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DOE OSTI2025

Excess Density as a Descriptor for Electrolyte Solvent Design

Electrolytes mediate interactions between the cathode and anode and determine performance characteristics of batteries. Mixtures of multiple solvents are often used in electrolytes to achieve desired properties, such as viscosity, dielectric constant, boiling point, and melting point. Conventionally, multi-component electrolyte properties are approximated with linear mixing, but in practice, significant deviations are observed. Excess quantities can provide insights into the molecular behavior of the mixture and could form the basis for designing high-performance electrolytes. Here we investigate the excess density of commonly used Li-ion battery solvents such as cyclic carbonates, linear carbonates, ethers, and nitriles with molecular dynamics simulations. We additionally investigate electrolytes consisting of these solvents and a salt. The results smoothly vary with mole percent and are fit to permutation-invariant Redlich-Kister polynomials. Mixtures of similar solvents, such as cyclic-cyclic carbonate mixtures, tend to have excess properties that are lower in magnitude compared to mixtures of dissimilar substances, such as carbonate-nitrile mixtures. We perform experimental testing using our automated test stand, Clio, to provide validation to the observed simulation trends. We quantify the structure similarity using SOAP fingerprints to create a descriptor for excess density, enabling the design of electrolyte properties. To a first approximation, this will allow us to estimate the deviation of a mixture from ideal behavior based solely upon the structural dissimilarity of the components.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Fast and Scalable Synthesis of LiNi 0.5 Mn 1.5 O 4 Cathode by Sol–Gel-Assisted Microwave Sintering

High-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is a promising cathode material for high-energy-density and high-power-density lithium-ion batteries (LIBs). The high cost of the currently available LIBs needs to be addressed urgently for wide application in the transport sector (electric vehicles, buses) and large-scale energy storage systems (ESS). Of significance, herein, novel fast and scalable microwave-assisted synthesis of LNMO is reported, which leads to a production cost cut. X-ray diffraction (XRD) analysis confirms the formation of the desired phase with high crystallinity. Field emission scanning (FE-SEM) and transmission electron microscopy (TEM) analyses indicate that the synthesized phase is of nanometric size (50–150 nm) due to an extremely short sintering time (20 min). The material synthesized at 750 °C shows a higher initial discharge capacity (130 mA h g -1 ) than that synthesized at 650 °C (115 mA h g -1 ). The materials heat treated at higher temperatures show better electrochemical performance in terms of initial capacity, rate capability, and improved cycling. The improved electrochemical performance of LNMO at 750 °C is attributed to the formation of a stable crystal structure, low charge transfer resistance at the electrode/electrolyte interface, high electrical conductivity due to the presence of a disorder structure, and improved ionic diffusivity.

25 ENERGY STORAGE↗
DOE OSTI2024

Nonsolvating Fluoroaromatic Cosolvent Enabled Long-Term Cycling of High-Voltage Lithium-Ion Batteries with Organosulfur Electrolytes

Here, the structure–activity relationships of nonsolvating cosolvents for organosulfur-based electrolyte systems were revealed. The performance of nonsolvating dilutant fluorobenzene (FB) was compared to various fluorinated ether dilutants in high-voltage electrolytes containing a concentration of 1.2 M LiPF 6 dissolved in fluoroethylene carbonate (FEC), ethyl methyl sulfone (EMS), and the dilutant. In a high-voltage and high-loading LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cell configuration, the organosulfur-based electrolyte containing FB dilutant enabled superior electrochemical performance compared to the electrolytes using other nonsolvating fluorinated ether formulations. Moreover, the FB-containing electrolyte exhibited the highest ionic conductivity and lowest viscosity among all organosulfur-based electrolytes containing nonsolvating dilutant. These improvements are attributed to the enhanced physical properties of electrolyte and lithium-ion mobility. Furthermore, by employing first-principles simulations, the observed suppression of side reactions at high voltage is linked to FB’s lower reactivity toward singlet dioxygen, which is likely produced at the NMC interface. Overall, FB is considered an excellent diluent that does not impede cell operation by mass decomposition at the cathode.

