RESUMEN
Magnesium rechargeable batteries (MRBs) promise to be the next post lithium-ion batteries that can help meet the increasing demand for high-energy, cost-effective, high-safety energy storage devices. Early prototype MRBs that use molybdenum-sulfide cathodes have low terminal voltages, requiring the development of oxide-based cathodes capable of overcoming the sulfide's low Mg2+ conductivity. Here, we fabricate an ultraporous (>500 m2 g-1) and ultrasmall (<2.5 nm) cubic spinel MgMn2O4 (MMO) by a freeze-dry assisted room-temperature alcohol reduction process. While the as-fabricated MMO exhibits a discharge capacity of 160 mAh g-1, the removal of its surface hydroxy groups by heat-treatment activates it without structural change, improving its discharge capacity to 270 mAh g-1âthe theoretical capacity at room temperature. These results are made possible by the ultraporous, ultrasmall particles that stabilize the metastable cubic spinel phase, promoting both the Mg2+ insertion/deintercalation in the MMO and the reversible transformation between the cubic spinel and cubic rock-salt phases.
RESUMEN
Rechargeable magnesium batteries are promising candidates for post-lithium-ion batteries, owing to the large source abundance and high theoretical energy density. However, there remain few reports on constructing practical cells with oxide cathodes and Mg anodes at room temperature. In this work, we compare the reaction behavior of various MnO2 polymorph cathodes in two representative electrolytes: Mg[TFSA]2/G3 and Mg[Al(hfip)4]2/G3. In Mg[TFSA]2/G3, discharge capacities of the MnO2 cathodes are well consistent with the changes in Mg composition, where nanorod-like α-MnO2 and λ-MnO2 show the capacities of about 100 mA h g-1 at room temperature. However, this electrolyte has the disadvantage that the Mg anodes are easily passivated. In contrast, Mg[Al(hfip)4]2/G3 allows highly reversible deposition/dissolution of Mg anodes, whereas the discharge process of the MnO2 cathodes involves a large part of side reactions, in which the MnO2 active material takes part in some reductive reaction together with electrolyte species instead of the expected Mg2+ intercalation. Such an unstable electrode/electrolyte interface would lead to continuous degradation on/near the cathode surface. Thus, the interfacial stability between the oxide cathodes and the electrolytes must be improved for practical applications.
RESUMEN
In this work, we focus on Mg-Fe-O and Mg-Ni-O with Mg-rich compositions as positive-electrode materials for magnesium rechargeable batteries, and prepare them by a thermal decomposition of precipitates obtained by a solution method. It is indicated from X-ray diffraction patterns that the Mg-Fe-O and Mg-Ni-O samples have the spinel and rocksalt structures, respectively. X-ray absorption near edge structures indicate that Fe and Ni are trivalent and divalent, respectively, in the Mg-rich oxides. From charge/discharge cycle test, it is demonstrated that the Mg-Fe-O shows higher discharge capacity than the other and then has good cycle performance while keeping a discharge capacity over 100 mA h g-1. To gain deeper understanding on a relationship between the electrode properties and the crystal structure of the Mg-Fe-O, the crystal structure is investigated by a Rietveld refinement using a synchrotron X-ray diffraction profile and an analysis on total correlation functions. It is indicated from these studies that a vacant octahedral site in the spinel structure is partially occupied by the excess Mg in the synthesized sample. This structural feature might result in a stable charge/discharge cycle performance of the Mg-rich Mg-Fe-O.
