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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Cathodic Protection Modeling for Hanford Underground Double-Shell Tank Farms

Hanford stores millions of gallons of radioactive and chemically hazardous waste from the production of weapon materials in tank farms consisting of underground carbon-steel storage tanks surrounded by reinforced concrete. Six of these Hanford tank farms use double-shell storage tanks (DSTs). The DST farms were constructed from 1968 to 1986 with a planned 40–50 year design life, so some are already operating beyond their initial life expectancy. Ultrasonic testing (UT) has indicated significant thinning on the bottom of the secondary (outer) liner of these tanks, believed to arise from groundwater intrusion driving concrete side corrosion. There is no direct access to the steel/concrete interface between the tank and the concrete pad, making it difficult to apply a chemical-based mitigation strategy or to conduct repairs, but cathodic protection (CP) is a possible method to inhibit further concrete-side corrosion. Hanford already uses CP to protect below grade steel piping within the tank farms and connected to the tanks, but this system was not designed to protect the tank bottoms. CP design must account for the structures surrounding the DSTs, including the steel reinforcing bars (rebar) within the concrete pad and vault, various process lines, and the existing CP system. In this study, finite element analysis (FEA) modeling was carried out to simulate CP protection of 1) a single tank and CP anode to develop options for modeling the rebar and to compare to a simpler circuit model and 2) the entire Hanford AN tank farm as a representative example consisting of seven tanks, associated piping, and both existing and new CP anodes. Both circuit and FEA models predict that significant protective current could be delivered to the bottoms of the tanks with the addition of tank-protection anodes below the depth of the tanks. Simulations with only the existing pipe-protection anodes active confirmed that only a very small current to the tank bottoms is predicted under present conditions. Multiple simplified representations of the dome and wall rebar were tested to reduce the computational complexity of the tank-farm simulations, resulting in modeling the rebar as edge elements with a prescribed effective circumference that matches the real rebar surface area. The geometry of the rebar is also simplified into horizontal hoops around the tank walls and radial rebar over the dome with increased effective circumference to retain the target surface area. This simplification was found to greatly reduce the complexity and solution time of the models without large changes in current distributions, especially to the tank bottom. A range of values were tested for model parameters such as soil and concrete resistivities and polarization resistance to investigate their impact on the current and electric potential distributions. Depending on the parameters used, FEA simulations predict some risk of overprotection, particularly on the piping system; since overprotection can also lead to surface damage associated with hydrogen gas generation at the interface (e.g. hydrogen embrittlement or damage to coatings), this needs to be considered when refining the design of the new CP system. Comparison between the FEA models and the circuit model representation demonstrated that the circuit model could not match the predicted FEA current distribution, even when using the exact same surface areas. This discrepancy appeared to be at least partly attributable to the impact of the relative positions of the tank components and anodes to each other and to the ground surface. The FEA model accounts for the relative positions since it solves the governing equations in three dimensions, but the circuit model cannot account for the positioning. In particular, the circuit model underpredicts the current to the tank bottom and overpredicts the current to the dome compared to FEA for the baseline geometry. The FEA models omitted the electrically isolated rebar in the bottom concrete slab. However, a circuit based stray current model estimated that only 2.1% of the total current through the slab would stray into the rebar, corresponding to ~0.21 A for a target current density of 2 mA/ft2 to the tank bottom. The estimated corrosion driven by this amount of stray current is predicted to yield a lifetime of >400 years for the minimum rebar diameter, assuming an acceptable cross-section area loss of 10%.

d'Entremont, Anna [Savannah River National Laborat↗
DOE OSTI2026

Enhancing Oxygen Evolution Reaction and Stability in Proton-Conducting Solid Oxide Electrolysis Cells (p-SOECs) via a Porous Gadolinium-Doped Ceria Interlayer

