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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Quantum Chemical Characterization of Factors Affecting the Neutral and Radical-Cation Newman–Kwart Reactions

Details of the electronic and geometric structures of stationary points along the reaction coordinate of the Newman Kwart rearrangement, which transforms an O- arylthiocarbamate to an S-arylcarbamothioate, are examined using quantum chemical methods for a large number of compounds considering both the thermal reactions of uncharged substrates as well as the corresponding reactions of radical cation substrates generated under photoredox conditions. The uncharged mechanism, which has intrinsically high 298 K free energies of activation (in excess of 30 kcal.mol -1 ), has the character of nucleophilic aromatic substitution and is thus accelerated by electron-withdrawing substituents on the aromatic ring. The radical cationic mechanism, by contrast, has 298 K free energies of activation that are typically below 20 kcal.mol -1 , and is accelerated by electron donating substituents on the aromatic ring, which stabilize the hole character that is transferred to this fragment from the thiocarbamate fragment as the reaction proceeds. Opportunities to further accelerate the radical cation reaction are revealed by computational assessment of alternative amino groups for the thiocarbamate functionality.

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

Intramolecular Polarization Contributions to the pKa’s of Carboxylic Acids Through the Chain Length Dependence of Vibrational Tag-Shifts in Cryogenically Cooled Pyridinium-(CH2)n-COOH (n = 1-7) Cations

The pKa’s of acids are known to depend on the ionic strength of an electrolyte solution, an effect that qualitatively results from electrostatic interactions of the acid and conjugate base with proximal ions. Here we explore an intramolecular variation on this theme in which a carboxylic acid group is tethered to a pyridinium cationic charge center with increasingly long alkyl linkages in the series Py+-(CH2)n-COOH, with n = 1-7. The effective acidities of the carboxylic acid group in the isolated cations are determined by recording the red-shifts in the frequencies of the acid OH stretches upon attachment to D2 and N2 molecules, measured by using cryogenic ion spectroscopy. The short chains indeed lead to substantial increases in acidity, with the effect falling off in the range of n = 4-5. The response of the CO stretch on the acid head group is surprisingly strong and, in contrast to the expected red shift of the OH, displays a blue shift as the chain length is reduced. Electronic structure calculations recover these trends and indicate that the proximal cationic charge center acts to draw electron density away from the acid C=O bond. This acts to blue shift the CO stretch while weakening the C-C bond that attaches the head group to the chain.

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

Activation, Dehydrogenation, and Carbon–Carbon Coupling of Methane by Iridium Cations Studied by Infrared Multiple Photon Dissociation Spectroscopy and Density Functional Theory

Products resulting from the sequential activation of one, two, three, and four methane molecules by atomic iridium cations were characterized by gas-phase infrared multiple photon dissociation spectroscopy and density functional theory (DFT) calculations. Iridium cations were generated using a laser ablation source and reacted with methane in a linear radiofrequency ion trap before mass analysis and spectroscopic interrogation in a Fourier transform ion cyclotron resonance mass spectrometer coupled to the free-electron laser for intracavity experiments (FELICE) beamline. Product ions were irradiated using infrared light over the 250–1500 cm –1 range. Comparisons between the experimental and DFT-calculated spectra enabled structural determination of the products formed. The observed products include HIrCH + , Ir(CH 2 ) 2 + , H s Ir(C 3 H 5 ) + , and Ir(CH 3 ) s (C 3 H 5 ) + , where the subscript s denotes a syn orientation of the two ligands. Furthermore, formation of the latter two products provides evidence for efficient C–H bond activation and subsequent C–C coupling on the atomic iridium cation.

Chemical reactions↗
DOE OSTI2020

Cation, Anion, and Radical Isomers of C4H4N: Computational Characterization and Implications for Astrophysical and Planetary Environments

Nitrogen-containing ions and molecules in the gas phase have been detected in non-Earth environments such as dark molecular clouds and more recently in the atmosphere of Saturn's moon Titan. These molecules may serve as precursors to larger heterocyclic structures that provide the foundation of complex biological molecules. On Titan, molecules of m/z 66 have been detected by the Cassini mission, and species of the empirical formula C 4 H 4 N may contribute to this signature. We have characterized seven isomers of C 4 H 4 N in anionic, neutral radical, and cationic states using density functional theory. Structures were optimized using the range-separated hybrid ωB97X-V with the cc-pVTZ and aug-cc-pVTZ basis sets. Anionic and radical C4H4N favor cyclic structures with aromatic and quasi-aromatic electron arrangements, respectively. Interestingly, ionization from the radical surface to the cation induces significant changes in structural stability, and the global minimum for positively charged isomers is CH 2 CCHCNH + , a pseudo-linear species reminiscent of cyanoallene. Select formation pathways to these structures from Titan's existing or postulated gas-phase species, reactions that are also relevant for other astrophysical environments, are discussed. By characterizing C 4 H 4 N isomers, we have identified energetically stable anionic, radical, and cationic structures that may be present in Titan's atmosphere and dark molecular clouds.