RESUMEN
High-performance electrolytes are at the heart of magnesium battery development. Long-term stability along with the low potential difference between plating and stripping processes are needed to consider them for next-generation battery devices. Within this work, we perform an in-depth characterization of the novel Mg[Al(hfip)4]2 salt in different glyme-based electrolytes. Specific importance is given to the influence of water content and the role of additives in the electrolyte. Mg[Al(hfip)4]2-based electrolytes exemplify high tolerance to water presence and the beneficial effect of additives under aggravated cycling conditions. Finally, electrolyte compatibility is tested with three different types of Mg cathodes, spanning different types of electrochemical mechanisms (Chevrel phase, organic cathode, sulfur). Benchmarking with an electrolyte containing a state-of-the-art Mg[B(hfip)4]2 salt exemplifies an improved performance of electrolytes comprising the Mg[Al(hfip)4]2 salt and establishes Mg[Al(hfip)4]2 as a new standard salt for the future Mg battery research.
RESUMEN
Spinel-type MgMn2O4, prepared by a propylene-oxide-driven sol-gel method, has a high surface area and structured bimodal macro- and mesopores, and exhibits good electrochemical properties as a cathode active material for rechargeable magnesium batteries. However, because of its hydrophilicity and significant water adsorption properties, macroscopic aggregates are formed in composite slurry-coated cathodes when 1-methyl-2-pyrrolidone (NMP) is used as a non-aqueous solvent. Functionalising the surface with phenylphosphonate groups was found to be an easy and effective technique to render the structured MgMn2O4 hydrophobic and suppress aggregate formation in NMP-based slurries. This surface functionalisation also reduced side reactions during charging, while maintaining the discharge capacity, and significantly improved the coulombic efficiency. Uniform slurry-coated cathodes with active material fractions as high as 93 wt% can be produced on Al foils by this technique employing carbon nanotubes as an electrically conductive support. A coin-type full cell consisting of this slurry-coated cathode and a magnesium alloy anode delivered an initial discharge capacity of â¼100 mA h g-1 at 25 °C.
RESUMEN
A novel metallurgical approach was adopted to enhance the electrochemical activity of Mg anodes for magnesium rechargeable batteries. The primary electrochemical processes were considered to be grain boundary-mediated. Therefore, appropriate control of the grain size combined with Ca alloying of the Mg anode resulted in a remarkable electrochemical Mg2+/Mg0 cycling activity.
RESUMEN
The development of noncorrosive but highly efficient electrolytes has been a long-standing challenge in magnesium rechargeable battery (MRB) research fields. As fluorinated alkoxyborate-based electrolytes have overcome serious problems associated with conventional electrolytes, they are regarded as promising for practical MRB applications. An electrolyte containing representative magnesium fluorinated alkoxyborate Mg[B(HFIP)4]2 ([B(HFIP)4]: tetrakis(hexafluoroisopropoxy) borate) was prepared through general synthetic routes using Mg(BH4)2; however, it shows poor electrochemical magnesium deposition/dissolution behavior. Herein, we report an alternative synthetic route of highly reactive Mg[B(HFIP)4]2 and several critical issues associated with the use of Mg[B(HFIP)4]2/glyme electrolytes in MRBs. The cycling performance of the electrolytes as well as the synthetic reproducibility of the salt was significantly improved upon adopting a transmetalation reaction between certain magnesium and boron compounds for the salt preparation. Despite the outstanding electrochemical activity of Mg[B(HFIP)4]2/glyme, the electrolytes were unstable with the magnesium metal. The remarkably high dissociativity of Mg[B(HFIP)4]2 in glyme solutions and the resulting enhanced induction interaction of Mg2+ with coordinated glymes make the solutions reductively unstable. Surface passivation by [TFSA]-based electrolytes (TFSA: bis(trifluoromethanesulfonyl)amide) effectively suppressed the decomposition of Mg[B(HFIP)4]2/glyme electrolytes. This passivation simultaneously caused a large overpotential for electrochemical cycling. The short-circuiting of the cells upon repeated deposition/dissolution cycling is rather problematic. Here, the findings disclose the issues of fluorinated alkoxyborate-based electrolyte solutions that should be resolved for practical MRB materialization. We also emphasize the importance of systematic strategies in manipulating the electrolytes and interfaces as well as base magnesium metal based on each appropriate approach.
