Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In thi...Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In this paper,the M-edge spectra of La ions and the M-edge,L-edge,and K-edge spectra of Mn ions in LaMnO3 are calculated by considering both the free-ion multiplet calculation and the crystal field effects.We analyze spectral shapes,identify peak origins,and estimate the oxidation states of La and Mn ions in LaMnO3 theoretically.It is concluded that La ions in LaMnO3 predominantly exist in the trivalent state,while Mn ions exist primarily in the trivalent state with a minor presence of tetravalent ions.Furthermore,the calculated spectra are in better conformity with the experimental spectra when the proportion of Mn3+is 90%and Mn4+is 10%.This article enhances our comprehension of the oxidation states of La and Mn within the crystal and also provides a valuable guidance for spectroscopic investigations of other manganates.展开更多
The development of high-performance and low-cost cathode materials is of great significance for the progress in lithium-ion batteries.The use of Co and even Ni is not conducive to the sustainable and healthy developme...The development of high-performance and low-cost cathode materials is of great significance for the progress in lithium-ion batteries.The use of Co and even Ni is not conducive to the sustainable and healthy development of the power battery industry owing to their high cost and limited resources.Here,we report LiMn_(2)O_(4)integrated with coating and doping by Sn self-segregation.Auger electron energy spectrum and soft X-ray absorption spectrum show that the coating is Sn-rich LiMn_(2)O_(4),with a small Sn doping in the bulk phase.The integration strategy can not only mitigate the Jahn–Teller distortion but also effectively avoid the dissolution of manganese.The as-obtained product demonstrates superior high initial capacities of 124 mAh·g^(-1)and 120 mAh·g^(-1)with the capacity retention of 91.1%and 90.2%at 25℃and55℃after 50 cycles,respectively.This novel material-processing method highlights a new development direction for the progress of cathode materials for lithium-ion batteries.展开更多
The powder crystals of RMnO3（R=Er, Tm） with hexagonal and orthorhombic structures were prepared under hydrothermal conditions. The different structural phases of the title compounds were controllably formed from dif...The powder crystals of RMnO3（R=Er, Tm） with hexagonal and orthorhombic structures were prepared under hydrothermal conditions. The different structural phases of the title compounds were controllably formed from different kinds of precursors at different reaction temperatures. All of the samples were characterized by powder X-ray diffraction, scanning electron microscopy, inductively coupled plasma analysis, and variable temperature magnetic susceptibility. Their structures were refined by Rietveld method from powder X-ray diffraction data. The measurement of magnetic behavior shows antiferromagnetic orderings at Neel temperatures around 80 and 40 K for the hexagonal and orthorhombic phases, respectively.展开更多
Li-ion batteries(LIBs)have gained wide recognition as effective energy storage devices and power supply sources due to their exceptional volumetric energy density,mass energy density and cycling performance.The cathod...Li-ion batteries(LIBs)have gained wide recognition as effective energy storage devices and power supply sources due to their exceptional volumetric energy density,mass energy density and cycling performance.The cathode materials,a key component of LIBs,play a crucial role in determining the electrochemical performance of these batteries.Therefore,there is an increasing demand to explore and investigate suitable high-energy electrode materials that can provide greater capacity and output voltage for the next generation of LIBs.This paper aims to provide a comprehensive overview of the latest researches on five typical high-voltage cathode materials.Specifically,this review will focus on the detailed analysis of their crystalline structures,reaction mechanisms during cycling,current research status and strategies aimed at improving or enhancing their overall electrochemical performance.Overall,the insights presented in this review will help researchers design and develop high-energy cathode materials with improved performance for the next generation of LIBs.展开更多
