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

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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Investigating the Tropospheric Chemistry of Acetic Acid Using the Global 3‐D Chemistry Transport Model, STOCHEM‐CRI

Abstract Acetic acid (CH 3 COOH) is one of the most abundant carboxylic acids in the troposphere. In the study, the tropospheric chemistry of CH 3 COOH is investigated using the 3‐D global chemistry transport model, STOCHEM‐CRI. The highest mixing ratios of surface CH 3 COOH are found in the tropics by as much as 1.6 ppb in South America. The model predicts the seasonality of CH 3 COOH reasonably well and correlates with some surface and flight measurement sites, but the model drastically underpredicts levels in urban and midlatitudinal regions. The possible reasons for the underprediction are discussed. The simulations show that the lifetime and global burden of CH 3 COOH are 1.6–1.8 days and 0.45–0.61 Tg, respectively. The reactions of the peroxyacetyl radical (CH 3 CO 3 ) with the hydroperoxyl radical (HO 2 ) and other organic peroxy radicals (RO 2 ) are found to be the principal sources of tropospheric CH 3 COOH in the model, but the model‐measurement discrepancies suggest the possible unknown or underestimated sources which can contribute large fractions of the CH 3 COOH burden. The major sinks of CH 3 COOH in the troposphere are wet deposition, dry deposition, and OH loss. However, the reaction of CH 3 COOH with Criegee intermediates is proposed to be a potentially significant chemical loss process of tropospheric CH 3 COOH that has not been previously accounted for in global modeling studies. Inclusion of this loss process reduces the tropospheric CH 3 COOH level significantly which can give even larger discrepancies between model and measurement data, suggesting that the emissions inventory and the chemical production sources of CH 3 COOH are underpredicted even more so in current global models.

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

Optimization of Structural Flood Mitigation Strategies

The dynamics of flooding are primarily influenced by the shape, height, and roughness (friction) of the underlying topography. For this reason, mechanisms to mitigate floods frequently employ structural measures that either modify topographic elevation, for example, through the placement of levees and sandbags, or increase roughness, for example, through revegetation projects. However, the configuration of these measures is typically decided in an ad hoc manner, limiting their overall effectiveness. The advent of high–performance surface–water modeling software and improvements in black–box optimization suggest that a more principled design methodology may be possible. This paper proposes a new computational approach to the problem of designing structural mitigation strategies under physical and budgetary constraints. It presents the development of a problem discretization amenable to simulation–based, derivative–free optimization. However, meta–heuristics alone are found to be insufficient for obtaining quality solutions in a reasonable amount of time. As a result, this paper proposes novel numerical and physics–based procedures to improve convergence to a high–quality mitigation. Furthermore the efficiency of the approach is demonstrated on hypothetical dam break scenarios of varying complexity under various mitigation budget constraints. In particular, experimental results show that, on average, the final proposed algorithm results in a 65% improvement in solution quality compared to a direct implementation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Implementation of an Orographic Drag Scheme Considering Orographic Anisotropy in All Flow Directions in the Earth System Model CAS‐ESM 2.0

Abstract A reasonable representation of orographic anisotropy in earth system models is vital for improving weather and climate modeling. In this study, we implement the orographic drag scheme, including 3‐D orographic anisotropy (3D‐AFD), into the Chinese Academy of Sciences Earth System Model version 2 (CAS‐ESM 2.0). Three groups of simulations named sensitivity run, medium‐range forecast, and seasonal forecast respectively are conducted using the updated CAS‐ESM model and validated against station observation and reanalysis data. These simulations are run using the three schemes—3D‐AFD scheme, the 3D orographic anisotropy scheme for the eight‐direction (3D‐8x), and the 2D isotropic scheme (2D)—to compare their performance in CAS‐ESM 2.0. Sensitivity runs show that the 3D‐AFD provide more continuous transition of calculated drag as function of wind direction than the 3D‐8x, while the drag calculated using the 2D scheme show no variation with change of wind direction. Enhanced drag in the medium range and seasonal forecast using the updated CAS‐ESM alleviates part of the winter wind speed bias over the Tibetan Plateau (TP) and the cold bias over TP and the Siberian polar region. It is shown that the 3D‐AFD scheme alleviates more bias than that of the 3D‐8x scheme (by wind speed reduction of 1 ∼ 2 m/s and temperature of 1 ∼ 2 K) especially in the seasonal forecast. The results suggest that reasonable representation of the orographic anisotropy is important in climate modeling.