RESUMEN
Spinel-type MgMn2O4 nanoplates â¼10 nm thick were prepared as a positive electrode for magnesium rechargeable batteries by the transformation of metal hydroxide nanoplates. Homogeneous coating with a vanadate layer thinner than 3 nm was achieved on the spinel oxide nanoplates via coverage of the precursor and subsequent mild calcination. We found that the spinel oxide nanoplates with the homogeneous coating exhibit improved electrochemical properties, such as discharge potential, capacity, and cyclability, due to the enhanced insertion and extraction of magnesium ions and suppressed decomposition of electrolytes. The nanometric platy morphology of the spinel oxide and the vanadate coating act synergistically for the improvement of the electrochemical performance.
RESUMEN
To clarify the origin of the polarization of magnesium deposition/dissolution reactions, we combined electrochemical measurement, operando soft X-ray absorption spectroscopy (operando SXAS), Raman, and density functional theory (DFT) techniques to three different electrolytes: magnesium bis(trifluoromethanesulfonyl)amide (Mg(TFSA)2)/triglyme, magnesium borohydride (Mg(BH4)2)/tetrahydrofuran (THF), and Mg(TFSA)2/2-methyltetrahydrofuran (2-MeTHF). Cyclic voltammetry revealed that magnesium deposition/dissolution reactions occur in Mg(TFSA)2/triglyme and Mg(BH4)2/THF, while the reactions do not occur in Mg(TFSA)2/2-MeTHF. Raman spectroscopy shows that the [TFSA]- in the Mg(TFSA)2/triglyme electrolyte largely does not coordinate to the magnesium ions, while all of the [TFSA]- in Mg(TFSA)2/2-MeTHF and [BH4]- in Mg(BH4)2/THF coordinate to the magnesium ions. In operando SXAS measurements, the intermediate, such as the Mg+ ion, was not observed at potentials above the magnesium deposition potential, and the local structure distortion around the magnesium ions increases in all of the electrolytes at the magnesium electrode|electrolyte interface during the cathodic polarization. Our DFT calculation and X-ray photoelectron spectroscopy results indicate that the [TFSA]-, strongly bound to the magnesium ion in the Mg(TFSA)2/2-MeTHF electrolyte, undergoes reduction decomposition easily, instead of deposition of magnesium metal, which makes the electrolyte inactive electrochemically. In the Mg(BH4)2/THF electrolyte, because the [BH4]- coordinated to the magnesium ions is stable even under the potential of the magnesium deposition, the magnesium deposition is not inhibited by the decomposition of [BH4]-. Conversely, because [TFSA]- is weakly bound to the magnesium ion in Mg(TFSA)2/triglyme, the reduction decomposition occurs relatively slowly, which allows the magnesium deposition in the electrolyte.
RESUMEN
Magnesium batteries have the potential to be a next generation battery with large capability and high safety, owing to the high abundance, great volumetric energy density, and reversible dendrite-free capability of Mg anodes. However, the lack of a stable high-voltage electrolyte, and the sluggish Mg-ion diffusion in lattices and through interfaces limit the practical uses of Mg batteries. Herein, a spinel MgIn2 S4 microflower-like material assembled by 2D-ultrathin (≈5.0 nm) nanosheets is reported and first used as a cathode material for high-temperature Mg batteries with an ionic liquid electrolyte. The nonflammable ionic liquid electrolyte ensure the safety under high temperatures. As prepared MgIn2 S4 exhibits wide-temperature-range adaptability (50-150 °C), ultrahigh capacity (≈500 mAh g-1 under 1.2 V vs Mg/Mg2+ ), fast Mg2+ diffusibility (≈2.0 × 10-8 cm2 s-1 ), and excellent cyclability (without capacity decay after 450 cycles). These excellent electrochemical properties are due to the fast kinetics of magnesium by the 2D nanosheets spinel structure and safe high-temperature operation environment. From ex situ X-ray diffraction and transmission electron microscopy measurements, a conversion reaction of the Mg2+ storage mechanism is found. The excellent performance and superior security make it promising in high-temperature batteries for practical applications.
