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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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Reducing Cost of Chlorinated Volatile Organic Compound Remediation by Transitioning from Active to Passive Soil Vapor Extraction - 20157

Areas of high chlorinated volatile organic compound (cVOC) contamination at the Savannah River Site (SRS) have been undergoing remediation via soil vapor extraction, sometimes coupled with thermal treatments to enhance extraction rates. These active systems are effective in removing large amounts of contaminant mass from the subsurface and mitigating the impacts to groundwater. However, as extraction rates decline, costs must be evaluated with respect to the benefit of continued active operation. A decision framework for identifying conditions when a transition to a more passive remediation is appropriate has been developed with state and federal regulatory agencies. Two remediation areas have recently been transitioned from active soil vapor extraction (ASVE) to passive soil vapor extraction (PSVE) at the SRS. Performance evaluation goals including plume stabilization, overall mass removal trends, environmental sustainability and costs were considered in transitioning from active remediation to passive technologies at both sites. At the Dynamic Underground Stripping (DUS) project at the M-Area Settling Basin, ASVE was combined with steam injection to extract cVOCs during active operations. Steam injection occurred from September 2005 to September 2009. DUS utilized 63 steam injection wells, 34 active vapor extraction wells, and 3 active soil vapor extraction units (SVEUs). Two active SVEUs had 60 horsepower blowers; the third had a 25-horsepower blower. Mass removal was closely tracked during DUS operations; over 181,437 kilograms (400,000 pounds) of cVOCs were removed while active steam injection occurred. After steaming was stopped, ASVE continued. The 34 active wells were evaluated in 2012. The ASVE wells were grouped into categories of high, medium, and low extraction rates. High producing wells remained connected to a single active SVEU. Low producing wells were abandoned, and the medium producing wells were transitioned to PSVE (Microblowers{sup TM}). Microblowers{sup TM} utilize a dedicated blower per well and are solar powered. This passive technology provides energy, maintenance, and operation costs savings while still providing an efficient reduction in cVOC migration to groundwater. In 2018, the remaining ASVE wells were evaluated again. The purpose of this testing was to identify which wells removed the most mass. An optimal well configuration was determined. The criteria to discontinue ASVE was removal of less than 18 kilograms (40 pounds) per week of cVOCs. After 3 months of shutdown (rebound conditions), 2.7 kilograms (5.9 pounds) of cVOCs per week were being removed. Data from the rebound test justified ending ASVE and transitioning wells with higher extraction rates to PSVE. Wells that had depleted the cVOC mass within their zone of influence were abandoned. Performance data from existing PSVE wells justified ending PSVE at wells with depleted extraction rates. Currently the system has 16 PSVE wells operating. Another ASVE system was being used to treat cVOC contaminated soil at the A-Area Miscellaneous Rubble Pile (AMRP) at SRS. System operation began in 2004, with 7 ASVE wells connected to a 60- horsepower blower. Mass removal rates and contaminant concentrations remained consistently low over the ASVE lifespan at AMRP. This indicated that mass removal was diffusion limited. With this data, the 7 ASVE wells were transitioned to PSVE in 2017. Twelve pressure monitoring points were also transitioned to PSVE wells. AMRP currently has 19 PSVE wells operating. Both transitions from active to passive remediation had concurrence from the United States Environmental Protection Agency and the South Carolina Department of Health and Environmental Control. These transitions ensure that only the necessary amount of energy is being exerted to remediate the environment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

A Dose Assessment Model for Radioactive Waste Exposed by Gully Erosion at West Valley - 20513

