The phase transition of Li2Mn2O4 spinel at high temperature was investigated by XRD, TG/DTA, average oxidation state of Mn and cyclic voltammeric techniques. The results reveal that the Li2Mn2O4 spinel is unstable. At...The phase transition of Li2Mn2O4 spinel at high temperature was investigated by XRD, TG/DTA, average oxidation state of Mn and cyclic voltammeric techniques. The results reveal that the Li2Mn2O4 spinel is unstable. At high temperature, it is easy to transform into [Li2-2x]tet[Mn2-xLix]octO4, which accompanies the formation of Li2MnO3 impurities. The phase transition is associated with the transfer of Li+ from tetrahedral 8a sites to octahedral 16d sites. With the increasing sintering temperature from 450 ℃ to 850 ℃, the phase structure varies from lithiated-spinel Li2Mn2O4 to Li4Mn5O12-like to LiMn2O4-like and finally to rock-salt LiMnO2-like. In addition, a way of determining x with average oxidation state of Mn and the content of Li2MnO3 was also demonstrated.展开更多
Li x Mn 2O 4 spinels were prepared by in situ redox precipitation hydrothermal synthesis method, and characterized by XRD, BET, TGA, TEM and SEM etc. , and the effects of many factors on the properties of as prepared ...Li x Mn 2O 4 spinels were prepared by in situ redox precipitation hydrothermal synthesis method, and characterized by XRD, BET, TGA, TEM and SEM etc. , and the effects of many factors on the properties of as prepared Li x Mn 2O 4 samples were investigated. The results demonstrated that Li x Mn 2O 4 spinels can be synthesized under milder conditions by in situ redox precipitation hydrothermal synthesis method. Li x Mn 2O 4 spinels are cubic and symmetrical, and have a better stability at less than 700 ℃, their surface areas and particle sizes were strongly affected by crystallization temperature and time, pH value, calcination temperature and time. The optimal conditions of Li x Mn 2O 4 synthesis were determined as follows: the alkalinity(pH value) was 9; the crystallization temperature and time were more than 240 ℃ and 48 h, respectively; the calcination temperature and time were between 700-750 ℃ and 6-12 h, respectively; the molar ratio of Li to Mn was less than 1.2/2.展开更多
Improvement of elevated-temperature performance of Li1.02Cr0.1Mn1.9O4 cathode material by silicious surface modification was studied. The Li1.02Cr0.1Mn1.9O4 cathode material was treated by silanes coupling agent and t...Improvement of elevated-temperature performance of Li1.02Cr0.1Mn1.9O4 cathode material by silicious surface modification was studied. The Li1.02Cr0.1Mn1.9O4 cathode material was treated by silanes coupling agent and then heated at 580 ℃ to remove organic material. The structures of the modified and unmodified Li1.02Cr0.1Mn1.9O4 were characterized by SpectraPlus, SEM and XRD. The results show that the surface layer of Li1.02Cr0.1Mn1.9O4 material is found to be rich in silicious compound. X-ray diffraction show that all the samples have perfect spinel structure. The electrochemical characterization of modified Li1.02Cr0.1Mn1.9O4 cathode material was tested. The cycle stability of charge/discharge at 55℃ is improved. The results of the charge/discharge curves show that the modified Li1.02Cr0.1Mn1.9O4 has better performance than those unmodified according to the inhibition of decline of reversible capacity of spinel Li1.02Cr0.1Mn1.9O4. Therefore, cycle performance is improved so obviously that 86.03% of the initial capacity is preserved after 100 cycles.展开更多
The cathode material Li 1+ x Mn 2O 4 was prepared by a modified citric acid complexation method. The influences of temperature, sintering time and n (Li)/ n (Mn) ratio on the structure of the products have been explor...The cathode material Li 1+ x Mn 2O 4 was prepared by a modified citric acid complexation method. The influences of temperature, sintering time and n (Li)/ n (Mn) ratio on the structure of the products have been explored, characterized and tested by XRD, TEM, BET measurements. The sample sintered at 750 ℃ for 12 h had greater charge/discharge capacity, better cyclic stability under electric current charge/discharge cycle. The initial capacity reached 120 mA·h/g with the charge/discharge efficieney of 98% and maintained 115 mA·h/g after 50 cycles.展开更多
