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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Fergusonite-type CeNbO{sub 4+δ}: Single crystal growth, symmetry revision and conductivity

Large fergusonite-type (ABO{sub 4}, A=Ce, B=Nb) oxide crystals, a prototype electrolyte composition for solid oxide fuel cells (SOFC), were prepared for the first time in a floating zone mirror furnace under air or argon atmospheres. While CeNbO{sub 4} grown in air contained CeNbO{sub 4.08} as a minor impurity that compromised structural analysis, the argon atmosphere yielded a single phase crystal of monoclinic CeNbO{sub 4}, as confirmed by selected area electron diffraction, powder and single crystal X-ray diffraction. The structure was determined in the standard space group setting C12/c1 (No. 15), rather than the commonly adopted I12/a1. AC impedance spectroscopy conducted under argon found that stoichiometric CeNbO{sub 4} single crystals showed lower conductivity compared to CeNbO{sub 4+δ} confirming interstitial oxygen can penetrate through fergusonite and is responsible for the higher conductivity associated with these oxides. - Graphical abstract: Large fergusonite-type CeNbO{sub 4} crystals were prepared for the first time in a floating zone mirror furnace. Crystal growth in an argon atmosphere yielded a single phase monoclinic CeNbO4, as confirmed by selected area electron diffraction, powder and single crystal X-ray diffraction. The structure was determined in the standard space group setting C12/c1 (No. 15), rather than the commonly adopted I12/a1. AC impedance spectroscopy found CeNbO{sub 4} single crystals showed lower conductivity compared to CeNbO{sub 4+δ} confirming interstitial oxygen can penetrate through fergusonite and is responsible for the higher conductivity associated with these oxides. Highlights: • Preparation of single crystals of CeNbO{sub 4} using a floating zone mirror furnace. • Correction to the crystal symmetry of the monoclinic form of CeNbO{sub 4}. • Report the conductivity of a single crystal of CeNbO{sub 4}.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Synthesis and investigation of proton conductivity for intercalated kaolinite with 4-amidinopyridinium chloride

The proton-conducting materials have potential application in devices such as fuel cells. In this study, a mineral kaolinite-based proton conducting material, kaolinite-4-amidinopyridinium hydrochloride (K-4-APy–HCl), was synthesized by the intercalated compound kaolinite-4-amidinopyridine (K-4-APy) adsorbing volatilizing HCl. The thermogravimetric analysis (TG), powder X-ray diffraction (PXRD) and IR spectrum confirmed the HCl successfully inserting into the interlayer space of kaolinite and the 4-aminopyridine being protonated. The intercalation efficiency is estimated to be ca. 85.6%. With respect to K-4-APy, the interlayer space expends by 1.53 Å. The thermal decomposition mechanism was studied by PXRD and TG techniques. The K-4-APy–HCl shows proton conductivity with σ=3.379×10{sup −8} S cm{sup −1} at 373 K and E{sub a}=1.159 eV in the anhydrous condition, which are comparable to MOFs-based proton conducting materials. - Graphical abstract: The intercalated hybrid of mineral kaolinite with 4-amidinopyridinium hydrochloride is prepared to use as proton conducting material. - Highlights: • A new strategy is proposed for preparation of kaolinite-based proton conductor. • Intercalatied hybrid was prepared by sequentially inserting 4-amidinopyridine and adsorbing HCl. • The proton conductivity of intercalated hybrid is comparable to MOFs-based proton-conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Sodium superionic conduction in tetragonal Na{sub 3}PS{sub 4}

