钠离子硫化物固态电解质研究进展

doi:10.19799/j.cnki.2095-4239.2020.0108

摘要/Abstract

摘要：

全固态钠离子电池由正极、固态电解质和负极三部分组成，固态电解质作为导通离子隔绝电子的核心部件，既需要高的离子电导率，又要求良好的电解质-电极的固固接触和界面稳定性以维持有效的离子传输。硫化物电解质因具有众多优势而备受关注。近年来，在提高其离子电导率方面已取得较大进展，在对其化学稳定性、与电极材料的界面稳定性等方面研究还在不断深入。本文通过对近期相关文献的梳理，讨论了目前钠离子硫化物无机固态电解质的发展概况，分别对硫化物电解质的制备工艺、结构以及电导率做了系统评述，着重介绍了机械化学合成、固相烧结、以及化学液相合成的方法，系统分析了基于Na₃PS₄和Na₃SbS₄的三元硫化物，以及基于Na₁₁Sn₂PS₁₂和Na₁₁Sn₂SbS₁₂的四元硫化物的成分设计策略，重点总结了阴离子和阳离子掺杂所导致的钠离子空位/间隙、离子结合能、晶格软化、钠离子分布、结构对称性等变化对优化离子输运的作用机制。同时，总结了基于硫化物电解质的全固态钠电池界面特性的研究进展，主要分析了正极-电解质固固接触的改善策略和金属负极-电解质界面失效机理和稳定性提升措施，表明解决界面问题的紧迫性。最后，展望了钠离子硫化物电解质下一步可能的发展方向。

关键词: 硫化物电解质, 全固态钠电池, 制备工艺, 离子电导率, 界面

Abstract:

All-solid-state sodium-ion batteries consist of positive and negative electrodes and solid electrolyte. Solid electrolytes need not only high ionic conductivity, but also good electrolyte-electrode solid contact and their interfacial stability. Among diverse sodium-ion solid electrolytes including oxides, sulfides, borohydrides, and polymers, sulfides are extremely attractive because of the advantages of high ionic conductivity and elastic modulus, good electrical contact with electrodes by cold-processing or solution coating, and broad temperature stability. In recent year, significant progress has been achieved on their ionic conductivity, while their chemical stability and interfacial stability toward the electrodes still need in-depth studies. Herein, the progress regarding sulfide-based sodium-ion solid electrolytes is reviewed, which contains their preparation techniques, chemical structure, and ion transport. The mechanochemical synthesis, solid-state reaction, and solution synthesis methods are mainly discussed. The design strategies regarding the Na₃PS₄- and Na₃SbS₄-based ternary phase systems and the Na₁₁Sn₂PS₁₂- and Na₁₁Sn₂SbS₁₂-based quaternary phase systems are summarized. The influencing mechanism of cation- and anion-doping on Na⁺ vacancies/interstitials, Na⁺-lattice binding energy, lattice softening, Na⁺ distribution, and space groups is analyzed. In parallel, the interfacial performance between electrolyte and electrodes in all-solid-state batteries is reviewed, including the solid-solid contact between positive electrode and electrolyte and the interfacial stability between negative electrode and electrolyte. It is urgent to solve the interfacial issue arisen regarding sulfide solid electrolytes. In the last, some suggestions are presented for the further investigations on sulfide-based sodium-ion solid electrolytes.

Key words: sulfide-based solid electrolytes, solid-state sodium batteries, synthesis technique, ionic conductivity, interface

贾曼曼, 张隆. 钠离子硫化物固态电解质研究进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2020.0108.

Manman JIA, Long ZHANG. Recent development on sulfide solid electrolytes for solid-state sodium batteries[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2020.0108.

图/表 8

图1

图2

图3

表1

不同成分的钠离子硫化物电解质"

