This paper presents the computational assessment of the electrochemical stability of a series of alkyl methylimidazolium-based ionic liquids for their use as lithium battery electrolytes. The oxidation and reduction potentials of the constituent cation and anion of each ionic liquid with respect to a Li(+)/Li reference electrode were calculated using density functional theory following the method of thermodynamic cycles, and the electrochemical stability windows (ESW)s of these ionic liquids were obtained. The effect of varying the length of alkyl side chains of the methylimidazolium-based cations on the redox potentials and ESWs was investigated. The results show that the limits of the ESWs of these methylimidazolium-based ionic liquids are defined by the oxidation potential of the anions and the reduction potential of alkyl-methylimidazolium cations. Moreover, ionic liquids with [PF6](-) anion have a wider ESW. In addition to characterizing structure-function relationships, the accuracy of the computational approach was assessed through comparisons of the data against experimental measurements of ESWs. The potentials calculated by the thermodynamic cycle method are in good agreement with the experimental data while the HOMO/LUMO method overestimates the redox potentials. This work demonstrates that these approaches can provide guidance in selecting ionic liquid electrolytes when designing high-voltage rechargeable batteries.

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In composite battery electrode architectures, local limitations in ionic and electronic transport can result in nonuniform energy storage reactions. Understanding such reaction heterogeneity is important to optimizing battery performance, including rate capability and mitigating degradation and failure. Here, we use spatially resolved X-ray diffraction computed tomography to map the reaction in a composite electrode based on the LiFePO 4 active material as it undergoes charge and discharge. Accelerated reactions at the electrode faces in contact with either the separator or the current collector demonstrate that both ionic and electronic transport limit the reaction progress. The data quantify how nonuniformity of the electrode reaction leads to variability in the charge/discharge rate, both as a function of time and position within the electrode architecture. Importantly, this local variation in the reaction rate means that the maximum rate that individual cathode particles experience can be substantially higher than the average, control charge/discharge rate, by a factor of at least 2−5 times. This rate heterogeneity may accelerate rate-dependent degradation pathways in regions of the composite electrode experiencing fasterthan-average reaction and has important implications for understanding and optimizing rate-dependent battery performance. Benchmarking multiscale continuum model parameters against the observed reaction heterogeneity permits extension of these models to other electrode geometries.

Rechargeable batteries employing metal negative electrodes (i.e., anodes) are attractive next-generation energy storage devices because of their greater theoretical energy densities compared to intercalation-based anodes. An important consideration for a metal's viability as an anode is the efficiency with which it undergoes electrodeposition and electrodissolution. The present study assesses thermodynamic deposition/dissolution efficiencies and associated nucleation rates for seven metals (Li, Na, K, Mg, Ca, Al, and Zn) of relevance for battery applications. First-principles calculations were used to evaluate thermodynamic overpotentials at terraces and steps on several low-energy surfaces of these metals. In general, overpotentials are observed to be the smallest for plating/stripping at steps and largest at terrace sites. The difference in the coordination number for a surface atom from that in the bulk was found to correlate with the overpotential magnitude. Consequently, because of their low bulk coordination, the body-centered alkali metals (Li, Na, and K) are predicted to be among the most thermodynamically efficient for plating/stripping. In contrast, metals with larger bulk coordination such as Al, Zn, and the alkaline earths (Ca and Mg) generally exhibit higher thermodynamic overpotentials. The rate of steady-state nucleation during electrodeposition was estimated using a classical nucleation model informed by the present first-principles calculations. Nucleation rates are predicted to be several orders of magnitude larger on alkali metal surfaces than on the other metals. This multiscale model highlights the sensitivity of the nucleation behavior on the structure and composition of the electrode surface.

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