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At least 1,135 records · Page 63

Large-cell Monte Carlo renormalization of irreversible growth processes

Monte Carlo sampling is applied to a recently formulated direct-cell renormalization method for irreversible, disorderly growth processes. Large-cell Monte Carlo renormalization is carried out for various nonequilibrium problems based on the formulation dealing with relative probabilities. Specifically, the method is demonstrated by application to the 'true' self-avoiding walk and the Eden model of growing animals for d = 2, 3, and 4 and to the invasion percolation problem for d = 2 and 3. The results are asymptotically in agreement with expectations; however, unexpected complications arise, suggesting the possibility of crossovers, and in any case, demonstrating the danger of using small cells alone, because of the very slow convergence as the cell size b is extrapolated to infinity. The difficulty of applying the present method to the diffusion-limited-aggregation model, is commented on.

Nakanishi, H.↗

Correlating energy density induced residual stress, porosity, and mechanical property variations in directed energy deposition using neutron diffraction and imaging techniques

In a directed energy deposition (DED) process, the energy density deposited into the materials drives the structure and properties. The energy density is influenced by several printing parameters, such as laser power, hatch spacing, scanning speed, etc. In this study, 316L stainless steels samples were fabricated with varying hatch spacing aiming to induce variations in sample microstructure and properties. A combination of techniques including engineering neutron diffraction, neutron computed tomography, and tensile testing, were employed to correlate the structure and macroscopic properties. Porosity was predominantly observed at the bottom of the deposited materials and was effectively reduced by decreased hatch spacing. Correlatively, compressive residual stress was observed at the bottom of the specimens, while internal stress is largely determined by the hatch spacing. The residual stress in general decreases as the hatch spacing decreases. The maximum ultimate tensile strength (UTS) was found to increase from 517.4 to 528.6 MPa with a strain increased from 0.847 to 0.897 as the hatch spacing decreased from 0.45 to 0.42 mm. However, further increase in energy density by reducing the hatch spacing resulted in a significant decrease in UTS (as low as 452 MPa). This work provides new insights from bulk non-destructive techniques into correlating energy density induced residual stress, porosity, and mechanical property variations in directed energy deposition.

316L stainless steel↗

High-Performance, Hybrid Polymer Membrane for Carbon Dioxide Separation from Ambient Air

The Department of Energy (DOE) seeks to develop carbon capture materials specifically tailored for Direct Air Capture (DAC) processes. Related to this, they require recipients to develop novel DAC materials such as: solvents, membranes, or sorbents that demonstrate high affinities or capacities for carbon dioxide (CO2) at concentrations typically available in air and at near ambient conditions. Toward this, InnoSense LLC (ISL) is developing High-Performance, Hybrid Polymer Membranes (HypoMemTM) for Carbon Dioxide Separation from Ambient Air. HypoMem consists of two major layers. The first layer is the active layer which contains the active ingredients that help to separate CO2 from ambient air. The second is the support layer that provides good mechanical support to have a free-standing membrane without interfering with the properties of the active layer.

20 FOSSIL-FUELED POWER PLANTS↗

Defining the Minimal Set of Microbial Genes Required for Valorization of Lignin Biomass (Final Report)

