The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its...The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its practical application is hindered by the lack of a compatible electrolyte.Herein,a spray pyrolysis-based energy-saving synthesis method as well as a diluted low concentration electrolyte(0.5 M LiPF_(6) in a mixture of fluoroethylene carbonate/dimethyl carbonate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(FEC:DMC:TTE,1:4:5 by volume))are proposed to address these challenges.Owing to the unique features of the precursor prepared by spray pyrolysis,well-crystallized LNMO single-crystal can be obtained within 1 h calcination at 900℃.Besides,the fluorinated interphases derived from the diluted low concentration electrolyte not only mitigate the Mn dissolution and Al corrosion at the cathode side,but also suppresses dendritic Li deposition at the anode side,thus enabling stable cycling of both LNMO and Li metal anode.Thus,30μm Li|LNMO(1.75 m A h cm^(-2))cells achieve a high capacity retention(90.9%)after 168 cycles in the diluted low concentration electrolyte.展开更多
Oxygen deficiency has crucial effects on the crystal structure and electrochemical performance of spinel oxide lithium electrode materials such as LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode.In particular,the oxygen stoichio...Oxygen deficiency has crucial effects on the crystal structure and electrochemical performance of spinel oxide lithium electrode materials such as LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode.In particular,the oxygen stoichiometry on the crystal surface differs from that on the crystal interior in LNMO.The detection of local oxygen loss in LNMO and its correlation with the crystal structure and the cycling stability of LNMO remain challenging.In this study,the effect of oxygen deficiency in LNMO controlled by sintering temperature on the surface crystal structure and electrochemical performance of LNMO is comprehensively investigated.The high concentration of oxygen vacancies segregates at the surface regions of LNMO forming a thin rock‐salt and/or deficient spinel surface layer.The atomic‐level surface structure reconstruction was demonstrated by annular dark‐field and annular brightfield techniques.For the synthesis of LNMO,the higher sintering temperature results in higher crystallinity but the higher oxygen deficiency in LNMO.The high crystallinity of LNMO would increase the thermal stability of LNMO cathodes while the high content of oxygen deficiency would decrease the surface structural stability of LNMO.Therefore,the LNMO sintered at a medium temperature of 850°C achieved the best capacity retention.The results suggest a competitive function mechanism between oxygen stoichiometry and the crystallinity of LNMO on the cycling performance of LNMO.展开更多
LiMn_(0.5)Fe_(0.5)PO_(4) has attracted great interest due to its good electrochemical performance and higher operating voltages.This has led to a greater than 30 percent higher energy density than for commercial Li Fe...LiMn_(0.5)Fe_(0.5)PO_(4) has attracted great interest due to its good electrochemical performance and higher operating voltages.This has led to a greater than 30 percent higher energy density than for commercial Li Fe PO4 olivine cathodes.Understanding the phase transition behaviors and kinetics of this material will help researchers to design and develop next generation cathodes for Li-ion batteries.In this study,we investigated non-equilibrium phase transition behaviors in a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material during charge–discharge processes by varying current rates(C-rates)using synchrotron in-situ X-ray techniques.These methods included wide angle X-ray scattering(in-situ WAXS)and X-ray absorption spectroscopy(in-situ XAS).The WAXS spectra indicate that the phase transition of LiMn_(0.5)Fe_(0.5)PO_(4) material at slow C-rates is induced by a two-phase reaction.In contrast,at a high C-rate(5 C),the formation of an intermediate phase upon discharge is clearly observed.Concurrently,the oxidation numbers of the redox reactions of Fe^(2+)/Fe^(3+)and Mn^(2+)/Mn^(3+)were evaluated using in-situ XAS.This combination of synchrotron in-situ X-ray techniques gives clear insights into the non-equilibrium phase transition behavior of a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material.This new understanding will be useful for further developments of this highly promising cathode material for practical commercialization.展开更多
