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 4O 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 react...Natural layered aluminosilicate Kaolinite Al 4[Si 4O 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+2 x 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 ≤0 4. A specimen with x =0 3 possesses a maximum ionic conductivity which reaches up to 1 03×10 -2 s/cm at 723 K and the activation energy is 29 63 kJ/mol.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
While argyrodite sulfides are getting more and more attention as highly promising solid-state electrolytes(SSEs)for solid batteries,they also suffer from the typical sulfide setbacks such as poor electrochemical compa...While argyrodite sulfides are getting more and more attention as highly promising solid-state electrolytes(SSEs)for solid batteries,they also suffer from the typical sulfide setbacks such as poor electrochemical compatibility with Li anode and high-voltage cathodes and serious sensitivity to humid air,which hinders their practical applications.Herein,we have devised an effective strategy to overcome these challenging shortcomings through modification of chalcogen chemistry under the guidance of theoretical modeling.The resultant Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)delivered excellent electrochemical compatibility with both pure Li anode and high-voltage LiCoO_(2)cathode,without compromising the superb ionic conductivity of the pristine sulfide.Furthermore,the current SSE also exhibited highly improved stability to oxygen and humidity,with further advantage being more insulating to electrons.The remarkably enhanced compatibility with electrodes is attributed to in situ formation of helpful electrolyte–electrode interphases.The formation of in situ anode–electrolyte interphase(AEI)enabled stable Li plating/stripping in the Li|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li symmetric cells at a high current density up to 1 mA cm^(-2)over 200 h and 2 mA cm^(-2)for another 100 h.The in situ amorphous nano-film cathode–electrolyte interphase(CEI)facilitated protection of the SSE from decomposition at elevated voltage.Consequently,the synergistic effect of AEI and CEI helped the LiCoO_(2)|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li full-battery cell to achieve markedly better cycling stability than that using the pristine Li_(6)PS_(5)Cl as SSE,at a high area loading of the active cathode material(4 mg cm^(-2))in type-2032 coin cells.This work is to add a desirable SSE in the argyrodite sulfide family,so that high-performance solid battery cells could be fabricated without the usual need of strict control of the ambient atmosphere.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 4O 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+2 x 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 ≤0 4. A specimen with x =0 3 possesses a maximum ionic conductivity which reaches up to 1 03×10 -2 s/cm at 723 K and the activation energy is 29 63 kJ/mol.
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。
基金supported in part by the Zhengzhou Materials Genome Institutethe National Natural Science Foundation of China(No.52171082,51001091,51571182,111174256,91233101,51602094,11274100)the Program for Science&Technology Innovation Talents in the Universities of Henan Province(18HASTIT009)。
文摘While argyrodite sulfides are getting more and more attention as highly promising solid-state electrolytes(SSEs)for solid batteries,they also suffer from the typical sulfide setbacks such as poor electrochemical compatibility with Li anode and high-voltage cathodes and serious sensitivity to humid air,which hinders their practical applications.Herein,we have devised an effective strategy to overcome these challenging shortcomings through modification of chalcogen chemistry under the guidance of theoretical modeling.The resultant Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)delivered excellent electrochemical compatibility with both pure Li anode and high-voltage LiCoO_(2)cathode,without compromising the superb ionic conductivity of the pristine sulfide.Furthermore,the current SSE also exhibited highly improved stability to oxygen and humidity,with further advantage being more insulating to electrons.The remarkably enhanced compatibility with electrodes is attributed to in situ formation of helpful electrolyte–electrode interphases.The formation of in situ anode–electrolyte interphase(AEI)enabled stable Li plating/stripping in the Li|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li symmetric cells at a high current density up to 1 mA cm^(-2)over 200 h and 2 mA cm^(-2)for another 100 h.The in situ amorphous nano-film cathode–electrolyte interphase(CEI)facilitated protection of the SSE from decomposition at elevated voltage.Consequently,the synergistic effect of AEI and CEI helped the LiCoO_(2)|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li full-battery cell to achieve markedly better cycling stability than that using the pristine Li_(6)PS_(5)Cl as SSE,at a high area loading of the active cathode material(4 mg cm^(-2))in type-2032 coin cells.This work is to add a desirable SSE in the argyrodite sulfide family,so that high-performance solid battery cells could be fabricated without the usual need of strict control of the ambient atmosphere.
