硅酸盐学报

全固态锂电池锂镧锆氧陶瓷电解质的强化与薄膜化

PDF下载

包成帅 ¹^,² , 温佳杰 ¹ , 吴梅芬 ¹^,² , 郑楚均 ¹^,² , 温兆银 ¹^,²

硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1655-1671

收起

硅酸盐学报 |全固态电池发展专刊—综合评述 2025 , 53 (6) : 1655 -1671

全固态锂电池锂镧锆氧陶瓷电解质的强化与薄膜化

全屏

包成帅¹^,², 温佳杰¹, 吴梅芬¹^,², 郑楚均¹^,², 温兆银¹^,²

作者信息

^1．中国科学院上海硅酸盐研究所，能量转换材料重点实验室，上海 200050

^2．中国科学院大学，北京 100049

通讯作者:

温兆银（1963—），男，博士，研究员。

作者简介:

包成帅（1998—），男，博士研究生。

Strengthening and Thin-Filming of Garnet-Type Solid-State Electrolyte Ceramic Electrolyte for All-Solid-State Lithium Batteries

Chengshuai BAO¹^,², Jiajie WEN¹, Meifen WU¹^,², Chujun ZHENG¹^,², Zhaoyin WEN¹^,²

Affiliations

^1.CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 200050, China

^2.University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding Author:

WEN Zhaoyin (1963-), male, Ph.D., Professor. E-mail: zywen@mail.sic.ac.cn

BAO Chengshuai (1998-), male, Doctoral candidate. E-mail: baochengshuai@qq.com

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20250009

文章导航

摘要

收起

石榴石型固体电解质（LLZO）以其优异的热稳定性和耐高压性能、快速的锂离子传输特性以及对锂金属良好的兼容性，被认为是高安全性、高能量密度固态锂金属电池极具潜力的电解质材料。在LLZO陶瓷电解质微观结构中，晶界对电解质的离子电导率、电子电导率以及机械性能有重要的影响，这些因素进一步决定了电池的长期稳定性；将陶瓷电解质薄膜化是实现固态锂金属电池高能量密度的重要条件。本文综述了陶瓷晶界对电池体系的作用机制以及相应的改性策略，并对目前LLZO陶瓷电解质的薄膜化进展进行了总结，最后对LLZO陶瓷基电解质的未来发展趋势进行了展望，为推动LLZO陶瓷电解质在固态锂金属电池中的实际应用提供参考。

关键词

石榴石型固态电解质 / 晶界改性 / 电解质薄膜

Abstract

收起

With the rapid advancement of portable electronic devices, electric vehicles, and large-scale energy storage grids, next-generation rechargeable batteries with higher energy densities and enhanced safety have attracted much attention. Solid-state lithium metal batteries with high-safety solid-state electrolytes and lithium metal at the maximum specific capacity as an anode hold a tremendous potential for the next generation of rechargeable batteries. As a critical component of solid-state lithium metal batteries, solid-state electrolytes play a pivotal role in advancing their development. The existing solid-state electrolyte materials (i.e., organic polymer electrolytes, oxide electrolytes, sulfide electrolytes, and halide electrolytes) are systematically investigated, with the oxide solid-state electrolytes standing out due to their excellent overall performance. To achieve the practical application of oxide solid-state electrolytes, substantial research efforts are directed at modifying ceramic grain boundaries to improve ionic conductivity and mechanical properties and reduce electronic conductivity. Also, research on ceramic films is equally important to achieve a high energy density.

The sintering process of ceramics is a critical factor affecting material properties, especially for the improvement of grain boundary. Relative density, grain boundary strength, and ionic/electronic conductivity are dominant factors impacting the long-term stability of the battery, with relative density as the most fundamental performance of ceramic electrolyte that enables other characteristics to be manifested effectively. The regulation of the preparation process, including powder preparation method, ceramic sintering temperature, and atmosphere, can effectively enhance the ceramic relative density. The powder preparation route, in particular, has a considerable effect on the final properties of LLZO ceramic, such as grain size and size distribution, relative density, microstructure, and ionic/electronic conductivity. In the sintering, some parameters such as sintering temperature, dwelling time, pressure, and the lithium oxide atmosphere play a crucial role in promoting the densification of LLZO ceramic.

