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 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
The spinel lithium manganese oxide cathode materials were prepared by adipic acid-assisted sol-gel method at 350～900 ℃ in air. The effects of water content of solution, molar ratio between metal ion and adipic acid,...The spinel lithium manganese oxide cathode materials were prepared by adipic acid-assisted sol-gel method at 350～900 ℃ in air. The effects of water content of solution, molar ratio between metal ion and adipic acid, cooling rate, synthesis temperature and particle sizes on structure and electrochemical performance of LiMn_2O_4 are investigated by X-ray diffraction (XRD), and cyclic voltammetry (CV). The result shows that the structure and electrochemical performance of LiMn_2O_4 are greatly affected by synthesis condition, and the optimal synthesis condition is determined. Charge-discharge test reveals that the particle size and cooling rate have significant effects on the electrochemical performance of LiMn_2O_4 cathode materials.展开更多
Modified lithium manganese oxides were prepared by solid-state reaction of LiMn_(2)O_(4)and LiCoO_(2)as raw materials.A study was carried out by TG-DSC,XRD,DSC and electrochemical to analyse the reaction process and s...Modified lithium manganese oxides were prepared by solid-state reaction of LiMn_(2)O_(4)and LiCoO_(2)as raw materials.A study was carried out by TG-DSC,XRD,DSC and electrochemical to analyse the reaction process and structural characterization of products.The results show that the LiMn_(2)O_(4)reacts chemically with LiCoO_(2)at high temperature.All of Li and partial Co atoms can insert into the LiMn_(2)O_(4)crystal lattice and a newly formed spinel phase-modified LiMn_(2)O_(4)was obtained.The distribution of Co content is even in modified LiMn_(2)O_(4)compound.The modified LiMn_(2)O_(4)compound exhibits improved cycling stability at room and elevated temperature in comparison with the pure LiMn_(2)O_(4).展开更多
Electron density plays an important role in determining the properties of functional materials.Revealing the electron density distribution experimentally in real space can help to tune the properties of materials.Spin...Electron density plays an important role in determining the properties of functional materials.Revealing the electron density distribution experimentally in real space can help to tune the properties of materials.Spinel Li Mn2 O4 is one of the most promising cathode candidates because of its high voltage,low cost,and non-toxicity,but suffers severe capacity fading during electrochemical cycling due to the Mn dissolution.Real-space measurement of electron distribution of Li Mn2 O4 experimentally can provide direct evaluation on the strength of Mn–O bond and give an explanation of the structure stability.Here,through high energy synchrotron powder x-ray diffraction(SPXRD),accurate electron density distribution in spinel Li Mn2 O4 has been investigated based on the multipole model.The electron accumulation between Mn and O atoms in deformation density map indicates the shared interaction of Mn–O bond.The quantitative topological analysis at bond critical points shows that the Mn–O bond is relatively weak covalent interaction due to the oxygen loss.These findings suggest that oxygen stoichiometry is the key factor for preventing the Mn dissolution and capacity fading.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
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
KVPO_(4)F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium-ion batteries(PIBs),but limits in sluggish ion transport and severe volume change cause...KVPO_(4)F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium-ion batteries(PIBs),but limits in sluggish ion transport and severe volume change cause insufficient potassium storage capability.Here,a high-energy and low-strain KVPO_(4)F composite cathode assisted by multifunctional K_(2)C_(4)O_(4)electrode stabilizer is exquisitely designed.Systematical electrochemical investigations demonstrate that this composite cathode can deliver a remarkable energy density up to 530 Wh kg^(-1)with 142.7 mAh g^(-1)of reversible capacity at 25 mA g^(-1),outstanding rate capability of 70.6 mAh g^(-1)at 1000 mA g^(-1),and decent cycling stability.Furthermore,slight volume change(~5%)and increased interfacial stability with thin and even cathode-electrolyte interphase can be observed through in situ and ex situ characterizations,which are attributed to the synergistic effect from in situ potassium compensation and carbon deposition through self-sacrificing K_(2)C_(4)O_(4)additive.Moreover,potassium-ion full cells manifest significant improvement in energy density and cycling stability.This work demonstrates a positive impact of K_(2)C_(4)O_(4)additive on the comprehensive electrochemical enhancement,especially the activation of high-voltage plateau capacity and provides an efficient strategy to enlighten the design of other high-voltage cathodes for advanced high-energy batteries.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.