Xie, Jinbo↗
DOE OSTI2025

Assessing Clouds in GFDL's AM4.0 With Different Microphysical Parameterizations Using the Satellite Simulator Package COSP

We evaluate cloud simulations using satellite simulators against multiple observational data sets. These simulators have been run within the Geophysical Fluid Dynamics Laboratory's Atmosphere Model version 4.0 (AM4.0), as well as an alternative configuration where a fully two‐moment Morrison‐Gettelman cloud microphysical parameterization with prognostic precipitation (MG2) is applied, denoted as AM4‐MG2. The modeled cloud spatial distributions, vertical profiles, phase partitioning, cloud‐to‐precipitation transitions, and radiative effects compare reasonably well with satellite observations. Model biases include the under‐prediction of total and low‐level clouds, especially optically thin/intermediate clouds with cloud optical depth of less than 23, but the over‐prediction of thick clouds, indicating “too few, too bright” biases. These biases counteract each other, and give rise to reasonable estimates of cloud radiative effects. The underestimate of low‐level clouds is associated with too early and too frequent drizzle/precipitation formation. The precipitation bias is improved in AM4‐MG2, where the autoconversion scheme initiates the precipitation more realistically. There also exist discrepancies between models and observations for midlevel and high‐level clouds. Additional biases include the underestimate of liquid cloud fraction and the overestimate of ice cloud fraction.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Assessing Simulations of Forest Hurricane Disturbance and Recovery in Puerto Rico by ELM-FATES Using Field Measurements

In the past three decades, Puerto Rico (PR) experienced five hurricanes that met or exceeded category three, and they caused severe forest structural damage and elevated tree mortality. To improve our mechanistic understanding of hurricane impacts on tropical forests and assess hurricane-affected forest dynamics in Earth system models, we use in situ forest measurements at the Bisley Experimental Watersheds in Northeast PR to evaluate the Functionally Assembled Terrestrial Ecosystem Simulator coupled with the Energy Exascale Earth System Model Land Model (ELM-FATES). The observations show that before Hurricane Hugo, 77.3% of the aboveground biomass (AGB) is from the shade-tolerant plant function type (PFT). The Hugo-induced mortality rates are over ~50%, and they induce a ~39% AGB reduction, which recovers to a level like the pre-Hugo condition in 2014, following a second, lower intensity hurricane, Georges. We perform numerical experiments that simulate damage from Hugo and Georges on the forests, including defoliation, sapwood and structural biomass damage, and hurricane-induced mortality. ELM-FATES can reasonably represent coexistence between the two PFTs–light-demanding and shade-tolerant–for both the pre-Hugo and post-Hugo conditions. The model represents a reasonable size distribution of mid-and large-sized trees although it underestimates AGB, likely due to the overestimated nonhurricane mortality. ELM-FATES temporarily stimulated leaf biomass and diameter increment after Georges, an effect that should be tested with observations of future hurricane defoliation events. This research indicates that addressing model-data mismatches in tree mortality and understory dynamics are essential to simulation of more extreme hurricane effects under climate change.

58 GEOSCIENCES↗
DOE OSTI2025

Impacts of Bulk Microphysics Scheme Structural Choices on Simulations of Rain Initiation Through Drop Coalescence

