Polymer electrolytes typically exhibit diminished ionic conductivity due to the presence of correlation effects between the cations and anions. Microscopically, transient ionic aggregates, e.g. {\it ion-pairs}, {\it ion-triplets} or higher order ionic clusters, engender ionic correlations. Employing {\it all-atom} simulation of a model polymer electrolyte comprising of poly(ethylene oxide) and lithium iodide, the ionic correlations are explored through construction of elementary functions between pairs of the ionic species that qualitatively explains the spatio-temporal nature of these correlations. Furthermore, commencing from the exact Einstein-like equation describing the collective diffusivity of the ions in terms of the average diffusivity of the ions (i.e. the self terms) and the correlations from distinct pairs of ions, several phenomenological parameters are introduced to keep track of the simplification procedure that finally boils down to the recently proposed phenomenological model by Stolwijk-Obeidi (SO) [N. A. Stolwijk and S. Obeidi, Phys. Rev. Lett. 93, 125901, 2004]. The approximation parameters, which can be retrieved from simulations, point to the necessity of additional information in order to fully describe the correlation effects apart from merely the fraction of ion-pairs which apparently accounts for the correlations originating from only the nearest neighbor structural correlations. These parameters are close to but not exactly unity as assumed in the SO model. Finally, as an application of the extended SO model one is able to estimate the dynamics of the free and non-free ions as well as their fractions from the knowledge of the single particle diffusivities and the collective diffusivity of the ions.
We study the segmental dynamics of poly(ethylene oxide) (PEO) from microscopic simulations in the neat polymer and a polymer electrolyte (PEO/LiBF$_4$) by analyzing the normal modes. We verify the applicability of the Rouse theory, specifically for the polymer electrolyte where dynamic heterogeneities, arising from cation-polymer interactions, alter the mobility non-uniformly along the chains. We find that the Rouse modes for both the systems are orthogonal despite the presence of non-exponential relaxation of the modes and violation of the Gaussian self-similarity of the chains. The slowdown …
The addition of filler particles to polymer electrolytes is known to increment their ionic conductivity (IC). A detailed understanding of how the interactions between the constituent materials are responsible for the enhancement, remains to be developed. A significant contribution is ascribed to an increment of the polymer amorphous fraction, induced by the fillers, resulting in the formation of higher ionic conductivity channels in the polymer matrix. However, the dependence of IC on the particle weight load and its composition on the polymer morphology is not fully understood. This work inve…
The observed temperature dependence of electrical conduction in polymer electrolytes is usually fitted with two separated equations: an Arrhenius equation at low temperatures and Vogel-Tamman-Fulcher (VTF) at high temperatures. We report here a derivation of a single equation to explain the variation of electrical conduction in polymer electrolytes at all temperature ranges. Our single equation is in agreement with the experimental data
Recent experimental observations of anisotropic conductivity in stretched polymer electrolytes films of the polyethylene oxide family are discussed. The main experimental observations, enhancement of the ionic diffusion and conductivity in the stretch direction and decrease in these transport coefficients in the normal direction are interpreted in terms of an effective two-phase model. This two-phase model is based on the idea that a highly conducting phase is associated with oriented molecular structures which are surrounded by poorly conducting boundary regions. This model is evaluated withi…
Structure of polymer electrolytes membranes, e.g., Nafion, inside fuel cell catalyst layers has significant impact on the electrochemical activity and transport phenomena that determine cell performance. In those regions, Nafion can be found as an ultra-thin film, coating the catalyst and the catalyst support surfaces. The impact of the hydrophilic/hydrophobic character of these surfaces on the structural formation of the films and, in turn, on transport properties, has not been sufficiently explored yet. Here, we report about classical Molecular Dynamics simulations of hydrated Nafion thin-fi…
This paper examines the response of electrolyte-saturated polymer gels, embedded with charged spherical inclusions, to a weak gradient of electrolyte concentration. These composites present a model system to study microscale electrokinetic transport processes, and a rigorous theoretical prediction of the bulk properties will benefit novel diagnostic applications. An electrokinetic model was presented in an earlier publication, and the response of homogeneous composites to a weak electric field was calculated. In this work, the influence of the inclusions on bulk ion fluxes and the strength of …
In the present article, we have studied the effect of the salt concentration (LiPF6) on transport properties and ion dynamics of blend solid polymer electrolyte (PEO PAN) prepared by solution cast technique. Fourier transform infrared (FTIR) spectroscopy confirms the presence of microscopic interactions such as polymer ion and ion ion interaction evidenced by a change in peak area of anion stretching mode. The fraction of free anions and ion pairs obtained from the analysis of FTIR implies that both influence the ionic conductivity with different salt concentration. The complex dielectric perm…
The electrical impedance response of Gelatin based solid polymer electrolyte to gamma irradiation is investigated by impedance spectroscopy. An analysis based on Poisson-Nernst-Plank model, incorporating fractional time derivatives is carried out. A detailed derivation for anomalous impedance function is given.The model involves boundary conditions with convolution of the fractional time derivative of ion density and adsorption desorption relaxation kinetics. A fractional diffusion-drift equation is used to solve the bulk behavior of the mobile charges in the electrolyte. The complex adsorptio…
Electronic conduction in conjugated polymers is of emerging technological interest for high-performance optoelectronic and thermoelectric devices. A completely new aspect and understanding of the conduction mechanism on conducting polymers is introduced, allowing the applicability of materials to be optimized. The charge-transport mechanism is explained by direct experimental evidence with a very well supported theoretical model.
