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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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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration

Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlO x infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnO x infiltration, especially one that is initiated by AlO x priming, has not received much attention because highly reactive hydroxyl groups generated by AlO x -priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnO x VPI. Here, we interrogate the ZnO x infiltration mechanism in AlO x -primed poly(methyl methacrylate) (PMMA) in comparison to the control AlO x -only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlO x network can quickly saturate the AlO x infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnO x infiltration using divalent DEZ precursor, once activated via AlO x -priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlO x -priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnO x .

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct Evidence of Charge Transfer upon Anion Intercalation in Graphite Cathodes through New Electronic States: An Experimental and Theoretical Study of Hexafluorophosphate

Graphite intercalation compounds continue to be central to technologies for electrochemical energy storage from anodes in established Li-ion batteries to cathodes in beyond Li-ion concepts paired with multivalent anodes. When used as a cathode, graphite intercalates a variety of anions with PF 6 - being among the most common. Paired with Li intercalation at the anode, the corresponding dual carbon battery yields high energy and power densities. Given the available choice of anions as intercalants, it is important to elucidate how the graphite structure accommodates them in order to tailor the molecular species to maximize charge and reversibility. However, the changes in electronic structure of the host graphite lattice upon anion intercalation are poorly understood compared to cations, which represent a fundamentally different reaction. Herein, PF 6 -intercalated graphite has been studied using techniques sensitive to electronic structure, namely, X-ray Raman spectroscopy (XRS), X-ray absorption near-edge spectroscopy (XANES), and X-ray emission spectroscopy (XES). Complementary full-potential, all-electron density functional theory calculations yielded excellent agreement with the spectra, thus providing insight into charge compensation in the graphite lattice. In particular, a pre-$π^*$ feature emerged in XRS/XANES, which is direct evidence of the removal of charge from the host lattice to compensate the intercalated anions, leading to an overall lowering of the Fermi energy level. This is expected to be characteristic of many intercalants in anion-intercalated graphite. The unambiguous identification of the origin of the pre-$π^*$ spectral feature, which is frequently seen in graphitic systems, is of broad interest to the spectroscopy of graphitic systems beyond the practical implications of anion-induced changes in the electronic properties for real devices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization

The tremendous improvement in performance and cost of lithium-ion batteries (LIBs) have made them the technology of choice for electrical energy storage. While established battery chemistries and cell architectures for Li-ion batteries achieve good power and energy density, LIBs are unlikely to meet all the performance, cost, and scaling targets required for energy storage, in particular, in large-scale applications such as electrified transportation and grids. The demand to further reduce cost and/or increase energy density, as well as the growing concern related to natural resource needs for Li-ion have accelerated the investigation of so-called "beyond Li-ion" technologies. In this review, we will discuss the recent achievements, challenges, and opportunities of four important "beyond Li-ion" technologies: Na-ion batteries, K-ion batteries, all-solid-state batteries, and multivalent batteries. Here, the fundamental science behind the challenges, and potential solutions toward the goals of a low-cost and/or high-energy-density future, are discussed in detail for each technology. While it is unlikely that any given new technology will fully replace Li-ion in the near future, "beyond Li-ion" technologies should be thought of as opportunities for energy storage to grow into mid/large-scale applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Surface Reactivity Analysis of the Crude Oil–Brine–Limestone Interface for a Comprehensive Understanding of the Low-Salinity Waterflooding Mechanism

