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中国物理学会期刊

温度调控镁金属阳极枝晶生长的相场模拟

CSTR: 32037.14.aps.75.20260240

Phase-field simulation study on temperature-controlled dendrite growth in magnesium metal anodes

CSTR: 32037.14.aps.75.20260240
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  • 镁电池因镁资源储量丰富且具有较高的体积能量密度, 近年来受到广泛关注. 虽然相较于传统锂电池, 镁负极的枝晶生长趋势较弱, 但在高电流密度下, 枝晶问题依然不可避免. 因此, 必须深入研究镁枝晶的生长机制, 以规避其带来的安全性风险. 本研究基于相场法, 在开源软件MOOSE框架下构建了热-电化学耦合模型, 系统研究了温度对镁枝晶生长行为的影响机理. 模型中, 镁离子扩散系数采用阿伦尼乌斯形式表征, 模拟了不同环境温度下镁电沉积的形貌演化、离子浓度分布及电势场特征. 结果表明, 温度升高显著提升镁离子扩散速率, 缓解界面浓度极化, 削弱尖端效应, 使沉积界面趋于平整、枝晶形态由针状向块状转变, 枝晶生长速率下降, 形核数量减少. 在相同枝晶长度条件下, 350 K时的稳定沉积层厚度较280 K提升约7倍. 温度调控通过平衡扩散过程与反应过程, 有效抑制枝晶纵向生长, 增强沉积均匀性. 本研究揭示了温度对镁枝晶生长的调控机制, 为提升镁电池充电安全性与界面稳定性提供了理论依据与模拟支持.

     

    Magnesium batteries have garnered significant attention due to the abundant magnesium resources (approximately 3000 times more abundant in the Earth’s crust than lithium) and their high volumetric energy density (3833 mAh/cm3). Although magnesium anodes exhibit a weaker tendency for dendrite growth compared to conventional lithium batteries, uncontrolled magnesium dendrite growth remains unavoidable under high current densities, posing serious safety risks. In this study, a thermodynamically coupled electrochemical phase-field model is developed within the open-source MOOSE framework to systematically investigate temperature effects on magnesium dendrite growth. The model integrates electrode kinetics, mass transport, interfacial anisotropy, and thermal effects, with the magnesium ion diffusion coefficient characterized using the Arrhenius form. Simulations across 278 K to 350 K reveal that elevated temperatures significantly enhance ion diffusion rates, with diffusion coefficients increasing approximately fivefold from 278 K to 350 K, effectively alleviating concentration polarization at the interface. This timely ion replenishment mitigates localized current density concentration at dendrite tips, promoting a smoother deposition front. As temperature increases, dendritic morphology transitions from sharp needle-like to coarser block-like structures, accompanied by reduced longitudinal growth rates and diminished secondary nucleation. Quantitative analysis shows that under equivalent dendrite length conditions (50 μm), the stable deposition layer thickness at 350 K is approximately seven times greater than at 278 K (increasing from ~6 μm to 42 μm). Thermal regulation achieves a balanced interplay between diffusion processes and electrochemical reaction kinetics, transitioning the deposition mechanism from diffusion-limited to mixed control, effectively suppressing vertical dendrite penetration while enhancing deposit uniformity. This study elucidates the regulatory mechanisms of temperature on magnesium dendrite growth, providing theoretical foundations for optimizing magnesium battery operating conditions, enhancing charging safety, and improving interfacial stability.

     

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