Highlights: • Na{sub 3}PS{sub 4} base solid electrolytes were fabricated by various synthetic routes. • The formation of phases in Na{sub 3+5x}P{sub 1–x}S{sub 4} depends on reaction conditions. • Tetragonal phase III showed the highest conductivity of 3.39 × 10{sup -3} S cm{sup -1}at 25 °C. • Structural analysis revealed the 3D conduction pathway in the tetragonal phase III. • Na{sub 3}PS{sub 4} functions as a solid electrolyte in all-solid-state sodium batteries. - Abstract: Sodium superionic conductors are highly promising as solid electrolytes for all-solid-state sodium batteries, with the capacity to improve energy and power density of liquid-electrolyte-based batteries and to address their safety issues. However, the ionic conductivity of sodium electrolytes remains roughly one order of magnitude lower than that of lithium systems. Herein, we report a synthesis method for a sodium superionic conductor, tetragonal Na{sub 3}PS{sub 4}, with an ionic conductivity of 3.39 × 10{sup −3} Scm{sup −1} at 25 °C—the highest value yet reported among sulfide-type sodium conductors. The high conductivity is achieved through quenching from 700 °C, which introduces sodium vacancies, and annealing at 450 °C, which increases vacancies and expands lattice volume. The phase is comprised of a framework of isolated PS{sub 4} tetrahedra, with partial distribution of Na over 3D pathways. The high intrinsic conductivity together with low grain boundary contribution and soft mechanical properties make Na{sub 3}PS{sub 4} a promising candidate for sodium solid electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Effect of graphite morphology on the tensile strength and thermal conductivity of cast iron

Highlights: • The graphite morphology is characterized from 3D structure using X–ray tomography. • The size, distribution, shape and interconnectivity of graphite are estimated. • The influences of graphite morphology on tensile properties and thermal conductivity are evaluated. • The mechanism of tensile strength and the model of thermal conductivity are discussed. - Abstract: Graphite morphology is a very important parameter affecting the properties of cast iron. In this study, the graphite morphology was characterized using both 3D and 2D structures. The experimental results revealed that when the graphite was less spheroidal, the graphite had greater interconnectivity in the 3D structure of the cast iron. The size, distribution, volume fraction, and shape of the graphite were estimated. Moreover, the influences of the graphite's morphology, size, and distribution on the tensile property and thermal conductivity at different temperatures were estimated. The experimental results revealed that with an increase in temperature, the thermal conductivity initially increased, and then decreased, whereas the tensile strength decreased slightly at first, and then decreased rapidly. In addition, with an increase in the percentage of compacted graphite, the tensile strength decreased and the thermal conductivity increased. The fracture surfaces of tensile specimens were also estimated. Finally, the mechanism of tensile strength and the model of thermal conductivity were investigated.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Synthesis, thermal expansion and high-temperature electrical conductivity of Co-doped (Y,Ca)FeO{sub 3−δ} with orthorhombic perovskite structure

Highlights: • (Y,Ca)(Fe,Co)O{sub 3−δ} was prepared via citrate-based route with annealing at 1150–1200 °C. • Y{sub 0.9}Ca{sub 0.1}Fe{sub 0.8}Co{sub 0.2}O{sub 3−δ} demonstrates low thermal expansion coefficient of 11.9 ppm K{sup −1}. • Oxides do not react with YSZ and GDC up to 1000 °C and 1100 °C, respectively. • Compounds demonstrate higher electrical conductivity in comparison with Y{sub 0.9}Ca{sub 0.1}FeO{sub 3}. • Pr-doped (Y,Ca)(Fe,Co)O{sub 3−δ} demonstrate both higher electrical conductivity and TEC. - Abstract: Orthorhombic perovskites Y{sub 1−x}Ca{sub x}Fe{sub 1−y}Co{sub y}O{sub 3−δ} (0.1 ≤ x ≤ 0.2, 0.1 ≤ y ≤ 0.2 and x = 0.1, y = 0.3) were synthesized in air by the citrate route at 1150–1300 °C. High-temperature X-ray powder diffraction (HT XRPD) data for Y{sub 0.9}Ca{sub 0.1}Fe{sub 0.8}Co{sub 0.2}O{sub 3−δ} at 25–800 °C showed no phase transition with calculated thermal expansion coefficient (TEC) of 11.9 ppm K{sup −1}. High-temperature electrical conductivity measurements revealed almost composition independent conductivity values of 22–27 S/cm at 900 °C. No chemical interaction of Y{sub 0.8}Ca{sub 0.2}Fe{sub 0.9}Co{sub 0.1}O{sub 3−δ} with (Zr,Y)O{sub 2−x} (YSZ) or (Ce,Gd)O{sub 2−x} (GDC) was observed up to 1000 °C and 1100 °C, respectively. Partial replacement of Y by Pr according to formula Y{sub 0.8−z}Pr{sub z}Ca{sub 0.2}Fe{sub 0.7}Co{sub 0.3}O{sub 3−δ}, 0.1 ≤ z ≤ 0.35, leads to an increase of both electrical conductivity up to 50 S/cm (z = 0.3) at 900 °C and dilatometry measured TEC up to 15.1 ppm K{sup −1}. Moderate values of electrical conductivity in combination with low TEC and stability towards chemical interaction with typical SOFC electrolytes make Co-doped Y{sub 1−x}Ca{sub x}FeO{sub 3−δ} promissing cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC)

