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Using Holey Graphene for Improved Interfacial Contact in Solid Electrolyte Ionic Conductivity Measurements

Solid-state batteries (SSBs) are poised to become the batteries of the future with advantages such as higher energy density, lighter weight, versatile geometry, and greater safety due to low flammability risk. An important parameter of the solid electrolyte (SE) used is its ionic conductivity. The ionic conductivity is generally calculated from the bulk resistance of a SE pellet, measured from the electrochemical impedance spectroscopy data. The SE pellet is typically prepared from the electrolyte powder by dry compression and is sandwiched between two blocking current collectors to obtain the impedance spectroscopy data. One of the challenges in conducting this measurement is poor interfacial contacts between the SE pellet and the current collector surfaces. Therefore, measurements reported in the literature may underestimate the true ionic conductivity of a given electrolyte. Holey graphene is a carbon nanomaterial with high electrical conductivity and unique dry compressibility, which is unusual for carbon materials but similar to many oxide and sulfide SEs. In this work, it is demonstrated that adding a thin layer of holey graphene between the electrolyte and the stainless steel current collectors significantly improves the interfacial contact. The ionic conductivity values obtained in the effort were sometimes several times higher than the data measured for SEs without the holey graphene layers. This work calls for more standardized measurement procedures to reduce the discrepancies in reported ionic conductivity values.

Solid state battery↗
NASA NTRS2024

The Global Mapping of Electron Precipitation and Ionospheric Conductance From Whistler-Mode Chorus Waves

Auroral precipitation is the second major energy source after solar irradiation that ionizes the Earth’s upper atmosphere. Diffuse electron aurora caused by wave-particle interaction in the inner magnetosphere (L < 8) takes over 60% of total auroral energy flux, strongly contributing to the ionospheric conductance and thus to the ionosphere-thermosphere dynamics. This paper quantifies the impact of chorus waves on the diffuse aurora and the ionospheric conductance during quiet, medium, and strong geomagnetic activities, parameterized by AE <100, 100 < AE < 300, and AE > 300, respectively. Using chorus wave statistics and inner-magnetosphere plasma conditions from Timed History Events and Macroscale Interactions during Substorms (THEMIS) observations, we directly derive the energy spectrum of diffuse electron precipitation under quasi-linear theory. We then calculate the height-integrated conductance from the wave-driven aurora spectrum using the electron impact ionization model of Fang et al. (Geophys. Res. Lett., 2010, 37) and the MSIS atmosphere model. By utilizing Fang’s ionization model, the US Naval Research Laboratory Mass Spectrometer and Incoherent Scattar Radar (NRLMSISE-00) model from 2000s for the neutral atmosphere components, and the University of California, Los Angeles (UCLA) Full Diffusion Code, we improve upon the standard generalization of Maxwellian diffuse electron precipitation patterns and their resulting ionosphere conductance. Our study of global auroral precipitation and ionospheric conductance from chorus wave statistics is the first statistical model of its kind. We show that the total electron flux and conductance pattern from our results agree with those of Ovation Prime model over the pre-midnight to post-dawn sector as geomagnetic activity increases. Our study examines the relative contributions of upper band chorus (UBC) and lower band chorus wave (LBC) driven conductance in the ionosphere. We found LBC waves drove diffuse electron precipitation significantly more than UBC waves, however it is possible that THEMIS data may have underestimated the upper chorus band wave observations for magnetic latitudes below 65 degrees. ° .

diffuse auroral precipitation↗
DOE OSTI2016

Thermal Conductivity and Diffusivity for SiC Fibers for Use in ATF Cladding Composites