Low-salinity waterflooding (LSWF) has proven to improve oil recovery in carbonate formations through rock wettability alteration, although the underlying mechanism remains elusive. Multivalent ionic exchange and calcite dissolution have usually been investigated using geochemical analysis in secondary coreflooding. In this work, coreflooding, in tertiary mode, coupled with a surface reactivity analysis approach was employed to investigate the interplay of wettability alteration mechanisms such as mineral dissolution, electrostatic bond attraction, and the effect of pH at in situ conditions. Improved oil recovery (IOR) in tertiary mode observed by coreflooding in Indiana limestone rocks showed an ionic strength dependence, that is, reducing brine ionic strength resulted in an increase in oil recovery. Coreflooding results showed that the seawater and low-salinity brines deprived of Mg 2+ ions resulted in the lowest IOR in tertiary mode, indicating the significance of Mg 2+ on IOR in limestone rocks. Similar results were observed through the contact angle measurement showing the limestone rock wettability state dependence on ionic strength and the effect of Mg2+ ions. Surface reactivity analysis showed an increase in solution pH, Ca 2+ and Mg 2+ ions concentration in the effluent solution from the coreflooding in tertiary mode using low salinity brines (about 40 and 20% increase in the effluent composition for Ca 2+ and Mg 2+ , respectively). These changes in solution composition were used to calculate the in situ oil–brine and rock–brine zeta potential using a validated surface complexation model, showing the changes of zeta potential as brine is injected into limestone rocks. The results show that using seawater-like brine in tertiary mode resulted in no mineral dissolution or ionic exchange. However, improved oil recovery (IOR) using such seawater-like brine was due to wettability alteration caused by reduced electrostatic bond attraction associated with Mg 2+ ions [from 2.6 × 10 –13 (mol/m 2 ) 2 for formation water salinity to 1.5 × 10 –13 (mol/m 2 ) 2 for seawater salinity]. Using low-salinity brines in tertiary mode improved oil recovery by mineral dissolution, resulting in oil desorption and an increase in solution pH. Finally, the increase in solution pH also resulted in reduced electrostatic bond attraction which lead to rock wettability alteration using low-salinity brines.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2022

Selective and Chemical-Free Removal of Toxic Heavy Metal Cations from Water Using Shock Ion Extraction

Electrochemical methods are known to have attractive features and capabilities when used for ion separations and water purification. In this study, we developed a new process called shock ion extraction (shock IX) for selective and chemical-free removal of toxic heavy metals from water. Shock IX is a hybrid process that combines shock electrodialysis (shock ED) and ion exchange using an ion exchange resin wafer (IERW), and this method can be thought of functionally as an electrochemically assisted variation of traditional ion exchange. In particular, shock IX exhibits greater ion removal and selectivity for longer periods of time, compared to the use of ion exchange alone. Here, the use of an IERW in shock ED also increases multivalent ion selectivity, reduces energy consumption, and improves the hydrodynamics and scalability of the system.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Influence of Nd(II) and Nd(III) Ions on the Speciation and Kinetic Dynamics of Radiolytic Transients in Molten LiCl-KCl Eutectic Salt Mixtures

In the pyrochemical reprocessing of used nuclear fuel, understanding the effects of ionizing radiation on the chemical behavior of fission products in molten chloride eutectic salt is crucial. Here, this study investigates the impact of radiation on the chemical and kinetic speciation of Nd ions in molten LiCl-KCl eutectic, which are challenging to separate due to their multivalent oxidation states and comproportionation reactions. Electron pulse radiolysis techniques were used to determine transient absorption spectra, chemical kinetics, and activation parameters for the reaction of Nd ions with the primary products of molten LiCl-KCl eutectic radiolysis: the solvated electron (e S - ) and dichlorine radical anion (Cl 2 •- ). Initially, Nd(III) reacted rapidly with e S - , forming Nd(II) with a second-order rate coefficient of k = (4.54 ± 0.07) × 10 10 M -1 s -1 at 673 K. The resulting Nd(II) ions then reacted slowly with Cl 2 •- , regenerating Nd(III) with an estimated rate of k = (1.72 ± 0.04) × 10 10 M -1 s -1 at 673 K. Additionally, the comproportionation reaction of Nd(III) and Nd(s) to form Nd(II) was monitored chemically and electrochemically. This work suggests that the comproportionation reaction of Nd(III) with Nd(s) to form Nd(II) is unstable in molten LiCl-KCl eutectic.

