锆酸镧锂固态电解质合成过程多因素影响

doi:10.19799/j.cnki.2095-4239.2022.0646

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (5): 1625-1635.doi: 10.19799/j.cnki.2095-4239.2022.0646

锆酸镧锂固态电解质合成过程多因素影响

雷蕾¹(), 高鹏¹, 冯娜娜², 蔡坤鹏¹, 张海¹, 张扬¹^,²()

^1.清华大学能源与动力工程系，热科学与动力工程教育部重点实验室，北京 100084
^2.清华大学山西清洁能源研究院，山西太原 030000

收稿日期:2022-11-02 修回日期:2022-11-20 出版日期:2023-05-05 发布日期:2023-05-29
通讯作者: 张扬 E-mail:lei_lei@mail.tsinghua.edu.cn;yang-zhang@mail.tsinghua.edu.cn
作者简介:雷蕾（1992—），女，博士，助理研究员，研究方向为能源功能材料制备与表征，E-mail：lei_lei@mail.tsinghua.edu.cn；
基金资助:
国家自然科学基金项目(52176116);清华大学山西清洁能源研究院创新种子基金

The influences of multifactors in the synthesis progress on the characteristics of lithium lanthanum zirconate solid electrolytes

Lei LEI¹(), Peng GAO¹, Nana FENG², Kunpeng CAI¹, Hai ZHANG¹, Yang ZHANG¹^,²()

^1.Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Energy and Power Engineering, Tsinghua University, Beijing 100084, China
^2.Shanxi Research Institute for Clean Energy Tsinghua University, Taiyuan 030000, Shanxi, China

Received:2022-11-02 Revised:2022-11-20 Online:2023-05-05 Published:2023-05-29
Contact: Yang ZHANG E-mail:lei_lei@mail.tsinghua.edu.cn;yang-zhang@mail.tsinghua.edu.cn

摘要/Abstract

摘要：

本工作采用化学共沉淀方法合成石榴石型Li₇La₃Zr₂O₁₂(LLZO)固态电解质，借助扫描电子显微镜(SEM)、X射线衍射(XRD)、电化学阻抗谱分析等系统研究了制备过程中烧结工艺、球磨、Al元素掺杂及压片压力等参数对样品颗粒尺寸、立方相稳定、致密化行为以及最终固态电解质锂离子电导率的影响。研究结果表明，热压烧结或湿法球磨均有利于提高固态电解质片的致密度，但样品的最终离子电导率受晶相结构影响表现不佳，相比而言干法球磨、常压烧结能够很好地合成立方相c-LLZO且结构中的杂相随温度升高而减少。为了解决随温度升高产生的颗粒粗化问题，由两步烧结代替一步烧结获得小粒径、高致密度固态电解质，同时增强了Al掺杂离子的稳定结构作用。最终，干法球磨、经750 MPa冷压成型、1100 ℃×6 h-1200 ℃×20 h两步烧结获得的Al掺杂LLZO电解质离子电导率最高，达1.52×10^-4 S/cm，这是其稳定立方结构和高致密度形貌共同作用的结果。本研究有助于推动陶瓷材料的制备与应用，为固态电池技术研发提供指导。

关键词: 固态电解质, 化学共沉淀, 高温烧结, 铝掺杂, 球磨

Abstract:

Lithium lanthanum zirconate (Li₇La₃Zr₂O₁₂, LLZO) solid-state electrolytes were synthesized using the chemical coprecipitation method. The effects of the operation parameters of the sintering process, ball milling, Al doping, and compression force on the grain boundary, phase, densification, and final Li⁺ ion conductivity were evaluated using various characterization techniques, e.g., scanning electron microscopy (SEM), powder X-ray diffraction (XRD), and electrochemical impedance spectroscopy (EIS) analyses. Wet ball milling using isopropanol as a grinding aid or hot-pressed sintering is beneficial for improving the density of LLZO pellets. However, the Li⁺ ion conductivities at room temperature of the samples is low due to their poor structures. The cubic phase structure (c-LLZO) was synthesized via dry ball milling and pressure less sintering, and the crystal structures became pure as the sintering temperature increased. To solve the subsequent problem of the grain coarsening, a two-step sintering was proposed instead of one-step sintering to synthesize LLZO electrolytes with small particle sizes and high relative density. At the same time, the effect of Al doping in stabilizing the cubic structure was also enhanced using the two-step sintering. Finally, the as-prepared Al-doped LLZO solid-state electrolyte obtained via dry ball milling, cold pressing at 750 MPa, and two-step sintering of 1100 ℃ for 6 h and 1200 ℃ for 20 h exhibited the highest ionic conductivity (1.52×10^-4 S/cm), mainly owing to its cubic garnet structure and the highest relative density. This research will shed light on preparing and applying LLZO-related ceramic materials, providing a solid basis and guidance for developing solid-state battery technology.

