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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Mixed-Anion Contact Ion-Pair Formation Enabling Improved Performance of Halide-Free Mg-Ion Electrolytes

In this article, discovery of stable and efficient electrolytes that are compatible with magnesium metal anodes and high-voltage cathodes is crucial to enabling energy storage technologies that can move beyond existing Li-ion systems. Many promising electrolytes for magnesium anodes have been proposed with chloride-based systems at the forefront; however, Cl-containing electrolytes lack the oxidative stability required by high-voltage cathodes. In this work, we report magnesium trifluoromethanesulfonate (triflate) as a viable coanion for Cl-free, mixed-anion magnesium electrolytes. The addition of triflate to electrolytes containing bis(trifluoromethane sulfonyl) imide (TFSI – ) anions yields significantly improved Coulombic efficiency, up to a 100 mV decrease in the plating/stripping overpotential, improved tolerance to trace H 2 O, and improved oxidative stability (0.35 V improvement compared to that of hybrid TFSI-Cl electrolytes). Based on 19 F nuclear magnetic resonance and Raman spectroscopy measurements, we propose that these improvements in performance are driven by the formation of mixed-anion contact ion pairs, where both triflate and TFSI – are coordinated to Mg 2+ in the electrolyte bulk. The formation of this mixed-anion magnesium complex is further predicted by the density functional theory to be thermodynamically driven. Collectively, this work outlines the guiding principles for the improved design of next-generation electrolytes for magnesium batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Critical Insights into Solvent Choice for High-Voltage Organosulfur Electrolytes

Organosulfur electrolytes are promising candidates for enabling high-voltage cathodes due to their superior oxidative stability compared to conventional carbonate-based systems. However, their viscous nature and inability to passivate the anode necessitate the use of passivating agents and diluents to achieve meaningful charge/discharge rates. In this study, we investigate the use of cyclic fluorinated carbonates (CFCs) to form passivating interphases on electrode surfaces, aiming to optimize electrolyte performance in high-voltage systems. Electrolyte formulations containing 1.2 M LiPF 6 in a CFC:sulfone:1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TTE) mixture (2/5/3 V/V/V) were assessed in full-cell configurations with a LiNi 0.8 Mn 0.1 Co 0.1 O 2 (FCG-NMC) cathode and a 4.5 V upper cutoff potential. The results reveal that 3-3-3-trifluoropropylene carbonate (TFPC) combined with ethyl methyl sulfone (EMS) optimizes electrolyte performance, resulting in lower resistance buildup and reduced capacity loss compared to commercial electrolytes. We also explore the failure mechanisms of several carbonate/sulfone mixtures and identify key considerations for electrolyte compatibility in high-voltage systems. TFPC enhances cycling stability and lowers overall cell resistance, while fluoroethylene carbonate (FEC) formulations, despite higher ionic conductivity, fail to form adequate passivation layers, leading to rapid capacity loss. Additionally, EMS provides superior physical properties that avoid common failure modes seen with other sulfone solvents like methyl isopropyl sulfone and tetramethylene sulfone. Furthermore, this study underscores the importance of carefully selecting passivating carbonates and sulfone solvents to improve electrolyte performance and expand the viability of high-voltage electrolyte systems.

LiNi0.8Mn0.1Co0.1O2 cathode↗
DOE OSTI2026

Identifying Bounds of Inorganic Content in Solventless Processing of Hybrid Solid Electrolytes