以不同的镍源和锰源采用共沉淀法制备LiNi_(0.5)Mn_(1.5)O_(4)正极材料,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试等手段,对制备的LiNi_(0.5)Mn_(1.5)O_(4)材料进行表征和分析。结果表明:以硫酸镍和硫酸锰为原料制得LiNi_(0...以不同的镍源和锰源采用共沉淀法制备LiNi_(0.5)Mn_(1.5)O_(4)正极材料,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试等手段,对制备的LiNi_(0.5)Mn_(1.5)O_(4)材料进行表征和分析。结果表明:以硫酸镍和硫酸锰为原料制得LiNi_(0.5)Mn_(1.5)O_(4)材料的XRD谱图没有杂质峰,SEM图像显示颗粒细小且分散均匀,电化学测试显示在0.2C下首次放电比容量为115.83 m Ah/g,相比于其他镍源和锰源制备的LiNi_(0.5)Mn_(1.5)O_(4)材料,具有更优的电化学性能。展开更多
LiNi_(0.5)Mn_(1.5)O_(4) and LiMn_(2)O_(4) with novel spinel morphology were synthesized by a hydrothermal and postcalcination process.The synthesized LiMn_(2)O_(4) particles(5–10 lm)are uniform hexahedron,while the L...LiNi_(0.5)Mn_(1.5)O_(4) and LiMn_(2)O_(4) with novel spinel morphology were synthesized by a hydrothermal and postcalcination process.The synthesized LiMn_(2)O_(4) particles(5–10 lm)are uniform hexahedron,while the LiNi_(0.5)Mn_(1.5)O_(4) has spindle-like morphology with the long axis 10–15 lm,short axis 5–8 lm.Both LiMn_(2)O_(4) and LiNi_(0.5)Mn_(1.5)O_(4) show high capacity when used as cathode materials for Li-ion batteries.In the voltage range of 2.5–5.5 V at room temperature,the LiNi_(0.5)Mn_(1.5)O_(4) has a high discharge capacity of 135.04 mA·h·g^(-1) at 20 mAg^(-1),which is close to 147 mA·h·g^(-1)(theoretical capacity of LiNi_(0.5)Mn_(1.5)O_(4)).The discharge capacity of LiMn_(2)O_(4) is 131.08 mA·h·g^(-1) at 20 mAg^(-1).Moreover,the LiNi_(0.5)Mn_(1.5)O_(4) shows a higher capacity retention(76%)compared to that of LiMn_(2)O_(4)(61%)after 50 cycles.The morphology and structure of LiMn_(2)O_(4) and LiNi_(0.5)Mn_(1.5)O_(4) are well kept even after cycling as demonstrated by SEM and XRD on cycled LiMn_(2)O_(4) and LiNi_(0.5)Mn_(1.5)O_(4) electrodes.展开更多
The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)has been attracted great attention as lithium ion cathode material due to its high voltage and large energy density.However,the practical application of LNMO is still limited by...The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)has been attracted great attention as lithium ion cathode material due to its high voltage and large energy density.However,the practical application of LNMO is still limited by poor cycling stability.Herein,to improve the cycling stability of spinel LNMO,it was treated with anneal process at 900℃for 2 h after prepared by traditional solid-state method(LNMO-A).LNMO-A sample presented better electrochemical property especially under high rate,with capacity of 91.2 mAhg^(-1) after 1000 cycles under 10 C.Its superior electrochemical property was ascribed to the anneal process,resulting a stable crystal structure,indicated by XRD and Raman results of electrodes after 1000 cycles under 10 C and the longer solid-solution reaction,revealed by in-situ XRD.In addition,the optimized particle size,micro morphology and the larger BET area surface induced by the recrystallization in anneal process also contributes to its superior electrochemical property.What's more,the thin layer,which interacted LNMO-A particles with each other,induced by particles remelting in anneal process is also beneficial for its excellent electrochemical property.This study not only improved the electrochemical properties by anneal process,but also revealed the origins and mechanisms for its improvement.展开更多
Transition metal cation ordering is essential for controlling the electrochemical performance of cubic spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),which is conventionally adjusted by optimizing the high temperature sintering...Transition metal cation ordering is essential for controlling the electrochemical performance of cubic spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),which is conventionally adjusted by optimizing the high temperature sintering and annealing procedures.In this present work,multiple characterization techniques,including 6,7Li NMR,XRD and HRTEM,have been combined to trace the phase transformation and morphology evolution during synthesis.It has been illustrated that simultaneous formation of LiMn_(2)O_(4)(LMO)and LiNiO_(2)(LNO)binary oxides and their conversion into highly reactive LixNi^(3+)_(y)Mn_(3.5+)_(z)O ternary intermediate is a thermal dynamically difficult but crucial step in the synthesis of LNMO ternary oxide.A new strategy of modifying the intermediates formation pathway from binary mode to ternary mode using thermal regulating agent has been adopted.LNMO synthesized with thermal regulating agent exhibits supreme rate capability,long-cycling performance(even at elevated temperature)and excellent capacity efficiency.At a high rate of 100 C,the assembled battery delivers a discharge capacity of 99 mAh g^(-1).This study provides a way to control the formation pathway of complex oxides using thermal regulating agent.展开更多
