LiNixCoyMn_(2)O_(2)(NCM,x≥0.8,x+y+z=1)cathodes have attracted much attention due to their high specific capacity and low cost.However,severe anisotropic volume changes and oxygen evolution induced capacity decay and ...LiNixCoyMn_(2)O_(2)(NCM,x≥0.8,x+y+z=1)cathodes have attracted much attention due to their high specific capacity and low cost.However,severe anisotropic volume changes and oxygen evolution induced capacity decay and insecurity have hindered their commercial application at scale.In order to overcome these challenges,a kind of tantalum(Ta)doped nickel-rich cathode with reduced size and significantly increased number of primary particles is prepared by combining mechanical fusion with high temperature co-calcination.The elaborately designed micro-morphology of small and uniform primary particles effectively eliminates the local strain accumulation caused by the random orientation of primary particles.Moreover,the uniform distribution of small primary particles stabilizes the spherical secondary particles,thus effectively inhibiting the formation and extension of microcracks.In addition,the formed strong Ta-O bonds restrain the release of lattice oxygen,which greatly increases the structural stability and safety of NCM materials.Therefore,the cathode material with the designed primary particle morphology shows superior electrochemical performance.The 1 mol%Ta-modified cathode(defined as1%Ta-NCM)shows a capacity retention of 97.5%after 200 cycles at 1 C and a rate performance of 137.3 mAh g^(-1)at 5 C.This work presents promising approach to improve the structural stability and safety of nickel-rich NCM.展开更多
Promoting inorganic-rich solid-electrolyte interphase (SEI) formation by constructing anion-rich solvated structures is a promising strategy for improving the long-term cycling of lithium-metal batteries.However,the i...Promoting inorganic-rich solid-electrolyte interphase (SEI) formation by constructing anion-rich solvated structures is a promising strategy for improving the long-term cycling of lithium-metal batteries.However,the increase of anions within the solvated structure inevitably reduces the coordination of Li^(+) with the solvent,which leads to a low lithium diffusion coefficient and a decreased lithium conductivity.Here,high entropy electrolyte is achieved by increasing the molecular diversity in electrolyte.Multiple anions (TFSI^(-),FSI^(-),NO_(3)^(-) and PF_(6)^(-)) presented in entropy electrolyte individually coordinate with Li^(+),creating a diverse and anion-rich solvation structure.The large variety of solvation structures leads to a diversified Li^(+) diffusion barriers in the electrolyte,which results in the increase of channels available for Li^(+) diffusion.Thus,three-dimensional diffusion with high Li^(+) diffusion coefficient occurs in HE electrolytes.Furthermore,the anion-rich solvation structures promote the formation of the inorganic-rich SEI.As a result,over 2000 h of reversible Li plating/stripping with a low overpotential less than 27 mV is achieved in Li||Li cell using electrolyte modified by high-entropy strategy.Besides,the Li||LFP full cell with a negative capacity/positive capacity (N/P) ratio of 4.52 exhibits remarkably enhanced cycling stability,retaining 83.6% of its initial capacity after 150 cycles.This strategy offers a novel approach for accelerating Li^(+) transport kinetics and constructing stable SEI in lithium metal batteries.展开更多
基金financial support provided by the National Natural Science Foundation of China(52271201)the Science and Technology Department of Sichuan Province(2025NSFTD0005,2022YFG0100,2022ZYD0045)。
文摘LiNixCoyMn_(2)O_(2)(NCM,x≥0.8,x+y+z=1)cathodes have attracted much attention due to their high specific capacity and low cost.However,severe anisotropic volume changes and oxygen evolution induced capacity decay and insecurity have hindered their commercial application at scale.In order to overcome these challenges,a kind of tantalum(Ta)doped nickel-rich cathode with reduced size and significantly increased number of primary particles is prepared by combining mechanical fusion with high temperature co-calcination.The elaborately designed micro-morphology of small and uniform primary particles effectively eliminates the local strain accumulation caused by the random orientation of primary particles.Moreover,the uniform distribution of small primary particles stabilizes the spherical secondary particles,thus effectively inhibiting the formation and extension of microcracks.In addition,the formed strong Ta-O bonds restrain the release of lattice oxygen,which greatly increases the structural stability and safety of NCM materials.Therefore,the cathode material with the designed primary particle morphology shows superior electrochemical performance.The 1 mol%Ta-modified cathode(defined as1%Ta-NCM)shows a capacity retention of 97.5%after 200 cycles at 1 C and a rate performance of 137.3 mAh g^(-1)at 5 C.This work presents promising approach to improve the structural stability and safety of nickel-rich NCM.
基金supported by the National Natural Science Foundation of China (21905033, 52271201)the Science and Technology Department of Sichuan Province (2022YFG0100,2022ZYD0045)。
文摘Promoting inorganic-rich solid-electrolyte interphase (SEI) formation by constructing anion-rich solvated structures is a promising strategy for improving the long-term cycling of lithium-metal batteries.However,the increase of anions within the solvated structure inevitably reduces the coordination of Li^(+) with the solvent,which leads to a low lithium diffusion coefficient and a decreased lithium conductivity.Here,high entropy electrolyte is achieved by increasing the molecular diversity in electrolyte.Multiple anions (TFSI^(-),FSI^(-),NO_(3)^(-) and PF_(6)^(-)) presented in entropy electrolyte individually coordinate with Li^(+),creating a diverse and anion-rich solvation structure.The large variety of solvation structures leads to a diversified Li^(+) diffusion barriers in the electrolyte,which results in the increase of channels available for Li^(+) diffusion.Thus,three-dimensional diffusion with high Li^(+) diffusion coefficient occurs in HE electrolytes.Furthermore,the anion-rich solvation structures promote the formation of the inorganic-rich SEI.As a result,over 2000 h of reversible Li plating/stripping with a low overpotential less than 27 mV is achieved in Li||Li cell using electrolyte modified by high-entropy strategy.Besides,the Li||LFP full cell with a negative capacity/positive capacity (N/P) ratio of 4.52 exhibits remarkably enhanced cycling stability,retaining 83.6% of its initial capacity after 150 cycles.This strategy offers a novel approach for accelerating Li^(+) transport kinetics and constructing stable SEI in lithium metal batteries.
