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At least 379 records · Page 21

The effects of vanadium substitution on one-dimensional tunnel structures of cryptomelane: Combined TEM and DFT study

Rational design of energy storage materials requires mechanistic understanding which relies on atomic scale characterization of structure and defects. In this paper we utilize vanadium (V)-substituted one-dimensional cryptomelane as a model material to study structural features critical to electrochemical reversibility of the cathode in lithium-ion batteries. We found the substitution of manganese (Mn) atoms in the tunnel wall with V enhances structural uniformity in the parent KMn 8 O 16 material by inhibiting formation of irregular (2 × 3 and 2 × 1) manganese oxide tunnel structures. Upon lithiation, both transmission electron microscopy (TEM) and density functional theory (DFT) reveal significant structural evolution, eventually resulting in phase separation and formation of highly reduced manganese oxide. During this process, Mn 4+ accepts electrons donated by intercalated Li, while the V 4+ substituent is not electrochemically reduced but acts to stabilize the tunnel framework structure. As a result, the V substituted material shows higher operating voltage and improved electrochemical reversibility. Our results highlight the benefits of V-substitution in cryptomelane, and the significance of integrating characterization with simulation for understanding and developing design principles for lithium ion battery materials.

25 ENERGY STORAGE↗

Green Methanol via an Integrated Direct Air Capture, CO 2 Electrolyzer, and Hydrogenation Reactor

This project pioneered a groundbreaking reactor design to produce green methanol by harnessing the electrochemical CO 2 reduction reaction (eCO 2 RR), a cornerstone of power-to-fuels technology. The effort integrated three innovative technologies to achieve carbon-neutral methanol production at a target cost of under $\$$800/ton: 1. Direct Air Capture (DAC): Using a cutting-edge sorbent material developed at Holocene, scalable models were developed to integrate captured atmospheric CO₂ into the reactor system. 2. Intermediate-Temperature CO 2 Electrolyzer: Developed by the University of Tennessee (UTK), this electrolyzer utilizes a cost-effective, proton-conducting solid acid electrolyte (CsH 2 PO 4 , CDP) and a mixed-metal oxide cathode. It achieves high faradaic efficiencies (>98%) by effectively suppressing hydrogen evolution at high current densities, converting CO 2 to CO with remarkable selectivity. 3. Catalysis and Reactor Engineering: Oak Ridge National Laboratory (ORNL) contributed world-class expertise in heterogeneous catalysis and reactor design. Their advanced ASPEN modeling drove systems integration and supported techno-economic and life cycle analyses. This effort was further bolstered by partnerships with industry leaders Air Company and Plug Power, who provided critical guidance on scaling, systems engineering, and the integration of water electrolyzers into large-scale operations. During Phase 1, the team focused on modeling and validating a lab-scale reactor demonstrating the feasibility of the integrated approach. Key accomplishments include a 52% increase in current density at 0.8 V while maintaining >98% CO faradaic efficiency, successful 10× scale-up of the electrolyzer with performance within 5% of coin-cell results, best-in-class durability (168-hour test at 0.6 V with 0.14 mA/cm 2 -h degradation), validated TEA confirming the $\$$800/ton methanol target, and completed preliminary LCA showing potential for net-negative GHG emissions under renewable energy scenarios.

10 SYNTHETIC FUELS↗

Solvation, Rational Design, and Interfaces: Development of Divalent Electrolytes

Rechargeable multivalent ion batteries are promising tools to complement current lithium-ion batteries for a future of diverse energy storage needs. Divalent Mg and Ca are attractive candidates for their high crustal abundance, high volumetric anode capacity, and infrequent dendrite formation during electrochemical cycling. Electrolyte research is central to these efforts and continually improves coulombic efficiencies towards the ideal 100%. This mini-review discusses recent work towards fundamental understandings that push these chemistries towards practical use. Piecing together compatible cathode and electrolytes for a complete practical multivalent ion battery lacks a cohesive method for further development and refinement. Understanding liquid solvation, utilizing rational design, and probing interfacial interactions are focal points that govern electrolyte performance. The combination of these areas will be critical for meaningful development.

