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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
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 OSTI2022

Direct Recycling of Lithium-Ion Battery Cathodes: A Multi-Stage Annealing Process to Recover the Pristine Structure and Performance

Direct recycling is an alternative low-cost process that retains the structure of the lithium-ion battery cathode rather than going through materials dissolution and repurification. While the process shows promise, various steps need to be better understood and studied to identify possible roadblocks, cost intensive steps, and needed variations in protocol that may be necessary based on the feedstock of recycled cathodes available. In this study, we have evaluated the process of thermal relithiation as it applies to end-of-life cathode materials. For recovered end-of-life cathodes, approximately 20% of the useable lithium has been lost due to solid electrolyte interface formation, parasitic reactions, and particle isolation; this lost lithium contributes to higher cell impedance and a gradual shift in electrode potentials. As a first step in the direct recycling process, this lithium needs to be restored not only to recover capacity but also to eliminate surface vacancies and hinder surface reconstruction that may increase impedance and impact performance. Here, we have optimized a coating method followed by a two-stage annealing process that restores a model delithiated NMC333 material to pristine performance. Comparisons to single-stage processes are made, and new characterization tools have been used to better understand the processes.

25 ENERGY STORAGE↗
DOE OSTI2024

The Role and Substitution of Cobalt in the Cobalt‐Lean/Free Nickel‐Based Layered Transition Metal Oxides for Lithium Ion Batteries

Here, the Nickel-based layered transition metal oxide cathode represented by NCM (LiNi x Co y Mn z O 2 , x+y+z=1) and NCA (LiNi x Co y Al z O 2 , x+y+z=1) is widely used in the electric vehicle market due to its specific capacity and high working potential, in which Cobalt (Co) plays a huge role in improving the structural stability during the cycle. However, the limited supply of Co, due to its scarcity and the influence of geopolitics, poses a significant constraint on the further advancement of the Nickel-based layered transition metal oxide cathode in the field of energy storage. In this paper, the mechanism of Co in the Nickel-based layered transition metal oxides is reviewed, including its critical role for structural stability such as the inhibition of cationic mixing and the release of lattice oxygen et al. Subsequently, it outlines various strategies to enhance the performance of Co-lean/free materials, such as ion doping, including single-ion doping and multi-ion co-doping, and various surface coating strategies, so as to eliminate the adverse effects of Co loss on materials. Ultimately, this paper offers a glimpse into the promising future of Cobalt-free strategies for high performance of Nickel-based layered transition metal oxides.

25 ENERGY STORAGE↗
DOE OSTI2022

Li-Ion Battery Electrode Contact Resistance Estimation by Mechanical Peel Test

Li-ion battery electrode electronic properties, including bulk conductivity and contact resistance, are critical parameters affecting cell performance and fast-charge capability. Contact resistance between the coating and current collector is often the largest electronic resistance in an electrode and is affected by chemical, microstructural, and interfacial variations. Direct measurements of contact resistance and bulk conductivity have proven to be challenging. In their absence, a mechanical electrode peel test is often used to compare adhesion and electrical contact resistance. However, using a micro-flexible-surface probe, contact resistance can be directly determined. Here, this work compares contact resistance and mechanical peel strength of multiple commercial-grade HE5050 and NCM523 cathodes and graphite and silicon anodes. It was found that peel strength correlates well with contact resistance in a carefully curated data set (p < 0.05) and in some situations may be a good metric to estimate electrical properties. However, there were distinct outliers in the data set, indicating that peel strength may not accurately reflect electrical properties when there is significant variation in electrode composition. These results illustrate the value of the micro-flexible-surface probe in quantifying contact resistance and bulk conductivity to better understand how battery composition and processing steps affect microstructure and resulting cell performance.

