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化学进展 2023, Vol. 35 Issue (8): 1177-1190 DOI: 10.7536/PC221220 前一篇   后一篇

• 综述 •

全固态钠离子电池及界面改性

杨冬荣1,2,3, 张达1,2,3,*(), 任昆1,2,3, 李付鹏1,2,3, 东鹏1,2,3, 张家庆1,2,3, 杨斌1,2,3, 梁风1,2,3,*()   

  1. 1 昆明理工大学 云南省有色金属真空冶金重点实验室 昆明 650093
    2 昆明理工大学真空冶金国家工程研究中心 昆明 650093
    3 昆明理工大学冶金与能源工程学院 昆明 650093
  • 收稿日期:2022-12-28 修回日期:2023-05-24 出版日期:2023-08-24 发布日期:2023-07-18
  • 作者简介:

    张达 昆明理工大学讲师,2021年于昆明理工大学冶金与能源工程学院获博士学位,主要从事纳米材料的等离子体制备和改性、新能源材料与器件等方面研究。

    梁 风 昆明理工大学教授,博士生导师,日本九州大学客座教授。于日本东京工业大学获博士学位。入选国家人力资源与社会保障部资助高层次留学回国人才计划、云南省高端科技人才、昆明理工大学首批学术青蓝计划等多项人才计划。主要从事高能量密度储能器件(固态离子电池、金属空气电池等)、等离子体制备和改性纳米材料等方面研究。

  • 基金资助:
    国家自然科学基金项目(12175089); 国家自然科学基金项目(12205127); 云南省重点研发计划项目(202103AF140006); 云南省科技厅应用基础研究计划项目(202001AW070004)
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All Solid-State Sodium Batteries and Its Interface Modification

Dongrong Yang1,2,3, Da Zhang1,2,3(), Kun Ren1,2,3, Fupeng Li1,2,3, Peng Dong1,2,3, Jiaqing Zhang1,2,3, Bin Yang1,2,3, Feng Liang1,2,3()   

  1. 1 Key Laboratory for Nonferrous Vacuum Metallurgy of Yunnan Province, Kunming University of Science and Technology,Kunming 650093, China
    2 National Engineering Research Center of Vacuum Metallurgy, Kunming University of Science and Technology, Kunming 650093, China
    3 Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
  • Received:2022-12-28 Revised:2023-05-24 Online:2023-08-24 Published:2023-07-18
  • Contact: *e-mail: liangfeng@kust.edu.cn (Feng Liang);zhangda@kust.edu.cn (Da Zhang)
  • Supported by:
    National Natural Science Foundation of China(12175089); National Natural Science Foundation of China(12205127); Key Research and Development Program of Yunnan Province(202103AF140006); Applied Basic Research Programs of Yunnan Provincial Science and Technology Department(202001AW070004)

全固态钠离子电池具有原料成本低、安全性高以及能量密度高等特点,在移动电源、电动汽车和大规模储能系统领域表现出巨大的应用潜力。然而全固态钠离子电池的发展和规模化应用亟需解决固体电解质室温离子电导率低、界面电荷转移阻抗大、固体电解质与电极界面兼容性和接触差等问题。本文结合近年来全固态钠离子电池相关报道和本课题组研究成果,概述了β-Al2O3型固体电解质、NASICON型固体电解质、硫化物固体电解质、聚合物固体电解质、复合固体电解质的研究进展及发展趋势;综述了全固态钠离子电池界面特性、固体电解质表面修饰、电极/固体电解质界面改性最新研究成果;最后对全固态钠离子电池界面改性策略发展方向进行了展望。本综述有助于加深对全固态钠离子电池界面科学问题的认识,并对固态钠离子电池的发展应用形成理论指导。

关键词： 全固态钠离子电池, 固体电解质, 界面, 改性

All solid-state sodium batteries have great potential for portable electronics, electric vehicles, and large-scale energy storage applications due to the low cost of sodium, high security, and high energy density. However, the development and large-scale application of all-solid-state sodium ion batteries urgently need to solve the problems such as low ion conductivity of solid electrolyte, high charge-transfer impedance on interface, insufficient interfacial contact, and compatibility issues between electrodes and electrolytes solid electrolyte. Herein, combining the latest reports with our research findings, the research progress and development trend of β-Al2O3 electrolytes, NASICON electrolytes, sulfide electrolytes, polymer electrolytes, and composite electrolytes were summarized. The latest achievements in interface characteristics, the modification strategies of the interface between the electrodes and solid electrolytes and modification methods for surfaces of solid electrolytes were reviewed. Finally, the development direction of interface modification strategy for solid-state sodium ion batteries was prospected. This review have contributed to understand the interface science issues of all solid-state sodium ion batteries and provides a theoretical guidance for the development and application of solid-state sodium ion batteries.