Solid-state lithium batteries require safe, robust electrolytes to enable higher energy densities and improved safety over conventional cells. Hybrid polymer–ceramic electrolytes are a promising solution, combining the processability of polymers with the high ionic conductivity and mechanical strength of inorganic fillers. In this work, we demonstrate a solventless, UV-curing method to produce hybrid solid electrolytes using a poly(ethylene glycol) dimethyl ether (PEGDME)-based photocurable matrix incorporating Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) or Li 7 La 3 Zr 2 O 12 (LLZO) ceramic electrolyte. Inorganic filler loadings up to ∼55 wt.% could be successfully incorporated via this process which was the highest inorganic content at which the slurry remains processable and cured into a uniform film. The resulting UV-cured composite electrolytes remain flexible and exhibit room-temperature ionic conductivities on the order of 10 −4 S·cm −1 , along with notably improved lithium-ion transference numbers compared to conventional polymer electrolytes. Similar performance and processing limits were observed for both LAGP and LLZO, indicating that ceramic filler chemistry does not significantly affect the UV-curing process or the electrolyte's ion transport properties in this regime. Eliminating solvents from fabrication not only simplifies processing and mitigates environmental concerns but also enables higher solid contents that enhance mechanical strength and help suppress lithium dendrite formation. In conclusion, this scalable approach thus paves the way for manufacturing robust composite solid electrolytes for next-generation solid-state batteries (SSBs).

Batteries↗
DOE OSTI2023

Real time lithium metal calendar aging in common battery electrolytes

Li metal anodes are highly sought after for high energy density applications in both primary commercial batteries and next-generation rechargeable batteries. In this research, Li metal electrodes are aged in coin cells for a year with electrolytes relevant to both types of batteries. The aging response is monitored via electrochemical impedance spectroscopy, and Li electrodes are characterized post-mortem. It was found that the carbonate-based electrolytes exhibit the most severe aging effects, despite the use of LiBF 4 -based carbonate electrolytes in Li/CF x Li primary batteries. Highly concentrated LiFSI electrolytes exhibit the most minimal aging effects, with only a small impedance increase with time. This is likely due to the concentrated nature of the electrolyte causing fewer solvent molecules available to react with the electrode surface. LiI-based electrolytes also show improved aging behavior both on their own and as an additive, with a similar impedance response with time as the concentrated LiFSI electrolytes. Since I − is in its most reduced state, it likely prevents further reaction and may help protect the Li electrode surface with a primarily organic solid electrolyte interphase.

25 ENERGY STORAGE↗
DOE OSTI2022

Understanding Solid-Electrolyte Interphase Formation at the Lithium Metal Anode of Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are one of the most promising chemistries for the next generation of energy storage devices. In a standard Li-S cell, the metallic lithium anode is an essential component of the battery due to its low density, extremely high theoretical specific capacity, and very low negative electrochemical potential. However, several challenges related to the use of Li metal have prevented this battery technology from becoming commercially available. For instance, Li-anodes are highly reactive, which results in the continuous decomposition of the electrolyte and the formation of the solid-electrolyte interphase (SEI) layer. This, combined with the non-uniform deposition of Liions during plating at the anode surface, can seriously affect the performance, cycling, and safety of the battery. In addition, it has been suggested that a controlled SEI formation at the metallic Li anode can yield enhanced battery performance. Hence, a comprehensive understanding of how the SEI layer is formed can help elucidate improvements in this battery technology. In this work, the formation of the SEI layer in Li-S batteries is investigated using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The stability of liquid organic-based electrolyte components, salt concentration, electron-rich environments, and the use of inorganic solid-state electrolyte (SSE) materials are explored in order to provide molecular-level fundamental insights into how the nature and composition of the electrolyte can alter the initial stages of the SEI formation. The products of electrolyte decomposition and electro-/chemical reaction pathways of liquid electrolyte component such as solvent and salts are predicted from AIMD simulations of electrolyte-anode interfaces. Energetics of reactions from DFT ground-state optimizations are also presented to confirm the decomposition mechanisms. Some significant differences are then drawn regarding the use of low and high salt concentrations. Simulations under electron-rich environments show additional multielectron electrochemical reactions of solvent and salt decomposition taking place due to the excess of electrons and the presence of radical anions in the solution. Finally, the initial stages of formation, stability, and main constituents of interfaces between Li-metal and Sbased electrodes with sulfide-based SSEs are characterized in detail.