36 - MATERIALS SCIENCE↗
DOE OSTI2021

Screening Ionic Liquids Based on Ionic Volume and Electrostatic Potential Analyses

Ionic liquids are known to have tunable solvation properties, based on the pairing of different anions and cations, but the compositional landscape is vast and challenging to navigate efficiently. Some computational screening protocols are available, but they can be either time-consuming or difficult to implement. Herein, we perform a detailed investigation of the fundamental role of electrostatic interactions in these systems. We effectively develop a bridge between the previous volume-based approach (VBA) with a quantum structure–property relationship (QSPR) approach to create fast, simple screening guidelines. We propose a new parameter that is applicable to both monovalent and multivalent ions, the ionic polarity index (IPI), which is defined as the ratio of the average electrostatic surface potential ($\bar{V}$) of the ion to the net charge of the ion (q). The IPI correlation has been tested on a diverse dataset of 121 ions and reliable predictions can be obtained within a homologous series of ionic liquid compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Influence of Long-Range Forces on the Transition States and Dynamics of NaCl Ion-Pair Dissociation in Water

We study NaCl ion-pair dissociation in a dilute aqueous solution using computer simulations both for the full system with long-range Coulomb interactions and for a well-chosen reference system with short-range intermolecular interactions. Analyzing results using concepts from Local Molecular Field (LMF) theory and the recently proposed AI-based analysis tool “State predictive information bottleneck” (SPIB), we show that the system with short-range interactions can accurately reproduce the transition rate for the dissociation process, the dynamics for moving between the underlying metastable states, and the transition state ensemble. Contributions from long-range interactions can be largely neglected for these processes because long-range forces from the direct interionic Coulomb interactions are almost completely canceled (>90%) by those from solvent interactions over the length scale where the transition takes place. Thus, for this important monovalent ion-pair system, short-range forces alone are able to capture detailed consequences of the collective solvent motion, allowing the use of physically suggestive and computationally efficient short-range models for the dissociation event. Here, we believe that the framework here should be applicable to disentangling mechanisms for more complex processes such as multivalent ion disassociation, where previous work has suggested that long-range contributions may be more important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Room-Temperature Calcium Plating and Stripping Using a Perfluoroalkoxyaluminate Anion Electrolyte

Multivalent ion chemistries, like Ca 2+ , used in energy storage boast the potential to utilize solid metallic anodes and provide high volumetric energy density. The promise of such systems relies on the ability to incorporate high-voltage cathode materials while sustaining robust plating and stripping at the anode. These processes are dependent on an electrochemically stable electrolyte for ion transport and storage. In this work, we report an addition to the limited pool of nonaqueous electrolytes capable of plating and stripping calcium at room temperature. The synthesis and structural properties of calcium tetrakis(perfluoro-tert-butoxy) aluminate (Ca[TPFA] 2 ) are described along with the electrochemical performance during plating and stripping (up to 55% Coulombic efficiency) and a proof of concept for full cell viability with a CuS cathode material. X-ray experiments were used to study both the bulk solvation structure around calcium and possible decomposition pathways of the weakly coordinating TPFA anion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ion Solvation-Driven Liquid–Liquid Phase Separation in Divalent Electrolytes with Miscible Organic Solvents

Liquid–liquid phase separation (LLPS) is a common phenomenon, but LLPS of electrolytes prepared in miscible organic solvents is rarely documented. Here we report four cases of LLPS that occur in MgTFSI 2 or ZnTFSI 2 electrolytes in mixed organic solvents. The conditions for the formation of this LLPS share four common features: cations with high charge density; bulky anions with low charge density; a strongly coordinating solvent with high compressibility; and a relatively weak coordinating solvent with low relative permittivity and high mobility. With these conditions, the cations tend to draw the strongly coordinating solvents together to form a densely-packed, energetically-favorable ion solvation region, while the cosolvents with low relative permittivity tend to repel ions to form an ion-depleted dilute phase. Furthermore, in the dilute upper layer with more than 300 solvent molecules per cation, ion pairs and large ion aggregates are clearly evidenced, due to the incomplete screening of electrostatic interactions by the weaker cosolvent. This LLPS driven by ion solvation may be more common in multivalent electrolytes and is a design consideration with mixed solvents that should not be overlooked.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes

