Function Of Salt Concentration Research Articles

Complete Electrochemical Characterization and Limiting Current of Polyacetal Electrolytes

We investigate a polyacetal-based electrolyte, poly(1,3,6-trioxocane) (P(2EO-MO)) mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, and report full electrochemical characterization of the transport parameters and a thermodynamic property in comparison to the previously reported poly(ethylene oxide) (PEO) electrolyte data [D. Gribble et al., J. Electrochem. Soc., 166, A3228 (2019)]. While the steady-state current fraction (ρ +) of P(2EO-MO) electrolyte is greater than that of PEO electrolyte in the entire salt concentration window we explored, the rigorously defined transference number using Newman’s concentrated solution theory () appears to be similar to that of PEO electrolyte. On the basis of full electrochemical characterization, we calculate the salt concentration profile as a function of position in the cell and predict limiting current density (i L L) as a function of salt concentration. Experimental data were compared to the predicted values. The non-monotonic behaviors were observed both in prediction and experimental results with offset peak positions. We find that the limiting current density of P(2EO-MO) electrolyte is systematically lower than that of PEO electrolyte in most of the salt concentrations with the exception of r av = 0.05. It is noteworthy that even though one measure of electrolyte efficacy (κρ +) is superior in P(2EO-MO) electrolyte, the limiting current density, which is another metric of electrolyte efficacy at high currents, is not greater in P(2EO-MO).

Polyelectrolyte complexation of charged IDPs driven by the entropy of counterion release

The two IDPs ProTα and H1 bear large opposite net charges (−44 and +53, respectively) and bind to each other with very high affinity; however, the complex remains disordered and represents a limiting case in the spectrum of disorder in IDP complexes [1,2]. Temperature-dependent single-molecule FRET (smFRET) experiments and isothermal titration calorimetry (ITC) reveal ProTα-H1 complexation to be enthalpically unfavourable. Rather, counterion release entropy is an important thermodynamic driving force for complexation, as suggested by affinity measurements with smFRET as a function of salt concentration and using different salts.

Comparing measurement of limiting current in block copolymer electrolytes as a function of salt concentration with theoretical predictions

Optimizing electrolyte performance is crucial for the widespread adoption of electrochemical energy storage. We demonstrate that limiting current provides a robust criterion for determining the optimum electrolyte. Experiments were conducted on rigid block copolymer electrolytes comprising mixtures of polystyrene-block-poly(ethylene oxide) copolymer (SEO) and lithium bis(trifluoromethanesulfonyl) imide salt (LiTFSI) over a salt concentration range from rav = 0.04 to rav = 0.20 (rav is the molar ratio of lithium ions to ethylene oxide). We show that the maximum limiting current density is 4.3 mA cm−2 at rav = 0.12. The dependence of limiting current on salt concentration is in good agreement with predictions from Newman's concentrated solution theory with no adjustable parameters.

A new approach to investigate the ionic conductivity of NaCl and KCl solutions via impedance spectroscopy

Lima et al. [1] employed electrical impedance spectroscopy to analyze the electrical impedance behavior of dilute aqueous potassium chloride (KCl) and sodium chloride solutions in the frequency range of 10−1 Hz to 106 Hz (NaCl). The complex impedance Z* data from the solutions were modeled using an analogous electrical circuit that closely matched the experimental data. The electrical characteristics of the solutions were studied as a function of the cation types. The Debye model accurately describes the bulk effects of K+ and Na+ cations. However, it appeared that the analysis presented just the equivalent circuit components as a function of salt concentration. As a result, the current work used a simulation procedure to generate complex impedance (Z*) data from electrical parameters derived from the analogous circuit. To highlight the high-frequency relaxation processes occurring, extrapolation to a broader frequency range was performed. Furthermore, theoretical considerations were introduced in order to derive complex conductivity (σ*) from complex admittance (Y*). In the complex impedance (Z*) and admittance (Y*), there was a good correlation between all parameters derived from both processes. The key relaxation process characteristics, such as ionic strength, relaxation time, and conductivity values at low and high frequencies, were then retrieved. As a function of salt concentration, all of these parameters were evaluated and discussed.