RESUMEN
Li+ ion hopping conduction in highly concentrated solutions of lithium bis(fluorosulfonyl)amide (LiFSA) dissolved in dinitrile solvents, namely succinonitrile, glutaronitrile, and adiponitrile, was investigated. Phase behaviors of the LiFSA/dinitrile binary mixtures assessed by differential scanning calorimetry suggested that LiFSA and the dinitriles form stable solvates in a molar ratio of 1 : 2. For succinonitrile, a glass forming room temperature liquid is formed when [LiFSA]/[succinonitrile] > 1. The corresponding glutaronitrile and adiponitrile mixtures have melting points below 60 °C. The self-diffusion coefficients of Li+, FSA-, and dinitrile measured with pulsed field gradient NMR suggested that Li+ ion diffuses faster than anion and dinitrile in the liquids of composition [LiFSA]/[dinitrile] = 1/0.8, indicating emergence of Li+ ion hopping conduction. X-ray crystallography for the LiFSA-(dinitrile)2 solvates and Raman spectroscopy for the liquids with composition [LiFSA]/[dinitrile] > 1 revealed that the two cyano groups of the dinitrile coordinate to two different Li+ ions and form solvent-bridged structures of (Li+-dinitrile-Li+). In addition, the Raman spectra suggested that ionic aggregates (Li+-FSA--Li+) are formed in the liquids with composition [LiFSA]/[dinitrile] > 1. Although there is frequent ligand (dinitrile and/or anion) exchange for each Li+ ion in the liquid state, the polymeric network structures (solvent-bridged structure and ionic aggregates) restrict the facile motion of ligands because each ligand is interacting with multiple Li+ ions in the highly concentrated electrolytes. This induces the faster diffusion of the Li+ ion than that of the ligands, i.e., hopping conduction of Li+ through ligand exchange. Electrochemical measurements clarified that the [LiFSA]/[succinonitrile] = 1/0.8 electrolyte possesses a relatively high Li+ transport ability (limiting current density > 7 mA cm-2) thanks to the Li+ hopping conduction, regardless of its extremely high viscosity (3142 mPa s) and relatively low conductivity (0.26 mS cm-1) at room temperature. Furthermore, this electrolyte was shown to have a high Li+ transference number (>0.6), exhibited reversible Li metal deposition/dissolution i.e. suppression of reductive decomposition of the solvent, and could be successfully applied to graphite and LiNi1/3Mn1/3Co1/3O2 half-cells.
RESUMEN
To achieve a sustainable-energy society in the future, next-generation highly efficient energy storage technologies, particularly those based on multivalent metal negative electrodes, are urgently required to be developed. Magnesium rechargeable batteries (MRBs) are promising options owing to the many advantageous chemical and electrochemical properties of magnesium. However, the substantially low working voltage of sulfur-based positive electrodes may hinder MRBs in becoming alternatives to current Li-ion batteries. We proposed halide-free noncorrosive ionic liquid-based electrolytes incorporating Mg[TFSA]2 for high-voltage MRB applications. Upon the complexation of Mg[TFSA]2 with tetraglyme (G4) and strict control of the liquid states, the electrolytes achieved excellent anodic stability up to 4.1 V vs. Mg2+/Mg even at 100 °C. The modest electrochemical activities for magnesium deposition/dissolution in the [Mg(G4)][TFSA]2/ionic liquid electrolyte can be improved by certain modifications to the coordination state of [TFSA]-. Dialkyl sulfone was found to be effective in changing the coordination state of [TFSA]- from associated to isolated (free). This coordination change successfully promoted magnesium deposition/dissolution reactions, particularly in the coexistence of ether ligand. By contrast, the coordination of Mg2+ by strongly donating agents such as dimethyl sulfoxide and alkylimidazole led to the complexes inactive electrochemically, suggesting that interaction between Mg2+ and coordination agents predominates the fundamental electrochemical activity. We also demonstrated that an enhancement in the electrochemical activity of electrolytes contributed to improvements in the cycling ability of magnesium batteries with 2.5 V-class MgMn2O4 positive electrodes.