25 ENERGY STORAGE↗
DOE OSTI2020

Recent Developments and Challenges in Hybrid Solid Electrolytes for Lithium-Ion Batteries

Lithium-ion batteries (LIBs) have attracted worldwide research interest due to their high energy density and long cycle life. Solid-state LIBs improve the safety of conventional liquid-based LIBs by replacing the flammable organic electrolytes with a solid electrolyte. Among the various types of solid electrolytes, hybrid solid electrolytes (HSEs) demonstrate great promise to achieve high ionic conductivity, reduced interfacial resistance between the electrolyte and electrodes, mechanical robustness, and excellent processability due to the combined advantages of both polymer and inorganic electrolyte. This article summarizes recent developments in HSEs for LIBs. Approaches for the preparation of hybrid electrolytes and current understanding of ion-transport mechanisms are discussed. The main challenges including unsatisfactory ionic conductivity and perspectives of HSEs for LIBs are highlighted for future development. The present review provides insights into HSE development to allow a more efficient and target-oriented future endeavor on achieving high-performance solid-state LIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Anomalous Thermal Decomposition Behavior of Polycrystalline LiNi 0.8 Mn 0.1 Co 0.1 O 2 in PEO-Based Solid Polymer Electrolyte

we report that replacing liquid electrolytes (LEs) with polymer electrolytes has been considered a promising approach to developing next-generation lithium-ion batteries (LIBs) with high energy density and superior safety. Nevertheless, compared with the extensive research on the electrochemical stability of the cathode/polymer electrolyte interfaces, reports on their thermal behaviors are rare to date. Herein, this work systematically investigates the thermal stability of two typical layered oxide cathodes, LiCoO 2 (LCO) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), with poly(ethylene oxide) (PEO) electrolyte and with carbonate LEs, respectively. It is found that the oxygen release from the cathodes plays a central role in thermal runaway. Replacing the LE with PEO electrolyte can considerably improve the thermal stability of LCO, but surprisingly, deteriorate that of NMC811. The reason is that the surface of single-crystalline LCO particles can be effectively passivated by the PEO electrolyte during heating, but PEO cannot sufficiently passivate all the primary particles of NMC811 owing to insufficient interface wettability of PEO electrolyte within the polycrystalline secondary NMC811 particles. The findings in this work collectively formulate valuable guidance for improving the safety of polymer-electrolyte-based as well as other types of all-solid-state lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Electrolyte Design for Fast‐Charging Lithium‐Based Batteries

Fast charging is essential for the widespread adoption of lithium (Li)-ion batteries, but it is fundamentally limited by sluggish interfacial kinetics, Li plating, and electrolyte instability at high current densities. Over the past decade, electrolyte engineering has emerged as a key strategy to address these challenges. This review summarizes the development of fast-charging electrolytes over the past ten years and outlines a design framework. Electrolyte formulations are first deconstructed into their main components—solvents, salts, and functional additives—and representative strategies for tuning solvation structure and interphase chemistry are discussed to suppress Li plating and improve interfacial kinetics. The discussion then extends to advanced electrolyte systems, particularly localized high-concentration electrolytes (LHCEs), and their compatibility with different anode chemistries. Advanced characterization techniques are also summarized and categorized based on destructiveness, spatial and temporal resolution, quantitative analysis, and the chemical species or processes probed across multiple length scales. Recent progress in AI-enabled electrolyte discovery and battery management system (BMS) strategies for optimized fast-charging protocols is further highlighted. Finally, perspectives are presented on translating electrolyte innovations from academic research to practical applications, with emphasis on cell format, realistic operating conditions, and manufacturability.

25 ENERGY STORAGE↗
DOE OSTI2022

Ethylene Carbonate–Free Electrolytes for Stable, Safer High–Nickel Lithium–Ion Batteries