25 ENERGY STORAGE↗
DOE OSTI2025

Atomic layer deposited aluminum nitride for interface protection of lithium germanium thiophosphate solid electrolytes

Lithium germanium thiophosphate (LGPS) is an attractive solid-state electrolyte material due to its exceptionally high ionic conductivity (~1.2 × 10 –2 S cm –1 ), comparable to many organic liquid electrolytes commonly used in batteries. Despite the high conductivity of LGPS, the susceptibility of LGPS to deleterious degradation reactions has impeded its commercial adoption into solid-state batteries. In particular, the poor voltage stability of LGPS with high-voltage cathode or lithium metal potentials often results in dramatically increasing cell impedance during galvanic cycling. Here, we use aluminum nitride (AlN) as a protection layer for Li metal anode, applied directly to the LGPS at 250 °C using plasma-enhanced atomic layer deposition, to enhance cell performance by preventing LGPS-Li metal reactions. We compare the surface chemistry and electrochemical cycling performance of atomic layer-deposited AlN grown using both plasma N 2 and NH 3 precursors. Galvanostatic cycling and electrochemical impedance spectroscopy show that AlN-coated LGPS cells perform better than bare LGPS cells in contact with Li metal anodes, with the AlN able to improve cycling longevity by over a factor of 3 in certain cases. Finally, we utilize x-ray photoelectron spectroscopy (XPS) line scans to highlight the slow room-temperature reactivity between AlN and evaporated lithium metal, and a computational model is built to aid further XPS analysis.

25 ENERGY STORAGE↗
DOE OSTI2023

Oxygen Reduction at PtNi Alloys in Direct Methanol Fuel Cells—Electrode Development and Characterization

Catalyst layers made from novel catalysts must be fabricated in a way that the catalyst can function to its full potential. To characterize a PtNi alloy catalyst for use in the cathode of Direct Methanol Fuel Cells (DMFCs), the effects of the manufacturing technique, ink composition, layer composition, and catalyst loading were here studied in order to reach the maximum performance potential of the catalyst. For a more detailed understanding, beyond the DMFCs performance measurements, we look at the electrochemically active surface area of the catalyst and charge-transfer resistance, as well as the layer quality and ink properties, and relate them to the aspects stated above. As a result, we make catalyst layers with optimized parameters by ultrasonic spray coating that shows the high performance of the catalyst even when containing less Pt than commercial products. Using this approach, we can adjust the catalyst layers to the requirements of DMFCs, hydrogen fuel cells, or polymer electrolyte membrane electrolysis cells.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Synthesis of high-density olivine LiFePO 4 from paleozoic siderite FeCO 3 and its electrochemical performance in lithium batteries

The lithium-ion cathode material olivine LiFePO 4 (LFP) has been synthesized for the first time from natural paleozoic iron carbonate (FeCO 3 ). The ferrous carbonate starting material consists of the mineral siderite at about 92 wt. % purity. Because FeCO 3 has divalent iron, the reaction with lithium dihydrogen phosphate (LiH 2 PO 4 ) provides a unique method to develop iron-(II) containing LFP in an inert atmosphere. Since siderite FeCO 3 is a common mineral that can be directly mined, it may, therefore, provide an inexpensive route for the production of LFP. After carbon-coating, the LFP yields a capacity in the range of 80–110 mAh g -1 LFP (in one chosen specimen sample), which is lower than commercially available LiFePO 4 (150–160 mAh g -1 LFP ). However, the tap density of LFP derived from siderite is noticeably high at 1.65 g cm -3 . The material is likely to be improved with powder purification, nanosized processing, and more complete carbon-coating coverage with increased optimization.

36 MATERIALS SCIENCE↗
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 OSTI2021

Multifunctional Separator Allows Stable Cycling of Potassium Metal Anodes and of Potassium Metal Batteries