RESUMEN
Recent studies have suggested that a Li ion hopping or ligand- or anion-exchange mechanism is largely involved in Li ion conduction of highly concentrated liquid electrolytes. To understand the determining factors for the Li ion hopping/exchange dominant conduction in such liquid systems, ionic diffusion behavior and Li ion coordination structures of concentrated liquid electrolytes composed of lithium bis(fluorosulfonyl)amide (Li[FSA]) and keto ester solvents with two carbonyl coordinating sites of increasing intramolecular distance (methyl pyruvate (MP), methyl acetoacetate (MA), and methyl levulinate (ML)) were studied. Diffusivity measurements of MP- and MA-based concentrated electrolytes showed faster Li ion diffusion than the solvent and FSA anion, demonstrating that Li ion diffusion was dominated by the Li ion hopping/exchange mechanism. A solvent-bridged, chain-like Li ion coordination structure and highly aggregated ion pairs (AGGs) or ionic clusters e.g. Lix[FSA]y(y-x)- forming in the electrolytes were shown to contribute to Li ion hopping conduction. By contrast, ML, with greater intramolecular distance between the carbonyl moieties, is more prone to form a bidentate complex with a Li cation, which increased the contribution of the vehicle mechanism to Li ion diffusion even though similar AGGs and ionic clusters were also observed. The clear correlation between the unusual Li ion diffusion and the solvent-bridged, chain-like structure provides an important insight into the design principles for fast Li ion conducting liquid electrolytes that would enable Li ion transport decoupled from viscosity-controlled mass transfer processes.
RESUMEN
From the viewpoint of element strategy, non-Li batteries with promising negative and positive electrodes have been widely studied to support a sustainable society. To develop non-Li batteries having high energy density, research on electrolyte materials is pivotal. Solvate ionic liquids (SILs) are an emerging class of electrolytes possessing somewhat superior properties for battery applications compared to conventional ionic liquid electrolytes. In this account, we describe our recent efforts regarding SIL-based electrolytes for Li, Na, K, and Mg batteries with respect to structural, physicochemical, and electrochemical characteristics. Systematic studies based on crystallography and Raman spectroscopy combined with thermal/electrochemical stability analysis showed that the balance of competitive cation-anion and cation-solvent interactions predominates the stability of the solvate cations. We also demonstrated battery applications of SILs as electrolytes for non-Li batteries, particularly for Na batteries.
RESUMEN
The phase behavior of binary mixtures of triglyme (G3) and Mg[TFSA]2 (TFSA: bis(trifluoromethanesulfonyl)amide) was investigated, towards the development of a Mg2+-based room-temperature solvate ionic liquid (SIL) electrolyte. In a 1 : 1 molar ratio, G3 and Mg[TFSA]2 form a thermally stable complex (decomposition temperature, Td: 240 °C) with a melting point (Tm) of 70 °C, which is considerably lower than that of the analogous tetraglyme (G4) system (137 °C). X-ray crystallography of a single crystal of [Mg(G3)][TFSA]2 revealed that a single Mg2+ cation is coordinated by a single, distorted, tetradentate G3 molecule from one side, and two monodentate [TFSA]- anions, with transoid conformation, from the reverse side to form an ion pair. Raman spectra of [Mg(G3)][TFSA]2 in the molten state revealed the presence of different coordination structures, as the liquid exhibits changes in the vibrational modes corresponding to G3 and the [TFSA]- anion compared to those observed for the solid. Investigation of the ion pair stabilization energies by DFT calculations suggests that higher stability cation complexes and ion pairs co-exist in the molten state than those observed in the crystalline state. These results imply that the coordination structures of the ion pairs play a key role in providing SILs with low Tm. To decrease the Tm further, several asymmetric homologues of G3, which have higher conformational flexibility than G3, were investigated. Notably, a 1 : 1 mixture of Mg[TFSA]2 with G3Bu (where one of the terminal methyl groups of G3 is substituted for a butyl group) formed a thermally stable complex (Td: 251 °C) without any distinct Tm and showed reasonable ionic conductivity at room-temperature, indicating partial dissociation of ions. In this electrolyte, which showed high oxidative stability, quasi-reversible Mg deposition/dissolution was achieved, indicating that Mg2+-based room-temperature SILs can be utilized as a new class of Mg electrolyte.
