LATP、LAGP固态电解质材料合成改性路线研究现状及展望

doi:10.19799/j.cnki.2095-4239.2024.0459

摘要/Abstract

摘要：

固态电解质作为固态电池的关键组件，因其能够匹配高比容量的正、负极材料，实现更高的能量密度，并从根本上解决液态锂离子电池的安全隐患，而备受关注。其中，NASICON型的Li₁₊_x Al _x Ti_2-_x (PO₄)₃(LATP，0≤ x≤0.5)和Li₁₊_x Al _x Ge_2-_x (PO₄)₃(LAGP，0≤x≤0.5)氧化物固态电解质，因其出色的空气稳定性、高离子电导率、低廉的原料成本以及温和的合成条件，成为固态电解质商业化的有力竞争者。然而，传统的实验合成和改性优化方法研发成本高、周期长、效率低。理解LATP/LAGP中离子输运机制，探索材料合成新方法，提高材料研发的效率是当前研究的重点。本文详细探讨了LATP/LAGP材料的晶体结构、离子传导机制、合成制备技术、性能提升策略以及机器学习辅助材料合成等方面的研究进展。此外，通过综合分析合成成本与产物性能，总结了具有工业化潜力的合成优化路径，并结合具体实例展示了机器学习在固态电解质领域的广阔应用前景。最后，文章还分析了当前LATP、LAGP固态电解质研究中存在的不足，并从基础研究、工程应用和商业化推广三个维度展望了未来的发展方向。

关键词: LATP/LAGP固态电解质, Li⁺传输机理, 合成方法, 掺杂改性, 机器学习

Abstract:

Solid-state electrolytes are essential components of solid-state batteries, garnering significant attention for their potential to pair effectively with high-capacity cathode and anode materials, enhance energy density, and address the safety issues inherent in liquid lithium-ion batteries. Among these, NASICON-type oxide solid electrolytes, such as Li₁₊_x Al _x Ti_2-_x (PO₄)₃ (LATP, 0 ≤ x ≤ 0.5) and Li₁₊_x Al _x Ge_2-_x (PO₄)₃ (LAGP, 0 ≤ x ≤ 0.5), stand out due to their excellent air stability, high ionic conductivity, low-cost raw materials, and favorable synthesis conditions, making them strong candidates for commercial applications. However, traditional methods for optimizing synthesis and modification are often costly, time-consuming, and inefficient. Current research focuses on elucidating ion transport mechanisms, exploring novel synthesis techniques, and enhancing the efficiency of material development for LATP and LAGP. This paper reviews the advancements in LATP and LAGP research, including their crystal structures, ion conduction mechanisms, synthesis methods, performance enhancement strategies, and the integration of machine learning in material synthesis. By evaluating synthesis costs and product performance, the study identifies optimal synthesis pathways with potential for industrial application. Specific examples illustrate the promising role of machine learning in advancing the field of solid-state electrolytes. The paper concludes with an analysis of existing research gaps and outlines future directions for basic research, engineering applications, and commercial promotion of LATP and LAGP solid-state electrolytes.

Key words: LATP/LAGP solid-state electrolytes, Li⁺ transport mechanism, synthesis methods, doping modification, machine learning

中图分类号:

TM 911

陈桢, 李贤傲, 徐艺维, 刘欣, 申泽骧, 陈明华. LATP、LAGP固态电解质材料合成改性路线研究现状及展望[J]. 储能科学与技术, 2024, 13(11): 3826-3855.

Zhen CHEN, Xian'ao LI, Yiwei XU, Xin LIU, Zexiang SHEN, Minghua CHEN. Current research status and future prospects of the synthesis and modification routes for LATP and LAGP solid electrolytes[J]. Energy Storage Science and Technology, 2024, 13(11): 3826-3855.