Co-precipitation is an important issue in chemical analysis, where it is often undesirable, but in some cases, it can be exploited. The Zn0.5Mn0.5−xLi2xFe2O4 nanomaterials (x = 0.0, 0.1, 0.2, 0.3 and 0.4) wa...Co-precipitation is an important issue in chemical analysis, where it is often undesirable, but in some cases, it can be exploited. The Zn0.5Mn0.5−xLi2xFe2O4 nanomaterials (x = 0.0, 0.1, 0.2, 0.3 and 0.4) was afforded by utilizing co-precipitation method. The structural and optical characteristics were analyzed for the samples employing X-ray diffraction (XRD), Fourier transforms infrared spectroscopy (FTIR) and Ultraviolet-visible spectrophotometer (UV-Vis). XRD revealed that the structure of certain nanoparticles is a cubic spinel with space group (Fd-3m) and crystallite size in the scale 124 - 150 nm. Lattice parameter was determined to increments with Li+1 and that may occur due to the larger ionic radius of the Li1+ ion. FTIR spectroscopy confirmed the form of spinel ferrite and explicated the properties of absorption bands approximately 593, 1111, 1385, 1640, 2922 and 3430. The energy band gap was estimated for all samples with diverse ratios and was observed in the range of 2.58 - 2.52 eV.展开更多
The organic carbon source coating LiFe_(x)Mn_(1-x)PO_(4)suffers from the problem of non-uniform carbon cladding.Too thick carbon cladding layer instead hinders the de-embedding of lithium ions.In this paper,we choose ...The organic carbon source coating LiFe_(x)Mn_(1-x)PO_(4)suffers from the problem of non-uniform carbon cladding.Too thick carbon cladding layer instead hinders the de-embedding of lithium ions.In this paper,we choose cornstalk as the carbon source,then LiFe_(0.5)Mn_(0.5)PO_(4)@cornstalk-C(LFMP@C-C)with 3D anchoring structure is prepared by the solvothermal method.The results show that the LFMP with cornstalk as the carbon source has better performance compared to the sucrose-coated LFMP material(LFMP@C).The discharge capacity of LFMP@C-C is 116 mAh/g for the first cycle at 1 C and the capacity retention rate is 94.0%after 500 cycles,and the discharge capacity of LFMP@C-C is more than 17.17%higher than that of LFMP@C.展开更多
基金supported by the Fund of University of South China (No.201RGC013 and N0.200XQD052)。
文摘The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its practical application is hindered by the lack of a compatible electrolyte.Herein,a spray pyrolysis-based energy-saving synthesis method as well as a diluted low concentration electrolyte(0.5 M LiPF_(6) in a mixture of fluoroethylene carbonate/dimethyl carbonate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(FEC:DMC:TTE,1:4:5 by volume))are proposed to address these challenges.Owing to the unique features of the precursor prepared by spray pyrolysis,well-crystallized LNMO single-crystal can be obtained within 1 h calcination at 900℃.Besides,the fluorinated interphases derived from the diluted low concentration electrolyte not only mitigate the Mn dissolution and Al corrosion at the cathode side,but also suppresses dendritic Li deposition at the anode side,thus enabling stable cycling of both LNMO and Li metal anode.Thus,30μm Li|LNMO(1.75 m A h cm^(-2))cells achieve a high capacity retention(90.9%)after 168 cycles in the diluted low concentration electrolyte.
基金National Natural Science Foundation of China,Grant/Award Numbers:22075003,22090043,U1930401,U2030206。
文摘Oxygen deficiency has crucial effects on the crystal structure and electrochemical performance of spinel oxide lithium electrode materials such as LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode.In particular,the oxygen stoichiometry on the crystal surface differs from that on the crystal interior in LNMO.The detection of local oxygen loss in LNMO and its correlation with the crystal structure and the cycling stability of LNMO remain challenging.In this study,the effect of oxygen deficiency in LNMO controlled by sintering temperature on the surface crystal structure and electrochemical performance of LNMO is comprehensively investigated.The high concentration of oxygen vacancies segregates at the surface regions of LNMO forming a thin rock‐salt and/or deficient spinel surface layer.The atomic‐level surface structure reconstruction was demonstrated by annular dark‐field and annular brightfield techniques.For the synthesis of LNMO,the higher sintering temperature results in higher crystallinity but the higher oxygen deficiency in LNMO.The high crystallinity of LNMO would increase the thermal stability of LNMO cathodes while the high content of oxygen deficiency would decrease the surface structural stability of LNMO.Therefore,the LNMO sintered at a medium temperature of 850°C achieved the best capacity retention.The results suggest a competitive function mechanism between oxygen stoichiometry and the crystallinity of LNMO on the cycling performance of LNMO.