Electrolytes as nanostructured materials are very attractive for batteries or other types of electronic devices. (PEO)8ZnCl2 polymer electrolytes and nanocomposites (PEO)8ZnCl2/TiO2 were prepared from PEO and ZnCl2 and with addition of TiO2 nanograins. The influence of TiO2 nanograins was studied by small-angle X-ray scattering (SAXS) simultaneously recorded with wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) at the synchrotron ELETTRA. It was shown by previous impedance spectroscopy (IS) that the room temperature conductivity of nanocomposite polymer electrolyt…
Five parameters of a model of a polymer electrolyte membrane fuel cell cathode (the porosity of the gas diffusion layer, the porosity of the catalyst layer, the exchange current density of the oxygen reduction reaction, the effective ionic conductivity of the electrolyte, and the ratio of the effective diffusion coefficient of oxygen in a flooded spherical agglomerate particle to the squared particle radius) were determined by the least square fitting of experimental polarization curves. The values of parameters obtained in this work indicate that ionic conduction and gas-phase transport are t…
Blend solid polymer electrolyte based on PEO, PVP complexed with lithium LiBOB were synthesized by solution cast technique and impact of LiBOB on the morphology, structure, and electrochemical properties is examined. The XRD and FESEM analysis reveals the enhancement of amorphous content on salt addition. The FTIR spectroscopy evidences the complex formation. The ionic conductivity for optimized system was two order higher than salt free system, i.e. ~0.5x10-5 S cm-1 (@RT) and increases to ~0.65 mS cm-1 (@100 oC) for O/Li=16 and temperature dependent conductivity follows Arrhenius nature. The …
Correlated anion and cation motion can significantly reduce the overall ion conductivity in electrolytes versus the ideal conductivity calculated based on the diffusion constants alone. Using coarse-grained molecular dynamics simulations, we calculate conductivity and the degree of uncorrelated ion motion in salt-doped homopolymers and block copolymers as a function of concentration and interaction strengths. Calculating conductivity from ion mobility under an applied electric field increases accuracy versus the typical use of fluctuation dissipation relationships in equilibrium simulations. I…
The free standing solid polymer nanocomposite films has been prepared through standard solution cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X Ray diffraction studies clearly reflect the formation of complex formation as no corresponding salt peak appeared in the diffractograms. The FTIR analysis suggested a clear and convincing evidence of polymer ion, ion ion and polymer ion nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte…
We report electrical characterization of monolayer molybdenum disulfide (MoS2) devices using a thin layer of polymer electrolyte consisting of poly(ethylene oxide) (PEO) and lithium perchlorate (LiClO4) as both a contact-barrier reducer and channel mobility booster. We find that bare MoS2 devices (without polymer electrolyte) fabricated on Si/SiO2 have low channel mobility and large contact resistance, both of which severely limit the field-effect mobility of the devices. A thin layer of PEO/ LiClO4 deposited on top of the devices not only substantially reduces the contact resistance but also …
Hybrid electrolyte materials comprising polymer-ionic salt matrixes embedded with garnet particles constitute a promising class of materials for the realization of all-solid-state batteries. In addition to providing solutions to the safety issues inherent to current liquid electrolytes, hybrid polymer electrolytes offer advantages over other solid-state electrolytes. This is because their functional properties such as ionic conductivity, electrochemical stability, mechanical and thermal properties can be tailored to a particular application by independently optimizing the properties of the con…
Solid polymer electrolytes (SPE) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li-ion conductivity remains a barrier to technological viability. SPEs are designed to maximize Li-ion diffusivity relative to the anion, while maintaining sufficient salt solubility. It is thus remarkable that polyethylene oxide (PEO), the most widely used SPE, exhibits Li-ion diffusivity that is an order of magnitude smaller than that of typical counter-ions, such as TFSI, at moderate salt concentrations. Here, we show that Lewis-basic polymers like PEO in…
A free standing transparent film of solid state polymer electrolyte based on PEO/PAN + NaPF6 with different compositions of nano sized TiO2 in weight percent (x = 0, 1, 2, 5, 10, 15, 20 ) is synthesized by using standard solution cast technique. The homogeneous surface of above polymer composition is examined by FESEM. The microscopic interaction among polymer, salt and nanoceramic filler has been analyzed by Fourier Transformed Infra-Red (FTIR) spectroscopy. The reduction of ion pair formation in polymeric separator is clearly observed on addition of nanofiller in the polymer salt complex fil…