Multivalent-ion battery technologies are increasingly attractive options for meeting diverse energy storage needs. Calcium ion batteries (CIB) are particularly appealing candidates for their earthly abundance, high theoretical volumetric energy density, and relative safety advantages. Here, at present, only a few Ca-ion electrolyte systems are reported to reversibly plate at room temperature: for example, aluminates and borates, including Ca[TPFA] 2 , where [TPFA] - = [Al(OC(CF 3 ) 3 ) 4 ] - and Ca[B(hfip) 4 ] 2 , [B(hfip) 4 ] 2 – = [B(OCH(CF 3 ) 2 ) 4 ] - . Analyzing the structure of these salts reveals a common theme: the prevalent use of a weakly coordinating anion (WCA) consisting of a tetracoordinate aluminum/boron (Al/B) center with fluorinated alkoxides. Leveraging the concept of theory-aided design, we report an innovative, one-pot synthesis of two new calcium-ion electrolyte salts (Ca[Al(tftb) 4 ] 2 , Ca[Al(hftb) 4 ] 2 ) and two reported salts (Ca[Al(hfip) 4 ] 2 and Ca[TPFA] 2 ) where hfip = (-OCH(CF 3 ) 2 ), tftb = (-OC(CF 3 )(Me) 2 ), hftb = (-OC(CF 3 ) 2 (Me)), [TPFA] - = [Al(OC(CF 3 ) 3 ) 4 ] - . We also reveal the dependence of Coulombic efficiency on their inherent propensity for cation–anion coordination.

25 ENERGY STORAGE↗
DOE OSTI2023

Aqueous Interfaces in Chemical Separations

Chemical separations play a vital role in refinery and reprocessing of critical materials, such as platinum group metals, rare earths, and actinides. The choice of separation system─whether it is liquid–liquid extraction (LLE), sorbents, or membranes─depends on specific needs and applications. In almost all separation processes, the desired metal ions adsorb or transfer across an aqueous interface, such as the solid/liquid interface in sorbents or oil/water interfaces in LLE. Despite these separation technologies being extensively used for decades, our understanding of the molecular-scale mechanisms governing ion adsorption and transport at interfaces remains limited. This knowledge gap presents a significant challenge in meeting the increasing demands for these critical materials due to their growing use in advanced technologies. Fortunately, recent advancements in surface-specific experimental and computational techniques offer promising avenues to bridge this gap and facilitate the development of next-generation separation systems. Interestingly, unanswered questions regarding interfacial phenomena in chemical separations hold great relevance to various fields, including energy storage, geochemistry, and atmospheric chemistry. Therefore, the model interfacial systems developed for studying chemical separations, such as amphiphilic molecules assembled at a solid/water, air/water, or oil/water interface, may have far-reaching implications, extending beyond separations and opening doors to addressing a wide range of scientific inquiries. This perspective discusses recent interfacial studies elucidating amphiphile–ion interactions in chemical separations of metal ions. Finally, these studies provide direct, molecular-scale information about solute and solvent behavior at aqueous interfaces, including multivalent and complex ions in highly concentrated solutions, which play key roles in LLE of critical materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes

The emergence of magnesium and calcium batteries as potential beyond Li ion energy storage technologies has generated significant interest into the fundamental aspects of alkaline earth metal cation coordination in multivalent electrolytes and the impact of coordination on application-critical electrolyte properties such as solubility, transport, and electrochemical stability. Understanding these details in calcium electrolytes is of immediate importance due to recent, unprecedented demonstrations of reversible calcium metal electrodeposition in a limited number of ethereal solvent-based systems. In this work, we provide insight connecting Ca 2+ coordination tendencies to important calcium battery electrolyte properties. Our results demonstrate a clear solvent:Ca 2+ coordination strength trend across a series of cyclic ether and linear glyme solvents that controls the extent of ion association in solutions of “weakly” coordinating salts. We apply understanding gained from these results to rationalize relative anion:Ca 2+ coordination tendencies and attendant Ca 2+ coordination structures using two oxidatively stable anions of particular interest for current battery electrolytes. Armed with this understanding of solvent and anion interactions with Ca 2+ , we demonstrate and interpret differences in electrochemical calcium deposition behavior across several electrolyte exemplars with varying solvent and anion coordination strengths. Our findings demonstrate that solvents exhibiting especially strong coordination to Ca 2+ , such as triglyme, can inhibit reversible calcium deposition despite effective elimination of anion:Ca 2+ coordination while solvents exhibiting more modest coordination strength, such as 1,2-dimethoxyethane, may enable deposition provided anion:Ca 2+ coordination is substantially limited. These results reveal that the strength of coordination of both anion and solvent should be considered in the design of electrolytes for calcium batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Quantifying the Correlation between Coordination Chemistry, Interfacial Formation, and Electrochemical Performances for Mg Battery Electrolytes