Double-Layer Capacitances Caused by Ion–Solvent Interaction in the Form of Langmuir-Typed Concentration Dependence

Variations of the double layer capacitances (DLCs) at a platinum electrode with concentrations and kinds of salts in aqueous solutions were examined in the context of facilitating orientation of solvent dipoles. With an increase in ionic concentrations, the DLCs increased by ca. a half and then kept constant at concentrations over 1 mol dm−3. This increase was classically explained in terms of the Gouy–Chapman (GC) equation combined with the Stern model. Unfortunately, measured DLCs were neither satisfied with the Stern model nor the GC theory. Our model suggests that salts destroy hydrogen bonds at the electrode–solution interface to orient water dipoles toward the external electric field. A degree of the orientation depends on the interaction energy between the salt ion and a water dipole. The statistical mechanic calculation allowed us to derive an equation for the DLC as a function of salt concentration and the interaction energy. The equation took the Langmuir-type in the relation with the concentration. The interaction energy was obtained for eight kinds of salts. The energy showed a linear relation with the interaction energy of ion–solvent for viscosity, called the B-coefficient.

Heteroaggregation rate coefficients between oppositely charged particles in a mixing flow: Effect of surface charge density and salt concentration

Heteroaggregation, namely, aggregation between dissimilar colloidal particles, is a common phenomenon in natural and industrial processes. However, understanding on heteroaggregation in flow fields is not sufficient due to the lack of experimental data for well-characterized colloids. Thereby, we measured heteroaggregation rate coefficients between oppositely charged and nearly equal-sized polystyrene latex spherical particles in a mixing flow as a function of salt concentration at pH 5 with focusing on the effect of difference in surface charge densities. We found that the enhancement of heteroaggregation rates with increasing surface charge density is not significant. At low salt concentration, the rates are enhanced through the increase in the range of electrical double layer attraction. This finding is supported by the theoretical aggregation rates based on trajectory analysis in both a simple shear flow and an extensional flow. In particular, the calculated rate with the extensional flow is in better agreement with the experimental rates, suggesting that the flow in the smallest eddies of a turbulence can be more likely represented by an extensional flow rather than a shear flow.

Self-Exchange of Polyelectrolyte in Multilayers: Diffusion as a Function of Salt Concentration and Temperature

Polymer chain diffusion within a hydrated polyelectrolyte complex, PEC, has been measured using an ultrathin film format prepared by the layer-by-layer method. Isotopically labeled self-exchange of deuterated poly(styrene sulfonate), dPSS, with undeuterated PSS of the same narrow molecular weight distribution permitted reliable estimates of whole-molecule diffusion coefficients, D. Narrow molecular weight distribution poly(diallyldimethylammonium), PDADMA, was used as the polycation for the PEC. Extensive pretreatment of starting films was undertaken to remove residual stress, anisotropy, and layering. PSS/PDADMA “multilayers,” PEMUs, thin enough to provide substantial exchange of polyelectrolyte, even with diffusion coefficients as low as 10–16 cm2 s–1, as a function of salt concentration and temperature were measured for this PEC, which has a glass-transition temperature, Tg, close to room temperature. Two molecular weights of dPSS, about 15 and 100 kDa, presumed to be below and above the entanglement molecular weight, respectively, both diffused faster at higher temperatures with respective activation energies, Ea, of about 21 and 53 kJ mol–1, the latter about the same as Ea for the place exchange between two pairs of PSS:PDADMA. Studies of the linear viscoelastic response of macroscopic PECs showed a difference of about 8 °C in the Tg of the two lengths of PSS complexed with the same PDADMA. Increasing concentrations of NaCl influenced D of 100 kDa PSS but not 15 kDa PSS at room temperature. D was faster in the region of the film near the solution interface, again attributed to a lower Tg caused by greater water content at this interface.

Aqueous Electrolytes, MXene‐Based Supercapacitors and Their Self‐Discharge

Significant efforts have been dedicated to developing Ti3C2Tz‐based MXene aqueous supercapacitors (SCs) with improved energy and power densities. Notably less research has been devoted to an equally important characteristic of aqueous SCs, viz. self‐discharge (SD). The SD rates are rarely reported despite their crucial importance from a practical point of view. Herein, the SD rates in four different aqueous electrolytes: H2SO4, KOH, LiCl, and LiBr in Ti3C2Tz‐based aqueous SCs are compared. For the latter two, the SD rates vary as a function of salt concentration in the electrolytes with higher LiCl or LiBr concentrations having the lowest SD rates, viz. 78.3% and 81.5% in 14 m LiCl and LiBr, respectively, after 10 h. Further, the influence of dissolved oxygen and the purities of the starting powders are examined, and it is concluded that parasitic reactions, including oxygen, are responsible for the SD.