Project Goals: Lignin is the second most abundant biopolymer on earth and represents a critically underutilized biomass resource for hydrocarbon feedstocks. Despite substantial effort, there is still no efficient process to convert lignin to useable carbon-based platform chemicals and materials. The goal of this project is identify a minimal set of microbial enzymes necessary for lignin breakdown and sufficient for the synthesis of valuable chemical intermediates from lignin isolated as a byproduct of lignocellulosic ethanol production. These genes will be then used to engineer functional whole cell biocatalysts for tunable lignin metabolism. To date, although a number of enzymes have been associated with lignin degradation, most have been tested in isolation (as individual enzymes) and on drastically different substrates -- often dyes that are not related to lignin. In contrast, lignin utilization in nature likely occurs by microbial consortia with multiple enzymes acting synergistically. We propose to examine two separate stages of lignin breakdown carried out by the microbes that do it best: (1) early breakdown of native polymeric lignin into soluble fragments by a set of sequenced wood-rotting fungal species, and (2) downstream metabolism of these soluble lignin fragments to useful chemical intermediates by a panel of sequenced soil saprophytes. Our approach involves testing sets of genes that will be assayed combinatorially in the context of a heterologous expression host. The resulting engineered strains will be systematically assayed using soluble lignin fragments, synthetic defined polymeric lignin, and finally lignin directly sourced from lignocellulosic processing streams. In addition to resulting in a functional whole cell biocatalyst for lignin utilization, we anticipate that this approach will allow us to address key unanswered questions about lignin metabolism in nature, including: (1) Why does the Trametes versicolor genome contain 25 different class II peroxidases? (2) What is the role of laccases in lignin metabolism? Why do some aggressive lignin degraders have many laccases (e.g. >7 in T. versicolor) while others have none (e.g. P. chrysosporium)? (3) How is peroxide provided in a controlled manner to drive peroxidase activity without causing the enzyme inhibition that is so often observed in vitro? (4) What strategies do microbial lignin degraders use to avoid the problem of repolymerization during active lignin degradation? and (5) Can microbial lignin metabolism be diverted for high level production of defined aromatics? A final critical question is whether combining key minimal sets of enzymes from a wide range of organisms will result in engineered strains capable of highly efficient, streamlined pathways for lignin utilization that can be tuned for a specific carbon output. This effort will leverage DOE investments in microbial genome sequencing, and secure a critical channel for lignin biomass utilization that will also help to render lignocellulosic a viable feedstock for the production of renewable liquid biofuels.

59 BASIC BIOLOGICAL SCIENCES↗

Studies of Magmatic Inclusions in the Basaltic Martian Meteorites Shergotty, Zagami, EETA 79001 and QUE 94201

Currently there are 12 meteorites thought by planetary scientists to be martian samples, delivered to the Earth after violent impacts on that planet's surface. Of these 12 specimens, 4 are basaltic: Shergotty, Zagami, EETA 79001 and QUE 94201. Basalts are particularly important rocks to planetary geologists- they are the most common rocks found on the surfaces of the terrestrial planets, representing volcanic activity of their parent worlds. In addition, because they are generated by partial melting of the mantle and/or lower crust, they can serve as guide posts to the composition and internal processes of a planet. Consequently these four meteorites can serve as 'ground-truth' representatives of the predominant volcanic surface rocks of Mars, and offer researchers a glimpse of the magmatic history of that planet. Unfortunately, unraveling the parentage of a basaltic rock is not always straightforward. While many basalts are simple, unaltered partial melts of the mantle, others have undergone secondary processes which change the original parental chemistry, such as assimilation of other crustal rocks, mixing with other magmas, accumulation, re-equilibration between mineral species after crystallization, loss of late-stage magmatic fluids and alteration by metamorphic or metasomatic processes. Fortunately, magmatic inclusions can trap the evolving magmatic liquid, isolating it from many of these secondary processes and offering a direct look at the magma during different stages of development. These inclusions form when major or minor phases grow skeletally, surrounding small amounts of the parental magma within pockets in the growing crystal. The inclusion as a whole (usually consisting of glass with enclosed crystals) continues to represent the composition of the parental magma at the time the melt pocket closed, even when the rock as a whole evolves under changing conditions. The four basaltic martian meteorites contain several distinct generations of melt inclusions; those found within early-forming pigeonite, intermediate and late-forming Ti, Fe-oxides and sulfides, and intermediate to late-forming phosphates. In this summer' s study we have made a detailed study of all of the various forms of inclusions found within the 4 basaltic martian meteorites listed above. Glasses and minerals within the inclusions were analyzed using the Camera SX-100 Electron Microprobe in Building 31. The mineralogy and textural context of the inclusions will then be used to explore the crystallization history of these specimens, and to investigate any differences in crystallization history or parental magma compositions between these rocks. In this manner, the magmatic inclusions provide a road map backwards toward the 'parental' compositions for the basaltic martian meteorites and provide significant insight into the igneous processes found within the crust of Mars.

