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At least 145 records · Page 8

Localized High Concentration Electrolytes for High Voltage Lithium-Metal Batteries: Correlation between the Electrolyte Composition and Its Reductive/Oxidative Stability

We demonstrate a first-principles screening methodology as an effective tool to explore electrolyte formulations for the new generation of high energy density rechargeable batteries. We study the liquid structure and electronic properties in dilute electrolytes, high concentration electrolytes (HCE), and localized high concentration electrolytes (LHCE), with focus on electrolyte formulations based on lithium bis(fluorosulfonyl)imide (LiFSI), dimethyl carbonate (DMC), and bis(2,2,2-trifluoroethyl) ether (BTFE) as a diluent. We describe the solvation complexes in the dilute electrolyte and explore structural changes triggered by the increase in lithium salt concentration for HCEs and the diluent effects in LHCEs. In HCE formulations, there is a 4-fold coordination environment of lithium-ions as in the dilute electrolyte, but the number of lithium-ion interactions with O atoms from FSI- anions dominates. In these solutions, the ability of the FSI- anions to interact with multiple lithium-ions allows complex 3D network formation and influences the reductive/oxidative behavior of the electrolyte. Interestingly, in LHCEs, the BTFE diluent molecules do not change the 3D solution structure when diluting the HCE formulation from 5.49 to 3.83 M. However, there is a composition threshold where the structural and electronic behavior may change. We show that diluting the HCE electrolyte with BTFE down to 1.77 M breaks the three-dimensional solution structure into an island-like solvation complex. We relate these structural changes to the electronic properties of the electrolytes finding a causal relationship between the reductive/oxidative behavior and the lithium-oxygen interaction mechanisms in the solvated complexes. The coordination with lithium-ions lowers the electrolyte LUMO and HOMO levels: the higher is the number of interactions with lithium-ions, the more likely the solvent molecule, FSI- anion, or diluent molecule is to be reduced and the less likely it is to become oxidized. The evolution of the solvated ion structure in HCE and LHCE suggests a close connection to a corresponding change in the lithium-ion transport mechanisms for these electrolytes.

anions, molecules, oxygen, solvents, electrolytes↗

Impact of fluorination on Li + solvation and dynamics in ionic liquid-hydrofluoroether locally concentrated electrolytes

The thermal, physical, structural, and transport properties of ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide [PYR14][TFSI] and Li-salts of lithium (nonafluorobutane)(trifluoromethanesulfonyl)imide [Li][IM14] and [Li][TFSI] (0 ≤ x Li ≤ 0.3), with addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) (0 ≤ x TTE ≤ 0.45) were studied. While [IM14] increases glass transition, TTE improves conductivity over a wider liquidus range. Li + is solvated primarily by [TFSI] with some contribution by [IM14]. However, both 7 Li- 19 F HOESY NMR and spatial distribution functions (SDFs) derived from molecular dynamics (MD) indicate short contacts between the fluorines of TTE and Li + . This is a result of tighter anion-solvated Li + without aggregation of the Li + solvates, consistent with Raman measurements, thus confirming the existence of fluorous domains in the bulk which leads to improved fluidity and a Li + diffusivity of 1.26 x 10 –12 m 2 /s at 0 °C (x Li = 0.20) with a Li + transference of 0.16. Improved transport properties translated to a higher capacity of the TTE/IL electrolyte in a Li||LiFePO 4 half-cell with 95mAh/g at 0.1C, compared to the IL electrolyte without TTE (60 mAh/g). Furthermore, this study demonstrates the tunability of solvation and transport properties in IL electrolytes by asymmetric fluorinated anions and hydrofluoroether co-solvents for low temperature Li-ion batteries.