36 MATERIALS SCIENCE↗
DOE OSTI2016

Impedance spectroscopy and conduction mechanism of LiAlP{sub 2}O{sub 7} material

Highlights: • X-ray diffraction analysis reveals the structure for LiAlP{sub 2}O{sub 7} compound. • Modulus study confirmed the grain relaxation. • The equivalent circuit consists of parallel combination of (R{sub g}//CPE{sub g}) series for region I and (R{sub g}//CPE{sub g}) series with CPE{sub e} for region II. • The conductivity is due to CBH model for region I and NSPT model for region II. - Abstract: LiAlP{sub 2}O{sub 7} compound has been obtained by standard solid-state reaction technique and found to crystallize in the monoclinic system with P2{sub 1/a} space group. The impedance plots are well fitted to two equivalent circuit models. The dc conductivity follows Arrhenius behavior with two different activation energies Ea(I) = 0.84 eV for T < 610 K and Ea(II) = 0.93 eV for T > 610 K. Actually, the values of activation energies obtained from the dc conductivity and the relaxation frequency are similar, and hence the transport in the titled compound can be described through a hopping mechanism, dominated by the motion of Li{sup +} ions. Besides, the frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. The NSPT model and the CBH model is the most applicable conduction mechanism in region (I) and (II), respectively. The ion transport is due to the hopping of Li{sup +} ions along [100] tunnels direction. The conduction mechanism is studied with the help of Elliot’s theory, and the Elliot’s parameters are determined.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Seebeck coefficient and thermal conductivity of doped armchair graphene nanoribbon in the presence of magnetic field

Highlights: • Theoretical calculation of Seebeck coefficient and thermal conductivity of electrons on grapheme nanoribbon. • The investigation of the effect of magnetic field and ribbon width on temperature dependence of thermoelectric properties of nanoribbon. • The study of thermopower as a function of magnetic field and temperature. - Abstract: We address the thermal conductivity and Seebeck coefficient of armchair graphene nanoribbon within tight binding model Hamiltonian in the presence of magnetic field. The possible effects of ribbon width, magnetic field chemical potential on thermoelectric properties are investigated. Green's function approach has been employed in order to calculate transport coefficients of the system. We have also found the temperature dependence of the thermal conductivity for various ribbon widths and chemical potentials. Our results show a peak appears in temperature dependence of thermal conductivity of insulator nanoribbon for low magnetic fields. Upon increasing magnetic field, thermal conductivity shows a monotonic decreasing behavior and peak disappears. Our results show the increase of chemical potential causes to decreasing behavior for thermal conductivity. Moreover we study the effects of magnetic field on temperature behavior of thermopower of insulator graphene nanoribbon in details.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Alternating current conduction mechanisms of RbMgPO4 compound

