锂离子电池富镍正极基础科学问题：径向有序多晶调控及机理

王硕; 武文斌; 王鑫; 任莉; 左美华; 邢王燕; 范未峰; 张彬; 向伟

锂离子电池富镍正极基础科学问题：径向有序多晶调控及机理

王硕¹,
武文斌¹,
王鑫¹,
任莉¹,
左美华²,
邢王燕²,
范未峰³,
张彬³,
向伟^{1, 2, 3, ,}

1.
成都理工大学　材料与化学化工学院, 成都 610059
2.
宜宾光原锂电材料有限公司, 宜宾 644002
3.
宜宾锂宝新材料有限公司, 宜宾 644000

基金项目: 国家自然科学基金(21805018)；四川省科技计划项目(2022ZHCG0018；2023NSFSC0117；2023ZHCG0060)；中国博士后科学基金项目(2022M722704)；宜宾市动力电池“揭榜挂帅”项目(2022JB005)

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
计量
- 文章访问数: 173
- HTML全文浏览量: 77
- 被引次数: 0
出版历程
- 收稿日期: 2023-01-30
- 修回日期: 2023-02-28
- 录用日期: 2023-03-03
- 网络出版日期: 2023-03-21

Basic scientific problems of nickel-rich cathode for lithium-ion battery: Regulation and formation mechanism of radially oriented parties

1.
School of Materials, Chemistry and Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China
2.
Yibin Guangyuan Lithium Electric Material Co. Ltd, Yibin 644002, China
3.
Yibin Libao New Materials Co., Ltd, Yibin 644000, China

Funds: National Natural Science Foundation of China (21805018); Sichuan Sience and Tehnology Program (2022ZHCG0018; 2023NSFSC0117; 2023ZHCG0060); Project Funded by China Postdoctoral Science Foundation (2022M722704); Yibin Sience and Tehnology Program (2022JB005)

摘要

摘要: 目的一次晶粒径向有序组装的二次颗粒能够较好抑制微裂纹的产生并提供快速的Li扩散路径，是高端多晶富镍锂电正极材料理想的形态。近年来，研究人员通过对前驱体沉淀结晶和正极高温锂化结晶调控，获得了具有较大长宽比晶粒有序组装的富镍正极材料。然而，关于富镍正极径向有序结构调控方法及形成机理的论述，特别是关于径向有序氢氧化物前驱体的调控方法、关键参数对有序结构的影响等并无详细的阐述。因此，分析径向有序组装的晶粒在氢氧化物前驱体结晶及锂化煅烧结晶的过程的机制与调控方法，对开发高性能富镍正极材料极为重要。内容：本文首先介绍了多晶富镍正极径向有序结构调控的必要性及其电化学性能提升的作用机制。传统随机排列的一次晶粒由于充放电过程中的各向异性体积收缩膨胀导致二次颗粒微裂纹的形成。随着循环的进行，微裂纹从二次颗粒内部扩展到表面，使因开裂引发的一系列表面、结构失效持续加重。径向有序排列的多晶颗粒由沿径向方向有序堆积的一次晶粒组成。在充放电过程中各一次晶粒协同膨胀和收缩，显著地抑制二次颗粒微裂纹的产生，促进活性材料的循环稳定性。径向有序富镍正极的合成包括前驱体沉淀结晶调控及锂化煅烧结晶调控，以继承源于前驱体的晶体织构。在氢氧化物前驱体的共沉淀过程中，前驱体的晶体结构、一次颗粒尺寸形貌、生长堆积方式等受到pH、氨浓度、体系温度、进料方式、搅拌速度、反应器类型、体系固含量等因素的影响。其中，pH、氨浓度、搅拌速度、体系固含量最为显著。相对较高的氨浓度和相对较低pH可形成相对较适宜的晶体成核速率，降低晶粒间形成大量新晶核和形成新的晶粒的情况发生，进而使单个一次晶粒生长占据主导，确保形成的多晶前驱体内一次晶粒在径向方向具有较大的尺寸，可从二次颗粒内核贯穿到颗粒表面。相反，过低氨浓度和过高的pH组合、反应器内较高的固含量导致的晶体成核位点增加，将引发快速的晶体成核。二次颗粒表面的部分晶粒生长至一定尺寸后很快被新形成的晶粒所覆盖，被困于二次颗粒内部，导致一次晶粒停滞生长，无法在径向方向形成具有较大尺寸的一次晶粒。通过调整上述条件，减少颗粒生长过程中的晶体不可控成核和团聚是形成有序堆叠的特定尺寸的一次晶粒组装前驱体的关键因素。为避免锂化过程中因长时间或过高温度的煅烧使一次晶粒过度熔融长大(或粗化)，使径向有序前驱体的晶粒尺寸及组装方式在锂化过程予以保留，可通过相对较低的煅烧温度(时间)、引入可阻碍Ni、Co、Mn基质原子跨晶界扩散的掺杂元素或可改变单个一次颗粒特定晶面的表面能的掺杂元素来调控晶粒组装的有序性。
- 富镍正极材料 /
- 径向有序结构 /
- 氢氧化物前驱体 /
- 沉淀结晶 /
- 煅烧
Abstract: Secondary particle assembed with radial oriented primary grains can inhibit the formation of microcracks and provide a good Li⁺ diffusion path, and it is an ideal morphology for high-end polycrystalline Ni-rich cathode materials. In recent years, some researchers have obtained nickel-rich cathode materials assembed with grains with large length-width ratio by regulating precursor precipitation crystallization and high temperature lithium crystallization. However, the regulation method and formation mechanism of the radially oriented structure of Ni-rich cathode, especially the regulation method of the radially oriented hydroxide precursor and the influence of the key parameters on the radially oriented structure, have not been elaborated. In this paper, the necessity of regulating the radially oriented structure of polycrystalline Ni-rich cathode and the mechanism on enhancing electrochemical performance are introduced. Secondly, the regulation method and formation mechanism of the radially oriented polycrystalline Ni-rich cathode are introduced, including the influence of the key parameters of precipitation crystallization process (pH, ammonia concentration and solid content) on the radially oriented precursor, and the influence of temperature and doping elements induced in calcination process on the maintenance of the oriented structure of precursor. Finally, the challenges facing for the regulation of radially oriented Ni-rich cathode are discussed.
- nickel rich cathode material /
- radially oriented structure /
- hydroxide precursor /
- precipitation crystallization /
- calcination