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The spinel lithium manganese oxide cathode materials were prepared by adipic acid-assisted sol-gel method at 350～900 ℃ in air. The effects of water content of solution, molar ratio between metal ion and adipic acid, cooling rate, synthesis temperature and particle sizes on structure and electrochemical performance of LiMn_2O_4 are investigated by X-ray diffraction (XRD), and cyclic voltammetry (CV). The result shows that the structure and electrochemical performance of LiMn_2O_4 are greatly affected by synthesis condition, and the optimal synthesis condition is determined. Charge-discharge test reveals that the particle size and cooling rate have significant effects on the electrochemical performance of LiMn_2O_4 cathode materials.
文摘Modified lithium manganese oxides were prepared by solid-state reaction of LiMn_(2)O_(4)and LiCoO_(2)as raw materials.A study was carried out by TG-DSC,XRD,DSC and electrochemical to analyse the reaction process and structural characterization of products.The results show that the LiMn_(2)O_(4)reacts chemically with LiCoO_(2)at high temperature.All of Li and partial Co atoms can insert into the LiMn_(2)O_(4)crystal lattice and a newly formed spinel phase-modified LiMn_(2)O_(4)was obtained.The distribution of Co content is even in modified LiMn_(2)O_(4)compound.The modified LiMn_(2)O_(4)compound exhibits improved cycling stability at room and elevated temperature in comparison with the pure LiMn_(2)O_(4).
基金Beijing Natural Science Foundation,China(Grant No.Z190010)the National Key Research and Development Program of China(Grant No.2019YFA0308500)+2 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB07030200)Key Research Projects of Frontier Science of Chinese Academy of Sciences(Grant No.QYZDB-SSW-JSC035)the National Natural Science Foundation of China(Grant Nos.51421002,51672307,51991344,52025025,and 52072400).
文摘Electron density plays an important role in determining the properties of functional materials.Revealing the electron density distribution experimentally in real space can help to tune the properties of materials.Spinel Li Mn2 O4 is one of the most promising cathode candidates because of its high voltage,low cost,and non-toxicity,but suffers severe capacity fading during electrochemical cycling due to the Mn dissolution.Real-space measurement of electron distribution of Li Mn2 O4 experimentally can provide direct evaluation on the strength of Mn–O bond and give an explanation of the structure stability.Here,through high energy synchrotron powder x-ray diffraction(SPXRD),accurate electron density distribution in spinel Li Mn2 O4 has been investigated based on the multipole model.The electron accumulation between Mn and O atoms in deformation density map indicates the shared interaction of Mn–O bond.The quantitative topological analysis at bond critical points shows that the Mn–O bond is relatively weak covalent interaction due to the oxygen loss.These findings suggest that oxygen stoichiometry is the key factor for preventing the Mn dissolution and capacity fading.
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.
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.
基金the financial support from the National Key R&D Program of China(Grant No.2023YFE0202000)the National Natural Science Foundation of China(Grant No.52102213)+1 种基金Natural Science Foundation of Jilin Province(Grant No.20230101128JC)Double-Thousand Talents Plan of Jiangxi Province(jxsq2023102005)
文摘KVPO_(4)F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium-ion batteries(PIBs),but limits in sluggish ion transport and severe volume change cause insufficient potassium storage capability.Here,a high-energy and low-strain KVPO_(4)F composite cathode assisted by multifunctional K_(2)C_(4)O_(4)electrode stabilizer is exquisitely designed.Systematical electrochemical investigations demonstrate that this composite cathode can deliver a remarkable energy density up to 530 Wh kg^(-1)with 142.7 mAh g^(-1)of reversible capacity at 25 mA g^(-1),outstanding rate capability of 70.6 mAh g^(-1)at 1000 mA g^(-1),and decent cycling stability.Furthermore,slight volume change(~5%)and increased interfacial stability with thin and even cathode-electrolyte interphase can be observed through in situ and ex situ characterizations,which are attributed to the synergistic effect from in situ potassium compensation and carbon deposition through self-sacrificing K_(2)C_(4)O_(4)additive.Moreover,potassium-ion full cells manifest significant improvement in energy density and cycling stability.This work demonstrates a positive impact of K_(2)C_(4)O_(4)additive on the comprehensive electrochemical enhancement,especially the activation of high-voltage plateau capacity and provides an efficient strategy to enlighten the design of other high-voltage cathodes for advanced high-energy batteries.
