High-voltage nickel-rich layered cathodes possess the requisite,such as excellent discharge capacity and high energy density,to realize lithium batteries with higher energy density.However,such materials suffer from s...High-voltage nickel-rich layered cathodes possess the requisite,such as excellent discharge capacity and high energy density,to realize lithium batteries with higher energy density.However,such materials suffer from structural and interfacial instability at high voltages(>4.3 V).To reinforce the stability of these cathode materials at elevated voltages,lithium borate salts are investigated as electrolyte additives to generate a superior cathode-electrolyte interphase.Specifically,the use of lithium bis(oxalato)borate(LiBOB)leads to an enhanced cycling stability with a capacity retention of 81.7%.Importantly,almost no voltage hysteresis is detected after 200 cycles at 1C.This outstanding electrochemical performance is attributed to an enhanced structural and interfacial stability,which is attained by suppressing the generation of micro-cracks and the superficial structural degradation upon cycling.The improved stability stems from the formation of a fortified borate-containing interphase which protects the highly reactive cathode from parasitic reactions with the electrolyte.Finally,the decomposition process of LiBOB and the possible adsorption routes to the cathode surface are deduced and elucidated.展开更多
开发匹配高电压正极的锂金属电池是实现高能量存储系统的关键.因此,研发可以同时为锂金属负极和高电压正极产生稳定界面相的先进电解液非常必要.LiNO_(3)作为高效的固体电解质界面相添加剂被广泛应用于醚基电解液中,然而其在碳酸脂类电...开发匹配高电压正极的锂金属电池是实现高能量存储系统的关键.因此,研发可以同时为锂金属负极和高电压正极产生稳定界面相的先进电解液非常必要.LiNO_(3)作为高效的固体电解质界面相添加剂被广泛应用于醚基电解液中,然而其在碳酸脂类电解液中的低溶解性严重限制了其在高压锂金属电池中的应用.本文利用磷酸三甲酯助溶剂提高LiNO_(3)在碳酸乙基甲酯/氟代碳酸乙烯酯电解液中的溶解度,并赋予电解液阻燃性能.此外,通过添加双草酸硼酸锂(LiBOB)进一步提高正负极的界面稳定性.结果表明,该电解液对锂金属负极和高电压层状氧化物正极均具有较高的兼容性.在2.8–4.3 V电压范围内,Li||LiCoO_(2)和Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)电池在1.2 mA cm^(-2)电流密度下循环300周后的容量保持率分别为80.2%和84.2%.更令人惊喜的是,负/正极容量比为3.33的Li||NCM811电池在相同的充放电条件下循环150周后的容量保持率仍高达~80%.本论文对富含LiNO_(3)的阻燃型高压电解液的研究将为通过界面相调控研发安全的高比能锂金属电池提供理论指导.展开更多
柔性钠离子电池(SIBs)在便携式和可穿戴设备中具有巨大的应用潜力,因为它们在特定情况下具有适用性和价格优势.在正极材料中,磷酸盐电极材料具有结构稳定性好、工作电位高和寿命长的优点.然而,由于对制造要求苛刻,反应复杂,以及柔性基...柔性钠离子电池(SIBs)在便携式和可穿戴设备中具有巨大的应用潜力,因为它们在特定情况下具有适用性和价格优势.在正极材料中,磷酸盐电极材料具有结构稳定性好、工作电位高和寿命长的优点.然而,由于对制造要求苛刻,反应复杂,以及柔性基材的缺失等问题,柔性磷酸盐电极材料的设计仍然是一个巨大的挑战.在此,我们报道了在柔性多孔碳纳米纤维上垂直生长的VO_(2)纳米片原位转化为三维氟磷酸钒钠纳米棒阵列(PCNF@NVOPF NR).PCNF@NVOPF NR实现了兼具柔性与高压正极电极的特点,并具有长期循环稳定性(4500次循环后容量保持率为87.6%).阵列结构可以确保快速的钠反应动力学和低界面电阻.此外,PCNF@NVOPF NR//PCNF@VO_(2)NS@C钠离子全电池表现出高能量和功率密度(220.5 W h kg^(-1)和9400 W kg^(-1)).这种用于柔性正极的材料设计策略可促进实用钠离子电池的商业化.展开更多
基金the financial support from the Chinese Scholarship Council(CSC).Moreover,the authors would like to acknowledge the financial support from the Helmholtz Association and the European Commission in the frame of the SiGNE project(875557)Jae-Kwang Kim acknowledges the support from the Advancement of Technology(KIAT)and the National Research Foundation of Korea(NRF)grant funded by the Korea Government(P0011933 and 2021R1A4A2001687).
