Monophosphides and bi-metallic phosphides have attracted considerable interest for their high-capacity Li-storage capacity, but are currently plagued by the sluggish charge transfer kinetics and large volume changes that hinder their practical applications. Herein, we design a triple-disordered-cation phosphide of GaGeSiP₃ that combines the benefits of the high capacity of Si, high reactivity of P, fast Li ion conduction of Ge, and the self-healing capability of liquid metallic Ga. The GaGeSiP₃ multinary compound features high configurational entropy, with excellent electronic conductivity, rapid Li-ion diffusion, and better resistance to volume change compared to the parent phases of GaGe₂P₃, GaSi₂P₃, Ge, and Si. Crystallographic and spectrographic analyses, electrochemical characterization and theoretical simulations confirm that GaGeSiP₃ undergoes a reversible lithium storage mechanism based on a combination of intercalation and conversion reactions. The GaGeSiP₃ anode delivers a high specific capacity of 1667 mA h g⁻¹ with an initial coulombic efficiency of 90.3% and a low average operating potential of 0.47 V. Moreover, we further create graphite-modified GaGeSiP₃ that combines intercalation and conversion storage to deliver a high rate capacity of 949 mA h g⁻¹ at 20.0 mA cm⁻², and an exceptional cycling stability to retain a capacity of 1121 mA h g⁻¹ after 2000 cycles at 6.0 mA cm⁻². Inspired by this unique feature of high structural entropy, we further synthesized quaternary mixed-cation ZnGaGeSiP₄, CuGaGeSiP₄, and AlGaGeSiP₄; quinary mixed-cation ZnCuGaGeSiP₅, ZnAlGaGeSiP₅, and CuAlGaGeSiP₅; and hexanary mixed-cation ZnCuAlGaGeSiP₆, where the crystalline size was reduced due to the enhanced structural entropy. This work opens up a new synthesis paradigm, which overcomes the thermodynamic immiscibility among different metals and non-metals, for creating an attractive family of high-entropy multinary mixed-cation phosphides as advanced energy storage materials.

中文翻译：

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用于快速稳定锂离子存储的高熵磷化物的通用合成

单磷化物和双金属磷化物因其高容量的锂存储能力而引起了人们的极大兴趣，但目前受到缓慢的电荷转移动力学和大的体积变化的困扰，阻碍了它们的实际应用。在此，我们设计了一种三重无序阳离子磷化物GaGeSiP ₃，它结合了Si的高容量、P的高反应性、Ge的快速Li离子传导以及液态金属Ga的自愈能力的优点。与GaGe ₂ P ₃、GaSi ₂ P ₃、Ge和Si母相相比， ₃元化合物具有高构型熵、优异的电子传导性、快速的锂离子扩散以及更好的抗体积变化能力。晶体学和光谱分析、电化学表征和理论模拟证实，GaGeSiP ₃经历了基于插层和转化反应组合的可逆锂存储机制。 GaGeSiP _{3阳极具有 1667 mA hg} ⁻¹的高比容量，初始库仑效率为 90.3%，平均工作电压为 0.47 V。此外，我们进一步创建了石墨改性的 GaGeSiP ₃，它将插层和转换存储结合在一起，在20.0 mA cm ^{-2下提供949 mA hg -1}的高倍率容量，以及卓越的循环稳定性，在6.0 mA cm ^{-2下循环2000次后仍保持1121 mA hg -1}的容量。受这种独特的高结构熵特征的启发，我们进一步合成了四元混合阳离子ZnGaGeSiP ₄、CuGaGeSiP ₄和AlGaGeSiP ₄；五元混合阳离子ZnCuGaGeSiP ₅、ZnAlGaGeSiP ₅和CuAlGaGeSiP ₅；和六元混合阳离子ZnCuAlGaGeSiP ₆，由于结构熵的增强，晶体尺寸减小。这项工作开辟了一种新的合成范式，克服了不同金属和非金属之间的热力学不混溶性，创建了一系列有吸引力的高熵多元混合阳离子磷化物作为先进的储能材料。