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
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
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
A normal spinel LiMn_2O_4 as cathode material for lithium-ion cells wascycled galvanostatically (0.2 C) at 55 deg C. To determine the contribution of each voltage plateauto the total capacity fading of the cathode upo...A normal spinel LiMn_2O_4 as cathode material for lithium-ion cells wascycled galvanostatically (0.2 C) at 55 deg C. To determine the contribution of each voltage plateauto the total capacity fading of the cathode upon repeated cycling, the capacities in each plateauwere separated by differentiation of voltage vs. capacity. The results how that the capacity fadingin the upper voltage plateau is more rapidly than that in the lower during discharging, while incharging process, it fades slower than that in the lower voltage range. The increased capacity shiftand aggravated self-discharge/electrolyte oxidation during discharging contribute to a high fadingrate in the upper step. Capacity shift also takes place during charging process, which againenhancing the fading rate of the lower voltage plateau. An increase in capacity shift, as a resultof an increase in polarization of the cell, plays a major role in determining the fading rate ineach voltage plateau, further reflecting the thickening of the passivation layer on the activeparticles, and the accumulation of electrolyte decomposition. The relative capacity loss formodified spinels is well correlated with the relative increase in the polarization of thehalf-cells, confirming the above causes for capacity fade of this kind of cathode material.展开更多
The spinel LiMn_2O_(4-δ)Fδ cathode materials were synthesized by solid-state reaction, With calculated amounts of LiOH·H_2O, MnO_2(EMD). LiF. The results of electrochemical test demonstrated that these new mate...The spinel LiMn_2O_(4-δ)Fδ cathode materials were synthesized by solid-state reaction, With calculated amounts of LiOH·H_2O, MnO_2(EMD). LiF. The results of electrochemical test demonstrated that these new materials exhibited excellent electrochemical properties.Its initial capacity reached -115 mAb·g^(-1) and reversible efficiency is about 100%. After 60 cycles. its capacity was still around 110 mAh· g^(-1), with nearly 100% reversible efficiency,展开更多
通过溶胶凝胶法制备出LiMn_2O_4和LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)锂离子电池正极材料,并用XRD、SEM、XPS、充放电测试和CV对其结构、形貌、化学成份以及电化学性能进行了研究。结果表明,Mg、Br的掺杂未改变LiMn_2O_4的结构。在0...通过溶胶凝胶法制备出LiMn_2O_4和LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)锂离子电池正极材料,并用XRD、SEM、XPS、充放电测试和CV对其结构、形貌、化学成份以及电化学性能进行了研究。结果表明,Mg、Br的掺杂未改变LiMn_2O_4的结构。在0.5 C倍率下,LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)的放电比容量为119 m Ah/g,与LiMn_2O_4相比,其首次放电比容量提高了3.6%,循环100次后,Li Mn1.92Mg0.08O3.84Br0.16的容量保持率高达86.9%。在5 C倍率下,LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)的放电比容量为91.1 m Ah/g,比LiMn_2O_4提高了24.1%。实验表明,Mg、Br共同掺杂提高了LiMn_2O_4的放电比容量,并明显改善其循环稳定性和倍率性能,从而获得了较好的综合电化学性能。展开更多
The spinel-type LiMn_(2)O_(4) is a promising candidate as cathode material for rechargeable Li-ion batteries due to its good thermal stability and safety.Experimentally,it is observed that in this compound there occur...The spinel-type LiMn_(2)O_(4) is a promising candidate as cathode material for rechargeable Li-ion batteries due to its good thermal stability and safety.Experimentally,it is observed that in this compound there occur the structural phase transitions from cubic(Fd3m)to tetragonal(I4_(1)/amd)phase at slightly below room temperature.To understand the phase transition mechanism,we compare the Gibbs free energy between cubic phase and tetragonal phase by including the configurational entropy.Our results show that the configurational entropy contributes substantially to the stability of the cubic phase at room temperature due to the disordered Mn^(3+)/Mn^(4+)distribution as well as the orientation of the Jahn-Teller elongation of the Mn^(3+)O_(6) octahedron in the the spinel phase.Meanwhile,the phase transition temperature is predicted to be 267.8 K,which is comparable to the experimentally observed temperature.These results serve as a good complement to the experimental study,and are beneficial to the improving of the electrochemical performance of LiMn_(2)O_(4) cathode.展开更多
为进一步提高动力电池正极材料锰酸锂(LiMn_2O_4)的循环稳定性,通过溶胶-凝胶法用快离子导体La_(0.8)Sr_(0.2)MnO_3作为包覆材料对LiMn_2O_4进行表面修饰,探讨了不同包覆量对复合材料电化学性能的影响。采用X射线衍射仪(XRD)、场发射扫...为进一步提高动力电池正极材料锰酸锂(LiMn_2O_4)的循环稳定性,通过溶胶-凝胶法用快离子导体La_(0.8)Sr_(0.2)MnO_3作为包覆材料对LiMn_2O_4进行表面修饰,探讨了不同包覆量对复合材料电化学性能的影响。采用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)和透射电子显微镜(TEM)对样品的微观结构以及形貌进行表征。结果表明:La_(0.8)Sr_(0.2)MnO_3的包覆并没有改变LiMn_2O_4晶体结构及空间构型;相比纯的LiMn_2O_4样品,La_(0.8)Sr_(0.2)MnO_3包覆后的样品颗粒表面较为粗糙;涂层为薄膜状结构,均匀且完全包覆在LiMn_2O_4颗粒的表面。利用电化学测试方法测试其电化学性能,测试结果表明,当La_(0.8)Sr_(0.2)MnO_3包覆量为5%时,具有较好的电化学性能,首次放电比容量为127.4 m A·h/g(0.1 C),25℃循环400次后容量保持率为91.2%,55℃循环100次后容量保持率为91.1%;与未经表面修饰的样品相比,其首次放电比容量为119.1 m A·h/g(0.1 C),400次的容量保持率为61.9%,100次容量保持率为77.9%,La_(0.8)Sr_(0.2)MnO_3包覆后的样品的电化学性能尤其是循环性能得到明显的提高。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.