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

Degradation of Anion Exchange Membranes by Cation Elimination: Impact on Water Uptake, Nanostructure, and Ionic Mobility

Anion exchange membranes (AEMs) are an attractive platform for fuel cell and electrolysis technologies since they enable the use of cheaper, nonplatinum group metal electrodes and components. However, the widespread adoption of AEM-based devices is limited by chemical degradation of the AEM in the highly alkaline medium of operation. Experimental studies report three major pathways of degradation, including substitution (S N 2), elimination (E2), and backbone cleavage. The decline in membrane performance is likely due to a cumulative effect of several pathways, which has proven to be difficult to disentangle through experiments. Here we use coarse-grained molecular simulations to isolate the impact of E2 degradation, where cationic sites are replaced by an alkene group, on AEM water uptake, nanoscale morphology, structure of the ion-conducting channels, water mobility, and ionic conductivity. Our studies focus on the well-studied model AEM polyphenylene oxide with tetraalkylammonium cationic sites (PPO-TMA). We find that about half of the hydrophobic groups resulting from the degradation retract into the hydrophobic domains of the membrane. The reduction in ion exchange capacity (IEC) and the hydrophobicity of the alkene groups decrease both the equilibrium water uptake (%WU) and the number of water molecules per cation (λ) of the membrane. Interestingly, the evolution of λ with the IEC seems to follow that of undegraded PPO-TMA membranes. Additionally, we ascribe this to the similarity between the structure of the degraded monomer and the neutral one in the polymer. We conclude that most of the performance losses originate in the lower hydration of the degraded membrane.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Stability and Compressibility of Cation-Doped High-Entropy Oxide MgCoNiCuZnO 5

High-entropy oxides (HEOx) are multicomponent (≥5) complex oxides that possess material properties and functions unexpected from their constituent simple oxides. Previous studies demonstrated that a cation-doped HEOx, MgCoNiCuZnO 5 , shows good catalytic activity, excellent ionic conductivity, and high energy storage. The structural and mechanical stabilities of materials are pivotal to their applications. However, how temperature and pressure influence the structural stability of cation-doped HEOx and how doping affects the mechanical properties are yet to be understood. In this work, we investigated the structural stabilities of undoped and Li/Mn-doped MgCoNiCuZnO 5 in heating or under compression using in situ synchrotron X-ray diffraction (XRD), and determined their elastic moduli using high-pressure XRD. Our results show that the HEOx compounds are structurally stable at temperatures up to ~450 °C or at pressures up to ~50 GPa, and that Li/Mn doping makes the HEOx more compressible. Our molecular static (MS) calculations predicted that the formation reaction of a HEOx is endothermic, consistent with the fact that a single-phase HEOx can only be produced at high temperatures. The MS calculations also revealed that the observed doping-induced elastic softening stems from the introduction of the Li-O/Mn-O ionic bonds in the HEOx compound, which are weaker than other cation-oxygen ionic bonds in the undoped HEOx. These findings will be indispensable to engineer HEOx materials for use in ion batteries, catalysis, and other fields.

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

Sodium Cationization Enables Exotic Deprotonation Sites on Gaseous Mononucleotides

In this work, we report observation and photoelectron spectroscopic characterization of sodium cationization on four doubly deprotonated mononucleotide dianions Na + ·[dNMP-2H] 2- (N = A, G, C, or T) in the gas phase. Multiple tautomers with distinct deprotonated sites are identified, in which Na+ enables novel double deprotonation patterns and folds resultant mononucleotide dianions. The most stable isomer for the whole family is derived from detaching one proton from phosphate and the other from nucleobase (amino group for N = A, G and C, but nitrogen atom for T), while a high-lying isomer with protons detached separately from phosphate and hydroxy group of sugar coexist. Particularly, an exotic deprotomer with both protons deprived from guanosine is populated as well. This work thus displays a remarkably diverse binding landscape enabled by sodium cationization, a potentially critical element in developing general formulism to better model metal cation and nucleotide interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achieved by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.

