New lithium fast ion conductors of Li1.2 ＋ x - y Yx Ti1.9 - x Al0.1Si0. 1Wy P2.9 - y O12 based on LiTi2（PO4）3 were prepared by high temperature solid state reaction using refined natural kaolinite as a starting mat...New lithium fast ion conductors of Li1.2 ＋ x - y Yx Ti1.9 - x Al0.1Si0. 1Wy P2.9 - y O12 based on LiTi2（PO4）3 were prepared by high temperature solid state reaction using refined natural kaolinite as a starting material. X-ray powder diffraction analysis indicates that a phase with Nasieon-like structure exists together with other phases in the composition range of x =0.1, y≤0.2 and x =0.2,y ≤0.2. AC impedance measurements show that the initial composition with x = 0.10, y = 0.10 possesses the highest ionic conductivity of 1.65 × 10^-5 S·cm^-1 at room temperature, while the sample with initial composition of x =0.20, y =0.10 has the best ionic conductivity of 6. 53 × 10^-3S·cm^-1 at 573 K and decomposes at 3.0 V.展开更多
Perovskite type lithium fast ion conductors of Li 3 x La 0.67- x In y Ti 1-2 y P y O 3 system were prepared by solid state reaction. X ray powder diffraction shows that perovskite solid...Perovskite type lithium fast ion conductors of Li 3 x La 0.67- x In y Ti 1-2 y P y O 3 system were prepared by solid state reaction. X ray powder diffraction shows that perovskite solid solution forms in the ranges of x =0.10～0.12, y ≤0.2. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of 1×10 -4 and 1× 10 -5 S·cm -1 at 25 ℃ respectively. The compositions have low bulk activation energies of 20 kJ·mol -1 in the temperature ranges of 298～523 K and total activation energies of 40 kJ·mol -1 in the temperature ranges of 298～623 K.展开更多
Natural layered aluminosilicate Kaolinite Al_(4)[Si_(4)O_(10)](OH)_(8)has been used as a starting material for preparing a new system of lithium fast ion conductors by high temperature(1073-1223 K)solid state reaction...Natural layered aluminosilicate Kaolinite Al_(4)[Si_(4)O_(10)](OH)_(8)has been used as a starting material for preparing a new system of lithium fast ion conductors by high temperature(1073-1223 K)solid state reactions.X-ray powder diffraction and a.c.impedance technique were used to characterize the compositions of the Li_(1+2x)Al_(x)Zr_(2-x)Si_(x)P_(3-x)O_(12)system.A single pure solid solution phase with R3c space group can be formed in the composition range of x≤04.A specimen with x=03 possesses a maximum ionic conductivity which reaches up to 103×10^(-2)s/cm at 723 K and the activation energy is 2963 kJ/mol.展开更多
Liquid plasticizers with a relatively higher dielectric coefficient like ethylene carbonate(EC),propylene carbonate(PC),and ethyl methyl carbonate(EMC) are the most commonly used electrolyte materials in commercial re...Liquid plasticizers with a relatively higher dielectric coefficient like ethylene carbonate(EC),propylene carbonate(PC),and ethyl methyl carbonate(EMC) are the most commonly used electrolyte materials in commercial rechargeable lithium batteries(LIBs) due to their outstanding dissociation ability to lithium salts.However,volatility and fluidity result in their inevitable demerits like leakage and potential safety problem of the final LIBs.Here we for the first time device a subtle method to prepare a novel thermal-stable and non-fluid poly(carbonate) solid-state electrolyte to merge EC with lithium carriers.To this aim,a series of carbonate substituted imidazole ionic plastic crystals(G-NTOC) with different polymerization degrees have been synthesized.The resulting G-NTOC shows an excellent solid-state temperature window(R.T.-115℃).More importantly,the maximum ionic conductivity and lithium transference number of the prepared G-NTOC reach 0.36 × 10^(-3) S cm^(-1) and 0.523 at 30℃,respectively.Galvanostatic cycling test results reveal that the developed G-NTOC solid-state electrolytes are favorable to restraining the growth of lithium dendrite due to the excellent compatibility between the electrode and the produced plastic crystal electrolyte.The fabricated LiIG-NTOCILiFeP04 all-solid-state cell initially delivers a maximum discharge capacity of 152.1 mAh g^(-1) at the discharge rate of 0.1 C.After chargingdischarging the cell for 60 times,Coulombic efficiency of the solid-state cell still exceeds 97%.Notably,the LiIG-NTOCILiFeP04 cell can stably light a commercial LED with a rated power of 0.06 W for more than1 h at 30℃,and the output power nearly maintains unchanged with the charging-discharging cycling test,implying a sizeable potential application in the next generation of solid-state LIBs.展开更多
