Optimal thermodynamic conditions to minimize kinetic by-products in aqueous materials synthesis
Optimal thermodynamic conditions to minimize kinetic by-products in aqueous materials synthesis
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DOI：
10.1038/s44160-023-00479-0
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发表时间：
2024-01
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通讯作者：
Zheren Wang;Yingzhi Sun;Kevin Cruse;Yan Zeng;Yuxing Fei;Zexuan Liu;J. Shangguan;Young-Woon Byeon;KyuJung Jun;T. He;Wenhao Sun;G. Ceder
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文献类型：
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作者：
Zheren Wang;Yingzhi Sun;Kevin Cruse;Yan Zeng;Yuxing Fei;Zexuan Liu;J. Shangguan;Young-Woon Byeon;KyuJung Jun;T. He;Wenhao Sun;G. Ceder
通过确定目标相的稳定区域，相图为材料合成提供了实质性的预测能力。然而，热力学相图不提供明确的信息，不希望的副产物相的动力学竞争力。在这里，我们提出了一个定量和可计算的热力学度量，以确定合成条件下，形成动力学竞争的副产品的倾向是最小化。我们假设，当目标相和所有其他竞争相的最小能量之间的自由能差最大化时，热力学竞争最小化。我们通过两种经验方法验证了这一假设的水材料合成：第一，通过分析331水合成配方文本挖掘从文献中;第二，通过系统的实验合成LiIn（IO 3）4和LiFePO 4在广泛的水电化学条件。我们的研究结果表明，即使是在热力学Pourbaix图的稳定区域内的合成条件下，相纯合成仅发生在与不希望的相的热力学竞争最小化时。
Phase diagrams offer substantial predictive power for materials synthesis by identifying the stability regions of target phases. However, thermodynamic phase diagrams do not offer explicit information regarding the kinetic competitiveness of undesired by-product phases. Here we propose a quantitative and computable thermodynamic metric to identify synthesis conditions under which the propensity to form kinetically competing by-products is minimized. We hypothesize that thermodynamic competition is minimized when the difference in free energy between a target phase and the minimal energy of all other competing phases is maximized. We validate this hypothesis for aqueous materials synthesis through two empirical approaches: first, by analysing 331 aqueous synthesis recipes text-mined from the literature; and second, by systematic experimental synthesis of LiIn(IO3)4and LiFePO4across a wide range of aqueous electrochemical conditions. Our results show that even for synthesis conditions that are within the stability region of a thermodynamic Pourbaix diagram, phase-pure synthesis occurs only when thermodynamic competition with undesired phases is minimized.