Proton-conducting solid oxide electrolysis cells (p-SOECs) offer a promising pathway for intermediate temperature (400-600 °C) hydrogen production. However, they still face critical challenges related to sluggish oxygen evolution reaction (OER) kinetics and low Faradaic efficiencies. Here, in this work, we demonstrate that introducing a thin (~0.8 µm) porous Gd 0.1 Ce 0.9 O 1.95 (GDC) interlayer between a BaCo 0.8 Zr 0.1 Zn 0.1 O 3-δ (BCZZ) oxygen electrode and electrolyte significantly enhances p-SOEC performance. The GDC interlayer reduces polarization resistance by 48% (0.54 to 0.28 O cm 2 ) and increases Faradaic efficiency from 63% to 81% at -0.8 A/cm 2 and 600 °C. GDC interlayer p-SOECs display elevated effective H 2 current densities compared to control p-SOECs and reach up to -1.22 A/cm 2 at 1.3 V. Mechanistic studies on the interactions between GDC and BCZZ reveal that GDC intrinsically promotes OER kinetics by significantly reducing the polarization activation energy (Ea p ), dropping from 1.45 to 1.22 eV for full p-SOECs and 0.98 to 0.76 eV for symmetric cells. This promotional effect is localized in the electrochemically active region near the electrolyte interface. Durability testing for over 1500 hours under 50% H 2 O conditions indicates that the GDC interlayer also improves long-term stability, with a degradation rate 53% lower than control p-SOECs. By pinpointing the interfacial region where GDC exerts its promotional effect, highlighting its role in enhancing OER kinetics, and establishing interlayer engineering as a powerful technique, this work provides a unified pathway to simultaneously improve p-SOEC activity, Faradaic efficiency, and durability.

08 - HYDROGEN↗
DOE OSTI2024

Enhancing corrosion resistance of lightweight metal alloys through laser shock peening

In this study, we investigated the effects of laser shock peening (LSP) on the corrosion resistance of lightweight metal alloys, specifically AA6061 and AZ31. LSP was performed underwater, using a nanosecond pulse laser and without using a protective coating or layer on the workpiece. The corrosion behaviors of these alloys were analyzed through electrochemical tests, including open circuit potential, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements. The results demonstrated that LSP significantly improved the polarization resistance, and higher laser power intensities led to increased corrosion resistance and reduced corrosion rates. This enhancement in anti-corrosion performance is attributed to the formation of a protective oxide layer on the surface, acting as a barrier against corrosion. In conclusion, the findings underscore the potential of laser surface treatment as a viable technique for enhancing the corrosion resistance of lightweight metal alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Corrosion Behavior of Hydrophobic Coatings in Aqueous CO2 Environments

Internal corrosion is caused by gas impurities such as CO2, moisture, and H2S, leading to material degradation. To combat this, the National Energy Technology Laboratory (NETL) developed a novel hydrophobic coating to reduce surface hydrophobicity and enhance the corrosion resistance of steel. NETL’s approach uses multi-layer hydrophobic coatings, a novel and promising coating that could potentially revolutionize the industry's approach to internal corrosion mitigation. This work aims to investigate the corrosion performance of the hydrophobic coating and determine the water uptake. Electrochemical corrosion experiments were carried out on bare X65 carbon steel without and with coating in 3.5 wt.% NaCl saturated with CO2 at 20 °C to follow the water uptake as a function of exposure time. Linear polarization resistance (LPR) was used to determine the corrosion rate for carbon steel immersed in a NaCl electrolyte saturated with CO2. Electrochemical impedance spectroscopy (EIS) of uncoated and coated bare carbon steel was investigated. The analyses of impedance models and water uptake behaviors of hydrophobic coatings were studied for 200 hours during the corrosion process. The water uptake was estimated using the Brasher and Kingsbury relation. The results showed that the superhydrophobic coating that was developed used innovative nano-based materials to act as protection layers on the surface of metallic parts against mechanical aggressors, corrosion, and fouling agents.

corrosion behavior↗
DOE OSTI2025

Nano-Engineered Interfaces in Dual-Layer Electrodes for Protonic Ceramic Cells with Enhanced Stability and Kinetics