Fast ion conductor materials screening based on high-throughput calculations involves enormous computing tasks.The process usually includes structural optimization,energy calculation,charge analysis and ionic migratio...Fast ion conductor materials screening based on high-throughput calculations involves enormous computing tasks.The process usually includes structural optimization,energy calculation,charge analysis and ionic migration performance estimation.The first one involves looking for the equilibrium atomic positions in huge amount of candidate compounds or derivative structures,and the computational cost is always high because of the task-intensive features.The last one relates to the kinetic problems,for which the time-consuming transition state theory and the molecular dynamics are the main simulation methods.In this work,two predictive models,ionic migration activation energy model and structural optimization model,are developed based on machine learning(ML)techniques to accelerate the process of estimating activation energy and relaxing the doped crystal structures,respectively.By training 3136 energy barrier data calculated by bond valence(BV)method,an ionic migration activation energy model(Ea model)with mean absolute error(MAE)of 0.26 eV on testing data set is obtained.We apply this model and filter LiBiOS as a promising fast Li^(+)conductor from 49 Licontaining hetero-anionic compounds.Although the model-predicted result shows relatively low energy barrier,further analysis indicates that the high carrier formation energy restricts the ionic transportability.Therefore,we substitute fractional Li^(+)with Mg^(2+)in LiBiOS to relieve the large difficulty of forming carriers in the structure.In order to fast explore the optimal doping scheme,we develop the structural optimization model(E-f model)containing the ML-based energy and force prediction to accelerate the structural optimization under various LieMg ratio and doping configurations.Decent doping scheme Li_(1-2x)Mg_(x)BiOS(x=0.1875)shows much better Li^(+)migration performance compared with LiBiOS without substitution.This method of screening fast ion conductor materials and finding optimal doping scheme will extremely accelerate materials explorations.展开更多
Fast ion conductor is a kind of solid material possessing excellent character of translation ion at room temperature. Its translation ion power is almost the same as that of melt salt. In recent years, a few natural m...Fast ion conductor is a kind of solid material possessing excellent character of translation ion at room temperature. Its translation ion power is almost the same as that of melt salt. In recent years, a few natural minerals with the open structure are found that they展开更多
Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at hig...Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at high temperature (1000～1300 ℃) for about 30 h using refined natural kaolinite and Sc 2O 3. The X ray diffraction analysis shows that a Nasicon like structure with R3c space group can be found in the composition range of x =0.1, 0.2, y ≤0.2. The maximum lithium ion conductivity is 1.19×10 -4 S·cm -1 for the composition with x =0.1, y =0.08 at room temperature, and its activation energy is 30.6 kJ·mol -1 in the temperature range of 150～300 ℃. The systems with these compositions have high conductivity of about 10 -2 S·cm -1 at 300 ℃.展开更多
Perovskite type lithium fast ion conductors of Li 3 x La 0.67- x Y y Ti 1-2 y Nb y O 3 system were prepared by solid state reaction. X Ray powder diffraction shows that a single phase ...Perovskite type lithium fast ion conductors of Li 3 x La 0.67- x Y y Ti 1-2 y Nb y O 3 system were prepared by solid state reaction. X Ray powder diffraction shows that a single phase perovskite solid solution with orthorhombic structure forms in the ranges of x =0.10, y <0.075. Over this composition range the another phase, Y 2O 3 hexagonal phase is found. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10 -4 S·cm -1 and 10 -5 S·cm -1 at 25 ℃ respectively. The compositions have low bulk activation energies of about 20 kJ·mol -1 and total activation energies of about 40 kJ·mol -1 in the temperature range of 298～523 K, respectively.展开更多
