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• 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]

Abstract: In this paper, a photoanode of compact TiO2 film with a small specific surface area has been developed to discuss the effects of interlayer in the dye/modification material alternating assembly structure. The compact film photoanode could avoid the complexity and various influence factors of porous film as light scattering and different diffusion rates of electrolyte in the pores. It is beneficial to discuss the effects of alternating assembly structure. From the discussion based on compact TiO2 film, it was indicated that the suitable material used for the interlayer of alternating assembly structure should show relatively strong alkalinity and higher energy level than the Lowest Unoccupied Molecular Orbital (LUMO) of dye molecules. The former is easier for the absorption of a second layer of dyes, and the latter ensured the generated electrons of the second layer of dye can inject into the conduction band of TiO2. Using the obtained suitable material as interlayer of alternating assembly structure enhanced the conversion efficiency of DSCs remarkably. [Copyright &y& Elsevier]

Abstract Polycrystalline nickel ferrite (NiFe 2 O 4) thin films were fabricated by pulsed laser deposition (PLD) and coated with nanometer layer of lithium phosphorus oxynitride (LiPON) by radio frequency magnetron sputtering (RF sputtering). Physical characterizations demonstrated that NiFe 2 O 4 thin films were not destroyed by LiPON coating with 50 nm thickness. Discharge capacity of LiPON coated NiFe 2 O 4 thin film after 50 cycles at 5 μA cm−2 was 849 mAh g−1, much higher than the counterpart value of pristine NiFe 2 O 4 thin film (449 mAh g−1), while rate capability was also greatly enhanced. Ex situ TEM investigation confirmed the two-steps reaction mechanism between NiFe 2 O 4 and Li, which includes an irreversible decomposition reaction of NiFe 2 O 4 in the first discharge process and reversible reactions between NiO, Fe 2 O 3 and their nanosized metal particles afterward. The significant improvement on the electrochemical performance was ascribed to the amorphous LiPON layer on the surface, which suppressed the volume expansion of electrode, the formation of delaminated particles and generation of cracks on electrode surface, as proved by ex situ SEM and AFM results. The LiPON coating is an effective approach to enhance the electrochemical performance of conversion materials for lithium ion batteries. Highlights • Pristine and LiPON coated NiFe 2 O 4 thin films were fabricated. • LiPON coating benefits the electrochemical performance of NiFe 2 O 4 thin film. • Conversion mechanism was confirmed by ex situ TEM technique for the first time. • Ex situ SEM and AFM results explained the effect of LiPON coating. [ABSTRACT FROM AUTHOR]

• A system-level thermal-electrochemical model of thermal batteries during activation stage is built. • Fuse strip has important effects on the activation process of thermal batteries. • The difference of internal resistance between the unactivated and activated state can reach 12 orders of magnitude. As the primary reserve batteries widely used in military domain, the intricate thermal-electrochemical behaviors and tiny time scale of the activation process make the development of thermal batteries a pain-stacking work, as lacking of the precise model to guide the design process. In this study, a system-level thermal-electrochemical model for evaluating the main technical indexes of LiSi/FeS 2 thermal batteries during activation stage is built, which comprehensively considers the main physical and chemical processes such as combustion, heat transfer, phase change, ion transport, voltage variation and so on. The activation characteristics of two types of 5-cell thermal batteries are predicted by this model, and the activation voltages of the two batteries are tested to validate the model. The model possesses the high precision with error less than 5 % by comparing the simulation results of activation voltage with that of experiment results. Specifically, the model reveals that the instantaneous temperature of pyrotechnic pellet after combustion is around 1570 K, and the electrolyte becomes molten and its internal resistance sharply decreases to mΩ level when the temperature reaches its melting point. The variation process of activation voltage is mainly dominated by the geometry size of cell stack and the thickness ratio of pyrotechnic pellet to single cell, besides, the activation time can be considered to be the peak value time of activation voltage. Fuse strip has important effects on the activation process of thermal batteries, especially in the rapid increase period of activation voltage, and the heat transfer is the time-limited step of the activation process. The difference of internal resistance between the unactivated state and activated state of thermal batteries can reach 12 orders of magnitude. These results indicate that our model can perform well in evaluating the activation process of thermal batteries and guiding the optimal design. [ABSTRACT FROM AUTHOR]