Atmospheric sintering is still the most common, simple, and low-cost method to prepare LLZO ceramics although it has a longer sintering time and a higher sintering temperature, compared to the pressurized sintering. The prolonged high-temperature process leads to lithium loss and the formation of impurity phases like La₂Zr₂O₇ in the electrolyte, which is detrimental to reducing the densification and ionic conduction behavior of the ceramics. To promote the densification and lower the sintering temperature, various kinds of sintering aids are adopted to assist the sintering process. A variety of low melting point additives, such as Li₃BO₃, LiO₂-B₂O₃-SiO₂-CaO-Al₂O₃, etc., are used as ceramic sintering aids. Subsequently, optimization of sintering processes and sintering aids are emerging, such as embedding-sintering, atmosphere-reversible control additives, lithium source-green body separation sintering, endogenous atmosphere sintering aids, etc.. LLZO ceramics sintered in the endogenous atmosphere with sintering additive of Li₆Zr₂O₇ can realize the densities of up to 97.21% in the absence of mother powder and under atmospheric pressure.

In highly densified LLZO ceramics, dendrite growth and even piercing of the ceramic sheet are still inevitable, indicating that dendrite growth is related to ceramic relative density and ionic conductivity and is also closely related to the electronic conductivity and fracture toughness of ceramics. Multifunctional additives are reported to regulate the compositions, microstructures, as well as physical and electrochemical properties at the internal grain boundaries of LLZO ceramic in addition to improving the relative density and ionic conductivity of the ceramics. Among them, (Li₂O)_0.733(ZrO₂)_0.267, Li₆Zr₂O₇, Li₂WO₄, Li₂CuO₂, LaTiO₃, etc., are considered as effective sintering additives.

To realize the high energy density of solid-state lithium metal batteries, thin-filming of ceramic electrolyte has attracted recent attention. Since the reduction of the thickness of LLZO ceramic leads to a decrease in the mechanical properties of the ceramics, a balance between the thickness and strength of the electrolyte is of great significance. Realizing the thin-film of LLZO ceramic through rational structural design is crucial to achieving a high energy density of solid-state batteries. In this case, ceramic films with different structures, such as single-layer dense ceramic, multilayer ceramic, and single-layer porous ceramic, are reported. A lithium-metal battery based on an interface-optimized 74 μm-thick single-layer dense LLZO ceramic has the excellent long-cycle stability of more than 800 cycles. A lithium-symmetric battery based on an optimized 115 μm-thick multilayer ceramic exhibits an ultra-high critical current density of 100 mA·cm^-2. A 12 μm-thick single-layer porous ceramic composited with a polymer electrolyte is expected to achieve energy densities of greater than 350 W·h·kg^-1. In addition, the quality of the green body (i.e., uniformity, flatness, and residual stress) and the sintering regime have a significant effect on the phase purity, ionic conductivity, surface state, and film flatness of LLZO after sintering due to the high sintering temperature of LLZO as well as the volatile properties of Li, La, Zr, and O in the composition. Therefore, some novel preparation processes to prepare ceramic films are developed in recent years. In particular, the combination of tape-casting and ultrafast-sintering has a promising application in the preparation of LLZO ceramic films.

Summary and prospects

Although significant progress is made in the development of garnet-type solid-state electrolytes, their practical application in all-solid-state lithium batteries still faces challenges. Future research should focus on some key issues, i.e., the application of artificial intelligence and high-throughput computing in ceramic sintering additives, the development of new preparation methods for ceramic thin films, and the preparation, evaluation, and analysis of the full battery. Moreover, it is essential for the practical application of ceramic-based solid-state lithium metal batteries to simultaneously adapt testing standards, characterization techniques and failure analysis methods.

Key words

garnet-type solid-state electrolyte / grain boundary / electrolyte film

引用本文

包成帅, 温佳杰, 吴梅芬, 郑楚均, 温兆银. 全固态锂电池锂镧锆氧陶瓷电解质的强化与薄膜化. 硅酸盐学报, 2025 , 53 (6) : 1655 -1671 . DOI: 10.14062/j.issn.0454-5648.20250009

Chengshuai BAO, Jiajie WEN, Meifen WU, Chujun ZHENG, Zhaoyin WEN. Strengthening and Thin-Filming of Garnet-Type Solid-State Electrolyte Ceramic Electrolyte for All-Solid-State Lithium Batteries[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1655 -1671 . DOI: 10.14062/j.issn.0454-5648.20250009

基金

收起

国家自然科学基金区域联合基金重点项目(U20A20248)
国家重点研发计划(2022YFB3807700)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2025年第53卷第6期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20250009

接收时间：2025-01-03
首发时间：2026-10-22
出版时间：2025-06-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2025-01-03
修回日期：2025-01-23

基金

国家自然科学基金区域联合基金重点项目(U20A20248)

国家重点研发计划(2022YFB3807700)

作者信息

^1．中国科学院上海硅酸盐研究所，能量转换材料重点实验室，上海 200050

^2．中国科学院大学，北京 100049

通讯作者:

温兆银（1963—），男，博士，研究员。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250009

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

关闭全屏

BibTeX
EndNote
RefWorks
TxT