助力钠电池储能：预钠化技术研究新进展

doi:10.19799/j.cnki.2095-4239.2025.0399

摘要/Abstract

摘要：

钠与锂具有相似的物理化学性质，且钠资源储量丰富、分布广泛，因此钠离子电池被认为是锂离子电池储能体系的重要补充，在大规模储能应用和短时高频储能应用中展现出广阔前景。然而，储钠负极材料的初始库伦效率（ICE）普遍较低，无法发挥其理论容量。预钠化技术作为目前最有效的活性钠补偿策略之一，可有效弥补活性钠的损失。本文全面分析了近年来预钠化技术面临的主要挑战，总结了针对挑战所提出的新方法，并根据各类钠源的氧化还原性质，将目前的预钠化技术分为还原型预钠化技术和氧化型预钠化技术，对比了各类预钠化方法的优缺点及工业化难度，重点分析阐述了各类预钠化技术的作用机理和研究现状，展望了预钠化技术的发展前景。旨在深化对预钠化技术的理解，为优化和开发适用于高功率场景的可规模化应用的新型预钠化技术提供理论指导和创新思路。结合现有研究成果，提出固态氧化型预钠化材料有望实现全生命周期多次补钠，为实现高功率、高能量密度钠离子电池提供技术基础。

关键词: 钠离子电池, 预钠化, 库伦效率, 长寿命, 高能量密度, 高功率密度

Abstract:

Sodium and lithium share similar physicochemical properties, and sodium resources are abundant and widely distributed. Therefore, sodium-ion batteries (SIBs) are considered a promising complement to lithium-ion battery energy storage systems, demonstrating broad prospects for large-scale energy storage and short-term high-frequency energy storage applications. However, the initial Coulombic efficiency (ICE) of sodium-storage anode materials is generally low, preventing them from achieving their theoretical capacity. Prelithiation technology, as one of the most effective active sodium compensation strategies, can effectively mitigate active sodium loss. This paper comprehensively analyzes the major challenges faced by pre-sodiation technology in recent years and summarizes novel approaches proposed to address these challenges. Based on the redox properties of various sodium sources, current pre-sodiation techniques are categorized into reductive pre-sodiation and oxidative pre-sodiation. The advantages, disadvantages, and industrialization feasibility of different pre-sodiation methods are compared, with a focus on elucidating their mechanisms and research progress. Furthermore, the development prospects of pre-sodiation technology are discussed. The aim of this review is to deepen the understanding of pre-sodiation technology and provide theoretical guidance and innovative insights for optimizing and developing novel pre-sodiation techniques suitable for high-power applications at scale. Based on existing research, we propose that solid-state oxidative pre-sodiation materials hold promise for enabling multiple sodium replenishment throughout the battery's lifecycle, thereby laying a technical foundation for high-power, high-energy-density sodium-ion batteries.

Key words: sodium-ion batteries, pre-sodiation, coulombic efficiency, long cycle life, high energy density, high power density

中图分类号:

TM 912.9

向靖宇, 钟伟, 程时杰, 谢佳. 助力钠电池储能：预钠化技术研究新进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0399.

Jingyu Xiang, Wei Zhong, Shijie Cheng, Jia Xie. Boosting Sodium Battery Energy Storage: New Research Progress of Pre-sodiation Technology[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0399.