Electrolytes↗
DOE OSTI2023

Tuning Transport via Interaction Strength in Cationic Conjugated Polyelectrolytes

Tuning polymer-ion interaction strength is critical for balancing ion solvation and transport in solid polymer electrolytes for battery applications. In mixed Li + /electron conducting systems for improved battery binders, the design space is further complicated by seemingly opposing design rules for electron and ion conducting polymers. Conjugated polymers functionalized with cationic side chains have demonstrated high ionic conductivity, lithium transport, and electronic conductivity by combining long-range polymer ordering with diffuse ion interactions. Herein, we demonstrate a family of mixed conducting polythiophenes functionalized with a range of cationic side chains, namely imidazolium, trimethylammonium, and ammonium groups. The strength of ionic interactions and structure of the side chains govern lithium-selective transport, resulting in high Li + conductivity (~10 –4 S/cm at 80 °C) and electronic conductivity. The more diffuse imidazolium ion affords labile ionic interactions, resulting in higher lithium transference than the other cations studied. Electronic conductivity is also higher in the imidazolium system, stemming from the ability of the planar side chains to stack while also accommodating the bulky TFSI – counterions. Finally, these results demonstrate the importance of interaction strength in ion transport while also indicating that the physical structure of the side chain has an impact on electronic conduction. The imidazolium group strikes a balance, achieving superior properties across all metrics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Control of Structural Hydrophobicity and Cation Solvation on Interlayer Water Transport during Clay Dehydration

Swelling clay hydration/dehydration is important to many environmental and industrial processes. Experimental studies usually probe equilibrium hydration states in an averaged manner and thus cannot capture the fast water transport and structural change in interlayers during hydration/dehydration. Using molecular simulations and thermogravimetric analyses, we observe a two-stage dehydration process. The first stage is controlled by evaporation at the edges: water molecules near hydrophobic sites and the first few water molecules of the hydration shell of cations move fast to particle edges for evaporation. The second stage is controlled by slow desorption of the last 1–2 water molecules from the cations and slow transport through the interlayers. The two-stage dehydration is strongly coupled with interlayer collapse and the coordination number changes of cations, all of which depend on layer charge distribution. Furthermore, this mechanistic interpretation of clay dehydration can be key to the coupled chemomechanical behavior in natural/engineered barriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

All-inorganic Germanium nanocrystal films by cationic ligand exchange

In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.

14 SOLAR ENERGY↗
DOE OSTI2020

Enabling Facile Anionic Kinetics through Cationic Redox Mediator in Li-Rich Layered Cathodes

Anionic oxygen redox has aroused great interests in developing high-capacity Li-ion battery cathode materials. The fundamental understanding of this concept, compared to cationic redox, has promoted extensive studies on lithium transition metal oxides including those of 4d and 5d transition metals. Lithium ruthenium oxide has been found to exhibit a reversible anionic redox upon cycling. However, lithium-rich layered oxide with anionic redox is still facing great challenges such as sluggish kinetics. Here we investigate the effect of cationic redox on the kinetics of anionic reaction when they are strongly coupled. We report the cobalt substituted lithium ruthenium oxide, where all Ru, Co and O redox participate in the charge compensation mechanism in relatively defined voltage regions. Additionally, the improved anionic kinetics is attributed to the fast cationic Co redox process that serves as a redox mediator. Our work sheds light into the potential direction to address the commonly believed sluggish anionic kinetics in high-capacity oxygen-redox cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2025

Efficient Self-Sensitized Photochemical CO 2 Reduction Using [Re(bpy 2+ )(CO) 3 (I)] 2+ and [Re(bpy 2+ )(CO) 3 (CH 3 CN)] 3+ Photocatalysts with Pendent Ammonium Cations