Development of a Polarizable Force Field for Molecular Dynamics Simulations of Lithium-Ion Battery Electrolytes: Sulfone-Based Solvents and Lithium Salts.

A many-body polarizable force field (PFF) was developed for molecular dynamics (MD) simulations of sulfone-based solvents and lithium salts. Development of the polarizable force field included parameterization of atomic polarizabilities, electrostatic interactions, and van der Waals interactions of electrolyte components. 1λ6-thiolane-1,1-dione or sulfolane (SLF) compound was selected as one of the most appropriate solvents for high-voltage battery electrolytes. Atomic polarizabilities for the sulfolane solvent and lithium salts were obtained by means of a combination of quantum mechanics (QM) and molecular mechanics (MM) approaches using the isotropic atomic dipole polarizable (IADP) model. High-quality atomic polarizabilities were refined for 10 atomic types. Intermolecular interactions of Li+ ions with SLF were parameterized to reproduce the binding energies at the MP2/aug-cc-pvDZ level of theory in the gas phase. Intermolecular interactions of Li+ ions with polyatomic anions, such as nitrate [NO3]-, tetrafluoroborate [BF4]-, perchlorate [ClO4]-, hexafluorophosphate [PF6]-, bis(fluorosulfonyl)imide [FSI]-, and bis(trifluoromethylsulfonyl)imide [TFSI]-, were parameterized employing a similar methodology. A series of molecular dynamics simulations was performed for sulfolane-based electrolytes at several different lithium salt concentrations. Thermodynamic, structural, and transport properties were evaluated to validate the force field parameters against available simulation and experimental data. Transport properties of sulfolane were significantly improved as compared with those obtained from MD simulations using a nonpolarizable force field (NFF). A newly developed polarizable potential was shown to reproduce Li+ ion dynamics as a function of salt concentration. Faster diffusion of Li+ ions, among other electrolyte components, was obtained for high salt concentration electrolytes.

Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes

Hybrid organic-inorganic block copolymer electrolytes are of interest to enable batteries containing lithium metal anodes. The conductive block is a standard polymer electrolyte of poly(ethylene oxide) and the mechanically rigid block is an inorganic poly(acryloisobutyl polyhedral oligomeric silsesquioxane) polymer. In this paper, we compare a poly(acryloisobutyl polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS) triblock copolymer and a poly(ethylene oxide)-b- poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide salt. We have experimentally measured the limiting current density in lithium symmetric cells containing hybrid organic-inorganic electrolytes at 90 °C. The cells were polarized at a large range of applied current density. The diblock copolymer electrolyte exhibited a clear plateau in cell potential at all current densities below the limiting current density. At low applied current density, the triblock copolymer electrolyte also exhibited a clear plateau in cell potential. At currents approaching the limiting current density, the triblock copolymer electrolyte exhibited an underdamped potential profile. The cell potential did not reach a plateau at current densities above the limiting current in both systems. The diblock and triblock copolymer electrolytes were fully characterized using electrochemical methods to determine the ionic conductivity, cation current fraction, salt diffusion coefficient, and open circuit voltage as a function of salt concentration. Cell potential and salt concentration as functions of position in the cell at various current densities were calculated using Newman's concentrated solution theory. The theoretical limiting current density was calculated to be the current density at which salt is depleted at the cathode. We see quantitative agreement between experimental measurements and theoretical predictions for the limiting current density in the diblock copolymer electrolyte which has an ordered structure at all salt concentrations, while the experimental limiting current density is lower than the theoretical prediction for the triblock copolymer electrolyte, which exhibits a disordered morphology at high salt concentrations.

