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At least 1,261 records · Page 70

Method for Comparing Porous Carbon Electrode Performance in Redox Flow Batteries

In this paper, we present a method for comparing porous electrodes for use in redox flow batteries. By comparing physical and electrochemical properties of six carbon cloth electrodes (CCEs) including hydraulic permeability, Ohmic resistance, and mass transport overpotential, we show how optimal engineering conditions such as compression and electrolyte flow rates can be derived. These results are combined and applied to a quinone-based redox flow battery, leading to a peak power density around 0.4 W cm –2 for several different CCEs. This method can be applied broadly to other electrode architectures and flow battery chemistries, and provides a comprehensive framework for their comparison.

25 ENERGY STORAGE↗

Editors’ Choice—Uncovering the Role of Alkaline Pretreatment for Hydroxide Exchange Membrane Fuel Cells

Alkaline pretreatment is perceived as an essential step for high-performance hydroxide exchange membrane fuel cells (HEMFCs), but its exact function is not fully understood. Here we show that alkaline pretreatment is only necessary when carboxylates are generated from platinum- or palladium-catalyzed oxidation of primary alcohol solvents during membrane electrode assembly (MEA) fabrication. When alkaline pretreatment is needed, bicarbonates are a better choice than the most commonly used hydroxide bases. We further demonstrate that MEAs with Pt/Pd-free catalysts, which can be used in HEMFCs, exhibit a better performance without the alkaline pretreatment: a voltage of 0.64 V at 1.0 A cm −2 and a peak power density of 0.69 W cm −2 in H 2 /O 2 . The optimization or elimination of the alkaline pretreatment will simplify the fabrication process for fuel cells and thus reduces their manufacturing costs.

Shi, Lin↗

Editors’ Choice—Examining Performance and Durability of Anion Exchange Membrane Fuel Cells with Novel Spirocyclic Anion Exchange Membranes

A series of spirocyclic copolymer membranes with varying ion exchange capacities (IECs) were investigated to probe the impact of polymer properties on in situ fuel cell performance and stability. In-situ electrochemical tests and post-mortem electron microscopy analysis of cross-sectioned membrane electrode assemblies (MEAs) have been combined with voltage loss breakdown analysis to evaluate the performance and degradation of different MEAs, and to probe the catalyst morphology and electrode structure at different stages of operation. Voltage loss breakdown results show that membrane degradation and kinetic losses played only a minor role in observed performance degradation and that performance losses were primarily related to increasing mass transport losses. From microscopy studies, carbon corrosion and Pt nanoparticle growth were identified at both the cathode and anode although more pronounced on the cathode resulting in significant structural changes. The membrane with the lowest IEC (1.3 mmolg −1 ) demonstrated the lowest peak power density ~ 1.16 W cm −2 , however, it showed the most stable performance (constant 0.6 A cm −2 hold) with ~ 5% degradation over 540 h. Isolation of performance losses and microscopic analysis of electrodes for anion exchange membrane fuel cells has not been reported previously, and these results help identify critical performance degradation concerns.

25 ENERGY STORAGE↗

High Performance SrFe 0.2 Co 0.4 Mo 0.4 O 3–δ Ceramic Anode Supported Low-Temperature SOFCs

The development of alternative ceramic anodes for low-temperature solid oxide fuel cells (LT-SOFCs) is essential to overcome the inherent challenges such as redox instability and coking associated with Ni-based cermet anodes. Moreover, due to the large electrolyte ohmic loss at low temperature, it is critical to developing an electrode supported cell that allows electrolyte thickness reduction. Here we successfully demonstrated a high performance SrFe 0.2 Co 0.4 Mo 0.4 O 3–δ (SFCM) ceramic anode supported LT-SOFC with a peak power density of 730 mW cm –2 and 300 mW cm –2 at ambitious low temperatures of 550 °C and 450 °C, respectively, in humidified H 2 . The new anode material SFCM exhibits exceptional conductivity of over 30 S cm –1 at 450 °C in humidified H 2 , providing essential current collection capability as an anode backbone appropriate for the infiltration of Ni-gadolinia doped ceria (GDC) electrocatalysts. Compared to conventional Ni-cermet anodes, the nano-sized Ni-GDC particles in our SFCM based electrode significantly improves the cell stability in hydrocarbon gases. We demonstrated a stable long-term operation over a period of 380 h in CH 4 –containing gas mixtures at 450 °C with a voltage degradation rate of 4% per 1000 h at a constant current of 0.2 A*cm –2 . Furthermore, our results demonstrate a high performance ceramic anode with high stability for low temperature operation.