This study examines how different structural choices in bulk microphysics schemes impact the simulation of warm rain initiation. A single liquid category (SLC) approach prognosing up to four moments of a single drop size distribution (DSD) is compared to the traditional two-category, two-moment approach with separate DSDs for cloud and rain (four total prognostic variables). Different methods for calculating tendencies of the prognostic variables from drop collision-coalescence are also tested: a discretized numerical-integration approach, machine learning via neural networks, lookup tables, and traditional power law fits. Relative to simulations using a bin microphysics model, SLC gives smaller error overall than the two-category approach when numerical integration is used to calculate the collision-coalescence tendencies for both. Replacing the numerical integration with a pre-computed lookup table reduces computational cost with little loss of accuracy. However, using fitted power laws with SLC to represent the collision-coalescence tendencies substantially reduces accuracy and leads to an order of magnitude increase in error. It is also demonstrated that with SLC, reasonably accurate solutions are obtained using only three prognostic moments, while a two-moment SLC scheme leads to substantial error. Overall, both the choice of prognostic moments (e.g., SLC vs. two-category) and method to calculate the collision-coalescence tendencies are important to consider for minimizing errors in bulk schemes. SLC with a sufficiently detailed calculation of the collision-coalescence tendencies provides accurate solutions for a reasonable computational cost, providing a viable alternative to the traditional two-category, two-moment approach for bulk microphysics.

320 (cloud physics and chemistry)↗
DOE OSTI2015

Patched bimetallic surfaces are active catalysts for ammonia decomposition

In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Atomic-scale origin of the low grain-boundary resistance in perovskite solid electrolyte Li 0.375 Sr 0.4375 Ta 0.75 Zr 0.25 O 3

Oxide solid electrolytes (OSEs) have the potential to achieve improved safety and energy density for lithium-ion batteries, but their high grain-boundary (GB) resistance generally is a bottleneck. In the well-studied perovskite oxide solid electrolyte, Li 3x La 2/3-x TiO 3 (LLTO), the ionic conductivity of grain boundaries is about three orders of magnitude lower than that of the bulk. In contrast, the related Li 0.375 Sr 0.4375 Ta 0.75 Zr 0.25 O 3 (LSTZ0.75) perovskite exhibits low grain boundary resistance for reasons yet unknown. Here, we use aberration-corrected scanning transmission electron microscopy and spectroscopy, along with an active learning moment tensor potential, to reveal the atomic scale structure and composition of LSTZ0.75 grain boundaries. Vibrational electron energy loss spectroscopy is applied for the first time to reveal atomically resolved vibrations at grain boundaries of LSTZ0.75 and to characterize the otherwise unmeasurable Li distribution therein. We find that Li depletion, which is a major reason for the low grain boundary ionic conductivity of LLTO, is absent for the grain boundaries of LSTZ0.75. Instead, the low grain boundary resistivity of LSTZ0.75 is attributed to the formation of a nanoscale defective cubic perovskite interfacial structure that contained abundant vacancies. Our study provides new insights into the atomic scale mechanisms of low grain boundary resistivity.

25 ENERGY STORAGE↗
DOE OSTI2023

Combining data and theory for derivable scientific discovery with AI-Descartes

Abstract Scientists aim to discover meaningful formulae that accurately describe experimental data. Mathematical models of natural phenomena can be manually created from domain knowledge and fitted to data, or, in contrast, created automatically from large datasets with machine-learning algorithms. The problem of incorporating prior knowledge expressed as constraints on the functional form of a learned model has been studied before, while finding models that are consistent with prior knowledge expressed via general logical axioms is an open problem. We develop a method to enable principled derivations of models of natural phenomena from axiomatic knowledge and experimental data by combining logical reasoning with symbolic regression. We demonstrate these concepts for Kepler’s third law of planetary motion, Einstein’s relativistic time-dilation law, and Langmuir’s theory of adsorption. We show we can discover governing laws from few data points when logical reasoning is used to distinguish between candidate formulae having similar error on the data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A North Atlantic synthetic tropical cyclone track, intensity, and rainfall dataset

Tropical Cyclones (TCs) cause significant socio-economic damages to the US and Caribbean coastal regions annually, making it important to understand TC risk at the local-to-regional scales. However, the short length of the observed record and the substantial computational expense associated with high-resolution climate models make it difficult to assess TC risk using either approach. To overcome these challenges, we developed a database of synthetic TCs using the Risk Analysis Framework for Tropical Cyclones (RAFT). The database includes 40,000 synthetic TC tracks, along-track intensities and storm-induced precipitation. TC tracks generated in RAFT are in reasonable agreement with the observed spatial distribution of TC tracks and basin-scale TC statistics. Specifically, along the coast, spatial variations in TC crossing probability and extreme winds upon landfall are well-reproduced by RAFT with R-squared values of 0.81 and 0.73, respectively. In summary, the synthetic TC database constructed with RAFT provides a reasonable pathway for the robust assessment of North Atlantic TC wind and rainfall risks.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Standardized protocols for evaluating platinum group metal-free oxygen reduction reaction electrocatalysts in polymer electrolyte fuel cells

