Intimately mixed copper, cobalt, and iron fluorides resulting from the insertion of fluorine into a LDH template.

The advancement of lithium-ion batteries (LIBs) with high performance is crucial across various sectors, notably in space exploration. This advancement hinges on the development of innovative cathode materials. Our research is dedicated to pioneering a new category of cathodes using fluorinated multimetallic materials, with a specific focus on diverging from the traditional Ni, Co, and Mn-based NMC chemistries by substituting nickel and manganese with copper and iron which are more sustainable elements. Our goal is also to enhance the robustness of cathodes upon cycling by substituting oxygen with fluorine as the metal-ligand. To achieve this, an intimate composite blend of CuF2 and FeF3, through the multi-metallic template fluorination (MMTF) methodology using a layered double hydroxide (LDH) as a precursor has been designed. Each of these components was carefully selected for its distinct attributes, including high redox potential, elevated energy density, substantial theoretical capacity, and improved cyclability. The composition denoted as (Cu1.5Co0.5)2+(Fe0.75Al0.25)3+ has been selected for fluorination because it maximizes Fe3+ and Cu2+ amount in the screened LDHs. Subsequently, this particular LDH was fluorinated through solid-gas fluorination at different temperatures (200, 350, and 500 °C) using gaseous molecular fluorine (F2). A comprehensive characterization of these materials using various techniques, including X-ray diffraction (XRD), 57Fe Mössbauer spectrometry, scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX), and inductively coupled plasma analyses (ICP-AES) was conducted, and the evolution of LDH upon fluorination has revealed an intermediate porous texture particularly sensitive to hydration. Two original crystallographic phases are else obtained by fluorination: one formed by the hydration of the amorphous intermediate compound: Cu3Fe1.5Al0.5F12(H2O)12 an anti-perovskite structure and another stabilized through the combination of solid gas fluorination and LDH precursor yielding an original CoFeF5-type phase. Raman operando during cyclic voltammetry measurement applied on a sample fluorinated at 500 °C and used as a cathode in front of lithium metal was finally conducted to validate redox activity and mechanism.

Single-Atomic Dispersion of Fe and Co Supported on Reduced Graphene Oxide for High-Performance Lithium-Sulfur Batteries.

High theoretical energy density and low cost make lithium-sulfur (LSB) batteries a promising system for next-generation energy storage. LSB performance largely depends on efficient reversible conversion of elemental sulfur to Li2S. Here, well-designed sulfur host materials including Fe or Co single atoms embedded on N-doped reduced graphene oxide (MNC/G with M = Fe or Co) are proposed to tackle the LSB challenges and enhance the electrochemical performance. Using a combination of Mössbauer spectroscopy and high-resolution scanning electron microscopy, the atomic dispersion of Co and Fe was revealed up to relatively high mass loadings. After optimization of the electrolyte/sulfur (E/S) ratio, FeNC/G shows the most promising cycle performance combining a constant high discharge capacity at low E/S values with the lowest polarization. In particular, the material FeNC/G@S with a high sulfur loading (9.4 mg cm-2) delivers a high area capacity of 7.7 mAh cm-2 under lean electrolyte conditions (6 mL g-1).

Investigating the abnormal conductivity behaviour of divalent cations in low dielectric constant tetraglyme-based electrolytes.

Solutions made of tetraglyme (G4) containing Ca(TFSI)2 have been studied as models to understand the solvation structure and the conductivity properties of multivalent ions in low dielectric constant ethereal electrolytes. These solutions have been characterised using electrochemical impedance spectroscopy, rheological measurement, and Raman spectroscopy. The ionic conductivity of these electrolytes shows an intriguing non-monotonic behaviour with temperature which deviates from the semi-empirical Vogel-Tammann-Fulcher equation at a critical temperature. This behaviour is observed for both Mg(TFSI)2 and Ca(TFSI)2, but not LiTFSI, indicating a difference in the solvation structure and the thermodynamic properties of divalent ions compared to Li+. The origin of this peculiar behaviour is demystified using temperature-controlled Raman spectroscopy and first-principles calculations combined with a thermodynamic analysis of the chemical equilibrium of Ca2+ ion-pairing versus solvation. As long-range electrostatic interactions are critical in solutions based on low dielectric ethereal solvents, a periodic approach is here proposed to capture their impact on the solvation structure of the electrolyte at different salt concentrations. The obtained results reveal that the thermodynamic and transport properties of Ca(TFSI)2/G4 solutions stem from a competition between enthalpic (ionic strength) and entropic factors that are directly controlled by the solution concentration and temperature, respectively. At high salt concentrations, the ionic strength of the solution favours the existence of free ions thanks to the strong solvation energy of the polydentate G4 solvent conjugated with the weak complexation ability of TFSI-. At elevated temperatures, the configurational entropy associated with the release of a coordinated G4 favours the formation of contact ion-pairs due to its flat potential energy surface (weak strain energy), offering a large configuration space. Such a balance between ion-pair association and dissociation not only rationalises the ionic conductivity behaviour observed for Ca(TFSI)2/G4 solutions, but also provides valuable information to extrapolate the ionic transport properties of other electrolytes with different M(TFSI)n salts dissolved in longer-chain glymes or even poly(ethylene oxide). These findings are essential for the understanding of solvation structures and ionic transport in low-dielectric media, which can further be used to design new electrolytes for Li-ion and post Li-ion batteries as well as electrocatalysts.