基金Project(20406024) supported by the National Natural Science Foundation of China Project(76600) supported by the Postdoctoral Science Foundation of Central South University, China
文摘The phase transition of Li2Mn2O4 spinel at high temperature was investigated by XRD, TG/DTA, average oxidation state of Mn and cyclic voltammeric techniques. The results reveal that the Li2Mn2O4 spinel is unstable. At high temperature, it is easy to transform into [Li2-2x]tet[Mn2-xLix]octO4, which accompanies the formation of Li2MnO3 impurities. The phase transition is associated with the transfer of Li+ from tetrahedral 8a sites to octahedral 16d sites. With the increasing sintering temperature from 450 ℃ to 850 ℃, the phase structure varies from lithiated-spinel Li2Mn2O4 to Li4Mn5O12-like to LiMn2O4-like and finally to rock-salt LiMnO2-like. In addition, a way of determining x with average oxidation state of Mn and the content of Li2MnO3 was also demonstrated.
文摘Li x Mn 2O 4 spinels were prepared by in situ redox precipitation hydrothermal synthesis method, and characterized by XRD, BET, TGA, TEM and SEM etc. , and the effects of many factors on the properties of as prepared Li x Mn 2O 4 samples were investigated. The results demonstrated that Li x Mn 2O 4 spinels can be synthesized under milder conditions by in situ redox precipitation hydrothermal synthesis method. Li x Mn 2O 4 spinels are cubic and symmetrical, and have a better stability at less than 700 ℃, their surface areas and particle sizes were strongly affected by crystallization temperature and time, pH value, calcination temperature and time. The optimal conditions of Li x Mn 2O 4 synthesis were determined as follows: the alkalinity(pH value) was 9; the crystallization temperature and time were more than 240 ℃ and 48 h, respectively; the calcination temperature and time were between 700-750 ℃ and 6-12 h, respectively; the molar ratio of Li to Mn was less than 1.2/2.
文摘Improvement of elevated-temperature performance of Li1.02Cr0.1Mn1.9O4 cathode material by silicious surface modification was studied. The Li1.02Cr0.1Mn1.9O4 cathode material was treated by silanes coupling agent and then heated at 580 ℃ to remove organic material. The structures of the modified and unmodified Li1.02Cr0.1Mn1.9O4 were characterized by SpectraPlus, SEM and XRD. The results show that the surface layer of Li1.02Cr0.1Mn1.9O4 material is found to be rich in silicious compound. X-ray diffraction show that all the samples have perfect spinel structure. The electrochemical characterization of modified Li1.02Cr0.1Mn1.9O4 cathode material was tested. The cycle stability of charge/discharge at 55℃ is improved. The results of the charge/discharge curves show that the modified Li1.02Cr0.1Mn1.9O4 has better performance than those unmodified according to the inhibition of decline of reversible capacity of spinel Li1.02Cr0.1Mn1.9O4. Therefore, cycle performance is improved so obviously that 86.03% of the initial capacity is preserved after 100 cycles.
文摘The cathode material Li 1+ x Mn 2O 4 was prepared by a modified citric acid complexation method. The influences of temperature, sintering time and n (Li)/ n (Mn) ratio on the structure of the products have been explored, characterized and tested by XRD, TEM, BET measurements. The sample sintered at 750 ℃ for 12 h had greater charge/discharge capacity, better cyclic stability under electric current charge/discharge cycle. The initial capacity reached 120 mA·h/g with the charge/discharge efficieney of 98% and maintained 115 mA·h/g after 50 cycles.
