电化学（中英文） ›› 2022, Vol. 28 ›› Issue (2): 2108431. doi: 10.13208/j.electrochem.210843
所属专题： “下一代二次电池”专题文章
王加义1,2, 郭胜楠1, 王新2,*(
), 谷林1, 苏东1,*()
收稿日期:2021-09-13
修回日期:2021-10-28
出版日期:2022-02-28
发布日期:2021-11-02
Jia-Yi Wang1,2, Sheng-Nan Guo1, Xin Wang2,*(), Lin Gu1, Dong Su1,*()
Received:2021-09-13
Revised:2021-10-28
Published:2022-02-28
Online:2021-11-02
Contact:
*Tel: (86-758)6635020, E-mail:
摘要：
高镍层状氧化物具有成本低、能量密度高的优点,被认为是新一代锂离子电池的理想正极材料。然而,由于在使用中其结构的耐久性与安全性问题,在实际应用过程中仍然面临着严峻的挑战。深入了解电极材料容量衰减过程中的结构演变对发展高性能层状氧化物电极材料具有重要的指导意义。本文综述了近年来高镍层状氧化物正极失效机理的研究进展,包括从高镍层状氧化物的内部结构演变、表面成分变化和热失控条件下的性质等方面,进行了详细的梳理。之后,本文介绍了国内外最新的高镍层状氧化物的改性策略,并对高镍氧化物正极结构研究的发展方向进行了总结和展望。
王加义, 郭胜楠, 王新, 谷林, 苏东. 锂离子电池高镍层状氧化物正极结构失效机制[J]. 电化学（中英文）, 2022, 28(2): 2108431.
Jia-Yi Wang, Sheng-Nan Guo, Xin Wang, Lin Gu, Dong Su. Structural Degradation of Ni-Rich Layered Oxide Cathode for Li-Ion Batteries[J]. Journal of Electrochemistry, 2022, 28(2): 2108431.
Figure 1
Illustration showing the failure mechanisms of Ni-rich NMC cathode. Reproduced with permission of Ref.[46], copyright 2020 Elsevier. Reproduced with permission of Ref.[47], copyright 2019 Wiley-VCH. Reproduced with permission of Ref.[48], copyright 2013 Wiley-VCH. (color on line)
Figure 2
(A) The production of intergranular crack. Reproduced with permission of Ref.[46], copyright 2020 Elsevier. The (B, D) topographic and (C, E) corresponding Log(resistance) images at different stages of the sample. Reproduced with permission of Ref.[55], copyright 2018 Elsevier. (F) The stress distribution of NMC811 at different SOC values. Reproduced with permission of Ref.[56], copyright 2021 American Chemical Society. (color on line)
Figure 3
(A) Schematic diagram showing microcrack generation of NMC and (B) the corresponding SEM images of NMC with di-fferent Ni contents; Reproduced with permission of Ref.[59], copyright 2018 American Chemical Society. (C) SEM images of the cathode after different cycles. Reproduced with permission of Ref.[60], copyright 2013 Wiley-VCH. (color on line)
Figure 4
(A) In-situ XRD pattern of NMC811 cathode. Lattice changes of (B) a-axis and (C) c-axis as a function of voltage. Reproduced with permission of Ref.[37], copyright 2019 Wiley-VCH. (D) 6Li spin-echo ex-situ NMR spectra of NMC811; (E) the schematic diagram of phase transformation along the c-axis. The grey, green, pink and purple balls represent Li, Ni, Co and Mn atoms, respectively. Reproduced with permission of Ref.[61], copyright 2019 Elsevier. (color on line)
Figure 5
(A) STEM image of cycled NMC333 particles; (B) the atomic resolution STEM image and (C) the corresponding ABF image along [010] axis; (D) the corresponding schematic diagram; (E) the STEM image of NMC333 and (F) the corresponding strain map; (G) the corresponding schematic diagram. Reproduced with permission of Ref.[62], copyright 2017 Nature Publishing Group. (color on line)
Figure 6
(A) The HAADF-STEM image, (B) Na element distribution of the selected area, (C) the atomic distribution of the selected area with L-type ion diffusion. (D) The HAADF image, (E) the Na element distribution, (F) the atomic distribution of the selected area with D-type ion diffusion. Reproduced with permission of Ref.[64], copyright 2019 Wiley-VCH. The STEM images with (G) pure APB, (H) APB and TB, and (I) TB before and after the delithiation. Reproduced with permission of Ref.[65], copyright 2020 Wiley-VCH. (color on line)
Figure 7
(A) Typical phase transformation schematic diagram. Reproduced with permission of Ref.[47], copyright 2019 Wiley-VCH. (B) The high-resolution STEM images of (B) pristine and (C) cycled NMCT particle as well as FFT patterns for the layered and reconstruction part. Reproduced with permission of Ref.[73], copyright 2014 Nature Publishing Group. (D) the structure evolution of NMC cathode under different voltages. Reproduced with permission of Ref.[74], copyright 2014 Wiley-VCH. (color on line)
Figure 8
STEM images of NMC811 after (A) 0 cycle, (B) 20 cycles, (C) 50 cycles and (D) 100 cycles. The STEM image of NMC811 at different regions including (E) layered phase; (F) disordered layered phase; (G) defect rock salt phase and (H) rock salt phase. Reproduced with permission of Ref.[76], copyright 2018 Elsevier. (I) the spacing ratio of the c direction and a direction; the lattice mismatch in the c and a directions; the schematic diagram showing structures of the (J) active NMC811 and (K) fatigued NMC811. Reproduced with permission of Ref.[79], copyright 2021 Nature Publishing Group. (color on line)
Figure 9
(A) The schematic diagram of the side reactions in the electrode-electrolyte interface. Reproduced with permission of Ref.[47], copyright 2019 Wiley-VCH. (B) the relation between anode/cathode working voltage and the energy level of electrolyte. Reproduced with permission of Ref.[80], copyright 2017 Royal Society of Chemistry. (C) the electrolyte decomposition mechanism on NMC811. Reproduced with permission of Ref.[81], copyright 2020 Royal Society of Chemistry. (color on line)
Figure 10
(A) the relationship of thermal stability, capacity and capacity retention. Reproduced with permission of Ref.[86], copyright 2013 Elsevier. (B) TR-XRD/MS patterns. Reproduced with permission of Ref.[87], copyright 2013 American Chemical Society. (C-E) the cathode component illustration and the possible reaction mechanisms. Reproduced with permission of Ref.[88], copyright 2021 Elsevier. (color on line)
Figure 11
(A) STEM images of NMC442 at 230 °C for 0 min, 12 min, 26 min and 40 min. (B) the constructed FEM model for NMC442 particle. (C) structure evolution of NMC442 particle caused by the oxygen release. Reproduced with permission of Ref.[90], copyright 2018 American Chemical Society. (D-F) the HRTEM images of LiNiO2 at 230 °C for 0 min, 1 min and 8 min. Reproduced with permission of Ref.[91], copyright 2021 Cell Press. (color on line)
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