Here, this is the first report of a multifunctional separator for potassium-metal batteries (KMBs). Here, double-coated tape-cast microscale AlF 3 on polypropylene (AlF 3 @PP) yields state-of-the-art electrochemical performance: symmetric cells are stable after 1000 cycles (2000 h) at 0.5 mA cm –2 and 0.5 mAh cm –2 , with 0.042 V overpotential. Stability is maintained at 5.0 mA cm –2 for 600 cycles (240 h), with 0.138 V overpotential. Postcycled plated surface is dendrite-free, while stripped surface contains smooth solid electrolyte interphase (SEI). Conventional PP cells fail rapidly, with dendrites at plating, and “dead metal” and SEI clumps at stripping. Potassium hexacyanoferrate(III) cathode KMBs with AlF 3 @PP display enhanced capacity retention (91% at 100 cycles vs 58%). AlF 3 partially reacts with K to form an artificial SEI containing KF, AlF 3 , and Al 2 O 3 phases. The AlF 3 @PP promotes complete electrolyte wetting and enhances uptake, improves ion conductivity, and increases ion transference number. The higher of K + transference number is ascribed to the strong interaction between AlF 3 and FSI – anions, as revealed through 19 F NMR. The enhancement in wetting and performance is general, being demonstrated with ester- and ether-based solvents, with K-, Na-, or Li- salts, and with different commercial separators. In full batteries, AlF 3 prevents Fe crossover and cycling-induced cathode pulverization.

NMB↗
DOE OSTI2021

In situ XAS study of the local structure of the nano-Li 2 FeSiO 4 /C cathode

Despite the challenges in achieving its full theoretical capacity of reversible extraction of two Li ions, the Li 2 FeSiO 4 (LFS) cathode shows a remarkable cycling stability once its low electronic conductivity is addressed. By studying the local structure around the iron during electrochemical cycling using in situ x-ray absorption spectroscopy (XAS), it is possible to gain insight into the factors which determine the electrochemical properties of this material. In order to practically perform in situ XAS studies, the charge/discharge of LFS was maximized using two approaches: (a) reducing the particle size of LFS samples from micro-scale to nano-scale in order to reduce the diffusion path for intercalating ions; and (b) applying a conductive coating to each nanoparticle to facilitate electron transfer. A family of LFS materials was synthesized and characterized using x-ray diffraction, and scanning electron microscopy with energy dispersive analysis for structural and morphological analysis, as well as cyclic voltammetry and cycling tests for electrochemical performance diagnosis. This material was then characterized by in situ XAS. The results provide insight into the stable electrochemical performance of LFS and suggest new synthetic routes to reaching the theoretical capacity.

25 ENERGY STORAGE↗
DOE OSTI2020

Hollow-cathode chemical vapor deposition of thick, low-stress diamond-like carbon films

A radio-frequency (RF), hollow-cathode plasma source with confining magnetic field is described for the chemical vapor deposition of thick ( > 10 µm), amorphous diamond-like carbon ablator films for inertial confinement fusion applications. Plasma is characterized by optical emission spectroscopy, while properties of the resultant films are measured by a combination of profilometry, Rutherford backscattering spectrometry, elastic recoil detection analysis, X-ray diffraction, Raman spectroscopy, and atomic force microscopy. The dependence of the deposition rate, film density, elemental composition, self-bias and residual stress is reported as a function of RF power. Higher density films were found when using Ar plasma, than N 2 or H 2 plasma. The coatings produced are x-ray amorphous, exhibit low compressive stress ( ~ 100 MPa), high density ( < 1.7 g/cm 3 ), hydrogen content of ~ 30 at.%, and a low average roughness of 0.75 nm. Finally, applications of these films as tunable-density ablators for inertial confinement fusion experiments are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Robust Large-Scale Dynamic Windows using Reversible Metal Electrodeposition