25 ENERGY STORAGE↗
DOE OSTI2025

Scalable mechanochemical synthesis of high-quality Prussian blue analogues for high-energy and durable potassium-ion batteries

Prussian blue analogues (PBAs) are recognized as promising cathode materials for potassium-ion batteries (PIBs), particularly the low-cost and high-energy K 2 Mn[Fe(CN) 6 ](KMnF). However, conventional solution-based synthesis inevitably introduces [Fe(CN) 6 ] 4− defects and lattice water while suffering low synthesis efficiency, unfavorable to the improvement of electrochemical performance and scalability. Here, in this work, we report a simple solvent-free mechanochemical strategy for the synthesis of a wide variety of K 2 M[Fe(CN) 6 ] (M = Mn, Mg, Ca, etc.) with negligible defects and water, and it is unprecedented to achieve kilogram-level products of high-quality KMnF within just 10 minutes. The as-prepared KMnF delivers a high energy density of 590 Wh kg −1 at 0.2 C and exhibits an astonishing stability over 10 000 cycles and rate ability up to 50 C in a potassium metal half-cell. Encouragingly, a high-areal-capacity pouch cell with 2.2 mAh cm −2 (16.5 mg cm −2 ) exhibits a capacity retention of 80.7% after 500 cycles. Furthermore, systematic in situ characterization reveals underlying mechanism insights into structure–performance relationships. Specifically, the fully coordinated Mn–N 6 octahedral configuration effectively suppresses Mn 3+ Jahn–Teller distortion, enabling reversible phase transitions under both high-voltage and long-term cycling conditions. In addition, minimal defects provide sufficient redox centers, while the continuous three-dimensional framework facilitates rapid K + diffusion kinetics. This work provides a new opportunity for the ultrafast, universal and scalable synthesis of high-quality PBAs, facilitating the practical application of PIBs while enabling precise structural and compositional design of novel PBAs.

Mechanochemical method↗
DOE OSTI2023

Challenges and Prospects of Sodium‐Ion and Potassium‐Ion Batteries for Mass Production

The exponential growth of the lithium‐ion (LIB) market is causing a significant disparity between the supply chain and demand for its resources. In this regard, sodium‐ion and potassium‐ion batteries are promising alternatives to LIBs due to their low cost. However, the larger sizes of Na + and K + ions create challenges that prevent them from achieving energy densities comparable to LIBs while maintaining an acceptable cycle life. Here, in this perspective, the aim is to evaluate the status of Na‐ion and K‐ion batteries and the challenges associated with them on both fundamental and commercial levels. The focus is on the structural instability arising from phase transitions during cycling, intricate chemical degradation processes, and potential avenues for enhancing their performance with a specific goal of improving their viability for grid‐scale energy storage. Materials production and abundance limitations for the chemistries of the state‐of‐the‐art materials and account for critical parameters from both the perspective of researchers and investors are analyzed. This analysis aims to provide insights into the strategic trade‐offs required to effectively implement the technology in real‐world applications, such as grid‐scale storage and other areas. Furthermore, the utilization of metals with low or no supply‐chain problems as an important aspect of these trade‐offs is considered.

25 ENERGY STORAGE↗
DOE OSTI2023

The Linkage Between Electro-Chemical Mechanical Instabilities in Battery Materials

Battery chemistry must be diversified to achieve a sustainable energy landscape by effectively utilizing renewable energy sources. Alkali metal-ion, all-solid-state, metal–air batteries, and multivalent batteries offer unique cost, safety, raw material abundance, energy, and power density solutions. However, realizing these “beyond Li-ion batteries” must uncover their working principles and performance & property relationships. In this aspect, mitigating chemo-mechanical instabilities in the structure and surface of the electrodes plays a crucial role in their performance. Unfortunately, the coupling between electrochemical and mechanical interactions is often poorly understood due to a lack of operando characterization. Here, this review article explains the working principles of curvature measurement and digital image correlation for measuring stress and strain generations in battery materials. We provided specific examples of how these operando mechanical measurements shed light on instabilities in alkali metal ion electrodes, solid electrolytes, Li-O 2 batteries, and aqueous Zn-ion batteries. Operando mechanical measurements offer an effective way to map changes in the physical fingerprint of the battery materials, therefore providing crucial information to elucidate instabilities in battery materials.