We report the ion transport mechanisms in succinonitrile (SN) loaded solid polymer electrolytes containing polyethylene oxide (PEO) and dissolved lithium bis(trifluoromethane)sulphonamide (LiTFSI) salt using molecular dynamics simulations. We investigated the effect of temperature and loading of SN on ion transport and relaxation phenomenon in PEO-LiTFSI electrolytes. It is observed that SN increases the ionic diffusivities in PEO-based solid polymer electrolytes and makes them suitable for battery applications. Interestingly, the diffusion coefficient of TFSI ions is an order of magnitude hig…
Polymer electrolytes are promising candidates for the next generation lithium-ion battery technology. Large scale screening of polymer electrolytes is hindered by the significant cost of molecular dynamics (MD) simulation in amorphous systems: the amorphous structure of polymers requires multiple, repeated sampling to reduce noise and the slow relaxation requires long simulation time for convergence. Here, we accelerate the screening with a multi-task graph neural network that learns from a large amount of noisy, unconverged, short MD data and a small number of converged, long MD data. We achi…
We investigate ion and polymer dynamics in polymer electrolytes PPO-LiClO4 performing 2H and 7Li NMR line-shape analysis. Comparison of temperature dependent 7Li and 2H NMR spectra gives evidence for a coupling of ion and polymer dynamics. 2H NMR spectra for various salt concentrations reveal a strong slow down of the polymer segmental motion when the salt content is increased. The 2H NMR line shape further indicates that the segmental motion is governed by dynamical heterogeneities. While the width of the distribution of correlation times G(log tau) is moderate for low and high salt content, …
We report the development of redox-active conjugated polymers with potential application to electrochemical energy storage. Side chain engineering enables processing of the polymer electrodes from solution, stability in aqueous electrolytes and efficient transport of ionic and electronic charge carriers. We synthesized a 3,3' dialkoxybithiophene homo polymer (p type polymer) with glycol side chains and prepared naphthalene 1,4,5,8-tetracarboxylic-diimide-dialkoxybithiophene (NDI gT2) copolymers (n type polymer) with either a glycol or zwitterionic side chain on the NDI unit. For the latter, we…
A safe lithium-sulfur (Li-S) battery employs a composite polymer electrolyte based on a poly(ethylene glycol) dimethyl ether (PEGDME) solid at room temperature. The electrolyte membrane enables a stable and reversible Li-S electrochemical process already at 50°C, with low resistance at the electrode/electrolyte interphase and fast Li+ transport. The relatively low molecular weight of the PEGDME and the optimal membrane composition in terms of salts and ceramic allow a liquid-like Li-S conversion reaction by heating at moderately high temperature, still holding the solid-like polymer state of t…
A carbon corrosion model is developed based on the formation of surface oxides on carbon and platinum of the polymer electrolyte membrane fuel cell electrode. The model predicts the rate of carbon corrosion under potential hold and potential cycling conditions. The model includes the interaction of carbon surface oxides with transient species like OH radicals to explain observed carbon corrosion trends under normal PEM fuel cell operating conditions. The model prediction agrees qualitatively with the experimental data supporting the hypothesis that the interplay of surface oxide formation on c…
Present paper reports, the structural, microstructural, electrical, dielectric properties and ion dynamics of a sodium based solid polymer electrolyte films comprising of PEO8-NaPF6+ x wt. % SN. The structural and surface morphology properties have been investigated by XRD and FESEM. Different microscopic interaction among the polymer, salt and SN have been analyzed through FTIR. The dielectric permittivity and loss tangent enable us to estimate the dc conductivity, dielectric strength, double layer capacitance, and relaxation time. The loss tangent relaxation peak shifts towards high-frequenc…
The PEO3:LiCF3SO3 polymer electrolyte has attracted significant research due to its enhanced stability at the lithium/polymer interface of high conductivity polymer batteries. Experimental studies have shown that, depending on the preparation conditions, both the PEO3:LiCF3SO3 crystalline complex and the PEO3:LiCF3SO3 amorphous phase can be formed. However, previous theoretical investigations focused on the short chain amorphous PEO3:LiCF3SO3 system. We report ab initio density-functional-theory calculations of crystalline PEO3:LiCF3SO3. The calculated results about the bonding configuration, …