文摘A normal spinel LiMn_2O_4 as cathode material for lithium-ion cells wascycled galvanostatically (0.2 C) at 55 deg C. To determine the contribution of each voltage plateauto the total capacity fading of the cathode upon repeated cycling, the capacities in each plateauwere separated by differentiation of voltage vs. capacity. The results how that the capacity fadingin the upper voltage plateau is more rapidly than that in the lower during discharging, while incharging process, it fades slower than that in the lower voltage range. The increased capacity shiftand aggravated self-discharge/electrolyte oxidation during discharging contribute to a high fadingrate in the upper step. Capacity shift also takes place during charging process, which againenhancing the fading rate of the lower voltage plateau. An increase in capacity shift, as a resultof an increase in polarization of the cell, plays a major role in determining the fading rate ineach voltage plateau, further reflecting the thickening of the passivation layer on the activeparticles, and the accumulation of electrolyte decomposition. The relative capacity loss formodified spinels is well correlated with the relative increase in the polarization of thehalf-cells, confirming the above causes for capacity fade of this kind of cathode material.
文摘The spinel LiMn_2O_(4-δ)Fδ cathode materials were synthesized by solid-state reaction, With calculated amounts of LiOH·H_2O, MnO_2(EMD). LiF. The results of electrochemical test demonstrated that these new materials exhibited excellent electrochemical properties.Its initial capacity reached -115 mAb·g^(-1) and reversible efficiency is about 100%. After 60 cycles. its capacity was still around 110 mAh· g^(-1), with nearly 100% reversible efficiency,
文摘通过溶胶凝胶法制备出LiMn_2O_4和LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)锂离子电池正极材料,并用XRD、SEM、XPS、充放电测试和CV对其结构、形貌、化学成份以及电化学性能进行了研究。结果表明,Mg、Br的掺杂未改变LiMn_2O_4的结构。在0.5 C倍率下,LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)的放电比容量为119 m Ah/g,与LiMn_2O_4相比,其首次放电比容量提高了3.6%,循环100次后,Li Mn1.92Mg0.08O3.84Br0.16的容量保持率高达86.9%。在5 C倍率下,LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)的放电比容量为91.1 m Ah/g,比LiMn_2O_4提高了24.1%。实验表明,Mg、Br共同掺杂提高了LiMn_2O_4的放电比容量,并明显改善其循环稳定性和倍率性能,从而获得了较好的综合电化学性能。
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12174162,51962010,12064015,and 12064014).
文摘The spinel-type LiMn_(2)O_(4) is a promising candidate as cathode material for rechargeable Li-ion batteries due to its good thermal stability and safety.Experimentally,it is observed that in this compound there occur the structural phase transitions from cubic(Fd3m)to tetragonal(I4_(1)/amd)phase at slightly below room temperature.To understand the phase transition mechanism,we compare the Gibbs free energy between cubic phase and tetragonal phase by including the configurational entropy.Our results show that the configurational entropy contributes substantially to the stability of the cubic phase at room temperature due to the disordered Mn^(3+)/Mn^(4+)distribution as well as the orientation of the Jahn-Teller elongation of the Mn^(3+)O_(6) octahedron in the the spinel phase.Meanwhile,the phase transition temperature is predicted to be 267.8 K,which is comparable to the experimentally observed temperature.These results serve as a good complement to the experimental study,and are beneficial to the improving of the electrochemical performance of LiMn_(2)O_(4) cathode.
文摘为进一步提高动力电池正极材料锰酸锂(LiMn_2O_4)的循环稳定性,通过溶胶-凝胶法用快离子导体La_(0.8)Sr_(0.2)MnO_3作为包覆材料对LiMn_2O_4进行表面修饰,探讨了不同包覆量对复合材料电化学性能的影响。采用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)和透射电子显微镜(TEM)对样品的微观结构以及形貌进行表征。结果表明:La_(0.8)Sr_(0.2)MnO_3的包覆并没有改变LiMn_2O_4晶体结构及空间构型;相比纯的LiMn_2O_4样品,La_(0.8)Sr_(0.2)MnO_3包覆后的样品颗粒表面较为粗糙;涂层为薄膜状结构,均匀且完全包覆在LiMn_2O_4颗粒的表面。利用电化学测试方法测试其电化学性能,测试结果表明,当La_(0.8)Sr_(0.2)MnO_3包覆量为5%时,具有较好的电化学性能,首次放电比容量为127.4 m A·h/g(0.1 C),25℃循环400次后容量保持率为91.2%,55℃循环100次后容量保持率为91.1%;与未经表面修饰的样品相比,其首次放电比容量为119.1 m A·h/g(0.1 C),400次的容量保持率为61.9%,100次容量保持率为77.9%,La_(0.8)Sr_(0.2)MnO_3包覆后的样品的电化学性能尤其是循环性能得到明显的提高。