Enhancing interfacial stability and charge transfer in protonic ceramic cells (PCCs) remains a critical challenge, as structural degradation and interfacial resistance often compromise durability and efficiency. Here, we report a nanoengineered dual-layer oxygen electrode architecture designed to address these limitations by introducing a fine-grained nanoparticle interfacial contact layer beneath a porous catalytic backbone. The nanoscale powders, through enhanced sintering activity, densify into a robust interfacial layer that promotes strong chemical bonding, uniform adhesion, and continuous ionic/electronic pathways with the BCZYYb electrolyte. This hierarchical architecture mitigates delamination, redistributes mechanical stress, and establishes efficient charge and mass transport channels without relying on corrosive surface treatments. Electrochemical evaluation demonstrates that the dual-layer design markedly reduces interfacial polarization resistance and accelerates electrode kinetics. Compared to the single-layer counterpart, the architecture achieves a peel strength of 44.53 N/cm 2 , a 40% improvement in peak power density (0.96 W cm –2 at 600 °C), and a 130% enhancement in electrolysis current density (4.78 A cm –2 at 1.57 V). Faradaic efficiency remains as high as 88% under high steam concentrations, underscoring minimal charge loss during practical operation. Notably, the electrode retains stability across 450–600 °C and under transient voltage cycling, with impedance spectra confirming suppressed interfacial resistance growth over prolonged use. These results highlight nanoscale interface engineering as a powerful route to enhance both mechanical robustness and electrochemical kinetics in PCCs. The demonstrated scalability and durability of this architecture provide a versatile platform for advancing solid-state electrochemical systems, including reversible fuel cells and high-efficiency hydrogen production technologies.

Faradaic efficiency↗
DOE OSTI2025

Optimization of La 2 NiO 4+δ Electrolysis Cell Oxygen Electrode through Surfactant-Enabled LaCoO 3±δ Nanocatalyst Deposition

Lanthanum nickelate (LNO) has shown promise as a Cr-resistant air electrode material for SOECs but has suboptimal surface oxygen exchange properties. Nanocoating of the LNO surface with lanthanum cobaltite (LCO) was chosen to improve cell performance as a surface oxygen conductor. The work focused on the implementation of a two-step nano-LCO film deposition utilizing catechol molecules in a porous LNO electrode. The subgoals of the work were to maintain nanosized LCO particles/ grains to increase active surface area and to control the regularity/ homogeneity of the coating across the microstructure. To achieve these goals, a novel surfactant-enhanced liquid infiltration method was utilized, where nucleation sites were spread across the electrode structure to control the location and size of LCO particles. Various catechol surfactant compositions were evaluated for their ability to control the kinetics of nanoparticle deposition and the homogeneity of the coating. Chelated LCO was characterized by X-ray diffraction (XRD), which found a substantial improvement in LCO formation with surfactant addition and determined polymerized norepinephrine to be the best-performing surfactant, with 88.4% pure LCO formed at low temperature. X-ray photoelectron spectroscopy (XPS) confirmed LCO nanostructures formed by the two-step infiltration process, showing no impurities and a stable perovskite structure. Deposition kinetics were analyzed using atomic force microscopy (AFM), correlating infiltration times and solution molarity to nanoparticle size and distribution, the results of which were confirmed in symmetrical cell samples by scanning electron microscopy (SEM). Electrochemical impedance spectroscopy (EIS) testing demonstrated substantial improvements in polarization resistance, where the nanocoating reduced the resistance by ∼55% to 0.152 Ω·cm 2 at 700 °C and 0.039 Ω·cm 2 at 800 °C. Electrical conductivity relaxation (ECR) at this temperature confirmed an improved surface oxygen exchange coefficient of the LCO + LNO heterostructure predicted by the Bode data from EIS, alongside a reduction in activation energy by about 30%.

Deposition↗
DOE OSTI2025

Conformal high-entropy oxide coatings enable fast and durable surface oxygen reactions

Developing active and durable air electrodes for efficient oxygen reactions is challenging for protonic ceramic cells (PCCs), especially at temperatures below 550°C. Here, in this study, we report a rationally designed conformal coating with a high-entropy PrNi 0.2 Mn 0.2 Co 0.2 Fe 0.2 Cu 0.2 O 3−δ (PNMCFC) perovskite structure on the surface of a state-of-the-art PrBaCo 2 O 5+δ (PBC) air electrode. The formed hybrid air electrode (PNMCFC-PBC) shows faster surface oxygen kinetics and a more stable phase structure in high-humidity air than the bare PBC electrode. Further density functional theory calculations suggest that the conformal coating mitigates Ba segregation at the interface and improves oxygen-related reactions, enhancing overall stability and electrocatalytic performance. The cells with the developed hybrid electrodes show encouraging electrochemical performance at 550°C: a polarization resistance of 0.72 Ω cm 2 , a peak power density of 1.30 W cm −2 , an electrolysis current density of −1.36 A cm −2 at 1.3 V, and reasonable operating stabilities (∼200 h at 550°C).