图/表 9

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参考文献 74

1	KUNDU D, TALAIE E, DUFFORT V, et al. The emerging chemistry of sodium ion batteries for electrochemical energy storage [J]. Angewandte Chemie International Edition, 2015, 54(11): 3431-48.
2	KALAMARAS E, MAROTO-VALER M M, SHAO M, et al. Solar carbon fuel via photoelectrochemistry [J]. Catalysis Today, 2018, 317: 56-75.
3	BIN D, WANG F, TAMIRAT A G, et al. Progress in Aqueous Rechargeable Sodium‐Ion Batteries [J]. Advanced Energy Materials, 2018, 8(17): 1703008.
4	NAYAK P K, YANG L, BREHM W, et al. From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises [J]. Angewandte Chemie International Edition, 2018, 57(1): 102-20.
5	ZHENG W, LIANG G, LIU Q, et al. The promise of high-entropy materials for high-performance rechargeable Li-ion and Na-ion batteries [J]. Joule, 2023, 7(12): 2732-48.
6	ELLIS B L, NAZAR L F. Sodium and sodium-ion energy storage batteries [J]. Current Opinion in Solid State and Materials Science, 2012, 16(4): 168-77.
7	CHAYAMBUKA K, MULDER G, DANILOV D L, et al. Sodium‐Ion Battery Materials and Electrochemical Properties Reviewed [J]. Advanced Energy Materials, 2018, 8(16): 1800079.
8	SONG J, XIAO B, LIN Y, et al. Interphases in Sodium‐Ion Batteries [J]. Advanced Energy Materials, 2018, 8(17): 1703082.
9	EFTEKHARI A, KIM D-W. Sodium-ion batteries: New opportunities beyond energy storage by lithium [J]. Journal of Power Sources, 2018, 395: 336-48.
10	XU H, LI H, WANG X. The Anode Materials for Lithium‐Ion and Sodium‐Ion Batteries Based on Conversion Reactions: a Review [J]. ChemElectroChem, 2023, 10(9): e202201151.
11	MASQUELIER C, CROGUENNEC L. Polyanionic (phosphates, silicates, sulfates) frameworks as electrode materials for rechargeable Li (or Na) batteries [J]. Chemical Reviews, 2013, 113(8): 6552-91.
12	QIU S, XIAO L, SUSHKO M L, et al. Manipulating Adsorption–Insertion Mechanisms in Nanostructured Carbon Materials for High‐Efficiency Sodium Ion Storage [J]. Advanced Energy Materials, 2017, 7(17): 1700403.
13	LI Y, LIU G, CHE J, et al. Review on layered oxide cathodes for sodium‐ion batteries: Degradation mechanisms, modification strategies, and applications [J]. Interdisciplinary Materials, 2024, 4(1): 24-51.
14	CHEN M, LIU Q, WANG S W, et al. High‐Abundance and Low‐Cost Metal‐Based Cathode Materials for Sodium‐Ion Batteries: Problems, Progress, and Key Technologies [J]. Advanced Energy Materials, 2019, 9(14): 1803609.
15	CHENG L-P, LUO G, ZHAO Q-Q, et al. Synthesis, structures and luminescence of silver (I) thiolate nanoclusters based on anion templates [J]. SCIENTIA SINICA Chimica, 2017, 47(6): 695-704.
16	QIAO S, ZHOU Q, MA M, et al. Advanced Anode Materials for Rechargeable Sodium-Ion Batteries [J]. ACS Nano, 2023, 17(12): 11220-52.
17	QIAN J, WU C, CAO Y, et al. Prussian Blue Cathode Materials for Sodium‐Ion Batteries and Other Ion Batteries [J]. Advanced Energy Materials, 2018, 8(17): 1702619.
18	LIANG J-M, ZHANG L-J, XILI D-G, et al. Research progress on tin-based anode materials for sodium ion batteries [J]. Rare Metals, 2020, 39(9): 1005-18.
19	SUN L, ZENG J, WAN X, et al. Recent progress of interface modification of layered oxide cathode material for sodium‐ion batteries [J]. Electron, 2024, 2(2): e31.
