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At least 343 records · Page 19
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DOE OSTI2024

Ionic Thermoelectric Generators in Vertical and Planar Topologies Based on Fluorinated Polymer Hybrid Materials with Ionic Liquids

Abstract Ionic thermoelectrics (TEs), in which voltage generation is based on ion migration, are suitable for applications based on their low cost, high flexibility, high ionic conductivity, and wide range of Seebeck coefficients. This work reports on the development of ionic TE materials based on the poly(vinylidene fluoride‐trifluoroethylene), Poly(VDF‐co‐TrFE), as host polymer blended with different contents of the ionic liquid, IL, 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI]. The morphology, physico‐chemical, thermal, mechanical, and electrical properties of the samples are evaluated together with the TE response. It is demonstrated that the IL acts as a nucleating agent for polymer crystallization. The mechanical properties and ionic conductivity values are dependent on the IL content. A high room temperature ionic conductivity of 0.008 S cm −1 is obtained for the sample with 60 wt% of [EMIM][TFSI] IL. The TE properties depend on both IL content and device topology‐vertical or planar‐the largest generated voltage range being obtained for the planar topology and the sample with 10 wt% of IL content, characterized by a Seebeck coefficient of 1.2 mV K −1 . Based on the obtained maximum power density of 4.9 µW m −2 , these materials are suitable for a new generation of TE devices.

Pereira, Nelson↗
DOE OSTI2024

Amorphous Oxyhalide Matters for Achieving Lithium Superionic Conduction

The recently surged halide-based solid electrolytes (SEs) are great candidates for high-performance all-solid-state batteries (ASSBs), due to their decent ionic conductivity, wide electrochemical stability window, and good compatibility with high-voltage oxide cathodes. In contrast to the crystalline phases in halide SEs, amorphous components are rarely understood but play an important role in Li-ion conduction. Here, we reveal that the presence of amorphous component is common in halide-based SEs that are prepared via mechanochemical method. The fast Li-ion migration is found to be associated with the local chemistry of the amorphous proportion. Taking Zr-based halide SEs as an example, the amorphization process can be regulated by incorporating O, resulting in the formation of corner-sharing Zr–O/Cl polyhedrons. This structural configuration has been confirmed through X-ray absorption spectroscopy, pair distribution function analyses, and Reverse Monte Carlo modeling. The unique structure significantly reduces the energy barriers for Li-ion transport. As a result, an enhanced ionic conductivity of (1.35 ± 0.07) × 10 –3 S cm –1 at 25 °C can be achieved for amorphous Li 3 ZrCl 4 O 1.5 . In addition to the improved ionic conductivity, amorphization of Zr-based halide SEs via incorporation of O leads to good mechanical deformability and promising electrochemical performance. In conclusion, these findings provide deep insights into the rational design of desirable halide SEs for high-performance ASSBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl

Li 2 OHCl is an exemplar of the antiperovskite family of ionic conductors, for which high ionic conductivities have been reported, but in which the atomic-level mechanism of ion migration is unclear. The stable phase is both crystallographically defective and disordered, having similar to 1/3 of the Li sites vacant, while the presence of the OH(- )anion introduces the possibility of rotational disorder that may be coupled to cation migration. In this work, complementary experimental and computational methods are applied to understand the relationship between the crystal chemistry and ionic conductivity in Li 2 OHCl , which undergoes an orthorhombic to cubic phase transition near 311 K (approximate to 38 degrees C) and coincides with the more than a factor of 10 change in ionic conductivity (from 1.2 x 10 -5 mS/cm at 37 degrees C to 1.4 x 10 -3 mS/cm at 39 degrees C). X ray and neutron experiments conducted over the temperature range 20-200 degrees C, including diffraction, quasi-elastic neutron scattering (QENS), the maximum entropy method (MEM) analysis, and ab initio molecular dynamics (AIMD) simulations, together show conclusively that the high lithium ion conductivity of cubic Li2OHCl is correlated to "paddlewheel" rotation of the dynamic OH - anion. The present results suggest that in antiperovskites and derivative structures a high cation vacancy concentration combined with the presence of disordered molecular anions can lead to high cation mobility.

