储能科学与技术 ›› 2025, Vol. 14 ›› Issue (9): 3259-3268.doi: 10.19799/j.cnki.2095-4239.2025.0225

• 储能材料与器件 • 上一篇    

复合石墨锂离子电池性能研究

白晓宇(), 筵亚静, 张志荣, 孔令丽   

  1. 天津力神聚元新能源科技有限公司,天津 300384
  • 收稿日期:2025-03-07 修回日期:2025-03-28 出版日期:2025-09-28 发布日期:2025-09-05
  • 通讯作者: 白晓宇 E-mail:baixiaoyu@lishen.com.cn
  • 作者简介:白晓宇(1994—),女,硕士,从事锂离子电池负极材料开发,E-mail:baixiaoyu@lishen.com.cn

Research on the performance of composite graphite lithium-ion batteries

Xiaoyu BAI(), Yajing YAN, Zhirong ZHANG, Lingli KONG   

  1. Tianjin Lishen Juyuan New Energy Technology Co. , Ltd. , Tianjin 300384, China
  • Received:2025-03-07 Revised:2025-03-28 Online:2025-09-28 Published:2025-09-05
  • Contact: Xiaoyu BAI E-mail:baixiaoyu@lishen.com.cn

摘要:

天然石墨具有容量高、电压平台稳定、成本低的优势,但其缺陷多,电解液相容性差而未得到广泛应用。数码领域锂离子电池负极材料主要使用针状焦或石油焦制备的人造石墨。为了研究天然石墨与人造石墨复合负极对数码锂离子电池性能的影响,以软包充电宝电池为研究对象,采用SEM、激光粒度分析、比表面积分析和电化学阻抗谱等方法,对负极材料及组装的电池进行分析,评估复合石墨(C-Gr,70%人造石墨+30%天然石墨)和纯人造石墨(A-Gr)对电池电化学性能的影响。研究发现,复合石墨负极材料制备电池的DCIR,SEI膜阻抗和电荷转移阻抗较大,导致电池内部温升高,极化大,大倍率、恒功率以及低温放电的性能下降。复合石墨负极材料比表面积较大,导致高温满电存储时电解液副反应产物增加,残余和恢复容量降低。常温循环500次,复合石墨负极材料制备电池的容量保持率为76%,比人造石墨负极材料低11.6%,厚度膨胀率和内阻增长率分别比人造石墨负极材料高1.8%和26.3%。SEM分析表明,复合石墨负极材料循环后SEI膜明显增厚,裂纹较多,造成可逆容量衰退。同时,负极材料的恶化对正极材料的结构稳定性产生间接影响,复合石墨负极材料循环后电池Ni、Co、Mn金属元素溶出较多,Mn元素溶出含量约为人造石墨负极材料的2倍,三元材料颗粒裂纹严重,骨架结构被破坏。

关键词: 锂离子电池, 人造石墨, 复合石墨, 阻抗, SEI膜

Abstract:

Natural graphite possesses advantages such as high capacity, stable voltage platform, and low cost; however, it suffers from defects and poor electrolyte compatibility, limiting its widespread application. In the digital field, the anode material of lithium-ion batteries primarily comprises artificial graphite prepared from needle coke or petroleum coke. This study investigates the effect of a composite anode consisting of natural graphite and artificial graphite on the performance of digital lithium-ion batteries, using pouch cells as the research object. The anode materials and assembled batteries were analyzed using scanning electron microscopy (SEM), laser particle size analysis, specific surface area analysis, and electrochemical impedance spectroscopy, among other methods. The electrochemical performance of batteries utilizing composite graphite (C-Gr; 70% artificial graphite + 30% natural graphite) and pure artificial graphite (A-Gr) anodes was evaluated. The results show that the direct current internal resistance, solid electrolyte interphase (SEI) film impedance, and charge transfer impedance of composite graphite anodes are relatively high, leading to greater internal temperature rise, significant polarization, and reduced performance during high-rate, constant power, and low-temperature discharge conditions. The large specific surface area of the composite graphite anode increases the side reactions with the electrolyte, resulting in decreased residual capacity and recovery capacity after full-charge storage at high temperatures. After 500 cycles at room temperature, the capacity retention of the composite graphite anode was 76%, which was 11.6% lower than that of the artificial graphite anode. Furthermore, the thickness swelling rate and internal resistance growth rate were 1.8% and 26.3% higher than those of the artificial graphite anode, respectively. SEM analysis reveals significant thickening and increased cracking of the SEI film on the composite graphite anode after cycling, leading to reversible capacity fading. In addition, the degradation of the anode material indirectly affects the structural stability of the cathode material. After cycling with the composite graphite anode, more Ni, Co, and Mn elements dissolved from the cathode material, with Mn content approximately double that of the artificial graphite anode. Severe particle cracking and skeleton structure destruction were also observed in the ternary cathode material.

Key words: lithium-ion battery, artificial graphite, composite graphite, impedance, SEI film

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