Search

• Self-discharge kinetics behavior of Li-Si anode is investigated by theoretical model and experiment. • Effective diffusion coefficients of soluble lithium in porous electrode are determined to verify the availability of model. • Effects of temperature, discharge current and electrode thickness on self-discharge kinetics behavior are discussed. • The three factors are coupled in the form of arrhenius equation by multivariate nonlinear regression. Self-discharge has significant influence on the service life of thermal batteries. The kinetics process of self-discharge depends on both the structure evolution and intrinsic property of electrodes. Herein, the kinetics model to quantify the self-discharge degree of the Li-Si anode is constructed according to the structure of thermal cells. Typical operation and preparation parameters, i.e. temperature, discharge current and electrode thickness, are evaluated based on the specially designed combined-discharge scheme. Then the effective diffusion coefficients (D eff) of soluble lithium (Li0) that are affected by the three variables are calculated and fitted. The calculation results consequently confirm self-discharge process of the Li-Si anode can be described by the derived equations exactly, and then the process is demonstrated to be diffusion-controlled. Further, D eff increase at the higher temperature and larger discharge current, while decrease with the increased electrode thickness, which is analyzed by scanning electron microscope and X-ray microcomputed tomography. The entire effects on D eff can be coupled in one fitting expression based on Arrhenius equation, and the apparent activation energies decrease under the larger discharge current and smaller electrode thickness. Finally, the additional experiments were conducted to verify the accuracy of the fitting expression. [Display omitted] [ABSTRACT FROM AUTHOR]

Li 3 P-VP nanocomposite has been formed by a homemade pulsed laser deposition route and its electrochemical characteristic with lithium is reported for the first time. It displays high lithium storage capability as electrode material for secondary lithium ion batteries. The Li 3 P-VP nanocomposite exhibits high specific discharge capacity of 1040.4 mAh g−1 between 0.01 and 4.0 V and the specific capacity can still maintain 95% after 50 cycles. Ex situ transmission electron microscopy reveals that VP 2 is generated from Li 3 P and VP after the first charging process to 4.0 V, while Li 3 P and V are found to be the final discharge products. In the recharging process, VP and VP 2 are formed as the delithiated products. Unlabelled Image • Li 3 P-VP nanocomposite thin film was fabricated by PLD. • High capacity of 1040.4 mAh g−1 was achieved and 95% was kept after 50 cycles. • VP 2 was generated from Li 3 P and VP after the first charging process to 4.0 V. • Reversible conversion mechanism to V and Li 3 P was suggested for VP-VP 2. [ABSTRACT FROM AUTHOR]