As part of the accident tolerant fuels (ATF) initiative, there is a need to understand the thermophysical properties of cladding for these fuels. One potential cladding material is silicon carbide (SiC) ceramic matrix composite reinforced with SiC fibers because of the corrosion resistance, resistance to hydrogen formation, high bulk thermal conductivity, and favorable mechanical properties of SiC. However, data about the thermal properties of individual SiC fibers in these composites is absent in the literature. This paper presents the measured axial thermal conductivity and thermal diffusivity of a leading SiC fiber (HiNicalon Type S) via a thermal measurement technique (transient electrothermal technique, TET) optimized for thin fibers. The results show that the measured properties are significantly lower than bulk values for SiC. Because of the low neutron absorption, as well as excellent thermal and mechanical properties, zircaloy has primarily been used for the fuel cladding in many nuclear reactors. A major drawback of the zircaloy is its hydrogen generation vulnerability. This issue has been known for some time, but the explosion of hydrogen accident in the Fukushima Daiichi nuclear disaster has motivated efforts for accident tolerant fuels (ATF) and their cladding as suitable substitutes for zircaloy. Fuel cladding made of silicon carbide (SiC) ceramic matrix composite (CMC) is an attractive alternative to the zircaloy. Investigation on the tubular monolithic a-SiC polytropes indicates that it has superior oxidation (hydrogen production) resistance (three orders of magnitude slower) than zircaloy. Additionally, it has well-documented, favorable mechanical properties, along with high temperature corrosion resistance. However, its bulk thermal properties can vary significantly depending on polytrope, the grain size, grain boundary, or impurities. At room temperature, SiC has a thermal conductivity as high as 490 Wm{sup -1}K{sup -1}, where the {sup 6}H polytrope has the highest conductivity. Thermal measurements of the SiC CMC are usually accomplished by laser flash method for thermal diffusivity (a) and thermal conductivity is indirectly calculated through the relationship k=aρcp. Depending on the manufacturing method and the reinforced fiber, the composite thermal conductivity varies from <10 Wm{sup -1}K{sup -1} to ∼70 Wm{sup -1}K{sup -1}. While the flash method is convenient for the measurement of the composite, it is difficult to apply to the measurement of individual fibers. Because of this, the thermal properties of individual SiC fibers is not present in the literature. Because the SiC fiber manufacturing process is different than that of the SiC matrix in the CMC, the properties of the bulk material might be erroneous when applied to the fiber. Being able to measure the fiber properties independently and directly allows for an understanding of the effect of the manufacturing process on the fiber and the opportunity to potentially improve or control the thermal properties of the composite. This improved accuracy can be achieved by measuring the fiber with a technique optimized for individual fiber measurement, known as the Transient Electrothermal Technique or TET. This paper presents the thermal conductivity and diffusivity of a leading SiC fiber (HiNicalon Type S). Measurements are performed with the TET, with the resulting properties being significantly lower than the bulk values of SiC, which is one possible explanation for relatively low CMC values. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Thermal conductivity of (VO 2 ) 1-x Cu x composites across the phase transition temperature

In this paper, the thermal conductivity across the metal-insulator transition (MIT) of hot-pressed polycrystalline vanadium dioxide (VO 2 ) samples is studied. The change in the total thermal conductivity (k) of hot-pressed VO 2 is insignificant across the MIT temperature. By adding copper (Cu) to make (VO 2 ) 1-x Cu x composites with x from 0 to 0.5, we find an increase in the electrical conductivity from 4 × 10 4 S m -1 to 1 × 10 6 S m -1 at 120 °C, resulting in an electronic thermal conductivity increase from 0.38 W m -1 K -1 for x = 0 to 3.8 W m -1 K -1 for x = 0.3, which is a significant increase. However, the total thermal conductivity did not increase due to the decrease in the value of the Lorenz number by an order of magnitude than its standard value using the Wiedemann-Franz relationship. Finally, on the basis of our experimental result, an empirical model is proposed to explain the thermal conductivity behavior of all (VO 2 ) 1-x Cu x samples with different Cu concentrations.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Two highly proton-conductive molecular hybrids based on ionized water clusters and poly-Keggin-anion chains