25 ENERGY STORAGE↗

Pathways Toward High-energy Li-sulfur Batteries, Identified via Multi-reaction Chemical Modeling

Here we present a 1D model of a Li-Sulfur battery with physically derived geometric parameters and thermodynamically consistent electrochemical kinetics. The approach enables straightforward comparison of proposed Li-S mechanisms and provides insights into the influence of polysulfide intermediates on battery discharge. Comparing predictions from multiple mechanisms demonstrates the need for both lithiated and non-lithiated polysulfide species, and highlights the challenge of developing parameter estimates for complex electrochemical mechanisms. The model is also used to explore cathode design strategies. Discharge performance and polysulfide concentrations for electrolyte/sulfur ratios in the range 2–4 μ L mg −1 identifies trade-offs that limit battery energy and power density, and highlights the risk of polysulfide precipitation. New cathode and electrolyte approaches must limit polysulfide concentrations in the electrolyte, both to unlock better rate capabilities in Li-S technology and to prevent capacity fade due to polysulfide precipitation.

25 ENERGY STORAGE↗

Bismuth Electrocatalyst Enabling Reversible Redox Kinetics of a Chelated Chromium Flow Battery Anolyte

Metal electrocatalysts have been reported to improve the electron transfer kinetics of aqueous redox flow battery electrolytes on various types of carbon electrodes. In this work, we electrodeposited bismuth metal onto a carbon paper anode of a redox flow battery containing our previously reported polyaminocarboxylate-chelated chromium electrolyte. Depositing 0.58 mg cm –2 of bismuth metal enabled an electrochemically reversible electron transfer for the Cr(II)/Cr(III) couple, resulting in a 3.9% voltage efficiency increase over ten cycles at 100 mA cm –2 across an 80% state of charge window, while maintaining >99% current efficiency. The bismuth electrocatalyst provided other improvements, such as a 13% increase in average discharge power density when cycling at 80% energy efficiency, along with a 60% decrease in charge transfer resistance and 12% decrease in the full cell area specific resistance. A chelated bismuth complex was also utilized as a bismuth source for electrodeposition, providing an example of how polyaminocarboxylate ligands can be further implemented into efforts towards improving the energy efficiency of aqueous redox flow batteries.

25 ENERGY STORAGE↗

Review—Development of Highly Active and Stable Catalyst Supports and Platinum–Free Catalysts for PEM Fuel Cell

Metal-free, metal-containing, and template-assisted metal-containing nitrogen-modified carbon-based catalysts carbon composite supports, and highly active and electrochemically stable hybrid cathode catalysts for oxygen reduction reaction are reviewed in this manuscript. Here, novel procedures are developed for the synthesis of (i) highly catalytically active PGM-free catalyst and stable carbon composite catalyst supports. The carbon composite catalyst supports are engineered with optimized BET surface area and pore size distribution and with a well-defined kinetic and mass transfer region during the reaction and their performance is dicussed in detail in this review. The surface activation results in increasing carbon graphitization and inclusion of non-metallic active sites on the support surface. The USC catalysts exhibit the initial performance of 0.91 V and a maximum power density of 177 mW cm –2 , with well-defined kinetic and mass-transfer regions and ~2.5% H 2 O 2 production. Activated carbon composite support (ACCS) is modified to optimize its kinetic activity and its electrochemical stability shows excellent thermal stability and support stability under simulated start-up/shut-down operating conditions. The stabilities of various supports developed in this study are compared with those of a commercial Pt/C catalyst. The active sites for the ORR identified with electrochemical and physicochemical methods are pyridinic-N and quaternary-N.

