Designing Next Generation Rechargeable Battery Materials from First-PrinciplesPublic Deposited
Technology has advanced rapidly, especially in the twenty-first century, influencing our day-to-day life on unprecedented levels. Most such advances in technology are closely linked to, and often driven by, the discovery and design of new materials. It follows that the discovery of new materials can not only improve existing technologies but also lead to revolutionary ones. In particular, there is a growing need to develop new energy materials that are reliable, clean, and affordable for emerging applications such as portable electronics, electric vehicles, and power grid systems. Many researchers have been actively searching for more cost-effective and clean electrode materials for lithium-ion batteries (LIBs) during the last few decades. These new electrode materials are also required to achieve higher electrochemical performance, compared to the already commercialized electrodes. Unfortunately, discovering the next sustainable energy materials based on a traditional ‘trial-and-error’ method via experiment would be extremely slow and difficult. In the last two decades, computational compilations of battery material properties such as voltage, diffusivity, and phase stability against irreversible phase transformation(s) using first-principles density functional theory (DFT) calculations have helped researchers to understand the underlying mechanism in many oxide materials that are used as LIB electrodes. Here, we have examined the (001) and (111) surface structures of LiMn2O4 (LMO) spinel cathode materials using DFT calculations within the generalized gradient approximation (GGA) + U approach. Our theoretical results explain the observation of a wide spectrum of polyhedral shapes between (001)- and (111)-dominated LMO particles in experiments, which can be described by the narrow range of surface energies and their sensitivity to synthesis conditions. We further show that single-layer graphene coatings help suppress manganese dissolution in LMO by chemically interacting with Mn3+ at the (001) LMO surface, promoting an oxidation state change to Mn4+. In addition, we find that graphene defects also react with H2O and generated HF, protecting the active cathode materials from the attack of HF generated in the electrolyte during cycling. The carbonyl and epoxy functional groups in graphene oxide (GO) serve as a physical barrier to mitigate Mn ion dissolution into the liquid electrolyte, stabilizing the overall cell cycling performance. Next, we examine the occurrence of low- and high-temperature LiCoO2 structures and their observed voltage profiles in order to understand the complex structural and electrochemical behaviors. Moreover, a structural search is conducted to identify a new over-lithiated spinel oxide composition, i.e., Fd3̅m LiNi0.8125Co0.1875O2, which may have potential for exploitation in structurally-integrated, ‘layered-spinel’ cathode system. We have further investigated the structural and electrochemical properties of ‘layered-layered-spinel’ xLi2MnO3·yLiNi0.5Co0.2Mn0.3O2·zLiNi0.5Mn1.5O4 cathode materials using both experiment and theory. Lastly, the idea of a multi-faceted high-throughput (HT) screening approach has been performed within the Open Quantum Materials Database (OQMD) framework to discover possible Li-rich Li2MIO3-Li2MIIO3 pair combinations (MI,II = elements from the periodic table) that can offer better structural stability, favorable metal-mixing behavior, coherent interfaces, and high energy. Our approach involving computational design of novel materials and systems will accelerate the development of new sustainable energy solutions for meeting global demands.