Harvey, Ralph P.↗

Effects of lead and lean in multi-axis directed energy deposition

Here, the present study examines the effect of varying laser incidence angles on textural, microstructural, and geometric characteristics of directed energy deposition (DED) processed materials, providing a more comprehensive outlook on participating laser-matter interaction phenomena and ultimately devising strategies to ameliorate print performance. In this study, single-layer, single-/multi-track specimens were processed to examine the effect of non-orthogonal angular configurations on bead morphology, microstructure, phase composition, and textural representation of DED-processed 316L stainless steel materials. It was observed that bead size decreased at increasing lead and lean angles. Asymmetry in the distribution of the bead morphology as a function of lead angle indicates better catchment for acute lead angle configurations over obtuse configurations. No significant differences in phase composition, texture, and microstructure were observed in moderate off-axis configurations. When the penetration depth for the deposits was below 20 μm, columnar structures dominated the microstructure of the deposited material. At deeper penetration depths, columnar and equiaxed structures were observed at the bead-substrate interface and center of the bead, respectively. Compared to powder-blown DED, wire-DED dilution profiles were found to be asymmetric in both orthogonal and non-orthogonal wire DED samples.

36 MATERIALS SCIENCE↗

Interfacial Chemistry Involved in Selective Separation of NMC/LMO and LCO/LMO Binary Cathode Materials by Froth Flotation Using Oleic Acid

The variability in cathode compositions within recycled lithium-ion battery (LIB) feedstocks poses a significant challenge to efficient downstream refining processes. This study demonstrates the feasibility of using froth flotation with oleic acid as a collector to selectively separate lithium nickel-manganese-cobalt oxide (NMC) and lithium cobalt oxide (LCO) from lithium manganese oxide (LMO) materials. Laboratory-scale flotation tests achieved an 80% separation efficiency in a single stage, producing a froth product with >90% purity of NMC/LCO at approximately 90% yield. Concurrently, the LMO materials were enriched in the sink product with ∼90% purity and ∼90% yield. This approach was further validated using recycled cathode materials, confirming its applicability to realistic feedstocks. The underlying mechanism governing the selective separation of NMC/LCO from LMO was investigated using ζ-potential measurements, contact angle measurements, bubble-particle attachment experiments, and X-ray photoelectron spectroscopy (XPS) analysis. Both contact angle and bubble-particle attachment results confirmed that oleic acid adsorption rendered NMC and LCO surfaces hydrophobic, thereby enhancing flotation recovery. At pH 5, oleic acid adsorbed preferentially onto NMC and LCO surfaces via electrostatic interactions, while exhibiting minimal adsorption on LMO surfaces. However, separation efficiency deteriorated at higher pH, which was attributed to the co-flotation of LMO materials caused by oleate chemisorption on MnOH + species. This work establishes froth flotation as a viable cathode/cathode separation strategy, providing a low-cost, scalable pathway to preconcentrate and enrich nickel-rich and cobalt-rich cathode active materials from incompatible cathode chemistries for direct recycling or hydrometallurgical processing. Furthermore, this study reveals, for the first time, the mechanism of oleate adsorption on the surface of different cathode materials.

PH↗

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO 2 Capture from Air: Roles of Atmospheric Water

Direct air capture (DAC) processes for extraction of CO 2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al 2 O 3 , is explored in detail. By combining CO 2 adsorption measurements, oxidative degradation rates, elemental analyses, solid-state NMR and in situ IR spectroscopic analysis in conjunction with 18 O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. Here we demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of biomass burning and aerosol loading and transport in South America utilizing geostationary satellites

This study attempts to assess the extent of burning and associated aerosol transport regimes in South America and the South Atlantic using geostationary satellite observations, in order to explore the possible roles of biomass burning in climate change and more directly in atmospheric chemistry and radiative transfer processes. Modeling and analysis efforts have suggested that the direct and indirect radiative effects of aerosols from biomass burning may play a major role in the radiative balance of the earth and are an important factor in climate change calculations. One of the most active regions of biomass burning is located in South America, associated with deforestation in the selva (forest), grassland management, and other agricultural practices. As part of the NASA Aerosol Interdisciplinary Program, we are utilizing GOES-7 (1988) and GOES-8 (1995) visible and multispectral infrared data (4, 11, and 12 microns) to document daily biomass burning activity in South America and to distinguish smoke/aerosols from other multi-level clouds and low-level moisture. This study catalogues the areal extent and transport of smoke/aerosols throughout the region and over the Atlantic Ocean for the 1988 (July-September) and 1995 (June-October) biomass burning seasons. The smoke/haze cover estimates are compared to the locations of fires to determine the source and verify the haze is actually associated with biomass burning activities. The temporal resolution of the GOES data (half-hourly in South America) makes it possible to determine the prevailing circulation and transport of aerosols by considering a series of visible and infrared images and tracking the motion of smoke, haze and adjacent clouds. The study area extends from 40 to 70 deg W and 0 to 40 deg S with aerosol coverage extending over the Atlantic Ocean when necessary. Fire activity is estimated with the GOES Automated Biomass Burning Algorithm (ABBA). To date, our efforts have focused on GOES-7 and GOES-8 ABBA development, algorithm development for aerosol monitoring, data acquisition and archiving, and participation in the SCAR-C and SCAR-B field programs which have provided valuable information for algorithm testing and validation. Implementation of the initial version of the GEOS-8 ABBA on case studies in North, Central, and South America has demonstrated the improved capability for monitoring diurnal fire activity and smoke/aerosol transport with the GOES-8 throughout the Western Hemisphere.