25 ENERGY STORAGE↗

Characterization of Electrochemical Behavior for Aqueous Organic Redox Flow Batteries

Use of aqueous redox flow batteries with organic redox-active materials holds great promise for large-scale and sustainable energy storage. The development of low-cost, highly efficient aqueous redox flow batteries lies in a comprehensive understanding of the electrochemical behaviors of redox-active compounds. In this work, an alkaline redox battery with organic dihydroxyphenazine sulfonate (DHPS) anolyte and ferro-/ferricyanide (Fe(CN) 6 ) catholyte is investigated as a typical example of aqueous redox flow batteries using organic redox-active materials. The electrochemical kinetics of DHPS and Fe(CN) 6 are separately characterized using the symmetrical cell design. The resistance components are calculated directly from the experimental measurement. The key kinetic parameters are extracted and compared for DHPS and Fe(CN) 6 electrolytes. The extracted parameters are validated with symmetrical and full flow cell simulations at different operating conditions. Key parameters and internal loss are also compared with all-vanadium redox flow batteries, representing current state of the art. In addition, our extracted key parameters from a symmetrical flow cell are compared with the measured key parameters by cyclic voltammetry, a widely deployed electroanalytical technique. The cell performance prediction of DHPS anolyte on a 780 cm 2 interdigitated cell is made and found the power density is peaked at 475 mW cm -2 at our measurement condition.

25 ENERGY STORAGE↗

Electrospun Nanofiber Electrodes for High and Low Humidity PEMFC Operation

MEAs with nanofiber mat electrodes containing Pt/C catalyst and Nafion binder were fabricated and evaluated. The electrodes were prepared by electrospinning a solution of catalyst powder, salt-form Nafion (with Na + , Li + , or Cs + as the sulfonic acid counterion), and a carrier polymer of either polyethylene oxide or poly(acrylic acid). The carrier polymer was extracted prior to MEA testing by a hot water soaking step. The resulting fibers were 15%–17% porous, with a core–shell-like morphology (a coating of primarily Nafion on the fiber surface). MEAs with anode/cathode catalyst loadings of 0.1 mg Pt cm −2 each and a Nafion 211 membrane produced high power at both high and low relative humidity (RH) conditions in H 2 /air fuel cell tests, e.g., a maximum power density of 919 mW cm −2 at 100% RH and 832 mW cm −2 at 40% RH for a test at 80 °C and 200 kPa abs . The presence of nm-size pores within the fibers trapped water via capillary condensation during low RH feed gas testing, thus maintaining a high proton conductivity of the Nafion binder in the anode and cathode while minimizing/eliminating ionic isolation of catalyst particles in low water content, poorly conductive binder.

25 ENERGY STORAGE↗

Adverse Effects of Trace Non-polar Binder on Ion Transport in Free-standing Sulfide Solid Electrolyte Separators

Sulfide solid-state electrolyte (SE) possesses high room-temperature ionic conductivity. However, fabrication of the free-standing, sheet-type thin sulfide SE film electrolyte to enable all-solid-state batteries to deliver high energy and power density remains challenging. Herein we show that argyrodite sulfide (Li 6 PS 5 Cl) SE can be slurry cast to form free-standing films with low (≤5 wt%) loadings of poly(isobutylene) (PIB) binder. Two factors contribute to a lower areal specific resistance (ASR) of the thin film SEs benchmarked to the pristine powder pellet SSE counterparts: i) 1–2 orders reduced thickness and ii) reasonably comparable ionic conductivity at room temperature after the isostatic pressing process. Nevertheless, an increasing polymer binder loading inevitably introduced voids in the thin film SEs, compromising anode/electrolyte interfacial ion transport. Our findings highlight that electrolyte/electrode interfacial stability, as well as the selection of slurry components, including sulfide SE, binder, and solvent, play essential roles in thin film sulfide electrolyte development.

25 ENERGY STORAGE↗

Application of Cyclic Voltammetry with W Electrodes for Measurement of High CaO Concentration in Molten CaCl 2

Molten CaCl 2 is a useful electrolyte for certain pyroprocessing techniques, and the solubility of oxide ions in this salt is a critical characteristic of many of these techniques. CaO is a byproduct of direct oxide reduction (DOR), so the concentration of oxide ions can be used to determine the extent of these reactions. Using cyclic voltammetry (CV) with tungsten electrodes, the CaO concentration in the salt up to approximately 5 wt% was correlated to both oxidation peak height and power density values. This correlation was demonstrated in both equilibrium and transient conditions. CV is a promising method for the in situ real-time monitoring of CaO concentrations in DOR processes.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Simulating Discharge Curves of an All-Aqueous TRAB to Identify Pathways for Improving System Performance

