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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Quantitative assessment of environmental phenomena on maximum pit size predictions in marine environments

Maximum pit sizes were predicted for dilute and concentrated NaCl and MgCl 2 solutions as well as sea-salt brine solutions corresponding to 40% relative humidity (RH) (MgCl 2 -rich) and 76% RH (NaCl-rich) at 25 °C. A quantitative method was developed to capture the effects of various cathode evolution phenomena including precipitation and dehydration reactions. Additionally, the sensitivity of the model to input parameters was explored. Despite one's intuition, the highest chloride concentration (roughly 10.3 M Cl – ) did not produce the largest predicted pit size as the ohmic drop was more severe in concentrated MgCl 2 solutions. Therefore, the largest predicted pits were calculated for saturated NaCl (roughly 5 M Cl – ). Next, it was determined that pit size predictions are most sensitive to model input parameters for concentrated brines. However, when the effects of cathodic reactions on brine chemistry are considered, the sensitivity to input parameters is decreased. Although there was not one main input parameter that influenced pit size predictions, two main categories were identified. Under similar chloride concentrations (similar RH), the water layer thickness (WL), and pit stability product, (i · x) sf , are the most influential factors. When varying chloride concentrations (RH), changes in WL, the brine specific cathodic kinetics on the external surface (captured in the equivalent current density (i eq )), and conductivity (k o ) are the most influential parameters. Finally, it was noted that dehydration reactions coupled with precipitation in the cathode will have the largest effect on predicted pit size, and cause the most significant inhibition of corrosion damage.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

A lightweight and metal-free current collector for battery anode applications

The requirement for high energy density batteries is driving the development of high-capacity electrode materials while reducing the amount of inactive battery components such as separators, binders, and current collectors. Though current collectors are an inactive component, they are still required for successful working of a battery cell. Conventional current collectors include aluminum foil for cathode and copper foil for anode. Copper foil is quite heavy (8.7 mg/cm 2 ) for 10μm thickness. Therefore, there is a need for a lightweight current collector for anode applications. In this work, a metal-free current collector comprised of aligned carbon fiber (CFs) layer filled with carbon nanotubes (CNTs) mixed in polymer (P) is developed to be used as a current collector for anodes. Further, anodes coated on the CF-CNT-P showed lower charge transfer resistance and improved rate capability compared with the anodes fabricated on conventional copper foil-based current collectors. The CF-CNT-P are lighter (≈1.5 mg/cm 2 ) than the commonly used copper foil (8.7 mg/cm 2 ), which will increase the gravimetric energy density.

25 ENERGY STORAGE↗
DOE OSTI2022

Redox-homogeneous, gel electrolyte-embedded high-mass-loading cathodes for high-energy lithium metal batteries

Lithium metal batteries have higher theoretical energy than their Li-ion counterparts, where graphite is used at the anode. However, one of the main stumbling blocks in developing practical Li metal batteries is the lack of cathodes with high-mass-loading capable of delivering highly reversible redox reactions. To overcome this issue, here we report an electrode structure that incorporates a UV-cured non-aqueous gel electrolyte and a cathode where the LiNi 0.8 Co 0.1 Mn 0.1 O 2 active material is contained in an electron-conductive matrix produced via simultaneous electrospinning and electrospraying. This peculiar structure prevents the solvent-drying-triggered non-uniform distribution of electrode components and shortens the time for cell aging while improving the overall redox homogeneity. Moreover, the electron-conductive matrix eliminates the use of the metal current collector. When a cathode with a mass loading of 60 mg cm -2 is coupled with a 100 µm thick Li metal electrode using additional non-aqueous fluorinated electrolyte solution in lab-scale pouch cell configuration, a specific energy and energy density of 321 Wh kg -1 and 772 Wh L -1 (based on the total mass of the cell), respectively, can be delivered in the initial cycle at 0.1 C (i.e., 1.2 mA cm -2 ) and 25 °C.