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Electro-Chemo-Mechanical Evolution at the Garnet Solid Electrolyte–Cathode Interface

Solid-state batteries promise higher energy density and improved safety compared with lithium-ion batteries. However, electro-chemomechanical instabilities at the solid electrolyte interface with the cathode and the anode hinder their large scale implementation. Here, in this study, we focus on resolving electro-chemo-mechanical instability mechanisms and their onset conditions between a state-of-the-art cathode, LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), and the garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. We used thin-film NMC622 on LLZO pellets to place the interfacial region within the detection depth of the X-ray characterization techniques. The experimental probes of the near-interface region included in operando X-ray absorption spectroscopy and ex situ focused ion beam scanning electron microscopy. Electrochemical degradation was not observable during cycling at room temperature with 4.3 V versus Li/Li + charge voltage cutoff, or with stepwise potentiostatic hold up to 4.1 V versus Li/Li + . In contrast, secondary phases including reduced transition metal species (Ni 2+ , Co 2+ ) were found after cycling up to 4.3 V versus Li/Li + at 80 °C and during potentiostatic hold at 4.3 V versus Li/Li + (Ni 2+ ). Intergranular cracks between NMC622 grains and delamination at the NMC622|LLZO interface occurred readily after the first charge. These interface reaction products and mechanical failure lowered the capacity and cell efficiency due to partial loss of the NMC622 phase, partial loss of contact at the interface, and a higher polarization resistance. Electrochemical instability between delithiated NMC622 and LLZO could be mitigated by using a low charge voltage cutoff or cycling at lower temperature. Ways to engineer the mechanical properties to avoid crack deflection and delamination at the interface are also discussed for enhancing mechanical stability.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Task Sharing of Proton Incorporation in Vertically Aligned Nanocomposite Triple Conductors: Growth, Structure, and Surface Exchange Kinetics

As protonic ceramic electrolysis cells emerge for efficient H 2 production, there is a need to develop air electrode materials enabling fast, durable steam splitting and proton incorporation. Single-phase triple conductors may fail to satisfy the myriad performance/stability requirements, and their critical charge-carriers (holes, oxygen vacancies, and protons) are in competition, limiting their concentrations. Instead, we propose task-sharing, vertically aligned nanocomposites (VANs), comprising a proton conductor (BaZr 0.9 Y 0.1 O 3-δ ) and a redox-active mixed ionic electronic conductor (Ce 0.9 Pr 0.1 O 2-δ ), that may enable rapid proton surface exchange at the solid–gas interface and transport along the solid–solid heterointerfaces. We grew VANs by pulsed laser deposition and investigated the interplay between their processing conditions, structure, and proton and oxygen surface exchange kinetics. We varied the substrate temperature, laser repetition rate, laser fluence, and processing oxygen pressure. The crystallinity and phases were characterized by grazing-incidence X-ray diffraction, and the strain and structural order as a function of depth were evaluated by angle-dependent synchrotron X-ray pair distribution function analysis. To evaluate the potential for interdiffusion, the formation energies of substitutional defects were simulated with density functional theory. Corresponding structural analysis and elemental mapping were performed by scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy-loss spectroscopy, indicating distinct nanoscale compositional regions with a hierarchical structure embedded in individual VANs columns and minimal interdiffusion across a bilayer film. Proton and oxygen surface exchange coefficients (k H , k O ) and polarization resistances were evaluated by electrical and optical relaxations and impedance spectroscopy of VAN-incorporated protonic ceramic electrochemical cells, respectively, at 400–500 °C, demonstrating values comparable to some of the best-known triple and mixed conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Improving protonic ceramic electrochemical cell performance via a dual-phase reaction-sintered bilayer electrolyte