Here, the rise of magnesium batteries as promising post-Li-ion energy storage technologies has sparked considerable attention toward understanding the fundamental aspects of coordination chemistry concerning Mg cations in multivalent electrolytes. This exploration includes investigating how coordination influences crucial electrolyte properties like solubility, electroreduction stability, and the formation of the interphase, all of which are pivotal for practical battery applications. Despite recent progress in developing a few functional electrolytes, a comprehensive understanding of the solvation structure that can facilitate efficient Mg deposition performance and the formulation of general design rules based on the solvation structure is still lacking. In our study, we endeavor to establish a connection between solvent and anion interactions with Mg 2+ , interface formation, and cycling performance through a series of organic ether solvents (tetrahydrofuran, glyme, diglyme, and triglyme) and amine solvents (dimethylamine, 3-methoxypropylamine, and dimethoxyethylamine). Our findings reveal a distinct coordination trend for solvent/Mg 2+ and (Mg-TFSI):solvent across various solvents, which dictates the extent of ion pairing for TFSI salts with increasing solvent molecule size and denticity. The solvated species in the bulk electrolyte across different solvents lead to diverse interfacial chemistries with varying decomposition components. We also explore the cycling efficiency as well as Mg deposition overpotentials for different solvents. A correlation analysis was conducted to assess the interplay between the structure and performance. Lastly, we apply the insights gained from these results to tailor the relative anion/Mg 2+ coordination structures using cosolvent systems, aiming for improved cell performance.

25 ENERGY STORAGE↗
DOE OSTI2020

Potentiodynamics of the Zinc and Proton Storage in Disordered Sodium Vanadate for Aqueous Zn-Ion Batteries

A rechargeable Zn-ion battery is a promising aqueous system, where coinsertion of Zn 2+ and H + could address the obstacles of the sluggish ionic transport in cathode materials imposed by multivalent battery chemistry. However, there is a lack of fundamental understanding of this dual-ion transport, especially the potentiodynamics of the storage process. Here, a quantitative analysis of Zn 2+ and H + transport in a disordered sodium vanadate (NaV 3 O 8 ) cathode material has been reported. Collectively, synchrotron X-ray analysis shows that both Zn 2+ and H + storages follow an intercalation storage mechanism in NaV 3 O 8 and proceed in a sequential manner, where intercalations of 0.26 Zn 2+ followed by 0.24 H + per vanadium atom occur during discharging, while reverse dynamics happens during charging. We find that such a unique and synergistic dual-ion sequential storage favors a high capacity (265 mA h g –1 ) and an energy density (221 W h kg –1 ) based on the NaV 3 O 8 cathode and a great cycling life (a capacity retention of 78% after 2000 cycles) in Zn/NaV 3 O 8 full cells.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Selectivity of Electrochemical Ion Insertion into Manganese Dioxide Polymorphs

