LiMn_(2)O_(4)(LMO)electrochemical lithium-ion pump has gained widespread attention due to its green,high efficiency,and low energy consumption in selectively extracting lithium from brine.However,collapse of crystal s...LiMn_(2)O_(4)(LMO)electrochemical lithium-ion pump has gained widespread attention due to its green,high efficiency,and low energy consumption in selectively extracting lithium from brine.However,collapse of crystal structure and loss of lithium extraction capacity caused by Mn dissolution loss limits its industrialized application.Hence,a multifunctional coating was developed by depositing amorphous AlPO_(4)on the surface of LMO using sol-gel method.The characterization and electrochemical performance test provided insights into the mechanism of Li^(+)embedment and de-embedment and revealed that multifunctional AlPO_(4)can reconstruct the physical and chemical state of LMO surface to improve the interface hydrophilicity,promote the transport of Li^(+),strengthen cycle stability.Remarkably,after 20 cycles,the capacity retention rate of 0.5AP-LMO reached 93.6%with only 0.147%Mn dissolution loss.The average Li^(+)release capacity of 0.5AP-LMO//Ag system in simulated brine is 28.77 mg/(g h),which is 90.4%higher than LMO.Encouragingly,even in the more complex Zabuye real brine,0.5AP-LMO//Ag can still maintain excellent lithium extraction performance.These results indicate that the 0.5AP-LMO//Ag lithium-ion pump shows promising potential as a Li^(+)selective extraction system.展开更多
电控离子交换(Electrochemically switched ion exchange,ESIX)系统内对电极具有保持溶液电中性、增强提锂效果且使系统形成闭合回路的关键作用。在ESIX技术盐湖提锂过程中人们主要关注锂离子捕获电极,关于对电极的研究较少。而本文研...电控离子交换(Electrochemically switched ion exchange,ESIX)系统内对电极具有保持溶液电中性、增强提锂效果且使系统形成闭合回路的关键作用。在ESIX技术盐湖提锂过程中人们主要关注锂离子捕获电极,关于对电极的研究较少。而本文研究了不同类型对电极对ESIX系统提锂性能的影响。分别采用聚吡咯/导电炭黑/聚偏二氟乙烯(PPy/C/PVDF)、活性炭/导电炭黑/聚偏二氟乙烯(AC/C/PVDF)和石墨板电极作为ESIX系统中锰酸锂/导电炭黑/聚偏二氟乙烯(LiMn_(2)O_(4)/C/PVDF)提锂膜电极的对电极,考察了这3种ESIX系统在氯化物型高镁锂比模拟卤水(Mg/Li~50)中的提锂性能。结果表明,当PPy/C/PVDF作为对电极时可有效吸附卤水中Cl^(-),且ESIX系统提锂性能最优,Li^(+)吸附量为13.9 mg/g;当PPy/C/PVDF电极湿膜厚度增加至1 mm时,ESIX系统对Li^(+)的提取率可达44.2%,Li^(+)/Mg^(2+)分离因子可达56.82。因此,针对不同的阴离子型盐湖卤水设计匹配的对电极对ESIX技术在盐湖提锂领域的发展具有重要的理论指导意义。展开更多
The present commercial spinel LiMn_(2)O_(4) delivers only 90 m Ah/g–115 m Ah/g,far lower than the theoretical specific capacity.It degrades fast caused by the Jahn–Teller effect,Mn dissolution and related side react...The present commercial spinel LiMn_(2)O_(4) delivers only 90 m Ah/g–115 m Ah/g,far lower than the theoretical specific capacity.It degrades fast caused by the Jahn–Teller effect,Mn dissolution and related side reactions that consume Li inventory.In this work,Zr doping is employed to improve the structural stability and electrochemical performance of spinel LiMn_(2)O_(4).Li_(1.06)Mn_(1.94-x)Zr_xO_4(x=0,0.01,0.02,0.04)have been successfully synthesized by a simple solid-state reaction method and evaluated as cathode for lithium ion batteries(LIB).Li_(1.06)Mn_(1.92)Zr_(0.02)O_4 is superior cathode material with a high capacity of 122 m Ah/g at 1-C rate;long cycle stability,98.39%retention after 100 cycles at 1-C rate,excellent high rate performance 107.1 m Ah/g at 10-C rate,and high temperature performance 97.39%retention after 60 cycles.These are thought to be related to Zr doping effectively stabilizing the spinel LiMn_(2)O_(4),by forming stronger Zr–O bonds in the octahedron,suppressing the Jahn–Teller effect,thus improving electrochemical performance.展开更多
基金supported by the National Natural Science Foundation of China(21908082,22278426,and 22178154)the Jiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB629)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20221367)the China Postdoctoral Science Foundation(2021M701472)。
文摘LiMn_(2)O_(4)(LMO)electrochemical lithium-ion pump has gained widespread attention due to its green,high efficiency,and low energy consumption in selectively extracting lithium from brine.However,collapse of crystal structure and loss of lithium extraction capacity caused by Mn dissolution loss limits its industrialized application.Hence,a multifunctional coating was developed by depositing amorphous AlPO_(4)on the surface of LMO using sol-gel method.The characterization and electrochemical performance test provided insights into the mechanism of Li^(+)embedment and de-embedment and revealed that multifunctional AlPO_(4)can reconstruct the physical and chemical state of LMO surface to improve the interface hydrophilicity,promote the transport of Li^(+),strengthen cycle stability.Remarkably,after 20 cycles,the capacity retention rate of 0.5AP-LMO reached 93.6%with only 0.147%Mn dissolution loss.The average Li^(+)release capacity of 0.5AP-LMO//Ag system in simulated brine is 28.77 mg/(g h),which is 90.4%higher than LMO.Encouragingly,even in the more complex Zabuye real brine,0.5AP-LMO//Ag can still maintain excellent lithium extraction performance.These results indicate that the 0.5AP-LMO//Ag lithium-ion pump shows promising potential as a Li^(+)selective extraction system.
基金research on high power flexible battery in all sea depth(Grant No.2020-XXXX-XX-246-00)。
文摘The present commercial spinel LiMn_(2)O_(4) delivers only 90 m Ah/g–115 m Ah/g,far lower than the theoretical specific capacity.It degrades fast caused by the Jahn–Teller effect,Mn dissolution and related side reactions that consume Li inventory.In this work,Zr doping is employed to improve the structural stability and electrochemical performance of spinel LiMn_(2)O_(4).Li_(1.06)Mn_(1.94-x)Zr_xO_4(x=0,0.01,0.02,0.04)have been successfully synthesized by a simple solid-state reaction method and evaluated as cathode for lithium ion batteries(LIB).Li_(1.06)Mn_(1.92)Zr_(0.02)O_4 is superior cathode material with a high capacity of 122 m Ah/g at 1-C rate;long cycle stability,98.39%retention after 100 cycles at 1-C rate,excellent high rate performance 107.1 m Ah/g at 10-C rate,and high temperature performance 97.39%retention after 60 cycles.These are thought to be related to Zr doping effectively stabilizing the spinel LiMn_(2)O_(4),by forming stronger Zr–O bonds in the octahedron,suppressing the Jahn–Teller effect,thus improving electrochemical performance.