Rhenium(I) tricarbonyl complexes fac-[Re(bpy)(CO) 3 (L)]n + are the classical examples of self-sensitized photocatalysts capable of the dual roles of light absorption and catalysis. Here, in this work, a series of dicationic halido or tricationic solvento complexes fac-[Re(bpy 2+ )(CO) 3 X] n+ (PF 6 ) n (where X = Cl - or I - (n = 2), or CH 3 CN (n = 3) and bpy 2+ is bipyridine modified by two -CH 2 -(NMe3) + tetra-alkylammonium cations) have been investigated as self-sensitized and sensitized CO 2 reduction photocatalysts. Four structural isomers differing in the cation position have been tested in N,Nʹ-dimethylacetamide solvent (DMA) using 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole (BIH) as the electron donor, and the position of the cationic pendants has a significant impact on the catalyst turnover number and quantum efficiency (ϕ). Up to 455 self-sensitized turnovers of CO and a high photon efficiency (ϕ CO ) of 22% have been achieved. Time-resolved infrared spectroscopy and theoretical calculations were used to characterize the catalytic cycle including the ligand exchange between one-electron reduced (OER) halido and solvento species as well as the binding of CO 2 to the putative two-electron reduced (TER) species. The CO 2 -reactive TER catalyst was formed by disproportionation or intramolecular electron transfer between two forms of the OER catalyst as indicated by the formation of the fully oxidized catalyst concurrent with CO 2 binding. When [Ru(bpy) 3 ] 2+ was used as a sensitizer, catalyst durability improved, and the selectivity toward formate increased as high as 3.3:1 over CO (total TON = 1370) due to acidification of the reaction, which promotes formation of the hydride intermediate, as BIH was consumed and deprotonated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Cationic Ordering Coupled to Reconstruction of Basic Building Units during Synthesis of High-Ni Layered Oxides

Metal (M) oxides are one of the most interesting and widely used solids, and many of their properties can be directly correlated to the local structural ordering within basic building units (BBUs). One particular example is the high-Ni transition metal layered oxides, potential cathode materials for Li-ion batteries whose electrochemical activity is largely determined by the cationic ordering in octahedra (e.g., the BBUs in such systems). Yet to be firmly established is how the BBUs are inherited from precursors and subsequently evolve into the desired ordering during synthesis. A multimodal in situ X-ray characterization approach is employed to investigate the synthesis process in preparing LiNi 0.77 Mn 0.13 Co 0.10 O 2 from its hydroxide counterpart, at scales varying from the long-range to local individual octahedral units. Real-time observation corroborated by first-principles calculations reveals a topotactic transformation throughout the entire process, during which the layered framework is retained; however, due to preferential oxidation of Co and Mn over Ni, significant changes happen locally within NiO 6 octahedra. Specifically, oxygen loss and the associated symmetry breaking occur in NiO 6 ; as a consequence, Ni 2+ ions become highly mobile and tend to mix with Li, causing high cationic disordering upon formation of the layered oxides. Only through high-temperature heat treatment, Ni is further oxidized, thereby inducing symmetry reconstruction and, concomitantly, cationic ordering within NiO 6 octahedra. Finally, findings from this study shed light on designing high-Ni layered oxide cathodes and, more broadly, various functional materials through synthetic control of the constituent BBUs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Two-Dimensional Dion–Jacobson Hybrid Lead Iodide Perovskites with Aromatic Diammonium Cations

Two-dimensional (2D) halide perovskites have extraordinary optoelectronic properties and structural tunability. Among them, the Dion–Jacobson phases with the inorganic layers stacking exactly on top of each other are less explored. Herein, we present the new series of 2D Dion– Jacobson halide perovskites, which adopt the general formula of A'A n –1 Pb n I 3 n +1 (A' = 4-(aminomethyl)pyridinium (4AMPY), A = methylammonium (MA), n = 1–4). By modifying the position of the CH 2 NH 3 + group from 4AMPY to 3AMPY (3AMPY = 3-(aminomethyl)pyridinium), the stacking of the inorganic layers changes from exactly eclipsed to slightly offset. Here, the perovskite octahedra tilts are also different between the two series, with the 3AMPY series exhibiting smaller bandgaps than the 4AMPY series. Compared to the aliphatic cation of the same size (AMP = (aminomethyl)- piperidinium), the aromatic spacers increase the rigidity of the cation, reduce the interlayer spacing, and decrease the dielectric mismatch between inorganic layer and the organic spacer, showing the indirect but powerful influence of the organic cations on the structure and consequently on the optical properties of the perovskite materials. All A'A n –1 Pb n I 3 n +1 compounds exhibit strong photoluminescence (PL) at room temperature. Preliminary solar cell devices based on the n = 4 perovskites as absorbers of both series exhibit promising performances, with a champion power conversion efficiency (PCE) of 9.20% for (3AMPY)(MA) 3 Pb 4 I 13 -based devices, which is higher than the (4AMPY)(MA) 3 Pb 4 I 13 and the corresponding aliphatic analogue (3AMP)(MA) 3 Pb 4 I 13 -based ones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

ESI-MS Identification of the Cationic Phosphine-Ligated Gold Clusters Au1-Au22: Insight into the Gold-Ligand Ratio and Abundance of Larger Clusters