Two proton-conductive molecular hybrid complexes, {l_brace}[Zn(H{sub 2}O){sub 8}][H(H{sub 2}O){sub 2}](HINO){sub 4}(PMo{sub 12}O{sub 40}){r_brace}{sub n} (1) and {l_brace}[Mn(H{sub 2}O){sub 8}][H(H{sub 2}O){sub 2.5}](HINO){sub 4}(PMo{sub 12}O{sub 40}){r_brace}{sub n} (2), were constructed by introducing protonated water clusters, transition metal ionized water clusters and [PMo{sub 12}O{sub 40}]{sup 3-} anions in the gallery of H-bonding networks based on isonicotinic acid N-oxide (HINO). Single-crystal X-ray diffraction analyses at 293 K revealed that both complexes presented exactly the same three-dimensional (3D) hydrogen-bonded networks with large one-dimensional (1D) channels. Interestingly, [PMo{sub 12}O{sub 40}]{sup 3-} anions just filled in the 1D channels and self-assembled into poly-Keggin-anion chains. Thermogravimetric analyses both show no weight loss in the temperature range of 20-100 deg. C, indicating that all water molecules in the unit structure are not easily lost below 100 deg. C. Surprisingly, the proton conductivities of 1 and 2 in the temperature range of 85-100 deg. C under 98% RH conditions reached high proton conductivities of 10{sup -3} S cm{sup -1}. A possible mechanism of the proton conduction was proposed according to the experimental results. - Graphical abstract: Two molecular hybrids constructed by ionized water clusters and poly-Keggin-anion chains showed high proton conductivities of 10{sup -3} S cm{sup -1} in the temperature range of 85-100 deg. C under 98% relative humidity. Highlights: > Proton conductors have interested us from the point of its applications in fuel cells. > Heteropolyacids have suitable characteristics to be used as excellent proton conductors. > Two new supramolecular complexes based on [PMo{sub 12}O{sub 40}]{sup 3-} and isonicotinic acid N-oxide was constructed. > The structure was determined by using single-crystal X-ray diffraction data. > Both complexes showed good proton conductivities of 10{sup -3} S cm{sup -1} in the temperature range of 85-100 deg. C.

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

Mechanism of Contrasting Ionic Conductivities in Li 2 ZrCl 6 via I and Br Substitution

Understanding the complex structural and chemical factors that influence ionic conduction mechanisms is paramount for developing advanced inorganic superionic conductors in all‐solid‐state batteries, particularly halide solid electrolytes with excellent electrochemical oxidative stability and mechanical sinterability. Herein, contrasting ionic conduction behaviors in I − and Br − substituted Li 2 ZrCl 6 are revealed by combining experimental structural analyses and theoretical calculations. The inter‐slab distance along the c ‐axis, which varies with the anion substitution and M2‐M3 site disorder, is a key factor for opening the ab ‐plane conduction and facilitating the overall Li + conduction. Increased M3 site occupancy generally leads to contracted inter‐slab distance. The substantial increase in Li + conductivity upon I substitution (from 0.40 to 0.91 mS cm −1 ) originates from a sufficiently expanded lattice volume owing to its large ionic radii (I − = 2.20 Å), particularly inter‐slab distance that facilitates the ab intra‐plane Li + conduction, which also benefits from decreased M2‐M3 disorder. In contrast, Br (Br − = 1.96 Å) substitution results in insufficiently expanded Li + channels, which, exacerbated by increased M2‐M3 disorder, leads to degradation in Li + conductivity. Implementing I − substituted Li 2 ZrCl 6 resulted in superior electrochemical performance in LiCoO 2 ||Li‐In cells compared to those with an unsubstituted catholyte.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A Finite Difference Analysis of the Effect of Graphene Additions on the Electrical Conductivity of Polycrystalline Copper

A finite-difference method was used to explore the effect of graphene on the bulk electrical conductivity of copper-graphene composites. In this capacity, grain orientation information from pure copper and copper-graphene composites were used to generate synthetic 3D microstructures. The electrical conductivity of these microstructures were calculated using the finite difference method assuming different average grain sizes. From these calculations, we demonstrate that when high-conductivity grain boundaries are present within the microstructure arising from the presence of graphene, an increase in the bulk electrical conductivity is observed. On the other hand, the difference in textures between copper and copper-graphene composites may not account for a significant difference in bulk electrical conductivity. In comparison, the copper grain size has a considerably larger effect on electrical conductivity as previously anticipated. This is one of the first demonstrations of a physical basis for enhanced conductivity composites and presents pathways for further investigations on the effects of composite microstructural features, material interfaces and graphene content on electrical performance.