A new framework for modeling the effect of salt on interfacial adsorption of PFAS in environmental systems

Per- and polyfluoroalkyl substances (PFAS) are surface active contaminants of great environmental concern, due to their widespread historical use and their environmental persistence. Salts are known to have a profound influence on the interfacial behaviors of all ionic surfactants, including some of the most commonly detected PFAS. This work describes a new mass-action model for predicting the interfacial behavior of surfactants as a function of salt concentration. The three-parameter model is fit to interfacial tension data over a range of salt concentrations, and is then able to predict interfacial adsorption isotherms for the entire range from no added salt, up to 0.5 M added salt. The phenomenological nature of the model means that it is likely to provide more robust predictions for new systems and conditions than some of the existing empirical approaches, and the minimal number of adjustable parameters ensures that unique calibrations are possible with limited data. The model is found to be consistent with experimental data, and is bracketed by experimental values at low PFAS concentrations. Of particular interest, the model predicts the existence of sigmoidal adsorption isotherms at low salt concentrations, a deviation from isotherms calculated the commonly-used Szyszkowski equation; the observation is supported by a maximum in measured interfacial adsorption coefficient calculated from low-concentration surface tension measurements. Because adsorption affinities can vary by orders of magnitude with changing salt concentration, the ability to predict the effects of salt on adsorption is of critical importance for quantitative prediction of PFAS behavior in the environment.

Salt and Solvent effect on physicochemical properties and species organisation of Lithium fluorosulfonyl imide (FSI and TFSI) based electrolytes for Li-ion battery: Consequence on cyclability of LiNi0.8Co0.15Al0.05 (NCA) cathode

Herein we present a comparative study of the physicochemical and thermal properties of four electrolytes formulated with LiTFSI, LiFSI in binary (3EC/7EMC) and ternary (EC/PC/3DMC) mixture of solvents, as a function of salt concentration and temperature. By modeling the change on viscosity, ionic conductivity, with Arrhenius, Eyring and Jones-Dole-Kaminsky equations, we established the determinants parameters which influence the organization of solutions, in order to understand their consequences on electrochemical performances of LiNi0.8Co0.15Al0.05 (NCA) as cathode in Li-ion battery. Results shown that (3EC/7EMC + LiTFSI) present a double solvation sphere of Li+ and weak ionic association consequently it is poorly suited to the activation and cycling of NCA. While (EC/PC/3DMC + LiFSI) benefits from both a single sphere of solvation and strong ion-ion and ion-solvent interactions, making the polarization of the interfaces in this electrolyte suitable to the Li+ diffusion and to low interface resistances. These results demonstrate that the electrolyte properties such as viscosity, conductivity and thermal stability depend on several factors. Those related to species in solutions (solvents and salt ions), and those related to operating conditions such as temperature and concentration. All these parameters impact the ionic dissociation and solvation. This study shows the close-link between the organization of species in solutions, the physicochemical and thermal properties, and their impact on electrochemical performances in a Li-ion battery.

Concentration dependance of the capacitive to inductive transition observed in electrolytic solutions

We investigate, in a systematic way, the electric response of KCl, NaCl, CaCl2 and MgCl2 aqueous solutions as function of salt concentration. Our experimental data show that the cell’s reactance transits from capacitive to inductive regime at a well defined frequency. The transition depends critically on the salt concentration. The present work is motivated from published data in the literature showing deviations of the impedance spectra from the expected behavior, at high enough frequency as salt concentration increases. These data were interpreted by means of a mechanical model. We propose an alternative interpretation of the observed transition from capacitive to inductive regime, which is based on the parasitic inductance of the coaxial cables used in the experimental set-up. The dependence of the transition frequency on the concentration is investigated, and approximated formulae are obtained. A critical concentration where the capacitive to inductive regime transition jumps from a high to a low frequency region has been both experimentally located and theoretically deduced. Ion generation-recombination effects are shown to be important and taken into account. Solutions of divalent ions present a lower critical concentration than solutions of monovalent ions.

Ion Clusters and Networks in Water-in-Salt Electrolytes

Water-in-salt electrolytes (WiSEs) are a class of super-concentrated electrolytes that have shown much promise in replacing organic electrolytes in lithium-ion batteries. At the extremely high salt concentrations of WiSEs, ionic association is more complicated than the simple ion pair description. In fact, large branched clusters can be present in WiSEs, and past a critical salt concentration, an infinite percolating ionic network can form spontaneously. In this work, we simplify our recently developed thermodynamic model of reversible ionic aggregation and gelation, tailoring it specifically for WiSEs. Our simplified theory only has a handful of parameters, all of which can be readily determined from simulations. Our model is able to quantitatively reproduce the populations of ionic clusters of different sizes as a function of salt concentration, the critical salt concentration for ionic gelation, and the fraction of ions incorporated into the ionic gel, as observed from molecular simulations of three different lithium-based WiSEs. The extent of ionic association and gelation greatly affects the effective ionic strength of solution, the coordination environment of active cations that is known to govern the chemistry of the solid-electrolyte interface, and the thermodynamic activity of all species in the electrolyte.

