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DOE OSTI2020

Uncoupling Electrokinetic Flow Solutions

The continuum-scale electrokinetic porous-media flow and excess charge redistribution equations are uncoupled using eigenvalue decomposition. The uncoupling results in a pair of independent diffusion equations for “intermediate” potentials subject to modified material properties and boundary conditions. The fluid pressure and electrostatic potential are then found by recombining the solutions to the two intermediate uncoupled problems in a matrix-vector multiplication. Expressions for the material properties or source terms in the intermediate uncoupled problem may require extended precision or careful rewriting to avoid numerical cancellation, but the solutions themselves can typically be computed in double precision. The approach works with analytical or gridded numerical solutions and is illustrated through two examples. The solution for flow to a pumping well is manipulated to predict streaming potential and electroosmosis, and a periodic one-dimensional analytical solution is derived and used to predict electroosmosis and streaming potential in a laboratory flow cell subjected to low frequency alternating current and pressure excitation. The examples illustrate the utility of the eigenvalue decoupling approach, repurposing existing analytical solutions or numerical models and leveraging solutions that are simpler to derive for coupled physics.

58 GEOSCIENCES↗

DOE OSTI2026

Pore-Scale Transport Effects in Electrochemical CO 2 Reduction on Gold via Coupled Microkinetic-Transport Modeling

A pore-resolved modeling framework is developed to quantify how pore-scale transport affects the intrinsic microkinetics of CO 2 -to-CO on Au. A DFT-informed microkinetic model is coupled self-consistently to a Generalized-Modified Poisson–Nernst–Planck (GMPNP) transport description in a single, electrolyte-filled cylindrical pore, allowing local concentrations and potential to feed back into site-specific reaction rates. FIB-SEM is used to determine pore sizes within realistic electrode materials. Across pore diameters, d p = 10–6000 nm, the surface-averaged CO 2 reduction rate is systematically reduced relative to the ideal microkinetic baseline where mass transport is not accounted for; the effectiveness factor 𝜂 𝑠,CO 2 , which quantifies this ratio, decreases rapidly at more negative potentials and is about 1% near −1.0 V vs SHE due to reactant depletion. Spatial maps reveal pore-bulk alkalization that emerges at higher cathodic bias, with a small, near-wall pH dip due to electrostatic repulsion of hydroxide at the cathode interface. For a fixed aspect ratio L p /d p , narrower pores exhibit larger 𝜂 𝑠,CO 2 by shortening diffusion paths, whereas variations in the aspect ratio L p /d p play a secondary role. A dimensionless analysis (surface/bulk Damköhler numbers) delineates operating regimes. In conclusion, this work offers a concept for incorporating microkinetic models into homogenized porous-electrode models through effectiveness factors and pore-size distribution.

Au-catalyst↗

DOE OSTI2023

Field reversal in low pressure, unmagnetized radio frequency capacitively coupled argon plasma discharges

In general, the radio frequency (rf) electric field within a sheath points toward the metal electrode in low pressure, unmagnetized rf electropositive capacitively coupled plasma (CCP) glow discharges. This is due to the large ratio of electron to ion mobility and the formation of an ion sheath. In this work, we studied, using fully kinetic particle-in-cell simulations, a reversed electric field induced by the strong secondary electron emission during the phase of sheath collapse in a high-voltage rf-driven low pressure CCP glow discharge. We explored the transition behavior of the formation of field reversal as a function of driving voltage amplitude and found that field reversal starts to form at around 750 V, for a discharge with an electrode spacing of 4 cm at 10 mTorr argon pressure driven at 13.56 MHz. Accordingly, the energy distribution function of electrons incident on the electrode shows peaks from around 3 to 10 eV while varying the driving voltage from 150 to 2000 V, showing potentially beneficial effects in plasma material processing where relatively directional electrons are preferred to solely thermal diffusion electrons.