25 ENERGY STORAGE↗

Improving LiNiO 2 cathode performance through particle design and optimization

We report to enable further development of Ni-rich LiNi x Mn y Co 1-x-y O 2 (NMC, x ≥ 0.9) cathodes for commercial applications, fundamental understanding of the synthesis–property–performance relationships in the LiNiO 2 (LNO) parent phase is essential. In the present study, we report synthesis approaches to produce well-formed, similar-sized single-crystal LiNiO 2 (SC-LNO) with different shapes and dominating surface facets, and reveal the dependence of cathode rate performance and cycling stability on particle morphology and surface. While octahedron-shaped SC-LNO with the (012) surface shows better rate capability and improved ability in utilizing the kinetically slow anodic process in the 3.5 V region, cubic-shaped SC-LNO with the (104) surface delivers superior cycling stability, especially upon cycling at a high upper cutoff voltage of 4.6 V. Improvement in cycling stability is correlated with reduced surface reconstruction and preferential LiF formation through the interaction with the electrolyte on the (104) surface. Our study not only demonstrates the importance of particle morphology and surface design, it also provides key insights into desirable material properties for developing future LNO-based cathode materials with better performance.

25 ENERGY STORAGE↗

Screening and Development of Sacrificial Cathode Additives for Lithium‐Ion Batteries

Abstract This work presents a computational screening approach to identify Li‐rich transition‐metal oxide sacrificial cathode additives and provides experimental validation of antifluorite‐structured Li 6 MnO 4 as a potential candidate. Initial attempts to synthesize this compound result in low purity (≤40% by weight) owing to close thermodynamic competition with Li 2 O and MnO at low temperature. However, it is shown that a much higher purity of 85% by weight can be achieved by combining Li excess with rapid cooling from high temperature, which effectively stabilizes the Li 6 MnO 4 phase. The synthesized product delivers a high irreversible Li release capacity that exceeds 700 mAh g −1 by utilizing combined Mn oxidation (Mn 2+/3+ and Mn 3+/4+ ) and O oxidation. These results demonstrate that Li 6 MnO 4 may therefore be useful as a potential sacrificial cathode additive in Li‐ion batteries and motivate further investigation of other structurally‐related compounds. While attempts were made to synthesize two additional compounds among computationally screened candidates, it was not successful to experimentally realize the two candidates. The difficulty of experimental realization of the newly predicted materials remains a challenge and it is suggested that more efforts need to be devoted to developing computational techniques to precisely predict synthesizability and propose potential synthetic routes of the predicted materials.

Kim, Haegyeom↗

Efficient Electrocatalytic Synthesis of Ammonia from Water and Air in a Membrane‐Free Cell: Confining the Iron Oxide Catalyst to the Cathode

Ammonia is critical for food and chemical production; however, NH 3 synthesis is one of the largest industrial greenhouse gas producers. We report a path to an exceptionally high rate (2.3 × 10 –9 mol of NH 3 s –1 cm –2 ), CO 2 free NH 3 electrosynthesis from H 2 O and air under ambient electrolysis conditions (60 °C, 1 atm). Iron oxide (dispersed in hydroxide electrolyte) catalyzed NH 3 synthesis is probed at intermediate temperature (20–200 °C) and pressure (1–10 atm) with Monel mesh electrodes. Iron calcination preparation of the iron oxide catalyst is optimized by size, and then physically constrained to the reactive domain of the electrolysis cell cathode through use of mesh electrodes at even lower temperatures, allowing for an ambient, preferred electrosynthesis. These novel constraints enhance NH 3 catalyst utilization at low temperature and open future pathways to the addition of ion‐specific membranes to the high rate NH 3 synthesis cell.

