A review of NCM cathode and interface characteristics in all-solid-state lithium-ion battery with sulfide electrolytes

doi:10.11949/0438-1157.20231279

Abstract

Abstract:

All-solid-state lithium-ion battery (ASSLB) with sulfide electrolyte is regarded as the most effective solution to the safety problems and energy density improvement of traditional liquid lithium-ion batteries. The cathode material largely determines the basic performance of all-solid-state lithium-ion batteries, as one of the main part of lithium-ion batteries. The NCM cathode material has attracted widespread attention due to its advantages of higher energy density, lower cost, and compatibility with sulfide electrolytes. However, NCM cathode materials have some imperfections, such as low safety and poor cycle stability, and there are still many problems to be solved at its contact interface with sulfide electrolyte. Therefore, the research on the structure and interface optimization of NCM cathode material is of great significance to improve the energy density and stability of lithium-ion batteries. This paper focuses on the research of the current mainstream NCM cathode materials and the matching research of interface problems with sulfide-based solid electrolytes, expounding the challenges, solutions and development opportunities of NCM cathode materials. Prospects are proposed for the further development and application of NCM cathodes.

Key words: all-solid-state lithium-ion battery, NCM cathode, sulfide electrolytes, cathode/electrolyte interfaces

摘要：

采用硫化物电解质的全固态锂电池被视作解决传统液态锂电池安全问题与能量密度提升的最有效方案。正极材料作为锂电池的主要组成部分之一，很大程度上决定着全固态锂电池的基本性能。镍钴锰酸锂（NCM）三元体系正极材料因具备能量密度较高和成本较低的优点，以及与硫化物电解质的可兼容性而受到广泛关注。然而，NCM三元材料存在安全性低、循环稳定性差等缺点，与硫化物电解质接触界面仍存在许多问题亟待解决。因此，分析和研究NCM三元正极材料的结构组成和界面优化，对于提高全固态锂电池稳定性和安全性具有重要的意义。聚焦于当前主流三元正极材料以及与硫化物固态电解质界面问题的匹配性研究，阐述了NCM三元正极材料在全固态锂电池应用中所面临的挑战、解决策略和发展机遇，并对NCM三元正极的进一步发展和应用提出展望。

关键词: 全固态锂离子电池, NCM正极, 硫化物电解质, 正极/电解质界面

CLC Number:

TM 911

Bangjun GUO, Linan JIA, Xi ZHANG. A review of NCM cathode and interface characteristics in all-solid-state lithium-ion battery with sulfide electrolytes[J]. CIESC Journal, 2024, 75(3): 743-759.

郭邦军, 贾理男, 张希. 全固态硫化物锂电池中NCM正极及其界面研究[J]. 化工学报, 2024, 75(3): 743-759.

Figures/Tables 12

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改性策略	优点	缺点	文献
新型合成方法	减少合成过程后续相变，消除正极表面晶体缺陷，阻止颗粒内部晶间裂纹扩展	实验探究性为主，实际成功率较低，目前无法满足大规模生产需求	[21-23]
单晶化法	降低晶界应力，提升机械强度，均匀电化学反应，提高锂离子扩散系数，协调体积变化	制备工艺复杂，技术难度高，易产生杂相，倍率性能有待提升	[24-26]
离子掺杂法	抑制脱锂过程中的不可逆相变，抑制循环过程中不可逆相变，强化化学键结构稳定性	掺杂后稳定性易产生不一致，掺杂工艺复杂且不稳定	[27-31]
核壳构建与浓度梯度构建法	缓冲核壳内部应力，稳定粒子结构，均衡相变内应力，抑制裂纹生长	难以形成均一性包覆，包覆层比例有待改进	[32-36]

改性策略	优点	缺点	文献
新型合成方法	减少合成过程后续相变，消除正极表面晶体缺陷，阻止颗粒内部晶间裂纹扩展	实验探究性为主，实际成功率较低，目前无法满足大规模生产需求	[21-23]
单晶化法	降低晶界应力，提升机械强度，均匀电化学反应，提高锂离子扩散系数，协调体积变化	制备工艺复杂，技术难度高，易产生杂相，倍率性能有待提升	[24-26]
离子掺杂法	抑制脱锂过程中的不可逆相变，抑制循环过程中不可逆相变，强化化学键结构稳定性	掺杂后稳定性易产生不一致，掺杂工艺复杂且不稳定	[27-31]
核壳构建与浓度梯度构建法	缓冲核壳内部应力，稳定粒子结构，均衡相变内应力，抑制裂纹生长	难以形成均一性包覆，包覆层比例有待改进	[32-36]

存在问题	问题描述	文献
界面机械结构问题	体积的变化会引起电池内部的机械应力，导致微裂纹和接触损失，从而阻碍锂离子的输运，引起界面阻抗和容量损失，甚至导致与电解质的接触失效	[59-60]
空间电荷层效应	硫化物电解质电极电势高于NCM三元正极电势，因此，锂离子会从硫化物电解质移动到正极，从而界面上会形成一定厚度的局部锂离子耗尽的空间电荷层，尤其是在电池高速充放电时，会限制锂离子的快速转移，进而影响电池倍率性能	[61-63]
化学副反应与元素扩散	NCM正极与硫化物电解质化学副反应与元素扩散主要源于两种材料自身本征的性质，因两种材料接触时，化学副反应与元素扩散便会自发发生	[64-68]
电化学副反应	NCM与硫化物的电化学副反应主要在电池循环过程中发生，由于NCM三元正极的工作电压较高，在硫化物电解质中，PS₄基团与NCM三元正极之间存在高反应能量，导致不可避免的电化学副反应发生	[69-71]

存在问题	问题描述	文献
界面机械结构问题	体积的变化会引起电池内部的机械应力，导致微裂纹和接触损失，从而阻碍锂离子的输运，引起界面阻抗和容量损失，甚至导致与电解质的接触失效	[59-60]
空间电荷层效应	硫化物电解质电极电势高于NCM三元正极电势，因此，锂离子会从硫化物电解质移动到正极，从而界面上会形成一定厚度的局部锂离子耗尽的空间电荷层，尤其是在电池高速充放电时，会限制锂离子的快速转移，进而影响电池倍率性能	[61-63]
化学副反应与元素扩散	NCM正极与硫化物电解质化学副反应与元素扩散主要源于两种材料自身本征的性质，因两种材料接触时，化学副反应与元素扩散便会自发发生	[64-68]
电化学副反应	NCM与硫化物的电化学副反应主要在电池循环过程中发生，由于NCM三元正极的工作电压较高，在硫化物电解质中，PS₄基团与NCM三元正极之间存在高反应能量，导致不可避免的电化学副反应发生	[69-71]

解决方案	具体方法	优点	缺点	文献
表面涂层法	使用液相法、固相烧结法、原子层沉积法、物理气相沉积法、化学气相沉积法等方法，在正极表面包裹一层缓冲层物质	抑制界面副反应，提升Li⁺的迁移能力，降低界面电阻，降低电子电导率，提升界面力学性能	厚度难以均匀控制，包覆涂层易与原NCM颗粒形成新的界面	[72-86]
调整颗粒尺寸匹配法	利用外部机械力作用，使得研磨介质对原料进行碾磨、搅拌，使得原料颗粒反复地挤压、变形、断裂、焊合，通过球磨可以改变材料的颗粒尺寸，并去除表面杂质	优化正极NCM与电解质之间的配比，提升正极活性物质载量，提高锂离子传输效率	碾磨和搅拌过程中对正极颗粒造成破坏，NCM与电解质硬度差距大，匹配难度高	[51,87]