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

First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF

The formation mechanism and composition of the solid electrolyte interphase (SEI) in lithium ion batteries has been widely explored. However, relatively little is known about the function of the SEI as a transport medium. Such critical information is directly relevant to battery rate performance, power loss, and capacity fading. To partially bridge this gap in the case of inorganic SEI compounds, we report herein the results of first-principles calculations on the defect thermodynamics, the dominant diffusion carriers, and the diffusion pathways associated with crystalline LiF and NaF, which are stable components of the SEI in Li-ion and Na-ion batteries, respectively. The thermodynamics of common point defects are computed, and the dominant diffusion carriers are determined over a voltage range of 0-4 V, corresponding to conditions relevant to both anode and cathode SEI's. Our analyses reveal that for both compounds, vacancy defects are energetically more favorable, therefore form more readily than interstitials, due to the close-packed nature of the crystal structures. However, the vacancy concentrations are very small for the diffusion processes facilitated by defects. Ionic conductivities are calculated as a function of voltage, considering the diffusion carrier concentration and the diffusion barriers as determined by nudged elastic band calculations. These conductivities are more than ten orders of magnitude smaller in NaF than in LiF. As compared to the diffusivity of Li in other common inorganic SEI compounds, such as Li2CO3 and Li2O,the cation diffusivity in LiF and NaF is quite low, with at least three orders of magnitude lower ionic conductivities. The results quantify the extent to which fluorides pose rate limitations in Li and Na batteries.

Yildirim, Handan↗
DOE OSTI2017

Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes

Block copolymer electrolytes (BCEs) represent an attractive choice as solid-state ionic conductors for electrochemical technologies used in energy storage and conversion, water treatment, sensors, and data storage and processing. Unlocking the maximum ionic conductivity of BCEs requires an intimate understanding as to how the microphase separated structure influences transport properties. However, elucidating such knowledge remains elusive due to the challenging task of precisely engineering BCEs with a defined structure in bulk materials. In this work, we examined BCEs in a thin film format because it was amenable to attaining BCEs with a desired nanostructure. Specifically, we systematically investigated anion-conducting BCEs with different degrees of connectivity of the ionic domains. For the first time, we demonstrate that increasing terminal defects in the ionic domain from 1 terminal defect per mu m(2) to 20 terminal defects per mu m(2) ( a relatively small amount of defects) decreased ionic conductivity by 67% compared to the maximum value attained. Conversely, maximizing ionic domain connectivity increased the ionic conductivity by two-fold over a non-ordered BCE film. These experiments highlight that microphase separation alone was insufficient for ameliorating ionic conductivity in BCEs. Rather, microphase separation coupled with complete ionic domain connectivity realized BCEs with significantly enhanced ionic conductivity.

Arges, Christopher G. (ORCID:0000000317038323)↗
DOE OSTI2012

Nanoscale Thin Film Electrolytes for Clean Energy Applications

Ceria and zirconia based systems can be used as electrolytes to develop solid oxide fuel cells for clean energy production and to prevent air pollution by developing efficient, reliable oxygen sensors. In this study, we have used oxygen plasma assisted molecular beam epitaxy (OPA-MBE) to grow samaria doped ceria (SDC), to understand the role of dopant concentration and geometry of the films towards the ionic conduction in these thin films. We have also discussed the Gd doped CeO2 (GDC) and Gd stabilized ZrO2 (GSZ) multi-layer thin films to investigate the effect of interfacial phenomena on the ionic conductivity of these hetero-structures. We found the optimum concentration to be 15 mol % SmO1.5, for achieving lowest electrical resistance in SDC thin films. The electrical resistance decreases with the increase in film thickness up to 200 nm. The results demonstrate the usefulness of this study towards establishing an optimum dopant concentration and choosing an appropriate thin film thickness to ameliorate the conductance of the SDC material system. Furthermore, we have explored the conductivity of highly oriented GDC and GSZ multi-layer thin films, wherein the conductivity increased with an increase in the number of layers. The extended defects and lattice strain near the interfaces increase the density of oxygen vacancies, which leads to enhanced ionic conductivity in multi-layer thin films.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2018