Frazier, William E.↗
DOE OSTI2026

A Cheeger inequality for size-specific conductance

The μ-conductance measure proposed by Lovász and Simonovits is a size-specific conductance score that identifies the set with smallest conductance while disregarding those sets with volume smaller than a μ fraction of the whole graph. Using μ-conductance enables us to study the network structures in new ways. Here, in this manuscript, we study a modified spectral cut for μ-conductance that is a natural relaxation of the integer program of μ-conductance and show that the optimum of this program has a two-sided Cheeger inequality with μ-conductance.

Graph theory↗
DOE OSTI2020

Extrapolation of thermal conductivity in non-equilibrium molecular dynamics simulations to bulk scale

Predictions of the bulk scale thermal conductivity of solids using non-equilibrium molecular dynamics (MD) simulations have relied on the linear extrapolation of the thermal resistivity versus the reciprocal of the system length in the simulations. Several studies have reported deviation of the extrapolation from linearity near the micro-scale, raising a concern of its applicability to large systems. To investigate this issue, present work conducted extensive MD simulations of silicon with two different potentials (EDIP and Tersoff-II) for unprecedented length scales up to 10.3 μm and simulation times up to 530 ns. For large systems ≥0.35 μm in size the non-linearity of the extrapolation of the reciprocal of the thermal conductivity is mostly due to ignoring the dependence of the thermal conductivity on temperature. To account for such dependence, the present analysis fixes the temperature range for determining the gradient for calculating the thermal conductivity values. However, short systems ≤0.23 μm in size show significant non-linearity in the calculated thermal conductivity values using a temperature window of 500 ± 10 K from the simulations results with the EDIP potential. Since these system sizes are shorter than the mean phonon free path in EDIP (~0.22 μm), the nonlinearity may be attributed to phonon transport. For the MD simulations with the Tersoff-II potential there is no significant non-linearity in the calculated thermal conductivity values for systems ranging in size from 0.05 to 5.4 μm.

42 ENGINEERING↗
DOE OSTI2024

Alternating conduction and convection drying of paper – an experimental analysis with a continuous data acquisition approach

In conventional multi-cylinder drying of paper and board, both conductive drying from steam-heated dryer cylinders and convective drying by flowing air over the paper surface in the pockets are used. Conductive drying from steam-heated drying cylinders is a critical component in providing the necessary thermal energy to paper and board as they dry. Steam temperature and internal and external resistances at the contacting surface are critical process parameters influencing the conductive drying process. An experimental setup was developed to study the alternating conductive and convective drying of paper and board. Paper sheet moisture, temperature, and temperature distribution within the heated platen and the instantaneous heat flux as the sheet was being dried were measured. The instantaneous heat flux, contact heat transfer coefficient, and drying rates were determined as drying proceeds. Experimental results, as well as comparisons to literature and commercial data, are presented. The conductive heat transfer coefficients determined were compared to traditional correlations normally used in the modeling of paper drying. Similarly, the convective heat and mass transfer coefficients are also determined and compared to literature data. In addition to the evaluation of alternating conductive and convective drying characteristics of paper and board, the potential inclusion of auxiliary energy components will also be included. Experimental results from the conduction and convection drying system are presented. Furthermore, this data will be useful in process development, intensification of manufacturing processes, and modeling and simulation of paper drying processes.

