锂离子电池Ni-Co-Mn基正极材料前驱体的形核调控及机制

doi:10.3866/PKU.WHXB202404042

物理化学学报 >> 2025, Vol. 41 >> Issue (1): 100009.doi: 10.3866/PKU.WHXB202404042

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锂离子电池Ni-Co-Mn基正极材料前驱体的形核调控及机制

左稼暄¹^,†, 张坤²^,†, 王敬¹, 李喜飞¹^,³^,⁴^,*()

¹ 西安理工大学材料科学与工程学院, 先进电化学能源研究院, 西安 710048
² 格林美股份有限公司, 广东深圳 518101
³ 广东原能科技有限公司, 广东佛山 528223
⁴ 青海民族大学, 青海省纳米材料与技术重点实验室, 西宁 810007

收稿日期:2024-04-29 修回日期:2024-06-11 录用日期:2024-06-13 发布日期:2024-11-27
通讯作者: Email: xfli@xaut.edu.cn (李喜飞)
作者简介:
^†These authors contributed equally to this work.
基金资助:
陕西省重点研发计划国际科技合作计划(2024GH-ZDXM-02); 佛山市科技创新团队(1920001004098); 青海民族大学校级PI团队资助项目

Nucleation Regulation and Mechanism of Precursors for Nickel Cobalt Manganese-based Cathode Materials in Lithium-Ion Batteries

Jiaxuan Zuo¹, Kun Zhang², Jing Wang¹, Xifei Li¹^,³^,⁴^,*()

¹ Institute of Advanced Electrochemical Energy, School of Materials Science and Engineering, Xi'an University of Technology, Xi'an 710048, China
² GEM Co., Ltd., Shenzhen 518101, Guangdong Province, China
³ Guangdong Yuanneng Technologies Co., Ltd., Foshan 528223, Guangdong Province, China
⁴ Qinghai Provincial Key Laboratory of Nanomaterials and Nanotechnology, Qinghai Minzu University, Xining 810007, China

Received:2024-04-29 Revised:2024-06-11 Accepted:2024-06-13 Published:2024-11-27
Contact: Email: xfli@xaut.edu.cn (Xifei Li)
Supported by:
the Key Research and Development Program of Shaanxi(2024GH-ZDXM-02); Foshan Science and Technology Innovation Team Project(1920001004098); University-level Principle Investigator (PI) team of Qinghai Minzu University

摘要/Abstract

摘要：

三元正极材料具有较高的放电比容量、倍率性能和工作电压，成为锂离子电池正极材料代表之一。三元正极材料由前驱体经过嵌锂烧结拓扑转变而来，因此，前驱体材料直接决定了三元正极材料的电池性能。针对前驱体可控均匀沉淀需求和对共沉淀过程参数变化极度敏感特性，本综述首先阐述络合调控实现Ni、Co、Mn元素均匀共沉淀，及沉淀物过饱和度诱导溶液体系不同形核状态基本原理，其次从晶面择优生长结合溶解-再结晶模型讨论了前驱体一次颗粒和二次颗粒生长模式，最后从实际生产角度，基本涵盖共沉淀过程所有可调参数，并深入讨论了各种参数由低到高变化对共沉淀反应形核及前驱体材料理化性能的影响。本综述阐释的相关理论及规律可进一步延伸至富锂锰基前驱体、单晶用前驱体以及径向排列织构前驱体等高端产品研发。

关键词: 氢氧化物前驱体, 共沉淀反应, 过饱和度, 非均匀形核, 均匀形核, 反应参数

Abstract:

Nickel cobalt manganese-based cathode materials (NCMs) have emerged as key representatives in lithium-ion power batteries due to their high energy and power densities. The layered crystal structure of NCMs undergoes topological transformation from hydroxide precursor materials crystals. Therefore, the electrochemical performance of NCMs is directly influenced by factors such as particle size distribution, sphericity, and morphology of primary and secondary particles of precursor materials. The co-precipitation method is widely employed in laboratory and industry to produce batch precursor materials with uniform composition, adjustable structure, and high tap density. However, the co-precipitation process involves numerous adjustable parameters, and there exist significant variations in the growth parameters of precursors with different compositions and even different particle sizes within the same composition, resulting in poor characteristics such as bad sphericity, poor crystallinity, and low tap density. Addressing the need for controlled co-precipitation of nickel cobalt manganese-based precursors, this review began with an exposition on the basic theory of co-precipitation, elaborating on the principle of regulating precipitation rate and uniformity of Ni-Co-Mn elements through complexation. The heterogeneous nucleation (growth), homogeneous nucleation (independent nucleation), and the coexistence of two nucleation modes induced by different supersaturation of precipitates were explained according to different nucleation dominant modes. The growth theory of hexagonal nanosheet and rod-shaped primary particles was introduced from the perspective of preferential growth, while analyzing the growth pattern of secondary particle aggregates in terms of minimizing surface energy and following dissolving-recrystallization. From the viewpoint of practical production and application, this study comprehensively investigated adjustable parameters of the co-precipitation reaction process, including pH value, total ammonia concentration, solid content, reaction time, reaction temperature, base solution volume, stirring rate, tank reactor structure, aging time, reaction atmosphere, and drying atmosphere. The impact of varying each parameter from low to high on the nucleation of the co-precipitation reaction process and the physicochemical properties of precursors was extensively discussed. This systematic review contributes to a deeper understanding of the precursor nucleation process, facilitating the further development of relevant theories towards the advancement of products such as lithium-rich manganese-based precursors, single crystal precursors, and radially arranged texture precursors.

Key words: Hydroxide precursor, Co-precipitation reaction, Supersaturation, Heterogeneous nucleation, Homogeneous nucleation, Reaction parameter

左稼暄, 张坤, 王敬, 李喜飞. 锂离子电池Ni-Co-Mn基正极材料前驱体的形核调控及机制[J]. 物理化学学报, 2025, 41(1), 100009. doi: 10.3866/PKU.WHXB202404042

Jiaxuan Zuo, Kun Zhang, Jing Wang, Xifei Li. Nucleation Regulation and Mechanism of Precursors for Nickel Cobalt Manganese-based Cathode Materials in Lithium-Ion Batteries[J]. Acta Phys. -Chim. Sin. 2025, 41(1), 100009. doi: 10.3866/PKU.WHXB202404042

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202404042

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I1/100009

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锂离子电池Ni-Co-Mn基正极材料前驱体的形核调控及机制

Nucleation Regulation and Mechanism of Precursors for Nickel Cobalt Manganese-based Cathode Materials in Lithium-Ion Batteries

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