The Western New York Nuclear Service Center (WNYNSC), located approximately 48 km south of Buffalo, New York, is the site of a former nuclear fuel reprocessing and radioactive waste disposal facility. Spent nuclear fuel was processed there from 1966 to 1972, leaving behind radioactive and chemical wastes in two disposal areas and a waste tank farm. Site operations also resulted in releases of radioactivity to site soils, groundwater, and to surface waters draining the site. The New York State Energy Research and Development Authority (NYSERDA) and the U.S. Department of Energy (DOE) are collaborating in a process of decision making for decommissioning those facilities remaining at the WNYNSC following the completion of Phase 1 decommissioning. Neptune and Company, Inc. (Neptune) was contracted to develop a probabilistic performance assessment (PPA) computer model to assist the agencies in this process. The PPA Model includes a contaminant transport component focusing on the movement of contaminants within and among environmental media including groundwater and surface water transport, contaminant translocation by plants and animals, diffusion, and erosion. The model also includes evaluation of potential exposure and health effects for a Resident Farmer exposure scenario, where the Resident Farmer represents a critical group, described as that group of individuals reasonably expected to receive the greatest exposure to residual radioactivity for any applicable set of circumstances. The West Valley Site is located in the glaciated Allegheny Plateau region of western New York State. The waste reprocessing and disposal areas were constructed on a relatively fat area of plateau dissected by drainages of Buttermilk Creek, including Erdman Brook, Franks Creek, and Quarry Creek. An important aspect of the contaminant transport component of the PPA model is consideration of erosive processes such as slumping of the stream slopes and the advance of gullies from these streams. These erosion processes remove material from the plateau, growing the size of the creek valleys and making them wider and deeper. Of particular interest for the impact of erosion is radioactive waste contained in the Nuclear Regulatory Commission (NRC)-Licensed Disposal Area (NDA), the New York State-Licensed Disposal Area (SDA), and residual radiological inventory in the underground storage tanks at the Waste Tank Farm (WTF). The PPA Model is organized around geographically-defined facilities which were constructed upon the plateau, including the NDA, SDA, and WTF. Ongoing stream erosion processes will potentially transfer radioactive waste and residual inventory from these facilities to the ground surface on adjacent hillslope areas where erosion has breached the facility. Hence, it is important to evaluate the consequences of potential exposures to a Resident Farmer on the hillslopes below a breached facility. Two interrelated aspects of the dose assessment model related to hillslope exposure are discussed: 1) representation of the physical processes related to transport of radionuclides from facilities onto the hillslopes, and from the hillslopes into adjoining creeks where contaminated material migrates downstream with surface water and sediment, and; 2) adaptation of the activities associated with the Resident Farmer scenario to assess potential exposures to contamination in the hillslope areas. This discussion will cover the conceptual basis of the hillslope exposure and transport models, and also implementation in the PPA computer model. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

PREPARATION OF CLAY-COATED GLASS SURFACES FOR MICROFLUIDICS-BASED STUDY ON CLAY-FLUID INTERACTIONS

Unique characteristics of clay, even though make any clay abundant shales a good source of adsorbed gas, make them equally difficult to produce. The clay-water interaction can cause significant swelling and fines migration in the shale formation, both of which can significantly impair the overall hydrocarbon recovery from shale. Geomaterial micromodels, developed by functionalizing traditional glass or PDMS surface with geomaterials (e.g., calcite, quartz, clay) can represent the physico-chemical properties of the natural porous media and have been used during the last few years to understand and evaluate the solid-fluid physicochemical interactions. This study focuses on developing a clay-coated geomaterial surface and investigates the effect of base fluid's salinity on clay adsorption to the glass surface. Glass capillary tubes and straight channel borosilicate glass micromodels are coated with Illite clay minerals to represent the pore-scale clay chemistry of Caney Shale, a Mississippian unconventional play in Southern Oklahoma, USA. 10 wt.% of Illite clay slurries made with brines of four different salinities are used to coat the glass-capillary tubes to understand the effect of salinity in clay adsorption on the glass surface and overall coating quality. To achieve a stable coating and evaluate the impact of heat treatment on coating's stability, straight channel glass flow cells coated with Illite clay are heat-treated at low (25 °C) and high temperature (125 °C). Dynamic flooding tests were carried out with brines on the coated surface to evaluate the stability of the coating. The experiments' outcome indicated a strong relationship between the brine's salinity and the adsorption of clay particles on the glass surface. An increase in brine concentration resulted in improved adsorption of clay particles on the glass surface. Experiments involving heat treating the glass surface following the coating demonstrated significant improvement in the stability of the coating.