42 ENGINEERING↗
DOE OSTI2014

Microstructural Modeling of Thermal Conductivity of High Burn-up Mixed Oxide Fuel

Predicting the thermal conductivity of oxide fuels as a function of burn-up and temperature is fundamental to the efficient and safe operation of nuclear reactors. However, modeling the thermal conductivity of fuel is greatly complicated by the radially inhomogeneous nature of irradiated fuel in both composition and microstructure. In this work, radially and temperature-dependent models for effective thermal conductivity were developed utilizing optical micrographs of high burn-up mixed oxide fuel. The micrographs were employed to create finite element meshes with the OOF2 software. The meshes were then used to calculate the effective thermal conductivity of the microstructures using the BISON fuel performance code. The new thermal conductivity models were used to calculate thermal profiles at end of life for the fuel pellets. These results were compared to thermal conductivity models from the literature, and comparison between the new finite element-based thermal conductivity model and the Duriez–Lucuta model was favorable.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Mixed conductivity, structural and microstructural characterization of titania-doped yttria tetragonal zirconia polycrystalline/titania-doped yttria stabilized zirconia composite anode matrices

Taking advantage of the fact that TiO{sub 2} additions to 8YSZ cause not only the formation of a titania-doped YSZ solid solution but also a titania-doped YTZP solid solution, composite materials based on both solutions were prepared by solid state reaction. In particular, additions of 15 mol% of TiO{sub 2} give rise to composite materials constituted by 0.51 mol fraction titania-doped yttria tetragonal zirconia polycrystalline and 0.49 mol fraction titania-doped yttria stabilized zirconia (0.51TiYTZP/0.49TiYSZ). Furthermore, Y{sub 2}(Ti{sub 1-y}Zr{sub y}){sub 2}O{sub 7} pyrochlore is present as an impurity phase with y close to 1, according to FT-Raman results. Lower and higher additions of titania than that of 15 mol%, i.e., x=0, 5, 10, 20, 25 and 30 mol% were considered to study the evolution of 8YSZ phase as a function of the TiO{sub 2} content. Furthermore, zirconium titanate phase (ZrTiO{sub 4}) is detected when the titania content is equal or higher than 20 mol% and this phase admits Y{sub 2}O{sub 3} in solid solution according to FE-SEM-EDX. The 0.51TiYTZP/0.49TiYSZ duplex material was selected in this study to establish the mechanism of its electronic conduction under low oxygen partial pressures. In the pO{sub 2} range from 0.21 to 10{sup -7.5} atm. the conductivity is predominantly ionic and constant over the range and its value is 0.01 S/cm. The ionic plus electronic conductivity is 0.02 S/cm at 1000 {sup o}C and 10{sup -12.3} atm. Furthermore, the onset of electronic conductivity under reducing conditions exhibits a -1/4 pO{sub 2} dependence. Therefore, it is concluded that the n-type electronic conduction in the duplex material can be due to a small polaron-hopping between Ti{sup 3+} and Ti{sup 4+}. -- Graphical abstract: FE-SEM micrograph of a polished and thermal etched surface of a Ti-doped YTZP/Ti-doped YSZ composite material. Display Omitted Research highlights: {yields} Ti-doped YTZP/Ti-doped YSZ composite materials are mixed conductors under low partial pressures. {yields} From 5 mol% of TiO{sub 2}, Y{sub 2}(Ti{sub 1-y},Zr{sub y}){sub 2}O{sub 7} pyrochlore is present as a minor phase, being y close to 1 according to FT-Raman studies. {yields} The onset of the electronic conductivity under reducing conditions exhibit a -1/4 pO{sub 2} dependence. The n-type electronic conduction is due to a small polaron-hopping between Ti{sup 3+} and Ti{sup 4+}.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Highly conducting divalent Mg{sup 2+} cation solid electrolytes with well-ordered three-dimensional network structure