Influence of Polymer Backbone Fluorination on the Electrochemical Behavior of Single-Ion Conducting Multiblock Copolymer Electrolytes.

The presence of fluorine, especially in the electrolyte, frequently has a beneficial effect on the performance of lithium batteries owing to, for instance, the stabilization of the interfaces and interphases with the positive and negative electrodes. However, the presence of fluorine is also associated with reduced recyclability and low biodegradability. Herein, we present a single-ion conducting multiblock copolymer electrolyte comprising a fluorine-free backbone and compare it with the fluorinated analogue reported earlier. Following a comprehensive physicochemical and electrochemical characterization of the copolymer with the fluorine-free backbone, the focus of the comparison with the fluorinated analogue was particularly on the electrochemical stability toward oxidation and reduction as well as the reactions occurring at the interface with the lithium-metal electrode. To deconvolute the impact of the fluorine in the ionic side chain and the copolymer backbone, suitable model compounds were identified and studied experimentally and theoretically. The results show that the absence of fluorine in the backbone has little impact on the basic electrochemical properties, such as the ionic conductivity, but severely affects the electrochemical stability and interfacial stability. The results highlight the need for a very careful design of the whole polymer for each desired application, essentially, just like for liquid electrolytes.

Composite Anion-Exchange Membrane Fabricated by UV Cross-Linking Vinyl Imidazolium Poly(Phenylene Oxide) with Polyacrylamides and Their Testing for Use in Redox Flow Batteries.

Composite anion-exchange membranes (AEMs) consisting of a porous substrate and a vinyl imidazolium poly(phenylene oxide) (VIMPPO)/acrylamide copolymer layer were fabricated in a straightforward process, for use in redox flow batteries. The porous substrate was coated with a mixture of VIMPPO and acrylamide monomers, then subsequently exposed to UV irradiation, in order to obtain a radically cured ion-exchange coating. Combining VIMPPO with low-value reagents allowed to significantly reduce the amount of synthesized ionomer used to fabricate the mem- brane down to 15%. Varying the VIMPPO content also allowed tuning the ionic transport properties of the resulting AEM. A series of membranes with different VIMPPO/acrylamides ratios were prepared to assess the optimal composition by studying the changes of membranes properties-water uptake, area resistivity, permeability, and chemical stability. Characterization of the membranes was followed by cycling experiments in a vanadium RFB (VRFB) cell. Among three composite membranes, the one with VIMPPO 15% w/w-reached the highest energy efficiency (75.1%) matching the performance of commercial ion-exchange membranes (IEMs) used in VRFBs (Nafion® N 115: 75.0% and Fumasep® FAP 450: 73.0%). These results showed that the proposed composite AEM, fabricated in an industrially oriented process, could be considered to be a lower-cost alternative to the benchmarked IEMs.

Pristine and Modified Porous Membranes for Zinc Slurry-Air Flow Battery.

The membrane is a crucial component of Zn slurry-air flow battery since it provides ionic conductivity between the electrodes while avoiding the mixing of the two compartments. Herein, six commercial membranes (Cellophane™ 350PØØ, Zirfon®, Fumatech® PBI, Celgard® 3501, 3401 and 5550) were first characterized in terms of electrolyte uptake, ion conductivity and zincate ion crossover, and tested in Zn slurry-air flow battery. The peak power density of the battery employing the membranes was found to depend on the in-situ cell resistance. Among them, the cell using Celgard® 3501 membrane, with in-situ area resistance of 2 Ω cm2 at room temperature displayed the highest peak power density (90 mW cm-2). However, due to the porous nature of most of these membranes, a significant crossover of zincate ions was observed. To address this issue, an ion-selective ionomer containing modified poly(phenylene oxide) (PPO) and N-spirocyclic quaternary ammonium monomer was coated on a Celgard® 3501 membrane and crosslinked via UV irradiation (PPO-3.45 + 3501). Moreover, commercial FAA-3 solutions (FAA, Fumatech) were coated for comparison purpose. The successful impregnation of the membrane with the anion-exchange polymers was confirmed by SEM, FTIR and Hg porosimetry. The PPO-3.45 + 3501 membrane exhibited 18 times lower zincate ions crossover compared to that of the pristine membrane (5.2 × 10-13 vs. 9.2 × 10-12 m2 s-1). With low zincate ions crossover and a peak power density of 66 mW cm-2, the prepared membrane is a suitable candidate for rechargeable Zn slurry-air flow batteries.