Physics↗

DOE OSTI2022

Measurements of atoms and metastable species in N 2 and H 2 –N 2 nanosecond pulse plasmas

We report time-resolved, absolute number densities of metastable N 2 (A 3 Σ u + , v = 0, 1) molecules, ground state N 2 and H atoms, and rotational–translational temperature have been measured by tunable diode laser absorption spectroscopy and two-photon absorption laser-induced fluorescence in diffuse N 2 and N 2 –H 2 plasmas during and after a nanosecond pulse discharge burst. Comparison of the measurement results with the kinetic modeling predictions, specifically the significant reduction of the N 2 (A 3 Σ u + ) populations and the rate of N atom generation during the burst, suggests that these two trends are related. The slow N atom decay in the afterglow, on a time scale longer than the discharge burst, demonstrates that the latter trend is not affected by N atom recombination, diffusion to the walls, or convection with the flow. This leads to the conclusion that the energy pooling in collisions of N 2 (A 3 Σ u + ) molecules is a major channel of N 2 dissociation in electric discharges where a significant fraction of the input energy goes to electronic excitation of N 2 . Additional measurements in a 1% H 2 –N 2 mixture demonstrate a further significant reduction of N 2 (A 3 Σ u + , v = 0, 1) populations, due to the rapid quenching by H atoms accumulating in the plasma. Comparison with the modeling predictions suggests that the N 2 (A 3 Σ u + ) molecules may be initially formed in the highly vibrationally excited states. The reduction of the N 2 (A 3 Σ u + ) number density also diminishes the contribution of the energy pooling process into N2 dissociation, thus reducing the N atom number density. The rate of N atom generation during the burst also decreases, due to its strong coupling to N 2 (A 3 Σ u + , v) populations. On the other hand, the rate of H atom generation, produced predominantly by the dissociative quenching of the excited electronic states of N 2 by H 2 , remains about the same during the burst, resulting in a nearly linear rise in the H atom number density. Comparison of the kinetic model predictions with the experimental results suggests that the yield of H atoms during the quenching of the excited electronic state of N 2 by molecular H 2 is significantly less than 100%. The present results quantify the yield of N and H atoms in high-pressure H 2 –N 2 plasmas, which have significant potential for ammonia generation using plasma-assisted catalysis

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2016

Implications of Projected Climate Change for Groundwater Recharge in the Western United States

Existing studies on the impacts of climate change on groundwater recharge are either global or basin/ location-specific. The global studies lack the specificity to inform decision making, while the local studies do little to clarify potential changes over large regions (major river basins, states, or groups of states), a scale often important in the development of water policy. An analysis of the potential impact of climate change on groundwater recharge across the western United States (west of 100 degrees longitude) is presented synthesizing existing studies and applying current knowledge of recharge processes and amounts. Eight representative aquifers located across the region were evaluated. For each aquifer published recharge budget components were converted into four standard recharge mechanisms: diffuse, focused, irrigation, and mountain-systems recharge. Future changes in individual recharge mechanisms and total recharge were then estimated for each aquifer. Model-based studies of projected climate-change effects on recharge were available and utilized for half of the aquifers. For the remainder, forecasted changes in temperature and precipitation were logically propagated through each recharge mechanism producing qualitative estimates of direction of changes in recharge only (not magnitude). Several key patterns emerge from the analysis. First, the available estimates indicate average declines of 10-20% in total recharge across the southern aquifers, but with a wide range of uncertainty that includes no change. Second, the northern set of aquifers will likely incur little change to slight increases in total recharge. Third, mountain system recharge is expected to decline across much of the region due to decreased snowpack, with that impact lessening with higher elevation and latitude. Factors contributing the greatest uncertainty in the estimates include: (1) limited studies quantitatively coupling climate projections to recharge estimation methods using detailed, process-based numerical models; (2) a generally poor understanding of hydrologic flowpaths and processes in mountain systems; (3) difficulty predicting the response of focused recharge to potential changes in the frequency and intensity of extreme precipitation events; and (4) unconstrained feedbacks between climate, irrigation practices, and recharge in highly developed aquifer systems.

longitude↗

DOE OSTI2023

CHGNet as a pretrained universal neural network potential for charge-informed atomistic modelling