Menzel, Paul↗

Ni/NiO Reference Electrode Potential Measurements in Molten CaCl 2 –CaO

A direct oxide reduction (DOR) process is used to reduce PuO 2 to Pu metal via Ca metal. Molten CaCl 2 is commonly used as the electrolyte for this reaction. As the DOR reaction proceeds, CaO accumulates in the salt and must be measured in real-time to know when the reaction has gone to completion. Open circuit potential (OCP) was measured in this report between a reference electrode consisting of Ni/NiO contained in a MgO tube and a tungsten working electrode. Two methods of CaO additions were performed over several experiments, and both methods correlated to a 0.11 to 0.23 V decrease in OCP up to 14.4 wt% CaO. CaO concentrations were separately measured via sampling and acid-base titration. A plot of OCP versus concentration of CaO fits the Nernst equation with the CaO powder additions up to 5.2 wt% and also at the higher end of the CaO pellet concentration range. While the MgO tubes were observed to be structurally stable in the molten salt, scanning electron microscopy and energy dispersive X-ray spectroscopy showed that Mg in the tubes had been partially replaced with Ca.

36 MATERIALS SCIENCE↗

Large area deposition of low temperature processed SnO 2 as an ETL in inverted perovskite solar cell on flexible ITO-PET based substrate

Tin (IV) oxide (SnO 2 ) is a good electron transport material for perovskite photovoltaics high charge carrier mobility and superior stability Low temperature solution processability of SnO 2 low-cost fabrication lightweight and flexible perovskite solar cells on PET-based substrate Direct deposition of solution-processed SnO 2 on the top of perovskite is challenging solvent in compatibility with the perovskite materials To solve this problem, in this study we: synthesized SnO 2 nanoparticles functionalized them with acetate through ligand exchange allowing their dispersion in anhydrous ethanol

Chapagain, Sashil↗

Buried homojunction solar cells formed in p-InP during sputter deposition and hydrogen plasma processing

Although it is apparent that direct current (DC) magnetron sputter deposition of indium tin oxide (ITO) leads to the formation of a buried homojunction in single-crystal p-type InP, the actual mechanism of type conversion of the InP surface is not clear. Since sputter deposition of In2O3 has also led to high-quality cells, it appears that Sn is not the cause of type conversion. To investigate the junction formation process further, experiments involving the use of a pure hydrogen plasma have been performed, resulting in type conversion of Fe-doped InP surfaces and in solar cells with efficiencies over 16 percent (global). The results confirm that sputter deposition is not necessary to form this type of buried homojunction solar cell, and they suggest a fabrication process that may be used with other relevant photovoltaic materials.

Gessert, T. A.↗

Making & Breaking the Rules for DED Design

Design for Additive Manufacturing (DfAM) is widely used to describe design activities and guidelines employed in the creation of Additively Manufactured (AM) parts. Basic design rules for widely adopted processes like Powder Bed Fusion (PBF) are relatively understood including material performance, part size constraints, self-supporting angles, overhangs, wall thicknesses, and feature resolution. Complexity is often inherent with PBF using organically inspired solutions through generative design and topology optimization software to create designs that often cannot be realized via traditional manufacturing processes. The design rules for Directed Energy Deposition (DED) are less well known, and, in some cases, the lack of understanding is likely inhibiting broader application of the various DED processes. This presentation covers key design rules for DED fusion processes and elucidates opportunities like multi-material deposition and build approaches ranging from basic features to complex large-scale parts. Complementary to the opportunistic characteristics of DfAM for DED, Manufacture for AM (MfAM) encompasses the restrictive aspects of the manufacturing lifecycle with limitations due to bead width and wall thickness, self-supporting angles, surface texture, microstructural evolution, and residual stresses. AM enabled part design must always consider the entire value chain starting with incoming feedstock (e.g. plate, wire, or powder) and progressing through the printing process, post-processing (e.g. machining, inspection), and final system assembly. Key considerations, like the tradeoffs between feature resolution and build rate, for process and part selection and economic assessments will be discussed as DED is often traded against other AM processes. After highlighting typical DED design rules, we will also show how some of those rules can be broken via use cases and part designs that span the full spectrum of DED processes with examples of various DED part designs.