Triphenylphosphine (PPh3)-ligated gold clusters offer promising potential applications due to their relative ease of synthesis and usefulness in forming advanced cluster architectures. While previous studies reported cationic PPh3-ligated gold clusters with core sizes of Au1 - Au4, Au6 - Au11, and Au¬13 - Au14, there has not been definitive identification by mass spectrometry of larger clusters in the Au12 - Au25¬ range. Herein, we survey a polydisperse solution of cationic PPh3-ligated gold clusters using high mass-resolution (M/?M = 60,000) electrospray ionization mass spectrometry (ESI-MS). To improve the sensitivity and mass resolution of larger clusters for unambiguous identification, we increased the number of scan averages and reduced the range of mass collection windows to 200 m/z, thereby mitigating potential mass and ion abundance bias resulting from smaller “building block” gold clusters and other solution components present in higher abundance. In addition to the previously reported clusters, we identified several new species including Au5(PPh3)5+, Au12(PPh3)9HCl2+, Au15(PPh3)9Cl2+, Au16(PPh3)10Cl22+, Au17(PPh3)113+, Au18(PPh3)102+, Au19(PPh3)10Cl2+, Au20(PPh3)12H33+, Au21(PPh3)10Cl2+, and Au22(PPh3)10Cl22+, indicating that a full range of clusters between Au1 - Au22 may be observed in a single polydisperse solution. Considering all of the observed clusters, our findings provide evidence that the “magic number” icosahedral Au13 may be the transition point in cluster growth between smaller clusters, exhibiting a 1:1 gold-to-ligand ratio, and larger clusters, wherein subsequent gold atoms are added to the core without an equal number of accompanying ligands. Our method demonstrates that reducing the range of m/z collection windows and increasing the number of scan averages can improve instrument sensitivity for cationic gold clusters and enable a more complete survey of polydisperse solutions, thereby providing new insights to guide and validate the results of other characterization methods and theoretical calculations. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MH acknowledges support from the DOE Science Undergraduate Laboratory Internship (SULI) program. HH acknowledges support from the DOE Office of Workforce Development for Teachers and Scientist (WDTS) under the Visiting Faculty Program (VFP). This work was performed using EMSL, a national scientific user facility sponsored by the DOE's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle.

Hewitt, Michael↗
DOE OSTI2019

Tuning infrared plasmon resonances in doped metal-oxide nanocrystals through cation-exchange reactions

Metal-oxide nanocrystals doped with aliovalent atoms can exhibit tunable infrared localized surface plasmon resonances (LSPRs). Yet, the range of dopant types and concentrations remains limited for many metal-oxide hosts, largely because of the difficulty in establishing reaction kinetics that favors dopant incorporation by using the co-thermolysis method. Here we develop cation-exchange reactions to introduce p-type dopants (Cu + , Ag + , etc.) into n-type metal-oxide nanocrystals, producing programmable LSPR redshifts due to dopant compensation. We further demonstrate that enhanced n-type doping can be realized via sequential cation-exchange reactions mediated by the Cu + ions. Cation-exchange transformations add a new dimension to the design of plasmonic nanocrystals, allowing preformed nanocrystals to be used as templates to create compositionally diverse nanocrystals with well-defined LSPR characteristics. The ability to tailor the doping profile postsynthetically opens the door to a multitude of opportunities to deepen our understanding of the relationship between local structure and LSPR properties.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2023

A fluorinated cation introduces new interphasial chemistries to enable high-voltage lithium metal batteries

Abstract Fluorides have been identified as a key ingredient in interphases supporting aggressive battery chemistries. While the precursor for these fluorides must be pre-stored in electrolyte components and only delivered at extreme potentials, the chemical source of fluorine so far has been confined to either negatively-charge anions or fluorinated molecules, whose presence in the inner-Helmholtz layer of electrodes, and consequently their contribution to the interphasial chemistry, is restricted. To pre-store fluorine source on positive-charged species, here we show a cation that carries fluorine in its structure is synthesized and its contribution to interphasial chemistry is explored for the very first time. An electrolyte carrying fluorine in both cation and anion brings unprecedented interphasial chemistries that translate into superior battery performance of a lithium-metal battery, including high Coulombic efficiency of up to 99.98%, and Li 0 -dendrite prevention for 900 hours. The significance of this fluorinated cation undoubtedly extends to other advanced battery systems beyond lithium, all of which universally require kinetic protection of highly fluorinated interphases.

25 ENERGY STORAGE↗