25 ENERGY STORAGE↗
NASA NTRSDate not supplied

Ultrahigh Areal Capacity Holey Graphene Air Cathodes for Li-O2 and Li-CO2 Batteries

Advanced lithium (Li) batteries using gaseous cathode reactants such as oxygen (O2) and carbon dioxide (CO2)are attractive energy storage platforms because the gases are obtained externally and thus not accounted for in the total battery weight when fully charged.The discharge products at the cathode, typically Li2O2 for Li-O2 batteries and Li2CO3 for Li-CO2 batteries, are insoluble in the electrolyte.Therefore, in order for such batteries to function properly, an “air cathode”,which is a conductive scaffold within the battery cell,is required as a physical location for cathode electrochemical reactions to occur. Prior research has identified many carbon nanomaterials such as carbon nanotubes and graphene as viable choices for air cathode scaffold, while various metallic and metal-free catalytic systems integrated onto carbon-based air cathodes have been developed to improve the sluggish discharge and charge reactions. For future practical applications, the air cathode must exhibit a usable capacity per unit electrode area, or areal capacity, a critical parameter that has been largely overlooked so far in this field. In order to achieve high areal capacity, the air cathode must exhibit a sufficient amount of accessible void volume per unit electrode area while maintaining the conductive scaffold integrity during the entire electrochemical process. Here we present an ultrathick,holey graphene-based air cathode platform fabricated from a facile dry compression process that exhibits remarkable areal capacity values. Holey graphene is a carbon nanomaterial derived from graphene, but with nanometer sized holes through the nanosheet thickness.The presence of these holes enhances mass transport through electrode thickness and also enables the unique dry-press fabrication process that is not achievable using other carbon scaffold materials.The dry-pressed holey graphene air cathode platform is not only compatible with catalyst incorporation to improve battery reaction kinetics, but also allows for novel engineering of electrode architectures that is not achievable using conventional electrode fabrication approaches.The applications of such highly versatile, ultrahigh areal capacity air cathode platforms to both Li-O2 and Li-CO2 battery chemistries will be discussed.

Li-O2 batteries, Li-CO2 batteries, holey graphene,↗
DOE OSTI2023

Stabilizing High–Nickel Cathodes with High–Voltage Electrolytes

Electrolytes connect the two electrodes in a lithium battery by providing Li + transport channels between them. Advanced electrolytes are being explored with high-nickel cathodes and the lithium-metal anode to meet the high energy density and cycle life goals, but the origin of the performance differences with different electrolytes is not fully understood. Here, the mechanisms involved in protecting the high-capacity, cobalt-free cathode LiNiO 2 with a model high-voltage electrolyte (HVE) are delineated. The kinetic barrier posed by a thick surface degradation layer with poor Li + -ion transport is found to be the major contributor to the fast capacity fade of LiNiO 2 with the conventional carbonate electrolyte. In contrast, HVE reduces the side reactions between the electrolyte and the electrodes, leading to a thinner nano-interphase layer comprised of more beneficial species. Crucially, the HVE leads to a different surface reorganization pathway involving the formation of a thinner nanoscale LiNi 2 O 4 spinel phase on the LiNiO 2 surface. Finally, with a high 3D Li + -ion and electronic conductivity, the spinel LiNi 2 O 4 reorganization nanolayer preserves fast Li + transport across the cathode–electrolyte interface, reduces reaction heterogeneity in the electrode and alleviates intergranular cracking within secondary particles, resulting in superior long-term cycle life.

25 ENERGY STORAGE↗
DOE OSTI2020

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells (Final Report)

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co2O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Magnetized, radiofrequency-driven hollow cathode chemical-vapor deposition of ultrathick hydrogenated amorphous carbon

Amorphous carbon is an attractive material for next-generation inertial confinement fusion (ICF) ablators due to its amorphous structure, tunable density, compatibility with dopants, chemical inertness, and mechanical robustness. Ablators are typically deposited as ultrathick (10–200 μm) coatings on removable spherical templates. The deposition of such thick amorphous carbon films is challenging due to high intrinsic compressive stress, which causes film buckling and delamination. Here, we study the deposition of amorphous carbon films by magnetized, radiofrequency-driven hollow cathode chemical vapor deposition with a custom-designed source in Ne plasmas. Emphasis is on the hollow-cathode source design and effects of the plasma discharge power and the precursor flow rate on film properties. We demonstrate deposition rates of >1 μm/h for films with hydrogen content of ∼40 at. %, densities of 1.1–1.7 g/cm 3 , and trace quantities of oxygen impurities. In conclusion, we also demonstrate the feasibility of depositing thick hydrogenated amorphous carbon films (∼30 μm) for ICF applications.