基金the Science Achievement Scholarship of Thailand(SAST)for financial supportpartially supported by the Institute of Nanomaterials Research and Innovation for Energy(IN-RIE)+1 种基金the Research and Graduate Studies,Khon Kaen University(KKU)Synchrotron Light Research Institute(SLRI),Thailand。
文摘LiMn_(0.5)Fe_(0.5)PO_(4) has attracted great interest due to its good electrochemical performance and higher operating voltages.This has led to a greater than 30 percent higher energy density than for commercial Li Fe PO4 olivine cathodes.Understanding the phase transition behaviors and kinetics of this material will help researchers to design and develop next generation cathodes for Li-ion batteries.In this study,we investigated non-equilibrium phase transition behaviors in a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material during charge–discharge processes by varying current rates(C-rates)using synchrotron in-situ X-ray techniques.These methods included wide angle X-ray scattering(in-situ WAXS)and X-ray absorption spectroscopy(in-situ XAS).The WAXS spectra indicate that the phase transition of LiMn_(0.5)Fe_(0.5)PO_(4) material at slow C-rates is induced by a two-phase reaction.In contrast,at a high C-rate(5 C),the formation of an intermediate phase upon discharge is clearly observed.Concurrently,the oxidation numbers of the redox reactions of Fe^(2+)/Fe^(3+)and Mn^(2+)/Mn^(3+)were evaluated using in-situ XAS.This combination of synchrotron in-situ X-ray techniques gives clear insights into the non-equilibrium phase transition behavior of a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material.This new understanding will be useful for further developments of this highly promising cathode material for practical commercialization.
文摘以不同的镍源和锰源采用共沉淀法制备LiNi_(0.5)Mn_(1.5)O_(4)正极材料,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试等手段,对制备的LiNi_(0.5)Mn_(1.5)O_(4)材料进行表征和分析。结果表明:以硫酸镍和硫酸锰为原料制得LiNi_(0.5)Mn_(1.5)O_(4)材料的XRD谱图没有杂质峰,SEM图像显示颗粒细小且分散均匀,电化学测试显示在0.2C下首次放电比容量为115.83 m Ah/g,相比于其他镍源和锰源制备的LiNi_(0.5)Mn_(1.5)O_(4)材料,具有更优的电化学性能。
基金the National Natural Science Foundation of China(52022109 and 51834008)Beijing Municipal Natural Science Foundation(2202047)+1 种基金Science Foundation of China University of Petroleum,Beijing(2462018YJRC041 and 2462020YXZZ016)the Opening Project of State Key Laboratory of Advanced Chemical Power Sources(SKL-ACPS-C-20).
文摘LiNi_(0.5)Mn_(1.5)O_(4) and LiMn_(2)O_(4) with novel spinel morphology were synthesized by a hydrothermal and postcalcination process.The synthesized LiMn_(2)O_(4) particles(5–10 lm)are uniform hexahedron,while the LiNi_(0.5)Mn_(1.5)O_(4) has spindle-like morphology with the long axis 10–15 lm,short axis 5–8 lm.Both LiMn_(2)O_(4) and LiNi_(0.5)Mn_(1.5)O_(4) show high capacity when used as cathode materials for Li-ion batteries.In the voltage range of 2.5–5.5 V at room temperature,the LiNi_(0.5)Mn_(1.5)O_(4) has a high discharge capacity of 135.04 mA·h·g^(-1) at 20 mAg^(-1),which is close to 147 mA·h·g^(-1)(theoretical capacity of LiNi_(0.5)Mn_(1.5)O_(4)).The discharge capacity of LiMn_(2)O_(4) is 131.08 mA·h·g^(-1) at 20 mAg^(-1).Moreover,the LiNi_(0.5)Mn_(1.5)O_(4) shows a higher capacity retention(76%)compared to that of LiMn_(2)O_(4)(61%)after 50 cycles.The morphology and structure of LiMn_(2)O_(4) and LiNi_(0.5)Mn_(1.5)O_(4) are well kept even after cycling as demonstrated by SEM and XRD on cycled LiMn_(2)O_(4) and LiNi_(0.5)Mn_(1.5)O_(4) electrodes.