25 ENERGY STORAGE↗

Operando Depth-Resolved Measurement of Solvation Entropy, Interfacial Transport, and Charge-Transfer Kinetics in Lithium-Ion Batteries

Understanding and improving the performance and longevity of lithium-ion batteries critically depends on insight into the dynamic processes occurring at buried electrode-electrolyte interfaces. However, direct, depth-resolved, and operando diagnosis of these interfaces remains a longstanding challenge due to their inaccessibility beneath bulk materials, the limitations of conventional surface- and bulk-sensitive characterization tools, and the difficulty of maintaining realistic cell environments during measurement. These challenges have made it nearly impossible to uniquely resolve important interfacial properties such as charge transfer resistance, SEI (solid electrolyte interphase) resistance, and solvation entropy at the individual electrode interfaces within a working cell, information that is essential for mechanistic insight and accelerated battery design. Here, in this study, we report the development of multiharmonic electro-thermal spectroscopy (METS), an operando technique that enables depth-resolved measurement of solvation entropy, interfacial transport resistance, charge-transfer resistance, and SEI resistance at individual electrode-electrolyte interfaces within practical lithium-ion batteries. By leveraging frequency-dependent, thermal-wave sensing and interface-specific modeling, METS uniquely attributes interfacial properties to specific electrodes, as validated by comparison with traditional electrochemical impedance spectroscopy (EIS). The ability to spatially and temporally resolve interfacial processes in real time provides new diagnostic capabilities that are crucial for mechanistic studies of battery degradation and for the rapid development of next-generation energy storage systems.

Chalise, Divya [University of California, Berkeley↗

Exploring the influence of interfacial solvation on electrochemical CO 2 reduction using plasmon‐enhanced vibrational sum frequency generation spectroscopy

Although interfacial solvation plays an important role in determining carbon dioxide reduction (CO 2 R) kinetics, present understanding of the potential dependent properties of the electrochemical double layer under conditions relevant for CO 2 R remains limited. This article summarizes the development and recent applications of plasmon-enhanced vibrational sum frequency generation (VSFG) spectroscopy to study the effects of cation hydration and interfacial solvation on CO 2 R using CO as a vibrational Stark reporter. Results show that electrolyte cations retain their entire solvation shell upon adsorption to inactive sites, while active sites retain only a single water layer between the gold surface and the cation. Measurements also show that the total interfacial electric field can be separated into two contributions: one from the electrochemical double layer (Stern field) and another from the polar solvation environment (Onsager field). Surprisingly, correlating VSFG spectra with reaction kinetics reveals that it is the solvation-mediated Onsager field that governs the chemical reactivity at the electrode/electrolyte interface. Measuring the interfacial water spectra during electrocatalysis also provides evidence for the proton source during H2 evolution, which competes with CO 2 R in aqueous electrolyte. These findings highlight the importance of directly probing cation hydration and interfacial solvation, which mediates reaction kinetics at electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Low-Flammable Electrolytes for Stable Operation of High-Voltage Lithium-Ion Batteries

Despite being an effective flame retardant, trimethyl phosphate (TMP a ) is generally considered as an unqualified solvent for fabricating electrolytes used in graphite (Gr) based lithium ion batteries as it readily leads to Gr exfoliation and cell failure. In this work, by adopting the unique solvation structure of localized high-concentration electrolyte (LHCE) to TMP a and tuning the composition of the solvation sheath via electrolyte additive, excellent electrochemical performance can be achieved with TMPa based electrolytes in Gr||LiNi 0.8 Mn 0.1 Co 0.1 O 2 cells. After 500 charge/discharge cycles within the voltage range of 2.5-4.4 V, the batteries containing TMPa based LHCEs with proper additive can achieve a capacity retention of 85.4%, being significantly higher than cells using a LiPF 6 -organocarbonates baseline electrolyte (75.2%). Meanwhile, due to the flame retarding effect of TMP a , TMP a based LHCEs exhibit significantly reduced flammability compared with the conventional LiPF 6 -organocarbonates electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Entropic Penalty Switches Li + Solvation Site Formation and Transport Mechanisms in Mixed Polarity Copolymer Electrolytes

