钠离子电池有机正极补钠剂研究进展

doi:10.19799/j.cnki.2095-4239.2025.0921

摘要/Abstract

摘要：

钠离子电池预钠化技术提供活性钠离子的第二来源，抵消首次充电时负极不可逆的钠离子损失，进而提升正极材料利用率，有效缓解能量密度偏低问题。在众多预钠化技术中，有机正极补钠法环境适应性强，无需严格控制环境湿度，是推动预钠化技术大规模应用的理想选择。本文系统梳理并分析了已发表的有机正极补钠剂。根据官能团特征，本文将补钠剂划分为羧酸钠盐和酚钠盐两大类别，逐一介绍其核心特性，并从比容量、分解电压、反应产物、原材料价格等指标横向对比，清晰呈现各种补钠剂优劣。本文针对研究广泛的羧酸钠盐，深入剖析其补钠机理，详细阐释钠离子释放、有机阴离子失电子及重排的全过程，为理解作用机制提供思路。本文讨论了有机正极补钠剂分解产气和残留等关键问题。同时，本文介绍了主流改善方案：碳复合技术增强导电性，纳米化处理增大反应活性，双层涂布技术改善电极结构稳定性，为性能及应用优化提供可行路径。最后，提出未来有机正极补钠剂开发的设计原则，涵盖性能、工艺和成本等维度，期望为相关技术研发与应用提供指导。

关键词: 钠离子电池, 预钠化, 有机正极补钠剂

Abstract:

The pre-sodiation technology for sodium-ion batteries supplies an additional source of active sodium ions to compensate for the irreversible consumption of sodium ions at the anode during the first cycle. As a result, it improves the utilization efficiency of cathode active materials and alleviates the issue of low energy density. Among various pre-sodiation techniques, the organic sacrificial salts in Cathodes is particularly attractive due to its high environmental adaptability and does not require strict control of ambient humidity, making it a highly suitable candidate for large-scale implementation of pre-sodiation.This review focuses on organic sacrificial salts in Cathodes, systematically surveying and analyzing the relevant published literature. Based on the characteristics of functional groups, these organic sacrificial salts in Cathodes are categorized into two groups: sodium carboxylates and sodium phenoxides. The key characteristics of each type are introduced, and a comparative analysis is performed using metrics such as specific capacity, decomposition voltage, reaction products, and raw material cost, thereby highlighting the strengths and limitations of each category. Particular attention is given to sodium carboxylates, one of the most extensively studied classes, with an in-depth discussion of their compensation mechanism covering sodium ion release, oxidation of organic anions, and subsequent structural rearrangement to provide fundamental insights into the operational principles of such materials. Critical challenges associated with organic sacrificial salts in Cathodes, including gas evolution and residue formation upon decomposition, are also addressed. Furthermore, this review outlines mainstream strategies for performance enhancement, such as carbon compositing to improve electrical conductivity, nanonization to boost reactivity, and double-layer coating to reinforce electrode stability. These approaches offer viable routes for optimizing the performance and practicality of organic sacrificial salts in Cathodes. Finally, we propose design principles for future organic sacrificial salts in Cathodes, emphasizing performance, process compatibility and cost, which are expected to guide further research and development in this field.

Key words: Sodium-ion Battery, Pre-sodiation Strategies, Organic Sacrificial Salts in Cathodes

中图分类号:

TM912

王珂, 许斯奋, 邹庭丰. 钠离子电池有机正极补钠剂研究进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0921.

Ke Wang, Sifen Xu, Tingfeng Zou. Research Progress on Organic Sacrificial Salts in Cathodes for Sodium-Ion Batteries[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0921.

