纳米多孔β-Li3PS4固体电解质的溶剂脱除法制备及性能

doi:10.7503/cjcu20160333

摘要/Abstract

摘要：

以Li₂S和P₂S₅为反应物, 四氢呋喃为溶剂, 采用溶剂脱除法制备了室温下稳定的高离子电导率β-Li₃PS₄晶体电解质, 通过粉末X射线衍射、差热-热重分析、拉曼光谱、氮气吸附-脱吸和交流阻抗测试等方法对其性能进行表征, 研究了热处理温度对溶剂脱除程度、固体电解质结晶状态、比表面积、孔隙率和离子电导率的影响. 结果表明, 该方法制备得到的β-Li₃PS₄晶体可以在室温下稳定存在. 160 ℃加热条件下Li₃PS₄的离子电导率达到7.44×10^-6 S/cm. 热处理过程中四氢呋喃分3个阶段脱除, 导致产物颗粒表面和内部产生大量纳米孔. 大量纳米孔洞的存在提高了材料的表面能, 有利于新相形核, 加快了相变速度, 降低了相变温度, 使β-Li₃PS₄晶体在室温下保持稳定.

关键词: 固体电解质, 溶剂脱除法, 纳米多孔, β-Li3PS4

Abstract:

Room temperature-stable and highly ionic conductive crystal electrolyte β-Li₃PS₄ was fabricated via solvent-removing method using Li₂S and P₂S₅ as reactants, tetrahydrofuran as solvent. Then β-Li₃PS₄ was analyzed through X-ray diffraction, differential thermal analysis and thermogravimetry analysis, Raman spectrometry, N₂ adsorption-desorption analysis and electrochemical impedance spectroscopy. Effects of heat treatment temperature on solvent removing, crystallization, specific surface area, porosity, and ionic conductivity were investigated. The results show that solvent-removing method successfully stabilizes β-Li₃PS₄ at room temperature. When heated at 160 ℃, Li₃PS₄ reaches its highest ionic conductivity, 7.44×10^-6 S/cm. During the heating treatment, tetrahydrofuran solvent was removed in 3 stages, generating numerous nanopores at both surface and interior of the Li₃PS₄ particles. Those nanopores increase surface energy, which helps new phase nucleate, expedites crystalline transition, reduces phase transition temperature, and stabilizes β-Li₃PS₄ to room temperature.

Key words: Solid electrolyte, Solvent-removing method, Nanoporous, β-Li3PS4

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潘亦真, 李宇杰, 陈一民, 郑春满. 纳米多孔β-Li₃PS₄固体电解质的溶剂脱除法制备及性能. 高等学校化学学报, 2016, 37(7): 1232.

PAN Yizhen, LI Yujie, CHEN Yimin, ZHENG Chunman. Performance of Nano-porous β-Li₃PS₄ Prepared by Solvent Removing Method^†. Chem. J. Chinese Universities, 2016, 37(7): 1232.

图/表 10

Fig.1 DTA-TGA curves of Li3PS4·xTHF

Fig.2 Raman spectra of Li3PS4·xTHF heated at 80 ℃(a), 100 ℃(b) and 160 ℃(c)

Fig.3 XRD patterns of Li3PS4·xTHF heated at different temperaturesTemperature/℃: a. 25; b. 80; c. 100; d. 120;

Table 1 XRD data of Li3PS4 heated at different temperatures

Heating temperature/℃	Crystal face	2θ/(°)	d/nm	Peak width of half height/(°)
200	(102)	30.22	0.2955	0.139
160		30.18	0.2959	0.186
140		29.96	0.2980	0.220
200	(210)	17.89	0.4954	0.120
160		17.81	0.4976	0.162
140		17.65	0.5021	0.201
200	(220)	26.36	0.3379	0.148
160		26.30	0.3386	0.173
140		26.15	0.3404	0.181

Fig.4 SEM images of Li3PS4·xTHF before(A, B) and after(C, D) 160 ℃ heat treatment

Fig.5 Relationship between heating temperature and specific surface area

Fig.6 Pore diameter distribution of 160 ℃-heated Li3PS4

Fig.7 Impedance plot from the symmetrical cell containing 160 ℃-heated Li3PS4

Fig.8 Impedance plots from the symmetrical cell containing 160 ℃-(a), 180 ℃-(b) and 200 ℃-(c) heated Li3PS4

Fig.9 Logarithmic relationship between ionic conductivity and heating temperature

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纳米多孔β-Li₃PS₄固体电解质的溶剂脱除法制备及性能

Performance of Nano-porous β-Li₃PS₄ Prepared by Solvent Removing Method^†

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