钠离子电池硬碳负极材料的储钠机制及性能优化策略综述
A Review of Sodium Storage Mechanisms and Performance Optimization Strategies for Hard Carbon Anode Materials for Sodium-Ion Batteries
DOI: 10.12677/amc.2025.134050, PDF,   
作者: 张贺然, 何明益, 刘少敏*：安徽理工大学地球与环境学院，安徽 淮南
关键词: 钠离子电池；硬碳；负极；储钠机制；优化；Sodium-Ion Battery； Hard Carbon； Anode； Sodium Storage Mechanism； Optimization
摘要: 本文关注钠离子电池硬碳负极材料的技术瓶颈与突破。指出硬碳材料依靠多级孔道结构与低电位平台有着较高的储钠容量，却存在储钠机理上“插层–孔隙填充”与“吸附–插层复合”学术争议。而针对容量衰减与倍率性能不足问题提出的优化策略，突出依靠纳米形貌调控来提升离子传输效果，杂原子掺杂技术被用来制造活性储钠位置，开发闭孔结构定向设计以加强首效稳定性。该文通过机制剖析与方法论改进，给予高性能储能材料研发以理论支撑和实际参照作用。
Abstract: This paper focuses on the technological bottlenecks and breakthroughs of hard carbon anode materials for sodium-ion batteries. It points out that hard carbon materials, due to their multi-level pore structure and low-potential platform, have high sodium storage capacity, but there is academic controversy regarding the sodium storage mechanism: “intercalation-pore filling” versus “adsorption-intercalation composite”. Optimization strategies proposed to address capacity fading and insufficient rate performance emphasize nanomorphology manipulation to enhance ion transport, heteroatom doping techniques to create active sodium storage sites, and the development of closed-pore structure design to enhance initial efficiency stability. Through mechanism analysis and methodological improvements, this paper provides theoretical support and practical reference for the development of high-performance energy storage materials.
文章引用：张贺然, 何明益, 刘少敏. 钠离子电池硬碳负极材料的储钠机制及性能优化策略综述[J]. 材料化学前沿, 2025, 13(4): 493-505. https://doi.org/10.12677/amc.2025.134050

参考文献

[1] Goikolea, E., Palomares, V., Wang, S., de Larramendi, I.R., Guo, X., Wang, G., et al. (2020) Na-Ion Batteries—Approaching Old and New Challenges. Advanced Energy Materials, 10, Article ID: 2002055. [Google Scholar] [CrossRef] 
[2] Chayambuka, K., Mulder, G., Danilov, D.L. and Notten, P.H.L. (2020) From Li-Ion Batteries toward Li-Ion Chemistries: Challenges and Opportunities. Advanced Energy Materials, 10, Article ID: 2001310. [Google Scholar] [CrossRef] 
[3] Xu, G., Amine, R., Abouimrane, A., Che, H., Dahbi, M., Ma, Z., et al. (2018) Challenges in Developing Electrodes, Electrolytes, and Diagnostics Tools to Understand and Advance Sodium‐Ion Batteries. Advanced Energy Materials, 8, Article ID: 1702403. [Google Scholar] [CrossRef] 
[4] Pan, H., Hu, Y. and Chen, L. (2013) Room-Temperature Stationary Sodium-Ion Batteries for Large-Scale Electric Energy Storage. Energy & Environmental Science, 6, 2338-2360. [Google Scholar] [CrossRef] 
[5] Li, L., Zheng, Y., Zhang, S., Yang, J., Shao, Z. and Guo, Z. (2018) Recent Progress on Sodium Ion Batteries: Potential High-Performance Anodes. Energy & Environmental Science, 11, 2310-2340. [Google Scholar] [CrossRef] 
[6] 班荣泽, 赵麒, 刘璐, 等. 碳基复合材料用于钠离子电池负极研究进展[J]. 山东化工, 2024, 53(14): 100-102.
[7] 高远鹏, 袁文波, 刘嘉曦. 不同暴露晶面TiO2基钠离子电池负极材料的合成及电化学性能[J]. 广州化工, 2024, 52(23): 55-59, 113.
[8] Li, Y., Lu, Y., Adelhelm, P., Titirici, M. and Hu, Y. (2019) Intercalation Chemistry of Graphite: Alkali Metal Ions and Beyond. Chemical Society Reviews, 48, 4655-4687. [Google Scholar] [CrossRef] [PubMed]
[9] 曾杰, 张文华, 王帅, 等. 钠离子电池软硬碳负极材料研究进展[J]. 南昌工程学院学报, 2024, 43(3): 75-81.
[10] 赵琨瑀, 王英帅, 樊博建, 等. 钠离子电池生物质衍生硬碳负极材料的制备与研究进展[J]. 石油化工高等学校学报, 2025, 38(3): 32-43.
