生物质基硬碳储钠负极材料研究进展

Research progress on biomass-based hard-carbon anode materials for sodium storage

  • 摘要: 钠离子电池因其具有优异的低温性能、成本优势以及较高的安全性,有望逐渐成为锂离子电池在低速两轮车和大规模储能领域的补充者,开发低成本、高可逆容量和优异循环稳定性的钠离子电池负极材料成为行业难点,生物质基硬碳因其原料来源丰富、成本低廉、更易获得、碳产率高、环境友好且含有多种元素等优势而备受关注,其低廉的价格和独特的微观结构在众多钠离子电池负极材料中展现出明显的优势和巨大的商业潜力. 为了寻找和开发性能优异的生物质基硬碳材料,本文首先对钠离子在硬碳表面活性位点的吸附行为和进入石墨片层的过程顺序进行了分析,讨论了有争议的四种钠离子存储机制. 深入分析了钠离子在硬碳中的储存机理,并基于此进一步讨论了不同生物质基前驱体硬碳的差异,并通过硬碳负极的微观结构提出钠离子电池负极的优化策略,对钠离子电池的发展具有一定的指导意义.

     

    Abstract: Sodium-ion batteries are expected to gradually replace lithium-ion batteries in large-scale energy storage and two-wheeled electric vehicles because of their excellent low-temperature performance, cost advantages, and high safety. The development of sodium-ion battery anode materials with low cost, high reversible capacity, and excellent cycling stability is challenging for the industry. Because sodium ions are larger than lithium ions, graphite materials with long-range ordered structures suitable for lithium-ion battery anodes cannot be applied to sodium-ion batteries. Instead, the graphite domains of hard carbon materials are short and chaotically aligned, exhibiting a short-range ordered structure with local graphite zones inside the carbon layer. Moreover, the layer spacing of hard carbon is larger than that of graphite, which is conducive to the storage of sodium ions. Hard carbon is easily accessible and environmentally friendly, with a high carbon yield. Biomass-based hard carbon has attracted considerable attention because of its abundant raw material sources, low cost, easy accessibility, high carbon yield, environmental friendliness, and the presence of various elements. Its unique microstructure exhibits notable advantages and great commercial potential among several anode materials for sodium-ion batteries. The storage mechanism of sodium ions in hard carbon is controversial. Herein, we first analyze the adsorption behavior of sodium ions at the active sites on the hard carbon surface and the sequential process of their entry into the graphite scale layer. Moreover, we review four controversial sodium-ion storage mechanisms. Furthermore, we explore the storage mechanism of sodium ions in hard carbon and the differences between various biomass-based precursors. The content of each component and microstructure of different precursors vary, and several differences exist between nutshells, woody plants, and herbs. Their internal structural characteristics and different component contents play a key role in the performance of hard carbon. We enumerate the structural and component differences among various biomass-based precursors and summarize the distinctions in sodium-ion storage properties among different precursor hard carbons. To enhance the sodium storage performance of biomass-based hard carbon, an optimization strategy is proposed for sodium-ion battery anodes. This strategy involves manipulating the microstructure of the hard carbon anode, including adjusting the carbon layer spacing, pore structure, and specific surface area. In addition, the doping of elements, introduction of functional groups, and optimization of the electrolyte can improve the sodium storage performance of hard carbon. These insights can provide significant guidance for developing sodium-ion batteries.

     

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