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Improved Single-Ion Conductivity of Polymer Electrolyte via Accelerated Segmental Dynamics

Single-ion conducting polymer electrolytes (SICPEs) have many advantages for solid-state battery applications, while low conductivities remain the bottleneck for their practical applications. In this paper, a strategy that can significantly improve the ionic conductivity of SICPEs based on the concept of accelerated segmental dynamics was demonstrated by the evaluation of the thermal property, rheological behavior, morphology analysis, molecular dynamics simulation, and conductivity performance. With both “soft” poly(dimethylsiloxane) (PDMS) backbone and poly(ethylene glycol) (PEG) side chains, the obtained SICPE possesses faster segmental relaxation and higher lithium-ion conductivity. With lithium “transference” number close to unity, the obtained SICPE also shows excellent electrochemical stability against lithium metal electrodes. The clear relationship established between the segmental dynamics of polymer electrolyte and its ionic conductivity should contribute to achieve a solid electrolyte with improved ionic conductivity toward the next-generation solid-state battery.

Segmental Dynamics↗
DOE OSTI2022

Refined Classical Force Field for Choline Chloride and Ethylene Glycol Mixtures over Wide Composition Range

In this work, a classical force field based on the General Amber Force Field (GAFF) was refined for the simulation of choline chloride (ChCl) and ethylene glycol (EG) mixtures over a wide composition range by scaling the partial charges and van der Waals parameters. The scaling factors were derived by fitting the simulation results to only eight experimental density and viscosity data points of pure EG, and ChCl/EG mixtures at 1:2, 1:4, and 1:6 molar ratios. Using the refined force field, properties essential for electrochemical applications such as density, viscosity, self-diffusion coefficient, and ionic conductivity were calculated, and excellent agreement to experimental results was found even for compositions and temperatures not used in the fitting procedure. In addition, new experimental data for density, viscosity, and ionic conductivity are reported as a function of temperature and composition for this mixture. To the best of our knowledge, this is the first classical force field developed for the study of ChCl/EG mixtures over a composition range that includes the eutectic point. Using the new model, the liquid dynamics was studied in terms of ionic conductivity. It was found that the dynamics in ChCl/EG mixtures with ChCl mole fraction higher than 20% is similar to that of ionic liquids, high temperature molten salts, and highly concentrated water-in-salt electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2021

Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces

Recently, the interest in charged polymers has been rapidly growing due to their uses in energy storage and transfer devices. Yet, polymer electrolyte-based devices are not on the immediate horizon because of the low ionic conductivity. In the present study, we developed a methodology to enhance the ionic conductivity of charged block copolymers comprising ionic liquids through the electrostatic control of the interfacial layers. Unprecedented reentrant phase transitions between lamellar and A15 structures were seen, which cannot be explained by well-established thermodynamic factors. X-ray scattering experiments and molecular dynamics simulations revealed the formation of fascinating, thin ionic shell layers composed of ionic complexes. The ionic liquid cations of these complexes predominantly presented near the micellar interfaces if they had strong binding affinity with the charged polymer chains. Therefore, the interfacial properties and concentration fluctuations of the A15 structures were crucially dependent on the type of tethered acid groups in the polymers. Overall, the stabilization energies of the A15 structures were greater when enriched, attractive electrostatic interactions were present at the micellar interfaces. Contrary to the conventional wisdom that block copolymer interfaces act as “dead zone” to significantly deteriorate ion transport, this study establishes a prospective avenue for advanced polymer electrolyte having tailor-made interfaces.

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

Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures

Oxygen vacancies in proximity to surfaces and heterointerfaces in oxide thin film heterostructures have major effects on properties, resulting, for example, in emergent conduction behaviour, large changes in metal-insulator transition temperatures or enhanced catalytic activity. Here we report the discovery of a means of reversibly controlling the oxygen vacancy concentration and distribution in oxide heterostructures consisting of electronically conducting In2O3 films grown on ionically conducting Y2O3-stabilized ZrO2 substrates. Oxygen ion redistribution across the heterointerface is induced using an applied electric field oriented in the plane of the interface, resulting in controlled oxygen vacancy (and hence electron) doping of the film and possible orders-of-magnitude enhancement of the film's electrical conduction. The reversible modified behaviour is dependent on interface properties and is attained without cation doping or changes in the gas environment.