Highlights: • Two displacive reversible phase transitions located at T{sub 1} = 442/432 K and T{sub 2} = 460/445 K (heating/cooling). • The temperature dependence of conductivity was described in terms of Arrhenius relation. • The ac conductivity of this compound is proportional to ω{sup s} where the s values are between 0 and 2. • The (CBH) model was found to be the appropriate transport mechanism in RbMgPO{sub 4} compound. - Abstract: Rubidium magnesium monophosphate (RbMgPO{sub 4}) compound was prepared from highly pure constituents by solid state reaction. It was characterized by X-ray powder diffraction, IR, Raman, differential scanning calorimetry (DSC) and impedance spectroscopy. The infrared and Raman spectra were interpreted on the basis of PO{sub 4}{sup 3−} vibrations. DSC revealed two displacive and reversible phase transitions at T{sub 1} = 442/432 K and T{sub 2} = 460/445 K (heating/cooling). The electrical conductivity was measured in the frequency and temperature range 200 Hz-5 MHz and 423 K–523 K, respectively. The obtained results were analysed by fitting the experimental data to an equivalent circuit model. The temperature dependence of alternating and direct current conductivities (σ{sub ac}, σ{sub dc}) confirms the observed transitions in the calorimetric study; they were described in terms of Arrhenius relation. The activation energy’s values were determined in each phase. The AC conductivity behavior is ensured by a single process defined as a hopping transport mechanism. The conductivity frequency dependence was interpreted using the correlated barrier-hopping model (CBH) in all phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Heat transfer coefficients of moving particle beds from flow-dependent thermal conductivity and near-wall resistance

Accurate determination of heat transfer coefficients for flowing packed particle beds is essential to the design of particle heat exchangers and other thermal and thermochemical equipment. While such dense granular flows mostly fall into the well-known plug-flow regime, the discrete nature of granular materials alters the thermal transport processes in both the near-wall and bulk regions of flowing particle beds from their stationary counterparts. As a result, heat transfer correlations based on the stationary particle bed thermal conductivity could be inadequate for flowing particles in a heat exchanger. Most earlier works have achieved a reasonable agreement with experiments by treating granular heat transfer media as a plug-flow continuum with a near-wall thermal resistance in series. However, the thermal conductivity values of the continuum were often obtained from measurements on stationary beds owing to the difficulty of flowing bed measurements. In this work, it was found that the properties of a stationary bed are highly sensitive to the method of particle packing and there is a decrease in the particle bed thermal conductivity and increase in the near-wall thermal resistance, measured as an effective air gap thickness, on the onset of particle flow. These variations in thermal conductivity of stationary and flowing particle beds can lead to errors in heat transfer coefficient calculations. Therefore, the heat transfer coefficients for granular flows were calculated using experimentally determined flowing particle bed thermal conductivity and near-wall air gap for ceramic particles – CARBO CP 40/100 (mean diameter = 275 µm), HSP 40/70 (404 µm) and HSP 16/30 (956 µm); at velocities of 5–15 mm·s –1 ; and temperatures of 300–650 °C. The thermal conductivity and air gap values for CP 40/100 and HSP 40/70 were further used to calculate heat transfer coefficients across different particle bed temperatures and velocities for different parallel-plate heat exchanger dimensions. Furthermore, these calculations, which show good agreement with measured HTC values reported in literature, can be used as a guide for heat exchanger designs. Graphical abstract

14 SOLAR ENERGY↗
DOE OSTI2019

Reduced de-doping and enhanced electrical conductivity of polyaniline filled phenol-divinylbenzene composite for potential lightning strike protection application

In this study, phenolic resin was mixed with a cross-linking agent divinylbenzene (DVB) to prepare a polyaniline-based electrically-conductive thermosetting polymer composite. It has been shown that this Phenol-DVB mixture can undergo cationic polymerization in the presence of the dodecylbenzene sulfonic acid (DBSA)-doped polyaniline (PANI). Composites with different weight ratios of phenolic resin and DVB were mixed with a fixed weight of DBSA-PANI (i.e. 30 wt. %). Increasing the phenol content in the resin system was found to improve the electrical conductivity of the composite to almost 2700%. This improvement has been assigned to the reduced de-doping of polyaniline in phenol-DVB resin. Active sites of phenol effectively attached to the β carbon of DVB and reduced the proton subtracting species of DVB, leading to reduced de-doping of PANI. This behavior was studied through various characterization techniques including differential scanning calorimetry (DSC), FT-IR spectroscopy and Scanning Electron Microscopy (SEM). Electrical conductivity measurement, mechanical properties, and in-situ electrical conductivity measurements were performed to find the optimized properties of the composite. Optimized composites prepared with the composition of 30 wt. % DBSA-PANI and 70 wt. % of phenol-DVB (50 wt. % each), have shown electrical conductivity of 0.20 S/cm and a flexural modulus of 2.1 GPa, which is a significant improvement in the flexural properties of polymer based-thermosetting composites with similar electrical conductivity. Lastly, this material can be a potential candidate for the lightning strike protection of fiber reinforced plastics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Advancing ionomer design to boost interfacial and thin-film proton conductivity via styrene-calix[4]arene-based ionomers