We report the study of graphene devices in Hall-bar geometry, gated with a polymer electrolyte. High densities of 6 $\times 10^{13}/cm^{2}$ are consistently reached, significantly higher than with conventional back-gating. The mobility follows an inverse dependence on density, which can be correlated to a dominant scattering from weak scatterers. Furthermore, our measurements show a Bloch-Grüneisen regime until 100 K (at 6.2 $\times10^{13}/cm^{2}$), consistent with an increase of the density. Ubiquitous in our experiments is a small upturn in resistivity around 3 $\times10^{13}/cm^{2}$, whose …
Lithium salts with low coordinating anions like bis(trifluoromethanesulfonyl)imide (TFSI) have been the state-of-the-art for PEO-based 'dry' polymer electrolytes for three decades. Plasticizing PEO with TFSI-based ionic liquids (ILs) to form ternary solid polymer electrolytes (TSPEs) increases conductivity and Li$^+$ diffusivity. However, the Li$^+$ transport mechanism is unaffected compared to their 'dry' counterpart and essentially coupled to the dynamics of the polymer host matrix, which limits Li$^+$ transport improvement. Thus, a paradigm shift is hereby suggested: The utilization of more…
Ionic transport processes govern performance in many classic and emerging devices, ranging from battery storage to modern mixed-conduction electrochemical transistors. Here, we study local ion transport dynamics in polymer films using time-resolved electrostatic force microscopy (trEFM). We establish a correspondence between local and macroscopic measurements using local trEFM and macroscopic electrical impedance spectroscopy (EIS). We use polymer films doped with lithium bis(trifluoromethane)sulfonimide (LiTFSI) as a model system where the polymer backbone has oxanorbornenedicarboximide repea…
We use 2H NMR stimulated-echo spectroscopy to measure two-time correlation functions characterizing the polymer segmental motion in polymer electrolytes PPO-LiClO4 near the glass transition temperature Tg. To investigate effects of the salt on the polymer dynamics, we compare results for different ether oxygen to lithium ratios, namely, 6:1, 15:1, 30:1 and infinity. For all compositions, we find nonexponential correlation functions, which can be described by a Kohlrausch function. The mean correlation times show quantitatively that an increase of the salt concentration results in a strong slow…
Ionic liquid gating has been used to modify properties of layered transition metal dichalcogenides (TMDCs), including two-dimensional (2D) crystals of TMDCs used extensively recently in the device work, which has led to observations of properties not seen in the bulk. The main effect comes from the electrostatic gating due to strong electric field at the interface. In addition, ionic liquid gating also leads to ion intercalation when the ion size of gate electrolyte is small compared to the interlayer spacing of TMDCs. However, the microscopic processes of ion intercalation have rarely been ex…
Morphology of polymer electrolytes membranes (PEM), e.g., Nafion, inside PEM fuel cell catalyst layers has significant impact on the electrochemical activity and transport phenomena that determine cell performance. In those regions, Nafion can be found as an ultra-thin film, coating the catalyst and the catalyst support surfaces. The impact of the hydrophilic/hydrophobic character of these surfaces on the structural formation of the films has not been sufficiently explored yet. Here, we report about Molecular Dynamics simulation investigation of the substrate effects on the ionomer ultra-thin …
Synergetic Enhancement on Bulk and Grain Boundary Ionic Conduction of Mg Doped High-Entropy NASICON-Type Solid Electrolyte for Solid-State Na+ Batteries by Spray Flame Synthesis
In the development of low cost, sustainable, and energy-dense batteries, chloride-based compounds are promising catholyte materials for solid-state batteries owing to their high Na-ion conductivities and oxidative stabilities. The ability to further improve Na-ion conduction, however, requires an understanding of the impact of long-range and local structural features on transport in these systems. In this study, we leverage different synthesis methods to control polymorphism and cation disorder in Na-Y-Zr-Cl solid electrolytes and interrogate the impact on Na-ion conduction. We demonstrate the…
We report the development of graphite-based solar cells using a simple method and low cost materials. Suspension of graphite powder in mineral water was simply dropped onto the surface of fluorine-doped tin oxide glass (FTO) to form a thick film. Surprisingly, using mineral waters greatly improved the efficiency of the solar cell to reach the highest efficiency of 6.97%. Due to some minerals contained, the mineral water induced the development of fibrous structure between the graphite particles which is assumed to play a role as a bridge for the photoexcited electrons to quickly move to the el…