Veal, Boyd W.↗
DOE OSTI2014

Gel polymer electrolytes for batteries

Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at 25.degree. C.

25 ENERGY STORAGE↗
DOE OSTI2014

Electrical, optical and magnetic investigations on LiNiPO{sub 4} based olivines synthesized by solution combustion technique

Highlights: • Solution combustion technique and preparation of nanocrystalline olivine materials. • Olivine type LiNiPO{sub 4} based nanocrystalline materials and characterization. • AC electrical studies on olivine type LiNi{sub 1−x}M{sub x}PO{sub 4}(M = Cu{sup 2+}/Mg{sup 2+})based materials. • Enhancement of ionic conductivity in the nanocrystalline phase of LiNiPO{sub 4} material. - Abstract: Citric acid assisted solution combustion technique is explored for synthesis of supervalent Cu{sup 2+}/Mg{sup 2+} ion doped LiNiPO{sub 4} system. XRD, FT-IR and microscopy studies confirmed the formation of a well crystallized material at low concentration of dopants. Ionic conductivity increases for lower concentrations of dopants due to the increased channel size for Li{sup +} diffusion. Owing to inherent anti-site defects, ionic conductivity decreases with increase of dopant concentration. Magnetic studies are explored for confirmation of antiferromagnetic nature of ions. Wagner polarization method is used to elucidate the negligible contribution of electrons to total conductivity.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ionomer Optimization for Water Uptake and Swelling in Anion Exchange Membrane Electrolyzer: Oxygen Evolution Electrode

Water electrolysis using an anion conductive, solid polymer electrolyte is an attractive method for point-of-use hydrogen production. Recent advances in catalysts and anion exchange membranes (AEM) have made alkaline devices increasingly competitive with their acidic counterparts. However, less attention has been paid to the anion conductive ionomers (ACI) used in the fabrication of electrodes for AEM electrolyzers. The ACI contributes to ion conduction between the catalyst and bulk electrolyte and serves as a binder for adhering the catalyst to the gas diffusion layer and AEM. Ionic conductivity, water uptake and ionomer swelling are critical properties for electrode performance. High ion exchange capacity (IEC) in the ionomer is desired for reduced electrode resistance, however, it can lead to excess water uptake (WU) and disruptive ACI swelling. In this study, a series of poly(norbornene)-based ionomers were synthesized, characterized and used to fabricate oxygen evolving anodes for low-temperature AEM water electrolysis. The IEC of the ionomers (0 to 4.73 meq g −1 ) was adjusted by controlling the ratio of ion conducting to non-ion conducting norbornene monomers in the ACI tetrablock copolymers. Low conductivity ionomers are shown to yield the best-performing oxygen evolution electrodes, in the absence of ACI polymer cross-linking because they do not experience excessive water swelling. Light cross-linking within the anode ACI was used as a means to independently lower WU of the ionomer without compromising ionic conductivity. This control over water swelling allows higher ionic conductivity within the ACI to be used in water-fed electrolyzer applications. Other methods of water management were compared including the use of hydrophobic additives and adjustment of the ionomer concentration in the electrode. As a result, it was shown that the cell performance greatly benefits from a highly conductive ionomer in the oxygen evolution reaction electrode if the WU is managed.

