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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
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↗
NASA NTRS2003

Annealing Would Improve beta" - Alumina Solid Electrolyte

A pre-operational annealing process is under investigation as a potential means of preventing a sudden reduction of ionic conductivity in a Beta"-alumina solid electrolyte (BASE) during use. On the basis of tests, the sudden reduction of ionic conductivity, followed by a slow recovery, has been found to occur during testing of the solid electrolyte and electrode components of an alkali metal thermal-to-electric converter (AMTEC) cell. At this time, high-temperature tests of limited duration have indicated the superiority of the treated BASE, but reproducible tests over thousands of hours are necessary to confirm that microcracking has been eliminated. The ionic conductivity of the treated BASE is also measured to be higher than untreated BASE at 1,073 K in low-pressure sodium vapor. Microcracking resulting in loss of conductivity was not observed with treated BASE in one high-temperature experiment, but this result must be duplicated over very long testing times to be sure of the effect. Shorter annealing times (10 to 20 hours) were found to result in significantly less loss of mass; it may be necessary for the packed powder mixture to evolve some Na2O before the Na2O can leave the ceramic.

Williams, Roger↗
DOE OSTI2015

LiF dissolution by anion-binding-agent in LiCF x battery systems: Lower ohmic and interfacial resistance.

In this paper we will discuss our preliminary thermal and electrochemical data aimed at developing a robust nonflammable Li-CFx cell capable of wide temperature operation. To accomplish this goal, we are evaluating a thermally stable solvent comprised of an anion binding agent (ABA) and lithium fluoride (LiF), typically at a 1:1 molar ratio. In conventional carbonate based electrolytes, ABA is soluble while LiF remains insoluble. However, the neutral ABA solubilizes LiF and forms a salt complex represented as Li+(ABAF-). We are exploiting this unique feature and apply this strategy to CFx chemistry to improve cell performance, due to the CFx cell chemistry generating LiF as discharge product. Continuous solvation of the salt mixture during discharge allows for utilization of electrolytes initially containing sub stoichiometric amount of LiF. The practical benefits are reduced cell weight, mitigation of electrode fouling, and consequently better low temperature performance. Electrolytes containing dimethyl methyl phosphonate (DMMP), 1M tris(pentafluorophenyl) borane (TPFB) and varying concentrations of LiF (1M; 0.5M and 0.1M) were prepared and characterized for ionic conductivity and voltage stability. In general, ionic conductivity decreases with decreasing LiF concentration. The room temperature conductivity for the DMMP 1M TPFB:1M LiF is ~ 9mS/cm and ~3mS/cm for the 1M TPFB:0.1M LiF. Unlike the conductivity, the electrochemical voltage stability did not vary substantially with LiF concentration and the electrolytes showed a stable voltage window in the range 0-3.5V vs. Li + /Li, which is substantially wider than the Li-CFx cell voltage. Flammability measurement performed at our thermal abuse facility demonstrated that the electrolyte was nonflammable. Discharge performance of CFx materials obtained from several vendors was evaluated in 2032 coin cells at room temperature. Experimental results demonstrate a reduction in ohmic resistance and interfacial resistance during discharge for a cell containing lower concentrations of added LiF compared to ABA. These observations are a direct demonstration that the unbound ABA in the electrolyte dissolves the LiF generated in the discharge reaction.

25 ENERGY STORAGE↗
DOE OSTI2026

Origins of Enhanced Ion Transport in Nanostructured Anion-Conducting Polyelectrolytes

Ion-conducting polymer chemistry and microstructure profoundly impact membrane water uptake and ionic conductivity. Water uptake strongly impacts ionic conductivity; yet excess water uptake compromises ion-exchange membrane mechanical properties. Although nanophase separation has been proposed to overcome this trade-off, it is unclear how polymer backbone architecture governs ionic nanostructure and its subsequent impact on water uptake and conductivity. Here, we integrate experiments and molecular dynamics simulations to elucidate the role of backbone chemistry in governing ionic nanostructure, hydration behavior, and ion transport in anion-conducting polyelectrolytes (ACPs). We systematically investigate hydrocarbon polynorbornene (PNB)-based ACPs with three distinct backbone architectures: vinyl-addition polymerization (VAP), ring-opening metathesis polymerization (ROMP), and hydrogenated ROMP. While maintaining comparable ion exchange capacities (IECs) and identical side-chain chemistry, we isolate the effects of backbone structure. We show that nanophase-separated ionic nanostructures originate in the dry state and evolve upon hydration through heterogeneous water uptake, with water preferentially partitioning into ion-rich domains. This nanophase separation arises from a delicate interplay between ionic segregation propensity and the entropic barrier imposed by backbone stiffness. Specifically, flexible backbones intensify attractive ion–ion interactions by reducing the entropic penalty for backbone deformation, promoting nanophase separation, while rigid backbones suppress ionic nanostructure formation. Nanophase-separated ion domains locally concentrate water upon hydration, which in turn enables the connectivity required for fast transport at lower water concentration values. Furthermore, these findings demonstrate that backbone chemistry can be tuned as a design lever to promote nanophase separation and enhance ion transport without excessive water uptake.