Additive Manufacturing↗

Technical Gaps in Hanford High-Level Waste Solids Settling Behavior and Settling Time Evaluation for Direct Feed High-Level Waste (DFHLW) Operations

Settling of high-level waste (HLW) solids in process vessels is a key conceptual process step in providing HLW feed directly to the Hanford Waste Treatment and Immobilization Plant (WTP) HLW Vitrification Facility. Direct Feed High-Level Waste (DFHLW) is a potential approach to initiating HLW vitrification prior to completing of the WTP Pretreatment Facility. Settling would be used with subsequent supernatant decant to concentrate HLW feed. To support planning for DFHLW, Washington River Protection Solutions (WRPS) requested support from the Pacific Northwest National Laboratory to evaluate the current data set available to predict the time needed for HLW solids to settle, to identify gaps in the understanding and predictive capability of HLW solids waste settling times, and to provide scoping estimates of the potential settling time. Eight technical gaps were identified for predicting settling times and characteristics of the formed sediment layers including: Gap 1: In-Tank Settling Rates Faster than Settling of Laboratory Samples, Gap 2: Effect of Sludge Leaching/Washing on Predicted Settling Times, Gap 3: Predicting Waste Settling from Waste Chemistry (Waste Type), Gap 4: Predicting Waste Settling from Particle Size and Density Distributions (PSDDs), Gap 5: Insufficient Laboratory and In-Tank Settling Data to Represent Hanford Waste, Gap 6: Methods for Real-Time, In-Tank Tracking of Settling, Gap 7: Prediction of Sediment Erosion Resistance as a Function of Settling Time, and Gap 8: Prediction of Sediment Solids Content as a Function of Settling Time. In addition to the data gaps, an overarching observation of the settling rate and settled layer data is the significant variation in behavior. At similar solids concentrations, settling rates can vary by as much as 3 orders of magnitude depending on the source waste tank, and significantly different settling rates are noted between laboratory and in situ tests for the same waste tank. The range of average solids concentration in existing HLW sediment, which may have been quiescent for decades, can vary from less than 7 wt% to greater than 74 wt% solids. The shear strengths (or yield stresses) measured on laboratory samples range from less than 27 Pa to greater than 6400 Pa. These variations can challenge process planning for the application of a settle/decant process for DFHLW. This report describes the significance of the gaps to the settle/decant process and presents uncertainties by way of examples. Potential technical approaches for resolving these gaps are described and the estimated difficulty in resolving these gaps is evaluated. Based on the significance of the gap and the difficulty of resolution, recommendations are made to address specific gaps. Scoping estimates of the potential settling times for DFHLW solids have been made based on the existing data set with its associated gaps. Depending on the process vessel depth and final sediment concentration, substantial fractions of the scoping estimate results for settling times for characterized HLW exceed the 2-week period that has been previously assumed for process planning. There is also significant disparity, potentially greater than a factor of 5000 difference, in the estimated settling times depending on process vessel depth and final sediment solid concentration. This variation in results underscores the significance of the identified gaps and uncertainties with respect to process planning for utilizing settle/decant operations for DFHLW.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

In-situ measurement and control of the tool-workpiece interface temperature during friction stir processing of 304/304L stainless steel

Friction stir processing of 304/304L stainless steel is an area of interest for repair of spent nuclear fuel canisters. To enable repair without canister deflection or fracture, it is necessary to define the limitations for the depth of the processing zone which will be critically dependent on the thermal history of the material. Here, this work provides the first direct measurement of the interface temperature for friction stir processing of steel. The measured temperature is in the range of 850–1050 °C which is 20–30 % higher than previously reported values. Notably, the peak temperature occurs at the pin tip which is attributed to a higher sticking fraction and subsequently higher strain rate near the tool axis of rotation. Furthermore, a clear correlation between the temperature, grain size, and hardness is established within a single weld nugget and across different processing conditions. In the future, this data may lead to improved process modelling through direct validation and allow for property optimization through direct microstructure control.