以LiTi2(PO4)3为母体,以天然高岭石为起始原料,经高温固相反应制得了一系列新的锂快离子导体Li1.2+x-yYxTi1.9-xAl0.1Si0.1SyP2.9-yO12(以下简称Y S Lisicon)。X射线粉末衍射分析结果表明在x≤0.3,y<(0.2+x)的组成范围内均能得到类似...以LiTi2(PO4)3为母体,以天然高岭石为起始原料,经高温固相反应制得了一系列新的锂快离子导体Li1.2+x-yYxTi1.9-xAl0.1Si0.1SyP2.9-yO12(以下简称Y S Lisicon)。X射线粉末衍射分析结果表明在x≤0.3,y<(0.2+x)的组成范围内均能得到类似于Nasicon三方结构的相,同时还存在其他杂相。应用交流阻抗技术测定电导率的结果表明起始组成为x=0.1,y=0.15的合成物电导率最高,其在室温下的电导率为2.93×10-5S·cm-1,在673K时可达3.62×10-2S·cm-1,其在473～673K间的活化能为37.19kJ·mol-1,分解电压为3.0V。展开更多
文摘New lithium fast ion conductors of Li1.2 ＋ x - y Yx Ti1.9 - x Al0.1Si0. 1Wy P2.9 - y O12 based on LiTi2（PO4）3 were prepared by high temperature solid state reaction using refined natural kaolinite as a starting material. X-ray powder diffraction analysis indicates that a phase with Nasieon-like structure exists together with other phases in the composition range of x =0.1, y≤0.2 and x =0.2,y ≤0.2. AC impedance measurements show that the initial composition with x = 0.10, y = 0.10 possesses the highest ionic conductivity of 1.65 × 10^-5 S·cm^-1 at room temperature, while the sample with initial composition of x =0.20, y =0.10 has the best ionic conductivity of 6. 53 × 10^-3S·cm^-1 at 573 K and decomposes at 3.0 V.
文摘Perovskite type lithium fast ion conductors of Li 3 x La 0.67- x In y Ti 1-2 y P y O 3 system were prepared by solid state reaction. X ray powder diffraction shows that perovskite solid solution forms in the ranges of x =0.10～0.12, y ≤0.2. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of 1×10 -4 and 1× 10 -5 S·cm -1 at 25 ℃ respectively. The compositions have low bulk activation energies of 20 kJ·mol -1 in the temperature ranges of 298～523 K and total activation energies of 40 kJ·mol -1 in the temperature ranges of 298～623 K.
文摘Natural layered aluminosilicate Kaolinite Al_(4)[Si_(4)O_(10)](OH)_(8)has been used as a starting material for preparing a new system of lithium fast ion conductors by high temperature(1073-1223 K)solid state reactions.X-ray powder diffraction and a.c.impedance technique were used to characterize the compositions of the Li_(1+2x)Al_(x)Zr_(2-x)Si_(x)P_(3-x)O_(12)system.A single pure solid solution phase with R3c space group can be formed in the composition range of x≤04.A specimen with x=03 possesses a maximum ionic conductivity which reaches up to 103×10^(-2)s/cm at 723 K and the activation energy is 2963 kJ/mol.
基金the financial support of the National Natural Science Foundation of China (21961044, 22169024)the Yunnan University’s Research Innovation Fund for graduate students (2021Y394)。
文摘Liquid plasticizers with a relatively higher dielectric coefficient like ethylene carbonate(EC),propylene carbonate(PC),and ethyl methyl carbonate(EMC) are the most commonly used electrolyte materials in commercial rechargeable lithium batteries(LIBs) due to their outstanding dissociation ability to lithium salts.However,volatility and fluidity result in their inevitable demerits like leakage and potential safety problem of the final LIBs.Here we for the first time device a subtle method to prepare a novel thermal-stable and non-fluid poly(carbonate) solid-state electrolyte to merge EC with lithium carriers.To this aim,a series of carbonate substituted imidazole ionic plastic crystals(G-NTOC) with different polymerization degrees have been synthesized.The resulting G-NTOC shows an excellent solid-state temperature window(R.T.-115℃).More importantly,the maximum ionic conductivity and lithium transference number of the prepared G-NTOC reach 0.36 × 10^(-3) S cm^(-1) and 0.523 at 30℃,respectively.Galvanostatic cycling test results reveal that the developed G-NTOC solid-state electrolytes are favorable to restraining the growth of lithium dendrite due to the excellent compatibility between the electrode and the produced plastic crystal electrolyte.The fabricated LiIG-NTOCILiFeP04 all-solid-state cell initially delivers a maximum discharge capacity of 152.1 mAh g^(-1) at the discharge rate of 0.1 C.After chargingdischarging the cell for 60 times,Coulombic efficiency of the solid-state cell still exceeds 97%.Notably,the LiIG-NTOCILiFeP04 cell can stably light a commercial LED with a rated power of 0.06 W for more than1 h at 30℃,and the output power nearly maintains unchanged with the charging-discharging cycling test,implying a sizeable potential application in the next generation of solid-state LIBs.