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合成方法	特点	应用前景
熔融淬火法	工艺简单、致密度高、原料成本低且安全、能耗大、粉末粒径较大、易产生二次相、不易扩大规模	性能要求不高，但对成本敏感的领域
高温固相反应法	工艺简单、致密度高、原料成本低且安全、能耗适中、粉末粒径适中、相纯度适中、可实现量产	性能与成本折中的领域，市场前景广
溶胶-凝胶法	工艺复杂、致密度适中、原料成本昂贵且有毒、能耗低、粉末粒径小、相纯度高、量产难度大	生产成本较高，生产过程污染环境，大规模量产难度大
共沉淀法	工艺相对简单、致密度适中、原料成本适中且安全、能耗低、粉末粒径小、相纯度较高、可实现量产	性能与成本折中的领域，市场前景广
水热合成法	工艺相对简单、生产环境要求高、致密度适中、原料成本适中、能耗适中、粉末粒径小、相纯度高、量产难度大	对材料性能要求高，小规模生产或实验室研究

电解质	合成方法	烧结工艺	压片压力/MPa	密度 /(g/cm³)	离子电导率 /(mS/cm)	活化能 /eV	参考文献
LAGP	熔融淬火	800 ℃; 5 h	20	3.427	0.164	0.3	[54]

LATP	熔融淬火	850 ℃; 6 h	—	—	约0.1	0.325	[55]

LAGP	熔融淬火	800 ℃; 6 h	500	—	—	—	[56]

LATP	熔融淬火	1000 ℃;SPS 5 min	50	2.819	0.12	—	[59]
	溶胶凝胶	850 ℃;SPS 5 min	50	2.796	0.21	—
	混合前驱体	1000 ℃;SPS 5 min	50	2.921	1	—

LATP	熔融淬火	1000 ℃; SPS 5 min	50	2.819	0.12	—	[57]

LATP	熔融淬火	900 ℃; SPS 10 min	70	2.842	0.076	—	[95]

LATP	溶胶凝胶	650 ℃; SPS 8 min	45	2.94	1.12	0.25	[108]
LATP	溶胶凝胶	850 ℃;6 h	200	2.793	0.36	0.31	[108]

LATP	固相反应法	UHS 20A 100 s	200	2.652	0.467	0.249	[104]
LATP	固相反应法	900 ℃; 6 h	200	2.511	0.389	0.303	[104]

LAGP	固相反应法	UHS 19A 160 s	500	3.37	0.172	—	[103]
LAGP	固相反应法	850 ℃; 12 h	500	3.326	0.161	—	[103]

LAGP	熔融淬火	冷烧结120 ℃; 20 min 650 ℃; 5 min	400	2.71	0.0549	0.4	[107]

LAGP	固相反应法	900 ℃; 6 h	—	—	0.39	—	[63]

LATP	固相反应法	900 ℃; 10 h	—	—	0.15	0.36	[60]

LATP	固相反应法	950 ℃; 6 h	—	2.824	0.344	—	[66]

LATP	固相反应法	750 ℃	400	2.646	0.667	—	[67]

LATP	固相反应法	950 ℃; 3 h	200	2.705	0.215	0.398	[61]
LATP	溶胶凝胶	950 ℃; 3 h	200	2.793	0.413	0.364	[61]

LATP	溶胶凝胶	950 ℃; 6 h	200	2.852	2.09	0.29	[68]

LAGP	溶胶凝胶	900 ℃; 8 h	—	—	0.418	0.3	[71]

LATP	溶液辅助固相反应法	900℃; 5h	75	2.626	0.62	0.33	[93]

LATP	共沉淀法	900 ℃; 6 h	200	2.811	0.219	0.32	[77]

LAGP	共沉淀法	950 ℃; 10 h	6	—	0.587	—	[76]

LATP	共沉淀法	1050 ℃; 6 h	—	—	0.2	0.28	[79]

LATP	共沉淀法	900 ℃; 6 h	200	2.852	2.19	0.35	[78]

LATP	水热合成	900 ℃; 6 h	—	—	0.265	0.216	[81]

LATP	水热合成	1000 ℃; 12 h	20	2.86	0.481	0.3	[82]

LATP	水热合成	900 ℃; 3 h 1100 ℃; 3 h	—	2.913	2.7	0.17	[83]

LATP	水热合成	850 ℃; 2 h	—	—	0.48	—	[40]

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