此外，MWCNTs增强浆料电极的悬浮稳定性。这些优势赋予LSSFBs良好的倍率和循环性能。这项工作为优化LSSFBs的浆料电极提供了一种具有前景的策略。

关键词:

English

C-SnO₂/MWCNTs Composite with Stable Conductive Network for Lithium-based Semi-Solid Flow Batteries

Bowen Yang ^1, ,
Rui Wang ^2, ,
Benjian Xin ^1, ,
Lili Liu ^{1,
,} ,
Zhiqiang Niu ^{2,
,}

1.
Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China;
2.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Haihe Laboratory of Sustainable Chemical Transformations, College of Chemistry, Nankai University, Tianjin 300071, China

Corresponding author: Lili Liu, ; Zhiqiang Niu,

Received Date: 19 October 2023
Accepted Date: 09 November 2023
Revised Date: 09 November 2023
Fund Project:
The project was supported by the National Key Research and Development Program of China (2019YFA0705601) and the National Natural Science Foundation of China (51972231).

Abstract: Lithium-based semi-solid flow batteries (LSSFBs) could potentially be applied in large-scale energy storage systems due to their high safety and relatively independent equipment units. However, the electrochemical performance of LSSFBs is limited by the unstable contact between conductive additives and active materials, as well as the poor conductivity of active materials. Therefore, it is necessary to develop semi-solid electrodes with high stability and specific capacity to obtain LSSFBs with satisfied energy density. Herein, carbon-coated SnO₂/multi-walled carbon nanotubes (C-SnO₂/MWCNTs) composite was designed as the anode material of LSSFBs. In such composite, SnO₂ nanoparticles are uniformly distributed on the surface of MWCNTs and coated with carbon layer, which was identified by field-emission scanning electron microscopy, transmission electron microscopy and X-ray diffraction (XRD) results. In general, the traditional SnO₂ as active material in electrodes will suffer from volume expansion and collapse of structure, which will decline the cycle life of batteries. In this composite, the nanoparticle structure endows SnO₂ with more reaction active sites. Furthermore, MWCNTs and carbon layer can construct a stable conductive network, which enhances the electron transport in SnO₂-based electrodes. Simultaneously, MWCNTs and carbon layer also achieve an integrated architecture. Thus, the electron transfer dynamics of SnO₂-based electrodes could be improved and their volume expansion is effectively suppressed during charging/discharging process, resulting in improved rate and cycling performance. The coin-type batteries based on C-SnO₂/MWCNTs can maintain a discharge capacity of 725 mAh∙g⁻¹ after 100 cycles under a current density of 0.5 A∙g⁻¹. On the contrary, the discharge capacity of the batteries based on bulk SnO₂ almost disappears after 100 cycles, which is attributed to the poor conductivity and excessive volume expansion of electrode materials. In addition, the MWCNTs will enhance the suspension stability of the semi-solid electrode. When the mass fraction of the C-SnO₂/MWCNTs in the semi-solid electrode is 8.0%, the semi-solid electrode has superior suspension and electron conductivity, as well as suitable viscosity. Furthermore, the lithium storage mechanism of the semi-solid electrode was explored by ex situ XRD and X-ray photoelectron spectroscopy. The results show that, in C-SnO₂/MWCNTs composite, SnO₂ has a dual Li⁺ ions storage mechanism involving conversion and alloying reactions. When the flow rate is controlled with 5 mL∙min⁻¹, the conduction network reaches a dynamic balance, and the semi-solid electrode exhibits low charge transfer resistance. These advantages endow the LSSFBs with superior rate and cycling performance. The semi-solid flow batteries could maintain 42.4% of their initial capacity (690.8 mAh∙g⁻¹) after cycling for 962 h at 0.2 mA∙cm⁻². This work provides a promising strategy for optimizing the semi-solid electrode of LSSFBs.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

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通讯作者: 刘丽丽, E-mail: lililiuhappy@163.com; 牛志强, E-mail: zqniu@nankai.edu.cn

English

C-SnO₂/MWCNTs Composite with Stable Conductive Network for Lithium-based Semi-Solid Flow Batteries

Corresponding author: Lili Liu, ; Zhiqiang Niu,

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稳定导电网络结构的C-SnO2/MWCNTs复合材料用于锂浆料电池

通讯作者: 刘丽丽, E-mail: lililiuhappy@163.com; 牛志强, E-mail: zqniu@nankai.edu.cn

English

C-SnO2/MWCNTs Composite with Stable Conductive Network for Lithium-based Semi-Solid Flow Batteries

Corresponding author: Lili Liu, ; Zhiqiang Niu,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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通讯作者: 陈斌, bchen63@163.com

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