Large-scale simulations with complex electron interactions remain one of the greatest challenges for atomistic modelling. Although classical force fields often fail to describe the coupling between electronic states and ionic rearrangements, the more accurate ab initio molecular dynamics suffers from computational complexity that prevents long-time and large-scale simulations, which are essential to study technologically relevant phenomena. Here we present the Crystal Hamiltonian Graph Neural Network (CHGNet), a graph neural network-based machine-learning interatomic potential (MLIP) that models the universal potential energy surface. CHGNet is pretrained on the energies, forces, stresses and magnetic moments from the Materials Project Trajectory Dataset, which consists of over 10 years of density functional theory calculations of more than 1.5 million inorganic structures. The explicit inclusion of magnetic moments enables CHGNet to learn and accurately represent the orbital occupancy of electrons, enhancing its capability to describe both atomic and electronic degrees of freedom. We demonstrate several applications of CHGNet in solid-state materials, including charge-informed molecular dynamics in Li x MnO 2 , the finite temperature phase diagram for Li x FePO 4 and Li diffusion in garnet conductors. We highlight the significance of charge information for capturing appropriate chemistry and provide insights into ionic systems with additional electronic degrees of freedom that cannot be observed by previous MLIPs.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Pervasive symmetry-lowering nanoscale structural fluctuations in the cuprate La 2−𝑥 ⁢Sr 𝑥 ⁢Cu⁢O 4

The cuprate superconductors are among the most widely studied quantum materials, yet there remain fundamental open questions regarding their electronic properties and the role of structural degrees of freedom. Recent neutron and x-ray scattering measurements uncovered exponential scaling with temperature of the strength of orthorhombic fluctuations in the tetragonal phase of La 2−𝑥⁢ Sr 𝑥 ⁢Cu⁢O 4 and Tl 2 ⁢Ba 2 ⁢Cu⁢O 6+𝛿 , unusual behavior that closely resembles prior results for the emergence of superconducting fluctuations, and that points to a common origin rooted in inherent correlated structural inhomogeneity. Here, in this study, we use neutron and x-ray diffuse scattering to provide further insight into structural fluctuations in La 2−𝑥 ⁢Sr 𝑥 ⁢Cu⁢O 4 . We perform measurements up to temperatures that approach the melting point of the undoped parent compound, and we investigate the effects of in situ in-plane uniaxial elastic stress and plastic deformation. Our neutron scattering results for the parent compound La 2 ⁢Cu⁢O 4 reveal that short-range orthorhombic fluctuations persist to the maximum experimental temperature of nearly 1000 K, i.e., to a significant fraction of the crystallization temperature. At this temperature, the spatial characteristic length extracted from the momentum-space data is still about three lattice constants. The neutron scattering experiment enables quasistatic discrimination and reveals that the response is increasingly dynamic at higher temperatures. We also find that neither compressive elastic stress along the tetragonal [110] direction nor irreversible plastic deformation activating the ⟨100⟩⁢[001] slip system significantly alter the robust orthorhombic fluctuations. Overall, these results support the notion that these fluctuations couple to subtle, underlying inhomogeneity that underpins the cuprate phase diagram. Finally, in La 1.8⁢ Sr 0.2⁢ Cu⁢O 4 , we uncover low-energy structural fluctuations at a nominally forbidden reflection that are distinct from the orthorhombic distortions. While the origin of these fluctuations is not clear, they might be related to the presence of extended defects such as dislocations or stacking faults.

Spieker, R. J. [Univ. of Minnesota, Minneapolis, M↗

DOE OSTI2021

An unstructured C-grid type variational formulation for the sea ice dynamics

Historically, B-grid formulations of sea ice dynamics have been dominant because they have matched the grid type used by ocean models. The reason for the grid match is simple – it facilitates penetration of the curl of ice-ocean stress into the deep ocean with minimal numerical diffusivity because sea ice and ocean velocity are co-located. In recent years, as ocean models have increasingly progressed to C-grids, sea ice models have followed suit on quadrilateral meshes, but the implementation of an unstructured C-grid sea ice models is new. We present an unstructured C-grid discretization of the Elastic Viscous Plastic (EVP) rheology, where the velocity unknowns are discretized at the edges of the mesh cells with n-sides, where typically n is greater than or equal to four, rather than at the vertices, as in the B-grid. Our framework of choice is the Model for Prediction Across Scales (MPAS) within E3SM, the climate model of the U.S. Department of Energy, although our approach is general and could be applied to other models as well. While MPAS-Seaice is currently defined on a B-grid, MPAS-Ocean runs on a C-grid, hence interpolation operators are heavily used when coupled simulations are performed. In this work, we describe a mathematical formulation to transition the dynamics of MPAS-Seaice to a C-grid, in order to ultimately facilitate the coupling with MPAS-Ocean and reduce numerical errors associated with this communication. Numerical results are reported to highlight the features of the method.