new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn_(2)O_(4) from the waste of lithium-ion batteries in NaCl−CaCl_(2) melts at 750°C.The results show that the LiMn_(2)O_...new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn_(2)O_(4) from the waste of lithium-ion batteries in NaCl−CaCl_(2) melts at 750°C.The results show that the LiMn_(2)O_(4) reduction process by the electrochemical method on the coated electrode surface occurs in three steps:Mn(IV)→Mn(III)→Mn(II)→Mn.The products of this electro-deoxidation are CaMn2O4,MnO,(MnO)x(CaO)1−x,and Mn.Metal Mn appears when the electrolytic voltage increases to 2.6 V,which indicates that increasing the voltage may promote the deoxidation reaction process.With the advancement of the three-phase interline(3PI),electric deoxygenation gradually proceeds from the outer area of the crucible to the core.At high voltage,the kinetic process of the reduction reaction is accelerated,which generates double 3PIs at different stages.展开更多
Ni-Al2O3 cermet supported tubular solid oxide fuel cells(SOFCs)with different cathodes were fabricated by thermal spraying.The anode,electrolyte and cathode were deposited by atmospheric plasma spraying(APS)aimed at r...Ni-Al2O3 cermet supported tubular solid oxide fuel cells(SOFCs)with different cathodes were fabricated by thermal spraying.The anode,electrolyte and cathode were deposited by atmospheric plasma spraying(APS)aimed at reducing the manufacturing cost of SOFCs.Three porous composite cathodes of lanthanum strontium manganite(LSM)and yttria-stabilized zirconia(YSZ),lanthanum strontium cobalt oxide(LSC)and YSZ,LSC and scandia-stabilized zirconia(ScSZ)were prepared to investigate influence of cathode constitutions on the cell's performance.The electrode polarization can be improved through using a composite cathode.The maximum power density of the cell with APS YSZ electrolyte and LSC/ScSZ composite cathode is increased about 12%than pure LSM cathode.The maximum output power density of the cell with APS ScSZ electrolyte and LSC/ScSZ composite cathode reaches 1.0 W/cm 2 at 1000 o C.The further optimization of the performance of plasma-sprayed composite cathode can be made through improving the interface contact between YSZ electrolyte and composite cathode.展开更多
The transport properties and magnetoresistance of electron-doped manganate / insulator composites （Lao.sTeo.2MnO3）l-x/（ZrO2）x （x = 0, 0.3, and 0.5） are investigated. It is found that the metal-insulator transiti...The transport properties and magnetoresistance of electron-doped manganate / insulator composites （Lao.sTeo.2MnO3）l-x/（ZrO2）x （x = 0, 0.3, and 0.5） are investigated. It is found that the metal-insulator transition temperature of this system shifts to a lower value as the ZrO2 content increases. The introduction of ZrO2 enhances both the domain scattering and electron relative scattering in the metal transport region. In the adiabatic small polaron hopping transport region, the thermal activation energy seems invariable regardless of the ZrO2 content. The applica- tion of a magnetic field promotes the charge transportation capabilities of the composites, and the magnetoresistance is enhanced with an increase of the ZrO2 content. This could be attributed to the more remarkable modification effect of magnetic field on ordering degree in the composites than in pure Lao.sTe0.2MnO3.展开更多
In order to study the phase transformation between 1nm manganate and 0.7nm manganate, a series of Slum Me^(2+) manganates were made after the synthetic 1nm Na^+ manganate substituted with different kinds of divalent c...In order to study the phase transformation between 1nm manganate and 0.7nm manganate, a series of Slum Me^(2+) manganates were made after the synthetic 1nm Na^+ manganate substituted with different kinds of divalent cations. The X-ray diffraction analysis of wet S1nm Me^(2+) manganates after 24 h room temperature dry showed that their basal d-spacing had been changed, indicating that there was phase transformation between 1nm and 0.7nm manganates. Take 1nm manganates with unstable structure collapsed into 0. 7nm manganate by losing one interlayer OH-H_2O, while those with stable structure still retained the 1nm d-spacing. This factor reminds us that the manganese nodule samples must be kept in wet condition to avoid the misleading results. The structural stabdity of 1nn manganate is mainly controlled by the interlayer divalent cations. There is a possitive correlation between the amount of cations in the interlayer and the structural stability, while the capacity of different canons in stabilizing the structure of 1nm manganate is as follows: Ni > Cu > Co > Zn > Ca>Mg > Na.展开更多