Platinum group metal (PGM)-free electrocatalysts for the oxygen reduction reaction at the polymer electrolyte fuel cell cathode have shown substantial improvements in activity—especially those derived from transition metals, nitrogen and carbon. However, their stability and durability remain insufficient. A key to enabling future improvements and performance comparisons lies in the development of test protocols that are relevant to the operating conditions of the fuel cell cathode, can be completed within a reasonable time and are ubiquitously adopted. Here we propose and validate such protocols, designed with special attention to typical catalyst degradation mechanisms of PGM-free catalysts. The results of the cross-laboratory validation study using two different catalysts attest to the strength and feasibility of the proposed approach. We hope that the information provided here can serve as a broad and effective platform for assessing the performance and durability of PGM-free catalysts for polymer electrolyte fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2016

Amyloid structure exhibits polymorphism on multiple length scales in human brain tissue

Although aggregation of Aβ amyloid fibrils into plaques in the brain is a hallmark of Alzheimer's Disease (AD), the correlation between amyloid burden and severity of symptoms is weak. One possible reason is that amyloid fibrils are structurally polymorphic and different polymorphs may contribute differentially to disease. However, the occurrence and distribution of amyloid polymorphisms in human brain is poorly documented. Here we seek to fill this knowledge gap by using X-ray microdiffraction of histological sections of human tissue to map the abundance, orientation and structural heterogeneities of amyloid within individual plaques; among proximal plaques and in subjects with distinct clinical histories. A 5 µ x-ray beam was used to generate diffraction data with each pattern arising from a scattering volume of only ~ 450 µ3 , making possible collection of dozens to hundreds of diffraction patterns from a single amyloid plaque. X-ray scattering from these samples exhibited all the properties expected for scattering from amyloid. Amyloid distribution was mapped using the intensity of its signature 4.7 Å reflection which also provided information on the orientation of amyloid fibrils across plaques. Margins of plaques exhibited a greater degree of orientation than cores and orientation around blood vessels frequently appeared tangential. Variation in the structure of Aβ fibrils is reflected in the shape of the 4.7 Å peak which usually appears as a doublet. Variations in this peak correspond to differences between the structure of amyloid within cores of plaques and at their periphery. Examination of tissue from a mismatch case - an individual with high plaque burden but no overt signs of dementia at time of death - revealed a diversity of structure and spatial distribution of amyloid that is distinct from typical AD cases. As a result, we demonstrate the existence of structural polymorphisms among amyloid within and among plaques of a single individual and suggest the existence of distinct differences in the organization of amyloid in subjects with different clinical presentations.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Pure and Zn-doped Pt Clusters go Flat and Upright on MgO(100)

Pure and doped sub-nanoclusters can exhibit superb catalytic activity, which, however, strongly depends on their size, shape, composition, and the nature of the support. This work is about surface-deposited sub-nano Pt-based clusters, which are promising catalysts for the reactions of dehydrogenation. Using density functional theory and ab initio calculations, and an ab initio genetic algorithm for finding the global minima of clusters, we found a peculiar effect that Pt₅ and Pt₄Zn clusters exhibit upon deposition on MgO(100). Both of them change shapes from the gas phase 3-D form to a planar form, and they stand upright on the support. Several reasons are responsible for this behaviour. In part, clusters go flat due to the electron transfer from the support. Indeed, the anionic Pt₅- and Pt₄Zn- species are flat also in the gas phase. Charging induces the second-order Jahn–Teller effect (or partial covalency) facilitated by the recruitment of the higher-energy 6p atomic orbitals on Pt into the valence manifold, and that is the reason for the planarization of the anions. Secondly, clusters maximize interactions with the surface O atoms (resulting in further favouring of 2-D structures over 3-D), and avoid contacts with surface Mg atoms (resulting in upright morphologies).