This project funded the study and development of dynamic windows based on reversible metal electrodeposition (RME). Dynamic windows allow user control over light and heat flow into and out of buildings, which offer both advantages in building aesthetics (with worker productivity improvement of 2%) and energy efficiency (up to 20% savings) compared to static controls such as low emissivity coatings and blinds/shades. Despite these advantages, dynamic windows, which traditionally rely on electrochromic metal oxides or conductive organic molecules for light modulation have failed to significantly impact the market due to issues related to cost, color, and optical dynamic range. Dynamic windows based on reversible metal electrodeposition (RME) are an exciting alternative approach and have the potential to overcome the issues associated with traditional technologies. A RME dynamic window is an electrochemical cell that modulates light using the reversible electrodeposition of metal on and off a transparent conducting oxide (TCO), which serves as the working electrode. The electrolyte has nearly colorless metal salts dissolved, and application of a cathodic potential on the TCO reduces the metal cations across the TCO surface to their metallic form, making a thin film that is efficient at blocking out light. A reverse in polarity oxidizes the metal, where it dissolves into solution, returning the window back to transparent. The counter electrode typically employed is a metal mesh, which is used to balance the electrochemical reactions happening on the TCO working electrode. These RME dynamic windows have the largest dynamic range (capable of reaching <<0.1% transmission) with color neutral tinting of any existing technology using solution processed techniques, which positions the technology as a promising candidate to penetrate the residential market. We have successfully scaled up the windows from 25 cm2 to 929 cm 2 , and we have demonstrated significant improvements to both the cycle life (10,000 cycles in a 3-electrode half-cell) and shelf life (>1 month) of our windows. We have published our work in high impact journals (6 published and 2 manuscripts in prep), filed 5 patents, and have incorporated TYNT Technologies to commercialize the technology.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Direct Air Capture-Compatible Azolate and Amino Acid Ionic Liquids for Electrochemical CO 2 Reduction to CO on a Silver Cathode

Direct air capture (DAC) compatible ionic liquids (ILs) are attractive for integrating CO 2 capture and conversion due to their high CO 2 solubility at low partial pressures, tunable chemisorption mechanisms, low volatility, and wide electrochemical windows. However, very few ILs have high CO 2 uptake at DAC conditions (420 ppm CO 2 ), and even fewer have been evaluated for chemical compatibility and mechanistic continuity for combined capture and electrochemical CO 2 reduction (eCO 2 RR). We demonstrate that two representative DAC-capable ILs, [P 4444 ][Val] (amino acid-based) and [P 66614 ][5-Me-Imd] (azolate-based), exhibit favorable electrochemical reduction behavior. CO and H 2 were the dominant gas-phase products by GC, while 1 H and 13 C NMR confirmed negligible liquid-phase HCOOH. Chronoamperometry at moderate applied potentials (−2.0 to −2.5 V vs Ag/AgCl) in a two-compartment H-cell with a Ag coated carbon paper as the working electrode yielded steady-state current densities of ∼10 mA cm −2 with CO FE of 96% for [P 4444 ][Val] and 95% for [P 66614 ][5-Me-Imd], highlighting the role of viscosity and chemically absorbed CO 2 -IL species to provide highly selective CO formation while suppressing H 2 evolution.

amino acid ionic liquid↗
DOE OSTI2023

Electrospun Nanofiber Electrodes for High and Low Humidity PEMFC Operation

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

25 ENERGY STORAGE↗
DOE OSTI2022

Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells

Nitrogen-coordinated single atom iron sites (FeN 4 ) embedded in carbon (Fe–N–C) are the most active platinum group metal-free oxygen reduction catalysts for proton-exchange membrane fuel cells. Still, current Fe–N–C catalysts lack sufficient long-term durability and are not yet viable for practical applications. Here we report a highly durable and active Fe–N–C catalyst synthesized using heat treatment with ammonia chloride followed by high-temperature deposition of a thin layer of nitrogen-doped carbon on the catalyst surface. We propose that catalyst stability is improved by converting defect-rich pyrrolic N-coordinated FeN 4 sites into highly stable pyridinic N-coordinated FeN 4 sites. The stability enhancement is demonstrated in membrane electrode assemblies using accelerated stress testing and a long-term steady-state test (>300 h at 0.67 V), approaching a typical Pt/C cathode (0.1 mg Pt cm -2 ). The encouraging stability improvement represents a critical step in developing viable Fe–N–C catalysts to overcome the cost barriers of hydrogen fuel cells for numerous applications.