Liu, Xinye↗

Surface heterogeneity propagation and homogenization for pouch cell-scale Li metal anodes

Li metal anode is a promising candidate for next-generation energy storage systems and is widely explored in Li-ion and solid-state batteries. Despite its potential, Li metal anodes face instabilities during long-term cycling, especially when paired with NMC or sulfur-based cathodes, where Li is cycled at high capacities of 6-8 mAh/cm2, equivalent to a thickness of 30-40 µm. During such extensive utilization, degradation mechanisms such as excessive solid electrolyte interphase (SEI), dendrites, and dead Li emerge, and ultimately lead to sudden failure and reduced cycle life. The origin of the degradation mechanisms stem from surface heterogeneities introduced during Li foil manufacturing and storage [1, 2]. As cycling progresses, the local heterogeneities propagate, resulting in uneven Li utilization and degradation-prone regions across the electrode [3], which consequently induce performance variations at the cell level. This heterogeneity propagation is particularly pronounced in large-format pouch cells in practical applications, where the surface effects are magnified. Without a clear understanding of the multi-scale heterogeneities and the development of surface homogenization methods, the performance consistency will be compromised, hindering the commercialization of Li metal batteries. In this presentation, we investigate the evolution of surface heterogeneity propagation on commercially available Li foils. We discover that inhomogeneous Li utilization appears as early as the first half-cycle of formation, manifesting as localized clusters and pits. In pouch cell configurations, these features exhibit areal density variations across the electrode on a scale of millimeters. To improve Li utilization homogeneity, a scalable mechanical brushing method is introduced to remove the chemically heterogeneous surface passivation layer. Furtherore, the influence of utilization homogeneity on cell-to-cell consistency is evaluated using 32 Li-NMC811 pouch cells divided into as-received and brushed Li groups. On the brushed Li, clusters and pits are no longer observable, and the cells exhibit significantly improved consistency in discharge capacity trajectories and cycle lifetime. Overall, this study highlights the role of Li surface utilization homogeneity on long-term cycling performance. Our research provides a pathway for improving large-area electrode uniformity and establishing evaluation methods for cell-to-cell consistency, both are key steps toward the commercialization of Li metal batteries and beyond. [1] Otto, Svenja-K., et al. "In-depth characterization of lithium-metal surfaces with XPS and ToF-SIMS: toward better understanding of the passivation layer." Chemistry of Materials 33.3 (2021): 859-867. [2] Hatzell, Kelsey, et al. "Aligning lithium metal battery research and development across academia and industry." Joule (2024). [3] Kim, Sangwook, et al. "Calendar life of lithium metal batteries: Accelerated aging and failure analysis." Energy Storage Materials 65 (2024): 103147.

25 - ENERGY STORAGE↗

Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides

Electrochemical regeneration of organic hydrides is often hindered by the rapid dimerization of organic radicals produced as the first intermediates of these electrochemical transformations. Here, we utilize proton-coupled electron transfer to outcompete the undesired dimerization and achieve successful hydride regenerations of two groups of organic hydrides – acridines and benzimidazoles. An analysis of the critical factors that control the regeneration pathways of organic hydrides is demonstrated in this report.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inverted Geometry Ceramic Insulators in High Voltage DC Electron Guns for Accelerators

A direct current (dc) high voltage photo-emission electron gun operating at 130 kV is utilized at the Jefferson Lab (JLab) Continuous Electron Beam Accelerator Facility to generate spin-polarized electrons for nuclear physics experiments. Over the past decade, JLab has tested and implemented inverted-geometry ceramic insulators in photoguns, connecting the cathode electrode in vacuum to the high voltage power supply using commercial high voltage cables. This contribution reports on tests performed up to 375 kV dc, implementation of inverted insulators in a 300 kV dc photogun generating magnetized electron beams, and describes plans to develop a reliable insulator-cable connector for applying 500 kV dc to a future polarized beam photogun operating reliably and without field emission at 350 kV.