基金Natural Science Foundation of Shandong Province(ZR2018MEM017)。
文摘The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)has been attracted great attention as lithium ion cathode material due to its high voltage and large energy density.However,the practical application of LNMO is still limited by poor cycling stability.Herein,to improve the cycling stability of spinel LNMO,it was treated with anneal process at 900℃for 2 h after prepared by traditional solid-state method(LNMO-A).LNMO-A sample presented better electrochemical property especially under high rate,with capacity of 91.2 mAhg^(-1) after 1000 cycles under 10 C.Its superior electrochemical property was ascribed to the anneal process,resulting a stable crystal structure,indicated by XRD and Raman results of electrodes after 1000 cycles under 10 C and the longer solid-solution reaction,revealed by in-situ XRD.In addition,the optimized particle size,micro morphology and the larger BET area surface induced by the recrystallization in anneal process also contributes to its superior electrochemical property.What's more,the thin layer,which interacted LNMO-A particles with each other,induced by particles remelting in anneal process is also beneficial for its excellent electrochemical property.This study not only improved the electrochemical properties by anneal process,but also revealed the origins and mechanisms for its improvement.
基金financially supported by the National Natural Science Foundation of China(Grant No.21673065 and 21875057)the Key-Area Research and Development Program of Guangdong Province(No.1934212200002)the Innovation and Entrepreneurship Team Project of Zhuhai(No.ZH01110405170016PWC)。
文摘Transition metal cation ordering is essential for controlling the electrochemical performance of cubic spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),which is conventionally adjusted by optimizing the high temperature sintering and annealing procedures.In this present work,multiple characterization techniques,including 6,7Li NMR,XRD and HRTEM,have been combined to trace the phase transformation and morphology evolution during synthesis.It has been illustrated that simultaneous formation of LiMn_(2)O_(4)(LMO)and LiNiO_(2)(LNO)binary oxides and their conversion into highly reactive LixNi^(3+)_(y)Mn_(3.5+)_(z)O ternary intermediate is a thermal dynamically difficult but crucial step in the synthesis of LNMO ternary oxide.A new strategy of modifying the intermediates formation pathway from binary mode to ternary mode using thermal regulating agent has been adopted.LNMO synthesized with thermal regulating agent exhibits supreme rate capability,long-cycling performance(even at elevated temperature)and excellent capacity efficiency.At a high rate of 100 C,the assembled battery delivers a discharge capacity of 99 mAh g^(-1).This study provides a way to control the formation pathway of complex oxides using thermal regulating agent.
文摘Co-precipitation is an important issue in chemical analysis, where it is often undesirable, but in some cases, it can be exploited. The Zn0.5Mn0.5−xLi2xFe2O4 nanomaterials (x = 0.0, 0.1, 0.2, 0.3 and 0.4) was afforded by utilizing co-precipitation method. The structural and optical characteristics were analyzed for the samples employing X-ray diffraction (XRD), Fourier transforms infrared spectroscopy (FTIR) and Ultraviolet-visible spectrophotometer (UV-Vis). XRD revealed that the structure of certain nanoparticles is a cubic spinel with space group (Fd-3m) and crystallite size in the scale 124 - 150 nm. Lattice parameter was determined to increments with Li+1 and that may occur due to the larger ionic radius of the Li1+ ion. FTIR spectroscopy confirmed the form of spinel ferrite and explicated the properties of absorption bands approximately 593, 1111, 1385, 1640, 2922 and 3430. The energy band gap was estimated for all samples with diverse ratios and was observed in the range of 2.58 - 2.52 eV.
基金supported by CITIC Dameng Mining Industries Limited-Guangxi University Joint Research Institute of manganese resources utilization and advanced materials technology,Guangxi University-CITIC Dameng Mining Industries Limited Joint base of postgraduate cultivation,National Natural Science Foundation of China(No.11364003)Guangxi Innovation Driven Development Project(Nos.AA17204100,AA18118052)the Natural Science Foundation of Guangxi Province(No.2018GXNSFAA138186)。
文摘The organic carbon source coating LiFe_(x)Mn_(1-x)PO_(4)suffers from the problem of non-uniform carbon cladding.Too thick carbon cladding layer instead hinders the de-embedding of lithium ions.In this paper,we choose cornstalk as the carbon source,then LiFe_(0.5)Mn_(0.5)PO_(4)@cornstalk-C(LFMP@C-C)with 3D anchoring structure is prepared by the solvothermal method.The results show that the LFMP with cornstalk as the carbon source has better performance compared to the sucrose-coated LFMP material(LFMP@C).The discharge capacity of LFMP@C-C is 116 mAh/g for the first cycle at 1 C and the capacity retention rate is 94.0%after 500 cycles,and the discharge capacity of LFMP@C-C is more than 17.17%higher than that of LFMP@C.
