固体电解质界面层锂合金相的高通量筛选与界面离子输运研究

固体电解质界面层(SEI)对锂离子电池的电化学性能有着重要影响,理想的SEI层应同时具备良好的电子绝缘性、较高的离子电导率,以及一定的界面机械强度来承受锂沉积/剥离行为所伴随的体积变化和抑制锂枝晶形成。构筑LiF基人工SEI层已被证明是保护固态锂离子电池负极界面的有效策略。本工作通过材料数据库挖掘技术、高通量第一性原理计算和从头算分子动力学模拟对若干锂合金进行相图计算、扩散能垒计算,以评估其热力学稳定性和锂离子扩散能力,最终筛选出27种可用于LiF基人工SEI层锂离子导电相的锂合金材料。同时,对若干锂合金的晶体结构-扩散性质进行构效关系分析发现,锂合金晶体结构类型对锂离子扩散能力的影响比其元素组分更加显著,即I43d和Fm3m族群结构的锂合金具备非常优异的锂离子输运性能,而Pm3m和F43m族群结构的锂合金扩散通道狭窄,锂离子输运性能差。此外,本计算工作发现锂离子在LiF晶体中扩散迁移是极其困难的,而在LiF晶界和LiF/LiM合金界面迁移扩散阻力极小,藉此获得人工SEI界面层中锂离子输运的物理图像。

Lattice Boltzmann simulation of solute transport in a single rough fracture

In this study, the lattice Boltzmann method （LBM） was used to simulate the solute transport in a single rough fracture. The self-affine rough fracture wall was generated with the successive random addition method. The ability of the developed LBM to simulate the solute transport was validated by Taylor dispersion. The effect of fluid velocity on the solute transport in a single rough fracture was investigated using the LBM. The breakthrough curves （BTCs） for continuous injection sources in rough fractures were analyzed and discussed with different Reynolds numbers （Re）. The results show that the rough frac~＇e wall leads to a large fluid velocity gradient across the aperture. Consequently, there is a broad distribution of the immobile region along the rough fracture wall. This distribution of the immobile region is very sensitive to the Re and fracture geometry, and the immobile region is enlarged with the increase of Re and roughness. The concentration of the solute front in the mobile region increases with the Re. Furthermore, the Re and roughness have significant effects on BTCs, and the slow solute molecule exchange between the mobile and immobile regions results in a long breakthrough tail for the rough fracture. This study also demonstrates that the developed LBM can be effective in studying the solute transport in a rough fracture.

Three-dimensional analysis of spreading and mixing of miscible compound in heterogeneous variable-aperture fracture

As mass transport mechanisms,the spreading and mixing(dilution) processes of miscible contaminated compounds are fundamental to understanding reactive transport behaviors and transverse dispersion.In this study,the spreading and dilution processes of a miscible contaminated compound in a three-dimensional self-affine rough fracture were simulated with the coupled lattice Boltzmann method(LBM).Moment analysis and the Shannon entropy(dilution index) were employed to analyze the spreading and mixing processes,respectively.The corresponding results showed that the spreading process was anisotropic due to the heterogeneous aperture distribution.A compound was transported faster in a large aperture region than in a small aperture region due to the occurrence of preferential flow.Both the spreading and mixing processes were highly dependent on the fluid flow velocity and molecular diffusion.The calculated results of the dilution index showed that increasing the fluid flow velocity and molecular diffusion coefficient led to a higher increasing rate of the dilution index.

Quantifying the impact of mineralogical heterogeneity on reactive transport modeling of CO_(2)+O_(2) in-situ leaching of uranium