Sub-micrometer-thick ion-conducting polymer (ionomer) layers often suffer from poor ionic conductivity at the substrate/catalyst interface. The weak proton conductivity makes the electrochemical reaction at the cathode of proton-exchange-membrane fuel cells sluggish. To address this, here we report on a class of polystyrene-based ionomers having sub-nanometer-sized, sulfonated macrocyclic calix[4]arene-based pendants (PS-calix). In films with thickness comparable to that of ionomer-based binder layers, the conductivity of PS-calix film (~41 mS/cm) is ~13 times higher than that of the current state-of-the-art ionomer, Nafion. We observe a similar improvement in proton conductivity when PS-calix interfaces with Pt nanoparticles, demonstrating the potential of PS-calix in catalyst ink. Leveraging a favorable interfacial chemical composition, PS-calix enhances proton conduction at the film-substrate interface, a shortcoming of Nafion. Moreover, the water in PS-calix films diffuses faster than bulk water and the water confined in Nafion films, suggesting an important role played by sub-nanometer-sized calix[4]arene cavities in creating unique water/ion transport pathways.

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

Oxygen Affinity: The Missing Link Enabling Prediction of Proton Conductivities in Doped Barium Zirconates

Proton-conducting oxides, specifically doped barium zirconates, have garnered much attention as electrolytes for solid-state electrochemical devices operable at intermediate temperatures (400–600 °C). In chemical terms, hydration energy, E hyd , and proton–dopant association energy, E as , are two key parameters that determine whether an oxide exhibits fast proton conduction, but to date ab initio studies have for the most part studied each parameter separately, with no clear correlation with proton conductivity identified in either case. Here, we demonstrate that the oxygen affinity, E O.dopant , defined as the energy released when an oxide ion enters an oxygen vacancy close to a dopant atom, is the missing link between these two parameters and correlates well with experimental proton conductivities in doped barium zirconates. Ab initio calculations of point defects and their complexes in Sc-, In-, Lu-, Er-, Y-, Gd-, and Eu-doped barium zirconates are used to determine E hyd , E as , E O.dopant , and the hydrogen affinity, E H.host , of each system. These four energy terms are related by E hyd = E O.dopant + 2E H.host + 2E as . Complementary impedance spectroscopy measurements reveal that the stronger the calculated oxygen affinity of a system, the higher the proton conductivity at 350 °C. Although the proton trapping site is also an important factor, the results show that oxygen affinity is an excellent predictor of proton conductivity in these materials.

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

Role of Fast Dynamics in Conductivity of Polymerized Ionic Liquids

Polymerized ionic liquids (PolyILs) are promising candidates for a broad range of technologies. However, the relatively low conductivity of PolyILs at room temperature has strongly limited their applications. In this work, we provide new insights into the roles of various microscopic parameters controlling ion transport in these polymers, which are crucial for their rational design and practical applications. Using broadband dielectric spectroscopy and neutron and light scattering techniques, we found a clear connection between the activation energy for conductivity, fast dynamics, and high-frequency shear modulus in PolyILs at their glass transition temperature (T g ). In particular, our analysis reveals a correlation between conductivity and the amplitude of fast picosecond fluctuations at T g , suggesting the possible involvement of fast dynamics in lowering the energy barrier for ion conductivity. We also demonstrate that both the activation energy for ion transport and the amplitude of the fast fluctuations depend on the high-frequency shear moduli of PolyILs, thus identifying a practically important parameter for tuning conductivity. Finally, the parameters recognized in this work and their connection to the ionic conductivity of PolyILs set the stage for a deeper understanding of the mechanism of ion transport in PolyILs in the glassy state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Investigating Electron Conductivity Regimes in the Bacterial Cytochrome Wire OmcS

