Unveiling Oxygen Evolution Reaction on LiCoO₂ Cathode: Insights for the Development of High‐Performance Aqueous Lithium‐ion Batteries

Abstract

Aqueous lithium‐ion batteries (ALIBs) are attracting significant attention as promising candidates for safe and sustainable energy storage systems. This paper delves into the crucial aspects of ALIB technology focusing on the interaction between LiCoO2 (lithium cobalt oxide) cathode material and water electrolytes, with a specific emphasis on the Oxygen Evolution Reaction (OER) process. Fundamental understanding of the electrochemical behavior of LiCoO2 in aqueous electrolytes is crucial for enhancing the performance, safety, and longevity of ALIBs using LiCoO2 as the cathode material.Through a comprehensive periodic density functional analysis of the LiCoO2‐water at the cathode interface, the potential catalytic contributions to the OER mechanism of LiCoO2 are explored. The catalytic properties of LiCoO2 towards OER are investigated considering different steady states of the lowest energy surfaces of LiCoO2 and three different Li concentrations. Our results do not predict the formation of oxygen gas due to the expected large overpotentials, although the exergonic water decomposition to hydroxyl by means the first proton‐electron transfer is predicted at equilibrium potential. This work contributes to the fundamental understanding of LiCoO2 as cathode for aqueous lithium‐ion batteries, reporting the pros and cons of one of the most common cathode materials for traditional non‐aqueous batteries.

Thermally Labile Organic-Soluble Heterometal Diorganophosphate-Derived Efficient Electrocatalysts for the Oxygen Evolution Reaction

“…32−37 Considerable efforts have been devoted to the development of aqueous Li-ion batteries replacing the traditional organic electrolytes with less expensive water-based electrolytes. 38,39 Additionally, their wider exploitation for energy storage devices in the near future demands the recycling or regeneration of the cathode materials with crucial metals. The direct recycling for usage in Li-ion batteries requires regeneration of the cathode materials maintaining the structure, morphology, and composition of the cathode materials.…”

“…Lithium-transition-metal orthophosphates (Fe, Ni, Co, and Mn) have been extensively studied as cathode materials in lithium-ion batteries owing to their high energy density and better thermodynamic stability and safety at higher voltage due to the covalently bonded PO 4 group. ,− Among these, olivine LiCoPO 4 provides a higher operating voltage of 4.8 V vs Li/Li + compared to the already commercialized LiFePO 4 (3.5 V vs Li/Li + ). − Besides, two other metastable polymorphs ( Pna 2 1 and Cmcm ) of LiCoPO 4 and lithium–cobalt metaphosphates and pyrophosphates have also been discovered in the past decade. − Considerable efforts have been devoted to the development of aqueous Li-ion batteries replacing the traditional organic electrolytes with less expensive water-based electrolytes. , Additionally, their wider exploitation for energy storage devices in the near future demands the recycling or regeneration of the cathode materials with crucial metals. The direct recycling for usage in Li-ion batteries requires regeneration of the cathode materials maintaining the structure, morphology, and composition of the cathode materials. , Thus, it is vital to study the interaction of cathode materials with aqueous electrolytes and their oxygen evolution reaction (OER) capabilities for recycling of spent Li-ion battery cathode materials or their development in an aqueous Li-ion battery.…”