[11] 邓涛, 张斌伟. 生物质衍生硬碳负极材料首圈库伦效率提升策略[J/OL]. 湘潭大学学报(自然科学版): 1-16. 2025-09-20. [Google Scholar] [CrossRef] 
[12] Wang, Y., Wang, Y., Liu, J., Pan, L., Tian, W., Wu, M., et al. (2017) Preparation of Carbon Nanosheets from Petroleum Asphalt via Recyclable Molten-Salt Method for Superior Lithium and Sodium Storage. Carbon, 122, 344-351. [Google Scholar] [CrossRef] 
[13] 李智萌. 钛基负极材料的设计、制备及其储钠性能研究[D]: [硕士学位论文]. 济南: 济南大学, 2024.
[14] 王沁云. 钛基钠离子电池负极材料的制备、电化学性能及理论计算研究[D]: [硕士学位论文]. 宁波: 宁波大学, 2021.
[15] Zhang, Y., Ding, Z., Foster, C.W., Banks, C.E., Qiu, X. and Ji, X. (2017) Oxygen Vacancies Evoked Blue TiO2(B) Nanobelts with Efficiency Enhancement in Sodium Storage Behaviors. Advanced Functional Materials, 27, Article ID: 1700856. [Google Scholar] [CrossRef] 
[16] Pothaya, S., Poochai, C., Tammanoon, N., Chuminjak, Y., Kongthong, T., Lomas, T., et al. (2023) Bamboo-Derived Hard Carbon/Carbon Nanotube Composites as Anode Material for Long-Life Sodium-Ion Batteries with High Charge/Discharge Capacities. Rare Metals, 43, 124-137. [Google Scholar] [CrossRef] 
[17] Dou, X., Hasa, I., Saurel, D., Vaalma, C., Wu, L., Buchholz, D., et al. (2019) Hard Carbons for Sodium-Ion Batteries: Structure, Analysis, Sustainability, and Electrochemistry. Materials Today, 23, 87-104. [Google Scholar] [CrossRef] 
[18] 所聪. 基于生物质基硬碳的钠离子电池电解液的性能优化[J]. 当代化工, 2025, 54(6): 1296-1303, 1309.
[19] Saurel, D., Orayech, B., Xiao, B., Carriazo, D., Li, X. and Rojo, T. (2018) From Charge Storage Mechanism to Performance: A Roadmap toward High Specific Energy Sodium‐Ion Batteries through Carbon Anode Optimization. Advanced Energy Materials, 8, Article ID: 1703268. [Google Scholar] [CrossRef] 
[20] Bommier, C., Surta, T.W., Dolgos, M. and Ji, X. (2015) New Mechanistic Insights on Na-Ion Storage in Nongraphitizable Carbon. Nano Letters, 15, 5888-5892. [Google Scholar] [CrossRef] [PubMed]
[21] Sun, N., Qiu, J. and Xu, B. (2022) Understanding of Sodium Storage Mechanism in Hard Carbons: Ongoing Development under Debate. Advanced Energy Materials, 12, Article ID: 2200715. [Google Scholar] [CrossRef] 
[22] Sun, N., Guan, Z., Liu, Y., Cao, Y., Zhu, Q., Liu, H., et al. (2019) Extended “Adsorption-Insertion” Model: A New Insight into the Sodium Storage Mechanism of Hard Carbons. Advanced Energy Materials, 9, Article ID: 1901351. [Google Scholar] [CrossRef] 
[23] Zhang, L., Wang, W., Lu, S. and Xiang, Y. (2021) Carbon Anode Materials: A Detailed Comparison between Na‐Ion and K‐ion Batteries. Advanced Energy Materials, 11, Article ID: 2003640. [Google Scholar] [CrossRef] 
[24] Zhang, B., Ghimbeu, C.M., Laberty, C., Vix‐Guterl, C. and Tarascon, J. (2015) Correlation between Microstructure and Na Storage Behavior in Hard Carbon. Advanced Energy Materials, 6, Article ID: 1501588. [Google Scholar] [CrossRef] 
[25] Li, Y., Xu, S., Wu, X., Yu, J., Wang, Y., Hu, Y., et al. (2015) Amorphous Monodispersed Hard Carbon Micro-Spherules Derived from Biomass as a High Performance Negative Electrode Material for Sodium-Ion Batteries. Journal of Materials Chemistry A, 3, 71-77. [Google Scholar] [CrossRef] 
[26] Yu, Z., Lyu, Y., Wang, Y., Xu, S., Cheng, H., Mu, X., et al. (2020) Hard Carbon Micro-Nano Tubes Derived from Kapok Fiber as Anode Materials for Sodium-Ion Batteries and the Sodium-Ion Storage Mechanism. Chemical Communications, 56, 778-781. [Google Scholar] [CrossRef] [PubMed]
