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<div> <div> <div> <p>Since their commercialization in the early 1990’s, rechargeable lithium ion batteries (LIBs) have become ever-present in consumer electronics, and the share of electric vehicles within the transportation sector has become much more significant. <i>Ab initio</i> modeling techniques - namely density functional theory (DFT) - have played a signifcant role in describing the atomic scale nature of Li+ insertion and removal chemistry in LIB electrode materials, and have been pivotal in accelerating the design of energy dense battery materials based on their bulk properties. Despite these advances, there remains a knowledge gap with respect to understanding the many complex reactions that occur at the surfaces and interfaces of rechargeable battery materials. This work considers several case studies of surface and interfacial reactions in energy storage materials, using DFT modeling techniques to develop strategies that can rationally control the interfacial chemistry for optimal electrochemical performance. </p><p><br></p><p> </p><div> <div> <div> <p>The first portion of this thesis aims to understand the role of interfacial modification strategies toward mitigating Mn dissolution from the spinel LiMn2O4 (LMO) surface. First, a thermodynamic characterization of LMO surface structures is performed in order to develop models of LMO substrates for subsequent computational surface science studies. A subset of these surface models are then used analyze interfacial degradation processes through delithiation-driven stress buildup and crack formation, as well as reaction mechanisms for ethylene carbonate and hydrofluoric acid to form surface Mn2+ ions that are susceptible to dissolution. Surface passivation mechanisms using protective oxide and metallic coatings are then analyzed, which elucidate an electronic structure-based descriptor for structure-sensitive atomic layer growth mechanisms and describe the changes in lithiation reactions of coated electrodes through electronic band alignment at the solid-solid interface. These studies of protective coatings describe previously overlooked physics at the electrode-coating interface that can aid in further development of coated electrode materials. Using the LMO substrate models, a thermodynamic framework for evaluating the solubility limits and surface segregation tendencies of cationic dopants is described in the context of stabilizing LMO surfaces against Mn loss. </p><p><br></p><p> </p><div> <div> <div> <p>Next, solid-solid interfacial models are developed to evaluate the role of nanostructure in catalyzing the lithiation of NiO to form reduced Ni and Li2O as concurrent discharge products. Applying a Ni/NiO multilayer morphology, interfacial energies are evaluated using DFT and implemented into a classical nucleation model at a heterogeneous interface. These calculations, alongside <i>operando</i> X-ray scattering measurements, are used to explain atomic scale mechanisms that reduce voltage hysteresis in metal oxide LIB conversion chemistry. </p><p><br></p><p> </p><div> <div> <div> <p>The structure between a Li metal anode and the lithium lanthanum titanate solid electrolyte are subsequently analyzed as a model system to understand potential inter- facial stabilization mechanisms in solid-state batteries. This analysis combines bulk, surface, and interfacial thermodynamics with <i>ab initio</i> molecular dynamics simulations to monitor the evolution of the interfacial structure over short time scales, which provides insights into the onset of degradation mechanisms. It is shown that the reductive instability of Ti4+ is the primary driving force for interfacial decomposition reactions, and that a lanthanum oxide interlayer coating is expected to stabilize the interface based on both thermodynamic and electronic band alignment arguments. </p><p><br></p><p> </p><div> <div> <div> <p>In the last part of this thesis, charge transfer kinetics are studied for several applications using constrained DFT (cDFT) to account for electronic coupling and reorganization energies between donor and acceptor states. Charge hopping mechanisms to and from dichalcogenide-based electrocatalysts during O2 and CO2 reduction/evolution reactions in Li-O2 and Li-CO2 battery systems are first evaluated. Then, the role of the spatial separation Li+ vacancies and interstitials on hole and electron polaron hopping in the prototypical LixCoO2 cathode is analzyed. The results demonstrate that Marcus rate theories using cDFT-derived parameters can reproduce experimentally observed anisotropies in electronic conductivity, whereas conventional transition state theory analyses of polaron hopping do not. Overall, this proof-of-concept study provides a framework to understand how charged species are transported in battery electrodes and are dependent on charge compensating defects.</p><p><br></p> <p>Finally, the key insights from these studies are discussed in the context of future directions related to the understanding and design of materials for electrochemical energy conversion and storage. </p> </div> </div> </div> </div> </div> </div> </div> </div> </div> </div> </div> </div> </div> </div> </div>

Journal articles are the formal medium for the communication of results among scientists, and often contain valuable data. However, manually collecting article data from a large field like lithium-ion battery chemistry is tedious and time consuming, which is an obstacle when searching for statistical trends and correlations to inform research decisions. To address this a platform for the automatic retrieval and analysis of large numbers of articles is created and applied to the field of lithium-ion battery chemistry. Example data produced by the platform is presented and evaluated and sources of error limiting this type of platform are identified, with problems related to text extraction and pattern matching being especially significant. Some solutions to these problems are presented and potential future improvements are proposed.

The anion-intercalation chemistries of graphite have the potential to construct batteries with promising energy and power breakthroughs. Here, we report the use of an ultrathin, positively charged two-dimensional poly(pyridinium salt) membrane (C2DP) as the graphite electrode skin to overcome the critical durability problem. Large-area C2DP enables the conformal coating on the graphite electrode, remarkably alleviating the electrolyte. Meanwhile, the dense face-on oriented single crystals with ultrathin thickness and cationic backbones allow C2DP with high anion-transport capability and selectivity. Such desirable anion-transport properties of C2DP prevent the cation/solvent co-intercalation into the graphite electrode and suppress the consequent structure collapse. An impressive PF6−-intercalation durability is demonstrated for the C2DP-covered graphite electrode, with capacity retention of 92.8% after 1000 cycles at 1 C and Coulombic efficiencies of > 99%. The feasibility of constructing artificial ion-regulating electrode skins with precisely customized two-dimensional polymers offers viable means to promote problematic battery chemistries.

As microfabrication techniques stepped into the millimeter and sub-sub-millimeter scale world, a large amount of microelectronics has been developed and even commercialized. Microbatteries are considered as the important components to continuously power microelectronics without interruption. Over past few decades, a great deal of research have been devoted into the development of microbatteries with high energy density, long cycling life and minimum footprint area. These researches mainly focus on the fabrication procedure, which contributes to reducing the footprint area. However, the battery chemistry investigation and optimization are always ignored, which have great impact on the microbatteries performances. How to take the battery chemistry into account when shrinking the size of microbatteries is a huge challenge. To take up the challenge, applying the energy-dense materials into the three-dimensional microstructures could be a direct strategy. Among different three-dimensional microstrucutres, Swiss-roll microtube was proven as an effective way to improve the energy density without influencing the electrochemical kinetics. As for the material choice, the Zn-MnO2 aqueous system with high theoretical capacity and safe working environment is a good candidate for microbatteries. More importantly, fabrication and modification of both the electrode and electrolyte is compatible with standard microfabrication process in the atmosphere. Based on this, Zn anode is modified by a photolithgraphable electrolyte with small-molecular stabilizer, while the MnO2 cathode is modified by the zincophilic binder. Then the Swiss-roll three-dimensional structure is elaborately designed through the strain-engineering rolled-up technology to accommodate the energy-dense and highly reversible materials. As the results, the gap between bulky and microscale batteries is successfully bridged.