Protonic ceramic electrochemical cells (PCCs) are promising energy conversion devices, but their fabrication remains challenging. In particular, the typical electrolytes for PCCs such as BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3−δ (7111) and BaCe 0.4 Zr 0.4 Y 0.1 Yb 0.1 O 3−δ (4411) suffer from intrinsic barium evaporation issues during high-temperature sintering. This tendency towards barium loss, combined with their highly refractory nature, leads to a tradeoff between sinterability and chemical stability. To address this tradeoff, we propose a bilayer electrolyte combining layers of 4411 and 7111 materials that is designed to enhance sinterability and conductivity through dual-phase reactive sintering. Our findings demonstrate that the bilayer structure exhibits shrinkage behavior closely matched to that of the fuel electrode substrate, with a higher shrinkage compared to a single-layer 4411 electrolyte. Utilizing this bilayer electrolyte structure, our PCCs achieve a peak power density of 637 mW∙cm −2 in fuel-cell mode and a current density of 1060 mA∙cm −2 at 1.3 V in electrolysis mode at 600 °C. Our PCCs demonstrate high Faradaic efficiency of 83% at 1.3 V and 500 °C. Hybrid distribution of relaxation times (DRT) polarization mapping further reveals that the bilayer structure reduces Ohmic and polarization resistance in both fuel-cell and electrolysis modes.

ceramic processing↗
DOE OSTI2024

The Effect of Sulfuric Acid Anodization on the Electrochemical Properties of Aluminum Alloy AlSi 10 Mg Prepared by Selective Laser Melting

Aluminum alloy, AlSi 10 Mg, prepared by selective laser melt (SLM) fabrication was anodized in 9.8% sulfuric acid (Type II) at 15 V for a total of 23 min. Experiments were performed to study the potentiostatic anodization process and its effects on the oxide coating morphology, thickness, and electrochemical properties of the alloy. Prior to anodization, the alloy microstructure is composed of aluminum cells encapsulated in a silicon network. Anodizing the abraded and polished AlSi 10 Mg surface produced a porous oxide layer with a thickness of 5μm. The oxide coating weight was 698 ± 29 mg/ft 2 . The oxide coating forms in the aluminum cells that are isolated from one another by the silicon eutectic phase. In electrochemical tests, the anodic and cathodic potentiodynamic polarization currents were suppressed by factors of 15× and 215×, respectively, as compared to the unanodized controls. The data indicate the anodic oxide coating suppresses the cathodic more than the anodic reaction rate. Linear polarization resistance (R p ) values increased by 279× after anodization. The corrosion current density values (j corr ) decreased by 133× after anodization. Taken together, the electrochemical data indicate the anodic oxide coating (unsealed) increases the corrosion resistance of the SLM alloy by two orders of magnitude.

Electrochemistry↗
DOE OSTI2024

Chromium-Free Coating for Al Alloy Corrosion Protection Based on a Novel Ti/Mg Oxyfluoride

Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF 6 2– fluoro-anion-based coating recipe containing boric acid and a Mg salt. Boric acid drove TiF 6 2– hydrolysis enabling up to micrometer-scale thick coatings. The Mg salt led to deposition of a novel crystalline phase Ti/Mg oxyfluoride coating with an approximate composition of Ti 5 MgO 7 F 8 . Corrosion protection performance was characterized by polarization resistance measurements during immersion in 5% aqueous NaCl solution and neutral salt fog exposure following ASTM B.117. The performance is discussed in terms of the presence of fluoride in the coating enabling active behavior during its gradual depletion (in corrosion environments) toward a final composition approaching TiO 2 . This active corrosion protection mechanism may be more generally applicable for transition metal-based coatings that do not have high oxidation state oxo-anions, but do have stable fluoro-anions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Corrosion of Zinc Cold Spray Coatings in a Wet Sweet and Sour Gas Environment