58 GEOSCIENCES↗

NASA NTRS2013

Bismuth Passivation Technique for High-Resolution X-Ray Detectors

The Athena-plus team requires X-ray sensors with energy resolution of better than one part in 3,000 at 6 keV X-rays. While bismuth is an excellent material for high X-ray stopping power and low heat capacity (for large signal when an X-ray is stopped by the absorber), oxidation of the bismuth surface can lead to electron traps and other effects that degrade the energy resolution. Bismuth oxide reduction and nitride passivation techniques analogous to those used in indium passivation are being applied in a new technique. The technique will enable improved energy resolution and resistance to aging in bismuth-absorber-coupled X-ray sensors. Elemental bismuth is lithographically integrated into X-ray detector circuits. It encounters several steps where the Bi oxidizes. The technology discussed here will remove oxide from the surface of the Bi and replace it with nitridized surface. Removal of the native oxide and passivating to prevent the growth of the oxide will improve detector performance and insulate the detector against future degradation from oxide growth. Placing the Bi coated sensor in a vacuum system, a reduction chemistry in a plasma (nitrogen/hydrogen (N2/H2) + argon) is used to remove the oxide and promote nitridization of the cleaned Bi surface. Once passivated, the Bi will perform as a better X-ray thermalizer since energy will not be trapped in the bismuth oxides on the surface. A simple additional step, which can be added at various stages of the current fabrication process, can then be applied to encapsulate the Bi film. After plasma passivation, the Bi can be capped with a non-diffusive layer of metal or dielectric. A non-superconducting layer is required such as tungsten or tungsten nitride (WNx).

Chervenak, James↗

DOE OSTI2025

Coherent Control over Nuclear Hyperpolarization Using an Optically Initializable Chromophore-Radical System

Chromophore radicals (CR) are emerging as important components for molecular quantum information science (QIS), especially in the context of quantum sensing. Here, we demonstrate that the optically hyperpolarized electrons in a 1,6,7,12-tetrakis(4-tert-butylphenoxy)-perylene-3,4,9,10-bis(dicarboximide) (tpPDI) covalently linked to a partially deuterated 1,3-bis(diphenylene)-d 16 -2-phenylallyl radical (BDPA-d 16 ) can be coherently manipulated via pulsed dynamic nuclear polarization (DNP) methods to transfer polarization to nuclear spins and back. Under light illumination at 85 K, electron hyperpolarization in BDPA is enhanced 2.1- to 2.4-fold over thermal polarization and lasts for more than 100 ms. By applying nuclear orientation via electron spin-locking (NOVEL) DNP, this optically amplified electron hyperpolarization was successfully transferred to a 1 H nuclear spin within the CR system and efficiently returned to the electron spin for readout via reverse-NOVEL. The NOVEL transfer efficiency of 65% amounts to a 688-fold nuclear spin hyperpolarization of the target nuclear spin, considering the 2.1-fold electron spin hyperpolarization. This reversible coherent manipulation of hyperpolarization transfer highlights the utility of CR systems to initialize and read out nuclear spin states in a disordered matrix at moderate cryogenic temperatures. Coupled with CRs’ environmental compatibility, tunability, and precise state initialization, these results highlight the promising role of nuclear spins in CRs for QIS applications, including quantum sensing and memory.

charge transfer↗

DOE OSTI2022

Rapid depletion analysis of flowing-pebble reactor systems at equilibrium using SCALE

