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
Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal o...Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal oxides and the poor intrinsic activities of transition metal sites lead to unsatisfactory ORR performance.In this study,eutectic molten salt(EMS)treatment is employed to reconstruct the atomic arrangement of MnFe_(2)O_(4)electrocatalyst as a prototype for enhancing ORR performance.Comprehensive analyses by using XAFS,soft XAS,XPS,and electrochemical methods reveal that the EMS treatment reduces the oxygen vacancies and spinel inverse in MnFe_(2)O_(4)effectively,which improves the electric conductivity and increases the population of more catalytically active Mn^(2+)sites with tetrahedral coordination.Moreover,the enhanced Mn-O interaction after EMS treatment is conducive to the adsorption and activation of O_(2),which promotes the first electron transfer step(generally considered as the ratedetermining step)of the ORR process.As a result,the EMS treated MnFe_(2)O_(4)catalyst delivers a positive shift of 40 mV in the ORR half-wave potential and a two-fold enhanced mass/specific activity.This work provides a convenient approach to manipulate the atomic architecture and local electronic structure of spinel oxides as ORR electrocatalysts and a comprehensive understanding of the structureperformance relationship from the molecular/atomic scale.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
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
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.
基金supported by the National Natural Science Foundation of China (12241502,52002367)the Fundamental Research Funds for the Central Universities (20720220010)the National Key Research and Development Program of China (2019YFA0405602)。
文摘Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal oxides and the poor intrinsic activities of transition metal sites lead to unsatisfactory ORR performance.In this study,eutectic molten salt(EMS)treatment is employed to reconstruct the atomic arrangement of MnFe_(2)O_(4)electrocatalyst as a prototype for enhancing ORR performance.Comprehensive analyses by using XAFS,soft XAS,XPS,and electrochemical methods reveal that the EMS treatment reduces the oxygen vacancies and spinel inverse in MnFe_(2)O_(4)effectively,which improves the electric conductivity and increases the population of more catalytically active Mn^(2+)sites with tetrahedral coordination.Moreover,the enhanced Mn-O interaction after EMS treatment is conducive to the adsorption and activation of O_(2),which promotes the first electron transfer step(generally considered as the ratedetermining step)of the ORR process.As a result,the EMS treated MnFe_(2)O_(4)catalyst delivers a positive shift of 40 mV in the ORR half-wave potential and a two-fold enhanced mass/specific activity.This work provides a convenient approach to manipulate the atomic architecture and local electronic structure of spinel oxides as ORR electrocatalysts and a comprehensive understanding of the structureperformance relationship from the molecular/atomic scale.
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。
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。
