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462 records · Page 26

Pure-Water-Fed Forward-Bias Bipolar Membrane CO 2 Electrolyzer

Coupling renewable electricity to reduce carbon dioxide (CO 2 ) electrochemically into carbon feedstocks offers a promising pathway to produce chemical fuels sustainably. While there has been success in developing materials and theory for CO 2 reduction, the widespread deployment of CO 2 electrolyzers has been hindered by challenges in the reactor design and operational stability due to CO 2 crossover and (bi)carbonate salt precipitation. Herein, we design asymmetrical bipolar membranes assembled into a zero-gap CO 2 electrolyzer fed with pure water, solving both challenges. By investigating and optimizing the anion-exchangelayer thickness, cathode differential pressure, and cell temperature, the forward-bias bipolar membrane CO 2 electrolyzer achieves a CO faradic efficiency over 80% with a partial current density over 200 mA cm –2 at less than 3.0 V with negligible CO 2 crossover. In addition, this electrolyzer achieves 0.61 and 2.1 mV h –1 decay rates at 150 and 300 mA cm –2 for 200 and 100 h, respectively. Postmortem analysis indicates that the deterioration of catalyst/polymer– electrolyte interfaces resulted from catalyst structural change, and ionomer degradation at reductive potential shows the decay mechanism. Furthermore, all these results point to the future research direction and show a promising pathway to deploy CO 2 electrolyzers at scale for industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling the core of fuel cell performance: engineering the ionomer/catalyst interface

The biggest obstacle to the widespread implementation of polymer electrolyte membrane fuel cells (PEMFCs) is their cost, primarily due to the use of platinum catalysts. The high intrinsic catalyst activity exhibited on a rotating disk electrode (RDE) is rarely realized in a membrane electrode assembly (MEA), which is a long-standing challenge for PEMFCs and a cause of low catalyst utilization. To translate the high RDE performance of a catalyst into a MEA, the design of an ideal ionomer/catalyst interface is proposed: a thin, conformal ionomer film covers the maximum surface of a Pt nanoparticle and thus simultaneously maximizes catalyst utilization, (i.e., high mass activity and electrochemically active surface area) and O 2 diffusion rate (i.e., high current density performance) without compromising proton conduction. Building such an interface is a long-standing challenge due to the lack of interaction between the ionomer and catalyst particles, resulting in large ionomer agglomerates and inhomogeneous ionomer coverage over the catalyst nanoparticle, with consequent poor fuel cell performance. In this work, this ionomer/catalyst interface has been engineered, utilizing the electrostatic attraction between positively charged catalyst and negatively charged ionomer particles in a catalyst ink and preserved in a solid catalyst layer. As a result, this interface leads to previously unachieved proton exchange membrane fuel cell performance in terms of both catalyst utilization (75% vs. 45%) and peak/rated power density (i.e., 1.430/0.930 W cm -2 , H 2 /air, cathode Pt loading: 0.1 mgPt cm -2 ) for pure Pt catalysts, even better than those of Pt alloy catalysts. This work demonstrates the formation of an interface in the liquid phase (using ultra-small-angle X-ray scattering in combination with cryo-TEM, isothermal–titration–calorimetry) and the preservation of the interface in the solid catalyst layer (using TEM) and estimates the effective coverage and thickness of the ionomer film (using limiting current density, RDE and fuel cell performance).

25 ENERGY STORAGE↗

Influence of Electrolyte Additives on Interfacial Stability of Manganese-Rich Lithium-Ion Battery Cathodes