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补钠剂类型	化合物	环境稳定性	比容量	总结
无机补钠剂	Na₂O/ Na₂O₂/ Na₃P/ Na₂S/ NaBH₄/ NaNH₂/ Na₂NiO₂ NaCrO₂/ Na₃PS₃O	遇水分解，干燥无法恢复活性	比容量243-864 mAh·g^-1	比容量较高，大部分遇水分解，干燥也无法恢复活性。
无机补钠剂	NaN₃/ Na₂CO₃/ NaNO₂	遇水再干燥后恢复活性	比容量243-864 mAh·g^-1	比容量较高，大部分遇水分解，干燥也无法恢复活性。
有机补钠剂	CHO₂Na/ C₂H₃O₂Na/ C₃H₅O₂Na / Na₂C₂O₄/ C₃H₂O₄Na₂/ C₄H₄O₄Na₂/ C₅H₆O₄Na₂/ C₂H₄NO₂Na/ C₄H₅NO₄Na₂/ C₅H₇NO₄Na₂/ C₁₀H₁₂N₂O₈Na₄·4H₂O/ C₁₄H₁₈N₃O₁₀Na₅/ Na₂C₃O₅/ C₄H₄Na₂O₅/ C₄H₄Na₂O₅/ C₆H₅Na₃O₇/ Na₂C₄O₄/ Na₂C₆O₆	遇水再干燥可恢复活性（可以在水溶液中合成）	比容量266-400 mAh·g^-1	比容量较低，绝大部分遇水再干燥可恢复活性。
有机补钠剂	Na₂C₆H₄O₂	易被空气氧化	比容量266-400 mAh·g^-1	比容量较低，绝大部分遇水再干燥可恢复活性。

名称	化学式	CAS	摩尔质量（g·mol^-1）	理论比容量(mAh·g^-1)	实测分解电压（V）	参考文献
甲酸钠	CHO₂Na	141-53-7	68.01	394.1	4.19-4.29	^[41]
乙酸钠	C₂H₃O₂Na	127-09-3	82.03	326.7	4.00-4.18	^[42]
丙酸钠	C₃H₅O₂Na	137-40-6	96.06	279.0	4.10	^[41]
草酸钠	Na₂C₂O₄	62-76-0	134.00	400.0	3.70-4.41	^[41,43-45]
丙二酸钠	C₃H₂O₄Na₂	141-95-7	148.03	362.1	3.82-3.98	^[41,46]
丁二酸钠	C₄H₄O₄Na₂	150-90-3	162.05	330.8	4.39	^[47]
戊二酸钠	C₅H₆O₄Na₂	13521-83-0	176.08	304.4	4.30	^[48]

名称	化学式	CAS	摩尔质量(g·mol^-1）	理论比容量(mAh·g^-1)	实测分解电压(V)	参考文献
氨基乙酸钠	C₂H₄NO₂Na	6000-44-8	97.05	276.1	3.85	^[49]
亚氨基二乙酸二钠	C₄H₅NO₄Na₂	928-72-3	177.06	302.7	3.82	^[48]
N-甲基亚氨二乙酸二钠	C₅H₇NO₄Na₂	/	191.09	280.5	3.60	^[48]
四水合乙二胺四乙酸四钠	C₁₀H₁₂N₂O₈Na₄·4H₂O	64-02-8	380.17	282.0	3.80	^[50]
二乙烯三胺五乙酸五钠	C₁₄H₁₈N₃O₁₀Na₅	140-01-2	503.26	266.3	4.00	^[51]

名称	化学式	CAS	摩尔质量(g·mol^-1）	理论比容量(mAh·g^-1)	实测分解电压(V)	参考文献
中草酸钠	Na₂C₃O₅	7346-13-6	162.01	330.8	4.00	^[53-54]
二甘醇酸二钠	C₄H₄Na₂O₅	/	178.05	301.0	4.35	^[48]
羟基丁二酸二钠	C₄H₄Na₂O₅	676-46-0	178.05	301.0	4.05	^[47]
柠檬酸三钠	C₆H₅Na₃O₇	68-04-2	258.07	311.5	4.02	^[55]

名称	化学式	CAS	摩尔质量(g·mol^-1）	理论比容量(mAh·g^-1)	实测分解电压(V)	参考文献
方酸钠	Na₂C₄O₄	/	158.02	339.2	3.60	^[57-59]
玫棕酸钠	Na₂C₆O₆	523-21-7	214.04	250.4	3.75	^[60-61]
邻苯二酚钠	Na₂C₆H₄O₂	/	154.07	347.9	2.40	^[62]