基于固态电解质的熔融碱金属电池研究进展

doi:10.3866/PKU.WHXB202301009

摘要/Abstract

摘要：

电池技术的发展对于可再生能源的应用非常重要。近年来基于固态电解质的熔融碱金属电池展现出应用于大规模储能系统的潜力。本文介绍基于beta-Al₂O₃和NASICON电解质的熔融钠电池(SELS电池)和基于石榴石型电解质的熔融锂电池(SELL电池)。固态电解质的结构和成分会显著影响其电导率和稳定性。因此，固态电解质的新型制备方法、掺杂技术以及表面改性技术是该领域的研究重点。截至目前，铅合金、金属氯化物、硫、硒和碘等材料已被证明可以作为SELS和SELL电池的正极，相应的电池体系具有不同的电化学性能、材料成本以及应用场景。本文对它们进行系统的归纳与比较。值得注意的是，SELS电池已经实现数百兆瓦时规模的储能系统应用，而SELL电池的技术成熟度仍然较低。但是，具有高能量密度、低运行温度以及制造成本的SELL电池具有良好的应用前景。同时，这两种电池的许多研究进展和技术成果可以共享，从而促进该领域的迅速发展。

关键词: 高温电池, 固态电解质, 电网储能, beta-氧化铝电解质, NASICON电解质, 石榴石型电解质

Abstract:

The development of energy storage technologies with high safety, low cost, and high energy densities is essential for the widespread use of renewable energy sources. Battery technology is one of the most promising candidates because of its pollution-free operation, high round-trip efficiency, flexible power and energy characteristics, long cycle life, and low maintenance cost. Although most batteries operate at room temperature, high-temperature systems are expected to perform better owing to improved electrolyte conductivity, faster reaction kinetics, and reduced interface impedance. The reported high-temperature batteries can be classified into liquid and solid electrolyte-based systems, with the latter having the potential to achieve higher energy densities while avoiding self-discharge effects. This review summarizes solid electrolyte-based liquid sodium and lithium batteries (SELS and SELL batteries). SELS batteries primarily use beta-Al₂O₃ and NASICON electrolytes, while SELL battery systems use garnet electrolytes. Because the microstructures and compositions of ceramic electrolytes significantly affect their conductivity and stability, novel manufacturing and element doping methods are being intensively investigated. Surface modification technology is also a major research focus to improve the wetting properties of molten alkali metals on the ceramic electrolyte, which assists to decrease interfacial resistance and increase the rate performance and power density of the battery. In addition, the selection of the cathode materials of SELS and SELL batteries has a significant impact on the energy and power densities, cycling stability, material cost, and application scenarios of the real devices. Until now, lead alloys, metal chlorides, sulfur, selenium, and iodine have been reported as potential choices. We describe in detail the reaction mechanisms, existing problems, and the latest research progress of these battery systems, with their electrochemical performance and raw material costs systematically summarized and compared. It is worth noting that the SELS and SELL batteries have different levels of technological maturity. In 2019, an energy storage system using SELS batteries with a capacity of 108 MW/648 MWh was built, whereas SELL battery research is a relatively emerging field. However, SELL batteries demonstrate promising application prospects because of their higher energy densities, lower operating temperatures, and competitive raw material costs. In addition, we believe that several research advancements and technical achievements related to these two types of batteries can be shared, with the future research directions listed in the conclusion section.

Key words: High-temperature battery, Solid electrolyte, Grid-scale energy storage, beta-Al₂O₃ electrolyte, NASICON electrolyte, Garnet electrolyte

王匡宇, 刘凯, 伍晖. 基于固态电解质的熔融碱金属电池研究进展[J]. 物理化学学报, 2023, 39(12), 2301009. doi: 10.3866/PKU.WHXB202301009

Kuangyu Wang, Kai Liu, Hui Wu. Molten Alkali Metal Batteries Based on Solid Electrolytes[J]. Acta Phys. -Chim. Sin. 2023, 39(12), 2301009. doi: 10.3866/PKU.WHXB202301009

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202301009

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I12/2301009

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	Battery type	Battery voltage (V)	Theoretical energy density (Wh∙kg⁻¹) ^a	Active material cost ($∙kWh⁻¹) ^b	Operating temperature (℃)
SELS battery	SELS-S	1.80	1236	1.2	300–350
	SELS-NiCl₂	2.58	788	14.8	270–350
	SELS-FeCl₂	2.35	729	0.7	270–350
	SELS-ZnCl₂	2.00	588	2.6	260
	SELS-NaI₃	3.30	393	60.0	110
SELL battery	SELL-Sn/Pb	0.72	73	339	240
	SELL-Bi/Pb	0.80	75	112.1	240
	SELL-AlCl₃	1.65	861	16.7	210
	SELL-brass/ZnCl₂	2.20	785	13.5	250
	SELL-Mo/FeCl₂	2.37	903	11.0	250
	SELL-S	2.00	2333	13.0	240–300
	SELL-Se	2.10	1212	29.9	240–300
	SELL-I₂	2.70	541	53.4	260

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