02 PETROLEUM↗
DOE OSTI2022

Development of Cr, Se, U, Sb, and Te isotopes as indicators of redox reactions, contaminant fate, and contaminant transport in aqueous systems: A review

Cr, Se, U, Sb, and Te are toxic, redox-active elements that are more mobile and environmentally problematic in their oxidized forms, and less mobile and bioavailable in their reduced forms. This chapter reviews the development of Cr, Se, U, Sb, and Te isotope ratio measurements as new indicators of redox reactions and contaminant migration. Reliable analytical methods exist, but are still evolving. Understanding of isotopic fractionation induced by various (bio)geochemical processes has been explored in dozens of publications, yet is far from complete: Reduction reactions, the major driver of isotopic variation, have been relatively well studied. However, the magnitude of fractionation is variable and the systematics of that variation are still being explored. Isotopic fractionation induced by oxidation reactions is not well understood. Non-redox reactions, which involve smaller changes in bonding of these elements, tend to induce less isotopic fractionation, but can nonetheless cause significant isotopic shifts. Field applications of Cr, Se, U isotope ratios have demonstrated that they are useful as indicators of reduction in natural systems. A few studies suggest they are also useful as indicators of oxidation and contaminant sources. The physical and chemical complexity of groundwater systems hinders accurate quantitative interpretation of Cr, Se, U isotope data using simple models. Numerical models have been developed that capture the behavior of complex, coupled systems and enable the most effective extraction of information from field data sets.

58 GEOSCIENCES↗
DOE OSTI2020

Chapter 14: Heat and Mass Transfer

Fluidized beds are used in a variety of processes due to their excellent heat and mass transfer properties. Heat transfer in fluidized beds can refer to interphase heat transfer, or more commonly to bed-to-surface heat transfer. Heat transfer between bubble phase and dense phase can be characterized by an interphase heat transfer coefficient. This chapter elaborates the derivation of the interphase heat transfer coefficient by an analogy to mass transfer. Mass transfer in fluidized beds usually refers to gas-to-particle mass transfer, or interphase mass transfer, where a component migrates from particles to fluids, or vice versa. The chapter describes the two major components of the interphase mass transfer: particle and fluid mass transfer in the dense phase; and bubble- to dense-phase mass transfer.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS↗
DOE OSTI2021

Impact of Oxygen Non-Stoichiometry on Near-Ambient Temperature Ionic Mobility in Polaronic Mixed-Ionic-Electronic Conducting Thin Films

Enhanced ionic mobility in mixed ionic and electronic conducting solids contributes to improved performance of memristive memory, energy storage and conversion, and catalytic devices. Ionic mobility can be significantly depressed at reduced temperatures, for example, due to defect association and therefore needs to be monitored. Measurements of ionic transport in mixed conductors, however, proves to be difficult due to dominant electronic conductivity. This study examines the impact of different levels of quenched-in oxygen deficiency on the oxygen vacancy mobility near room temperature as measured by a novel dynamic current-voltage analysis. A Pr 0.1 Ce 0.9 O 2-δ film was grown by pulsed laser deposition and subsequently annealed, from 400-600° C, in various oxygen partial pressures to modify its oxygen vacancy concentration while minimizing microstructural growth and cation segregation. To monitor changes in film non-stoichiometry, we leverage the existence of an optical absorption center, related to the oxidation state of Pr ions in Pr0.1Ce0.9O2-δ. The oxygen vacancy migration enthalpy was found to exhibit a small increase from 0.73± 0.04 to 0.79 ± 0.02 eV with increasing oxygen deficiency, while the pre-factor was found to increase by a factor of 135. Here, a nearly 13-fold increase in ionic mobility at 60 °C for increases in oxygen non-stoichiometry from 0.032 ± 0.001 to 0.042± 0.001 was thereby detected. Raman spectroscopy was employed to rule out changes in strain as the primary cause for the significant change in mobility. Several factors potentially contributing to the large pre-factor changes are examined and discussed. Insights into how ionic defect concentration can markedly impact ionic mobility should help in elucidating the origins of variations seen in nanoionic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structural Explanation of the Dielectric Enhancement of Barium Titanate Nanoparticles Grown under Hydrothermal Conditions

