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化学进展 2019, Vol. 31 Issue (1): 210-222 DOI: 10.7536/PC180434 前一篇   

• 综述 •

钠基固体电解质及其在能源上的应用

张庆凯, 梁风*(), 姚耀春, 马文会, 杨斌, 戴永年   

  1. 昆明理工大学冶金与能源工程学院 昆明理工大学真空冶金国家工程实验室 昆明理工大学复杂有色金属资源清洁利用国家重点实验室 昆明 650093
  • 收稿日期:2018-04-20 修回日期:2018-06-29 出版日期:2019-01-15 发布日期:2018-12-07
  • 通讯作者: 梁风
  • 基金资助:
    国家自然科学基金项目(51704136); 国家自然科学基金项目(11765010); 云南省应用基础研究面上项目(2016FB087); 云南省院士自由探索基金资助(2017HA006)
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Sodium-Based Solid-State Electrolyte and Its Applications in Energy

Qingkai Zhang, Feng Liang*(), Yaochun Yao, Wenhui Ma, Bin Yang, Yongnian Dai   

  1. Faculty of Metallurgy and Energy Engineering, National Engineering Laboratory for Vacuum Metallurgy, National Key Laboratory for Clean Application of Complex Non-ferrous Metal Resources, Kunming University of Science and Technology, Kunming 650093, China
  • Received:2018-04-20 Revised:2018-06-29 Online:2019-01-15 Published:2018-12-07
  • Contact: Feng Liang
  • About author:
    ** Corresponding author e-mail:
  • Supported by:
    The work was supported by the National Natural Science Foundation of China(51704136); The work was supported by the National Natural Science Foundation of China(11765010); The Application of Basic Research Projects of Yunnan Province(2016FB087); The Free Exploration Foundation of Yunnan Province(2017HA006)

由于以钠基固体电解质为核心的新型钠电池体系具有低成本和高安全性,在能源领域应用潜力巨大。高离子电导率和稳定性是钠基固体电解质应用于新型钠电池体系的前提。近年来,人们通过对制备方法改进和掺杂改性等方面的研究显著提高了钠基固体电解质的离子电导率和稳定性。此外,新型钠电池体系亟需解决固体电解质与电极间的界面接触性差和界面稳定性差等问题。本文首先总结了β″-Al2O3、NASICON型、硫化物类和聚合物类钠基固体电解质的研究进展,然后介绍了钠基固体电解质在以钠-硫电池,有机/水混合系钠-空气电池和全固态钠离子电池为代表的新型钠电池体系中的应用情况,并对界面问题和采取的解决策略进行系统论述。基于固体电解质的新型钠电池体系在能源上的大规模应用还需要电池材料、界面和电池设计等多方面的研究同时突破。

关键词： 钠基固体电解质, 离子电导率, 稳定性, 界面, 电池

Due to the low cost and high safety of the new sodium battery system using sodium-based solid electrolyte, the new sodium battery system has great potential for its applications in energy storage field. High ionic conductivity and stability of sodium-based solid electrolytes are prerequisites for its applications in new sodium battery systems. In recent years, people have significantly improved the ionic conductivity and stability of sodium-based solid electrolytes by improving preparation methods and doping modifications. In addition, the new sodium battery system needs to solve the interface problems such as poor interface contact and poor interface stability between the solid state electrolyte and the electrode. In this paper, we firstly summarize the research progress in ionic conductivity and stability of β″-Al2O3, NASICON, sulfides, and polymer of sodium-based solid electrolytes. Then the applications of sodium-based solid electrolytes in sodium-sulfur batteries, hybrid sodium-air batteries, and all-solid-state sodium-ion batteries are introduced. In view of the interface problems, the solving strategies are systematically discussed. The future large-scale applications in energy of the new sodium battery system based on solid state electrolytes need breakthroughs in many aspects such as battery materials, interfaces, and battery design.

Key words: sodium based solid-state electrolyte, ionic conductivity, stability, interface, battery
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钠基固体电解质及其电池体系简图[36]
Fig.1 Sodium-based solid-state electrolytes and related battery system diagram[36]
不同钠基固体电解质的性能对比
Table 1 Performance comparison of different sodium-based solid electrolytes
Solid-state electrolytes Advantages Disadvantages
β″-Al2O3 High thermal stability
High ionic conductivity		 Low mechanical property
Poor interface wetting
NASICON High chemical stability
High thermal stability		 Poor interface wetting
Sulfide High ionic conductivity Low chemical stability
Poor interface compatibility
Polymer High flexibility
Good interface wetting		 High cost
Low ionic conductivity
理想化结构示意图:(a)β-Al2O3;(b)β″-Al2O3[3]
Fig.2 Idealized structure diagram: (a) β-Al2O3; (b) β″-Al2O3[3]
NASICON单胞:(a)菱形结构;(b)单斜结构[4]
Fig.3 NASICON cell: (a) diamond structure; (b) monoclinic structure[4]
Na11Sn2PS12晶体结构图[33]
Fig.4 Crystal structure of Na11Sn2PPS12[33]
PEO中无定形区域钠离子传输示意图[40]
Fig.5 Schematic diagram of amorphous sodium ion transport in PEO[40]
钠基固体电解质离子电导率的总结
Fig.6 Summary of ionic conductivity of sodium-based solid-state electrolytes
(a)钠-硫电池结构图[6];(b)电流密度0.25 mA/cm2下电池循环性能图[73]
Fig.7 (a) Structure of sodium-sulfur battery[6]; (b) Battery cycling performance at current densities of 0.25 mA/cm2[73]
(a) 有机/水混合系钠-空气电池结构示意图;(b) 电池I-V曲线(实线)及能量密度-电压曲线(虚线)[76]
Fig.8 (a) Organic/water mixed metal-air battery structure diagram; (b) I-V curve (solid line) and energy density-voltage curve (dotted line) of the battery[76]
(a)全固态钠电池结构图;(b)固态电池NVP|IL|SE|Na超长的循环性能图(10 C,25 ℃)[27]
Fig.9 (a) The structure of all-solid-state battery; (b) cycling performance and columbic efficiency of the NVP/IL/SE/Na solid-state battery (10 C, 25 ℃) [27]
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