Hernandez-Garcia, C.↗

The 15 cm diameter ion thruster research

The startup reliability of a 15 cm diameter mercury bombardment ion thruster which employs a pulsed high voltage tickler electrode on the main and neutralizer cathodes is examined. Startup of the thruster is achieved 100% of the time on the main cathode and 98.7% of the time on the neutralizer cathode over a 3640 cycle test. The thruster was started from a 20 C initial condition and operated for an hour at a 600 mA beam current. An energy efficiency of 75% and a propellant utilization efficiency of 77% was achieved over the complete cycle. The effect of a single cusp magnetic field thruster length on its performance is discussed. Guidelines are formulated for the shaping of magnetic field lines in thrusters. A model describing double ion production in mercury discharges is presented. The production route is shown to occur through the single ionic ground state. Photographs of the interior of an operating-hollow cathode are presented. A cathode spot is shown to be present if the cathode is free of low work-function surfaces. The spot is observed if a low work-function oxide coating is applied to the cathode insert. Results show that low work-function oxide coatings tend to migrate during thruster operation.

Wilbur, P. J.↗

Advanced PGM-free Cathode Engineering for High Power Density and Durability

Polymer electrolyte fuel cells (PEFCs) are among the most promising technologies for future electric vehicles by using clean H2 with much-improved energy conversion efficiency, longer range, and rapid refueling. However, due to a large amount of platinum group metal (PGM) catalyst used in their electrodes, their prohibitively high cost hinders broad commercialization of PEFCs for transportation. Therefore, there is a critical need to develop low-cost, high-performance PGM-free cathode catalysts that have the potential to dramatically transform the economics of PEFC commercialization by reducing catalyst costs by one to two orders of magnitude. However, before PGM-free cathodes become viable, several technical challenges associated with PGM-free cathodes must be addressed, including insufficient activity and stability of the catalysts, as well as severe water flooding and large transport losses in the electrodes. Overcoming those barriers and ultimately meeting the challenging automotive PEFC performance targets was the focus of this comprehensive research and development effort on new PGM-free cathodes. To this end, we assembled a team including leading researchers from universities and industry with different but complementary expertise and capabilities. The project combined three novel and promising approaches: Advanced metal-organic framework (MOF)-derived M-N-C catalysts with a high activity and impressive durability, Novel PGM-free specific cathode architectures and fabrication strategies capable of addressing the substantial flooding and transport resistances in thicker cathodes by introducing engineered hydrophobicity through additives and support layers, and Advanced electrode ionomers with high proton conductivity for low ohmic losses across the electrode and more uniform catalyst utilization. The implementation of these new materials and electrode designs was supported by a suite of advanced experimental and simulation tools that allows us to identify performance and durability bottlenecks, devise solutions, and establish rational material design and synthesis targets. These methods include advanced electrochemical characterization, high-resolution imaging, and multi-scale modeling. In addition, the project team leveraged a broad cross-section of the ElectroCat consortium’s national laboratory facilities and expertise in advancing these materials and design strategies. Finally, the industry partners on the project facilitated the evaluation of scaled-up synthesis and manufacturing in the United States. Over its four-year period, the project made significant year-over-year advances in PGM-free cathode performance and viability. A combination of high activity and highly durable catalysts were developed through novel catalyst synthesis strategies, which met several performance and durability targets. More specifically, a catalyst prepared from MOFs and Fe2O3 nanoparticles with ammonium chloride and chemical vapor deposition treatments yielded a significant advancement in PGM-free cathode durability. Several novel strategies for fabricating cathodes were demonstrated, including those designed to reduce flooding and thickness of the cells for significantly increased volumetric power density. An optimized cathode with high conductivity ionomer and tuned ink processing for hydrophobicity yielded high fuel cell performance with new levels power density and maximum current. The scientific studies and modeling assessment also provided an outlook for future efforts, including a focus on catalysts with an increased density of the highly stable active sites developed in this project.

