Cathode surface coatings present one of the most popular and effective solutions to suppress cathode degradation and improve cycling performance of lithium-ion batteries (LIBs). In this work, we carry out an extensive high-throughput computational study to develop materials design principles governing amorphous cathode coating selections for LIBs. Our high-throughput screening includes descriptors to evaluate the thermodynamic stability, electrochemical stability, chemical reactivity with electrolytes and cathodes, and ionic diffusion of the cathode coatings. In the ionic diffusion analysis, we mainly focus on Li-containing compounds. From the 20 selected materials, we highlight the formidable challenge of mitigating oxygen diffusion when selecting an ideal cathode coating, and suggest 7 promising coating candidates: Li3B11O18, LiZr2(PO4)3, LiB3O5, LiPO3, LiSb3O8, LiAlSiO4 and LiTaSiO5. Combining the screening results and detailed ionic diffusion analysis of the selected cathode coatings, we summarize the general selection guidelines of amorphous cathode coatings for LIBs.

Development of Li+-containing electrolytes with improved transport properties requires reliable, reproducible, and ideally low volume techniques to rigorously understand ion-transport with varying composition. Precisely measuring the complete set of transport coefficients in liquid electrolytes under battery-relevant operating conditions is difficult and the reliability of these methods are sparsely described in electrolyte transport literature. In this work, we apply a potentiostatic polarization-based transport characterization approach typically used for polymer electrolytes to liquid electrolyte systems in an attempt to fully measure all transport coefficients (conductivity, total salt diffusion coefficient, thermodynamic factor and transference number) for the model system of LiPF6 in an ethylene carbonate - ethyl methyl carbonate (EC:EMC) mixture. Using systematic timescale and statistical analyses, we find that transport coefficients measured using potentiostatic polarization of Li-Li symmetric cells exhibit strong correlation to Li electrode interfacial resistance, indicating that such methods are probing both bulk and interfacial phenomena. This reveals a major roadblock in characterizing electrolyte systems where the interfacial resistance is significantly larger than ohmic electrolyte resistance. As a result, we find that methods that rely on potentiostatic Li metal stripping/plating do not readily result in reliable liquid electrolyte transport coefficients, unlike similar methods for solid polymer electrolytes, where interfacial resistances are typically smaller than electrolyte resistances at the elevated temperatures typically of interest for such electrolytes.

We provide a quantum chemical computational framework to calculate ion association constants relevant to lithium ion battery electrolytes. We compare our method to reported experimental values as the solvent, cation, and anion are varied. For solvent, anion, and cation variations, the standard errors are respectively 0.2 eV, 0.12 eV, and 0.11 eV for the chosen data set, where Pearson correlation values are all above 0.92.

Despite the extensive employment of binary/ternary mixed-carbonate electrolytes (MCEs) for Li-ion batteries, the role of each ingredient with regards to the solvation structure, transport properties, and reduction behavior is not fully understood. Herein, we report the atomistic modeling and transport property measurements of the Gen2 (1.2 M LiPF₆ in ethylene carbonate (EC) and ethyl methyl carbonate (EMC)) and EC-base (1.2 M LiPF₆ in EC) electrolytes, as well as their mixtures with 10 mol% fluoroethylene carbonate (FEC). Due to the mixing of cyclic and linear carbonates, the Gen2 electrolyte is found to have a 60% lower ion dissociation rate and a 44% faster Li⁺ self-diffusion rate than the EC-base electrolyte, while the total ionic conductivities are similar. Moreover, we propose for the first time the anion-solvent exchange mechanism in MCEs with identified energetic and electrostatic origins. For electrolytes with additive, up to 25% FEC coordinates with Li⁺, which exhibits a preferential reduction that helps passivate the anode and facilitates an improved solid electrolyte interphase. The work provides a coherent computational framework for evaluating mixed electrolyte systems.

Electrolytes featuring negatively charged polymers, such as nonaqueous polyelectrolyte solutions and polymerized ionic liquids, are currently under investigation as potential high cation transference number (t+) electrolytes for lithium-ion batteries. Herein, we use coarse-grained molecular dynamics simulations to characterize the Onsager transport coefficients of polyelectrolyte solutions as a function of chain length and concentration. For all the systems studied, we find that the rigorously computed transference number is substantially lower than that approximated by the ideal solution (Nernst-Einstein) equations typically used to characterize these systems due to the presence of strong anion-anion and cation-anion correlations. None of the polyelectrolyte solutions achieve t+ greater than that of the conventional binary salt electrolyte, with some solutions having negative t+. This work demonstrates that the Nernst-Einstein assumption does not provide a physically meaningful estimate of the transference number in these solutions and calls into question the expectation of polyelectrolytes to exhibit a high cation transference number.