[27] Gao, L., Ma, J., Li, S., Liu, D., Xu, D., Cai, J., et al. (2019) 2D Ultrathin Carbon Nanosheets with Rich N/O Content Constructed by Stripping Bulk Chitin for High-Performance Sodium Ion Batteries. Nanoscale, 11, 12626-12636. [Google Scholar] [CrossRef] [PubMed]
[28] Wang, P., Zhu, K., Ye, K., Gong, Z., Liu, R., Cheng, K., et al. (2020) Three-Dimensional Biomass Derived Hard Carbon with Reconstructed Surface as a Free-Standing Anode for Sodium-Ion Batteries. Journal of Colloid and Interface Science, 561, 203-210. [Google Scholar] [CrossRef] [PubMed]
[29] Zhang, Y., Li, X., Dong, P., Wu, G., Xiao, J., Zeng, X., et al. (2018) Honeycomb-Like Hard Carbon Derived from Pine Pollen as High-Performance Anode Material for Sodium-Ion Batteries. ACS Applied Materials & Interfaces, 10, 42796-42803. [Google Scholar] [CrossRef] [PubMed]
[30] Ren, X., Xu, S., Liu, S., Chen, L., Zhang, D. and Qiu, L. (2019) Lath-Shaped Biomass Derived Hard Carbon as Anode Materials with Super Rate Capability for Sodium-Ion Batteries. Journal of Electroanalytical Chemistry, 841, 63-72. [Google Scholar] [CrossRef] 
[31] 洪康, 张冲, 马宏莉, 等. 生物质硬炭基钠离子电池负极材料研究进展[J]. 化工进展: 1-10. 2025-09-20. [Google Scholar] [CrossRef] 
[32] 刘畅, 王彦淇, 周佰洵, 等. 钠离子电池硬碳负极材料的研究进展: 从材料设计到电化学性能优化[J]. 石油化工高等学校学报, 2025, 38(3): 1-9.
[33] 田中原, 吴洪钦, 王梓荃, 等. 木质素基钠离子电池负极材料研究进展[J]. 中国造纸, 2025, 44(4): 1-15.
[34] 比约恩∙尼克维斯特, 李威. 钠离子电池能否取代锂离子电池? [J]. 世界科学, 2025(4): 1.
[35] 吴朝晖, 黄军同, 陈亚兵, 等. 静电纺丝制备三明治结构的C@MoS2/C@C用于高性能钠离子电池[J]. 铜业工程, 2025(1): 47-55.
[36] Xiao, Z.X., Xia, C.C., Li, Z.F., et al. (2018) Mechanism of Na-Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping. Advanced Materials, 30, Article ID: 1804168.
[37] Alvin, S., Chandra, C. and Kim, J. (2020) Extended Plateau Capacity of Phosphorus-Doped Hard Carbon Used as an Anode in Na-and K-Ion Batteries. Chemical Engineering Journal, 391, Article ID: 123576. [Google Scholar] [CrossRef] 
[38] Wang, K., Sun, F., Wang, H., Wu, D., Chao, Y., Gao, J., et al. (2022) Altering Thermal Transformation Pathway to Create Closed Pores in Coal‐Derived Hard Carbon and Boosting of Na+ Plateau Storage for High‐Performance Sodium‐Ion Battery and Sodium‐Ion Capacitor. Advanced Functional Materials, 32, Article ID: 2203725. [Google Scholar] [CrossRef] 
[39] Li, Y., Lu, Y., Meng, Q., Jensen, A.C.S., Zhang, Q., Zhang, Q., et al. (2019) Regulating Pore Structure of Hierarchical Porous Waste Cork‐Derived Hard Carbon Anode for Enhanced Na Storage Performance. Advanced Energy Materials, 9, Article ID: 1902852. [Google Scholar] [CrossRef] 
[40] 沈雨可, 李欢, 马紫峰, 等. 钠离子电池硬碳负极材料的孔结构表征方法综述[J]. 石油化工高等学校学报, 2025, 38(3): 10-19.
[41] 于鑫, 郭华军, 王志兴, 等. 调控竹制硬碳微观结构助力钠离子电池高效储钠(英文) [J]. 中南大学学报(英文版), 2024, 31(12): 4497-4509.
[42] 余雁, 贺杰, 于改改, 等. 钠离子电池硬碳负极闭孔结构与平台容量的研究进展[J]. 电池工业, 2024, 28(6): 352-357.
[43] 张京涛, 吉闫, 左宇程, 等. 柚子皮基钠离子电池硬碳孔结构的调控及其储钠性能研究[J]. 现代化工, 2024, 44(9): 114-118.
[44] 王阳峰, 侯佳傲, 朱紫宸, 等. 钠离子电池硬碳闭孔结构研究进展[J]. 储能科学与技术, 2025, 14(2): 555-569.
[45] Zhou, S., Tang, Z., Pan, Z., Huang, Y., Zhao, L., Zhang, X., et al. (2022) Regulating Closed Pore Structure Enables Significantly Improved Sodium Storage for Hard Carbon Pyrolyzing at Relatively Low Temperature. SusMat, 2, 357-367. [Google Scholar] [CrossRef]