08 HYDROGEN↗

Simulating hindered grain boundary diffusion using the smoothed boundary method

Abstract Grain boundaries can greatly affect the transport properties of polycrystalline materials, particularly when the grain size approaches the nanoscale. While grain boundaries often enhance diffusion by providing a fast pathway for chemical transport, some material systems, such as those of solid oxide fuel cells and battery cathode particles, exhibit the opposite behavior, where grain boundaries act to hinder diffusion. To facilitate the study of systems with hindered grain boundary diffusion, we propose a model that utilizes the smoothed boundary method to simulate the dynamic concentration evolution in polycrystalline systems. The model employs domain parameters with diffuse interfaces to describe the grains, thereby enabling solutions with explicit consideration of their complex geometries. The intrinsic error arising from the diffuse interface approach employed in our proposed model is explored by comparing the results against a sharp interface model for a variety of parameter sets. Finally, two case studies are considered to demonstrate potential applications of the model. First, a nanocrystalline yttria-stabilized zirconia solid oxide fuel cell system is investigated, and the effective diffusivities are extracted from the simulation results and are compared to the values obtained through mean-field approximations. Second, the concentration evolution during lithiation of a polycrystalline battery cathode particle is simulated to demonstrate the method’s capability.

Materials Science↗

Revealing the coupled oxygen and hypochlorite chemistry in saltwater batteries through operando pH and oxygen monitoring

Saltwater batteries (SWBs) that utilize Na⁺ ions from seawater have emerged as promising candidates for low-cost and sustainable grid-scale energy storage. To date, the cathode reaction mechanism of SWBs has been predominantly described by oxygen evolution and reduction reactions (OER/ORR). However, this assumption is valid only under idealized ocean-like conditions with constant pH and continuous oxygen replenishment. In practical systems, SWBs operate in finite volumes of saltwater, where saltwater composition dynamically evolves during cycling. Here, in this work, we systematically investigate the cathode reaction mechanisms of SWBs under finite saltwater conditions using galvanostatic cycling combined with electrochemical diagnostics and operando monitoring of dissolved oxygen and pH. Our results reveal that the cathode chemistry during SWB operation is considerably more complex than previously assumed. In addition to OER and ORR, hypochlorite formation and consumption reactions, along with pH-dependent switching of dominant reaction pathways, play critical roles. We further identify the sequence and relative contributions of these reactions throughout charge–discharge cycling. These findings provide a comprehensive and mechanistically grounded understanding of SWB cathode processes under relatively realistic cell design and operation condition. The insights presented here establish a new framework for interpreting SWB electrochemistry and offer directions for future strategies aimed at improving performance, stability, and practical viability.

Hypochlorite redox reaction↗

Room-Temperature Calcium Plating and Stripping Using a Perfluoroalkoxyaluminate Anion Electrolyte

Multivalent ion chemistries, like Ca 2+ , used in energy storage boast the potential to utilize solid metallic anodes and provide high volumetric energy density. The promise of such systems relies on the ability to incorporate high-voltage cathode materials while sustaining robust plating and stripping at the anode. These processes are dependent on an electrochemically stable electrolyte for ion transport and storage. In this work, we report an addition to the limited pool of nonaqueous electrolytes capable of plating and stripping calcium at room temperature. The synthesis and structural properties of calcium tetrakis(perfluoro-tert-butoxy) aluminate (Ca[TPFA] 2 ) are described along with the electrochemical performance during plating and stripping (up to 55% Coulombic efficiency) and a proof of concept for full cell viability with a CuS cathode material. X-ray experiments were used to study both the bulk solvation structure around calcium and possible decomposition pathways of the weakly coordinating TPFA anion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration with Atomic-Scale Understanding

The development of a suitable catalyst for the oxygen reduction reaction (ORR) – the cathode reaction of proton exchange membrane fuel cells (PEMFC) – is necessary to push this technology towards widespread adoption. There have been substantial efforts to utilize bimetallic Pt-M alloys that adopt the ordered face-centered tetragonal (L10) phase in order to reduce the usage of precious metal, enhance the ORR performance, and improve catalyst stability. In this work, monodisperse Pt-Co nanocrystals (NCs) with well-defined size (4-5 nm) and cobalt composition (25-75 at%) were synthesized via colloidal synthesis. The transformation from the chemically disordered A1 (face-centered cubic, fcc) to the L10 phase was achieved via thermal annealing using both a conventional oven and a rapid thermal annealing process. The structure of the Pt-Co catalysts was characterized by a variety of techniques, including transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy in high-angle annular dark-field scanning transmission electron microscopy (STEM-EDS), small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), and inductively coupled plasma-optical emission spectrometry (ICP-OES). The effects of annealing temperature on the composition-dependent degree of ordering, and subsequent effect on ORR activity is described. This work provides insights regarding the optimal spatial distribution of elements at the atomic level to achieve enhanced ORR activity and stability.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Highly reversible Zn metal anode enabled by sustainable hydroxyl chemistry