[Display omitted] • The combined electrochemical and transport kinetic parameters of CoS 2 /LiCl-LiBr-KBr system at the varied high temperature were systematically studied. • The effects of electrochemical and transport behavior on the impedance characteristic of CoS 2 /LiCl-LiBr-KBr were explored by proposing a equivalent-circuit model. • The results of this research is basis for the design and optimization of the new thermal battery cell. Systematic researches of ionic transport and electrochemical characteristics have been seldom implemented for the porous CoS 2 electrode in ternary LiCl-LiBr-KBr, which are ideal and main form for advanced thermal batteries. In the work, we systematically measured the combined electrochemical and transport kinetic parameters of CoS 2 /LiCl-LiBr-KBr system at the varied high temperature. Specifically, we firstly explored the discharge mechanism of CoS 2 /molten LiCl-LiBr-KBr using galvanostatic discharge experiment and X-ray diffraction (XRD). For the ionic transport performance, the diffusion coefficient of active Li ions was calculated from cyclic voltammograms (CV) data, and the ionic conductivity of LiCl-LiBr-KBr and electric conductivity of CoS 2 and generated Co 9 S 8 were also measured. Then, the interfacial electrochemical characteristics (exchange current density and transfer coefficients) were comparatively studied by the electrochemical impedance spectroscopy (EIS) and linear sweep voltammograms (LSV) method. Based on the above-mentioned results, we further investigated the comprehensive effects of these factors on the electrochemical and transport behavior by proposing a equivalent-circuit model of the porous CoS 2 electrode soaked in LiCl-LiBr-KBr molten salts. The results of this research is basis for the design and optimization of the new thermal battery cell, and will contribute to a knowledge-based development of the advanced TBs in the future. [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]

Using first-principles calculations, we have systematically investigated the adsorption and diffusion behavior of Li in MoO 3 bulk, on MoO 3 (010) surface and in MoO 3 /graphene composite. Our results indicate that, in case of MoO 3 bulk, Li diffusion barriers in the interlayer and intralayer spaces are 0.55 eV and 0.58 eV respectively, which are too high to warrant fast Lithium-ion charge/discharge processes. While on MoO 3 (010) surface, Li exhibits a diffusion barrier as low as 0.07 eV which guarantees an extremely fast Li diffusion rate during charge/discharge cycling. However, in MoO 3 /graphene monolayer, Li diffusion barrier is at the same level as that on MoO 3 (010) surface, which also ensures a very rapid Li charge/discharge rate. The rapid Li charge/discharge rate in this system originates from the removal of the upper dangling O1 atoms which hinder the Li diffusion on the lower MoO 3 layer. Besides this, due to the interaction between Li and graphene, the Li average binding energy increases to 0.14 eV compared to its value on MoO 3 (010) surface which contributes to a higher voltage. Additionally, the increased ratio of surface area provides more space for Li storage and the capacity of MoO 3 /graphene composite increases up to 279.2 mAhg −1 . The last but not the least, due to the high conductivity of graphene, the conductivity of MoO 3 /graphene composite enhances greatly which is beneficial for electrode materials. In the light of present results, MoO 3 /graphene composite exhibits higher voltage, good conductivity, large Li capacity and very rapid Li charge/discharge rate, which prove it as a promising cathode material for high-performance lithium-ion batteries (LIBs). [ABSTRACT FROM AUTHOR]

[Display omitted] • A route is proposed to load nanoparticles and electrolyte into ceramic paper separator. • The proposed route is efficient and safe, which can be promoted to used in large scales. • Electrochemical performance of thermal batteries can be obviously improved with ceramic paper as separator. Composites consisted of ceramic paper, nanoparticles as well as molten salt electrolyte, are developed as the new electrolyte separators to substitute the traditional ones in thermal batteries, due to their flexible manufacture and good exhibition in electrochemical performance. However, the existed methods for fabricating the composites by roughly dip-coating with aqueous solutions, are suffering from drawbacks such as inefficiency, low consistence, or high temperature risk. Therefore, a new approach based on a melting-absorption-diffusion process, by using precursors without solvent, is developed. Firstly, the salts are accurately weighted. Then they melt on surfaces of ceramic papers and diffuse inside. After being treated at appropriate temperature for hours, high quality electrolyte separators based on ceramic papers are achieved. Compared to the traditional approaches, the new method can obviously increase and accurately control the amount of loaded nanoparticles and molten salts for each time. The achieved electrolyte separators also exhibit good electrochemical performance in single cells of thermal batteries compared with the traditional ones. With advantages like easy operation, high efficiency, and improved performance, this melting and in situ loading method holds broad prospect in preparing electrolyte separators at large scale. [ABSTRACT FROM AUTHOR]