A three-dimensionally well-ordered NASICON-type Mg{sup 2+} cation conductor, (Mg{sub x}Hf{sub 1−x}){sub 4/(4−2x)}Nb(PO{sub 4}){sub 3}, was firstly developed by partial substitution of lower valent Mg{sup 2+} cation onto the Hf{sup 4+} sites in a HfNb(PO{sub 4}){sub 3} solid to realize high Mg{sup 2+} cation conductivity even at moderate temperatures. Due to the formation of well-ordered NASICON-type structure, both the high Mg{sup 2+} cation conductivity below 450 °C and the low activation energy for Mg{sup 2+} cation migration was successfully realized for the (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{sub 4}){sub 3} solid. Pure Mg{sup 2+} cation conduction in the NASICON-type (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{sub 4}){sub 3} solid was directly and quantitatively demonstrated by means of two kinds of dc electrolysis. - Graphical abstract: Image of the Mg{sup 2+} cation conduction in NASICON-type (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{sub 4}){sub 3} and its Mg{sup 2+} conductivity. - Highlights: • We develop a three-dimensionally well-ordered NASICON-type Mg{sup 2+} cation conductor. • A high magnesium cation conductivity is realized even at moderate temperatures. • Divalent magnesium cation conduction is demonstrated directly and quantitatively.

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

Doping in controlling the type of conductivity in bulk and nanostructured thermoelectric materials

Doping of materials for thermoelectric applications is widely used nowadays to control the type of conductivity. We report the results of ab-initio calculations aimed at developing the consistent scheme for determining the role of impurities that may change the type of conductivity in two attractive thermoelectric classes of materials. It is demonstrated that alloying of TiNiSn with Cu makes the material of n-type, and alloying with Fe leads to p-type conductivity. Similar calculations for PbTe with small amount of Na substituting for Pb leads to p-type conductivity, while Cl substituting for Te makes PbTe an n-type material. It is shown also that for nano-grained materials the n-type conductivity should be observed. The effect of impurities segregating to the grain boundaries in nano-structured PbTe is also discussed. - Highlights: • Bulk and nano-grained TE materials were analyzed by DFT. • The electronic effects on both PbTe and TiNiSn were demonstrated. • The role of impurities on the conductivity type was analyzed. • Interfacial states in nano-grained PbTe affect the conductivity type.

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

Critical role of polymer-ceramic ion exchange for high conductivity composite electrolytes

Polymer-ceramic composites offer a path to enhance the transport and mechanical properties of solid electrolytes. However, an in-depth understanding of the extent and role of ion transport along and across polymer-ceramic interfaces in these systems is lacking. We have recently shown that Li-conducting Li 0.11 Na 0.24 K 0.02 La 0.43 TiO 2.82 (LMTO) nanorods can be prepared by a molten flux method, and the addition of 30–50 weight (wt.)% LMTO to a bis[(trifluoromethyl)sulfonyl]imide-vinyl ethylene carbonate-based single-ion conducting (SIC) polymer electrolyte leads to a two-fold enhancement in Li-ion conductivity, from 1.4 to 3.0 × 10 −5 S/cm at 30 °C. In the present study, we use NMR methods to identify the Li-ion transport pathways and determine the timescale of chemical exchange between the SIC polymer and LMTO ceramic components. Tracer exchange NMR indicates preferential transport through the polymer or polymer-interfacial regions, and exchange spectroscopy (EXSY) and a new isotope exchange method reveal negligible Li exchange between the SIC polymer and LMTO ceramic up to several days. Here, LMTO nanorods act as a passive filler. Our results further highlight that significant (e.g., 10- or 100-fold) conductivity enhancements in composite electrolytes can only be achieved 1) with ionically-conductive fillers, and 2) when both the ceramic and polymer components actively participate in long-range transport. For this, fast interfacial ion exchange is needed. In conclusion, this leads us to introduce a critical interfacial ion exchange time to evaluate whether a filler actively contributes to conduction in a composite electrolyte, and screen for promising polymer-ceramic pairings to accelerate the development of high conductivity solid electrolytes.

