锂离子电池富镍正极基础科学问题：晶粒形态及组装方式调控

曹梦圆; 王明星; 邓中莉; 范未峰; 向伟

doi:10.13801/j.cnki.fhclxb.20220907.002

锂离子电池富镍正极基础科学问题：晶粒形态及组装方式调控

doi: 10.13801/j.cnki.fhclxb.20220907.002

1.
成都理工大学　材料与化学化工学院，成都 610059
2.
宜宾锂宝材料有限公司，宜宾 644000

基金项目: 国家自然科学基金(21805018)；四川省科技厅应用基础研究基金(2020YJ0134)

详细信息

通讯作者:
向伟，博士，副教授，硕士生导师，研究方向为锂离子电池富镍正极材料　E-mail：xiangwei@cdut.edu.cn

中图分类号: TM912
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出版历程
- 收稿日期: 2022-06-24
- 修回日期: 2022-08-11
- 录用日期: 2022-09-01
- 网络出版日期: 2022-09-08
- 刊出日期: 2023-05-15

Basic scientific problems of nickel-rich cathode for lithium-ion battery: Morphology and accumulation regulation of primary particles

1.
School of Materials, Chemistry and Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China
2.
Yibin Libao New Materials CO., LTD, Yibin 644000, China

Funds: National Natural Science Foundation of China (21805018); Applied Basic Research Fundation of Science & Technology Department of Sichuan Provincial (2020YJ0134)

摘要

摘要: 晶粒辐射状组装的富镍正极具有较常规无序多晶更优的断裂韧性和Li⁺扩散速率，是快充长寿命锂离子电池理想的正极材料。近年来，部分研究者报道了系列富镍正极晶粒形态及组装方式调控研究进展，所开发的辐射状富镍正极性能优异，代表着全球顶尖水平，且相关技术应用于韩国电池巨头LG化学。然而，高度辐射状富镍正极材料的合成在国内尚处于起步阶段，且尚无合成辐射状富镍正极所需晶粒形态及组装方式调控的系统阐述。本文首先介绍富镍正极晶粒形态及组装方式调控的必要性；再综述了晶粒辐射状富镍正极所需前驱体沉淀结晶与其受控锂化的研究进展，并对沉淀及高温煅烧结晶调控晶粒形态及组装方式所涉及机制进行了分析，以期为国内相关专业人员开发高端富镍正极材料提供参考。
- 富镍正极材料 /
- 前驱体 /
- 沉淀结晶 /
- 掺杂 /
- 辐射状
Abstract: Compared with randomly oriented cathodes, nickel-rich cathodes assembled with radially oriented primary particle, which are ideal materials for fast charging and long-life lithium ion battery, have better fracture toughness and Li⁺ diffusion rate. In recent years, Some researchers have reported a series of studies on morphology and accumulation regulation of primary particles for nickel-rich cathode. The performance of the cathodes developed by his group is excellent, representing the top level in the world, and the related technology has recently been transferred to the South Korean battery giant LG Chem. However, the synthesis of cathodes assembled with radially oriented primary particles is still in its infancy in China, and there is no systematic elaboration for the morphology and accumulation regulation of primary particles required to synthesize the nickel-rich cathode. In this paper, the necessity for the morphology and accumulation regulation of primary particles is first introduced. Then, the research progresses about the precipitation and high-temperature lithiation crystallization of precursor for the cathodes are summarized, and the mechanism involved in regulation of precipitation and high temperature calcination crystallization is analyzed. This pare is hoped to provide reference for relevant domestic specialist staff when developing high-end nickel-rich cathode materials.
- nickel rich cathode material /
- precursor /
- precipitation crystallization /
- doping /
- radial

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图 1 常规无序组装 (a) 及辐射状组装 (b) 富镍正极结构、特点及颗粒截面SEM图像^[4]

Figure 1. Cross sectional SEM images and schematic illustration of the structure and characteristic of randomly oriented cathode (a) and radially oriented cathode (b)^[4]

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图 2 辐射状富镍正极形成过程示意图

Figure 2. Schematic illustration of the formation of radially oriented Ni-rich cathode

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图 3 pH值与氨浓度分别为10.5与6 mol·L⁻¹((a), (d))、11与4 mol·L⁻¹((b), (e))、11.5与2 mol·L⁻¹((c), (f)) 合成Ni_0.6Co_0.2Mn_0.2(OH)₂前驱体及其正极的截面SEM图像^[5]

