The formation of dendrites in alkali and alkaline earth-metal batteries leads to short circuit and catastrophic battery failure which hinders the development of high-energy-density battery technology. Herein, we investigate the thermodynamic origin of this complex phenomenon and show that kinetic transport limitation of metal cations in the electrolyte is not the only factor controlling the formation of dendrites. The specific behavior of Li, Na and Mg electrodes towards dendritic growth is straightforwardly deduced from the shape of their electro-capillary diagrams, as computed from a grand canonical DFT approach. The whisker and dendrite morphologies associated with the different growth regimes are fully rationalized by the present methodology and the critical parameters controlling the dendritic growth on metallic surfaces are clearly identified. Further improving the description of the interface by means of a simplified yet realistic SEI built on carbonate-based decomposition products, we show that the over-potentials at which each growth regime is expected to occur can be predicted at a quantitative level, hence allowing the design of chemical strategies to prevent dendrite growth at metallic surfaces. More specifically, high surface tension associated with low surface capacitance and low potential of zero-charge is the target triptych to favor safe battery operation and can be obtained through appropriate chemical engineering.

中文翻译：

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金属阳极电池中枝晶生长的热力学起源

碱金属和碱土金属电池中树枝状晶体的形成会导致电池短路和灾难性故障，从而阻碍了高能量密度电池技术的发展。在本文中，我们研究了这种复杂现象的热力学起源，并表明电解质中金属阳离子的动力学传输限制不是控制树枝状晶体形成的唯一因素。Li，Na和Mg电极对树突状生长的特定行为可以直接从其电毛细管图的形状中推导得出，如通过大型规范DFT方法计算得出的。通过本方法，与不同生长方式相关的晶须和枝晶形态得以完全合理化，并且清楚地确定了控制金属表面枝晶生长的关键参数。通过建立在碳酸盐基分解产物上的简化而又现实的SEI进一步改善了界面的描述，我们表明，可以在定量水平上预测每种生长方式预期发生的超电势。防止金属表面枝晶生长的化学策略设计。更具体地，与低表面电容和低零电势相关联的高表面张力是有利于电池安全操作的目标三联画，并可通过适当的化学工程获得。通过建立在碳酸盐基分解产物上的简化而又现实的SEI进一步改善了界面的描述，我们表明，可以在定量水平上预测每种生长方式预期发生的超电势。防止金属表面枝晶生长的化学策略设计。更具体地，与低表面电容和低零电势相关联的高表面张力是有利于电池安全操作的目标三联画，并可通过适当的化学工程获得。通过建立在碳酸盐基分解产物上的简化而又现实的SEI进一步改善了界面的描述，我们表明，可以在定量水平上预测每种生长方式预期发生的超电势。防止金属表面枝晶生长的化学策略设计。更具体地，与低表面电容和低零电势相关联的高表面张力是有利于电池安全操作的目标三联画，并可通过适当的化学工程获得。因此，可以设计化学策略来防止枝晶在金属表面生长。更具体地，与低表面电容和低零电势相关联的高表面张力是有利于电池安全操作的目标三联画，并可通过适当的化学工程获得。因此，可以设计化学策略来防止枝晶在金属表面生长。更具体地，与低表面电容和低零电势相关联的高表面张力是有利于电池安全操作的目标三联画，并可通过适当的化学工程获得。