Contents

1 Introduction

2 Solid-state electrolytes

3 Challenges for all solid-state sodium batteries

4 Interfaces engineering

4.1 Cathode/electrolyte interfaces

4.2 Anode/electrolytes interfaces

4.3 Structure design for interfaces engineering

5 Conclusion and future perspectives

Key words: all solid-state sodium batteries, solid-state electrolytes, interface, modification
()
图1 无机固体电解质(a,b,c,d,e)和有机聚合物固体电解质(f)性质对比图[27]
Fig.1 Performance comparison of (a, b, c, d, e) inorganic solid electrolytes, and (f) solid polymer electrolytes[27]
表1 常见无机固体电解质的特性和优缺点[40,41]
Table 1 The characteristics, advantages, and disadvantages of common inorganic solid electrolytes[40,41]
Type Selected materials Conductivity
(S·cm-1)		 Potential window
(V (vs Na+ / Na))		 Advantages Disadvantages
Oxides Na-β″-Al2O3, NASICON,
Na2M2TeO6,		 10-4 ~ 10-3 Up to 7 High thermal stability
High ionic conductivity		 High interface resistance
Poor interface wetting
Sulfides Na3PS4, Na11Sn2PS12, etc. 10-4 ~ 10-3 < 4 for Na3PS4
Others up to 5		 High ionic conductivity
High flexibility		 Low chemical stability,
Poor compatibility with Na
Polymer based PEO, PEG, PVDF-HFP, etc. 10-6 ~ 10-4 About 4.5 High flexibility
Good interface wetting		 Low ionic conductivity,
Low thermal stability
High cost
Boron
hydrides		 Na2-x(B12H12)x(B10H10)1-x
Na2-x(CB11H12)x(B12H12)1-x, etc.		 10-4 ~ 10-2 Up to 5 High thermal stability High chemical stability
High ionic conductivity		 Large interfacial resistance
Gel Polymer EPTA-NaPF6-PC/FEC/PS-NaPF6,
BP/PEO-HKUST-1-NaClO4-EC/
DEC/FEC, etc.		 10-4 ~ 10-3 Up to 5 High ionic conductivity
High flexibility
Good interfacial stability		 Low thermal stability
High cost
图2 (a)β-Al2O3和β″-Al2O3晶体结构[26];(b)Na3Zr2Si2PO12钠离子传输路径示意图[27];(c)Na3PS4晶体结构[26];(d)聚合物固体电解质Na+传导机理图[54]
Fig.2 (a) Crystal structures of β-Al2O3 and β″-Al2O3[26]; (b) schematic illustration of Na+ conducting pathways in Na3Zr2Si2PO12[27]; (c) crystal structures of the Na3PS4[26]; (d) schematic illustration of Na+ transport mechanism in polymer solid electrolytes[54]
图3 无机固体电解质Na+电导率随温度变化[87]:(a)NASICON;(b)硫化物固体电解质;(c)聚合物和复合固体电解质;(d)结晶态有机物、反钙钛矿和硼氢化物固体电解质
Fig.3 Temperature-dependent Na+ conductivities of inorganic solid electrolytes[87]: (a) NASICON; (b) sulfide solid electrolytes; (c) polymer and composite solid electrolytes; (d) crystalline organic, anti-perovskites and borohydrides solid electrolytes
图4 全固态钠离子电池示意图
Fig.4 Schematic illustration of the SSBs
图5 (a)NVP|IL/SE|Na电池界面示意图[58];(b)Na2S-Na3PS4-CMK-3复合正极示意图[95];(c)S-MSP20-Na3SbS4正极制备工艺[96];(d,e)正极活性材料与塑性晶体固体电解质复合正极示意图[97];(f)Na|PEO-SN-NaClO4/PAN-Na3Zr2Si2PO12-NaClO4|PB电池在0.2 C下循环性能图[98];(g)非对称固体电解质示意图
Fig.5 (a) Schematic of the interface for NVP|IL/SE|Na batteries[58]; (b) schematic of the Na2S-Na3PS4-CMK-3 composite cathode[95]; (c) preparation process for S-MSP20-Na3SbS4 cathode[96]; (d, e) schematic of plastic-crystal electrolyte and active material in composited cathode[97]; (f) cycling performance of the Na|PEO-SN-NaClO4/PAN-Na3Zr2Si2PO12-NaClO4|PB cell at 0.2 C[98]; and (g) illustration of the asymmetric solid electrolytes
图6 (a)PEALD构筑Al2O3钝化层示意图[105];(b)化学气相沉积石墨烯修饰NASICON表面示意图[106];(c)NaClO4/FEC溶液改性Na金属表面示意图[107];(d)Na|SnS2-Na3Zr2Si2PO12界面改性示意图[108];(e)固体电解质与金属Na界面接触模型[109];(f)Na-SiO2复合材料与NASICON界面[110]
Fig.6 (a) Schematic of PEALD process for Al2O3 layer[105]; (b) schematic of the CVD-grown graphene-like interlayer on NASICON surface[106]; (c) NaClO4/FEC modified surface of Na[107]; (d) schematic of the Na|SnS2-Na3Zr2Si2PO12 interface[108]; (e) contact model of SEs and sodium metallic[109]; (f) interfaces between Na-SiO2 composite and NASICON[110]
图7 (a)金属钠-碳复合负极与固体聚合物化学交联界面示意图[112];(b)Na-C|PEO20NaFSI| Na-C和Na|PEO20NaFSI|Na电池在0.1、0.2和0.3 mA下循环电压曲线[112];(c)正极和固体电解质叠层薄膜示意图[113];(d)Na2FeP2O7正极与β''-Al2O3电解质一体化结构示意图[114];(e)Pt|Na3-xV2-xZrx(PO4)3|Pt单相全固态电池示意图[115]
Fig.7 (a) Illustration of the interfaces between solid-state polymer and Na-C anode[112]; (b) voltage curves of the Na-C|PEO20NaFSI| Na-C and Na|PEO20NaFSI|Na batteries at a current density of 0.1, 0.2, and 0.3 mA[112]; (c) schematic of the cathode-supported solid electrolyte membrane[113]; (d) illustration of the Na2FeP2O7 and β''-Al2O3 integrated structure[114]; (e) schematic illustration of the Pt|Na3-xV2-xZrx(PO4)3|Pt battery[115]
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全固态钠离子电池及界面改性