25 ENERGY STORAGE↗
DOE OSTI2021

3D Artificial Solid-Electrolyte Interphase for Lithium Metal Anodes Enabled by Insulator–Metal–Insulator Layered Heterostructures

Despite considerable efforts to prevent lithium (Li) dendrite growth, stable cycling of Li metal anodes with various structures remains extremely difficult due to the direct contact of the liquid electrolyte with Li. Rational design of solid-electrolyte interphase (SEI) for 3D electrodes is a promising but still challenging strategy for preventing Li dendrite growth and avoiding lithium–electrolyte side reactions in Li-metal batteries. Here, a 3D architecture is constructed with g-C 3 N 4 /graphene/g-C 3 N 4 insulator–metal–insulator sandwiched nanosheets to guide uniform Li plating/stripping in the van der Waals gap between the graphene and the g-C 3 N 4 , and the function of which can be regarded as a 3D artificial SEI. Li deposition on the surface of g-C 3 N 4 is suppressed due to its insulating nature. However, its uniform lithiophilic sites and nanopore channels enable homogeneous lithium plating between the graphene and the g-C 3 N 4 , prohibiting the direct contact of the electrolyte with the Li metal. The use of the g-C 3 N 4 -layer-modified 3D anode enables long-term Li deposition with a high Coulombic efficiency and stable cycling of full cells under high cathode loading, limited Li excess, and lean electrolyte conditions. The concept of a 3D artificial SEI will shed light on developing safe and stable Li-metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2023

A Lattice Boltzmann Method for Predicting Porous Transport Layer Performance During Electrolysis

Electrolysis, the splitting of water into oxygen and hydrogen using electricity, is a sustainable way to produce green hydrogen for energy storage. In polymer electrolyte membrane (PEM) water electrolysis, water is brought into contact with charged catalyst layers and electrochemically separated into oxygen and hydrogen. The hydrogen product formed at the cathode is carried through the catalyst layer for eventual collection, while the oxygen by-product formed at the anode is removed from the surface via a multiphase interaction with circulating water and a solid porous transport layer (PTL). The design of this PTL aids in the detachment and advection of the oxygen by-product and thereby plays a role in the overall efficacy of the catalyst. In this presentation, we present our initial results modeling this multiphase system using a single-component, multiphase lattice Boltzmann method. We use the Shan-Chen model describing inter-particle forces to capture both the cohesion of the water (liquid) and oxygen (gas) phases and their interaction with the PTL (solid) (Shan and Chen, 1993). We use a Carnahan-Starling equation of state to model the effective density governing these inter-particle interactions which allows us to model this relatively high density ratio system (Carnahan and Starling, 1969). With these simulations, we show that the geometry and heterogeneity of the PTL geometry plays a large role in its ability to move oxygen away from the catalyst layer and the resulting bubble structures that are formed within the PTL. The current work demonstrates these effects using synthesized PTL geometries and 2D physics, which will be extended to experimentally-imaged PTL sections and 3D algorithms in the near future.

Boltzmann↗
DOE OSTI2020

Impact of electrode thick spot irregularities on polymer electrolyte membrane fuel cell initial performance

Polymer electrolyte membrane fuel cells have great potential for power generation in many applications, but to implement them on a larger scale, understanding of quality requirements, tolerances, and controls during manufacturing must improve. As part of this broad challenge, irregularities resulting from the membrane electrode assembly production process must be studied to determine if they impact the performance of the cell. One potential irregularity is a locally increased thickness of the coated or deposited electrode. In order to understand and provide insight into the impact of such irregularities, we intentionally created thick spots in the center of cathode electrodes. The thick spots fabricated by two different approaches were carefully characterized by optical microscopy, X-ray fluorescence spectroscopy and scanning electron microscopy (SEM). We found that the impact of the thick spots on the electrochemically active catalyst area and mass activity was minimal. However, specific electrode thick spot irregularities significantly impacted the mass transport properties of the cells. Based on SEM analysis, the likely cause of the performance drop is morphological changes associated with the creation of the thick spot irregularity. Spatial performance results obtained with a segmented cell system further indicated that the area of the performance impact exceeded that of the intentionally created thick spot.

