Study on Lithium Fast Ion Conductors of Li_(3x)La_(0.67-x) In_yTi_(1-2y)P_yO_3 System

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.

Synthesis and Characterization of Y^3＋, W^6＋-Doped Mineral Lithium Fast Ion Conductor Li1.2＋x-y YxTi1.9-xAl0.1Si0. 1Wy P2.9-yO12 System

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.

Preparation of LiTi_2(PO_4)_3 by the Sol-gel Method and Investigation of Its Formation Process

In this study,a novel solgel method has been developed to prepare LiTi2(PO4)3 lithium ion conductor as monophase at relatively low temperature(600).According to the XRD and IR analysis,the asprepared sample remained an amorphous state up to 500.The activation energy was calculated to be 252 kJ/mol according to the modified Kissinger equation.

Synthesis,Structure and Ionic Conductivity of La_(2/3-x)Li_(3x)MoO_4

A series of compounds, La 2/3- x Li 3 x MoO 4, were first prepared. Their structures are tetragonal scheelites with the cationic defects. The cell parameters a, c and values of c/a decrease with the increasing of the substitution amount (3 x ) of lithium ion. Cationic vacancies are getting more as Li + concentration is lower. The diffusion of lithium ion is predominant. The concentration of charge carriers increases with increasing the substitution amount (3 x ) of lithium ion, meanwhile, the concentration of cationic vacancies decreases. The conductivity approaches the best when the substitution amount (3 x ) of lithium ion is about 0.3. The conductivity of La 0.567 Li 0.3 MoO 4 is 6.5×10 -6 S·cm -1 at room temperature.

Enabling Argyrodite Sulfides as Superb Solid-State Electrolyte with Remarkable Interfacial Stability Against Electrodes

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.

In situ NMR diffusion coefficients assessment of lithium ion conductor using electrochemical priors and Arrhenius constraint——A computational study

In situ NMR measurements of the diffusion coefficients,including an estimate of signal strength,of lithium ion conductor using diffusion-weighting pulse sequence are performed in this study.A cascade bilinear model is proposed to estimate the diffusion sensitivity factors of pulsed-field gradient using prior information of the electrochemical performance and Arrhenius constraint.The model postulates that the active lithium nuclei participating electrochemical reaction are relevant to the NMR signal intensity,when discharge rate or temperature condition is varying.The electrochemical data and the NMR signal strength show a highly fit with the proposed model according our simulation and experiments.Furthermore,the diffusion time is constrained by temperature based on Arrhenius equation of reaction rates dependence.An experimental calculation of Li_4Ti_5O_（12）（LTO）/carbon nanotubes（CNTs） with the electrolyte evaluating at 20 ℃ is presented,which the b factor is estimated by the discharge rate.