Highly Concentrated Electrolytes: Electrochemical and Physicochemical Characteristics of LiPF6 in Propylene Carbonate Solutions

Highly concentrated electrolytes (HCEs) based on LiPF6 in propylene carbonate (PC) have been examined as lithium-ion battery electrolytes. These HCEs have lower ionic conductivities and higher viscosities than ethylene carbonate (EC) electrolytes with 1.2 M LiPF6, but they have higher Li+ ion transference numbers. Electrochemical cycling behaviour of LiNi0.8Co0.015Al0.05O2//graphite cells with 3.2 M LiPF6 in PC resembles that of cells with EC-based electrolytes; the HCE cells have higher impedance, which can be lowered by increasing test temperature. By employing Raman and infrared spectroscopy, combined with density functional theory and ab initio molecular dynamics simulations, we reveal that the Li+ solvation structure and speciation are key factors that determine cell performance. Two distinct regimes are observed as a function of salt concentration—in the conventional regime, the solvation number (SN) is mostly constant, while in the HCE regime it decreases linearly. Graphite exfoliation is suppressed only at very high salt concentrations (>2.4 M), where [PC] free /[Li+] < 1 and Results from the Advanced Electrolyte Model indicate that Li+ desolvation improves at higher LiPF6 concentrations, thereby mitigating PC co-intercalation into the graphite. However, Li+ ion transport is hindered in the HCEs, which increases impedance at both the oxide-positive and graphite-negative electrodes.

Electrochemical properties of poly(ethylene oxide) electrolytes above the entanglement threshold

Ion transport in electrolytes depends on three transport coefficients, conductivity (κ), salt diffusion coefficient (D), and the cation transference number with respect to the solvent velocity (t+0), and the thermodynamic factor (Tf). Current methods for determining these parameters involve four separate experiments, and the coupled nature of the equations used to determine them generally results in large experimental uncertainty. We present data obtained from 64 independent polymer electrolytes comprising poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The molecular weights of PEO ranged from 5 to 275 kg mol−1; these samples are all above the entanglement threshold. We minimize the experimental uncertainty in transport and thermodynamic measurements by exploiting the fact that ion transport in entangled polymer electrolytes should be independent of molecular weight. The dependence of κ, D, t+0, and Tf as a function of salt concentration in the range 0.035 ≤ r ≤ 0.30 are presented with a 95% confidence interval, where r is the molar ratio of lithium ions to ethylene oxide monomer units. While κ, D, and Tf are all positive as required by thermodynamic constraints, there is no constraint on the sign of t+0. We find that t+0 is negative in the salt concentration range of 0.093 ≤ r ≤ 0.189.

Ion Pairing, Clustering and Transport in a LiFSI-TMP Electrolyte as Functions of Salt Concentration using Molecular Dynamics Simulations

Battery capacity is highly related to ion-pairing mechanisms in electrolytes, since a cluster formation can lead to dead Li formation, reducing the number of charge carriers and leading to capacity fading. We use molecular dynamics simulations to model an electrolyte comprising trimethyl phosphate (TMP) solvent and a lithium bis(fluorosulfonyl)imide (LiFSI) salt, exploring effects of salt concentration on solvation and ion-transport. We simulate the LiFSI-TMP electrolyte for salt concentrations of 0.7, 1.43 and 3.82 molar. A statistical analysis was performed to study ion-pairing, clustering, diffusivity, conductivity, and coordination of Li-ions, providing insights into relations between molecular structures and transport properties. Molecular structure of ionic components changes as concentration increases, from a predominant solvent separated ion pair (SSIP) and contact ion pair (CIP) to aggregate salt (AGG) and ionic cluster formation. Given the formation of the ionic cluster, the diffusion mechanism followed by Li-ions changes from a hopping/exchange to a vehicular mechanism as concentration increases; this is reflected in a decrease of ionic conductivities. Ionicity was also calculated to reveal how the ionic motion changes from an uncorrelated to a correlated one as the salt concentration increases. We also compared our results with experimental calculations performed for similar electrolyte systems.

Molecular Level Differences in Ionic Solvation and Transport Behavior in Ethylene Oxide-Based Homopolymer and Block Copolymer Electrolytes.