Emerging solid polymer electrolyte (SPE) designs for efficient Li-ion (Li + ) conduction have relied on polarity and mobility contrast to improve conductivity. To further develop this concept, we employ simulations to examine Li + solvation and transport in poly(oligo ethylene methacrylate) (POEM) and its copolymers with poly(glycerol carbonate methacrylate) (PGCMA). We find that Li + is solvated by ether oxygens instead of the highly polar PGCMA, due to lower entropic penalties. The presence of PGCMA promotes single-chain solvation, thereby suppressing interchain Li + hopping. The conductivity difference between random copolymer PGCMA-r-POEM and block copolymer PGCMA-b-POEM is explained in terms of a hybrid solvation site mechanism. With diffuse microscopic interfaces between domains, PGCMA near the POEM contributes to Li + transport by forming hybrid solvation sites. The formation of such sites is hindered when PGCMA is locally concentrated. These findings help explain how thermodynamic driving forces govern Li + solvation and transport in mixed SPEs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spontaneous sodium ion storage behaviors of reduced graphene oxide anodes exceeding 100% Coulombic efficiency by modulated ion solvation

Rechargeable batteries are essential energy storage devices that power portable devices and electrical vehicles throughout the world. In general, it is thought that the electrochemical performance of rechargeable batteries is mostly determined by the electrodes within them and that the electrolyte plays a relatively passive role. However, ion transport and storage can be greatly influenced by the electrolyte solution structure, specifically, ion solvation within the bulk and ion desolvation across the electrode/electrolyte interfaces. Herein, we studied the role of the electrolyte as an active component of electrochemical energy storage devices. We found that with an appropriate electrolyte formulation, ion storage in disordered carbonaceous anode materials can occur spontaneously without externally supplied electrical energy. Reduced graphene oxide (RGO) in an ether-based electrolyte demonstrates ‘spontaneous' ion storage behaviors of adsorbing and inserting the solvated ions utilizing facilitated permeability and wettability of RGO, which results in Coulombic efficiency of ~145% due to additional charging capacity of ~180 mAh g -1 during electrochemical processes. The unexpected spontaneous ion storage behavior was extensively investigated using a combination of electrochemical analyses and diagnostics, advanced characterizations, and computational simulation. In conclusion, we believe the spontaneous ion storage behavior offers a new way to further improve the energy efficiency of practical rechargeable batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of the LiPF6 Concentration on the Interfacial Charge Transfer and Fast-charging Capabilities of Lithium-Ion Batteries

Fast-charging lithium-ion batteries (LIB) demand optimized electrolyte formulations to balance ionic conductivity, viscosity, and interfacial charge transfer kinetics. This study examines how LiPF 6 concentration shapes solvation structure, desolvation energy, charge transfer activation energy, and solid electrolyte interphase (SEI) properties, which are critical for fast-charging performance. Using Raman spectroscopy, electrochemical cycling, X-ray photoelectron spectroscopy, and atomistic modeling, we analyze how varying LiPF 6 concentrations impact interfacial and bulk transport properties. Our findings show that increasing LiPF 6 concentration alters lithium solvation structures, reduces desolvation energy, and accelerates charge transfer at the electrode interface. Higher concentrations lower the activation energy for charge transfer and suppress excessive SEI growth, improving interfacial kinetics. However, concentrations above a certain threshold increase viscosity and reduce ionic conductivity, limiting transport efficiency. These results offer insights into electrolyte solvation and interfacial charge transfer mechanisms, providing guidelines for designing next-generation fast-charging LIB electrolytes with enhanced efficiency, stability, and longevity.

Son, Seoung-Bum [Argonne National Laboratory (ANL)↗

From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure–property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg 2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg 2+ (with time scales ranging from 0.5 μs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg 2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. In conclusion, this observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

25 ENERGY STORAGE↗

Steric Effect Tuned Ion Solvation Enabling Stable Cycling of High-Voltage Lithium Metal Battery