25 ENERGY STORAGE↗
DOE OSTI2021

High spatial resolution temperature profile measurements of solid-oxide fuel cells

Temperature gradients resulting from local electrochemical reactions, current distribution and geometry of gas flow channels in solid oxide fuel cells (SOFCs) create thermal stresses, localized thermophysical property gradients and uneven property evolution, contributing to SOFC degradation. This paper presents a new method to perform temperature measurements (up to 800°C) at high spatial resolutions to monitor the operation of SOFCs. Using femtosecond laser irradiation, distributed fiber sensors were hardened for high temperature environment applications. Distributed fiber sensors were embedded in interconnected plates using an additive manufacturing method to perform temperature measurements with 4-mm spatial resolution during the operation of a planar fuel cell. The measurement revealed the impact of various H 2 fuel concentrations and current loads have on temperature profiles of the SOFC tested. Temperature variation on the anode side was found to be less than 5°C, and 3°C on the cathode side. The measurements were compared to results from a multiphysics fuel cell performance model simulating similar conditions. These simulations predicted similar temperature gradients, indicating the experimental data obtained is reasonable. The model also predicts that the effect of the embedded sensor has on the local temperature will be minimal and that the gradient of temperature in the gas channels will be captured despite the separation between the sensor and the gas flow. Finally, the high spatial resolution data harnessed by these distributed fiber sensors provides experimental support for model-based design and optimization to improve the operational efficiency and longevity of solid oxide fuel cells and fuel cell assemblies.

25 ENERGY STORAGE↗
DOE OSTI2021

Amphipathic Binder Integrating Ultrathin and Highly Ion-Conductive Sulfide Membrane for Cell-Level High-Energy-Density All-Solid-State Batteries

Current sulfide solid-state electrolyte (SE) membranes utilized in all-solid-state lithium batteries (ASLBs) have a high thickness (0.5–1.0 mm) and low ion conductance (<25 mS), which limit the cell-level energy and power densities. Therefore, based on ethyl cellulose's unique amphipathic molecular structure, superior thermal stability, and excellent binding capability, this work fabricates a freestanding SE membrane with an ultralow thickness of 47 µm. With ethyl cellulose as an effective disperser and a binder, the Li 6 PS 5 Cl is uniformly dispersed in toluene and possesses superior film formability. In addition, an ultralow areal resistance of 4.32 Ω cm -2 and a remarkable ion conductance of 291 mS (one order higher than the state-of-the-art sulfide SE membrane) are achieved. The ASLBs assembled with this SE membrane deliver cell-level high gravimetric and volumetric energy densities of 175 Wh kg -1 and 675 Wh L -1 , individually.

25 ENERGY STORAGE↗
DOE OSTI2021

All-in-one bipolar electrode: A new concept for compact and efficient water electrolyzers

Highly compact and efficient proton exchange membrane electrolyzer cells (PEMECs) are strongly desired for commercializing hydrogen production. Here, a novel concept of all-in-one bipolar electrode (AIOBE) is proposed for high-efficiency and compact PEMECs with the help of 3D printing and sputtering coating. AIOBE ideally integrated catalyst layer (CL)/gas diffusion layer/bipolar plate/current distributor/gasket, which significantly reduced component quantity on the cathode side of PEMECs from 5 to 1, cut down on part weight and volume, and drastically accelerated the fabrication and maintenance processes. Moreover, AIOBE with the micro-scale flat surface and nano-scale rough CL provided an ultralow ohmic resistance (~100 mOhm cm 2 ) and a high catalyst utilization. Finally, AIOBE delivered a practical voltage of 1.62 V and a high energy efficiency of 91% at 1000 mA/cm 2 , and its mass activity (4.48 A/mg Pt ) was 14 times higher than conventional PEMECs. In conclusion, this work provides a new route for developing highly compact electrochemical devices, such as fuel cells, electrolyzers for N 2 reduction and CO 2 conversion, and many more.

3D printing↗
DOE OSTI2024

Superionic conducting vacancy-rich β-Li 3 N electrolyte for stable cycling of all-solid-state lithium metal batteries