08 HYDROGEN↗
DOE OSTI2018

Ion-transport engineering of alkaline-earth hydrides for hydride electrolyte applications

The heavier alkaline-earth hydrides (AeH 2 ; Ae = Ca, Sr, Ba) are promising materials for hydrogen energy applications, due to their excellent ionic conductivity and thermal stability. We use first-principles calculations to elucidate their defect chemistry and ion-transport mechanisms. Based on calculated formation energies, we find that hydrogen vacancies ( V H ) are present in large concentrations, and hence, transport is vacancy-mediated. The vacancy migration barrier depends strongly on the charge state of the vacancy, with V H + yielding the lowest barriers. The activation energy for ionic transport, which is the sum of the migration barrier and formation energy, can be further reduced by lowering the formation energy of the vacancies. This goal can be achieved by doping with acceptors, such as alkali-metal impurities, which induces larger concentrations of V H + . We show that, with optimized conditions for doping, ionic conductivities can be improved by several orders of magnitude; for BaH 2 , the conductivity is on par with proton conductivity in the best proton-conducting oxides. For BaH 2 , we find K to be the optimal dopant for enhancing conductivity, and for CaH 2 and SrH 2 , we find Na to be optimal. Here, the resulting large ionic conductivity of hydrogen makes the heavier alkaline-earth hydrides strong candidates for electrolytes in hydrogen fuel cells.

08 HYDROGEN↗
DOE OSTI2015

Macroscopic strain controlled ion current in an elastomeric microchannel

We report on the fabrication of an ultra-high aspect ratio ionically conductive single microchannel with tunable diameter from ≈ 20 μm to fully closed. The 4 mm-long channel is fabricated in a Polydimethylsiloxane (PDMS) mold and its cross-sectional area is controlled by applying macroscopic compressive strain to the mold in a direction perpendicular to the channel length. We investigated the ionic conduction properties of the channel. For a wide range of compressive strain up to ≈ 0.27, the strain dependence of the resistance is monotonic and fully reversible. For strain > 0.27, ionic conduction suddenly shuts off and the system becomes hysteretic (whereby a finite strain reduction is required to reopen the channel). Upon unloading, the original behavior is retrieved. This reversible behavior is observed over 200 compression cycles. The cross-sectional area of the channel can be inferred from the ion current measurement, as confirmed by a Nano-Computed Tomography investigation. We show that the cross-sectional area decreases monotonically with the applied compressive strain in the reversible range, in qualitative agreement with linear elasticity theory. We find that the shut-off strain is affected by the spatial extent of the applied strain, which provides additional tunability. Our tunable channel is well-suited for multiple applications in micro/nano-fluidic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Synthesis and characterization of ionic liquid (EMImBF{sub 4})/Li{sup +} - chitosan membranes for ion battery

Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li{sup +} ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anion metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10{sup −2} S cm{sup −1} for chitosan to 1.30 × 10{sup −2} S cm{sup −1} for chitosan with EMImBF4/Li{sup +}, and this result was supported by analysis the surface morphology (SEM)

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

Polyimide-PEG Segmented Block Copolymer Membranes with High Proton Conductivity by Improving Bicontinuous Nanostructure of Ionic Liquid-Doped Films

The structure and properties of segmented block copolymer films of aromatic polyimide (PI) and poly(ethylene glycol) (PEG) doped with an ionic liquid are observed for potential polymer electrolyte membrane applications for fuel cells. Poly(amic acid) precursors of PI-PEG copolymers of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-(1,3-phenylenedioxy) dianiline, and bis(3-aminopropyl) terminated PEG (M n ≈ 1500) are synthesized and then thermally imidized in membrane films, followed by swelling in ethylammonium nitrate (EAN) ionic liquid. The small-angle X-ray scattering results from the EAN-doped PI-PEG copolymer films show disordered bicontinuous phase-separated nanostructures described by Teubner–Strey theory, with the interface fractal dimension determined from the Porod equation. Thermal annealing of the EAN-doped membranes at 100–140 °C results in increased correlation lengths and smoother interfaces of the bicontinuous nanostructures. Such improved nanostructures lead to the increased ionic conductivity by two to five times with the maximum conductivity of 210 mS cm -1 at 60 °C and 70% RH, much greater (nearly fivefold) than that of Nafion films, while maintaining the mechanical stability possibly up to 140 °C. Furthermore, the investigation of the disordered bicontinuous phase-separated nanostructure of EAN-doped PI-PEG copolymer membranes is highly relevant to understanding the nanostructures of hydrated Nafion membranes and segmented block copolymers in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