Several high-temperature gas-cooled reactor concepts (and more recently, salt-cooled designs such as the fluoride salt-cooled high-temperature reactor) feature core designs employing continuously circulating fuel pebbles. These reactor designs permit both continuous online refueling of fuel elements as well as higher overall achievable discharge burnups. However, rapid calculation of time-dependent fuel isotopic inventories proves challenging for this class of dynamic systems with current analysis tools. While iterative approaches employing coupled neutron transport have been developed to solve this issue, rapid depletion analysis techniques are needed to calculate time-dependent inventories for individual pebbles and batches (and thus the construction of full- core inventory at equilibrium). We propose a depletion analysis strategy for this type of system for cores at equilibrium. Drawing upon previous neutronic analysis of the PBMR-400 equilibrium core, we demonstrate the viability of developing collapsed one-group cross section libraries suitable for performing rapid depletion analyses with SCALE. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2023

Observations of Offshore Internal Boundary Layers

The growth of the marine internal boundary layer (MIBL, height h i ) with the shore-normal distance x, is a topic of continuing interest because of its applications in coastal dispersion, offshore wind farm siting, coastal air-sea fluxes and in evaporative ducting. Available data on MIBL are only scarce, given its difficult to measure the variability of coastal winds. During Coupled Air-Sea Processes and Electromagnetic Research (CASPER) campaigns an array of instrumentation was deployed to measure offshore spatial variability and its effect on electromagnetic wave propagation. Meteorological sensors (flux towers and remote sensing) were deployed along the coast of Point Mugu, California, on a research vessel and FLoating Instrument Platform (FLIP) provided surface layer and boundary layer observations. In this article, measurements from multiple remote sensing instruments, such as synchronized triple Doppler lidars, small boat operations with tethered lifting system, and radiosondes provide a holistic view of the MIBL growth and its spatial variability from the coast. A convective and stable MIBL observed during two intensive operating period days showed distinct growth characteristics off the coast of Point-Mugu. During stable stratified atmospheric conditions, an MIBL was observed at least up to 47 km from the coast. The growth of the MIBL within the nearshore adjustment zone was influenced by surrounding atmospheric, oceanographic, and topographic conditions. A new parameterization scheme is developed based on advection-diffusion balance equations accounting for upstream turbulence and compared with h i observations from Doppler lidar and profiles from small boat. An evaluation of existing IBL theories was also conducted.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1994

The coupling between flame surface dynamics and species mass conservation in premixed turbulent combustion

Current flamelot models based on a description of the flame surface dynamics require the closure of two inter-related equations: a transport equation for the mean reaction progress variable, (tilde)c, and a transport equation for the flame surface density, Sigma. The coupling between these two equations is investigated using direct numerical simulations (DNS) with emphasis on the correlation between the turbulent fluxes of (tilde)c, bar(pu''c''), and Sigma, (u'')(sub S)Sigma. Two different DNS databases are used in the present work: a database developed at CTR by A. Trouve and a database developed by C. J. Rutland using a different code. Both databases correspond to statistically one-dimensional premixed flames in isotropic turbulent flow. The run parameters, however, are significantly different, and the two databases correspond to different combustion regimes. It is found that in all simulated flames, the correlation between bar(pu''c'') and (u'')(sub S)Sigma is always strong. The sign, however, of the turbulent flux of (tilde)c or Sigma with respect to the mean gradients, delta(tilde)c/delta(x) or delta(Sigma)/delta(x), is case-dependent. The CTR database is found to exhibit gradient turbulent transport of (tilde)c and Sigma, whereas the Rutland DNS features counter-gradient diffusion. The two databases are analyzed and compared using various tools (a local analysis of the flow field near the flame, a classical analysis of the conservation equation for (tilde)(u''c''), and a thin flame theoretical analysis). A mechanism is then proposed to explain the discrepancies between the two databases and a preliminary simple criterion is derived to predict the occurrence of gradient/counter-gradient turbulent diffusion.