The ion insertion redox chemistry of manganese dioxide has diverse applications in energy storage, catalysis, and chemical separations. Unique properties derive from the assembly of Mn–O octahedra into polymorphic structures that can host protons and nonprotonic cations in interstitial sites. Despite many reports on individual ion-polymorph couples, much less is known about the selectivity of electrochemical ion insertion in MnO 2 . In this work, we use density functional theory to holistically compare the electrochemistry of A x MnO 2 (where A = H + , Li + , Na + , K + , Mg 2+ , Ca 2+ , Zn 2+ , Al 3+ ) in aqueous and nonaqueous electrolytes. We develop an efficient computational scheme demonstrating that Hubbard-U correction has a greater impact on calculating accurate redox energetics than choice of exchange-correlation functional. Using PBE+U, we find that for nonprotonic cations, ion selectivity depends on the oxygen coordination environments inside a polymorph. When H + is present, however, the driving force to form hydroxyl bonds is usually stronger. In aqueous electrolytes, only three ion-polymorph pairs are thermodynamically stable within water’s voltage stability window (Na + and K + in α-MnO 2 , and Li + in λ-MnO 2 ), with all other ion insertion being metastable. We find Al 3+ may insert into the δ, R, and λ polymorphs across the full 2-electron redox of MnO 2 at high voltage; however, electrolytes for multivalent ions must be designed to impede the formation of insoluble precipitates and facilitate cation desolvation. We also show that small ions coinsert with water in α-MnO 2 to achieve greater coordination by oxygen, while solvation energies and kinetic effects dictate water coinsertion in δ-MnO 2 . Finally, taken together, these findings explain reports of mixed ion insertion mechanisms in aqueous electrolytes and highlight promising design strategies for safe, high energy density electrochemical energy storage, desalination batteries, and electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Coordination-Dependent Chemical Reactivity of TFSI Anions at a Mg Metal Interface

Charge transfer across the electrode–electrolyte interface is a highly complex and convoluted process involving diverse solvated species with varying structures and compositions. Despite recent advances in in situ and operando interfacial analysis, molecular specific reactivity of solvated species is inaccessible due to a lack of precise control over the interfacial constituents and/or an unclear understanding of their spectroscopic fingerprints. However, such molecular-specific understanding is critical to the rational design of energy-efficient solid–electrolyte interphase layers. We have employed ion soft landing, a versatile and highly controlled method, to prepare well-defined interfaces assembled with selected ions, either as solvated species or as bare ions, with distinguishing molecular precision. Equipped with precise control over interfacial composition, we employed in situ multimodal spectroscopic characterization to unravel the molecular specific reactivity of Mg solvated species comprising (i.e., bis(trifluoromethanesulfonyl)imide, TFSI – ) anions and solvent molecules (i.e., dimethoxyethane, DME/G1) on a Mg metal surface relevant to multivalent Mg batteries. In situ multimodal spectroscopic characterization revealed higher reactivity of the undercoordinated solvated species [Mg-TFSI-G1] + compared to the fully coordinated [Mg-TFSI-(G1) 2 ] + species or even the bare TFSI – . These results were corroborated by the computed reaction pathways and energy barriers for decomposition of the TFSI – within Mg solvated species relative to bare TFSI – . Finally, we evaluated the TFSI reactivity under electrochemical conditions using Mg(TFSI) 2 –DME-based phase-separated electrolytes representing different solvated constituents. Based on our multimodal study, we report a detailed understanding of TFSI – decomposition processes as part of coordinated solvated species at a Mg-metal anode that will aid the rational design of improved sustainable electrochemical energy technologies.

25 ENERGY STORAGE↗
DOE OSTI2023

Computational Predictions of the Stability of Fluorinated Calcium Aluminate and Borate Salts

Energy storage concepts based on multivalent ions, such as calcium, have great potential to become next-generation batteries due to their low cost and comparable cell voltage and energy density to Li-ion batteries. However, the development of Ca batteries is still hindered by the lack of suitable materials that grant a long cycle life. Specific to electrolyte materials, developing a calcium salt that is chemically stable under ambient conditions and enables reversible electrodeposition of Ca is critical. In this work, we use first-principles calculations to study the intrinsic and reductive stability of twelve Ca salts with fluorinated aluminate and borate anions and analyze the decomposition products formed on the metal anode surface that are critical to early-stage solid electrolyte interphase formation. Here we found anions with significant steric hindrance and a high degree of fluorination are intrinsically less stable and deemed unviable designs for Ca salt. Aluminate salts are generally less reactive with the Ca anode than their borate counterparts, and a high degree of fluorination leads to weaker reductive stability. Calcium fluoride is the most prominent decomposition product on the anode surface, and carbide-like motifs were also found from the decomposition of the designed salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