Study of Anion Exchange Membrane Properties Incorporating N-spirocyclic Quaternary Ammonium Cations and Aqueous Organic Redox Flow Battery Performance.

Flexible cross-linked anion exchange membranes (AEMs) based on poly (p-phenylene oxide) grafted with N-spirocyclic quaternary ammonium cations were synthesized via UV-induced free-radical polymerization by using diallylpiperidinium chloride as an ionic monomer. Five membranes with ion exchange capacity (IEC) varying between 1.5 to 2.8 mmol Cl-·g-1 polymer were obtained and the correlation between IEC, water uptake, state of water in the membrane and ionic conductivity was studied. In the second part of this study, the influence of properties of four of these membranes on cell cycling stability and performance was investigated in an aqueous organic redox flow battery (AORFB) employing dimethyl viologen (MV) and N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride (TMA-TEMPO). The influence of membrane properties on cell cycling stability and performance was studied. At low-current density (20 mA·cm-2), the best capacity retention was obtained with lower IEC membranes for which the water uptake, freezable water and TMA-TEMPO and MV crossover are low. However, at a high current density (80 mA·cm-2), membrane resistance plays an important role and a membrane with moderate IEC, more precisely, moderate ion conductivity and water uptake was found to maintain the best overall cell performance. The results in this work contribute to the basic understanding of the relationship between membrane properties and cell performance, providing insights guiding the development of advanced membranes to improve the efficiency and power capability for AORFB systems.

Interplay of Structure and Dynamics in Lithium/Ionic Liquid Electrolytes: Experiment and Molecular Simulation.

Despite their promising use in electrochemical and electrokinetic devices, ionic-liquid-based electrolytes often exhibit complex behavior arising from a subtle interplay of their structure and dynamics. Here, we report a joint experimental and molecular simulation study of such electrolytes obtained by mixing 1-butyl 3-methylimidazolium tetrafluoroborate with lithium tetrafluoroborate. More in detail, experiments consisting of X-ray scattering, pulsed field gradient NMR, and complex impedance spectroscopy are analyzed in the light of molecular dynamics simulations to probe the structural, dynamical, and electrochemical properties of this ionic-liquid-based electrolyte. Lithium addition promotes the nanostructuration of the liquid as evidenced from the appearance of a scattering prepeak that becomes more pronounced. Microscopically, using the partial structure factors determined from molecular dynamics, this prepeak is shown to correspond to the formation of well-ordered positive/negative charge series and also large aggregates (Lin(BF4)4-m)(4-m+n)-, which develop upon lithium addition. Such nanoscale ordering entails a drastic decrease in both the molecular mobility and ionic conductivity. In particular, the marked association of Li+ cations with four BF4- anions and long ion pairing times, which are promoted upon lithium addition, are found to severely hinder the Li+ transport properties.

Perfluorosulfonyl Imide versus Perfluorosulfonic Acid Ionomers in Proton-Exchange Membrane Fuel Cells at Low Relative Humidity.

Designing highly conductive ionomers at high temperature and low relative humidity is challenging in proton-exchange membrane fuel cells. Perfluorosulfonyl imide ionomers were believed to achieve this goal, owing to their exceptional acidity and excellent thermal stability. Perfluorosulfonyl imide ionomers are less conductive than the analogous perfluorosulfonic acids despite similar membrane microstructure. In this study, the distinct behavior is rationalized by in situ synchrotron infrared spectroscopy during hydration. The protonation mechanism, formation of the protonic moiety and water clustering are totally different for the two different families of membranes. The ionization mediated by trans-to-cis conformational transition of the perfluorosulfonyl imide ionomer is not accompanied by the formation of hydronium ions. In contrast, Zundel-ion entities were identified as the elementary protonic complex, which is stable over the hydration range. The H-bond network of surrounding water molecules appears to be less connected and the protons remain highly localized and unavailable for efficient structural transport. The delocalization of protons and their mitigated interaction with the surrounding medium are prominent effects that negatively impact conductivity.

Magnesium Anthracene System-Based Electrolyte as a Promoter of High Electrochemical Performance Rechargeable Magnesium Batteries.