Trouve, A.↗

NASA NTRS2019

Contribution of ULF Wave Activity to the Global Recovery of the Outer Radiation Belt During the Passage of a High‐Speed Solar Wind Stream Observed in September 2014

Energy coupling between the solar wind and the Earth's magnetosphere can affect the electron population in the outer radiation belt. However, the precise role of different internal and external mechanisms that leads to changes of the relativistic electron population is not entirely known. This paper describes how ultralow frequency (ULF) wave activity during the passage of Alfvenic solar wind streams contributes to the global recovery of the relativistic electron population in the outer radiation belt. To investigate the contribution of the ULF waves, we searched the Van Allen Probes data for a period in which we can clearly distinguish the enhancement of electron ﬂuxes from the background. We found that the global recovery that started on 22 September 2014, which coincides with the corotating interaction region preceding a high‐speed stream and the occurrence of persistent substorm activity, provides an excellent scenario to explore the contribution of ULF waves. To support our analyses, we employed ground‐ and space‐based observational data and global magnetohydrodynamic simulations and calculated the ULF wave radial diffusion coefﬁcients employing an empirical model. Observations show a gradual increase of electron ﬂuxes in the outer radiation belt and a concomitant enhancement of ULF activity that spreads from higher to lower L‐shells. Magnetohydrodynamic simulation results agree with observed ULF wave activity in the magnetotail, which leads to both fast and Alfven modes in the magnetospheric nightside sector. The observations agree with the empirical model and are conﬁrmed by phase space density calculations for this global recovery period.

Silva, L. A. Da↗

DOE OSTI2025

A minor respiratory process with major global implications: is atmospheric methane oxidation in tree stems driven by stem respiration rather than microbial methanotrophy?

Tree stem surfaces are widely recognized as sites of carbon dioxide (CO₂) efflux and oxygen (O₂) influx, reflecting the dynamics of aerobic respiration of photosynthate substrates, such as sugars, delivered via the phloem. Stems are also largely considered passive conduits for methane (CH₄) produced in anoxic soils via microbial methanogenesis, where CH₄ is thought to be transported upward through the transpiration stream and/or diffusion and emitted through stem surfaces and the canopy. However, recent observations from dynamic stem chambers suggest that stems may also act as active sinks for atmospheric CH₄. Despite these findings, the extent and drivers of stem CH₄ consumption remain poorly characterized across biomes, species, and environmental gradients, and its quantitative relationship to stem respiration has not been established. Moreover, previous studies captured only snapshot fluxes, leaving diurnal patterns of CH₄ exchange uncharacterized. Here, we address these limitations by combining real-time measurements of stem CH₄ and O₂ uptake under ambient conditions in a California cherry tree, using a dynamic stem gas exchange system with three chambers receiving a continuous flow of ambient air and automated chamber and reference air sampling every 10 min. Our results confirm that stems of upland trees can actively consume both atmospheric CH₄ and O₂, but with decreasing temperature sensitivity as daily temperatures increase. Early mornings were marked by rapid influxes of both gases, followed by declining uptake as temperatures rose further. Methane uptake was tightly coupled with O₂ influx and represented a minor (0.012% ± 0.002%) fraction of stem respiratory activity, as determined by concurrent O₂ uptake. These findings suggest that while atmospheric CH₄ oxidation is a minor respiratory process in stems, it is strongly linked with stem physiological activity. This challenges the current assumption that terrestrial CH₄ uptake is driven solely by microbial methanotrophy and raises the possibility that living stem tissues may contribute to CH₄ oxidation through an as-yet-unidentified plant-based mechanism.

Atmospheric greenhouse gases↗

DOE OSTI2020

Experimental and DFT Calculated IR Spectra of Guests in Zeolites: Acyclic Olefins and Host-Guest Interactions