The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm -2 ) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-Li 3 N SSE. This vacancy-rich β-Li 3 N SSE shows a high ionic conductivity of 2.14 × 10 -3 S cm -1 at 25 °C and surpasses almost all the reported nitride-based SSEs. A Li- and N-vacancy-mediated fast lithium-ion migration mechanism is unravelled regarding vacancy-triggered reduced activation energy and increased mobile lithium-ion population. All-solid-state lithium symmetric cells using vacancy-rich β-Li 3 N achieve breakthroughs in high critical current densities up to 45 mA cm -2 and high capacities up to 7.5 mAh cm -2 , and ultra-stable lithium stripping and plating processes over 2,000 cycles. The high lithium compatibility mechanism of vacancy-rich β-Li 3 N is unveiled as intrinsic stability to lithium metal. In addition, β-Li 3 N possesses excellent air stability through the formation of protection surfaces. All-solid-state lithium metal batteries using the vacancy-rich β-Li 3 N as SSE interlayers and lithium cobalt oxide (LCO) and Ni-rich LiNi 0.83 Co 0.11 Mn 0.06 O 2 (NCM83) cathodes exhibit excellent battery performance. Extremely stable cycling performance is demonstrated with high capacity retentions of 82.05% with 95.2 mAh g -1 over 5,000 cycles at 1.0 C for LCO and 92.5% with 153.6 mAh g -1 over 3,500 cycles at 1.0 C for NCM83. Utilizing the vacancy-rich β-Li 3 N SSE and NCM83 cathodes, the all-solid-state lithium metal batteries successfully accomplished mild rapid charge and discharge rates up to 5.0 C, retaining 60.47% of the capacity. Notably, these batteries exhibited a high areal capacity, registering approximately 5.0 mAh cm -2 for the compact pellet-type cells and around 2.2 mAh cm -2 for the all-solid-state lithium metal pouch cells.

25 ENERGY STORAGE↗
DOE OSTI2025

Improving ICARUS Track Reconstruction Algorithms

The ICARUS experiment is part of the Short-Baseline Neutrino (SBN) program at Fermilab. The main goal of the experiment is to investigate the possibility of sterile neutrinos in the O(1 eV) mass region and provide clarification of the anomaly detected from the Liquid Scintillator Neutrino Detector (LSND) and MiniBooNE experiments. The ICARUS-T600 detector is a Liquid Argon Time Projection Chamber (LAr-TPC), that can provide excellent 3D imaging and calorimetric reconstruction of any ionizing particles. This detection technique allows a detailed study of neutrino interactions, spanning a wide energy spectrum (from a few keV to several hundreds of GeV). The detector consists of two identical adjacent modules, filled with a total of 760 tons of ultra-pure liquid argon. Each module houses two LAr-TPCs separated by a common cathode with a maximum drift distance of 1.5 m, equivalent to about 1 ms drift time for the nominal $500$ V/m electric drift field. The anode is made of three parallel wire planes positioned 3 mm apart, where the stainless-steel wires are oriented on each plane at a different angle with respect to the horizontal direction ($+60^\degree$,$-60^\degree$,$0^\degree$). The first two planes (Induction 1 and Induction 2) provide a non-destructive charge measurement, whereas the ionization charge is fully collected by the last collection plane. In total, 53248 wires with a 3 mm pitch and length up to 9 m are installed in the detector. In the first stage of the reconstruction, segments of waveforms corresponding to physical signals (hits) are searched for in the deconvolved wire waveform with a threshold-based hit-finding algorithm. Each hit is then fitted with a Gaussian, whose area is proportional to the number of drift electrons generating the signal. In the second stage of the reconstruction, hits are passed as input to Pandora, a framework software composed of different pattern recognition algorithms, that performs a 3D reconstruction of the full image recorded in the collected event, including the identification of interaction vertices and tracks and showers inside the TPC. These are organized into a hierarchical structure (called slice) of particles generated starting from a primary interaction vertex. In some cases, related to the inefficiencies in the hit detection or excessive deflection of the particle trajectory, Pandora breaks the particle's track into two or more smaller pieces and considers each piece as an independent track. We studied this phenomenon focusing on primary muons from ν_μ CC interactions contained in a single module with a track at least 20 cm long, to exclude delta rays. The study determined that about $7-8\%$ of the muon tracks are broken. Approximately $80\%$ of the times, Pandora assigns all segments of the track to the same slice (intra-slice track split), while in the remaining $20\%$ of the cases, one of the segments is associated with another slice (extra-slice track split). To mitigate this phenomenon, we designed an algorithm that detects and stitches the tracks broken by Pandora for the intra-slice split. In Monte Carlo simulations, the algorithm showed an efficiency exceeding $80\%$ and a purity exceeding $93\%$.

