钠离子电池正极预钠化技术进展

doi:10.19799/j.cnki.2095-4239.2024.1085

摘要/Abstract

摘要：

钠离子电池凭借原材料来源广泛、成本低廉等优势，被视作下一代非常重要的电化学储能技术。预钠化技术可通过引入额外的钠源，对首周充电时因生成界面而不可逆消耗的钠离子进行有效补充，进而有效提升电池的循环寿命与能量密度，在钠离子电池实际生产应用中具有重要价值。预钠化技术主要分为负极预钠化技术和正极预钠化技术，正极预钠化技术里的自牺牲型补钠剂预混法，因其操作简便，无需额外增添设备，有利于大规模推广。本文首先简单介绍了补钠剂的分类，然后梳理了这一方法在实际生产应用过程中存在的问题，具体涵盖生产储存环节的安全性与稳定性问题、电极制造过程中补钠剂的碱性以及粒径大小的问题，还有电池循环时分解电位过高、分解产物及其分解后对极片产生的影响等问题。随后本文归纳了近年来预钠化相关文献与专利中对应的解决方案，还对这一方法在无负极钠电池中的应用情况作了介绍。最后，本文对未来补钠剂的开发提出了相应的设计原则，并有望为正极预钠化技术的应用提供一定的指导与启发。

关键词: 钠离子电池, 预钠化, 自牺牲型补钠剂, 专利分析

Abstract:

Sodium-ion batteries are regarded as one of the crucial next-generation electrochemical energy storage technologies due to the advantages such as the wide availability of raw materials and low cost. The presodiation technique can effectively replenish the sodium ions that are irreversibly consumed due to the formation of the interface during the first-cycle charging by introducing an additional sodium source, and thus can effectively improve the cycle life and energy density of the batteries. It holds significant value in the practical production and application of sodium-ion batteries.The presodiation technique is mainly divided into anode presodiation technique and cathode presodiation technique. The self-sacrificial sodium supplement agent pre-mixing method within the cathode presodiation technique, due to its simple operation and without the necessity of adding extra equipment, is conducive to large-scale promotion. This article first briefly introduces the classification of sodium supplement agents. Then, it sorts out the problems existing in the practical production and application process of the self-sacrificial sodium supplement agent pre-mixing method. Specifically, these problems cover the safety and stability issues in the production and storage stage, the alkalinity and particle size aspects of the sodium supplement agent in the electrode manufacturing process, as well as issues such as excessive decomposition potential during battery cycling, decomposition products and their impacts on the electrode sheet after decomposition. Subsequently, this article summarizes the corresponding solutions in the presodiation-related literature and patents in recent years. Moreover, it also presents an introduction to the application of this method in anode-free sodium-metal batteries. Finally, this article puts forward corresponding design principles for the future development of sodium supplement agents and is expected to provide certain guidance and inspiration for the application of the cathode presodiation technique.

Key words: Sodium-ion batteries, Presodiation, Self-sacrificial sodiation supplement agents, Patent analysis

中图分类号:

TM 912

李昱, 李丹丹, 谢飞, 唐彬, 容晓晖, 梁沁沁, 胡勇胜. 钠离子电池正极预钠化技术进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2024.1085.

Yu Li, Dandan Li, Fei Xie, bin Tang, Xiaohui Rong, Qinqin Liang, Yongsheng Hu. Recent progress of cathode presodiation strategies in sodium ion batteries[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2024.1085.

