锂离子电池正极材料LiNi 0.5Co 0.2Mn 0.3O2和LiNi 0.5Co 0.2Mn 0.3O2/LiFePO4容量衰减原因分析

doi:10.13208/j.electrochem.161229

摘要/Abstract

摘要：

采用湿法球磨法制备了锂离子电池混合正极材料LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP). 通过X射线衍射(XRD)、扫描电子显微镜(SEM)、充放电测试和电化学阻抗谱测试(EIS)等方法研究对比了LiNi _0.5Co_0.2Mn _0.3O₂(NMC532)和LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP)的容量衰减机理，结果表明：循环50次和60℃高温存储后，NMC532/LFP的容量保持率分别为97.80%、86.48%，其循环和高温存储性能较好. 循环和高温存储后NMC532和NMC532/LFP的电荷传递阻抗Rct明显增大，但NMC532/LFP的Rct较小. NMC532和NMC532/LFP的I(003)/I(104)值都有所减小，但NMC532/LFP的I(003)/I(104)值比NMC532的大，即NMC532/LFP材料的阳离子混排现象有所改善. 循环后NMC532、NMC532/LFP颗粒没有出现明显的表面开裂和链接断裂现象，但NMC532颗粒有部分发生粉化. 高温储存后NMC532颗粒表面出现裂纹，且颗粒之间的链接断裂，NMC532/LFP颗粒表面出现轻微粉化. 材料结构规整度下降，阳离子混排程度加剧，电荷传递阻抗增大是NMC532和NMC532/LFP容量衰减的主要原因.

关键词: 湿法球磨法, 锂离子电池, 混合正极材料, LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ , 容量衰减机理

Abstract: The LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP) composite cathode material for lithium-ion battery was prepared by wet ball-milling. The capacity fading behaviors of LiNi _0.5Co_0.2Mn _0.3O₂ (NMC532) and LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP) were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), charge/discharge and electrochemical impedance spectroscopy (EIS) tests. The results indicated that the capacity retention values of NMC532/LFP were 97.80% and 86.48%, respectively, after 50 cycles and 60℃ high temperature storage. The NMC532/LFP exhibited better cycle performance and high temperature storage performance. Charge transfer impedance (Rct) values increased obviously after 50 cycles and high temperature storage, in particular, the R_ct value of NMC532/LFP was smaller. The I(003)/I(104) values of NMC532 and NMC532/LFP were reduced, while that of NMC532/LFP became larger, illustrating the cation mixed phenomenon was improved. There were no apparent particle cracking and particle fracture phenomena observed after 50 cycles, however, some NMC532 powder particles were obtained. The cracks were obaerved on the surface of NMC532 particles and among particles after high temperature storage, and the slight pulverization occurred on the surface of NMC532/LFP particles. Less ordered material structure, higher degree of cation mixing and increased charge transfer resistance might be mainly responsible for the capacity fading behaviors of NMC532 and NMC532/LFP.

Key words: wet ball-milling, Li-ion battery, composite cathode material, LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄ , capacity fading mechanism

中图分类号:

O646

胡燚，何湘柱, 邓忠德，孔令涌，尚伟丽. 锂离子电池正极材料LiNi _0.5Co_0.2Mn _0.3O₂和LiNi_0.5Co _0.2Mn _0.3O₂/LiFePO₄容量衰减原因分析[J]. 电化学（中英文）, 2017, 23(6): 675-683.

HU Yi HE Xiang-zhu DENG Zhong-de KONG Ling-yong SHANG Wei-li. Capacity Fading Analyses of LiNi _0.5Co_0.2Mn _0.3O₂and LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄Cathode Materials for Lithium-Ion Battery[J]. Journal of Electrochemistry, 2017, 23(6): 675-683.

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锂离子电池正极材料LiNi _0.5Co_0.2Mn _0.3O₂和LiNi_0.5Co _0.2Mn _0.3O₂/LiFePO₄容量衰减原因分析

Capacity Fading Analyses of LiNi _0.5Co_0.2Mn _0.3O₂and LiNi _0.5Co_0.2Mn _0.3O₂/LiFePO₄Cathode Materials for Lithium-Ion Battery

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