CO_(2)+O_(2) in-situ leaching(ISL)of sandstonetype uranium ore represents the third generation of solution mining in China.In this study,reactive transport modeling of the interaction between hydrodynamic and geochemical reactions is performed to enable better prediction and regulation of the CO_(2)+O_(2) in-situ leaching process of uranium.Geochemical reactions between mining solutions and rock,and the kinetic uranium dissolution controlled by O_(2)(aq)and bicarbonate(HCO_(3)-)are considered in the CO_(2)+O_(2) ISL reactive transport model of a typical sandstone-hosted uranium ore deposit in northern China.The reactive leaching of uranium is most sensitive to the spatial distribution of the mineralogical properties of the uranium deposit.Stochastic geostatistical models are used to represent the uncertainty on the spatial distribution of mineral grades.A Monte Carlo analysis was also performed to simulate the uranium production variability over an entire set of geostatistical realizations.The ISL stochastic simulation performed with the selected geostatistical realizations approximates the uranium production variability well.The simulation results of the ISL reactive transport model show that the extent of the uranium plume is highly dependent on mineralogical heterogeneity.The uncertainty analysis suggests the effect of uranium grade heterogeneity was found to be important to improve the accurate capture of the uncertainty.This study provides guidance for the accurate simulation and dynamic regulation of the CO_(2)+O_(2) leaching process of uranium at the scale of large mining areas.

Non-Darcy flows in layered porous media(LPMs)with contrasting pore space structures

Compared to single layer porous media,fluid flow through layered porous media(LPMs)with contrasting pore space structures is more complex.This study constructed three-dimensional(3-D)pore-scale LPMs with different grain size ratios of 1.20,1.47,and 1.76.The flow behavior in the constructed LPMs and single layer porous media was numerically investigated.A total of 178 numerical experimental data were collected in LPMs and single layer porous media.In all cases,two different flow regimes(i.e.,Darcy and Non-Darcy)were observed.The influence of the interface of layers on Non-Darcy flow behavior in LPMs was analyzed based pore-scale flow data.It was found that the available correlations based on single layer porous media fail to predict the flow behavior in LPMs,especially for LPM with large grain size ratio.The effective permeability,which incorporated the influence of the interface is more accurate than the Kozeny-Carman equation for estimating the Darcy permeability of LPMs.The inertial pressure loss in LPMs,which determines the onset of the Non-Darcy flow,was underestimated when using a power law expression of mean grain size.The constant B,an empirical value in the classical Ergun equation,typically equals 1.75.The inertial pressure loss in LPMs can be significantly different from it in single lager porous media.For Non-Darcy flow in LPMs,it is necessary to consider a modified larger constant B to improve the accuracy of the Ergun empirical equation.

Machine learning molecular dynamics simulation identifying weakly negative effect of polyanion rotation on Li-ion migration

Understanding the physical picture of Li ion transport in the current ionic conductors is quite essential to further develop lithium superionic conductors for solid-state batteries.The traditional practice of directly extrapolating room temperature ion diffusion properties from the high-temperature(>600 K)ab initio molecular dynamics simulations(AIMD)simulations by the Arrhenius assumption unavoidably cause some deviations.Fortunately,the ultralong-time molecular dynamics simulation based on the machine-learning interatomic potentials(MLMD)is a more suitable tool to probe into ion diffusion events at low temperatures and simultaneously keeps the accuracy at the density functional theory level.Herein,by the low-temperature MLMD simulations,the non-linear Arrhenius behavior of Li ion was found for Li3ErCl6,which is the main reason for the traditional AIMD simulation overestimating its ionic conductivity.The 1μs MLMD simulations capture polyanion rotation events in Li_(7)P_(3)S_(11) at room temperature,in which four[PS_(4)]^(3−)tetrahedra belonging to a part of the longer-chain[P_(2)S_(7)]4−group are noticed with remarkable rotational motions,while the isolated group[PS_(4)]^(3−)does not rotate.However,no polyanion rotation is observed in Li10GeP_(2)S12,β-Li3PS_(4),Li3ErCl6,and Li3YBr6 at 300 K during 1μs simulation time.Additionally,the ultralong-time MLMD simulations demonstrate that not only there is no paddle-wheel effect in the crystalline Li_(7)P_(3)S_(11) at room temperature,but also the rotational[PS_(4)]^(3−)polyanion groups have weakly negative impacts on the overall Li ion diffusion.The ultralong-time MLMD simulations deepen our understanding of the relationship between the polyanion rotation and cation diffusion in ionic conductors at room environments.