Synthetic Ium manganate has been made in the laboratory at low temperature. The d-spaciug of which shows 1. 002 nm, 0. 501 nm and 0. 34 nm respectively. As the analogue of natural 1nm manganate, it has been used for ...Synthetic Ium manganate has been made in the laboratory at low temperature. The d-spaciug of which shows 1. 002 nm, 0. 501 nm and 0. 34 nm respectively. As the analogue of natural 1nm manganate, it has been used for a serieS of experiments of divalent cations substitution. The results indicate that the 1nm manganate has very strong cation substitution capacity, which probable is the reason of the valuable metal such as Cu, Ni and Co enriched in the manganese nodules. The preference of canons substituting into S 1nm manganate is Cu>Co>Zn≥Ni>Ca>Mg. In the manganese nodules, the content of Ni is usually higher than that of Cu and Co, but in the cation substitution, the latter two are more preference than the former. One can infer from this differentiation that the post-deposition cation substitution is not the sole mechanism by which the valuable metals enter the manganese nodules. It could be the results of combined effects of both original formation and the post-deposition substitution of canons,which leads to the enrichment of valuable metal in the manganese nodules.展开更多
Spinel LiMn_(2)O_(4)is recognized as one of the most competitive cathode candidates for lithium-ion batteries ascribed to environmentally benign and rich sources.However,the wholesale application of LiMn_(2)O_(4)is pr...Spinel LiMn_(2)O_(4)is recognized as one of the most competitive cathode candidates for lithium-ion batteries ascribed to environmentally benign and rich sources.However,the wholesale application of LiMn_(2)O_(4)is predominately plagued by its severe capacity degradation,mainly associated with the innate Jahn-Teller effect.Herein,single-crystalline LiMn_(2)O_(4)with Eu^(3+) doping is rationally designed to mitigate the detrimental Jahn-Teller distortion by tuning the chemical environment of MnO_(6) octahedra and accommodating localized electron,based on the unique aspheric flexible 4f electron orbit of rare-earth metal ions.Notably,the stretching of MnO_(6) octahedron stemmed from the Jahn-Teller effect in Eu-doped LiMn_(2)O_(4)is effectively suppressed,confirmed by theoretical calculation.Meanwhile,the structural stability of the material has been significantly enhanced due to the robust Mn–O band coherency and weakened phase transition,proved by synchrotron radiation absorption spectrum and operando X-ray diffraction.The corresponding active cathode manifests superior long-cycle stability after 300 loops at 2C and displays only a 0.011%capacity drop per cycle even at 5C.Given this,this modification tactic sheds new light on achieving superior long-cycle performances by suppressing distortion in various cathode materials.展开更多
Low concentration alkaline leaching was used for predesilication treatment of low-grade pyrolusite. The effects of initial NaOH concentration, liquid-to-solid ratio, leaching temperature, leaching time and stirring sp...Low concentration alkaline leaching was used for predesilication treatment of low-grade pyrolusite. The effects of initial NaOH concentration, liquid-to-solid ratio, leaching temperature, leaching time and stirring speed on silica leaching rate were investigated and the kinetics of alkaline leaching process was studied. The results show that silica leaching rate reached 91.2% under the conditions of initial NaOH concentration of 20%, liquid-to-solid ratio of 4：1, leaching temperature of 180 ℃, leaching time of 4 h and stirring speed of 300 r/min. Shrinking-core model showed that the leaching process was controlled by the chemical surface reaction with activation energy Ea of 53.31 k J/mol. The fluidized roasting conditions for preparation of sodium manganate were optimized by the orthogonal experiments using the desiliconized residue. The conversion rate of sodium manganate was obtained to be 89.7% under the conditions of silica leaching rate of 91.2%, NaOH/MnO2 mass ratio of 3：1, roasting temperature of 500 ℃ and roasting time of 4 h, and it increased with the increase of silicon leaching rate.展开更多
The performance and mechanism of manganate preoxidation process for organics removal were investigated in the present paper.The results showed that manganate was a potentially powerful oxidizing agent and could make t...The performance and mechanism of manganate preoxidation process for organics removal were investigated in the present paper.The results showed that manganate was a potentially powerful oxidizing agent and could make the natural organic matter(NOM)concentration of sample solution increase.The process of manganate in combination with ferrous sulphate(FeMnO)was effective for organics removal and with the highest removal rate of 89%when the FeMnO dose was 0.18 mmol/L.The fluorescence analysis showed that the fluorescence intensity values related to hydrophobic acids and model humic acid polymers were the highest and the relative position of the main peak fluorescence intensity was shifted towards lower emission wavelengths,which indicated the reduction in the degree of aromaticity of residual organic matter fraction.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant No.11974253).
