镁离子电池正极材料的研究现状  

Research Status of Cathode Materials for Magnesium-Ion Batteries

作　　者：张琴 胡耀波[1,2] 王润 王俊 ZHANG Qin;HU Yaobo;WANG Run;WANG Jun(College of Materials Science and Engineering,Chongqing University,Chongqing 400044,China;National Engineering Research Center for Magnesium Alloys,Chongqing 400044,China)

机构地区：[1]重庆大学材料科学与工程学院,重庆400044 [2]国家镁合金材料工程技术研究中心,重庆400044

出　　处：《材料导报》2022年第7期128-138,共11页Materials Reports

基　　金：重庆大学中央高校基本科研业务费(2020CDCGCL005)。

摘　　要：石油和天然气等传统能源的过度消耗导致环境污染和能源危机日趋严重。因此,迫切需要开发环境友好、大规模且高效的储能装置来持续性地获取风能、太阳能等间歇性能源。而在各种储能技术中,二次电池因具有能量转换效率高、使用寿命长和成本低廉等优点而最具研发前景。与研究广泛的锂离子电池相比,镁离子电池理论上能够提供更多的电子,其容量是锂离子电池的2~3倍,且镁离子电池具有资源丰富、环境友好、无毒、价格低廉等优点,因此镁离子电池被认为是便携式设备和重载能源设备的一个有前途的候选产品。自2000年初一个成功的镁离子电池原型出现后,研究人员对镁离子电池展开了大量研究。但目前仍存在着一些问题严重阻碍了可充镁离子电池(RMBs)的商业化发展。由于Mg^(2+)具有高电荷密度、强的极化效应和缓慢的扩散动力学,开发出符合目前商业需求的正极材料仍是一个巨大挑战。RMBs正极材料主要包括过渡金属硫化物、过渡金属氧化物、聚阴离子型化合物和普鲁士蓝类似物等。过渡金属硫化物结构刚性较小,在充放电循环过程中不容易产生结构坍塌,但其存在离子捕获效应及缓慢的扩散动力学等缺陷。过渡金属氧化物具有比硫化物更高的电压,但该材料的结构刚性较大,循环性能差。具有介孔结构的聚阴离子型化合物有利于提高电池的电化学性能,但其导电性有待提高。具有开放可调结构的普鲁士蓝类似物有利于Mg^(2+)的快速脱嵌,但其与水性电解质的相容性较差。近年来,国内外对RMBs正极材料的研究报道显著增加,针对其存在的问题,研究人员主要从纳米化、结构调整、掺杂改性及包覆改性等方面进行材料的优化设计。本文主要对各种类的RMBs正极材料在国内外的研究状况进行了概括,包括其晶体结构、材料的研究现状及存在的问题,�Excessive consumption of traditional energy sources such as oil and natural gas has led to increasingly serious environmental pollution and ene-rgy crises.Therefore,it is imperative to develop environmentally friendly,large-scale and efficient energy storage devices to obtain intermittent energy such as wind and solar energy continuously.Among various energy storage technologies,secondary batteries have the best research and development prospects for their advantages of high energy conversion efficiency,long service life,and low cost.In comparison with the widely studied lithium-ion batteries,the magnesium-ion batteries can theoretically provide more electrons,which makes their capacity 2 to 3 times as large as that of the lithium-ion batteries.Furthermore,magnesium-ion batteries,owing the advantages of abundant resources,environmental friendliness,non-toxicity and low prices,are considered as one potential candidate for portable devices and heavy-duty energy equipment.A lot of studies on magnesium-ion batteries have been carried out since a successful prototype of magnesium-ion battery appeared in early 2000.However,the commercial development of rechargeable magnesium-ion batteries(RMBs)is still hampered by some challenges.At present,due to the high charge density,strong polarization effect and slow diffusion kinetics of Mg^(2+),it is still a great challenge to develop cathode materials that can meet the current commercial needs.RMBs cathode materials mainly include transition metal sulfides,transition metal oxides,polyanionic compounds and Prussian blue analogs.The transition metal sulfides have a low rigidity structure that is difficult to collapse during the charge-discharge cycle.However,some defects such as ion trapping effect and slow diffusion kinetics are found in transition metal sulfides.Transition metal oxides have higher voltage than sulfides but great structural rigidity and poor cycle performance of them can’t be ignored.The polyanionic compounds with mesoporous structure are beneficial to improv

关 键 词：镁离子电池 正极材料 硫化物 氧化物 聚阴离子型化合物 普鲁士蓝类似物 

分 类 号：TM912[电气工程—电力电子与电力传动]