Ethylene carbonate (EC) is an important component in state-of-the-art electrolytes for lithium-ion batteries (LIBs). However, EC is highly susceptible to oxidation on the surface of high-nickel layered oxide cathodes, making it undesirable for next-generation high-energy-density LIBs. In this study, a simple, yet effective, EC-free electrolyte (20F1.5M-1TDI) is presented by adding 20 wt% fluoroethylene carbonate (FEC) and 1 wt% lithium 4,5-dicyano-2-(trifluoromethyl)imidazole (LiTDI) into 1.5 M LiPF 6 in an ethyl methyl carbonate (EMC) electrolyte. The 20F1.5M-1TDI electrolyte is found to efficiently passivate the graphite anode and stabilize high-nickel cathodes by a synergistic decomposition of FEC and LiTDI. The LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA90)/graphite full cell with the 20F1.5M-1TDI electrolyte, therefore, exhibits an enhanced cycling stability and a suppressed voltage hysteresis growth compared to that with an EC-containing baseline electrolyte (1 M LiPF 6 in EC:EMC, 3:7 in weight, with 2 wt% vinyl carbonate). Advanced analytical tools, such as time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy, are employed to understand the underlying working mechanism of the EC-free electrolyte. Furthermore, the present study clearly showcases the great potential of EC-free electrolytes as a straightforward, practical approach for LIBs with high-nickel cathodes.

electrode/electrolyte interface↗
DOE OSTI2023

Coupling of Adhesion and Anti-Freezing Properties in Hydrogel Electrolytes for Low-Temperature Aqueous-Based Hybrid Capacitors

Solid-state zinc-ion capacitors are emerging as promising candidates for large-scale energy storage owing to improved safety, mechanical and thermal stability and easy-to-direct stacking. Hydrogel electrolytes are appealing solid-state electrolytes because of eco-friendliness, high conductivity and intrinsic flexibility. However, the electrolyte/electrode interfacial contact and anti-freezing properties of current hydrogel electrolytes are still challenging for practical applications of zinc-ion capacitors. Here, we report a class of hydrogel electrolytes that couple high interfacial adhesion and anti-freezing performance. The synergy of tough hydrogel matrix and chemical anchorage enables a well-adhered interface between hydrogel electrolyte and electrode. Meanwhile, the cooperative solvation of ZnCl 2 and LiCl hybrid salts renders the hydrogel electrolyte high ionic conductivity and mechanical elasticity simultaneously at low temperatures. More significantly, the Zn||carbon nanotubes hybrid capacitor based on this hydrogel electrolyte exhibits low-temperature capacitive performance, delivering high-energy density of 39 Wh kg –1 at –60 °C with capacity retention of 98.7% over 10,000 cycles. With the benefits of the well-adhered electrolyte/electrode interface and the anti-freezing hydrogel electrolyte, the Zn/Li hybrid capacitor is able to accommodate dynamic deformations and function well under 1000 tension cycles even at –60 °C. This work provides a powerful strategy for enabling stable operation of low-temperature zinc-ion capacitors.

25 ENERGY STORAGE↗
DOE OSTI2023

Mechanistic understanding of aging behaviors of critical-material-free Li 4 Ti 5 O 12 //LiNi 0.9 Mn 0.1 O 2 cells with fluorinated carbonate-based electrolytes for safe energy storage with ultra-long life span

Behind-the-meter storage (BTMS) systems - a viable method to minimize potential risk of blackout events and stabilize the grid - require a different type of cost-effective energy storage with excellent safety, ultra-long (>20 years) cycle life and reasonable energy density compared that of electric vehicles. To increase the energy density and reduce the cost of a long-term cyclable lithium-titanate-based cell, it is required to employ a critical-material-free high voltage cathode and an electrolyte with good electrochemical and transport properties. In this report the long-term electrochemical performance and behaviors of selected critical-material-free Li 4 Ti 5 O 12 (LTO)//LiNi 0.9 Mn 0.1 O 2 (LNMO) full cells for BTMS applications are evaluated and analyzed in the optimized voltage range of 1.4-2.7 V at 45 degrees C with different fluorinated carbonate-based electrolytes. The fluoroethylene carbonate (FEC)-based electrolyte cell shows the highest capacity retention of 57.9% and Coulombic efficiency (CE) of 99.96% after 1000 cycles, potentially attributed to a dense, homogenous and less resistive LiF-rich solid-electrolyte interphase (SEI) layer formed on the surface of LTO that may mitigate electrolyte decomposition and maintain relatively low cell impedance during cycling. The 3,3,3-fluoroethylmethyl carbonate (F-EMC)-based electrolyte cell, however, presents the worst performance with lower capacity and a sharp decrease of CE, due to unstable and non-uniform SEI formation and continuous oxidative electrolyte decomposition. This mechanistic understanding of cell aging behaviors and failure mechanisms with detailed analysis of surface chemistry and electrode morphology can guide design of new electrode chemistries and electrolyte formulations for the development of BTMS batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Solid-State, Single-Ion Conducting, Polymer Blend Electrolytes with Enhanced Li + Conduction, Electrochemical Stability, and Limiting Current Density