基金We acknowledge the National Natural Science Foundation of China(grant number 52022106)SAMSUNG Research China for financial support and idea explorationwell as Tianjin Supercomputer Center for providing computing resources.
文摘Fast ion conductor materials screening based on high-throughput calculations involves enormous computing tasks.The process usually includes structural optimization,energy calculation,charge analysis and ionic migration performance estimation.The first one involves looking for the equilibrium atomic positions in huge amount of candidate compounds or derivative structures,and the computational cost is always high because of the task-intensive features.The last one relates to the kinetic problems,for which the time-consuming transition state theory and the molecular dynamics are the main simulation methods.In this work,two predictive models,ionic migration activation energy model and structural optimization model,are developed based on machine learning(ML)techniques to accelerate the process of estimating activation energy and relaxing the doped crystal structures,respectively.By training 3136 energy barrier data calculated by bond valence(BV)method,an ionic migration activation energy model(Ea model)with mean absolute error(MAE)of 0.26 eV on testing data set is obtained.We apply this model and filter LiBiOS as a promising fast Li^(+)conductor from 49 Licontaining hetero-anionic compounds.Although the model-predicted result shows relatively low energy barrier,further analysis indicates that the high carrier formation energy restricts the ionic transportability.Therefore,we substitute fractional Li^(+)with Mg^(2+)in LiBiOS to relieve the large difficulty of forming carriers in the structure.In order to fast explore the optimal doping scheme,we develop the structural optimization model(E-f model)containing the ML-based energy and force prediction to accelerate the structural optimization under various LieMg ratio and doping configurations.Decent doping scheme Li_(1-2x)Mg_(x)BiOS(x=0.1875)shows much better Li^(+)migration performance compared with LiBiOS without substitution.This method of screening fast ion conductor materials and finding optimal doping scheme will extremely accelerate materials explorations.
基金Project supported by the National Natural Science Foundation of China
文摘Fast ion conductor is a kind of solid material possessing excellent character of translation ion at room temperature. Its translation ion power is almost the same as that of melt salt. In recent years, a few natural minerals with the open structure are found that they
文摘Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at high temperature (1000～1300 ℃) for about 30 h using refined natural kaolinite and Sc 2O 3. The X ray diffraction analysis shows that a Nasicon like structure with R3c space group can be found in the composition range of x =0.1, 0.2, y ≤0.2. The maximum lithium ion conductivity is 1.19×10 -4 S·cm -1 for the composition with x =0.1, y =0.08 at room temperature, and its activation energy is 30.6 kJ·mol -1 in the temperature range of 150～300 ℃. The systems with these compositions have high conductivity of about 10 -2 S·cm -1 at 300 ℃.
文摘Perovskite type lithium fast ion conductors of Li 3 x La 0.67- x Y y Ti 1-2 y Nb y O 3 system were prepared by solid state reaction. X Ray powder diffraction shows that a single phase perovskite solid solution with orthorhombic structure forms in the ranges of x =0.10, y <0.075. Over this composition range the another phase, Y 2O 3 hexagonal phase is found. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10 -4 S·cm -1 and 10 -5 S·cm -1 at 25 ℃ respectively. The compositions have low bulk activation energies of about 20 kJ·mol -1 and total activation energies of about 40 kJ·mol -1 in the temperature range of 298～523 K, respectively.
文摘以LiTi2(PO4)3为母体,以天然高岭石为起始原料,经高温固相反应制得了一系列新的锂快离子导体Li1.2+x-yYxTi1.9-xAl0.1Si0.1SyP2.9-yO12(以下简称Y S Lisicon)。X射线粉末衍射分析结果表明在x≤0.3,y<(0.2+x)的组成范围内均能得到类似于Nasicon三方结构的相,同时还存在其他杂相。应用交流阻抗技术测定电导率的结果表明起始组成为x=0.1,y=0.15的合成物电导率最高,其在室温下的电导率为2.93×10-5S·cm-1,在673K时可达3.62×10-2S·cm-1,其在473～673K间的活化能为37.19kJ·mol-1,分解电压为3.0V。