Rechargeable Zn metal batteries (RZMBs) may provide a more sustainable and lower-cost alternative to established battery technologies in meeting energy storage applications of the future. However, the most promising electrolytes for RZMBs are generally aqueous and require high concentrations of salt(s) to bring efficiencies toward commercially viable levels and mitigate water-originated parasitic reactions including hydrogen evolution and corrosion. Electrolytes based on nonaqueous solvents are promising for avoiding these issues, although full cell performance demonstrations with solvents other than water have been very limited. To address these challenges, we investigated MeOH as an alternative electrolyte solvent. These MeOH-based electrolytes exhibited exceptional Zn reversibility over a wide temperature range, with a Coulombic efficiency > 99.5% at 50% Zn utilization without cell short-circuit behavior for > 1,800 h. More important, this remarkable performance translates well to Zn || metal-free organic cathode full cells, supporting < 6% capacity decay after > 800 cycles at –40°C.

25 ENERGY STORAGE↗

Achieving SEI preformed graphite in flow cell to mitigate initial lithium loss

The irreversible lithium loss due to the formation of solid electrolyte interphase (SEI) in the initial cycle on the graphite anode greatly reduces the overall cell energy density of lithium ion batteries, that is, the lost Li ions from forming SEI lead to the decrease of Li ions for the intercalation. The method of cathode prelithiation has been widely explored to compensate this lithium loss. However, these cathode additives with high lithium contents inevitably lower the loading of the cathode active materials. In this work, we report a novel approach to solve this challenge, a facile graphite prelithiation method by preforming SEI layers on the surface of graphite powders (Pre-SEI graphite) utilizing a specially designed flow cell. The Li accommodation in the graphite anode can be controlled by the operating time and current density in the flow cell for the electrochemical SEI formation. As a result, we demonstrate a 10% initial Columbic efficiency increase of the LiFePO 4 electrode in a full cell configuration using the Pre-SEI graphite, compared with the pristine graphite anode. The electrochemical preformation of SEI on the graphite powders offers a complete solution to offset initial lithium loss without a sacrifice of active cathode material loading.

25 ENERGY STORAGE↗

A Comprehensive Understanding of the Aging Effects of Extreme Fast Charging on High Ni NMC Cathode

As the battery industry shifts toward high Ni content cathodes, such as LiNi 0.8 Mn 0.1 Co 0.1 O 2 [NMC811], a complete understanding of the degradation mechanisms of NMC811 under extreme fast charging (XFC) (XFC, ≤10–15 min charging) conditions is needed. Such comprehensive understanding would identify the most critical materials gaps that need to be addressed for enabling XFC long-life cells for electric vehicles. This study maps out the key aging mechanisms for NMC811 cycled at different XFC conditions (between 1C and 9C) for up to 1000 cycles. To acquire a fundamental understanding of utilization and degradation, cells are evaluated using a range of electrochemical techniques, and multimodal and multiscale microscopy techniques to quantify chemical, structural, and crystallographic degradation as a function of cycling conditions for the NMC cathode. When comparing NMC811 to NMC532, it is observed that NMC811 has a greater subsurface crystallographic degradation and displays a similar magnitude of subparticle cracking. However, the NMC811 maintains superior performance despite those advanced degradations. Here, the superior cycle life performance is attributed to the NMC811 particles having radially oriented grains and improved transport properties. NMC811 shows between 4.6× and 3.15× reduction in capacity fade than NMC532 for charging rates between 4C (e.g., 15-min charging) and 6C (10-min charging).

25 ENERGY STORAGE↗