Internal corrosion is a problem for steel pipelines transporting natural gas or CO 2 containing water and partial pressures of H 2 S higher than 0.3 kPa (0.05 psi). This work aims to mitigate internal corrosion in steel pipelines transporting natural gas containing H 2 S using cold spray coatings. Two types of the cold spray binary metallic coatings (zinc chromium [ZnCr]. zinc niobium [ZnNb]) were studied using electrochemical techniques: potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy. The corrosion resistance of cold spray coatings (ZnCr, ZnNb) was evaluated in an environment containing 4 bar CO 2 pressure, simulating the partial pressures found in gas transmission lines over a solution of 3.5 wt% NaCl heated to 40°C. A concentration of 0.003 M Na 2 S 2 O 3 ·5H 2 O, corresponding to H 2 S partial pressures around 0.079 bar (1.146 psi), was used to simulate sour conditions. Postcorrosion surface characterization was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive x-ray spectroscope (EDS) and x-ray diffraction analysis. The data showed that the presence of 0.003 M Na 2 S 2 O 3 ·5H 2 O shifted the corrosion potential to more anodic values and decreased the corrosion current density. Both coatings showed similar behavior after 1 h of exposure in the CO 2 /H 2 S environment, indicating that similar electrochemical reactions were occurring on ZnNb and ZnCr. SEM images and EDS surface analyses for specimens showed a significant change in the surface chemical composition of carbon steel coated with ZnNb and ZnCr after 24 h of immersion. In the presence of thiosulfate (under sour conditions), the formation of corrosion product layers (ZnCO 3 and ZnS) on top of ZnNb and ZnCr coatings increased their corrosion resistance, which helped to reduce their corrosion by a factor of 2. Under a sweet environment, the corrosion rates for steel coated with cold spray coatings after 14 d of exposure are lower than that for galvanized steel by a factor of 5 due to the ZnCO 3 layer formed on top of the coatings. The ZnCO 3 layer formed on the steel surface acts as a physical barrier against corrosion by blocking the diffusion of corrosive species to the surface. No localized attack was observed. ZnCr Cold spray coating with defect showed promising corrosion protection against CO 2 corrosion (sweet corrosion) after 14 d of exposure to a CO 2 environment. Here, the scratch on the coating simulated damage created in service, and it was deep enough to expose the substrate material (steel). The formation of zinc oxide (ZnO) and zinc carbonate (ZnCO 3 ) on the scratch confirmed the cathodic protection of the steel by ZnCr and ZnNb coatings.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Capturing soil moisture and salinity changes in flooded coastal forests using electrical resistivity and induced polarization

Geophysical methods provide high-resolution spatial measurements of physical quantities sensitive to changes in soil moisture and salinity and can be used to monitor soil hydrological responses to flooding. However, extracting quantitative hydrological information from geophysical data remains challenging. In this study, we extended existing petrophysical models to estimate soil moisture and salinity from electrical measurements to address this challenge. We manipulated two hydrologically isolated 2000 m 2 experimental plots by simultaneously inundating them with 265 m 3 of either freshwater or estuarine water. Repeated electrical resistivity and induced polarization measurements were used to image the water and solute infiltration along two transects that are 100 and 42 m in length. Petrophysical models derived from laboratory multi-salinity electrical measurements were used to estimate changes in soil moisture and fluid salinity from field measurements of real and imaginary conductivity during the ecosystem-scale flooding experiment. The real conductivity increased by ∼100% in the freshwater plot and ∼570% in the saltwater plot. The change in imaginary conductivity in the freshwater plot was <1 mS/m, whereas that of the estuarine water plot was ∼5 mS/m. Real conductivity shows dependence on soil moisture content with a coefficient of determination (R 2 ) > 0.7, while the imaginary conductivity shows a dependence on soil salinity with R 2 > 0.6. The results validate the use of electrical resistivity for estimating changes in soil moisture content in response to flooding. Combining electrical resistivity imaging with induced polarization measurements provides the possibility to account for changes in pore fluid conductivity.

Adebayo, Moses B. [Univ. of Toledo, OH (United Sta↗
DOE OSTI2026

Revealing the Defect‐Driven Ferroelectric Mechanisms of Aluminum Nitride

Wurtzite III-nitride compounds are CMOS-compatible with widespread industrial interest to exercise ferroelectricity, despite their polar structure being highly resistant to polarization reversal. Here, we induce and tune ferroelectric properties in w-AlN via direct-write ion-beam processing, using nanoscale patterned defect engineering as a post-growth alternative to conventional cation substitution. Nanometric piezoresponse spectroscopy of the focused He + beam patterned defect concentrations in ferroelectric Al 0.92 B 0.08 N measures a localized 10x enhancement in effective piezoresponse and 40% reduction in switching barrier. The irradiation-induced point defects convert piezoelectric AlN into a ferroelectric system with site-saturated nucleation and raise the dielectric susceptibility, switched polarization, and effective piezoelectric coefficient. Enhanced defect-lattice interactions in AlN increase carrier conduction and phonon scattering loss but preserve long-range crystallinity. Here, based on atomistic analysis of nudged elastic band density functional theory calculations and reactive force field simulations, both nitrogen vacancies and defect complexes disrupt bond ordering, facilitating a line-by-line low-barrier switching of pristine AlN.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Inverse Consequences of the SnO 2 Protection Layers on Pt/C Catalysts in Proton-Exchange Membrane Fuel Cells