20	ZENG X, LI M, ABD EL‐HADY D, et al. Commercialization of Lithium Battery Technologies for Electric Vehicles [J]. Advanced Energy Materials, 2019, 9(27): 1900161.
21	SONG M, HU Z, YUAN C, et al. Locally Curved Surface with CoN4 Sites Enables Hard Carbon with Superior Sodium‐Ion Storage Performances at -40 ℃ [J]. Advanced Energy Materials, 2024, 14(23): 2304537.
22	CHEN J, ADIT G, LI L, et al. Optimization Strategies Toward Functional Sodium‐Ion Batteries [J]. Energy & Environmental Materials, 2023, 6(4): e12633.
23	CUI J, YAO S, KIM J-K. Recent progress in rational design of anode materials for high-performance Na-ion batteries [J]. Energy Storage Materials, 2017, 7: 64-114.
24	GABRIEL E, MA C, GRAFF K, et al. Heterostructure engineering in electrode materials for sodium-ion batteries: Recent progress and perspectives [J]. eScience, 2023, 3(5): 100139.
25	QIAN J, XIONG Y, CAO Y, et al. Synergistic Na-storage reactions in Sn4P3 as a high-capacity, cycle-stable anode of Na-ion batteries [J]. Nano Letters, 2014, 14(4): 1865-9.
26	QIAN J, CHEN Y, WU L, et al. High capacity Na-storage and superior cyclability of nanocomposite Sb/C anode for Na-ion batteries [J]. Chemical Communications 2012, 48(56): 7070-2.
27	BODENES L, DARWICHE A, MONCONDUIT L, et al. The Solid Electrolyte Interphase a key parameter of the high performance of Sb in sodium-ion batteries: Comparative X-ray Photoelectron Spectroscopy study of Sb/Na-ion and Sb/Li-ion batteries [J]. Journal of Power Sources, 2015, 273: 14-24.
28	WINKLER V, KILIBARDA G, SCHLABACH S, et al. Surface Analytical Study Regarding the Solid Electrolyte Interphase Composition of Nanoparticulate SnO2 Anodes for Li-Ion Batteries [J]. The Journal of Physical Chemistry C, 2016, 120(43): 24706-14.
29	PAN Y, ZHANG Y, PARIMALAM B S, et al. Investigation of the solid electrolyte interphase on hard carbon electrode for sodium ion batteries [J]. Journal of Electroanalytical Chemistry, 2017, 799: 181-6.
30	RAJAGOPALAN R, TANG Y, JIA C, et al. Understanding the sodium storage mechanisms of organic electrodes in sodium ion batteries: issues and solutions [J]. Energy & Environmental Science, 2020, 13(6): 1568-92.
31	BOMMIER C, JI X. Electrolytes, SEI Formation, and Binders: A Review of Nonelectrode Factors for Sodium-Ion Battery Anodes [J]. Small, 2018, 14(16): e1703576.
32	ZHANG M, LI Y, WU F, et al. Boost sodium-ion batteries to commercialization: Strategies to enhance initial Coulombic efficiency of hard carbon anode [J]. Nano Energy, 2021, 82: 105738.
33	YUAN Y, JAN S, WANG Z, et al. A simple synthesis of nanoporous Sb/C with high Sb content and dispersity as an advanced anode for sodium ion batteries [J]. Journal of Materials Chemistry A, 2018, 6(14): 5555-9.
34	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.
35	PATRA J, HUANG H-T, XUE W, et al. Moderately concentrated electrolyte improves solid–electrolyte interphase and sodium storage performance of hard carbon [J]. Energy Storage Materials, 2019, 16: 146-54.
36	HE H, SUN D, TANG Y, et al. Understanding and improving the initial Coulombic efficiency of high-capacity anode materials for practical sodium ion batteries [J]. Energy Storage Materials, 2019, 23: 233-51.
37	PALOMARES V, SERRAS P, VILLALUENGA I, et al. Na-ion batteries, recent advances and present challenges to become low cost energy storage systems [J]. Energy & Environmental Science, 2012, 5(3): 5884-901.
