钠离子电池煤基硬碳负极材料的研究进展及产业化挑战

doi:10.19964/j.issn.1006-4990.2024-0151

摘要/Abstract

摘要：

钠离子电池在智能电网和储能领域有着广泛的应用，但由于负极材料不可逆容量大、氧化还原电位高、循环性能差等因素限制了其发展。硬碳材料，尤其是煤基硬碳负极材料，因其较大的层间距、短程碳微晶结构、低成本、丰富的资源及较低的工作电位等优势，被认为是最具潜力的钠离子电池负极材料，但其存在容量较低、循环性能差、除杂困难等问题。因此，综述了钠离子电池煤基硬碳负极材料的重要性及煤基硬碳的制备与改性方法，阐述了活化、杂原子掺杂、预氧化、复合碳和机械球磨等改性策略对其电化学性能的影响。最后，提出产业化挑战中面临的问题及相应解决方案，并展望了煤基硬碳负极材料的研究方向。

关键词: 钠离子电池, 负极材料, 煤基硬碳, 改性策略, 产业化挑战

Abstract:

Sodium-ion batteries have been widely used in smart grid and energy storage fields，but their development is limited by the factors such as large irreversible capacity，high redox potential and poor cycle performance of anode materials.Hard carbon materials，especially coal-based hard carbon anode materials，are considered to be the most potential anode materials for sodium-ion batteries because of their advantages such as large layer spacing，short-range carbon microcrystalline structure，low cost，rich resources and low working potential.However，they have some problems such as low capacity，poor cycling performance and difficulty in impurity removal.Therefore，the importance of coal-based hard carbon anode materials for sodium ion batteries and the preparation and modification methods of coal-based hard carbon were reviewed.The effects of modification strategies such as activation，heteroatom doping，pre-oxidation，composite carbon and mechanical ball milling on their electrochemical properties were described.Finally，the problems faced in industrialization challenges and corresponding solutions were put forward，and the development direction of coal-based hard carbon anode materials was prospected.

Key words: sodium ion battery, anode material, coal-based hard carbon, modification method, industrialization challenge

中图分类号:

TM911

许有, 马路祥, 海春喜, 董生德, 许琪, 贺欣, 潘稳丞, 高亚文, 谌炬, 孙艳霞, 周园. 钠离子电池煤基硬碳负极材料的研究进展及产业化挑战[J]. 无机盐工业, 2024, 56(11): 30-38.

XU You, MA Luxiang, HAI Chunxi, DONG Shengde, XU Qi, HE Xin, PAN Wencheng, GAO Yawen, CHEN Ju, SUN Yanxia, ZHOU Yuan. Research progress and industrialization challenge of coal-based hard carbon anode materials for sodium ion batteries[J]. Inorganic Chemicals Industry, 2024, 56(11): 30-38.

图/表 5

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表1

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前驱体	炭化温度/℃	电解液	原始/改性	电流密度/（mA·g^-1）	可逆比容量/（mA·h·g^-1）	首次效率/ %	循环次数/ 次	比容量保持率/%
褐煤^［30］	1 200	1 mol/L NaPF₆ in EC/DMC	原始	20 2 000	256	82	300	78
亚烟煤^［31］	1 300	1 mol/L NaClO₄ in EC/DMC	原始	20 50	291	79.5	150	82
烟煤^［32］	1 400	1 mol/L NaPF₆ in EC/DMC	原始	20 1 000	314.3	82.8	500	90.1
无烟煤^［18］	1 200	0.8 mol/L NaPF₆ in EC/DMC	原始	40	222	81	600	89
烟煤^［33］	1 300	1 mol/L NaClO₄ in EC/DEC	预氧化	20 60	308.4 215.5	82.3	800	85.1
无烟煤^［21］	1 200	1 mol/L NaClO₄ in EC/DMC/EMC	N掺杂	100	253	73	500	87
亚烟煤^［40］	1 000	1 mol/L NaClO₄ in PC/EC with 5%FEC	预氧化	20 100	284.4 188.5	48.1	500	112.5
烟煤^［43］	1 200	1 mol/L NaClO₄ in PC/EC	预氧化	30 500	246.8 121.3	80.9	200	69.4
无烟煤^［9］	1 600	1 mol/L NaClO₄ in PC/EC with 5%FEC	机械球磨	30 1 500	382 176	50	2 000	80.2
褐煤^［51］	1 200	1 mol/L NaClO₄ in EC/DMC with 5%FEC	复合	30 50	356 316	82.9	100	91.3

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