Battery, Solid electrolyte↗
DOE OSTI2018

Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity

Owing to their inherent pore structure, porous metal–organic frameworks (MOFs) can undergo postsynthetic modification, such as loading extra-framework proton carriers. However, strategies for improving the proton conductivity for nonporous MOFs are largely lacking, although increasing numbers of nonporous MOFs exhibit promising proton conductivities. Often, high humidity is required for nonporous MOFs to achieve high conductivities, but to date no clear mechanisms have been experimentally identified. Here we describe the new materials MFM-550(M), [M(HL 1 )], (H 4 L 1 = biphenyl-4,4'-diphosphonic acid; M = La, Ce, Nd, Sm, Gd, Ho), MFM-550(Ba), [Ba(H 2 L 1 )], and MFM-555(M), [M(HL 2 )], (H 4 L 2 = benzene-1,4-diphosphonic acid; M = La, Ce, Nd, Sm, Gd, Ho), and report enhanced proton conductivities in these nonporous materials by (i) replacing the metal ion to one with a lower oxidation state, (ii) reducing the length of the organic ligand, and (iii) introducing additional acidic protons on the MOF surface. Increased framework proton density in these materials can lead to an enhancement in proton conductivity of up to 4 orders of magnitude. Additionally, we report a comprehensive investigation using in situ 2H NMR and neutron spectroscopy, coupled with molecular dynamic modeling, to elucidate the role of humidity in assembling interconnected networks for proton hopping. This study constructs a relationship between framework proton density and the corresponding proton conductivity in nonporous MOFs, and directly explains the role of both surface protons and external water in assembling the proton conduction pathways.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Photo-Cross-Linked Anion Exchange Membranes with Improved Water Management and Conductivity

Robust, cross-linked anion exchange membranes (AEMs) were prepared from solvent-processable polyisoprene- ran -poly(vinylbenzyltrimethylammonium chloride) (PI- ran -P- [VBTMA][Cl]) ionomers via photoinitiated thiol - ene chem- istry. Two series of membranes were prepared choosing two dithiol cross-linkers, 1,10-decanedithiol and 2,2 ' - (ethylenedioxy)diethanethiol, selected for their di ff erent hydro- phobicities. A strong correlation was found between the choice of dithiol cross-linker, water uptake, morphology, and the ion conductivity of the membranes. Results were compared with previous fi ndings of thermally cross-linked AEMs from analogous random copolymers. Comparably high chloride ion conductivities were obtained at low to moderate ion exchange capacities (IECs) with signi fi cantly low water uptake values. It was shown that by choosing a hydrophilic cross-linker ion cluster formation may be suppressed and ion conduction improved. This study highlights that it is possible to promote ion conductivities for low IEC membranes (<1 mmol/g) by forming well- connected, ion conducting network morphology. This observation paves the way for mechanically robust ion conducting membranes with enhanced conductivities and better water management.

Ertem, S. Piril↗
DOE OSTI2016

Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes

In this paper, we perform a joint experimental and computational study of ion transport properties in a systematic set of linear polyethers synthesized via acyclic diene metathesis (ADMET) polymerization. We measure ionic conductivity, σ, and glass transition temperature, T g , in mixtures of polymer and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. While T g is known to be an important factor in the ionic conductivity of polymer electrolytes, recent work indicates that the number and proximity of lithium ion solvation sites in the polymer also play an important role, but this effect has yet to be systematically investigated. Here, adding aliphatic linkers to a poly(ethylene oxide) (PEO) backbone lowers T g and dilutes the polar groups; both factors influence ionic conductivity. To isolate these effects, we introduce a two-step normalization scheme. In the first step, Vogel–Tammann–Fulcher (VTF) fits are used to calculate a temperature-dependent reduced conductivity, σ r (T), which is defined as the conductivity of the electrolyte at a fixed value of T – T g . In the second step, we compute a nondimensional parameter f exp , defined as the ratio of the reduced molar conductivity of the electrolyte of interest to that of a reference polymer (PEO) at a fixed salt concentration. We find that f exp depends only on oxygen mole fraction, x 0 , and is to a good approximation independent of temperature and salt concentration. Molecular dynamics simulations are performed on neat polymers to quantify the occurrences of motifs that are similar to those obtained in the vicinity of isolated lithium ions. Finally, we show that f exp is a linear function of the simulation-derived metric of connectivity between solvation sites. From the relationship between σ r and f exp we derive a universal equation that can be used to predict the conductivity of ether-based polymer electrolytes at any salt concentration and temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