Optimal thermodynamic conditions to minimize kinetic by-products in aqueous materials synthesis

Zheren Wang, Yingzhi Sun, Kevin Cruse, Yan Zeng, Yuxing Fei, Zexuan Liu, Junyi Shangguan, Young-Woon Byeon, KyuJung Jun, Tanjin He, Wenhao Sun* & Gerbrand Ceder*

*Co-Corresponding

Nature Synthesis (2024): 1-10.

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)4 and LiFePO4 across 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.