Block copolymer electrolytes (BCE) such as polystyrene-block-poly(ethylene oxide) (SEO) blended with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and composed of mechanically robust insulating and rubbery conducting nanodomains are promising solid-state electrolytes for Li batteries. Here, we compare ionic solvation, association, distribution, and conductivity in SEO-LiTFSI BCEs and their homopolymer PEO-LiTFSI analogs toward a fundamental understanding of the maximum in conductivity and transport mechanisms as a function of salt concentration. Ionic conductivity measurements reveal that SEO-LiTFSI and PEO-LiTFSI exhibit similar behaviors up to a Li/EO ratio of 1/12, where roughly half of the available solvation sites in the system are filled, and conductivity is maximized. As the Li/EO ratios increase to 1/5 the conductivity, of the PEO-LiTFSI drops nearly 3-fold, while the conductivity of SEO-LiTFSI remains constant. FTIR spectroscopy reveals that additional Li cations in the homopolymer electrolyte are complexed by additional EO units when the Li/EO ratio exceeds 1/12, while in the BCE, the proportion of complexed and uncomplexed EO units remains constant; Raman spectroscopy data at the same concentrations show that Li cations in the SEO-LiTFSI samples tend to coordinate more to their counteranions. Atomistic-scale molecular dynamics simulations corroborate these results and further show that associated ions tend to segregate to the SEO-LiTFSI domain interfaces. The opportunity for "excess" salt to be sequestered at BCE interfaces results in the retention of an optimum ratio of uncompleted and complexed PEO solvation sites in the middle of the conductive nanodomains of the BCE and maximized conductivity over a broad range of salt concentrations.

Molecular Origins of Free Energies Associated with Complex Interactions of Biological Polyelectrolyte-Like Disordered Proteins

Diverse molecular forces drive the interactions of intrinsically disordered proteins (IDPs) and result in complexes that cover a broad spectrum of structural plasticity. Prothymosin-α (ProTa) and linker Histone (H1) are two IDPs that bear large negative and positive net charges, respectively, and form a picomolar-affinity yet disordered complex [1] - the limiting case in the spectrum of structural plasticity in IDP complexes. Here we show that their interaction exhibits remarkable thermodynamic behavior. Single-molecule FRET-based affinity measurements as a function of salt concentrations and temperature show that the predominant driving force of binding is the entropy increase due to counterion release upon complexation. As a result, the affinity increases with temperature and is extremely sensitive to ionic strength. Single-molecule FRET also enables the identification of stoichiometrically defined ternary complexes of ProTa and H1 at equilibrium and how their stability depends on solution conditions. These ternary complexes have pronounced effects on the interaction kinetics of ProTa-H1 [2], and they complicate affinity measurements in ensemble experiments, because at the much higher protein concentrations required compared to single-molecule conditions, the observed apparent affinities contain contributions from both binary and ternary complexes. [1] Borgia et al., Extreme disorder in an ultrahigh-affinity protein complex (2018), Nature 555, 61-66. [2] Sottini et al., Polyelectrolyte interactions enable rapid association and dissociation in high-affinity disordered protein complexes (2020), Nature Communications (in press).

Structure and dynamics of highly concentrated LiTFSI/acetonitrile electrolytes.

High salt concentration has been shown to induce increased electrochemical stability in organic solvent-based electrolytes. Accompanying the change in bulk properties is a structural ordering on mesoscopic length scales and changes in the ion transport mechanism have also been suggested. Here we investigate the local structure and dynamics in highly concentrated acetonitrile electrolytes as a function of salt concentration. Already at low concentrations ordering on microscopic length scales in the electrolytes is revealed by small angle X-ray scattering, as a result of correlations of Li+ coordinating clusters. For higher salt concentrations a charge alternation-like ordering is found as anions start to take part in the solvation. Results from quasi-elastic neutron spectroscopy reveal a jump diffusion dynamical process with jump lengths virtually independent of both temperature and Li-salt concentration. The jump can be envisaged as dissociation of a solvent molecule or anion from a particular Li+ solvation structure. The residence time, 50-800 ps, between the jumps is found to be highly temperature and Li-salt concentration dependent, with shorter residence times for higher temperature and lower concentrations. The increased residence time at high Li-salt concentration can be attributed to changes in the interaction of the solvation shell as a larger fraction of TFSI anions take part in the solvation, forming more stable solvation shells.