Proton-exchange membrane fuel cells (PEMFCs) are promising energy-conversion systems, offering an appealing blend of high energy efficiency and low environmental impact. However, carbon corrosion of PEMFCs is known to significantly degrade their performance, remaining a critical challenge to overcome. In this study, we applied a Nb-doped SnO 2 (Nb-SnO 2 ) nanoparticle coating on Pt/C catalysts as a protective layer, with the Sn/C ratio in the precursors varying from 0.25:1 to 2.0:1. Contradictory behaviors of the coated Pt/C catalysts were observed at different Sn/C ratios. The Sn/C = 1.0 sample exhibited improved electrochemically active surface area retention after 500 cycles of accelerated stress testing (AST) but with more significant polarization and resistance increase observed in the polarization curves. In addition, agglomeration of Nb-SnO 2 particles was observed at a higher Sn/C ratio in the AST of a membrane electrode assembly, with less shrinkage of the total thickness of the Nb-SnO 2 -coated Pt/C electrode. We speculate that formation of Nb-SnO 2 agglomerates occurs once the protective layer is broken down or the unprotected carbon surface is corroded and that these Nb-SnO 2 agglomerates increase the tortuosity of the electron pathways and significantly increase the cell polarization.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

Nm-scale electrical resistance imaging on CdTe by scanning spreading resistance microscopy

Local resistance imaging can provide information on nm-scale carrier distribution in semiconductor devices. Scanning spreading resistance microscopy (SSRM), an atomic force microscopy-based nm-scale resistance mapping technique, has been developed for carrier delineation in Si microdevices. We report on the development and validation of SSRM on CdTe materials, by testing on molecular beam epitaxy (MBE) grown CdTe films. The probe/CdTe contact resistance was suppressed sufficiently below sample's spreading resistance by pressing the probe into the sample with ∼mN contact force and applying a large sample/probe forward bias voltage (V s ), which was understood by analyzing current-voltage (I-V) involving a serially connected insulating top layer with underlying spreading resistance. The carrier concentration as deduced from the resistance measurement, using a single mobility value, is consistent with Hall measurement with a standard deviation of 14% based on a set of MBE films with carrier concentrations in the range of 10 15 –10 16 /cm 3 . The doping polarity was readily identified by flipping V s polarity, where the resistance with reverse V s is orders of magnitude larger than forward V s . While focusing on the SSRM technique validation, we also show an example on an As-doped Cd(Se,Te) polycrystalline thin film of a high-performance CdTe solar cell, which illustrates the local resistance nonuniformity with up to two orders of magnitude differences, indicating if local mobility is roughly constant, local carrier concentration can have significant nonuniformity.

14 SOLAR ENERGY↗
DOE OSTI2026

Coupled Interfacial Kinetics and Transport Resistances Govern High-Current Behavior in Bipolar Membranes

Bipolar membranes (BPMs) enable electrochemical systems that operate across large pH gradients; however, high-current operation is often limited by voltage losses whose origins remain difficult to resolve in membrane−electrode assemblies. Here, we combine electrochemical impedance spectroscopy with distribution of relaxation times (EIS–DRT) analysis and operando synchrotron X-ray diffraction to examine interfacial polarization, membrane hydration, and transport in commercial and synthesized BPMs. EIS–DRT isolates the BPM-associated interfacial contribution and shows that the commercial BPM exhibits larger water-dissociation-associated overpotentials than the synthesized BPM. Operando hydration mapping shows that both membranes retain water at the bipolar junction during high-current operation, while anode-adjacent hydration gradients are more pronounced in the commercial membrane. These results indicate that high-current voltage losses are not governed by junction water starvation alone but by coupled interfacial polarization and transport resistances.

36 MATERIALS SCIENCE↗