Recent Advancements Towards Closing the Gap between Electrocatalysis and Battery Science Communities: The Computational Lithium Electrode and Activity–Stability Volcano Plots

Abstract

Despite of the fact that the underlying processes are of electrochemical nature, electrocatalysis and battery research are commonly perceived as two disjointed research fields. Herein, recent advancements towards closing this apparent community gap by discussing the concepts of the constrained ab initio thermodynamics approach and the volcano relationship, which were originally introduced for studying heterogeneously catalyzed reactions by first‐principles methods at the beginning of the 21st century, are summarized. The translation of the computational hydrogen electrode (CHE) approach or activity‐based volcano plots to a computational lithium electrode (CLiE) or activity–stability volcano plots, respectively, for the investigation of electrode surfaces in batteries may refine theoretical modeling with the aim that enhancements of the underlying concepts are transferred between the research communities. The presented strategy of developing novel approaches by interdisciplinary research activities may trigger further progress of improved theoretical concepts in the near future.

Atomically dispersed Pt–N4 sites as efficient and selective electrocatalysts for the chlorine evolution reaction

“…24-27 and Supplementary Note 2). The Pourbaix diagram was constructed using an ab-initio constrained thermodynamics approach; the reactants were adsorbed on the surface while restricting the subsequent formation of product 59 . Nevertheless, the active adsorbate structure, identified as the thermodynamically most stable structure, can promisingly serve as a starting point for the investigation of mechanistic pathways.…”

Comparison of the Conventional Volcano Analysis with a Unifying Approach: Material Screening Based on a Combination of Experiment and Theory

“…While the one-fold coordinatively unsaturated surface Ru atoms (Ru cus ) are reconciled as catalytically active sites for the OER over RuO 2 (110), all surface Ru 2f atoms are bridged by two oxygen atoms (O br ) each. Under typical OER conditions, that is, U > 1.23 V vs RHE, all Ru cus sites are capped by surface oxygen (O ot ), as shown in Figure a, or by another OER intermediate (OH ot , or OOH ot ). , The concrete surface configuration of the electrode material as a function of the applied electrode potential can be determined by the construction of an ab initio Pourbaix diagram, as described in the literature. − The formation of the OH, O, and OOH adsorbate in the electrocatalytic OER cycle refers to the mechanistic description put forward by Rossmeisl and co-workers: , In eqs 1 –4, Δ G j ( j = 1, 2, 3, 4) denotes the free-energy change for the stabilization of the OH ot , O ot , and OOH ot adsorbate on the RuO 2 (110) surface or the formation of O 2 , respectively. The sum of these four free-energy changes is fixed and amounts to 4.92 eV, i.e., 4· e · U 0 OER .…”

Not All Fluorination Is the Same: Unique Effects of Fluorine Functionalization of Ethylene Carbonate for Tuning Solid-Electrolyte Interphase in Li Metal Batteries

“…In this work, we use the thermodynamic analysis, employing the computational lithium electrode, , to find the feasibility of each interfacial reaction, which is calculated by subtracting the formation energy of the surface slab (isolated Li(100) or Li(110)) and the electrolyte molecule from the formation energy of the optimized geometry. The equation of the calculation is written as Δ G rxn = H Lisurf+electrolyte DFT – H Lisurf DFT – H electrolyte DFT , where “ H ” and “electrolyte” denote the formation enthalpy and the electrolyte of interest, respectively.…”