The development of efficient, inexpensive, and safe rechargeable batteries for large-scale environmentally benign cells is one of the key requirements to accommodate and satisfy various technological applications. To date, the development of magnesium battery as a promising candidate for next-generation battery systems has been hindered by the lack of high performance and stable electrolyte. In this work, we have developed an original, safe, and high-performance class of electrolytes based on a simple mixture of commercially available compounds, that is, Mg(TFSI)2, anthracene, MgCl2, and diglyme solvent. We have proven that anthracene induces stabilization of the reduced form of magnesium involving reversible magnesium plating/stripping with very high current density. The electrolyte investigated exhibits an unprecedented electrochemical stability window of up to 3.1 V, whereas MgCl2 addition allows the improvement of the Mg/electrolyte interface properties and enables a large cyclability of Mg/Mo6S8 Chevrel phase cell, allowing one to reach high performances.

Electrolyte Based on Easily Synthesized, Low Cost Triphenolate-Borohydride Salt for High Performance Mg(TFSI)2-Glyme Rechargeable Magnesium Batteries.

A new class of electrolyte based on TFSI- and triphenolate-borohydride anions was designed and produced which fulfill all requirements of easy synthesis, high ionic conductivity, wide potential window, and noncorrosion of Al current collector. The electrolyte composed of magnesium triphenolate borohydride and Mg(TFSI)2 in glyme simultaneously displays a high conductivity of 5.5 mS cm-1 at 25 °C and a reversible Mg plating/stripping with high current density and Coulombic efficiency at room temperature. By addition of a slight amount of MgCl2 to this electrolyte, a Coulombic efficiency of 90% in an SS/Mg cell, stable cycling performance, and a wide anodic potential of 3.4 V vs Mg2+/Mg on Al current collector can be reached. Reversible and efficient Mg insertion/deinsertion with a high capacity of 94 mAh g-1 and 96% Coulombic efficiency was obtained in a Mo6S8 Chevrel cathode phase.

Controlling Microstructure-Transport Interplay in Highly Phase-Separated Perfluorosulfonated Aromatic Multiblock Ionomers via Molecular Architecture Design.

Proton-conducting multiblock polysulfones bearing perfluorosulfonic acid side chains were designed to encode nanoscale phase-separation, well-defined hydrophilic/hydrophobic interfaces, and optimized transport properties. Herein, we show that the superacid side chains yield highly ordered morphologies that can be tailored by best compromising ion-exchange capacity and block lengths. The obtained microstructures were extensively characterized by small-angle neutron scattering (SANS) over an extended range of hydration. Peculiar swelling behaviors were evidenced at two different scales and attributed to the dilution of locally flat polymer particles. We evidence the direct correlation between the quality of interfaces, the topology and connectivity of ionic nanodomains, the block superstructure long-range organization, and the transport properties. In particular, we found that the proton conductivity linearly depends on the microscopic expansion of both ionic and block domains. These findings indicate that neat nanoscale phase-separation and block-induced long-range connectivity can be optimized by designing aromatic ionomers with controlled architectures to improve the performances of polymer electrolyte membranes.

Effects of Block Length and Membrane Processing Conditions on the Morphology and Properties of Perfluorosulfonated Poly(arylene ether sulfone) Multiblock Copolymer Membranes for PEMFC.

Perfluorosulfonated poly(arylene ether sulfone) multiblock copolymers have been shown to be promising as proton exchange membranes. The commonly used approach for preparation of the membrane is solvent casting; the properties of the resulting membranes are very dependent on the membrane processing conditions. In this paper, we study the effects of block length, selectivity of the solvent, and thermal treatment on the membrane properties such as morphology, water uptake, and ionic conductivity. DiMethylSulfOxide (DMSO), and DiMethylAcetamide (DMAc) were selected as casting solvents based on the Flory-Huggins parameter calculated by inversion gas chromatography (IGC). It was found that the solvent selectivity has a mild impact on the mean size of the ionic domains and the expansion upon swelling, while it dramatically affects the supramolecular ordering of the blocks. The membranes cast from DMSO exhibit more interconnected ionic clusters yielding higher conductivities and water uptake as compared to membranes cast from DMAc. A 10-fold increase in proton conductivity was achieved after thermal annealing of membranes at 150 °C, and the ionomers with longer block lengths show conductivities similar to Nafion at 80 °C and low relative humidity (30%).

Proton conducting ionic liquid organization as probed by NMR: self-diffusion coefficients and heteronuclear correlations.

The structure and local organization of new proton conducting ionic liquids (PCILs) obtained by reacting alkylamine with various acids were deciphered by complementary 1- and 2-D heteronuclear NMR experiments. One the one hand, PFG NMR yielded the self-diffusion coefficients of the PCIL components (and thus information on their possible concerted translational motions), while on the other hand, 13C, 1H, and 15N, 1H correlation and intermolecular Overhauser experiments gave insight into the nature of protonic species and ion-pairing behavior.