锂/钠离子电池纳米红磷负极结构调控与性能优化  

Structural modification and performance optimization of red phosphorus nanomaterials as anodes for lithium/sodium-ion batteries

作　　者：周怡[1,2] 苗文康 蔡岳玲 董余兵 欧斌[3] 李倩倩 ZHOU Yi;MIAO Wenkang;CAI Yueling;DONG Yubing;OU Bin;LI Qianqian(School of Materials Science and Engineering,Zhejiang Sci-Tech University,Hangzhou 310018,China;Material Genome Institute,Shanghai University,Shanghai 200444,China;Chinalco Intelligent Technology Development Co,Ltd,Hangzhou 311199,China)

机构地区：[1]浙江理工大学材料科学与工程学院,杭州310018 [2]上海大学材料基因组工程研究院,上海200444 [3]中铝智能科技发展有限公司,杭州311199

出　　处：《工程科学学报》2023年第9期1493-1508,共16页Chinese Journal of Engineering

基　　金：国家自然科学基金NSAF培养项目(U2230102);国家自然科学基金面上项目(11972219)。

摘　　要：开发高性能二次电池材料是缓解能源与环境危机的有效途径.商业锂离子电池石墨负极由于理论容量较低且在钠离子电池中几乎不显示容量,无法满足人类日益增长的能量需求.红磷由于理论容量高(2596 mA·h·g^(–1))、氧化/还原电位适宜、地球资源占比丰富以及价格低廉等优点成为碱金属离子电池研究中的热点,有望成为商业化大规模储能系统中应用的负极材料.但是,红磷在作为负极材料时具有导电性差、体积膨胀大等缺点,导致活性材料利用率低,电极粉化现象严重,电极循环稳定性差,严重限制了其在二次电池中的商业应用.最近研究表明,通过合理的结构设计可以有效地提高红磷的电子导电率及结构稳定性,进而改善红磷负极的循环稳定性和倍率性能,促进红磷在商业锂/钠离子电池中的广泛应用.本文综述了近年来纳米红磷负极材料在可控合成方法、结构设计与改性以及性能优化机理上的研究进展.最后,总结了目前红磷负极材料研究存在的问题,并提出可能的应对策略,对纳米红磷基负极材料未来在电池领域发展前景进行了展望,旨在促进其商业应用.Developing electrode materials for high-performance secondary batteries is one of the most effective approaches to alleviate energy and environmental crises.Nowadays,graphite anodes,which are widely used in commercial lithium-ion batteries,cannot satisfy the ever-growing energy needs of humans owing to their relatively low theoretical capacities and nearly no capacity in sodium-ion batteries.Therefore,developing new anodes with high capacity and energy density is necessary for next-generation large-scale energy systems.Red phosphorus has become an interesting topic in alkali-ion battery research and is expected to be commercially used as anode material in the next generation of secondary batteries owing to their intrinsic properties,such as their high activity,high theoretical specific capacity(2596 mA∙h∙g^(−1)),suitable oxidation–reduction potential,highly abundant earth resources,and low cost of lithium/sodium-ion batteries.However,red phosphorus exhibits poor electrical conductivity and large volume expansion when used as electrode material,resulting in low utilization of active material,serious electrode pulverization,and poor electrode cycling stability,which seriously hindered their commercial application in next-generation rechargeable batteries.Recent studies have shown that the cycle stability and electronic conductivity of red phosphorus can be improved by rational structural design,which promotes the electrochemical performance of red phosphorus anodes.For example,reducing the material size to the nanoscale can effectively shorten the diffusion path,enhancing the ion diffusion rate while alleviating the volume expansion and pulverization of the active substance.Additionally,the size reduction changes the band energy of the red phosphorus,which can transform indirect into direct bandgap semiconductors.Besides,the external characteristics of the active materials affect the performance by reducing the internal stress generated by the phase transformation in charging and discharging cycles.By modif

关 键 词：红磷 可充电电池 结构调控 性能优化机理 制备 

分 类 号：TM912.9[电气工程—电力电子与电力传动]