38	KUBOTA K, KOMABA S. Review—Practical Issues and Future Perspective for Na-Ion Batteries [J]. Journal of The Electrochemical Society, 2015, 162(14): A2538-A50.
39	DENG J, LUO W B, CHOU S L, et al. Sodium‐Ion Batteries: From Academic Research to Practical Commercialization [J]. Advanced Energy Materials, 2017, 8(4): 1701428.
40	GLUSHENKOV A M. Recent commentaries on the expected performance, advantages and applications of sodium-ion batteries [J]. Energy Materials, 2023: 300010.
41	JIN T, WANG P F, WANG Q C, et al. Realizing Complete Solid‐Solution Reaction in High Sodium Content P2‐Type Cathode for High‐Performance Sodium‐Ion Batteries [J]. Angewandte Chemie International Edition, 2020, 59(34): 14511-6.
42	ZHAO C, YAO Z, WANG Q, et al. Revealing High Na-Content P2-Type Layered Oxides as Advanced Sodium-Ion Cathodes [J]. Journal of the American Chemical Society, 2020, 142(12): 5742-50.
43	FANG K, TANG Y, LIU J, et al. Injecting Excess Na into a P2-Type Layered Oxide Cathode to Achieve Presodiation in a Na-Ion Full Cell [J]. Nano Letters, 2023, 23(14): 6681-8.
44	JO J H, CHOI J U, KONAROV A, et al. Sodium‐Ion Batteries: Building Effective Layered Cathode Materials with Long‐Term Cycling by Modifying the Surface via Sodium Phosphate [J]. Advanced Functional Materials, 2018, 28(14): 1705968.
45	TANG R, LI K, LIU C, et al. Long-lifespan benzoquinone-intercalated vanadium oxide with vacancies and disorders on the (00l) facets for efficient sodium-ion battery: A facile approach to Na+ capture and pre-sodiation [J]. Chemical Engineering Journal, 2023, 453: 139734.
46	ZHANG X, FAN C, HAN S. Improving the initial Coulombic efficiency of hard carbon-based anode for rechargeable batteries with high energy density [J]. Journal of Materials Science, 2017, 52(17): 10418-30.
47	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.
48	HOU L, LIU T, WANG H, et al. Boosting the Reversible, High‐Rate Na+ Storage Capability of the Hard Carbon Anode Via the Synergistic Structural Tailoring and Controlled Presodiation [J]. Small, 2023, 19(21): 2207638.
49	WANG Y, LU J, DAI W, et al. On the Practicability of the Solid‐State Electrochemical Pre‐Sodiation Technique on Hard Carbon Anodes for Sodium‐Ion Batteries [J]. Advanced Functional Materials, 2024, 34(40): 2403841.
50	TANG J, KYE D K, POL V G. Ultrasound-assisted synthesis of sodium powder as electrode additive to improve cycling performance of sodium-ion batteries [J]. Journal of Power Sources, 2018, 396: 476-82.
51	XIAO B, SOTO F A, GU M, et al. Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes [J]. Advanced Energy Materials, 2018, 8(24): 1801441.
52	TENG J, DAI B, ZHANG K, et al. Application of Sodium‐Rich Multifunctional Hard Carbon Synthesized via Multi‐Alloy Grafting Strategy for Presodiation in High‐Performance Sodium‐Ion Batteries [J]. Small, 2024, 20(49): 2407225.
53	SHEN Y, ZHANG J, PU Y, et al. Effective Chemical Prelithiation Strategy for Building a Silicon/Sulfur Li-Ion Battery [J]. ACS Energy Letters, 2019, 4(7): 1717-24.
54	WU C, HU J, YE L, et al. Direct Regeneration of Spent Li-Ion Battery Cathodes via Chemical Relithiation Reaction [J]. ACS Sustainable Chemistry & Engineering, 2021, 9(48): 16384-93.
55	ZHENG G, LIN Q, MA J, et al. Ultrafast presodiation of graphene anodes for high‐efficiency and high‐rate sodium‐ion storage [J]. InfoMat, 2021, 3(12): 1445-54.