The development of solid-state polymer electrolytes with high lithium conductivity is crucial to improve lithium-ion battery performance and ameliorate the safety challenges associated with current solvent-based electrolytes. Unfortunately, sluggish polymer segmental dynamics are known to constrain conductivity enhancements in solid-state polymer electrolyte systems, limiting overall performance. In this work, a glassy single-ion-conducting polymer, poly[lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] (PLiMTFSI), was blended with a flexible polymer, poly(oligo-oxyethylene methyl ether methacrylate) (POEM), and the impact of PLiMTFSI molecular weight and ion concentration on the thermal and ion-conducting behavior of blend electrolytes was investigated. High ionic conductivities approaching 1 × 10 -2 S/cm at 150 °C were realized in this polymer blend electrolyte system as a result of decoupling Li + transport from polymer segmental dynamics. The decoupled ion transport was attributed to the packing frustration of the glassy PLiMTFSI – sufficient percolating free volume was generated to produce effective ion diffusion pathways. This decoupling was tunable as the ion transport could be altered from being closely coupled to the polymer segmental dynamics (Vogel–Tammann–Fulcher-like) to hopping (Arrhenius-like) by increasing the PLiMTFSI molecular weight and ion concentration. Moreover, the immobilized TFSI anion resulted in high Li + selectivity (Li + transference number = 0.9), high electrochemical stability (up to 4.7 V against Li + / Li), and limiting current density of 1.8 mA/cm 2 (electrolyte thickness = 0.05 cm). These features suggest that this single-ion-conducting, polymer blend electrolyte might be a promising alternative to a benchmark system – salt-doped polyethylene oxide. Moreover, the above characteristics can support the battery operation at higher voltages using energy-dense Li metal anodes, with faster charging rates and enhanced energy/power densities. Altogether, the results suggest that polymer chain packing frustration can be exploited to overcome the constraints of slow polymer segmental relaxations to achieve rapid and highly selective ion transport and enhanced performance in solid-state polymer electrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

General Method for Determining Redox Potentials without Electrolyte

A novel method to determine redox potentials without electrolyte is presented here. The method is based on a new ability to determine the dissociation constant, $K°_d$, for ion pairs formed between any radical anion and any inert electrolyte counterion. These dissociation constants can be used to determine relative shifts of redox potential as a function of electrolyte concentration, connecting referenced potentials determined with electrochemistry (with 0.1 M electrolyte) to electrolyte-free values. Pulse radiolysis created radical anions enabling determination of equilibrium constants for electron transfer between anions of donor and acceptor molecules as a function of electrolyte concentration in THF. The measurements determined “composite equilibrium constants”, $K_{eqC}$, which contain information about the dissociation constant for the electrolyte cations, X + , with the radical anions of both the donor, $K°_d$(D –• ,X + ) and the acceptor, $K°_d$(A –• ,X + ). Dissociation constants were obtained for a selection of radical anions with tetrabutylammonium (TBA + ). The electrolyte was found to shift the reduction potentials of small molecules 1-methylpyrene and trans-stilbene by close to +130 mV whereas oligo-fluorenes and polyfluorenes experienced shifts of only (+25 ± 6) mV due to charge delocalization weakening the ion pair. These shifts for reduction of aromatic hydrocarbon molecules are smaller than shifts of +232 and +451 mV seen previously for benzophenone radical anion with TBA + and Na + respectively where the charge on the radical anion is localized largely on one C=O bond, thus forming a more tightly bound ion pair.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Prediction and Experimental Verification of Electrolyte Solvation Structure from an OMol25-Trained Interatomic Potential