The anaerobic bacterium Geobacter sulfurreducens produces extracellular, electronically conductive cytochrome polymer wires that are conductive over micron length scales. Structure models from cryo-electron microscopy data show OmcS wires form a linear chain of hemes along the protein wire axis, which is proposed as the structural basis supporting their electronic properties. However, the mechanism by which this heme arrangement supports long-range electronic conduction remains unknown. Structure models from cryo-electron microscopy data show these wires form a linear chain of hemes along the protein wire axis, which is proposed as the structural basis supporting their electronic properties. Existing computational models using static heme redox potentials and coupling energies fail to explain experimental observations, predicting conductances 10,000 to 100,000 times lower than measured values. Here, we investigate how dynamic disorder affects site energies, interheme coupling, and long-range electronic conductivity within these cytochrome wires. We introduce an approach to extract charge carrier site information directly from Kohn–Sham density functional theory, without employing projector schemes, and show that site and coupling energies are highly sensitive to changes in interheme geometry and the surrounding electrostatic environment. Unlike models that incorporate dynamic disorder as a thermally averaged quantity, our quantum charge carrier model incorporates proxies for dynamic disorder through decoherence corrections, yielding predicted diffusion coefficient closer to what is expected from experiment and comparable with other organic-based electronic materials. Based on these simulations, we propose that the instantaneous fluctuations of the local electrostatic environment can transiently lift energy degeneracies and delocalize charge carriers. Furthermore, these studies reveal how incorporating dynamic fluctuations associated with the environment resolves the discrepancy between theory and experiment in microbial cytochrome wires and highlight design principles for bioinspired, heme-based conductive materials.

Bioinorganic chemistry↗
DOE OSTI2016

Thermal Conductivity Comparison of Indium Gallium Zinc Oxide Thin Films: Dependence on Temperature, Crystallinity, and Porosity

Here, the cross-plane thermal conductivity of InGaZnO (IGZO) thin films was measured using the 3ω technique from 18 to 300 K. The studied morphologies include amorphous (a-IGZO), semicrystalline (semi-c-IGZO), and c-axis-aligned single-crystal-like IGZO (c-IGZO) grown by pulsed laser deposition (PLD) as well as a-IGZO deposited by sputtering and by solution combustion processing. The atomic structures of the amorphous and crystalline films were simulated with ab initio molecular dynamics. The film quality and texturing information was assessed by X-ray diffraction and grazing incidence wide-angle X-ray scattering. X-ray reflectivity was also conducted to quantify film densities and porosities. All the high-density films exhibit an empirical power-law temperature dependence of the thermal conductivity $κ \sim T^{0.6}$ in the specified temperature range. Among the PLD dense films, semi-c-IGZO exhibits the highest thermal conductivity, remarkably exceeding both films with more order (c-IGZO) and with less order (a-IGZO) by a factor of 4. The less dense combustion-synthesized films, on the other hand, exhibited lower thermal conductivity, quantitatively consistent with a porous film using either an effective medium or percolation model. All samples are consistent with the porosity-adapted Cahill–Pohl (p-CP) model of minimum thermal conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Site-Selective Modification of Lanthanum Oxychloride to Modulate Halide-Ion Conduction