Figure 3. Cross-sectional SEM images of precursor Ni_0.6Co_0.2Mn_0.2(OH)₂ and corresponding cathodes synthesized at 10.5 and 6 mol·L⁻¹ ((a), (d)), 11 and 4 mol·L⁻¹((b), (e)), 11.5 and 2 mol·L⁻¹ ((c), (f))^[5]

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图 4 全浓度梯度前驱体 (a) 及其正极 ((b), (c)) 截面TEM图像及SEM图像^[7]；((d)~(g)) 无序梯度壳前驱体及其正极SEM图像及截面TEM图像；((h)~(k)) 辐射状梯度壳前驱体及其正极SEM图像及截面TEM图像^[20]

Figure 4. Cross-sectional TEM and SEM images of the full concentration gradient precursor (a) and corresponding cathodes ((b), (c))^[7]; ((d)-(g)) SEM and TEM images of concentration gradient core-shell precursor and cathode with a nanoparticle shell; ((h)-(k)) SEM and TEM images of concentration gradient core-shell precursor and cathode with a nanorod shell^[20]

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图 5 辐射状前驱体在反应10 h ((a), (b))、20 h ((c), (d))、30 h ((e), (f)) 时中间体及成品 ((g), (h)) 的截面SEM图像^[16]

Figure 5. Cross-sectional SEM images of the medial product at time of 10 h ((a), (b)), 20 h ((c), (d)), 30 h ((e), (f)) and final product ((g), (h)) during the synthesis of radially oriented precursor^[16]

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图 6 (a) 前驱体和不同温度煅烧LiNi_0.78Co_0.1Mn_0.12O₂(FCG NCM78)的截面SEM图像；不同温度煅烧FCG NCM78的一次晶粒测量的宽度与长度比 (b) 及晶粒取向 (c)^[11]

Figure 6. (a) Cross-sectional SEM images of the precursor and LiNi_0.78Co_0.1Mn_0.1O₂(FCG NCM78) calcined at different temperature; Measured length and width ratio (b) and orientation (c) of primary FCG NCM78 particles calcined at various temperatures^[11]

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图 7 在720°C煅烧的LiNi_0.9Co_0.1O₂(P-NC) (a) 和LiNi_0.86Co_0.1Al_0.04O₂(4-Al-NCA) (b) 正极的截面SEM图像； (c) 在720℃煅烧的不同Al含量正极的一次晶粒的宽度及长宽比；在720℃煅烧的LiNi_0.88Co_0.1Al_0.02O₂(2-Al-NCA) (d) 和4-Al-NCA (e) 的TEM-EDX元素面分布和线扫结果^[16]

1-CG—Al doped Ni_0.9Co_0.1(OH)₂

Figure 7. Cross sectional SEM images of LiNi_0.9Co_0.1O₂ (P-NC) (a) and LiNi_0.86Co_0.1Al_0.04O₂ (4-Al-NCA) (b) cathodes lithiated at 720℃; (c) Primary particle width and aspect ratio (length/width) of cathodes with different Al content lithiated at 720°C; TEM-EDX elemental mapping and line scan results of LiNi_0.88Co_0.1Al_0.02O₂ (2-Al-NCA) (d) and 4-Al-NCA (e) cathodes lithiated at 720°C^[16]

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图 8 (a)未掺杂LiNi_0.9Co_0.1O₂(NC-90)及掺杂Mg、Al、Ti、Ta和Mo的LiNi_0.9Co_0.1O₂(Mg-NC90、Al-NC90、Ti-NC90、Ta-NC90和Mo-NC90)正极截面SEM图像^[21]；长径比与相对晶粒取向 (b)、长径比(长/宽) (c)和晶粒尺寸 (d) 作为氧化态函数的关系

Figure 8. (a) Cross-sectional SEM images of pristine LiNi_0.9Co_0.1O₂ (NC-90) and doped LiNi_0.9Co_0.1O₂ cathodes with Mg, Al, Ti, Ta and Mo (Mg-NC90, Al-NC90, Ti-NC90, Ta-NC90 and Ta-NC90)^[21]; Relationship between aspect ratio and relative grain orientation (b), aspect ratio (length/width) (c) and grain size (d) as a function of oxidation state

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