文摘Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In this paper,the M-edge spectra of La ions and the M-edge,L-edge,and K-edge spectra of Mn ions in LaMnO3 are calculated by considering both the free-ion multiplet calculation and the crystal field effects.We analyze spectral shapes,identify peak origins,and estimate the oxidation states of La and Mn ions in LaMnO3 theoretically.It is concluded that La ions in LaMnO3 predominantly exist in the trivalent state,while Mn ions exist primarily in the trivalent state with a minor presence of tetravalent ions.Furthermore,the calculated spectra are in better conformity with the experimental spectra when the proportion of Mn3+is 90%and Mn4+is 10%.This article enhances our comprehension of the oxidation states of La and Mn within the crystal and also provides a valuable guidance for spectroscopic investigations of other manganates.
基金supported by the International Science&Technology Cooperation of China(No.2019YFE0100200)the National Natural Science Foundation of China(No.53130202)the Basic Research Program of Shanxi Province,China(No.20210302123259)。
文摘The development of high-performance and low-cost cathode materials is of great significance for the progress in lithium-ion batteries.The use of Co and even Ni is not conducive to the sustainable and healthy development of the power battery industry owing to their high cost and limited resources.Here,we report LiMn_(2)O_(4)integrated with coating and doping by Sn self-segregation.Auger electron energy spectrum and soft X-ray absorption spectrum show that the coating is Sn-rich LiMn_(2)O_(4),with a small Sn doping in the bulk phase.The integration strategy can not only mitigate the Jahn–Teller distortion but also effectively avoid the dissolution of manganese.The as-obtained product demonstrates superior high initial capacities of 124 mAh·g^(-1)and 120 mAh·g^(-1)with the capacity retention of 91.1%and 90.2%at 25℃and55℃after 50 cycles,respectively.This novel material-processing method highlights a new development direction for the progress of cathode materials for lithium-ion batteries.
基金Supported by the National Natural Science Foundation of China(Nos.20631010 and 20771042)
文摘The powder crystals of RMnO3（R=Er, Tm） with hexagonal and orthorhombic structures were prepared under hydrothermal conditions. The different structural phases of the title compounds were controllably formed from different kinds of precursors at different reaction temperatures. All of the samples were characterized by powder X-ray diffraction, scanning electron microscopy, inductively coupled plasma analysis, and variable temperature magnetic susceptibility. Their structures were refined by Rietveld method from powder X-ray diffraction data. The measurement of magnetic behavior shows antiferromagnetic orderings at Neel temperatures around 80 and 40 K for the hexagonal and orthorhombic phases, respectively.
文摘Li-ion batteries(LIBs)have gained wide recognition as effective energy storage devices and power supply sources due to their exceptional volumetric energy density,mass energy density and cycling performance.The cathode materials,a key component of LIBs,play a crucial role in determining the electrochemical performance of these batteries.Therefore,there is an increasing demand to explore and investigate suitable high-energy electrode materials that can provide greater capacity and output voltage for the next generation of LIBs.This paper aims to provide a comprehensive overview of the latest researches on five typical high-voltage cathode materials.Specifically,this review will focus on the detailed analysis of their crystalline structures,reaction mechanisms during cycling,current research status and strategies aimed at improving or enhancing their overall electrochemical performance.Overall,the insights presented in this review will help researchers design and develop high-energy cathode materials with improved performance for the next generation of LIBs.
基金the National Nat-ural Science Foundation of China(No.51774143).