图/表 6

图1

图2

图3

图4

图5

图6

参考文献 44

1	DUNN B, KAMATH H, TARASCON J-M. Electrical energy storage for the grid: a battery of choices [J]. Science, 2011, 334(6058): 928-35.
2	YANG Z, ZHANG J, KINTNER-MEYER M C, et al. Electrochemical energy storage for green grid [J]. Chemical reviews, 2011, 111(5): 3577-613.
3	ARMAND M, TARASCON J-M. Building better batteries [J]. nature, 2008, 451(7179): 652-7.
4	GOODENOUGH J B, PARK K-S. The Li-ion rechargeable battery: a perspective [J]. Journal of the American Chemical Society, 2013, 135(4): 1167-76.
5	WHITTINGHAM M S. Lithium batteries and cathode materials [J]. Chemical reviews, 2004, 104(10): 4271-302.
6	HU Y-S, LI Y. Unlocking sustainable Na-ion batteries into industry [Z]. ACS Publications. 2021: 4115-7
7	XIE F, LU Y-X, CHEN L-Q, et al. Recent Progress in Presodiation Technique for High-Performance Na-Ion Batteries [J]. Chinese Physics Letters, 2021, 38(11): 136-43.
8	LIU X, TAN Y, LIU T, et al. A simple electrode‐level chemical presodiation route by solution spraying to improve the energy density of sodium‐ion batteries [J]. Advanced Functional Materials, 2019, 29(50): 1903795.
9	LIU M, ZHANG J, GUO S, et al. Chemically presodiated hard carbon anodes with enhanced initial coulombic efficiencies for high-energy sodium ion batteries [J]. ACS applied materials & interfaces, 2020, 12(15): 17620-7.
10	WANG H, XIAO Y, SUN C, et al. A type of sodium-ion full-cell with a layered NaNi 0.5 Ti 0.5 O 2 cathode and a pre-sodiated hard carbon anode [J]. RSC Advances, 2015, 5(129): 106519-22.
11	PI Y, GAN Z, YAN M, et al. Insight into pre-sodiation in Na3V2 (PO4) 2F3/C@ hard carbon full cells for promoting the development of sodium-ion battery [J]. Chemical Engineering Journal, 2021, 413: 127565.
12	MOEEZ I, JUNG H-G, LIM H-D, et al. Presodiation strategies and their effect on electrode–electrolyte interphases for high-performance electrodes for sodium-ion batteries [J]. ACS applied materials & interfaces, 2019, 11(44): 41394-401.
13	ZHANG B, DUGAS R, ROUSSE G, et al. Insertion compounds and composites made by ball milling for advanced sodium-ion batteries [J]. Nature communications, 2016, 7(1): 10308.
14	DE ILARDUYA J M, OTAEGUI L, DEL AMO J M L, et al. NaN3 addition, a strategy to overcome the problem of sodium deficiency in P2-Na0. 67 [Fe0. 5Mn0. 5] O2 cathode for sodium-ion battery [J]. Journal of Power Sources, 2017, 337: 197-203.
15	ZHANG Q, GAO X-W, SHI Y, et al. Electrocatalytic-driven compensation for sodium ion pouch cell with high energy density and long lifespan [J]. Energy Storage Materials, 2021, 39: 54-9.
16	SATHIYA M, THOMAS J, BATUK D, et al. Dual stabilization and sacrificial effect of Na2CO3 for increasing capacities of Na-ion cells based on P2-Na x MO2 electrodes [J]. Chemistry of Materials, 2017, 29(14): 5948-56.
17	SHEN B, ZHAN R, DAI C, et al. Manipulating irreversible phase transition of NaCrO2 towards an effective sodium compensation additive for superior sodium-ion full cells [J]. Journal of colloid and interface science, 2019, 553: 524-9.
18	PARK K, YU B-C, GOODENOUGH J B. Electrochemical and chemical properties of Na2NiO2 as a cathode additive for a rechargeable sodium battery [J]. Chemistry of Materials, 2015, 27(19): 6682-8.
19	SHANMUKARAJ D, KRETSCHMER K, SAHU T, et al. Highly efficient, cost effective, and safe sodiation agent for high‐performance sodium‐ion batteries [J]. ChemSusChem, 2018, 11(18): 3286-91.
20	PAN X, CHOJNACKA A, BéGUIN F. Advantageous carbon deposition during the irreversible electrochemical oxidation of Na2C4O4 used as a presodiation source for the anode of sodium-ion systems [J]. Energy Storage Materials, 2021, 40: 22-30.
21	NIU Y B, GUO Y J, YIN Y X, et al. High‐efficiency cathode sodium compensation for sodium‐ion batteries [J]. Advanced Materials, 2020, 32(33): 2001419.
22	YANG Y, WANG Z, DU C, et al. Decoupling the air sensitivity of Na-layered oxides [J]. Science, 2024, 385(6710): 744-52.
23	聂阳. 一种负极补钠添加剂、负极材料及钠离子电池, CN110707308B [P/OL].
	NIE Y. A sodium-supplementing additive for negative electrodes, a negative electrode material and a sodium-ion battery, CN110707308B [P/OL].
24	徐凯琪, 门双, 钟国彬, 等. 一种钠离子电池负极补钠添加剂、钠离子电池负极极片和钠离子电池, CN110690437B [P/OL].
	XU K Q, MEN S, ZHONG G B, et al. A Sodium-supplementing Additive for the Negative Electrode of Sodium-ion Batteries, a Negative Electrode Plate of Sodium-ion Batteries and Sodium-ion Batteries, CN110690437B [P/OL].
25	乔齐齐, 王鹏飞, 施泽涛, 等. 一种补锂或补钠的添加剂及其制备方法和应用, CN116454281A [P/OL].