RESUMEN
The interactions of glymes with alkali or alkaline earth metal cations depend strongly on the metal cations. For example, the stabilization energies (Eform) calculated for the formation of cation-triglyme (G3) complexes with Li+, Na+, K+, Mg2+, and Ca2+ at the MP2/6-311G** level were -95.6, -66.4, -52.5, -255.0, and -185.0 kcal mol-1, respectively, and those for the cation-tetraglyme (G4) complexes were -107.7, -76.3, -60.9, -288.3 and -215.0 kcal mol-1, respectively. The electrostatic and induction interactions are the major source of the attraction in the complexes; the contribution of the induction interactions to the attraction is especially significant in the divalent cation-glyme complexes. The binding energies of the cation-G3 complexes with Li+, Na+, K+, Mg2+, and Ca2+ and the bis(trifluoromethylsulfonyl)amide anion ([TFSA]-) were -83.9, -86.6, -80.0, -196.1, and -189.5 kcal mol-1, respectively, and they are larger than the binding energies of the corresponding cation-G4 complexes (-73.6, -75.0, -77.4, -172.1, and -177.2 kcal mol-1, respectively). The binding energies and conformational flexibility of the cation-glyme complexes also affect the melting points of equimolar mixtures of glyme and TFSA salts. Furthermore, the interactions of the metal cations with the oxygen atoms of glymes significantly decrease the HOMO energy levels of glymes. The HOMO energy levels of glymes in the cation-glyme-TFSA complexes are lower than those of isolated glymes, although they are higher than those of the cation-glyme complexes.
RESUMEN
Hydrofluoroethers have recently been used as the diluent to a lithium battery electrolyte solution to increase and decrease the ionic conductivity and the solution viscosity, respectively. In order to clarify the Li(+) local structure in the 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (HFE) diluted [Li(G4)][TFSA] (G4, tetraglyme; TFSA, bis(trifluoromethanesulfonyl)amide) solvate ionic liquid, Raman spectroscopic study has been done with the DFT calculations. It has turned out that the HFE never coordinates to the Li(+) directly, and that the solvent (G4) shared ion pair of Li(+) with TFSA anion (SSIP) and the contact ion pair between Li(+) and TFSA anion (CIP) are found in the neat and HFE diluted [Li(G4)][TFSA] solvate ionic liquid. It is also revealed that the two kinds of the CIP in which TFSA anion coordinates to the Li(+) in monodentate and bidentate manners (hereafter, we call them the monodentate CIP and the bidentate CIP, respectively) exist with the SSIP of predominant [Li(G4)](+) ion-pair species in the neat [Li(G4)][TFSA] solvate ionic liquid, and that the monodentate CIP decreases as diluting with the HFE. To obtain further insight, X-ray total scattering experiments (HEXTS) were carried out with the aid of MD simulations, where the intermolecular force field parameters, mainly partial atomic charges, have been newly proposed for the HFE and glymes. A new peak appeared at around 0.6-0.7 Å(-1) in X-ray structure factors, which was ascribed to the correlation between the [Li(G4)][TFSA] ion pairs. Furthermore, MD simulations were in good agreement with the experiments, from which it is suggested that the terminal oxygen atoms of the G4 in [Li(G4)](+) solvated cation frequently repeat coordinating/uncoordinating to the Li(+), although almost all of the G4 coordinates to the Li(+) to form [Li(G4)](+) solvated cation in the neat and HFE diluted [Li(G4)][TFSA] solvate ionic liquid.
