湿化学法制备石榴石型固态电解质Li7La3Zr2O12

doi:10.16085/j.issn.1000-6613.2021-1200

化工进展 ›› 2021, Vol. 40 ›› Issue (S2): 334-339.DOI: 10.16085/j.issn.1000-6613.2021-1200

湿化学法制备石榴石型固态电解质Li₇La₃Zr₂O₁₂

潘迪(), 孔江榕(), 刘欣楠, 黄美琪, 周涛

中南大学化学化工学院，锰资源高效清洁利用湖南省重点实验室，湖南长沙 410083

收稿日期:2021-06-07 修回日期:2021-06-26 出版日期:2021-11-12 发布日期:2021-11-12
通讯作者: 孔江榕
作者简介:潘迪（1996—），女，硕士研究生，研究方向为锂离子电池固态电解质。 E-mail: 3196721293@qq.com。
基金资助:
国家自然科学基金(21506259);湖南省科技计划(2016TP1007);湖南省教育厅优秀青年项目(19B038)

Preparation Li₇La₃Zr₂O₁₂ garnet solid-state electrolyte by wet-chemical technique

PAN Di(), KONG Jiangrong(), LIU Xinnan, HUANG Meiqi, ZHOU Tao

Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, Hunan, China

Received:2021-06-07 Revised:2021-06-26 Online:2021-11-12 Published:2021-11-12
Contact: KONG Jiangrong

摘要/Abstract

摘要：

锂电池因能量密度高、循环寿命长、绿色清洁等特点被广泛应用，但其液态电解质易泄漏、挥发，且隔膜易被锂枝晶刺穿造成短路，引发危险。固态电解质大多是不具燃烧性的无机材料，室温下离子电导率较高、电化学窗口宽且适用温度范围广。因此，采用固态电解质替代液态电解质具有十分重要的意义。相对于其他类型固态电解质，石榴石型氧化物Li₇La₃Zr₂O₁₂（LLZO）具有离子电导率高、电化学窗口宽（>5V vs. Li/Li⁺）、对锂稳定性好和热稳定性高等特点，是非常具有发展潜力的无机固态电解质。本文采用溶胶-凝胶法和低温燃烧法两种湿化学法合成LLZO粉末，对应的电解质片在40℃时的离子电导率分别为1.22×10^-5S/cm和3.87×10^-6S/cm，活化能分别为0.34eV和0.32eV。从实验结果综合比较，溶胶-凝胶法为最佳制备方法。

关键词: 石榴石型LLZO电解质, 溶胶-凝胶法, 低温燃烧法

Abstract:

Lithium-ion batteries are widely used as high energy density, long cycle life and green cleaning. However, lithium dendrite occurs easily in lithium-ion batteries with conditional leaky and volatile liquid electrolyte, which will cause short circuit and further danger. Solid-state electrolyte is nonflammable because most of them are inorganic material such as glass, ceramics and so on. Furthermore, solid-state has high ion conductivity at room temperature, wide electrochemical window, and extensive applicable temperature range. Therefore, it is very significant to replace traditional liquid electrolyte with solid-state electrolyte. Compared with other kinds of solid electrolytes, garnet oxide solid-state electrolyte Li₇La₃Zr₂O₁₂ (LLZO) with high ionic conductivity, wide electrochemical window (>5V vs. Li/Li⁺), stability to lithium metal and thermostabilization is a very promising inorganic solid electrolyte. Sol-gel method and low temperature combustion method were used to prepare LLZO powder in this work. The ionic conductivity at 40℃ and activation energy of the electrolyte pellets prepared by two methods were 1.22×10^-5 S/cm, 0.34eV and 3.87×10^-6 S/cm, 0.32eV, respectively. The result shows that sol-gel is more likely to be selected to prepare LLZO powder.

Key words: garnet-type LLZO electrolyte, sol-gel method, low temperature combustion method

中图分类号:

TQ152

潘迪, 孔江榕, 刘欣楠, 黄美琪, 周涛. 湿化学法制备石榴石型固态电解质Li₇La₃Zr₂O₁₂[J]. 化工进展, 2021, 40(S2): 334-339.

PAN Di, KONG Jiangrong, LIU Xinnan, HUANG Meiqi, ZHOU Tao. Preparation Li₇La₃Zr₂O₁₂ garnet solid-state electrolyte by wet-chemical technique[J]. Chemical Industry and Engineering Progress, 2021, 40(S2): 334-339.

图/表 11

参考文献 16

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方法	元件	20℃	40℃	60℃	80℃
溶胶-凝胶法	R₀/Ω	1733	1812	1073	552.1
	R₁/Ω	7109	5073	1846	596.8
	C₁/F	1.15×10^-10	1.73×10^-10	4.08×10^-10	9.62×10^-10
	Z_w-R/Ω	125470	169630	82638	32712
	Z_w-T/s	7.4500	1.0070	0.4148	0.1571
	Z_w-P	0.34074	0.50001	0.51923	0.55168
低温燃烧法	R₀/Ω	1733	1812	1073	552.1
	R₁/Ω	7109	5073	1846	596.8
	C₁/F	1.15×10^-10	1.73×10^-10	4.08×10^-10	9.62×10^-10
	Z_w-R/Ω	125470	169630	82638	32712
	Z_w-T/s	7.4500	1.0070	0.4148	0.1571
	Z_w-P	0.34074	0.50001	0.51923	0.55168

方法	元件	20℃	40℃	60℃	80℃
溶胶-凝胶法	R₀/Ω	1733	1812	1073	552.1
	R₁/Ω	7109	5073	1846	596.8
	C₁/F	1.15×10^-10	1.73×10^-10	4.08×10^-10	9.62×10^-10
	Z_w-R/Ω	125470	169630	82638	32712
	Z_w-T/s	7.4500	1.0070	0.4148	0.1571
	Z_w-P	0.34074	0.50001	0.51923	0.55168
低温燃烧法	R₀/Ω	1733	1812	1073	552.1
	R₁/Ω	7109	5073	1846	596.8
	C₁/F	1.15×10^-10	1.73×10^-10	4.08×10^-10	9.62×10^-10
	Z_w-R/Ω	125470	169630	82638	32712
	Z_w-T/s	7.4500	1.0070	0.4148	0.1571
	Z_w-P	0.34074	0.50001	0.51923	0.55168

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湿化学法制备石榴石型固态电解质Li₇La₃Zr₂O₁₂

Preparation Li₇La₃Zr₂O₁₂ garnet solid-state electrolyte by wet-chemical technique

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方法	相对密度/%	锂离子电导率（40℃）/S·cm^-1	活化能/eV
溶胶-凝胶法	92.0	1.22×10^-5	0.34
低温燃烧法	92.5	3.87×10^-6	0.32