Carbon based materials↗
DOE OSTI2026

4D-STEM Coupled with Unsupervised Machine Learning to Reveal at Large-Scale the Microstructural Evolution in Li- and Mn-Rich Cathodes

Li- and Mn-rich (LMR) layered oxides are known to exhibit a thin surface reconstruction layer, which grows during electrochemical cycling in a manner that depends on exposed crystallographic facets, cycling conditions, and electrolyte chemistry. Direct characterization of this layer has traditionally relied on high-resolution electron microscopy, which is inherently limited to small fields of view. Here, we employ four-dimensional scanning transmission electron microscopy (4D-STEM) combined with unsupervised machine-learning clustering to quantitatively map phase distributions over large areas and track their evolution in LMR cathodes during electrochemical aging. Our results show that the surface reconstruction layer consists predominantly of a rocksalt phase, whose thickness varies across different facets following activation cycling and becomes substantially thicker and more uniform during calendar aging. In contrast, a spinel-like phase is observed within the particle bulk. Large-area phase mapping and correlative high-resolution imaging reveal that this spinel-like phase preferentially nucleates at bulk crystallographic defects, including boundaries between 60°-rotated layered domains and associated mixed-phase regions, rather than exclusively at the particle surface. Our findings establish a mechanistic distinction between surface-driven rocksalt formation and bulk-defect-mediated spinel nucleation while demonstrating the unique capability of 4D-STEM to provide statistically robust, mesoscale insight into complex phase-evolution processes in LMR cathodes.

4D-STEM↗
DOE OSTI2023

Advancing ionomer design to boost interfacial and thin-film proton conductivity via styrene-calix[4]arene-based ionomers

Sub-micrometer-thick ion-conducting polymer (ionomer) layers often suffer from poor ionic conductivity at the substrate/catalyst interface. The weak proton conductivity makes the electrochemical reaction at the cathode of proton-exchange-membrane fuel cells sluggish. To address this, here we report on a class of polystyrene-based ionomers having sub-nanometer-sized, sulfonated macrocyclic calix[4]arene-based pendants (PS-calix). In films with thickness comparable to that of ionomer-based binder layers, the conductivity of PS-calix film (~41 mS/cm) is ~13 times higher than that of the current state-of-the-art ionomer, Nafion. We observe a similar improvement in proton conductivity when PS-calix interfaces with Pt nanoparticles, demonstrating the potential of PS-calix in catalyst ink. Leveraging a favorable interfacial chemical composition, PS-calix enhances proton conduction at the film-substrate interface, a shortcoming of Nafion. Moreover, the water in PS-calix films diffuses faster than bulk water and the water confined in Nafion films, suggesting an important role played by sub-nanometer-sized calix[4]arene cavities in creating unique water/ion transport pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photo-driven growth of a monolayer of platinum spherical-nanocrowns uniformly coated on a membrane toward fuel cell applications

Membrane electrode assemblies (MEAs) serve as the core units of polymer electrolyte membrane fuel cells (PEMFCs) and are regularly fabricated by painting a slurry of commercial Pt/C onto a membrane, leading to thick and disordered electrocatalyst layers (CLs). Herein, we report a photo-driven fabrication of MEAs with ultra-thin and ordered CLs by growing a monolayer of dendritic platinum spherical nanocrowns onto each side of a photocatalyst-modified membrane. This approach allows us to control the thickness and platinum loading of ordered CLs by simply varying the concentration of the platinum precursor under tungsten light irradiation. The resultant MEAs exhibit an excellent fuel cell power density of 1.01 ± 0.05 W cm –2 at a platinum loading of 53 ± 1.5 μg cm cathode –2 . Furthermore, this exceptional activity likely arises from the nanostructured platinum crowns, efficient mass transport, and uniform reaction rate in the ultrathin (59 ± 12 nm thick) and ordered CLs according to electrochemical and theoretical investigations.

25 ENERGY STORAGE↗
DOE OSTI2020

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly4 increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO 2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly 4 increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO 2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Chromium Tolerant, Highly Active and Stable Electrocatalytic Internal Surface Coating for Cathode of Commercial SOFCs (Final Report)