Ricci, Alessandro Maria [Pisa U.; INFN, Pisa] (ORC↗
DOE OSTI2020

Ca Cobaltites as Potential Cathode Materials for Rechargeable Ca-Ion Batteries: Theory and Experiment

Rechargeable Ca-based batteries can potentially achieve higher energy capacity than Li-ion batteries. The development of Ca-ion batteries, however, remains in its infancy, especially due to the challenge of finding cathode materials with high reversible capacity. In this work, we investigate properties of Ca cobaltites as Ca-ion intercalation cathodes, by means of density functional theory calculations validated by synthesis and electrochemical measurements. Computationally, we accessed thermodynamic, diffusion properties, energy capacity, and the voltage profiles for four Ca cobaltite compounds of different stoichiometry and Co oxidation states: Ca 3 Co 2 O 6 , CaCo 2 O 4 , Ca 2 Co 2 O 5 , and [Ca 2 CoO 3 ][CoO 2 ] 1.62 . We found good stability and relatively low migration barriers of some Ca cobaltites during cycling with the layered CaCo 2 O 4 having the lowest Ca migration barrier of 0.7 eV and the highest theoretical capacity. To validate our calculations, we synthesized Ca 3 Co 2 O 6 , CaCo 2 O 4 , and [Ca 2 CoO 3 ][CoO 2 ] 1.62 with the Pechini method and, subsequently, to test the electrochemical extraction of Ca.

25 ENERGY STORAGE↗
DOE OSTI2021

Discharging Behavior of Hollandite α-MnO 2 in a Hydrated Zinc-Ion Battery

Hollandite, α-MnO 2 , is of interest as a prospective cathode material for hydrated zinc ion batteries (ZIBs); however, the mechanistic understanding of the discharge process remains limited. Herein, a systematic study on the initial discharge of α-MnO 2 cathode under hydrated environment was reported using density functional theory (DFT) in combination with complementary experiments, where the DFT predictions well described the experimental measurements on discharge voltages and manganese oxidation states. According to the DFT calculations, both protons (H + ) and zinc ions (Zn 2+ ) contribute to the discharging potentials of α-MnO 2 observed experimentally, where the presence of water plays an essential role during the process. This study provides valuable insights into the mechanistic understanding of the discharge of α-MnO 2 in hydrated ZIBs, emphasizing the crucial interplay among the H 2 O molecules, the intercalated Zn 2+ or H + ions, and the Mn 4+ ions on the tunnel wall to enhance the stability of discharged states and, thus, the electrochemical performances in hydrated ZIBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Impact of SO 2 on NiFe Nanoparticle Exsolution and Dissolution from LaFe 0.9 Ni 0.1 O 3 Perovskite Oxides

Ni-doped LaFeO 3 perovskite oxide is a promising cathode material for solid oxide electrolysis cells (SOECs) designed for CO 2 /H 2 O coelectrolysis. Here, the performance of LaFe 0.9 Ni 0.1 O 3 is being investigated under real-world conditions that include exposure to acid gases, such as SO 2 , relevant to SOEC operation. Experiments show that LaFe 0.9 Ni 0.1 O 3 exsolves NiFe nanoparticles, along with the formation of surface SO 4 2– and SO 3 2– after being exposed to 200 ppm of SO 2 . This suggests that the ionic diffusion of Ni 3+ and Fe 3+ between the bulk and the surface remains unaffected throughout the exsolution–dissolution–exsolution cycle. Thermochemical water splitting has been employed as a probe reaction to evaluate the catalytic properties of the exsolved NiFe nanoparticles. These nanoparticles demonstrated improved hydrogen production compared to bare perovskite oxide substrates. However, after exposure to SO 2 , the formation of Fe-rich NiFe nanoparticles led to poor thermocatalytic performance and rapid deactivation of the perovskite at elevated temperatures. Density functional theory (DFT) analysis was utilized to validate the experimental findings, indicating a significantly negative reaction energy for water splitting over exsolved Fe, as well as stronger binding of SO 2 to Fe than to Ni. Computational analysis further suggests that the presence of surface sulfate promotes the formation of Fe-rich NiFe nanoparticles, aligning with the experimental results. Overall, this study clarifies how SO 2 affects the structure of SOEC perovskite oxide candidate materials. Future engineering efforts should focus on enhancing nanoparticle exsolution and sulfur resistance, which is crucial for improving the hydrogen production capacity of La-based perovskite oxides for electro- and thermocatalytic water splitting in real environments containing acid gases.

Najimu, Musa [Univ. of Southern California, Los An↗