	QIAO Q Q, WANG P F, SHI Z T, et al. An additive for lithium or sodium supplementation, its preparation method and application, CN116454281A [P/OL].
26	张帅帅, 谢芳, 王卫江, 等. 一种补锂或补钠材料的制备方法及其所得产品和应用, CN116344819A [P/OL].
	ZHANG S S, XIE F, WANG W J, et al. A preparation method for a lithium or sodium supplementing material, the resulting product thereof and its application, CN116344819A [P/OL].
27	杨雪, 谢芳, 张帅帅. 正极补钠添加剂及其制备方法和应用, CN116111072A [P/OL].
	YANG X, XIE F, ZHANG S S. A sodium-supplementing additive for the positive electrode, its preparation method and application, CN116111072A [P/OL].
28	李魁, 曾伟雄, 李尚. 一种纳米草酸钠复合的正极活性材料及其应用, CN115954445B [P/OL].
	LI K, ZENG W X, LI S. A nano-sodium oxalate-composited positive electrode active material and its application, CN115954445B [P/OL].
29	ZHANG T, KONG J, SHEN C, et al. Converting Residual Alkali into Sodium Compensation Additive for High-Energy Na-Ion Batteries [J]. ACS Energy Letters, 2023, 8(11): 4753-61.
30	王海燕, 张睿, 唐有根, 等. 一种钠离子电池正极补钠添加剂、补钠方法、正极、柔性电极, CN114566650B [P/OL].
	WANG H Y, ZHANG R, TANG Y G, et al. A sodium-supplementing additive for the positive electrode of sodium-ion batteries, a sodium-supplementing method, a positive electrode and a flexible electrode, CN114566650B [P/OL].
31	董少海, 肖厚文, 米源, 等. 一种提升钠离子电池首次库伦效率和能量密度的方法、正极浆料、正极片和钠离子电池, CN116646460A [P/OL].
	DONG S H, XIAO H W, MI Y, et al. A method for improving the initial Coulombic efficiency and energy density of sodium-ion batteries, a positive electrode slurry, a positive electrode sheet and sodium-ion batteries, CN116646460A [P/OL].
32	周勇, 尚佩, 吴志荣, 等. 一种钠离子电池正极片及其制备方法及钠离子电池, CN116190570A [P/OL].
	ZHOU Y, SHANG P, WU Z R, et al. A positive electrode sheet for sodium-ion batteries, its preparation method and sodium-ion batteries, CN116190570A [P/OL].
33	请求不公布姓名, 刘静, 请求不公布姓名, 等. 一种钠离子电池正极浆料、正极极片、电池、制备方法, CN115663179A [P/OL].
	Request for anonymity, LIU J, Request for anonymity, et al. A positive electrode slurry for sodium-ion batteries, a positive electrode plate, a battery and a preparation method thereof, CN115663179A [P/OL].
34	张国栋, 王巍, 文佳琪. 复合补钠材料及制备方法、正极极片、钠电池、用电设备, CN116826060B [P/OL].
	ZHANG G D, WANG W, WEN J Q. Composite sodium-supplementing materials and their preparation method, positive electrode plates, sodium batteries and electrical equipment, CN116826060B [P/OL].
35	CHEN Y, ZHU Y, SUN Z, et al. Achieving High‐Capacity Cathode Presodiation Agent Via Triggering Anionic Oxidation Activity in Sodium Oxide [J]. Advanced Materials, 2024, 36(36): 2407720.
36	杨行, 张庆, 戚兴国, 等. 一种预钠化正极极片及其应用以及一种钠离子电池及其制备方法, CN114649504A [P/OL].
	YANG X, ZHANG Q, QI X G, et al. A pre-sodiated positive electrode plate and its application as well as a sodium-ion battery and its preparation method, CN114649504A [P/OL].
37	李静如, 赵子萌, 王世冠, 等. 补钠材料及其制备方法、正极极片、电极组件、电池和用电装置, CN116789191B [P/OL].
	LI J R, ZHAO Z M, WANG S G, et al. Sodium-supplementing materials, their preparation methods, positive electrode plates, electrode assemblies, batteries and electrical devices, CN116789191B [P/OL].
38	文佳琪, 黄汉川, 王巍. 补钠组合物、正极极片及其制备方法、钠离子电池, CN116706075B [P/OL].
	WEN J Q, HUANG H C, WANG W. Sodium-supplementing compositions, positive electrode plates and their preparation methods, sodium-ion batteries, CN116706075B [P/OL].
39	CAO M, XU L, GUO Y, et al. Air‐Stable Na3. 5C6O6 as a Sodium Compensation Additive in Cathode of Na‐Ion Batteries [J]. Small, 2024, 20(42): 2400498.
40	LIU X, TAN Y, WANG W, et al. Ultrafine sodium sulfide clusters confined in carbon nano-polyhedrons as high-efficiency presodiation reagents for sodium-ion batteries [J]. ACS Applied Materials & Interfaces, 2021, 13(23): 27057-65.
41	GUO Y-J, NIU Y-B, WEI Z, et al. Insights on electrochemical behaviors of sodium peroxide as a sacrificial cathode additive for boosting energy density of Na-ion battery [J]. ACS Applied Materials & Interfaces, 2021, 13(2): 2772-8.
42	聂阳, 孔权, 徐雄文. 一种补钠组合物及钠离子电池, CN115117558A [P/OL].
	NIE Y, KONG Q, XU X W. A sodium-supplementing composition and sodium-ion batteries, CN115117558A [P/OL].
43	ZHANG Y-Y, ZHANG C-H, GUO Y-J, et al. Refined Electrolyte and Interfacial Chemistry toward Realization of High-Energy Anode-Free Rechargeable Sodium Batteries [J]. Journal of the American Chemical Society, 2023, 145(47): 25643-52.
44	江卫军, 周世波, 郝雷明, 等. 一种钠离子电池及其制备方法, CN114583174B [P/OL].
	JIANG W J, ZHOU S B, HAO L M, et al. A sodium-ion battery and its preparation method, CN114583174B [P/OL].