The development of next-generation polymer-based electrolytes for energy storage applications would greatly benefit from a deeper understanding of transport phenomena in these systems. In this Perspective, we argue that the Onsager transport equations provide an intuitive but underutilized framework for analyzing transport in polymer-based electrolytes. Unlike the ubiquitous Stefan-Maxwell equations, the Onsager framework generates transport coefficients with clear physical interpretation at the atomistic level and can be computed easily from molecular simulations using Green-Kubo relations. Herein we present an overview of the Onsager transport theory as it applies to polymer-based electrolytes and discuss its relation to experimentally measurable transport properties and the Stefan-Maxwell equations. Using case studies from recent computational work, we demonstrate how this framework can clarify nonintuitive phenomena such as negative cation transference number, anticorrelated cation-anion motion, and the dramatic failure of the Nernst-Einstein approximation. We discuss how insights from such analysis can inform design rules for improved systems.

Detailed speciation of electrolytes as a function of chemical system and concentration provides the foundation for understanding bulk transport as well as possible decomposition mechanisms. In particular, multivalent electrolytes have shown a strong coupling between anodic stability and solvation structure. Furthermore, solvents that are found to exhibit reasonable stability against alkaline-earth metals generally exhibit low permittivity, which typically increases the complexity of the electrolyte species. To improve our understanding of ionic population and associated transport in these important classes of electrolytes, the speciation of Mg(TFSI)₂ in monoglyme and diglyme systems is studied via a multiscale thermodynamic model using first-principles calculations for ion association and molecular dynamics simulations for dielectric properties. The results are then compared to Raman and dielectric relaxation spectroscopies, which independently confirm the modeling insights. We find that the significant presence of free ions in the low-permittivity glymes in the concentration range from 0.02 to 0.6 M is well-explained by the low-permittivity redissociation hypothesis. Here, salt speciation is largely dictated by long-range electrostatics, which includes permittivity increases due to polar contact ion pairs. The present results suggest that other low-permittivity multivalent electrolytes may also reach high conductivities as a result of redissociation.

The theory of transport phenomena in multicomponent electrolyte solutions is presented here through the integration of continuum mechanics, electromagnetism, and nonequilibrium thermodynamics. The governing equations of irreversible thermodynamics, including balance laws, Maxwell's equations, internal entropy production, and linear laws relating the thermodynamic forces and fluxes, are derived. Green–Kubo relations for the transport coefficients connecting electrochemical potential gradients and diffusive fluxes are obtained in terms of the flux–flux time correlations. The relationship between the derived transport coefficients and those of the Stefan–Maxwell and infinitely dilute frameworks are presented, and the connection between the transport matrix and experimentally measurable quantities is described. To exemplify the application of the derived Green–Kubo relations in molecular simulations, the matrix of transport coefficients for lithium and chloride ions in dimethyl sulfoxide is computed using classical molecular dynamics and compared with experimental measurements.

Nonaqueous polyelectrolyte solutions have been recently proposed as high Li⁺ transference number electrolytes for lithium ion batteries. However, the atomistic phenomena governing ion diffusion and migration in polyelectrolytes are poorly understood, particularly in nonaqueous solvents. Here, the structural and transport properties of a model polyelectrolyte solution, poly(allyl glycidyl ether-lithium sulfonate) in dimethyl sulfoxide, are studied using all-atom molecular dynamics simulations. We find that the static structural analysis of Li⁺ ion pairing is insufficient to fully explain the overall conductivity trend, necessitating a dynamic analysis of the diffusion mechanism, in which we observe a shift from largely vehicular transport to more structural diffusion as the Li⁺ concentration increases. Furthermore, we demonstrate that despite the significantly higher diffusion coefficient of the lithium ion, the negatively charged polyion is responsible for the majority of the solution conductivity at all concentrations, corresponding to Li⁺ transference numbers much lower than previously estimated experimentally. We quantify the ion-ion correlations unique to polyelectrolyte systems that are responsible for this surprising behavior. These results highlight the need to reconsider the approximations typically made for transport in polyelectrolyte solutions.

High Li+ transference number electrolytes have attracted recent interest as a means to improve the energy density and rate capabilities of current lithium ion batteries. Here the viscosity and transport properties of a sulfonated polysulfone/poly(ethylene glycol) copolymer that displays both high transference number and high conductivity when dissolved in dimethyl sulfoxide (DMSO) are investigated for the first time in a battery-relevant solvent of nearly equivalent dielectric constant: mixed ethylene carbonate (EC)/dimethyl carbonate (DMC). The addition of a binary salt to each solution is investigated as a means to improve conductivity, and the diffusion coefficient of each species is tracked by pulse field gradient nuclear magnetic resonance (PFG-NMR). Through the 7Li NMR peak width and quantum chemistry calculations of the dissociation constant, it is shown that although the two solvent systems have nearly equivalent dielectric constants, the conductivity and transference number of the EC/DMC solutions are significantly lower as a result of poor dissociation of the sulfonate group on the polymer backbone. These results are the first study of polyelectrolyte properties in a battery-relevant solvent and clearly demonstrate the need to consider solvent properties other than the dielectric constant in the design of these electrolytes.