08 HYDROGEN↗
DOE OSTI2023

Directing High-Efficiency Na Plating with Carbon–Aluminum Junction Interfaces for Anode-Free Na Metal Batteries

Anode-free sodium metal batteries are highly promising for future energy storage but suffer from much faster cycling degradation as they are sensitive to even trace levels of irreversible side reactions. This work focuses on the most practical Al foil current collectors and systematically examined the effect of nano-sized carbon coating on improving the Na plating and stripping stability. We identified that the carbon-Al junction interface generated by carbon coating enabled more uniform Na depositing with lower overpotentials, delivering higher than 99.8% Faradaic efficiencies for a wide range of cycling currents between 0.5 and 3.0 mA cm -2 . This performance is much better than the 96.4% efficiency observed on uncoated Al foils under the same conditions, and was also confirmed under lean electrolyte and freezing electrolyte conditions, and can be attributed to the stronger interfacial binding and enhanced sodiophilic properties of the carbon-aluminum junction sites. Furthermore, these sites not only ensure uniform Na plating but also eliminates side reactions that would otherwise cause electrolyte depletion. As a result, Na-metal free full cells assembled with high capacity Na 3 V 2 (PO 4 ) 3 cathode delivered ~ 85% capacity retention for 100 cycles, higher than the 73% of retention of uncoated Al foil.

25 ENERGY STORAGE↗
DOE OSTI2022

Modification of LiMn 2 O 4 surfaces by controlling the Acid–Base surface chemistry of atomic layer deposition

In this combined theoretical and experimental study, we report the effects of Al precursor selection on the growth chemistry, interfacial structure, and electrochemistry of Al 2 O 3 coatings on spinel LiMn 2 O 4 (LMO) surfaces by atomic layer deposition (ALD). Five Al precursors, exhibiting a range of Lewis acid-base properties, were used to establish trends in the ALD Al 2 O 3 growth chemistry on LMO powders in comparison to redox-inactive planar silicon substrates. We show that the Lewis acid-base properties of the Al precursor ligands can be used to tune both the Mn oxidation states and the Al 2 O 3 coverage on the LMO surface. Density functional theory calculations are used to examine the reaction mechanism of each precursor on LMO surfaces, elucidating a correlation between the Lewis acidity of the ligands and the decomposition thermochemistry. In-depth X-ray photoelectron spectroscopy and in situ Fourier transform infrared spectroscopy measurements support these theoretical predictions and further reveal how different Al precursors modify the atomic and electronic structure near the LMO surface during ALD. While the Mn oxidation state is strongly influenced by the Lewis acidity of the precursor ligand, the surface coverage and thickness of the Al 2 O 3 coating are a more representative descriptor of the electrochemical performance measured in coin cell experiments. Finally, we show how the ligand acid-base properties of ALD precursors can be used to rationally tailor atomic layer growth mechanisms, which may enable atomic level control over the structure of functionalized interfaces for various applications related to catalysis, semiconductors, and energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cost-effective, Thin-film SOFCs for Reliable Power Generation (Final Report)

The project was aimed at developing and demonstrating an advanced solid-oxide fuel cell (SOFC) technology to cost-effectively and reliably generate electricity directly from hydrocarbon fuels (e.g., natural gas and coal-derived syngas) for distributed and central generation applications. The studied technology was built on a planar, porous metal-supported SOFC (MS-SOFC) with a unique thin-film structure having its anode intimately supported on a metal substrate. The porous metal support with graded porosity was fabricated from a low-cost scalable phase-inversion tape casting method. Anode, thin-film electrolyte, and cathode were sequentially deposited on the porous metal substrate using atmospheric plasma spray (APS). In this study, it was shown that the composition of the casting slurry could significantly influence the morphology of the metal support fabricated using the phase-inversion tape-casting method. Increasing the solid loading in the slurry favored the formation and growth of finger-like pores to a point, but the presence of excessive solid loading increased the viscosity of the casting slurry, restraining the growth of finger-like pores. With the increase in the amount of the binder polyethersulfone (PESf) in the slurry, well grown finger-like pores and a thin sponge-like layer were formed. Since the parameters of the APS process have a significant effect on the microstructure of coatings, which in turn affects or determines the SOFC cell performance, a series of metal-supported solid oxide fuel cells with a four-layer cell configuration of 430L/Ni-ScSZ/ScSZ/LSCF have been fabricated by a combination of phase inversion tape casting and APS techniques. Electrochemical testing of the cells fabricated from different deposition APS conditions revealed significant differences in cell performance.

30 DIRECT ENERGY CONVERSION↗