Accurate prediction of practical reduction electrode potentials(Ered)of electrolyte solvents of electrochemical energy storage devices relies on calculating the Gibbs free energy in their reduction reaction.However,th...Accurate prediction of practical reduction electrode potentials(Ered)of electrolyte solvents of electrochemical energy storage devices relies on calculating the Gibbs free energy in their reduction reaction.However,the emergence of new electrolyte solvents and additives leaves most of the reaction mechanisms unveiled.Here,we provide a machine-learning-assisted workflow of thermodynamically quantified Ered prediction for electrolyte solvents.A computational hydrogen electrode model based on density functional theory calculation is generalized for calculating the reaction free energy of electrochemical elementary steps.Machine-learning models are trained based on the organic and inorganic electrolyte solvents that possess experimentally identified reduction mechanisms.Validation of the best-scoring model is conducted by experimental validation of 6 additional solvents.Multiple thermodynamics features are found impactful on Ered through different chemical bonding with reaction intermediates.This workflow enables accurate Ered prediction for electrolyte solvents without identified reduction mechanisms,and is widely applicable in the electrochemical energy storage area.展开更多
基金supported by National Key Research and Development(R&D)Program of China(2022YFB4101600)National Natural Science Foundation of China(22179139,22379157)+1 种基金Key Research and Development(R&D)Projects of Shanxi Province(202102040201003)Fundamental Research Program of Shanxi Province(202203021211203),The authors appreciate Beijing Paratera Technology Co.,Ltd,and the Supercomputer Center in Lvliang,China,for providing computational resources.
文摘Accurate prediction of practical reduction electrode potentials(Ered)of electrolyte solvents of electrochemical energy storage devices relies on calculating the Gibbs free energy in their reduction reaction.However,the emergence of new electrolyte solvents and additives leaves most of the reaction mechanisms unveiled.Here,we provide a machine-learning-assisted workflow of thermodynamically quantified Ered prediction for electrolyte solvents.A computational hydrogen electrode model based on density functional theory calculation is generalized for calculating the reaction free energy of electrochemical elementary steps.Machine-learning models are trained based on the organic and inorganic electrolyte solvents that possess experimentally identified reduction mechanisms.Validation of the best-scoring model is conducted by experimental validation of 6 additional solvents.Multiple thermodynamics features are found impactful on Ered through different chemical bonding with reaction intermediates.This workflow enables accurate Ered prediction for electrolyte solvents without identified reduction mechanisms,and is widely applicable in the electrochemical energy storage area.
