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化学进展 2020, Vol. 32 Issue (6): 803-816 DOI: 10.7536/PC191004 前一篇   后一篇

• 综述与评论 •

P2结构层状复合金属氧化物钠离子电池正极材料

刘建文1, 姜贺阳1, 孙驰航1, 骆文彬1, 毛景2,**(), 代克化1,3,**()   

  1. 1. 东北大学冶金学院 沈阳 110819
    2. 郑州大学材料科学与工程学院 郑州 450001
    3. 天津师范大学化学学院 天津 300387
  • 收稿日期:2019-10-11 修回日期:2020-01-14 出版日期:2020-06-05 发布日期:2020-04-13
  • 通讯作者: 毛景, 代克化
  • 作者简介:
    ** Corresponding author e-mail: (Jing Mao); (Kehua Dai)
  • 基金资助:
    国家自然科学基金项目(51604244)
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P2-Structure Layered Composite Metal Oxide Cathode Materials for Sodium Ion Batteries

Jianwen Liu1, Heyang Jiang1, Chihang Sun1, Wenbin Luo1, Jing Mao2,**(), Kehua Dai1,3,**()   

  1. 1. School of Metallurgy, Northeastern University, Shenyang 110819, China
    2. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China
    3. Department of Chemistry, Tianjin Normal University, Tianjin 300387, China
  • Received:2019-10-11 Revised:2020-01-14 Online:2020-06-05 Published:2020-04-13
  • Contact: Jing Mao, Kehua Dai
  • Supported by:
    the National Natural Science Foundation of China(51604244)

目前,碱金属(锂、钠、钾等)离子电池中的锂离子电池已经广泛应用于社会生产生活的各个方面,有力地支撑了社会的自动化、信息化和智能化。然而,由于锂在地壳中的丰度较低,以较高丰度的钠为基础的钠离子电池引起了研究者和社会的广泛关注。其中,正极材料是制约钠离子电池实用化的重要因素之一,人们需要开发出面向实际应用的正极材料。P2结构层状复合金属氧化物钠离子电池正极材料具有资源丰富、制备简单、结构稳定、放电容量高、倍率性能好和循环稳定性较好等优点,获得了研究者的广泛关注,具有实用化前景。这一系列材料由于涉及到多种过渡金属元素的组合,较为复杂。本文针对含单一过渡金属、二元组分过渡金属、三元及以上组分过渡金属的P2结构材料及其优化改性进行了系统性梳理,力求厘清研究脉络,梳理研究思路,并给出了今后发展的方向与预测。P2结构材料的主要问题是提高其初始放电容量,氧还原的应用是解决这一问题的重要方向。此外,优化材料组分及采用具有丰富储量、低成本、高安全性和环境友好性的原材料是进一步降低成本并保护环境的重要研究方向。

关键词： 钠离子电池, 正极材料, 储能材料

Nowadays, lithium ion batteries as one of alkali metal(lithium, sodium, potassium, etc.) ion batteries have been widely used in all aspects of industry and life, and contribute to the success of automation, informatization and intelligence of society. However, due to the low abundance of lithium in the crust of earth, sodium-ion batteries based on sodium of high abundance have attracted extensive attention of researchers and society. Among all the component, cathode material is an important factor restricting the practicality of sodium ion batteries. Cathode materials need to be developed for practical application. P2-structure layered composite metal oxide sodium ion battery cathode material has many advantages, such as abundant resources, simple preparation, stable structure, high discharge capacity, good rate performance, good cycle stability, etc. It has attracted extensive attention of researchers and has a practical prospect. This series of materials are complex due to the combination of various transition metal elements. In this paper, the P2-structure materials containing single transition metal, binary transition metals, ternary transition metals and even more components and their optimization and modification are systematically reviewed. The future development prospects and predictions are given. The main problem of P2-structure cathode material is to improve the initial charge capacity. The use of oxygen redox is an important direction to solve this problem. In addition, optimizing the composition of materials and adopting raw materials with abundant reserves, low cost, high safety and environmental friendliness is also an important research direction for further reducing costs and protecting the environment.

Contents

1 Introduction
2 P2 structure materials composed by single transition metal
3 P2 structure materials composed by binary transition metals
4 P2 structure materials composed by ternary transition metals
5 Problems and optimization of P2 structure materials

5.1 Problems about P2 structure materials

5.2 Doping

5.3 Surface modification

6 Initial charge specific capacity enhanced by anion redox
7 Conclusion and perspective
Key words: sodium-ion batteries, cathode materials, energy storage materials
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图1 钠离子电池正极层状材料的分类与钠脱嵌引起的共边八面体MeO6和相变过程[46]
Fig. 1 Classification of Na-Me-O layered materials with sheets of edge-sharing MeO6 octahedra and phase transition processes induced by sodium extraction[46]
图2 O2、P2相过渡金属氧化物的晶体结构示意图 [69]
Fig. 2 Crystal structure illustration of layered oxides with O2 and P2 structures [69]
图3 (a) Na/NNMO电池首圈充放电状态的GITT曲线及(b)相应的钠离子扩散系数($D_{Na^{+}}$)在4.5 ~ 2.0 V之间;(c)Na/NNMO电池首圈充放电状态的GITT曲线以及(d) 相应的钠离子扩散系数($D_{Na^{+}}$)在2.0 ~ 1.5 V[89]
Fig. 3 (a) GITT curves for the charge and discharge states of the first cycle and (b) corresponding sodium-ion diffusion coefficient ($D_{Na^{+}}$) of Na/NNMO cell cycling between 4.5 and 2.0 V;(c) GITT curves for the charge and discharge states of the first cycle and (d) corresponding $D_{Na^{+}}$ of Na/NNMO cell cycling between 2.0 and 1.5 V electrode at current rate of 6C[89]
图4 10、20、30 C的循环性能,以及10 C对应的库仑效率[101]
Fig. 4 The cycling capacity at 10, 20, and 30 C, as well as the coulombic efficiency corresponding to 10 C[101]
图5 NCM55电极在1.5~4.3 V首次充放电和第二次充电的原位XRD图谱。黑色星号代表电池外壳的峰值[101]
Fig. 5 In situ XRD patterns collected during the first charge/discharge and second charge of the NCM55 electrode between 1.5 and 4.3 V. Black asterisks represent the peaks of the battery case[101]
图6 (a)循环伏安曲线和Na0.68Cu0.34Mn0.66O2首周充放电(b)曲线[104]
Fig. 6 (a) Cyclic voltammetry(CV) curve and(b) first charge/discharge curves of the Na0.68Cu0.34Mn0.66O2 electrode[104]
图7 Na2/3Ni1/3Mn7/12Fe1/12O2以5 C倍率循环300圈 [110]
Fig. 7 The cycling performance of Na2/3Ni1/3Mn7/12Fe1/12O2 at 5 C for 300 cycles [110]
图8 (a) x=1/12;(b) x=0时x-NNMF电极的In-situXRD图谱;(c) 0-NNMF电极对应的GCD[110]
Fig. 8 In-situ XRD patterns of x-NNMF electrodes with (a) x=1/12,(b) x=0; (c) the corresponding GCD profiles of 0-NNMF electrode[110]
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