We performed experimental and periodic density functional theory (DFT) IR spectroscopy to investigate the adsorption of acyclic olefins over both acidic and non-acidic zeolites. Two conjugated polyenes, 2,4-dimethyl-1,3-pentadiene (I) and 2,6-dimethyl-2,4,6-octatriene (II) were studied to probe organic intermediates that can form during methanol conversion, and that can lead to deactivating species known collectively as “coke.” We computed vibrational spectra using zeolite-adsorbed and gas-phase models for both neutral and protonated forms of I and II, and compared these DFT results to diffuse reflectance IR Fourier transform (DRIFT) spectra of zeolite-guest systems. Our experimental and computational results are precise enough to pinpoint that the gauche s-cis conformation of species I predominates during adsorption over de-aluminated zeolite beta. Computed zeolite-adsorbed spectra of the protonated species I and II best represent the DRIFT spectra obtained after the adsorption of the olefins on HMOR at 20 ?, with computed bands at 1543 and 1562 cm–1 for molecules I+ and II+, respectively, attributed to the allylic stretching mode, ?(C=C–C+). These computed band frequencies are within 6 cm–1 of experimental data and confirm that the interaction between neutral acyclic olefins and acidic zeolites leads to protonation of the olefin. Comparison of computed spectra of the protonated species in the gas phase to those in the zeolite indicates that the electrostatic interaction between alkenyl and alkadienyl cations and negative zeolite framework does not significantly impact the position of the allylic stretching bands. These results highlight that computed spectroscopy and thermodynamics coupled with experimental spectra can be used for elucidating complex mixtures in zeolites, and certain spectral features of adsorbed olefins can be accurately modeled by gas-phase calculations. ACKNOWLEDGMENTS BM and SMA were supported by the National Science Foundation under Award # CBET-1512442. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support (or partial support) of this research (#589978-ND5, EDH and FCJ). MDB was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Materials Science and Engineering. CJM was supported by the DOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated by Battelle for the U.S. DOE. Computing resources were generously provided through PNNL’s institutional computing (PIC).

Manookian, Babgen↗

DOE OSTI2023

The Linkage Between Electro-Chemical Mechanical Instabilities in Battery Materials

Battery chemistry must be diversified to achieve a sustainable energy landscape by effectively utilizing renewable energy sources. Alkali metal-ion, all-solid-state, metal–air batteries, and multivalent batteries offer unique cost, safety, raw material abundance, energy, and power density solutions. However, realizing these “beyond Li-ion batteries” must uncover their working principles and performance & property relationships. In this aspect, mitigating chemo-mechanical instabilities in the structure and surface of the electrodes plays a crucial role in their performance. Unfortunately, the coupling between electrochemical and mechanical interactions is often poorly understood due to a lack of operando characterization. Here, this review article explains the working principles of curvature measurement and digital image correlation for measuring stress and strain generations in battery materials. We provided specific examples of how these operando mechanical measurements shed light on instabilities in alkali metal ion electrodes, solid electrolytes, Li-O 2 batteries, and aqueous Zn-ion batteries. Operando mechanical measurements offer an effective way to map changes in the physical fingerprint of the battery materials, therefore providing crucial information to elucidate instabilities in battery materials.

25 ENERGY STORAGE↗

DOE OSTI2025

Synthetic Accessibility and Sodium Ion Conductivity of the Na8–x A x P2O9 (NAP) High-Temperature Sodium Superionic Conductor Framework

Advancement of solid-state electrolytes (SSEs) for all solid-state batteries typically focuses on modification of a known structural framework to improve conductivity, e.g., cation substitution for an immobile ion or varying the concentration of the mobile ions. Novel frameworks can be disruptive by enabling fast ion conduction aided by different structure and diffusion mechanisms, thereby unlocking optimal conductors with different properties. Herein, we perform a high-throughput survey of a structural framework for sodium ion conduction, Na8–x A x P2O9 (NAP), to understand the family’s thermodynamic stability, synthesizability, and ionic conduction. We show that the parent phase Na4TiP2O9 (NTP) undergoes a structural distortion (with accompanying conductivity transition) due to unstable phonons arising from pseudo-Jahn–Teller mode in the 1D titanium chains. Screening compounds in which Ti is substituted by other metals computationally reveal a number of candidates that are predicted to be low in formation energy and have high predicted ionic conductivities. High-throughput experimental and subsequent methodology optimization trials deliver one new compound, Na4SnP2O9 (NSP). X-ray diffraction (XRD), microscopy, and spectroscopy characterization indicate that the room-temperature structure of NSP is similar to the high-temperature, orthorhombic NTP phase but with some small unresolved structural differences. These uncharacterized structural details are speculated to limit the ion conductivity. Temperature-dependent XRD and electrochemical impedance spectroscopy indicate multiple coupled conductivity–structure transitions at a high temperature. We demonstrate the challenges with synthesis development and a priori identification of promising SSE phases as a major bottleneck in new (energy) materials development.

Chemical reactions↗