Thermally regenerative ammonia batteries (TRABs) are an emerging technology that use low temperature heat (T < 150 °C) to recharge a flow battery that produces electrical power on demand. The all-aqueous copper TRAB can provide high power densities and thermal energy efficiencies relative to other devices that harvest energy from waste heat, but its performance is adversely impacted by the crossover of undesired species through the membrane and lower cell voltages compared to conventional batteries. In this work, we developed a numerical model to simulate discharge curves while accounting for crossover inefficiencies without tracking all electrolyte species through the membrane. The model was able to successfully reproduce discharge curves across a diverse range of battery conditions using a single fitting parameter to account for decay of electrode standard potential due to species crossover with minimal error (< 5%). The model was then used to simulate different design scenarios to estimate changes in energy output from alterations to the aspects of the battery electrolyte chemistry. Results from this study are used to identify pathways for improving future TRAB designs with respect to energy capacity and cost-effectiveness of the technology.

25 ENERGY STORAGE↗

Meso-Structured Polymer Electrolyte Fuel Cell Electrode

Increasing the utilization of Pt and Pt alloy catalysts in polymer electrolyte fuel cell cathodes is critical to improving the high power density operation, particularly at low Pt loadings. State of the art electrodes are fabricated in an ink deposition process that leads to uncontrolled electrode architecture with random aggregates of functional domains (catalyst, ionomer, and pore volume) (1). The randomness in the domains induces high tortuosity transport pathways for ions and fluids, which cause severe transport resistance during high current density operation. Thin ionomer films cause additional transport resistance and poisoning of the Pt catalyst, which becomes more significant at low Pt loadings. Reducing the amount of ionomer in the catalyst domain without affecting the ionic transport resistance is key to improving the utilization of the Pt and reducing the transport resistance at low Pt loading. Rational design of the electrode structure with controlled low tortuous ionic transport pathways could improve performance. The introduction of the ionomer pathways could also enable reduction of the ionomer volume in the catalyst domain, reducing the transport resistance. Middelmen et al. proposed electrode structures consisting of aligned components in a low tortuosity configuration to improve performance (2). In this work, we present an alternative electrode structure based on a vertically aligned array of Nafion pillars in the cathode catalyst layer, as shown in Figure 1a. Figure 1b shows the SEM image of the Nafion pillars. Furthermore, Pt supported on carbon catalyst was deposited on the Nafion pillars to fabricate a meso-structured electrode. Nafion pillars provide high conductive and low tortuous pathways for protons, reducing the effective transport distance, and enabling reduction of the ionomer binder in the catalyst domain.

25 ENERGY STORAGE↗

Direct Recycling of End-of-Life Cathode Material Through Redox Chemistry Mediators

Lithium-ion batteries (LIBs) are ideal for electric vehicles and electronic devices because of their high-power density and outstanding cycle life. The need for recycled LIBs material is pivotal for the sustainability of the renewable energy industry. The recycling process needs to be both economically and environmentally conscious. Direct recycling is cheaper and generates the least amount of waste compared to pyrometallurgical and hydrometallurgical processes. Direct recycling explored in this work is useful for reclaiming precious minerals from the End-of-Life (EOL) LIBs material. The EOL material has varying lithium deficiency, hence, redox mediator relithiation restores the lithium content rapidly and at low cost. The redox mechanism relithiate EOL cathode material by shuttling charges very fast between lithium metal and EOL cathode material. The redox mediator is oxidized to create lithium rich solvent and reduced to relithiate EOL cathode material. However, the process is sensitive to pH changes. The redox reaction creates acidic solvent, which may cause lithium leaching. Therefore, use of lithium hydroxide (LiOH) to remove impurities on the surface of the EOL material and as a lithium source creates a basic solution to prevent lithium leaching and relithiate EOL material. This approach will potentially pave way for fast quality cathode material recovery at a low cost.

cathode material↗

Lightweight Solid Oxide Cell Design for Ammonia-fed SOFC Systems

A lightweight solid oxide fuel cell (SOFC) was developed by OxEon Energy that demonstrates the potential for increased specific power (kW/g) suitable for the requirements of electric Vertical Take-off and Landing (eVTOL) applications. Fuel flexibility was demonstrated in button cells and stacks using both legacy electrolyte-supported SOFC structure and the lightweight structure. Button cell and stack performance was nearly identical among hydrogen, ammonia, and reformed natural gas. Durability testing shows similarly stable performance in each fuel. A button cell test in ammonia at 800 °C using the lightweight cell structure measured area specific resistance (ASR) of 0.25 Ω-cm2 in H2/N2 and NH3 fuel feeds and showed a peak power density of 0.98 W/ cm2 in NH3 fuel. Short term hold at 0.7 V showed stable performance.