56	QIN N, SUN Y, HU C, et al. Boosting high initial coulombic efficiency of hard carbon by in-situ electrochemical presodiation [J]. Journal of Energy Chemistry, 2023, 77: 310-6.
57	WANG Z, CHEN S, QIU J, et al. Full‐Cell Presodiation Strategy to Enable High‐Performance Na‐Ion Batteries [J]. Advanced Energy Materials, 2023, 13(45): 2302514.
58	MAN Q, WEI C, TIAN K, et al. Molecular‐Level Design of High Flash Point Solvents Enables High‐Safety and Dual‐Function Chemical Presodiation of Hard Carbon and Alloy Anodes for High‐Performance Sodium‐Ion Batteries [J]. Advanced Energy Materials, 2024, 14(24): 2401016.
59	ZHANG S, WANG J, CHEN K, et al. Aromatic Ketones as Mild Presodiating Reagents toward Cathodes for High‐Performance Sodium‐Ion Batteries [J]. Angewandte Chemie International Edition, 2024, 63(10): e202317439.
60	FANG H, GAO S, REN M, et al. Dual‐Function Presodiation with Sodium Diphenyl Ketone towards Ultra‐stable Hard Carbon Anodes for Sodium‐Ion Batteries [J]. Angewandte Chemie International Edition, 2022, 62(2): e202214717.
61	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.
62	HU L, LI J, ZHANG Y, et al. Enhancing the Initial Coulombic Efficiency of Sodium‐Ion Batteries via Highly Active Na2S as Presodiation Additive [J]. Small, 2023, 19(46): 2304793.
63	JO J H, CHOI J U, PARK Y J, et al. A new pre-sodiation additive for sodium-ion batteries [J]. Energy Storage Materials, 2020, 32: 281-9.
64	JO C-H, CHOI J U, YASHIRO H, et al. Controllable charge capacity using a black additive for high-energy-density sodium-ion batteries [J]. Journal of Materials Chemistry A, 2019, 7(8): 3903-9.
65	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.
66	ZHONG W, HE R, PENG L, et al. Lifecycle Synergistic Prelithiation Strategy of Both Anode and Cathode for High‐Performance Lithium‐Ion Batteries [J]. Advanced Energy Materials, 2025: 2406007.
67	ZHONG W, LI S, LIU M, et al. Hierarchical spherical Mo2C/N-doped graphene catalyst facilitates low-voltage Li2C2O4 prelithiation [J]. Nano Energy, 2023, 115: 108757.
68	ZHONG W, WU Q, WU Y, et al. Scalable spray-dried high-capacity MoC1-x/NC-Li2C2O4 prelithiation composite for lithium-ion batteries [J]. Energy Storage Materials, 2024, 68: 103318.
69	ZHONG W, ZHANG C, LI S, et al. Mo2C catalyzed low-voltage prelithiation using nano-Li2C2O4 for high-energy lithium-ion batteries [J]. Science China Materials, 2022, 66(3): 903-12.
70	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.
71	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: 2407720.
72	CHEN S, WU G, JIANG H, et al. External Li supply reshapes Li deficiency and lifetime limit of batteries [J]. Nature, 2025, 638(8051): 676-83.
73	SONG Z, ZOU K, XIAO X, et al. Presodiation Strategies for the Promotion of Sodium-Based Energy Storage Systems [J]. Chemistry, 2021, 27(65): 16082-92.
74	ZHANG T, WANG R, HE B, et al. Recent advances on pre-sodiation in sodium-ion capacitors: A mini review [J]. Electrochemistry Communications, 2021, 129: 107090.

	代表方法	工艺兼容性	工业化难度	主要优点	主要缺点
富钠化正极	Na_0.85Li_0.12Ni_0.22Mn_0.66O₂	较差	较高	不会引入其他杂质	对材料有限制
固态还原型	钠金属箔/粉末	较差	高	补钠容量高	需惰性环境
液态还原型	萘钠溶液	好	中	工艺简单，可规模化	溶剂稳定性差
固态氧化型	草酸钠添加剂	良好	低	成本低，易于集成	副产物残留
液态氧化型	有机钠盐添加剂	好	较高	可多次补钠	补钠容量较低

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