Research Progresses of Sodium Cobalt Oxide as Cathode in Sodium Ion Batteries

doi:10.6023/A21060260

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (10): 1232-1243.DOI: 10.6023/A21060260 Previous Articles Next Articles

Review

钠离子电池钴酸钠正极材料研究进展

谢佶晟^a, 肖竹梅^a, 左文华^a, 杨勇^a^,^b^,^*()

a 厦门大学化学化工学院固体表面物理化学国家重点实验室厦门 361005
b 厦门大学能源学院厦门 361102

投稿日期:2021-06-09 发布日期:2021-07-20
通讯作者: 杨勇

作者简介:

谢佶晟, 2021年于厦门大学化学系获学士学位, 研究方向为钠离子电池层状过渡金属氧化物正极材料的失效及改性机理研究.

肖竹梅, 2018年于南开大学化学系获学士学位, 现为厦门大学化学化工学院杨勇教授课题组硕士研究生. 研究方向为锂、钠离子电池中高比能正极材料的反应机理研究.

左文华, 2020年于厦门大学获得博士学位, 师从杨勇教授, 目前主要从事钠离子电池层状过渡金属氧化物正极材料研究.

杨勇, 厦门大学闽江计划特聘教授, 博士生导师, 国家杰出青年科学基金获得者. 1992年获厦门大学理学博士学位, 1997~1998年任英国牛津大学访问科学家. 主要研究方向为能源电化学、材料物理化学及表面物理化学.

基金资助:
国家重点研发专项课题(2016YFB0901502); 厦门大学化学学科拔尖学生培养试验计划资助项目

Research Progresses of Sodium Cobalt Oxide as Cathode in Sodium Ion Batteries

Jisheng Xie^a, Zhumei Xiao^a, Wenhua Zuo^a, Yong Yang^a^,^b()

a State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
b School of Energy Research, Xiamen University, Xiamen 361102, China

Received:2021-06-09 Published:2021-07-20
Contact: Yong Yang
Supported by:
National Key Research and Development Program of China(2016YFB0901502); funding project of the Top-notch Students Scientific Development Pilot Program (Chemistry) of Xiamen University

Sodium ion batteries have regained widespread attention in the field of large-scale electrochemical energy storage by virtue of their widely distributed and low-cost sodium resources. Among many of the cathode materials (layered, tunnel-like, polyanionic type and Prussian-blue type, etc.), layered transition metal oxide materials have received extensive research attention due to the features of high specific capacity, relatively good electrochemical reversibility, and rich and adjustable chemical composition. Sodium cobalt oxide is one of the most typical layered transition metal oxides. A lot of research has been done about sodium cobalt oxide since the 1980s. Although compared with other energy storage systems (such as lithium cobalt oxide materials which has the similar composition), sodium cobalt oxide does not take more advantage in electrochemical performance (like rate performance, cycle performance, etc.), but it can be observed from the charge and discharge curve that sodium cobalt oxide has undergone complex electrochemical processes, which means that it has a bunch of information on the degradation mechanisms during the charge and discharge processes. The correlation studies of the failure mechanism during the charging and discharging processes of sodium cobalt oxide (including the structure changes and the charge compensation mechanisms) are of great significance for the deep understanding of the layered oxide systems in sodium ion batteries. Therefore, on the basis of introducing the common crystal structure types and the synthesis phase diagram of sodium cobalt oxides, this article focuses on reviewing the structure changes (including phase transition and Na⁺/ vacancy ordering) and charge compensation mechanisms of sodium cobalt oxides with different crystal structures during the charging and discharging. At the same time, the correlation between the mechanisms above and electrochemical performance is discussed. This review aims to provide support for the in-depth study and establishment of the structure-activity relationship in the electrochemical processes of layered transition metal oxide cathode materials.

Key words: sodium ion battery, cathode material, sodium cobalt oxide, structure change, charge compensation mechanism, structure-activity relationship

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Jisheng Xie, Zhumei Xiao, Wenhua Zuo, Yong Yang. Research Progresses of Sodium Cobalt Oxide as Cathode in Sodium Ion Batteries[J]. Acta Chimica Sinica, 2021, 79(10): 1232-1243.