1,2-Dimethoxyethane (DME) is a common electrolyte solvent for lithium metal batteries. Various DME-based electrolyte designs have improved long-term cyclability of high-voltage full cells. However, insufficient Coulombic efficiency at the Li anode and poor high-voltage stability remain a challenge for DME electrolytes. Here, we report a molecular design principle that utilizes a steric hindrance effect to tune the solvation structures of Li + ions. In this work, we hypothesized that by substituting the methoxy groups on DME with larger-sized ethoxy groups, the resulting 1,2-diethoxyethane (DEE) should have a weaker solvation ability and consequently more anion-rich inner solvation shells, both of which enhance interfacial stability at the cathode and anode. Experimental and computational evidence indicates such steric-effect-based design leads to an appreciable improvement in electrochemical stability of lithium bis(fluorosulfonyl)imide (LiFSI)/DEE electrolytes. Under stringent full-cell conditions of 4.8 mAh cm –2 NMC811, 50 μm thin Li, and high cutoff voltage at 4.4 V, 4 M LiFSI/DEE enabled 182 cycles until 80% capacity retention while 4 M LiFSI/DME only achieved 94 cycles. This work points out a promising path toward the molecular design of non-fluorinated ether-based electrolyte solvents for practical high-voltage Li metal batteries.

25 ENERGY STORAGE↗

Correlated Ion Transport Governed by Dynamic Local Structure in High Concentration and Localized High Concentration Electrolytes

Understanding the dynamics of cluster formation and network percolation provides the mechanistic link between microscopic solvation structure and transport in concentrated electrolytes, including localized high-concentration electrolytes (LHCEs). Although recent studies have shown LHCEs to form micelle-like aggregates at specific compositions, a quantitative understanding of how solvation structures and transport properties depend on salt–solvent–diluent ratios remains limited. Here, we integrate molecular dynamics with Onsager transport analyses to chart the evolution of solvation microstructure and associated ionic transport in LiFSI/DMC/TTE, achieving good agreement with experimental conductivities across composition. We show that micelle formation arises from a dynamic instability of the cation–anion network, and that network percolation is the primary determinant of conductivity. Two compositional thresholds emerge: A critical network concentration (CNC) and a critical micelle concentration (CMC) that delineate transitions from extended percolating networks to micelle-like clusters and then to fragments. These structural transitions rationalize the nonintuitive conductivity decrease at intermediate dilution despite monotonically decreasing viscosity and provide composition-level design rules for LHCEs.

Mohanakrishnan, Rohith Srinivaas [University of Ca↗

Electric-Field-Induced Spatially Dynamic Heterogeneity of Solvent Motion and Cation Transference in Electrolytes

While electric fields primarily result in migration of charged species in electrolytic solutions, the solutions are dynamically heterogeneous. Solvent molecules within the solvation shells of the cation will be dragged by the field while free solvent molecules will not. Here we combine electrophoretic NMR measurements of ion and solvent velocities under applied electric fields with molecular dynamics simulations to interrogate different solvation motifs in a model liquid electrolyte. Measured values of the cation transference number $(t^0_+)$ agree quantitatively with simulation-based predictions over a range of electrolyte concentrations. Solvent-cation interactions strongly influence the concentration-dependent behavior of $t^0_+$. We identify a critical concentration at which most of the solvent molecules lie within solvation shells of the cations. The dynamic heterogeneity of solvent molecules is minimized at this concentration where $t^0_+$ is approximately equal to zero.

42 ENGINEERING↗

Formation of Larger Solvation Shells in a LiFSI Salt Solution for Enhanced Li + Transport

Electrodes and electrolytes in Li-ion batteries (LIBs) are crucial for their electrochemical performance, and fabricating these materials to achieve the desired properties for improved efficiency is challenging. A recent study published in Nature ( Nature 2024, 627, 101−107) outlined guidelines for designing an electrolyte using fluoroacetonitrile (FACN), a small-molecule solvent with low solvation energy. This characteristic enables the formation of an anion-rich inorganic interphase in a 1.3 M lithium bis(fluorosulfonyl)imide (LiFSI) solution, facilitating higher ionic conductivity, even at low temperatures. The formation of a ligand channel was postulated and demonstrated in the simulation due to the attraction of small solvent molecules from the secondary solvation shell to the Li + ion in the primary solvation shell, thereby enhancing Li + transport. While that study primarily focused on Li + ion behavior in LIBs, the behavior of FACN in solutions with different lithium salts and what makes LiFSI in FACN outperform other systems remain to be explored. In conclusion, using an experimental technique sensitive to FACN molecules, here we directly observe formation of larger solvation shells in a LiFSI solution compared to the Li salts with different anions, consistent with the postulated ligand-channel-mechanism and potentially paving the way to achieving enhanced ionic conductivity and energy density during LIB operation.