Key words: solid-state electrolytes, chemical co-precipitation, high-temperature sintering, Al doping, ball milling

中图分类号:

TM 911.3

雷蕾, 高鹏, 冯娜娜, 蔡坤鹏, 张海, 张扬. 锆酸镧锂固态电解质合成过程多因素影响[J]. 储能科学与技术, 2023, 12(5): 1625-1635.

Lei LEI, Peng GAO, Nana FENG, Kunpeng CAI, Hai ZHANG, Yang ZHANG. The influences of multifactors in the synthesis progress on the characteristics of lithium lanthanum zirconate solid electrolytes[J]. Energy Storage Science and Technology, 2023, 12(5): 1625-1635.

图/表 9

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样品名称	球磨方式	铝掺杂	压片压力/MPa	烧结温度/℃、时长/h(压力/MPa)
LLZO-1150	干法	否	250	1150 ℃×20 h
LLZO-1180	干法	否	250	1180 ℃×20 h
LLZO-1200	干法	否	250	1200 ℃×20 h
LLZO-1200-HP	干法	否	250	1200 ℃×20 h-1200 ℃×2 h(40 MPa)
Wet-LLZO-1150	湿法	否	250	1150 ℃×20 h
Wet-LLZO-1180	湿法	否	250	1180 ℃×20 h
Wet-LLZO-1200	湿法	否	250	1200 ℃×20 h
LLZAO-1150	干法	是	250	1150 ℃×20 h
LLZAO-1180	干法	是	250	1180 ℃×20 h
LLZAO-1200	干法	是	250	1200 ℃×20 h
LLZAO-1100/1200-250	干法	是	250	1100 ℃×6 h-1200 ℃×20 h
LLZAO-1100/1200-500	干法	是	500	1100 ℃×6 h-1200 ℃×20 h
LLZAO-1100/1200-750	干法	是	750	1100 ℃×6 h-1200 ℃×20 h

样品	颗粒尺寸/μm	相对密度/%	离子电导率/(S/cm)	数据来源
LLZO-1150	10	81.1	1.23×10^-5	本工作
LLZO-1180	12.5	82.7	1.26×10^-5	本工作
LLZO-1200	17.5	82.7	1.42×10^-5	本工作
LLZO-1200-HP	—	97.7	6.66×10^-6	本工作
Wet-LLZO-1150	20	89.6	7.69×10^-6	本工作
Wet-LLZO-1180	26	90.0	9.95×10^-6	本工作
Wet-LLZO-1200	40	92.4	1.06×10^-5	本工作
LLZAO-1150	10	81.5	2.28×10^-5	本工作
LLZAO-1180	14	80.4	1.82×10^-5	本工作
LLZAO-1200	16	83.3	1.82×10^-5	本工作
LLZAO-1100/1200-250	10	92.7	8.82×10^-5	本工作
LLZAO-1100/1200-500	10	92.9	9.37×10^-5	本工作
LLZAO-1100/1200-750	10	93.1	1.52×10^-4	本工作(最佳样品)
LLZO	略大于10	略大于90	2×10^-4	参考文献[13]
Al-LLZO	6.23	86.8	2.02×10^-4	参考文献[8]
Al-LLZO	10	80	2.8×10^-6	参考文献[15]
Al-LLZO	5	57	6.3×10^-5	参考文献[3]
Ta-LLZO	15	92	6.9×10^-4	参考文献[5]
Ti-LLZO	8	90.7	1.91×10^-4	参考文献[7]

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锆酸镧锂固态电解质合成过程多因素影响

The influences of multifactors in the synthesis progress on the characteristics of lithium lanthanum zirconate solid electrolytes

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