Abstract When synthesized under certain conditions, barium titanate (BaTiO 3 , BTO) nanoparticles are found to have the non‐thermodynamic cubic structure at room temperature. These particles also have a several‐fold enhanced dielectric constant, sometimes exceeding 6000, and are widely used in thin‐layer capacitors. A hydrothermal approach is used to synthesize BTO nanocrystals, which are characterized by a range of methods, including X‐ray Rietveld refinement and the Williamson–Hall approach, revealing the presence of significant inhomogeneous strain associated with the cubic phase. However, X‐ray pair distribution function measurements clearly show the local structure is lower symmetry than cubic. This apparent inconsistency is resolved by examining 3D Bragg coherent diffraction images of selected nanocrystals, which show the existence of ≈50 nm‐sized domains, which are interpreted as tetragonal twins, and yet cause the average crystalline structure to appear cubic. The ability of these twin boundaries to migrate under the influence of electric fields explains the dielectric anomaly for the nanocrystalline phase.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Lattice Oxygen Redox Reversibility Modulation in Enhancing the Cycling Stability of Li-Rich Cathode Materials

The practical application of lithium-rich layered oxides is prohibited by the drawbacks such as severe capacity and voltage degradation resulting from unstable oxygen redox environment and the accompanied irreversible oxygen release. In this report a facile and effective strategy is proposed to regulate the oxygen redox chemistry via foreign Fe doping and its induced intrinsic transition metal (TM) doping as well as the in situ constructed spinel surface layer. The Fe doping, together with the induced intrinsic TM dual doping, can stabilize the lattice oxygen in the bulk due to the formed stronger Fe—O bond, and restrain the irreversible TM migration and then the undesirable phase transformation. More importantly, thermodynamical energy barrier of oxygen activation is dramatically decreased by the O 2p–Fe 3d charge-transfer, allowing stable oxygen redox activity. And the pre-constructed spinel layer can effectively stabilize the surface lattice oxygen and suppress harmful interfacial side-reactions. Such a simple optimizing method make the modified cathode exhibit a high specific capacity of 298 mAh g -1 at 0.2 C, outstanding cycling stability with a superior capacity and voltage retentions of 92.5% and 90.8%, respectively, after 400 cycles at 1 C. This study provides a new direction for developing advanced Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Interfacial Engineering Using Covalent Organic Frameworks in Polymer Composites for High‐Temperature Electrostatic Energy Storage

Abstract The use of inorganic nanofillers has been an effective method to improve high‐temperature capacitive performance of dielectric polymers, though there are unmet challenges such as undesirable organic–inorganic compatibility, and low efficiencies and energy densities. Herein, a surface functionalization strategy using covalent organic frameworks (COFs) is employed to address such challenges in realizing high‐performing polymer composites. Specifically, core–shell structured nanoparticles, where ZrO 2 nanoparticles act as the core and a COF material forms the shell, are constructed and composited with the polyetherimide (PEI) matrix. The design leverages the high electron affinity ( E A ) of the outer COF shell to create energy traps, thereby capturing free charges and limiting electrical conduction. Concurrently, the low E A and wide bandgap of the ZrO 2 core introduce energy barriers to impede charge injection and migration. This orchestrated “energy level cascade” results in a marked reduction of leakage current and energy loss. The resulting polymer composite showcases an impressive discharged energy density of 6.21 J cm −3 at an efficiency above 90%, with a maximum discharged energy density reaching 7.43 J cm −3 at 150 °C. These performance metrics position the PEI/ZrO 2 @COF polymer composite to surpass or be on par with state‐of‐the‐art high‐temperature PEI composites and other advanced polymer dielectrics.