Batteries↗

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↗

Factors Limiting Li+ Charge Transfer Kinetics in Li-ion Batteries

Understanding the factors limiting Li+ charge transfer kinetics in Li-ion batteries is essential in improving the rate performance, especially at lower temperatures. The Li+ charge transfer process involved in the lithium intercalation of graphite anode includes the step of de-solvation of the solvated Li+ in the liquid electrolyte and the step of transport of Li+ in the preformed solid electrolyte interphase (SEI) on electrodes until the Li+ accepts an electron at the electrode and becomes a Li in the electrode. Whether the de-solvation process or the Li+ transport through the SEI is a limiting step depends on the nature of the interphases at the electrode and electrolyte interfaces. Several examples involving the electrode materials such as graphite, lithium titanate (LTO), lithium iron phosphate (LFP), lithium nickel cobalt aluminum oxide (NCA) and solid Li+ conductor such as lithium lanthanum titanate or Li-Al-Ti-phosphate are reviewed and discussed to clarify the conditions at which either the de-solvation or the transport of Li+ in SEI is dominating and how the electrolyte components affect the activation energy of Li+ charge transfer kinetics. How the electrolyte additives impact the Li+ charge transfer kinetics at both the anode and the cathode has been examined at the same time in 3-electrode full cells. The resulting impact on Li+ charge transfer resistance, Rct, and activation energy, Ea, at both electrodes are reported and discussed.

Delp, Samuel A.↗

Fine‐Tuning Li‐Ion Solvation Structure by Enhanced Solvent‐Diluent Interactions for Long‐Cycling Lithium Metal Batteries

Achieving durable lithium (Li) metal anodes in liquid electrolytes remains challenging, primarily due to the instability of the formed solid-electrolyte interphases (SEIs). Modulating the Li-ion solvation structures is pivotal in forming a stable SEI for stabilizing Li metal anodes. Here a strategy is developed to fine-tune the Li-ion solvation structures through enhanced dipole–dipole interactions between the Li-ion-coordinated solvent and the non-Li-ion-coordinating diluent, for creating a stable SEI in the developed binary salt electrolyte. The enhanced dipole–dipole interactions weaken the coordination between Li-ions and the solvents while strengthening the interaction between Li-ions and dual anions, thereby facilitating the Li-ion transport and a robust anion-derived SEI with a distinct bilayer structure. Consequently, the developed electrolyte exhibited exceptional electrochemical performance in high energy-density Li||LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cells, with long calendar life, stable cyclability at 1 C, and reliable operation between 25 and −20 °C, and it also demonstrat remarkable cycling stability for a Li||NMC811 pouch cell with projected energy density of 402 Wh kg −1 , maintaining 80% capacity retention over 606 cycles under practical conditions.

25 ENERGY STORAGE↗

Water or Anion? Uncovering the Zn 2+ Solvation Environment in Mixed Zn(TFSI) 2 and LiTFSI Water-in-Salt Electrolytes

Applications of aqueous zinc batteries for grid-scale energy storage are limited by their poor reversibility and the competing water splitting reaction. The recent invention of a water-in-salt (WIS) electrolyte concept provides a new route enabling a stable and highly reversible aqueous zinc battery chemistry. In the present work, a mixed zinc bis(trifluoromethane sulfonyl)imide (Zn(TFSI) 2 ) and LiTFSI WIS electrolyte was studied using X-ray total scattering, X-ray absorption, and Fourier transform infrared spectroscopy in conjunction with classical molecular dynamics simulations. It was found that, in the highly concentrated WIS electrolyte consisting of 1 m Zn(TFSI) 2 and 20 m LiTFSI, Zn 2+ cations are mainly solvated by six waters in their first solvation shell, while the TFSI – anions are completely excluded. This ion solvation picture is fundamentally different from the previous understandings. The results suggest that additional studies are needed to fully understand the unusual stability and reversibility of zinc-WIS electrolyte-based batteries.

25 ENERGY STORAGE↗