Design principles for solid-state halide-ion conduction remain poorly defined despite the increasing importance of halide ions as charge carriers in a variety of energy storage and electrochemical computing technologies. Here, we employ a siteselective modification strategy in which aliovalent cations are preferentially introduced at the La 3+ crystallographic site of LaOCl in the 2c Wyckoff position, enabling controlled generation of chloride vacancies and modification of lattice dynamics to enhance chloride-ion conductivity. Aliovalent substitution of La 3+ with Mg 2+ , Ca 2+ , and Sr 2+ generates charge-compensating Cl vacancies while preserving the matlockite crystal structure. X-ray excited optical luminescence measurements with Dy 3+ as a reporter chromophore evidence vacancy-derived midgap electronic states and an extended energy range of radiation-less Auger electron emission corresponding to substantial modification of electronic structure and local electrostatic potentials. Ca alloying at 8−10 at. % increases the chloride-ion conductivity by three- to 4 orders of magnitude as compared to unalloyed LaOCl, whereas comparable amounts of Sr- and Mg-alloying in LaOCl imbue less pronounced conductivity enhancements. Temperature-dependent Raman spectroscopy measurements reveal that Ca- and Sr-alloying substantially soften the La−Cl sublattice and yield a more compliant crystal lattice that can deform to accommodate Cl-ion migration. Structure solutions derived from Rietveld refinements to powder Xray diffraction reveal larger O−La−Cl bond-angle deviations and enhanced out-of-plane cation displacements for Ca- and Sr-alloyed compositions as compared to Mg-alloyed LaOCl. Such local distortions enhance chloride-ion mobility by reshaping and flattening vacancy migration energy landscapes and by modulating lattice dynamics governing anion conduction. We further illustrate that coalloying of Ca with Mg and Sr induces a nonmonotonic conductivity−defect stoichiometry relationship that can be rationalized based on cooperative interactions. Together, these results establish site-selective aliovalent alloying of LaOCl as an effective route to halide-ion solid electrolytes and provide broadly generalizable design principles for site-selective modification to induce vacancy formation and lattice softening to engender facile anion transport

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

Approaching the Practical Conductivity Limits of Aerosol Jet Printed Silver

Previous efforts to directly write conductive metals have been narrowly focused on nanoparticle ink suspensions that require aggressive sintering (>200°C) and result in low-density, small-grained agglomerates with electrical conductivities <25% of bulk metal. Here, we demonstrate aerosol jet printing of a reactive ink solution and characterize high-density (93%) printed silver traces having near-bulk conductivity and grain sizes greater than the electron mean free path, while only requiring low temperature (80°C) treatment. We have developed a predictive electronic transport model which correlates the microstructure to the measured conductivity and identifies a strategy to approach the practical conductivity limit for printed metals. Our analysis of how grain boundaries and tortuosity contribute to electrical resistivity provides insight into the basic materials science that governs how an ink formulator or process developer might approach improving the conductivity. Transmission line measurements validate that electrical properties are preserved up to 20GHz, which demonstrates the utility of this technique for printed RF components. Finally, this work reveals a new method of producing robust printed electronics that retain the advantages of rapid prototyping and three-dimensional fabrication while achieving the performance necessary for success within the aerospace and communications industries.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Ion-Conducting Thermoresponsive Films Based on Polymer-Grafted Cellulose Nanocrystals

Mechanically robust, thermo-responsive, ion-conducting nanocomposite films are prepared from poly(2-phenylethyl methacrylate) grafted cellulose nanocrystals (MxG-CNC-g-PPMA). One-component nanocomposite films of the polymer grafted nanoparticle (PGN) MxG-CNC-g-PPMA are imbibed with 30 wt% imidazolium-based ionic liquid, to produce flexible ion-conducting films. These films with 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[H]) not only displays remarkable improvements in toughness (>25 times) and tensile strength (>70 times) relative to the corresponding nanocomposites consisting of the ionic liquid imbibed in the two component CNC/PPMA nanocomposite, but also shows higher ionic conductivity than the corresponding neat PPMA with the same wt.% of ionic liquid. Notably, the one-component film containing 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[E]) exhibits temperature responsive ionic conduction. The ionic conductivity decreases at around 60°C as a consequence of the lower critical solution temperature (LCST) phase transition of the grafted polymer in the ionic liquid, which leads to phase separation. Moreover, holding the MxG-CNC-g-PPMA/[E] film at room temperature for 24 hours returns the film to its original homogenous state. These materials exhibit properties relevant to thermal cutoff safety devices (e.g., thermal fuse) where a reduction in conductivity above a critical temperature is needed.

36 MATERIALS SCIENCE↗