文摘new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn_(2)O_(4) from the waste of lithium-ion batteries in NaCl−CaCl_(2) melts at 750°C.The results show that the LiMn_(2)O_(4) reduction process by the electrochemical method on the coated electrode surface occurs in three steps:Mn(IV)→Mn(III)→Mn(II)→Mn.The products of this electro-deoxidation are CaMn2O4,MnO,(MnO)x(CaO)1−x,and Mn.Metal Mn appears when the electrolytic voltage increases to 2.6 V,which indicates that increasing the voltage may promote the deoxidation reaction process.With the advancement of the three-phase interline(3PI),electric deoxygenation gradually proceeds from the outer area of the crucible to the core.At high voltage,the kinetic process of the reduction reaction is accelerated,which generates double 3PIs at different stages.
基金National Natural Science Foundation of China(50725101,51072161)
文摘Ni-Al2O3 cermet supported tubular solid oxide fuel cells(SOFCs)with different cathodes were fabricated by thermal spraying.The anode,electrolyte and cathode were deposited by atmospheric plasma spraying(APS)aimed at reducing the manufacturing cost of SOFCs.Three porous composite cathodes of lanthanum strontium manganite(LSM)and yttria-stabilized zirconia(YSZ),lanthanum strontium cobalt oxide(LSC)and YSZ,LSC and scandia-stabilized zirconia(ScSZ)were prepared to investigate influence of cathode constitutions on the cell's performance.The electrode polarization can be improved through using a composite cathode.The maximum power density of the cell with APS YSZ electrolyte and LSC/ScSZ composite cathode is increased about 12%than pure LSM cathode.The maximum output power density of the cell with APS ScSZ electrolyte and LSC/ScSZ composite cathode reaches 1.0 W/cm 2 at 1000 o C.The further optimization of the performance of plasma-sprayed composite cathode can be made through improving the interface contact between YSZ electrolyte and composite cathode.
基金Project supported by the National Natural Science Foundation of China (Grant No.61078057)the Northwestern Polytechnical University Foundation for Fundamental Research,China (Grant Nos.JC201048 and JC201155)
文摘The transport properties and magnetoresistance of electron-doped manganate / insulator composites （Lao.sTeo.2MnO3）l-x/（ZrO2）x （x = 0, 0.3, and 0.5） are investigated. It is found that the metal-insulator transition temperature of this system shifts to a lower value as the ZrO2 content increases. The introduction of ZrO2 enhances both the domain scattering and electron relative scattering in the metal transport region. In the adiabatic small polaron hopping transport region, the thermal activation energy seems invariable regardless of the ZrO2 content. The applica- tion of a magnetic field promotes the charge transportation capabilities of the composites, and the magnetoresistance is enhanced with an increase of the ZrO2 content. This could be attributed to the more remarkable modification effect of magnetic field on ordering degree in the composites than in pure Lao.sTe0.2MnO3.
文摘In order to study the phase transformation between 1nm manganate and 0.7nm manganate, a series of Slum Me^(2+) manganates were made after the synthetic 1nm Na^+ manganate substituted with different kinds of divalent cations. The X-ray diffraction analysis of wet S1nm Me^(2+) manganates after 24 h room temperature dry showed that their basal d-spacing had been changed, indicating that there was phase transformation between 1nm and 0.7nm manganates. Take 1nm manganates with unstable structure collapsed into 0. 7nm manganate by losing one interlayer OH-H_2O, while those with stable structure still retained the 1nm d-spacing. This factor reminds us that the manganese nodule samples must be kept in wet condition to avoid the misleading results. The structural stabdity of 1nn manganate is mainly controlled by the interlayer divalent cations. There is a possitive correlation between the amount of cations in the interlayer and the structural stability, while the capacity of different canons in stabilizing the structure of 1nm manganate is as follows: Ni > Cu > Co > Zn > Ca>Mg > Na.