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

D 5h [PhSiO 1.5 ] 10 synthesis via F – catalyzed rearrangement of [PhSiO 1.5 ] n . An experimental/computational analysis of likely reaction pathways

We describe here in this paper the synthesis and analysis of the reaction pathways leading to formation of the rare D 5h decaphenylsilsesquioxane (SQ) [PhSiO 1.5 ] 10 via F – catalyzed rearrangement of [PhSiO 1.5 ] n n = 8, 12, and oligomers initially synthesized from PhSi(OEt) 3 . Isolated yields of ~50% [PhSiO 1.5 ] 10 are obtained via rearrangement of all starting materials. The recovered starting materials can be re-equilibrated using catalytic F – to generate similar yields in second batches. These yields arise because [PhSiO 1.5 ] 10 exhibits higher solubility and better energy stabilization (10 kcal mol –1 theory) in CH 2 Cl 2 compared to [PhSiO 1.5 ] 8 or [PhSiO 1.5 ] 12 . Reaction intermediates were identified using time dependent 19 F NMR and MALDI-ToF mass spectrometry eventually equilibrating to form the 8: 10 : 12 cages in a 1 : 3 : 1.3 equilibrium in CH 2 Cl 2 . Experimental results coupled with modeling using the Gamess computational package provide multiple reasonable pathways for SQ rearrangements to [RSiO 1.5 ] 10 , starting from [RSiO 1.5 ] 8 . Heats of reaction for interconversion of the model intermediates [HSiO 1.5 ] x determined computationally, were used to select the most reasonable reaction pathways. The findings support a mechanism involving activation and cleavage of a T 8 cage corner by F – attachment, followed by the corners stepwise removal as [ i.e. RSi(OH) 3 ], followed thereafter by reinsertion forming [RSiO 1.5 ] 9 –OH followed by, insertion of another corner to form [RSiO 1.5 ] 10 –(OH) 2 and finally condensation to give [RSiO 1.5 ] 10 . The most enthalpically favorable path (–24 kcal mol –1 ) involves a hybrid mechanism.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Electrochemical properties and structural evolution of O3-type layered sodium mixed transition metal oxides with trivalent nickel

The electrochemical properties of NaNi 0.5 Co 0.5 O 2 and NaNi 0.5 Fe 0.5 O 2 and their structural transitions as a function of Na extraction associated with redox reactions are investigated. Synthesized in the O3-type layered structure, both materials show reasonable electrochemical activities at room temperature, delivering approximately 0.5 Na per formula unit at C/10 discharge. More Na can be reversibly cycled in NaNi 0.5 Co 0.5 O 2 at elevated temperature and/or in an extended voltage window, while NaNi 0.5 Fe 0.5 O 2 shows significant capacity fading at a high voltage cutoff which is likely due to Fe 4+ migration. In situ X-ray diffraction shows that the structural changes in the two materials upon desodiation are very different. NaNi 0.5 Co 0.5 O 2 goes through many different two-phase reactions including three different O3-type and three different P3-type structures during cycling, producing a voltage profile with multiple plateau-like features. In contrast, NaNi 0.5 Fe 0.5 O 2 has a smooth voltage profile and shows the typical O3–P3 phase transition without lattice distortion seen in other materials. Finally, this different structural evolution upon desodiation and re-sodiation can be explained by the electronic structure of the mixed transition metals and how it perturbs the ordering between Na ions differently.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Comparison of the polymorphs of VOPO 4 as multi-electron cathodes for rechargeable alkali-ion batteries

Multi-electron polyanion cathodes offer the potential for achieving both high voltage and high capacity in rechargeable alkali-ion batteries. Among the few materials known to exhibit multi-electron cycling, the polymorphs of VOPO 4 , which operate on the V 3+ –V 4+ –V 5+ redox couples, are particularly promising due to the high gravimetric capacities that have been achieved and the high voltage of the V 4+/5+ couple. In this work, we performed a systematic first principles investigation, supported by careful electrochemical characterization and published experimental data, of the relative thermodynamic stability, voltage, band gap, and diffusion kinetics for alkali intercalation into the β, ε and αI polymorphs of VOPO 4 . We find that all VOPO4 polymorphs remain reasonably stable with the insertion of one alkali ion per V, but are significantly destabilized with the insertion of two alkali ions per V. The voltages for Na insertion are ~0.33–0.69 V lower than those for Li insertion. We find that the αI polymorph is predicted to have higher Li + migration barriers and larger band gaps than the β and ε polymorphs, which account for the relatively worse electrochemical cycling performance observed. On the other hand, only the αI polymorph exhibits reasonably low barriers for Na + migration compared to the β and ε polymorphs, which are consistent with observed electrochemical performances reported thus far in the literature. We also show that differences in the voltage, kinetics and rate capability of these different polymorphs for Li and Na insertion can be traced back to their fundamentally different VO 6 /VO 5 -PO 4 frameworks.