Xie, Zongliang↗
DOE OSTI2024

The Key Role of Grain Boundary Dynamics in Revolutionizing the Potential of Solid Electrolytes

Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZO), argyrodite-type Li 6 PS 5 Cl (LPSC), and NASICON-type Li 1+x+y Al x (Ti,Ge) 2-x Si y P 3-y O 12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ultra-Fast Non-Volatile Resistive Switching Devices with Over 512 Distinct and Stable Levels for Memory and Neuromorphic Computing

Low-current multilevel programmability with inherent non-volatility and high stability of resistance states is required for both multi-bit memory storage and deep learning accelerators but is difficult to achieve. Here, in a resistive switching system, this work realizes >512 (>9 bits) distinct non-volatile conductance levels with stable retention for each state with current levels down to the nanoampere range, highly promising for potential integration with small processing nodes with ultra-low power consumption requirements. This is achieved by demonstrating a new thin film design concept that encompasses three key features: an ultra-thin epitaxial oxygen ionic switching layer that provides a tunable energy barrier at the bottom electrode, an overcoat amorphous layer that acts as an ion migration barrier for stable state retention, and a partial conductive filament as a localized electronic transport channel to the epitaxial switching layer. A large dynamic resistance range of up to seven orders of magnitude is achieved with reset-free transitions among intermediate states, and programmability is demonstrated with ultra-fast (20 ns) pulses. Artificial neural network (ANN) simulations, based on the experimental performance and its non-idealities, demonstrate close-to-ideal inference accuracies for various Modified National Institute of Standards and Technology (MNIST) data sets.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tetrahedral Tilting and Lithium‐Ion Transport in Halide Argyrodites Prepared by Rapid, Microwave‐Assisted Synthesis

Abstract This study demonstrates a rapid, dry, microwave‐assisted (MW) synthesis method that enables preparation of halide argyrodites ( , , ) in less than 20 min. The structures and ion transport properties of the resulting materials are compared with those synthesized by conventional solid‐state synthesis methods. The microwave‐assisted method leads to increased site disorder and elevated Arrhenius prefactors (), which lead to an order of magnitude improvement in the 30 ionic conductivity of MW‐. X‐ray pair distribution function analysis (XPDF) reveals significant rotational disorder of the units, which is impacted by the synthesis method, choice of halide, and presence of / site disorder. These rotational displacements are strongly correlated with ion transport, specifically and entropy of migration (). Overall, this study demonstrates a rapid synthesis route for preparing high‐quality halide argyrodite solid‐state electrolytes in less than 20 min, and further unravels atomistic insights into the interplay of structural disorder, rotational dynamics, and ion transport mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Design of Sodium Chalcohalide Solid Electrolytes with Mixed Anions for All‐Solid‐State Sodium‐Ion Batteries

Solid-state sodium-ion batteries (SSNIBs) have emerged as a promising alternative to lithium-ion systems for grid-scale energy storage, owing to sodium's abundance and the improved safety of solid-state designs. Among various solid-state electrolytes (SSEs), halide-based Na + SSEs offer high electrochemical stability but are limited by low ionic conductivity and poor thermal stability. Herein, a novel class of sodium hafnium chalcohalide SSEs is reported with a dual-anion (S 2− /Cl − ) framework, with a high ionic conductivity of 4.5 × 10 −4 S cm −1 . The incorporation of sulfur enhances Na⁺ mobility by reducing the migration barrier through increased anion polarizability and expanded diffusion pathways. Additionally, S 2− contributes to stronger interatomic bonding, leading to higher cohesive energy density, improved thermal stability, and mechanical robustness. These SSEs exhibit minimal sulfur oxidation and excellent chemical/electrochemical interface stability with different cathode materials, such as O3-layered NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 , and Na 3 V 2 (PO 4 ) 3 cathodes. As a result, SSNIBs with P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 employing the sodium hafnium chalcohalide SSEs demonstrate outstanding cycling performance, achieving a capacity retention of 88.5% after 200 cycles at 0.1 C. This study establishes a new design strategy for high-performance SSEs, demonstrating that mixed-anion frameworks offer a viable route to overcome the intrinsic limitations of single-anion electrolytes in next-generation SSNIBs.