[1]	郝定邦, 栗永利. 高倍率和长循环稳定性钠离子电池正极材料Na_0.85Ni_0.3Fe_0.2Mn_0.5O_1.95F_0.05@CuO的性能研究[J]. 储能科学与技术, 2024, 13(8): 2489-2498.
[2]	姚远, 宗若奇, 盖建丽. 钠离子电池锑基及铋基金属负极材料研究进展[J]. 储能科学与技术, 2024, 13(8): 2649-2664.
[3]	范利君, 吴保周, 陈珂君. 不同形貌FeS₂ 的可控制备及储钠特性研究[J]. 储能科学与技术, 2024, 13(8): 2541-2549.
[4]	周洪, 辛竹琳, 付豪, 张强, 魏凤. 基于专利数据挖掘的固态锂电池关键材料分析[J]. 储能科学与技术, 2024, 13(7): 2386-2398.
[5]	谭仕荣, 尹文骥, 曾翠鸿, 黎小琼, 訚硕, 纪方力, 胡思江, 王红强, 李庆余. 高温淬火对钠离子电池锰基层状正极材料结构和性能的影响[J]. 储能科学与技术, 2024, 13(7): 2399-2406.
[6]	徐雄文, 莫英, 周望, 姚环东, 洪娟, 雷化, 涂健, 刘继磊. 硬碳动力学特性对钠离子电池低温性能的影响及机制[J]. 储能科学与技术, 2024, 13(7): 2141-2150.
[7]	林炜琦, 卢巧瑜, 陈宇鸿, 邱麟媛, 季钰榕, 管联玉, 丁翔. 低温钠离子电池正极材料研究进展[J]. 储能科学与技术, 2024, 13(7): 2348-2360.
[8]	王立锋, 任乃青, 杨海, 姚雨, 余彦. 低温钠离子电池电解液研究进展[J]. 储能科学与技术, 2024, 13(7): 2206-2223.
[9]	李丹, 马铁, 刘汉浩, 郭丽. 高倍率钠离子电池炭包覆纳米铋负极材料[J]. 储能科学与技术, 2024, 13(6): 1775-1785.
[10]	冯仁超, 董宇, 朱新宇, 刘偲, 陈胜, 李达, 郭若禹, 王斌, 王炯辉, 李宁, 苏岳锋, 吴锋. 钠离子电池氧化石墨基负极研究进展[J]. 储能科学与技术, 2024, 13(6): 1835-1848.
[11]	所聪, 王阳峰, 朱紫宸, 杨雁. 钠离子电池软碳基负极的研究进展[J]. 储能科学与技术, 2024, 13(6): 1807-1823.
[12]	刘青宜. 钠离子电池的储能机制与性能提升策略[J]. 储能科学与技术, 2024, 13(6): 1871-1873.
[13]	赵毅伟, 张福华, 颜顺, 丁坤, 蓝海枫, 刘辉. 普鲁士蓝类钠离子电池正极材料导电性研究进展[J]. 储能科学与技术, 2024, 13(5): 1474-1486.
[14]	江成凡, 黄俊, 谢海波. 提高硬碳材料钠离子电池首次库仑效率的研究进展[J]. 储能科学与技术, 2024, 13(3): 825-840.
[15]	李珂, 郝奕帆, 方振华, 王静, 张松通, 祝夏雨, 邱景义, 明海. 高功率化学电源体系发展及军事应用分析[J]. 储能科学与技术, 2024, 13(2): 436-461.