文摘Synthetic Ium manganate has been made in the laboratory at low temperature. The d-spaciug of which shows 1. 002 nm, 0. 501 nm and 0. 34 nm respectively. As the analogue of natural 1nm manganate, it has been used for a serieS of experiments of divalent cations substitution. The results indicate that the 1nm manganate has very strong cation substitution capacity, which probable is the reason of the valuable metal such as Cu, Ni and Co enriched in the manganese nodules. The preference of canons substituting into S 1nm manganate is Cu>Co>Zn≥Ni>Ca>Mg. In the manganese nodules, the content of Ni is usually higher than that of Cu and Co, but in the cation substitution, the latter two are more preference than the former. One can infer from this differentiation that the post-deposition cation substitution is not the sole mechanism by which the valuable metals enter the manganese nodules. It could be the results of combined effects of both original formation and the post-deposition substitution of canons,which leads to the enrichment of valuable metal in the manganese nodules.
基金financially supported by the National Natural Science Foundation of China(U21A20284)the National Key Research and Development Program of China(2019YFC1907805)the Fundamental Research Funds for the Central Universities of Central South University(2021zzts0072)。
文摘Spinel LiMn_(2)O_(4)is recognized as one of the most competitive cathode candidates for lithium-ion batteries ascribed to environmentally benign and rich sources.However,the wholesale application of LiMn_(2)O_(4)is predominately plagued by its severe capacity degradation,mainly associated with the innate Jahn-Teller effect.Herein,single-crystalline LiMn_(2)O_(4)with Eu^(3+) doping is rationally designed to mitigate the detrimental Jahn-Teller distortion by tuning the chemical environment of MnO_(6) octahedra and accommodating localized electron,based on the unique aspheric flexible 4f electron orbit of rare-earth metal ions.Notably,the stretching of MnO_(6) octahedron stemmed from the Jahn-Teller effect in Eu-doped LiMn_(2)O_(4)is effectively suppressed,confirmed by theoretical calculation.Meanwhile,the structural stability of the material has been significantly enhanced due to the robust Mn–O band coherency and weakened phase transition,proved by synchrotron radiation absorption spectrum and operando X-ray diffraction.The corresponding active cathode manifests superior long-cycle stability after 300 loops at 2C and displays only a 0.011%capacity drop per cycle even at 5C.Given this,this modification tactic sheds new light on achieving superior long-cycle performances by suppressing distortion in various cathode materials.
基金Project(2015ZX07205-003)supported by the Major Science and Technology Program for Water Pollution Control and Treatment,ChinaProject(DY125-15-T-08)supported by the China Ocean Mineral Resources Research&Development ProgramProjects(21176026,21176242)supported by the National Natural Science Foundation of China
文摘Low concentration alkaline leaching was used for predesilication treatment of low-grade pyrolusite. The effects of initial NaOH concentration, liquid-to-solid ratio, leaching temperature, leaching time and stirring speed on silica leaching rate were investigated and the kinetics of alkaline leaching process was studied. The results show that silica leaching rate reached 91.2% under the conditions of initial NaOH concentration of 20%, liquid-to-solid ratio of 4：1, leaching temperature of 180 ℃, leaching time of 4 h and stirring speed of 300 r/min. Shrinking-core model showed that the leaching process was controlled by the chemical surface reaction with activation energy Ea of 53.31 k J/mol. The fluidized roasting conditions for preparation of sodium manganate were optimized by the orthogonal experiments using the desiliconized residue. The conversion rate of sodium manganate was obtained to be 89.7% under the conditions of silica leaching rate of 91.2%, NaOH/MnO2 mass ratio of 3：1, roasting temperature of 500 ℃ and roasting time of 4 h, and it increased with the increase of silicon leaching rate.
文摘The performance and mechanism of manganate preoxidation process for organics removal were investigated in the present paper.The results showed that manganate was a potentially powerful oxidizing agent and could make the natural organic matter(NOM)concentration of sample solution increase.The process of manganate in combination with ferrous sulphate(FeMnO)was effective for organics removal and with the highest removal rate of 89%when the FeMnO dose was 0.18 mmol/L.The fluorescence analysis showed that the fluorescence intensity values related to hydrophobic acids and model humic acid polymers were the highest and the relative position of the main peak fluorescence intensity was shifted towards lower emission wavelengths,which indicated the reduction in the degree of aromaticity of residual organic matter fraction.