文摘High-voltage nickel-rich layered cathodes possess the requisite,such as excellent discharge capacity and high energy density,to realize lithium batteries with higher energy density.However,such materials suffer from structural and interfacial instability at high voltages(>4.3 V).To reinforce the stability of these cathode materials at elevated voltages,lithium borate salts are investigated as electrolyte additives to generate a superior cathode-electrolyte interphase.Specifically,the use of lithium bis(oxalato)borate(LiBOB)leads to an enhanced cycling stability with a capacity retention of 81.7%.Importantly,almost no voltage hysteresis is detected after 200 cycles at 1C.This outstanding electrochemical performance is attributed to an enhanced structural and interfacial stability,which is attained by suppressing the generation of micro-cracks and the superficial structural degradation upon cycling.The improved stability stems from the formation of a fortified borate-containing interphase which protects the highly reactive cathode from parasitic reactions with the electrolyte.Finally,the decomposition process of LiBOB and the possible adsorption routes to the cathode surface are deduced and elucidated.
基金support by Guang Dong Basic and Applied Basic Research Foundation (2021A1515111008)。
文摘开发匹配高电压正极的锂金属电池是实现高能量存储系统的关键.因此,研发可以同时为锂金属负极和高电压正极产生稳定界面相的先进电解液非常必要.LiNO_(3)作为高效的固体电解质界面相添加剂被广泛应用于醚基电解液中,然而其在碳酸脂类电解液中的低溶解性严重限制了其在高压锂金属电池中的应用.本文利用磷酸三甲酯助溶剂提高LiNO_(3)在碳酸乙基甲酯/氟代碳酸乙烯酯电解液中的溶解度,并赋予电解液阻燃性能.此外,通过添加双草酸硼酸锂(LiBOB)进一步提高正负极的界面稳定性.结果表明,该电解液对锂金属负极和高电压层状氧化物正极均具有较高的兼容性.在2.8–4.3 V电压范围内,Li||LiCoO_(2)和Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)电池在1.2 mA cm^(-2)电流密度下循环300周后的容量保持率分别为80.2%和84.2%.更令人惊喜的是,负/正极容量比为3.33的Li||NCM811电池在相同的充放电条件下循环150周后的容量保持率仍高达~80%.本论文对富含LiNO_(3)的阻燃型高压电解液的研究将为通过界面相调控研发安全的高比能锂金属电池提供理论指导.
基金supported by the National Natural Science Foundation of China(51874362 and 22209208)。
文摘柔性钠离子电池(SIBs)在便携式和可穿戴设备中具有巨大的应用潜力,因为它们在特定情况下具有适用性和价格优势.在正极材料中,磷酸盐电极材料具有结构稳定性好、工作电位高和寿命长的优点.然而,由于对制造要求苛刻,反应复杂,以及柔性基材的缺失等问题,柔性磷酸盐电极材料的设计仍然是一个巨大的挑战.在此,我们报道了在柔性多孔碳纳米纤维上垂直生长的VO_(2)纳米片原位转化为三维氟磷酸钒钠纳米棒阵列(PCNF@NVOPF NR).PCNF@NVOPF NR实现了兼具柔性与高压正极电极的特点,并具有长期循环稳定性(4500次循环后容量保持率为87.6%).阵列结构可以确保快速的钠反应动力学和低界面电阻.此外,PCNF@NVOPF NR//PCNF@VO_(2)NS@C钠离子全电池表现出高能量和功率密度(220.5 W h kg^(-1)和9400 W kg^(-1)).这种用于柔性正极的材料设计策略可促进实用钠离子电池的商业化.