RESUMEN
We have characterized a novel aluminum-based homometallic double complex salt, incorporating discrete octa-coordinated cationic [Al(G3)2](3+) and hexa-coordinated anionic [Al(TfO)4(OH)2](3-) complexes (G3 = triglyme, TfO = trifluoromethanesulfonate). X-ray crystallography, Raman spectra, and DFT calculations demonstrate extraordinary weak Al(3+) coordination in [Al(G3)2](3+).
RESUMEN
Certain molten complexes of Li salts and solvents can be regarded as ionic liquids. In this study, the local structure of Li(+) ions in equimolar mixtures ([Li(glyme)]X) of glymes (G3: triglyme and G4: tetraglyme) and Li salts (LiX: lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]), lithium bis(pentafluoroethanesulfonyl)amide (Li[BETI]), lithium trifluoromethanesulfonate (Li[OTf]), LiBF4, LiClO4, LiNO3, and lithium trifluoroacetate (Li[TFA])) was investigated to discriminate between solvate ionic liquids and concentrated solutions. Raman spectra and ab initio molecular orbital calculations have shown that the glyme molecules adopt a crown-ether like conformation to form a monomeric [Li(glyme)](+) in the molten state. Further, Raman spectroscopic analysis allowed us to estimate the fraction of the free glyme in [Li(glyme)]X. The amount of free glyme was estimated to be a few percent in [Li(glyme)]X with perfluorosulfonylamide type anions, and thereby could be regarded as solvate ionic liquids. Other equimolar mixtures of [Li(glyme)]X were found to contain a considerable amount of free glyme, and they were categorized as traditional concentrated solutions. The activity of Li(+) in the glyme-Li salt mixtures was also evaluated by measuring the electrode potential of Li/Li(+) as a function of concentration, by using concentration cells against a reference electrode. At a higher concentration of Li salt, the amount of free glyme diminishes and affects the electrode reaction, leading to a drastic increase in the electrode potential. Unlike conventional electrolytes (dilute and concentrated solutions), the significantly high electrode potential found in the solvate ILs indicates that the solvation of Li(+) by the glyme forms stable and discrete solvate ions ([Li(glyme)](+)) in the molten state. This anomalous Li(+) solvation may have a great impact on the electrode reactions in Li batteries.
RESUMEN
We prepared a series of binary mixtures composed of certain K salts (KX) and pentaglyme (G5) with different salt concentrations and anionic species ([X](-): [(CF3SO2)2N](-) = [TFSA](-), [CF3SO3](-) = [TfO](-), [C4F9SO3](-) = [NfO](-), PF6(-), SCN(-)), and characterized them with respect to their phase diagrams, solvate structures, and physicochemical properties. Their phase diagrams and thermal stability strongly implied the formation of equimolar complexes. Single-crystal X-ray crystallography was performed on certain equimolar complexes, which revealed that G5 molecules coordinate to K(+) cations in a characteristic manner, like 18-crown-6 ether in the crystalline state, irrespective of the paired anions. The solvate structures in the molten state were elucidated by a combination of temperature-dependent Raman spectroscopy and X-ray crystallography. A drastic spectral variation was observed in the [K(G5)1][TfO] Raman spectra, indicating that solvate structures in the crystalline state break apart upon melting. The solvate stability of [K(G5)1]X is closely related to the ion-ion interaction of the parent salts. A stable solvate forms when the ion-dipole interaction between K(+) and G5 overwhelms the ion-ion interaction between K(+) and X(-). Furthermore, the physicochemical properties of certain equimolar mixtures were evaluated. A Walden plot clearly reflects the ionic nature of the molten equimolar complexes. Judging from the structural characteristics and dissociativity, we classified [K(G5)1]X into two groups, good and poor solvate ionic liquids.