This project is aimed to develop a chromium (Cr) tolerant, highly active, and stable coating layer on the internal surfaces of the porous composite cathode from commercially available SOFCs. Such coating layer was developed using the additive manufacturing process of Atomic Layer Deposition (ALD) and has been applied on the cathode consisting of either an electronic conductor of LaxSr 1-x MnyO 3-δ (LSM) or mixed ionic and electronic conducting La x Sr 1-x Co y Fe 1-y O 3-δ (LSCF). PI's work has demonstrated that the internal surface of cathode from the commercial cells, can be further tailored using ALD coating to dramatically enhance the cell performance. For instance, ALD layer consisting heterostructured nano composite of nano-Pt and nano-(Mn 0.8 Co 0.2 ) 3 O 4 oxide on the internal surface of porous LSM/YSZ cathode from SOFCs, has resulted in the large reduction of the cell polarizations resistance by up to 53%, and enormous increase of power density over 370%. For the cells with LSCF/Sm 2 O 3 doped CeO 2 (SDC) cathode, the conformal layer of nano-composite consisting of superjacent CoOx and subjacent minimum amount of Pt nano-grains has resulted in the power density enhancement by 126% for the large scale industry tubular cells at 750°C, and both the performance enhancement and nanostructure of the ALD layer are stable over ~ 2000 h continuous operation performed at industry test station. In the meanwhile, those ALD coating layer developed by PI's work is also inherently Cr-tolerant, and could act as physical barrier for preventing Cr diffusion into the cathode backbone, so as to mitigate the Cr poisoning effect on the cathode. In this project, the impact of Cr on the performance of those ALD coated commercial cells has been evaluated. Based on evolution of the cell performance, the ALD coating layer chemistry and ALD coating layer thickness has been optimized to maximize the overall Cr tolerance, cell power density and cell longevity. Different ALD coating has been applied onto the internal surface of LSM/YSZ and LSCF/SDC backbone respectively. The architecture/scaffold structures on the internal surface of different cathode, designed by this project, was catalogued and analyzed using High Resolution Transmission Electron Microscopy (HRTEM), and cell power/durability performance are assured via comprehensive electrochemical performance testing in the industry operation relevant conditions. The impact of the electrochemical operation current density, the water humidity, the cell operation temperature, and cell operation duration on the Cr tolerance of ALD coated cells has been systematically investigated. There is completely different nanostructure degradation mechanisms between LSM and LSCF cells induced by Cr contamination. For the LSCF/SDC baseline cell, With the Cr source, there is no apparent Sr surface segregation phase even for the baseline cell operated for 3000 h at 750 °C. With the Cr source, there is significant amorphous (SrCr)Ox phase accumulated in the original pore region. For the commercial baseline cells, Cr contaminants on the LSM electrode severely impacted the entire cell's electrochemical performance and nanostructure degradation. Those degradations include (1). Peak power density loss of 64 % after 109 h of operation. The dramatic increase in Rp (2). They are cracking at LSM/SSZ interface, LSM grains. SSZ remains intact but with (CrMn)Ox. By contrast, ALD coating (MnCo)Ox/Pt dramatically improves the Cr resistance, as follows (1). ALD-coated cell with a power density is 280-380 % of the baseline cell, depending on the ALD layer thickness. (2). For a cell with a 20 nm thick ALD layer, there is a large performance enhancement (> 200 % power density) induced by ALD coating of Cr-tolerant Mn 0.8 Co 0.2 Ox. (3). For a cell with a 20 nm thick ALD layer, after 168 h at 750 °C power density of the ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination for 109 h. The ALD coating on the internal surface of cathode developed by this project integrated multi-functions. Those multi-functions include (1). Dramatically improving the cell power density for the commercial cells; (2). Dramatically improving contamination resistance of the cathode, for being an excellent protection coating layer sealing off Cr contamination. (3). Dramatically increasing the cell longevity by potentially preventing the microstructure evolution and grain coarsening of the cathode. Overall, this project will provide a simple solution to simultaneously enhance power density and increase the reliability, robustness, and endurance of commercial SOFCs, over the entire operating temperature range of 650-800 °C. For the inherently functional SOFC, the ALD coating of LSM based cathode mitigate the Cr-contamination. Power density of ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination. In addition to SOFCs, the novel on-demand design approach and creation of multifunctional heterogeneous architecture on the electrode surface presented in this work opens further research for their application in other types of fuel cells, batteries, and sensors for which electrochemical reactions on the surface are similarly critical.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Photovoltage behaviour of p-Sb 2 S 3 photocathodes for hydrogen evolution: effect of n-In 2 S 3 passivation layers