Anions↗
DOE OSTI2017

Nanostructured Conductive Polymer Gels as a General Framework Material To Improve Electrochemical Performance of Cathode Materials in Li-Ion Batteries

Controlling architecture of electrode composites is of particular importance to optimize both electronic and ionic conduction within the entire electrode and improve the dispersion of active particles, thus achieving the best energy delivery from a battery. Electrodes based on conventional binder systems that consist of carbon additives and nonconductive binder polymers suffer from aggregation of particles and poor physical connections, leading to decreased effective electronic and ionic conductivities. Here we developed a three-dimensional (3D) nanostructured hybrid inorganic-gel framework electrode by in situ polymerization of conductive polymer gel onto commercial lithium iron phosphate particles. This framework electrode exhibits greatly improved rate and cyclic performance because the highly conductive and hierarchically porous network of the hybrid gel framework promotes both electronic and ionic transport. In addition, both inorganic and organic components are uniformly distributed within the electrode because the polymer coating prevents active particles from aggregation, enabling full access to each particle. The robust framework further provides mechanical strength to support active electrode materials and improves the long-term electrochemical stability. The multifunctional conductive gel framework can be generalized for other high-capacity inorganic electrode materials to enable high-performance lithium ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Influence of Water Transport Across Microscale Bipolar Interfaces on the Performance of Direct Borohydride Fuel Cells

Direct borohydride fuel cells (DBFCs) can operate at double the voltage of proton exchange membrane fuel cells (PEMFCs) by employing an alkaline NaBH 4 fuel feed and an acidic H 2 O 2 oxidant feed. The pH-gradient-enabled microscale bipolar interface (PMBI) facilitates the creation and maintenance of an alkaline environment at the anode and an acidic environment at the cathode for the borohydride oxidation and peroxide reduction reactions. However, given the need to dissociate water at the interface to ensure ionic conduction, PMBI can be efficient only when anion exchange ionomer (AEI) moieties enable fast water transport for autoprotolysis. Herein, a series of polynorbornene-based AEIs with a range of water uptake values are examined to unravel the optimum water uptake required to enable high performance DBFCs. The DBFC with PMBI configuration containing the optimal AEI composition delivers a current density of 302 mA cm –2 at 1.5 V and a peak power density of 580 mW cm –2 at 1 V. This AEI composition exhibits high hydroxide ionic conductivity of 90.7 mS cm –1 at 80 °C with an IEC of 2.01 mequiv g –1 and demonstrates impressive chemical stability by retaining 98.75% of its initial ionic conductivity after immersion into anolyte (3 M KOH and 1.5 M NaBH 4 ) at 70 °C for 536 h.

25 ENERGY STORAGE↗
DOE OSTI2012

Effect of Gd dopant concentration on the defect engineering in ceria nanostructures

Graphical abstract: Display Omitted Highlights: ► Investigates the ionic conductivity of defect engineered Gd doped nano scale ceria. ► Reveals that there exists an optimum concentration of dopant to engineer ceria with large O{sub 2} vacancies. ► For the first time the Nanosponge morphology observed in the Gd doped nanoceria. ► It is observed that 5% of Gd in ceria is optimum to induce appropriate amount of defects. ► Thereby an enhanced ionic conductivity is achieved in 5% Gd doped ceria. -- Abstract: In this study, the fabrication and characterization of pure and gadolinium (Gd) doped ceria nanostructures (Ce{sub 1−x}Gd{sub x}O{sub 2−δ} where x = 0.05, 0.1 and 0.2) are investigated. The origin of defect formation has been systematically investigated by XRD and UV-Visible Raman. All the fabricated ceria are found to be “Nanosponge” morphology which is observed by using FESEM technique. The charge transfer of O{sup 2−} ions and Ce{sup 3+}/Ce{sup 4+} in the ceria host due to these defect structures are studied by UV–DRS. Impedance analysis is showed an enhanced ionic conductivity for 5% Gd doped ceria compared to other concentration of Gd, revealing that the dopant concentration is a critical parameter in engineering a large number of vacancy defects in ceria nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Triple ionic–electronic conducting oxides for next-generation electrochemical devices

Triple ionic–electronic conductors (TIECs) are materials that can simultaneously transport electronic species alongside two ionic species. The recent emergence of TIECs provides intriguing opportunities to maximize performance in a variety of electrochemical devices, including fuel cells, membrane reactors and electrolysis cells. However, the potential application of these nascent materials is limited by lack of fundamental knowledge of their transport properties and electrocatalytic activity. The goal of this Review is to summarize and analyse the current understanding of TIEC transport and electrochemistry in single-phase materials, including defect formation and conduction mechanisms. In this work, we particularly focus on the discovery criteria (for example, crystal structure and ion electronegativity), design principles (for example, cation and anion substitution chemistry) and operating conditions (for example, atmosphere) of materials that enable deliberate tuning of the conductivity of each charge carrier. Lastly, we identify important areas for further advances, including higher chemical stability, lower operating temperatures and discovery of n-type TIEC materials.

25 ENERGY STORAGE↗
DOE OSTI2023

Fluorine-Substituted Lithium Chloride Solid Electrolytes for High-Voltage All-Solid-State Lithium-Ion Batteries

Lithium ternary halides are promising solid electrolytes, owing to their high ionic conductivity and reasonably high oxidative and chemical stability. Recently, fluorine substitution in Li 3 MCl 6 has been suggested as a promising approach for further enhancing oxidation stability. Accordingly, this study outlines a material design strategy for F-substituted Li 3 MCl 6 through systematic theoretical analyses. Calculations reveal that the mixing limit of F in Li 3 MCl 6–x F x is in the range of 0.5–1.5, and the resulting Li 3 MCl 6–x F x phases can retain ionic conductivity above 1 mS/cm up to x = 1.0. Additionally, the calculations also predict that the formation of F-containing passivating phases could increase the oxidation potential for Li3MCl5F to ~6.3 V. The proposed material design strategy is validated through the synthesis of Li 3 YCl 5 F, which is confirmed to show both high ionic conductivity and enhanced oxidation stability. The design guidelines presented herein can accelerate the potential use of halide-based electrolyte chemistries in high-voltage all-solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2016

A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life

Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na + ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm –1 at 25°C and 14 ms cm –1 at 80°C.

25 ENERGY STORAGE↗