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Fig. & Tab. 9

名称^a	优点	缺点
NaMnO₂	Mn自然丰度高, 理论容量高(243 mAh/g)	存在Jahn-Teller畸变, 充放电阶段多阶梯状曲线, 结构稳定性差, 循环性能差
NaFeO₂	Fe自然丰度极高, 低电压下充放电平台稳定, 电化学可逆性好	质量比容量低, 高电位下存在不可逆相变, 循环稳定性差
NaCoO₂	低电压下电化学可逆性较好, 离子电导率高	Co自然丰度极低, 成本高, 容量低, 充放电曲线多平台, 倍率性能差, 高电位下循环性能差

Table 1. Comparison of common layered transition metal oxide cathode materials in sodium ion batteries

Figure 1. The development history and important research progress of sodium cobalt oxide from 1981 to 2021[35⇓⇓⇓⇓-40] Reproduced with permission[35], Copyright 2003 Nature Publishing group. Reproduced with permission[36], Copyright 2011 Nature Publishing group. Reproduced with permission[37], Copyright 2014 American Chemical Society. Reproduced with permission[38], Copyright 1997 American physical Society. Reproduced with permission[39], Copyright 2013 Elsevier. Reproduced with permission[40], Copyright 2021 Elsevier.

Figure 3. (a) Comparison of charge/discharge curves of O3-, P′3-, and P2-type NaxCoO2 cells; (b) comparison of charge/discharge curves of LiCoO2 and NaCoO2 cells[10,49] Reproduced with permission[49], Copyright 2014 American Chemical Society.

Figure 4. (a) Phase change in the charge-discharge process of O3-NaxCoO2 [10]; (b) charge curve to the left and -dE/dx curve to the right for P'3-NaxCoO2 [11]; (c) charge curve and in situ XRD of O3-NaxCoO2[37]; (d) 23Na MAS-NMR of P'3-NaxCoO2 in different temperature[42]; (e) NaO6 prismatic environments for both P'3 and P3-NaxCoO2 to the right[42] Reproduced with permission[10], Copyright 1981 Elsevier. Reproduced with permission[11], Copyright 1983 Elsevier. Reproduced with permission[37], Copyright 2014 American Chemical Society. Reproduced with permission[42], Copyright 2008 the American physical Society.

. Comparison of phase changes of O3-LixCoO2与O3-NaxCoO2 in the charging and discharging processes

Figure 6. (a) 23Na MAS NMR spectra recorded as a function of temperature for three materials[58]; (b) cycling and phase transitions of Na0.7CoO2[36]; (c) GITT and in situ XRD of P2-NaxCoO2 during discharging[36]; (d) in situ XRD during the first charge/discharge of NaxCoO2[59] Reproduced with permission[58], Copyright 2009 American Chemical Society. Reproduced with permission[36], Copyright 2011 Nature Publishing group. Reproduced with permission[59], Copyright 2014 Elsevier

Figure 7. (a) The phase diagram of NaxCoO2[64]; (b) 23Na NMR spectra for NaxCoO2 (0.65<x<0.8)[69]; (c) models for the Na planes of NaxCoO2[70]; (d) proposed crystal structure of (A-C) Na0.84CoO2 and (D-F) Na0.71CoO2[71]; (e) room-temperature Raman spectra of (A) Na0.7CoO2, (B) Na2CO3, and Co3O4 and polarized spectra from (C) ab plane and (D) ac plane of the Na0.7CoO2, (E) Raman spectra from the ab surface of NaxCoO2 single crystals with x=0.7, 0.5, and 0.3 at room temperature[72] In (d), occupied Na positions are black dots and Na vacancies are open circles; x indicates the positions of the underlying Co atoms; dashed lines indicate that only one of the lines on z=0 and z=1/2 is occupied; calculated diffraction patterns are given below the models. Reprinted figures with permission[64], Copyright 2004 by the American Physical Society. Reproduced with permission[69], Copyright 2015 Elsevier. Reprinted figures with permission[70], Copyright 2004 by the American Physical Society. Reprinted figures with permission[71], Copyright 2008 by the American Physical Society. Reprinted figures with permission[72], Copyright 2006 by the American Physical Society

Figure 8. (a) (A) The first charging curves of Na0.74CoO2 from 2.6 to 3.8 V, (B) the Fourier transform of the Co K-edge EXAFS spectra[39]; (b) Co 2p3/2 XPS spectra of different stages in charging and discharging processes[39]; (c) O 1s XANES spectra's magnified view of NaxCoO2-δ[76]; (d) (A) O1s XPS spectra and (B) O K absorption edges for NaxCoO2-δ at different charge states[40] Reproduced with permission[39], Copyright 2013 Elsevier. Reproduced with permission[76], Copyright 2007 Elsevier. Reproduced with permission[40], Copyright 2021 Elsevier

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钠离子电池钴酸钠正极材料研究进展

Research Progresses of Sodium Cobalt Oxide as Cathode in Sodium Ion Batteries

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