A molecular-level understanding of electrolyte solvation structure and ion–ion correlations is critical to developing next-generation battery chemistries. Atomistic simulation capabilities with sufficient accuracy, speed, and transferability to deliver reliable structural insights while avoiding arduous system-specific reparameterization are thus highly desirable. Machine learning interatomic potentials (MLIPs) trained on large, chemically diverse data sets are revolutionizing computational chemistry, enabling molecular dynamics simulations of battery electrolytes with near-DFT accuracy over 10,000× faster than DFT. While previous MLIP training data sets with suitable elemental coverage for electrolytes have been based on inorganic materials, the Open Molecules 2025 (OMol25) data set provides large-scale molecular DFT MLIP training data with broad elemental coverage and specifically samples tens of millions of electrolyte configurations. Here, we integrate computational modeling with experimental validation to systematically assess the ability of large-scale MLIPs pretrained on materials data or on OMol25 to accurately resolve nanoscale structural organization and ion-solvation characteristics in Na-ion battery electrolytes across diverse physicochemical conditions and compositional regimes. We find that the OMol25-trained Universal Model of Atoms (UMA-OMol) predicts experimentally measured densities and X-ray structure factors in substantially better agreement compared to state-of-the-art models trained only on inorganic materials data. Using UMA-OMol, we further analyze systematic trends in solvation structure as a function of cation identity, anion chemistry, salt concentration, and solvent topology. We observe that increasing system temperature amplifies the heterogeneity within the solvation environment, perturbing cation–solvent interactions and promoting the formation of contact ion pairs (CIPs). Moreover, subtle variations in the solvent topology of glyme-based electrolytes cause pronounced changes in ion correlations and solvation structure. The experimental agreement and microscopic insights shown here position OMol25-trained MLIPs as a practical route to predictive, high-throughput electrolyte simulations beyond the limits of classical force fields and direct DFT molecular dynamics, serving as a powerful tool for accelerating the design of next-generation Na-ion battery electrolytes and beyond.

MLIPs↗
DOE OSTI2023

Electrolyte Reactivity on the MgV 2 O 4 Cathode Surface

Predictive understanding of the solvation-dependent reactivity and molecular interaction of electrolyte ions and solvent molecules on reactive electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at electrode-electrolyte interface (EEI) of multivalent Mg batteries. In this work, the isolated intrinsic reactivities of prominent chemical species present in magnesium bis(trifluoromethanesulfonimide) (Mg(TFSI) 2 ) in diglyme (G2) electrolytes, including ionic (TFSI - , [Mg(TFSI)] + , [Mg(TFSI):G2] + , [Mg(TFSI):2G2] + ) as well as neutral molecules (G2) on magnesium vanadate cathode (MgV 2 O 4 ) surface has been studied using a combination of first-principles calculations and multimodal analysis of well-defined cathode electrolyte interphase (CEI) layers. Here, our calculations show that non-solvated [Mg(TFSI)] + is the strongest adsorbing species on the MgV 2 O 4 surface compared to all other ions while fully solvated [Mg(TFSI):2G2] + are least favorable to decomposition. The cleavage of C-S bonds in TFSI - to form CF 3 - is predicted to be most desired pathway for all ionic species, which is followed by the cleavage of C-O bonds of G2 to yield CH 3 + or OCH 3 - species. The strong stabilization and electron transfer between ionic electrolyte species and MgV 2 O 4 is found to significantly favor these decomposition reactions on the surface compared to intrinsic gas phase dissociation. Experimentally, we used state-of-the-art ion soft landing to selectively deposit mass-selected TFSI - , [Mg(TFSI):G2] + and [Mg(TFSI):2G2] + on MgV 2 O 4 thin film to form well-defined electrolyte-MgV 2 O 4 interface. Analysis of soft-landed interphase using X-ray photoelectron, X-ray absorption near edge structure, electron energy-loss spectroscopies as well as transmission electron microscopy confirmed the presence of decomposition species (e.g., MgFx, carbonates) formed in the interfacial region and the higher amount of MgFx with [Mg(TFSI):G2] + , which corroborates the theoretical observation. Overall, we established the mechanistic pathway for the electrolyte-induced formation of passivating fluorides on MgV 2 O 4 cathode facilitated by the surface adsorption and charge transfer, which provided essential knowledge for rational design of stable electrolytes for multivalent cathodes.