The 1.76 eV band gap of antimony(iii) sulphide (Sb 2 S 3 ) makes this semiconductor material a promising light absorber for photoelectrochemical water splitting, but scalable fabrication approaches to efficient devices are still lacking. Here we show that compact Sb 2 S 3 films on FTO can be obtained by electrochemical growth from aqueous colloidal sulphur and antimony trichloride solutions, followed by mild annealing. These films can be converted into hydrogen evolution photocathodes after coating with In 2 S 3 passivation layers and the addition of Pt proton reduction co-catalysts. For the first time, vibrating Kelvin probe surface photovoltage (VKP-SPV) spectroscopy is used to observe the carrier dynamics in such photoelectrodes. While the bare Sb 2 S 3 films suffer from high surface recombination rates and poor electron extraction, the In 2 S 3 overlayer is found to raise the photovoltage and cathodic photocurrent density, due to passivation of surface defects and formation of a p–n heterojunction. In thick In 2 S 3 films, these benefits are offset by shading and slow electron transfer. Also, we find that O 2 strongly affects the band bending in the Sb 2 S 3 –air and In 2 S 3 –air junctions and their photovoltage. The optimised devices evolve H 2 at 77.5% Faradaic efficiency and with 0.084% applied bias photon-to-current efficiency (ABPE) at 0.12 V vs. RHE. The low ABPE value is attributed to Sb 2 S 3 sub-bandgap defects visible in SPV spectra, the random orientation of Sb 2 S 3 crystallites in the films, which inhibits charge transport, the absence of crystal facets of Sb 2 S 3 , and a detrimental Schottky junction at the FTO|Sb 2 S 3 interface.

de Araújo, Moisés A. [University of California, Da↗
DOE OSTI2021

Evidence that Surface-Segregated Sr Phases Can Be Removed in LSCF via Ceria Pre-Infiltration, Are Less Apt to Form in SSC

Here Ce 0.9 Gd 0.1 O 1.95−x (GDC) pre-infiltration was performed on 12 vol.% La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3−x (LSCF) or Sm 0.5 Sr 0.5 CoO 3−x (SSC) infiltrated GDC Solid Oxide Fuel Cell cathodes. The addition of 7.5 vol.% of ∼40 nm diameter GDC nanoparticles into a ∼30 μ m thick porous scaffold of partially-sintered, sub-micron GDC particles before LSCF infiltration 1) lowered the temperature needed to produce a LSCF-GDC polarization resistance ( R P ) of 0.1 Ohm*cm 2 by ∼50 °C, and 2) reduced the amount of 500 h, 650 °C open-circuit LSCF-GDC R P degradation from ∼37% to ∼6%. In contrast, GDC pre-infiltration had no effect on the initial SSC-GDC R P or the 19% in R P degradation observed during 500 h of 650 °C open-circuit aging. X-Ray Photoelectron Spectroscopy showed that GDC pre-infiltration lowered the concentration of strontium species on the surface of the initial and 650 °C-aged LSCF-GDC, but had no effect on the initial or aged SSC-GDC Sr concentrations. Similarly, Electrochemical Impedance Spectroscopy showed that for both the initial and aged LSCF-GDC, GDC pre-infiltration improved oxygen exchange at the infiltrate-backbone and infiltrate-gas interfaces, but had no effect on the SSC-GDC. Hence, GDC pre-infiltration was concluded to improve LSCF-GDC performance and durability by scavenging exsolved Sr-rich secondary phases that form on the interfaces of LSCF, but not SSC.

36 MATERIALS SCIENCE↗
NASA NTRS1990

Resonant tunneling IR detectors

Researchers propose a novel semiconductor heterojunction photodetector which would have a very low dark current and would be voltage tunable. A schematic diagram of the device and its band structure are shown. The two crucial components of the device are a cathode (InGaAs) whose condition band edge is below the conduction band edge of the quantum wells and a resonant tunneling filter (GaAs-AlGaAs). In a standard resonant tunneling device the electrodes are made of the same material as the quantum wells, and this device becomes highly conducting when the quantum levels in the wells are aligned with the Fermi level in the negatively biased electrode. In contrast, the researchers device is essentially non-conducting under the same bias conditions. This is because the Fermi Level of the cathode (InGaAs) is still well below the quantum levels so that no resonant transport occurs and the barriers (AlGaAs) effectively block current flow through the device. However, if light with the same photon energy as the conduction-band discontinuity between the cathode and the quantum wells, E sub c3-E sub c1, is shone on the sample, free carriers will be excited to an energy corresponding to the lowest quantum level in the well closest to the cathode (hv plue E sub c1 = E sub o). These electrons will resonantly tunnel through the quantum wells and be collected as a photocurrent in the anode (GaAs). To improve the quantum efficiency, the cathode (InGaAs) should be very heavily doped and capped with a highly reflective metal ohmic contact. The thickness of the device should be tailored to optimize thin film interference effects and afford the maximum absorption of light. Because the device relies on resonant tunneling, its response should be very fast, and the small voltages needed to change the responsivity should allow for very high frequency modulation of the photocurrent. In addition, the device is tuned to a specific photon energy so that it can be designed to detect a fairly narrow range of wavelengths. This selectivity is important for reducing the photocurrent due to spurious light sources.