组分	对称性	晶格常数 /(?)	电导率 /(mS cm^-1)	激活能/(eV)	原料；制备方法	掺杂效果	文献
Na₃PS₄	Cubic I43m		0.2-0.46	0.281-0.198	Na₂S+P₂S₅；500rpm球磨20h→270度烧结2h		^[34,47]
Na₃PS₄	Tetragonal P42₁c	6.6919 7.0838	3.39	0.173	Na₂S、P₂S₅；450度烧结8h→700度烧结12h		^[50]
Na_2.9PS_3.95Se_0.05	Cubic I43m		0.121	0.230	Na₂S+P₂S₅+Se；乙腈分散→80度干燥→270度退火	扩大Na⁺扩散通道；产生空位	^[44]
Na₃PSe₄	Cubic I43m	7.3094	1.16	0.210	Na+P+Se； 800度烧结12h	扩大晶格体积；降低Na⁺与骨架结合能	^[40]
Na₃PSe₄	Cubic I43m	7.3136	0.11	0.281	Na₂Se+P+Se；300度烧结12h	有空位形成	^[54]
Na₃SbSe₄	Cubic I43m	7.4920	3.70	0.190	Na+Sb+Se；700度烧结12h	扩大晶胞体积	^[53]
Na_2.9375PS_3.9375Cl_0.0625	Tetragonal P42₁c	6.9704 7.0925	1.14	0.249	Na₂S+P₂S₅+NaCl；800度烧结4h→420度退火2h	产生Na⁺空位	^[42]
94Na₃PS₄·6Na₄SiS₄	Cubic I43m	6.9978	0.74	0.260	Na₂S+P₂S₅+SiS₂；510rpm球磨15h→220度退火2h	提高Na2占位	^[35]
Na_3.1Ge_0.1P_0.9S₄	Cubic I43m	6.9950	0.212	0.21	Na₂S+P₂S₅+GeS₂；球磨10h→250度退火6h	提高Na⁺浓度	^[37]
Na_3.1Ti_0.1P_0.9S₄	Cubic I43m	6.9893	0.23	0.20	Na₂S+P₂S₅+TiS₂；球磨10h→250度退火6h	提高Na⁺浓度	^[37]
Na_3.1Sn_0.1P_0.9S₄	Cubic I43m	7.0088	0.25	0.18	Na₂S+P₂S₅+SnS₂；球磨10h→250度退火6h	提高Na⁺浓度	^[37]
Na₃P_0.62As_0.38S₄	Tetragonal P42₁c		1.46	0.256	Na₂S+P₂S₅+As₂S₅；510rpm球磨15h→270度退火2h	提高离子电导率、空气稳定性	^[36]
Na_2.730Ca_0.135PS₄	Cubic I43m	6.9768	1.40	0.346	Na₂S+P₂S₅+CaS；500rpm球磨5h→700度退火12h	提高钠离子空位	^[61]
Na₃SbS₄	Tetragonal P42₁c	7.1597 7.2906	3.00	0.250	Na+Sb+S；700度烧结12h		^[41]
Na₃SbS₄	Tetragonal P42₁c	7.1453 7.2770	1.10	0.200	Na₂S+Sb₂S₃+S；550度烧结→甲醇/水溶液法		^[63]
Na₃SbS₄	Tetragonal P42₁c		0.10-0.20	0.270-0.350	Na₂S+Sb₂S₃+S；溶于水→干燥后200度退火		^[45]
Na₃SbS₄	Cubic I43m	7.1570 7.2874	1.05	0.220	Na₃SbS₄·9H₂O；150度1h脱水		^[64]
Na_2.88Sb_0.88W_0.12S₄	Cubic I43m	7.1920	32	0.177	Na₂S+S +Sb₂S₃+WS₂；510rpm球磨5h/30h→275度退火	增大空位浓度，稳定立方相	^[69]
Na₁₀SnP₂S₁₂	Tetragonal P4₂/nmc	9.6800 13.6300	0.4	0.356	Na₂S+P₂S₅+SnS₂；380rpm球磨17h→700度退火		^[75]
Na₁₀GeP₂S₁₂	Tetragonal P4₂/nmc	9.5700 13.4300	0.024	0.4160	Na₂S+P₂S₅+SnS₂；510rpm球磨5h→235度退火1h		^[74]
Na₁₁Sn₂PS₁₂	Tetragonal I4₁/acd	13.6148 27.2244	1.40	0.250	Na₂S+P₂S₅+SnS₂；700度烧结2h并缓慢降温		^[76]
Na₁₁Sn₂PS₁₂	Tetragonal I4₁/acd	13.6436 27.2715	3.70	0. 387	Na₃PS₄+Na₄SnS₄；420度烧结24h		^[78]
Na₁₁Sn₂PSe₁₂	Tetragonal I4₁/acd	14.2741 28.5113	1.00		Na+P+Sn+Se；450rpm球磨15h→550度退火6h		^[80]

表1

图4

图5

图6

图7

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