DFT calculation↗
DOE OSTI2025

In Situ Study of Resistive Switching in a Nitride‐Based Memristive Device

Abstract Resistive switching (RS) devices with ultra‐low‐voltage threshold and reliable switching repeatability exhibits great potential applications in energy‐efficient data storage and neuromorphic computing. Understanding switching mechanisms at nanoscale is critical to design RS devices with improved performance. In this work, a lamella memristive device using focused ion beam (FIB) method based on the metal/TiO x /TiN/Si structure device is fabricated. In situ transmission electron microscopy (TEM) and current–voltage ( I–V ) characteristic demonstrate that the lamella device shows a volatile RS behavior with a threshold switching at ≈ ± 0.4 V. In situ scanning transmission electron microscopy (STEM) experiments with electron energy loss spectroscopy (EELS) reveal that the charge carriers such as oxygen vacancies migrate under positive/negative DC bias and modulate Schottky barriers at the top and bottom metal/semiconductor interfaces. The RS mechanism of the lamella device is based on the Schottky barriers modulation and Joule heating assisted electric field triggered thermal runaway (FTTR) occurred at the metal/semiconductor interfaces. The fundamental insights gained from this study presents a perspective on interface‐type RS devices processing and opens up new technological opportunities of fabricating ultra‐low‐energy memristive devices.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Ionic Precursors Transformed Into Vinyl Acetate Synthesis Catalyst via Reaction-Driven Restructuring

Conventional preparation of supported bimetallic catalysts relies on solution-mediated metal salt immobilization and pre-formation of alloy nanoparticles before reaction. Here, we report a fundamentally different synthesis strategy of using a physical mixture of salt precursors to generate an active catalyst during reaction. The catalytic structure is generated in situ from Pd3(OAc)6, Au(OH)3, and KOAc through H2 treatment and reaction-driven restructuring under vinyl acetate monomer (VAM) synthesis conditions. Ascertained from in situ X-ray diffraction and operando infrared spectroscopy analyses, reduction treatment produces segregated Pd and Au domains, and subsequent exposure to a VAM reaction mixture triggers dynamic extraction of Pd from the metal surface. This latter process, mediated by acetate-assisted redox cycles, facilitates Pd migration toward Au domains to form a near-surface localized Pd50Au50 alloy phase. Monometallic Pd domains serve as a reservoir of Pd to the alloy phase, leading to and sustaining a more Pd-enriched active surface and a higher population of accessible Pd sites, compared to a conventionally prepared K-PdAu/SiO2 catalyst. Consequently, this leads to a twofold increase in the VAM formation rate, demonstrating highly active bimetallic catalysts can be generated through the gas-phase treatment of physically mixed ionic precursors.

Cha, Byeong Jun [Rice University]↗
DOE OSTI2020

A Novel NASICON‐Type Na 4 MnCr(PO 4 ) 3 Demonstrating the Energy Density Record of Phosphate Cathodes for Sodium‐Ion Batteries

Abstract Sodium‐ion batteries (SIBs) have attracted incremental attention as a promising candidate for grid‐scale energy‐storage applications. To meet practical requirements, searching for new cathode materials with high energy density is of great importance. Herein, a novel Na superionic conductor (NASICON)‐type Na 4 MnCr(PO 4 ) 3 is developed as a high‐energy cathode for SIBs. The Na 4 MnCr(PO 4 ) 3 nanoparticles homogeneously embedded in a carbon matrix can present an extraordinary reversible capacity of 160.5 mA h g −1 with three‐electron reaction at ≈3.53 V during the Na + extraction/insertion process, realizing an unprecedentedly high energy density of 566.5 Wh kg −1 in the phosphate cathodes for SIBs. It is intriguing to reveal the underlying mechanism of the unique Mn 2+ /Mn 3+ , Mn 3+ /Mn 4+ , and Cr 3+ /Cr 4+ redox couples via X‐ray absorption near‐edge structure spectroscopy. The whole electrochemical reaction undergoes highly reversible single‐phase and biphasic transitions with a moderate volume change of 7.7% through in situ X‐ray diffraction and ex situ high‐energy synchrotron X‐ray diffraction. Combining density functional theory (DFT) calculations with the galvanostatic intermittent titration technique, the superior performance is ascribed to the low ionic‐migration energy barrier and desirable Na‐ion diffusion kinetics. The present work can offer a new insight into the design of multielectron‐reaction cathode materials for SIBs.

Zhang, Jian↗