Woodall, Jerry M.↗
NASA NTRSDate not supplied

Predicting Thermal Response in a Li-ion Cell on a UAV Fight Profile

As the energy storage devices continue to "pack" more energy in a small space, any damage, battery component failure, manufacturing defect, or electrically abusing the battery can lead to catastrophic thermal runaway events. A catastrophic thermal event in a cell leads to high temperature, in some instances spewing of battery materials due to gas development from side reactions initiated due to high internal temperatures. Also, a thermal runaway event can propagate from a single "failed" cell to the pack in a battery pack, leading to a more significant event. Mitigating a thermal runaway event is important in the commercial and automotive sectors. However, preventing such events in an electric aircraft (or air taxis) is paramount due to the lack of alternatives in the event of a failure. Battery prognostics algorithms allow the prediction of state-of-charge (SOC) and end-of-life (EOL) of a Li-ion battery in a UAV (unmanned air vehicle) [1]. For this presentation, we will extend this two-level battery predictive algorithm to predict SOC, EOL, and estimated maximum temperature during a simulated flight. The model is extended by integrating a lumped physics-driven thermal model for high current densities [2]. The parameters used to control SOC and EOL are maximum storable charge, time constant for Li-ion diffusivity in the carbon particles, and internal cell resistance. Cycling leads to an increase in the heat generated by an aged Li-ion cell with a LiyCoO2 (LCO) cathode and a LixC6 (MCMB) anode. The aging of a cell leads to increase in SEI layer thickness, the diffusion time for the lithium ions inside the electrodes, and the local reaction rates, in addition to the thermodynamic abuse caused by fixed cycling voltages controlled by a Battery Management System. As the battery ages, the cell resistance increases, while the onset temperature of the thermal runaway decreases (depends on the cell chemistry and cell abuse history). Any large deviation of the cell temperature from the estimated (expected) value can identify a faulty cell. Since SEI decomposition has the lowest onset temperature in the series of reactions leading to thermal runaway, the model considers the self-heating rate of the SEI decomposition as onset temperature (similar to Ref. [3]). The parameters in the Arrhenius equation for the SEI heating rate depend on the number of cycles, the cell's operating temperature, and the cell's abuse history [4,5]. Coupling the electrochemical, thermal, and aging model allow the prognostic algorithm to estimate a typical cell voltage and temperature as a function of age (cycling and calendar), whose departure from measured values from the BMS is used to identify a safety event. In addition, we will present the results from two simulated flight scenarios for a UAV: typical and extreme, since the power requirements vary significantly during take-off, landing, and changing altitudes, while the power requirements remain low during the cruise. For this presentation, the power requirement for a battery pack in a UAV is scaled to a single cell. This cell is cycled through a simulated profile, and the data is collected and used to predict a safety event.

Li-ion↗
DOE OSTI2020

Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a Li x TM 3-x O 4 -type spinel shell

The poor long-term cycling stability, including the fast capacity fade and the severe voltage decay, has become the main concern hindering the practical application of Li-rich layered oxides, a promising cathode for high- energy-density Li-ion battery. Herein, we design and electrochemically construct a ~10 nm-thick Li x TM 3-x O 4 - type (TM ¼Ni, Co, Mn, 0 3 O 4 -type spinel phase and the good Liþconductivity of LiMn 2 O 4 -type spinel phase. Systemic structural and electrochemical analysis demonstrate that, it slows down the activation rate of Li 2 MnO 3 component and efficiently alleviates the lattice O loss at high voltage (>4.5 V) and Mn dissolution, thereby suppressing the structural degradation from the layered phase to the spinel phase in the bulk, eventually significantly enhancing the long-term cycling stability. This study adds richness into the Mn-based spinel phase system and provides a new heterostructure design strategy to improve the electrochemical performance of Li-rich layered cathodes and beyond.

25 ENERGY STORAGE↗