HTML全文

图 1 (a)三种不同镍含量的富镍正极材料晶胞参数a、c及晶胞体积随充电电压的变化情况^[8]；(b)无序多晶及径向有序多晶充放电循环过程稳定性示意图^[15]；(c)径向有序多晶明场STEM^[15]；(d)径向有序多晶晶粒放大图、选取电子衍射及晶体结构示意图^[15]

Figure 1. (a) Variations of a- and c-axis lattice parameters and normalized unit cell volume as a function of the cell voltage^[8]; (b) Schematic illustration of mechanical stability of the cathodes with randomly oriented particles and radially oriented particles during charge and discharge cycling^[15]; (c) Bright-field STEM images of radially oriented particles^[15]; (d) Magnified TEM image of textured primary grains, electron diffraction pattern from region marked by yellow circle, and schematic drawing of crystal structure of oriented primary grains^[15]

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图 2 (a)氨存在下氢氧化物前驱体一次晶粒(001)晶面择优生长机制^{[18, 26]}；(b)球形二次颗粒团聚体的形成示意图^{[19, 26]}；(c)无序多晶横截面SEM图像及TEM图像^[2]；(d)具有无序堆积内核的二次颗粒的截面SEM图像^[24]；(e)晶粒密实生长的颗粒表面及截面SEM图像^[24]

Figure 2. (a) Preferential growth mechanism of (001) crystal plane for primary grain in the presence of ammonia^{[18, 26]}; (b) Formation mechanism of spherical secondary particle agglomerates^{[19, 26]}; (c) Cross-sectional SEM and TEM image of randomly oriented precursors^[2]; (d) SEM image of the particle with randomly oriented core^[24]; (e) SEM images of the particle with compact assembled grains^[24]

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图 3 反应时间为1 h (a)、2 h (b)、4 h (c)、6 h (d)、8 h (e)、10 h (f)、22 h (g)前驱体的SEM图像及晶粒组装为颗粒示意图(h) ^[20]

Figure 3. SEM images of the precursors obtained at reaction time for 1 h (a), 2 h (b), 4 h (c), 6 h (d), 8 h (e), 10 h (f), 22 h (g); (h) Diagrammatic sketch for the assembling of secondary particle^[20]

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图 4 (a)、(b)具有不同内核大小的径向有序放射状内核及树突状外部区域的前驱体^[25]；(c)、(d)具有不同孔隙率区域的径向有序前驱体及其示意图^[23]

Figure 4. (a), (b) Precursors with a radially oriented radial core and a dendritic outer region^[25]; (c), (d) Radial oriented precursor with different porosity regions and its corresponding schematic diagram^[23]

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图 5 (a)、(b)具有纳米晶粒的核壳前驱体的SEM及TEM图像^[27]；(c)、(d)具有径向有序纳米棒晶粒的核壳前驱体的SEM及TEM图像^[27]；(e)、(f)径向有序浓度梯度前驱体的截面SEM及TEM图像^[2]；(g)、(h)间断进料制备的无序浓度梯度前驱体的截面SEM及TEM图像^[2]

Figure 5. SEM (a) and TEM (b) image of the core-shell precursor with a nanoparticle shell^[27], SEM (c) and TEM (d) images of the core-shell precursor with a nanorod shell^[27], (e), (f) Cross-sectional SEM images and TEM images of radially oriented precursors with concentration gradient^[2], (g), (h) Cross-sectional SEM images and TEM images of randomly oriented precursors with concentration gradient^[2]

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图 6 (a)、(b)、(c)径向有序前驱体及其掺杂2%和4%Al的正极截面SEM图像^[2]；(d)、(e)径向有序前驱体Ni_0.9Co_0.1(OH)₂未掺杂及掺杂1% Ta在不同温度下煅烧的LiNi_0.9Co_0.1O₂ 截面SEM图像^[29]

Figure 6. Cross-sectional SEM images of radially oriented precursor (a) and corresponding cathodes with 2%Al (b) and 4%Al (c); (d), (e) Cross-sectional SEM images of pristine LiNi_0.9Co_0.1O₂ and Ta doped LiNi_0.9Co_0.1O₂ cathodes, lithiated at different temperatures

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