Lin, Yuh-Chieh↗
DOE OSTI2018

Modeling of canonical and C2'- O -thiophenylmethyl modified hexamers of RNA. Insights into the nature of structural changes and thermal stability

Modifying the ribose ring or the nucleobase within oligonucleotides of RNA is a strategy that has regained attention due to its potential to provide chemical stability, increase affinity towards a target, or introduce groups with bioorthogonal reactivity, among other applications. However introducing groups via synthetic routes can be a daunting process and may result in unexpected physical properties and structural variations. In addition, characterizing the effects of a modification within an oligonucleotide can be time consuming and expensive, e.g., NMR, crystallography. Thus the development of models that are accurate, reasonably priced and carried out over short periods of time is essential to the development of this field. In this paper we report on the development and validation of computational models that explain the nature of the structural and stability changes induced by the presence of a C2'-O-methylthiophene group at various positions within duplexes conformed by two 6-mers of modified RNA as well as random coils containing the same modification(s). Through analysis of the obtained models it was concluded that the presence of the methylthiophene moiety on two strands of RNA induces a conformational change around the torsion angle (κ°) that leads to lower values in the pseudorotational angle (δ°), thus resulting in an A-form α-helix with shorter distances between phosphates than those in canonical RNA. These results provide a reasonable explanation for the experimental observations, which display the thermal stabilization of the duplexes, and are guiding efforts from our groups to control the structure and function of RNA, i.e., via functionalization of the RNA structure for attaining thermal stability while retaining the structural properties of an A-form duplex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Elucidating the local structure of Li 1+ x Al x Ti 2– x (PO 4 ) 3 and Li 3 Al x Ti 2– x (PO 4 ) 3 ( x = 0, 0.3) via total scattering

Li 1+x Al x Ti 2–x (PO 4 ) 3 (LATP) and Li 3 Al x Ti 2–x (PO 4 ) 3 (x = 0, 0.3) are promising candidates in all-solid-state batteries due to their high room temperature conductivity of 10 –3 S cm –1 and air- and moisture-stability. They also exhibit unusual thermal expansion properties, with Li 1+x Al x Ti 2–x (PO 4 ) 3 showing near-zero thermal expansion along the a axis while Li 3 Al x Ti 2–x (PO 4 ) 3 exhibits polynomial positive thermal expansion along the a axis and polynomial negative thermal expansion along the c axis. A crucial component to understanding these properties is understanding the local structure. Total scattering is a powerful analytical technique as it provides information on the long-range, average structure as well as the local structure. Here, we report the first X-ray and neutron total scattering experiments performed on Li 1+x Al x Ti 2–x (PO 4 ) 3 and Li 3 Al x Ti 2–x (PO 4 ) 3 (x = 0, 0.3). We show that the PO 4 and TiO 6 polyhedra experience very little expansion of the P/Ti–O bonds up to 800 °C, nor is there much expansion when the Li content increases significantly. The minor thermal expansion of the nearest-neighbor bonds of the polyhedra is revealed to be the reason behind the unusual thermal expansion properties, causing the near-zero thermal expansion along a in Li 1+x Al x Ti 2–x (PO 4 ) 3 and moving as whole units in Li 3 Al x Ti 2–x (PO 4 ) 3 . The structural robustness of the framework is also the reason for the increased conductivity as Li content increases, as the framework remains undistorted as Li content increases, permitting Li-ion mobility as the number of charge carriers increases. Finally, this suggests that phosphate-based framework materials beyond LATP would also be a good material space to explore for new Li-ion (and other ion-) conducting materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