Cathode-electrolyte interphase formation↗
DOE OSTI2023

Dicarbonyl Electrolyte for High-Voltage Lithium Metal Batteries: Importance of the Entropy of Solvation in Bidentate Solvent

An electrolyte system based on dicarbonyl solvents has been proposed and implemented in lithium metal batteries (LMBs). Among several dicarbonyl solvents explored, dimethyl dicarbonate (DMDC) emerged as the most promising electrolyte candidate. Interestingly, despite the structural similarities between DMDC and its monocarbonyl counterpart DMC, the DMDC electrolyte exhibits higher solvent coordination, even at the same lithium-to-carbonyl ratio. Further, this leads to the formation of a more robust solid-electrolyte interphase and enhances the anodic stability of the electrolyte. Notably, in various electrolyte systems, the solvation energy is typically enthalpy-driven. However, the bidentate nature of DMDC introduces a significant role for the entropy of solvation because the Li + -DMDC complexes release fewer free molecules. With the addition of non-solvating co-solvent 1,1,2,2-tetrafluoro-ethyl 2,2,3,3-tetrafluoro-propyl ether (TTE), which reduces the viscosity of the electrolyte, the DMDC-TTE system enables remarkably stable cycling of the lithium anode by manipulating the entropy of solvation. This introduces a new strategy for tailoring functional electrolyte systems.

25 ENERGY STORAGE↗
DOE OSTI2025

The Role of Catholyte Modulation in Suppressing the Initial Capacity Fade of Zinc Electrolytic Manganese Dioxide Coin Cells

Despite its potential for zinc–manganese oxide batteries, electrolytic manganese dioxide (EMD) can experience capacity fade due to a deficiency in the Mn 2+ supply at the cathode electrolyte interphase (CEI) from side reactions, even in the presence of an electrolyte additive. In this work, electrolyte loading modulation at the cathode electrolyte interface (CEI) was correlated with Zn∥EMD cell capacity retention and cycling performance, as a proposed measure to curb the initial capacity fade observed in EMD. Initial galvanostatic charge/discharge cycling, with varied electrolyte loading, revealed severe capacity fade (from ~188 to 10 mAh g –1 for the highest loading of 200 μL) within the first 15 cycles. Such a decrease in cell capacity is correlated with the formation of a Mn 4+ deposit on the current collector and consequently, the Mn 2+ depletion at CEI, as was supported by elemental and Raman analyses. Interestingly, confinement of the electrolyte to the CEI at a lower (≤15 μL) electrolyte loading mitigated Mn 4+ side-deposition, maintaining the cell capacity at >80% over the first 15 cycles. Interfacial Mn supply/depletion could be monitored via voltammetric analysis based on changes of the Zn 2+ insertionreduction peak. Additional galvanostatic experiments corroborated the voltammetric interpretation and the proposed degradation pathway in the studied cell conditions. The outcomes of this work provide practical insight into coin-cell design and configuration strategies for developing Zn∥EMD batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li 10 Ge 1– x Sn x P 2 S 12

Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host framework. Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li 10 Ge 1–x Sn x P 2 S 12 . Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge density associated with the S 2– ions. This charge redistribution modifies the Li + substructure causing Li + ions to bind more strongly to the host framework S 2– anions, which in turn modulates the Li + ion potential energy surface, increasing local barriers for Li + ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations predict that this inductive effect occurs even in the absence of changes to the host framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid–electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