Electrical conductivity of dry, slow cooled (AgPO$_3$)$_{1-x}$(AgI)$_x$ glasses is examined as a function of temperature, frequency and glass composition. From these data compositional trends in activation energy for conductivity E$_A$(x), Coulomb energy E$_c$(x) for Ag$^+$ ion creation, Kohlrausch stretched exponent $β$(x), low frequency ($\varepsilon_s$(x)) and high-frequency ($\varepsilon_\infty$(x)) permittivity are deduced. All parameters except E$_c$(x) display two compositional thresholds, one near the stress transition, x = x$_c$(1)= 9%, and the other near the rigidity transition, x = …
Solid polymer electrolytes are considered a promising alternative to traditional liquid electrolytes in energy storage applications because of their good mechanical properties, and excellent thermal and chemical stability. A gap, however, still exists in understanding ion transport mechanisms and improving ion transport in solid polymer electrolytes. Therefore, it is crucial to bridge composition--structure and structure--property relationships. Here we demonstrate that size asymmetry, $λ$, represented by the ratio of counterion to charged monomer size, plays a key role in both the nanostructu…
Interfacial thermal transport between electrodes and polymer electrolytes can play a crucial role in the thermal management of solid-state lithium-ion batteries (SLIBs). Modifying the electrode surface with functional molecules can effectively increase the interfacial thermal conductance (ITC) between electrodes and polymers (e.g., electrolytes, separators); however, how they influence the interfacial thermal transport in SLIBs during charge/discharge remains unknown. In this work, we conduct molecular dynamics (MD) simulations to investigate the ITC between charged electrodes and solid-state …
As the periodicity in crystalline materials creates the optimal condition for electronic delocalization, one might expect that in partially crystalline conjugated polymers delocalization is impeded by intergrain transport. However, for the best conducting polymers this presumption fails. Delocalization is obstructed by interchain rather than intergrain charge transfer and we propose a model of weakly coupled disordered chains to describe the physics near the metal-insulator transition. Our quantitative calculations match the outcome of recent broad-band optical experiments and provide a consis…
This work presents a scalable method to produce robust all-solid electric double layer capacitors (EDLCs), compatible with roll-to-roll processes and structural laminate composite fabrication. It consists in sandwiching and pressing an ionic liquid (IL) based polymer electrolyte membrane between two CNT fiber sheet electrodes at room temperature, and laminating with ordinary plastic film. This fabrication method is demonstrated by assembling large area devices of up to 100 cm2 with electrodes fabricated in-house, as well as with commercial CNT fiber sheets. Free-standing flexible devices opera…
We present first-principles band calculations as well as structural optimization of the orthorhombic K$_1$C$_{60}$ polymerized phase. We found three-dimensional inter-fullerene bonding/anti-bonding characters consisting of $t_{1u}$ molecular orbitals with $p$-like symmetry in the conduction bands. The formation of the four-membered ring connecting the fullerenes lifts the $p_x$ band from the continuous $p_y$-$p_z$ band, where the z-axis is parallel to the chain. The asymmetry between $p_x$ and $p_y$ may play an important role in binding the chains with the rotational configuration proposed by …
As human activities expand into naturally or man-made radiation-prone environment, the need for radiation-hardened (Rad-Hard) electronic hardware surged. The state-of-the-art silicon-based and two-dimensional (2D) materials based Rad-Hard transistors can withstand up to 1 Mrad (Si) of total ionization dose (TID), while higher TID tolerance is being heatedly sought after. Here we present few-layer MoS$_2$ Rad-Hard field-effect transistors (FETs) with polymer solid electrolyte (PSE) gate dielectrics. The MoS$_2$ PSE-FETs exhibit a TID tolerance of up to 3.75 Mrad (Si) at a dose rate of 523 rad (…
We propose a microscopic, first-principles description of the ionic conduction in crystals. This formalism allows us to gain new insights into the ideal characteristics of general ionic conducting materials and, in particular, solid electrolytes. Using \textit{ab initio} calculations, we show that our formalism results in ionic mobilities consistent with experiments for several materials. Our work opens the possibility of developing solid electrolytes based on fundamental physical principles rather than empirical descriptions of the underlying processes.