Pike, Jenna↗

(Invited) Fuel Cell Component Durability for Million Mile Fuel Cell Trucks

While significant advances have been made and early commercial fuel cell light-duty vehicles (LDVs) are starting to be produced, fuel cells in the heavy-duty-vehicle (HDV) transportation sector (including trucks, long-haul semitrailers, maritime, trains, etc.) are nascent, despite the fact that advantages of fuel cells compared to both diesel and electric powertrains are very compelling in terms of emissions, charging time, efficiency, power-to-weight ratio, among others. However, the fuel-cell technology for HDVs requires a paradigm shift in fuel-cell research and development compared to LDVs, where the emphasis becomes efficiency and improvements in durability instead of a focus on increased power densities and lower cell costs. Heavy-duty applications require significantly longer vehicle lifetimes (>25,000 hours/1,000,000 miles for heavy-duty trucks), and therefore require improved fuel cell durability compared to light-duty vehicles. In 2020, HFTO formed the Million Mile Fuel Cell Truck Consortium (M2FCT) that includes a core team of five national laboratories to overcome durability and efficiency challenges in PEMFCs for heavy-duty applications with an initial focus on long-haul trucks. While targets and testing protocols have been developed for light-duty vehicles, the same level of targets and testing protocols have not been established for heavy-duty transportation. With operational times of greater than > 25,000 hours required, the need for well-developed accelerated stress tests (ASTs) is amplified. Results from these ASTs demonstrate the need for more durable electrode layers and well-controlled potential variations. Finally, this presentation will provide an overview of the DOE's Fuel Cell R&D approach, highlighting past and current activities, as well as strategies to enable fuel cell competiveness for heavy-duty applications.

25 ENERGY STORAGE↗

Decayheatml

This code is designed to predict and analyze the decay heat generated in molten salt reactors (MSRs) using a hybrid approach that combines machine learning and segmented polynomial fitting. The accurate prediction of decay heat is essential for reactor safety and the optimization of spent fuel storage. The code operates through several key components: 1) Data Architecture: It incorporates a modular data architecture that handles various MSR-specific operational parameters such as power density, humidity content, and air ingress. These parameters are sampled using Sobol sequences to ensure comprehensive coverage of operational uncertainties. 2) Machine Learning Framework: The code employs a diverse set of machine learning models, including polynomial regression, decision trees, random forests, gradient boosting, support vector regression, k-nearest neighbors, multi-layer perceptrons, and symbolic regression. These models are trained to predict decay heat over a wide temporal range, from immediate shutdown up to 10,000 years. 3) Region-Optimized Training: The temporal domain is divided into multiple regions, each modeled separately to capture distinct decay heat characteristics across different time scales. This approach significantly improves the accuracy and interpretability of predictions. 4) Segmented Polynomial Interpretation (SPI): The SPI method translates machine learning predictions into piecewise polynomial equations. These equations are physically interpretable and can be directly integrated into existing engineering workflows and safety analyses. 5) Front-End Interfaces: The code includes both a Jupyter notebook interface for research development and a Streamlit web application for operational deployment. These interfaces allow users to interactively explore decay heat predictions, adjust operational parameters, and visualize results in real-time. 6) Applications: The framework supports various applications, including safety system validation and spent fuel container optimization. It enables real-time evaluation of worst-case decay heat scenarios, informing the design of passive safety systems and optimizing container designs for long-term storage. Overall, this code provides a robust, accurate, and user-friendly tool for predicting decay heat in MSRs, enhancing reactor safety, and optimizing spent fuel management.

Retamales, Mauricio Eduardo Tano [Idaho National L↗

Non-circular electron beam spot welds in stainless steel alloys

Circularly symmetric-shaped spot welds are desirable for welding applications as they relate to heat and fluid flow conditions in the melt pool with predictable weld penetrations and repeatable results. Non-circular spot welds on the other hand result in undesirable and unpredictable weld penetrations or non-bridging of the liquid melt pool across the joint. Two known causes for non-circular melt pools occur when welding dissimilar metals, or when welding with skewed electron or laser beams that are not perpendicular to the surface. A largely unexplored additional factor, shown here, is an asymmetric power density distribution within the beam that can create non-circular melt pools even though the beam dimensions are much smaller than the melt pool itself.

36 MATERIALS SCIENCE↗