304 stainless steel↗

Access to Archived Astronaut Data for Human Research Program Researchers: Update on Progress and Process Improvements

Since the 2010 NASA directive to make the Life Sciences Data Archive (LSDA) and Lifetime Surveillance of Astronaut Health (LSAH) data archives more accessible by the research and operational communities, demand for astronaut medical data has increased greatly. LSAH and LSDA personnel are working with Human Research Program on many fronts to improve data access and decrease lead time for release of data. Some examples include the following: Feasibility reviews for NASA Research Announcement (NRA) data mining proposals; Improved communication, support for researchers, and process improvements for retrospective Institutional Review Board (IRB) protocols; Supplemental data sharing for flight investigators versus purely retrospective studies; Work with the Multilateral Human Research Panel for Exploration (MHRPE) to develop acceptable data sharing and crew consent processes and to organize inter-agency data coordinators to facilitate requests for international crewmember data. Current metrics on data requests crew consenting will be presented, along with limitations on contacting crew to obtain consent. Categories of medical monitoring data available for request will be presented as well as flow diagrams detailing data request processing and approval steps.

Lee, L. R.↗

Multistage Core Formation in Planetesimals Revealed by Numerical Modeling and Hf-W Chronometry of Iron Meteorites

Iron meteorites provide some of the most direct insights into the processes and timescales of core formation in planetesimals. Of these, group IVB irons stand out by having one of the youngest 182 Hf- 182 W model ages for metal segregation (2.9 ± 0.6 Ma after solar system formation), as well as the lowest bulk sulfur content and hence highest liquidus temperature. Here in this paper, using a new model for the internal evolution of the IVB parent body, we show that a single stage of metal-silicate separation cannot account for the complete melting of pure Fe metal at the relatively late time given by the Hf-W model age. Instead, a complex metal-silicate separation scenario is required that includes migration of partial silicate melts, formation of a shallow magma ocean, and core formation in two distinct stages of metal segregation. In the first stage, a protocore formed at ≈1.5 Ma via settling of metal particles in a mantle magma ocean, followed by metal segregation from a shallow magma ocean at ≈5.4 Ma. As these stages of metal segregation occurred at different times, the two metal fractions had different 182 W compositions. Consequently, the final 182W composition of the IVB core does not correspond to a single differentiation event, but represents the average composition of early- and late-segregated core fractions. Our best fit model indicates an ≈100 km radius for the IVB parent body and provides an accretion age of ≈0.1–0.5 Ma after solar system formation. The computed solidification time is, furthermore, consistent with the Re-Os age for crystallization of the IVB core.

58 GEOSCIENCES↗

ZnNi x Mn x Co 2–2 x O 4 Spinel as a High‐Voltage and High‐Capacity Cathode Material for Nonaqueous Zn‐Ion Batteries

Abstract Nonaqueous Zn‐ion batteries are regarded as one alternative for Li‐ion batteries. Such batteries not only afford attractive attributes of cost, but also embody the advantages of the high‐specific capacities of Zn anodes, as well as the wide potential window of nonaqueous electrolytes. To fully exploit these advantages, improved cathode materials are highly desired. In this manuscript, a new series of spinels, ZnNi x Mn x Co 2–2 x O 4 , are reported as cathode materials for nonaqueous Zn‐ion batteries. Full cells constructed using this new spinel ( x = 1/2) as a cathode paired with a metal anode showed capacities over 200 cycles of 174 mAh g −1 and an open circuit potential of 2.05 V. The battery exhibits an energy density of 305 Wh kg −1 , which is the highest energy density yet reported for a Zn‐intercalation cathode. The data show that the Zn 2+ ions reversibly intercalate into the spinel structure during the charge/discharge processes, a compositional transformation directly correlated with a multiply reversible conversion between Co 4+ /Co 3+ , Ni 4+ /Ni 3+ /Ni 2+ , and Mn 4+ /Mn 3+ oxidation states within the lattice. The data suggest that Mn, Ni cosubstitution for Co in ZnCo 2 O 4 is an efficient method to facilitate Zn‐deintercalation and enhance discharge capacity, which may provide some guidelines for designing more attractive multivalent cathodes materials.

Pan, Chengsi↗