Affordable, long-lasting energy storage has become critical to support increased electricity demand in recent years. Cobalt-free, lithium- and manganese-rich lithium nickel manganese oxide (LMR-NM) cathodes stand to reduce cost and supply-chain concerns associated with traditional cobalt-containing cathodes for lithium-ion batteries by leveraging more earth-abundant materials; however, they have shown issues with long-term cycling stability. Here, we investigate lithium difluoro(oxalate)borate (LiDFOB), tris(trimethylsilyl) phosphite (TMSPi), and vinylene carbonate (VC) electrolyte additives for their ability to improve cycling performance of LMR-NM (0.3 Li 2 MnO 3 + 0.7 LiMn 0.5 Ni 0.5 0 2 ) cells. Cryogenic scanning transmission electron microscopy (cryo-STEM) with electron energy loss spectroscopy enables the construction of a structure–function relationship between cathode electrolyte interphase (CEI) characteristics and the electrochemical performance of cells aged with these additives. We find the combination of 2 wt % TMSPi + 1 wt % LiDFOB performs better than any single additive, achieving a 28% improvement in specific capacity over the baseline electrolyte after long-term cycling. We attribute this to LiDFOB mitigating Mn ion dissolution, with cryo-STEM showing Mn stabilized up to the CEI surface, coupled with improved CEI structure and chemistry enabled by TMSPi, evidenced by a moderately thick (∼7–15 nm) CEI that appears to protect against further electrolyte reactions with the particle. These results, achieved through site-specific nanoscale characterization, directly reveal mechanisms through which electrolyte engineering can improve the performance of earth-abundant cathodes, enabling informed development of more affordable and reliable batteries to meet future energy storage needs.

25 ENERGY STORAGE↗

Mild-Annealed Molecular Layer Deposition (MLD) Tincone Thin Film as Photoelectrochemically Stable and Efficient Electron Transport Layer for Si Photocathodes

Metalcone thin films, composed of inorganic–organic hybrids, are synthesized using molecular layer deposition (MLD) through reactions between organometallic precursors (e.g., Sn, Al, and Ti) and organic reactants (e.g., ethylene glycol and glycerol). Despite their unique properties, metalcones exhibit significant vulnerability to water due to their organic components, limiting their potential in electrochemical applications. This study focuses on enhancing the photoelectrochemical stability of tincone thin films in aqueous electrolyte while preserving their hybrid characteristics through mild annealing in air at 250 °C. As-deposited and vacuum-annealed tincone thin films exhibited significant degradation under these conditions, while high-temperature-annealed (500 °C) tincone thin films offered improved stability with a significant decline in charge transfer efficiency. In contrast, mild annealing in air maintained the C–O bond at half level and improved the stability and charge transport without compromising the unique characteristics of tincone. This was confirmed by ellipsometry, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). Mild-annealed tincone deposited on a lightly doped p-type silicon (p-Si) photocathode produced a 20-fold increase in CO volume compared to high-temperature annealed tincone in a CO 2 -saturated potassium bicarbonate (KHCO 3 ) electrolyte with dispersed graphene oxide–cobalt phthalocyanine (GO-CoPc) under 1 sun illumination at 0.9 V vs reversible hydrogen electrode (RHE), while maintaining the faradaic efficiency for CO and H 2 . These results suggest that mild-annealed tincone thin films hold significant potential as protective charge transport layers on silicon photocathodes for the aqueous CO 2 reduction reaction (CO 2 RR).

Annealing (metallurgy)↗

Cyclable Variable Path Length Multilevel Structures for Lossless Ion Manipulations (SLIM) Platform for Enhanced Ion Mobility Separations

Ion mobility-mass spectrometry (IMS-MS) is increasingly used to analyze complex samples and provide structural information of unknown compounds. As the complexity of samples increases, there is a need to improve the resolution of IMS-MS instruments to increase the rate of molecular identification. In this work, we evaluated a cyclable and variable-pathlength multilevel Structures for Lossless Ion Manipulations (SLIM) platform to achieve a higher resolving power than previously possible. This new multilevel SLIM platform has eight separation levels connected by ion escalators and a path length of ~88 meters (~11 meters per level). Our new multilevel SLIM can also be operated in an ‘ion cycling’ mode where a set of return ion escalators transport ions from the eighth back to the first level, allowing even longer path lengths (and higher IMS resolution). The platform has been improved to enhance the ion transmission and IMS separation quality by reducing the spacing between SLIM boards as well as board thickness, reducing the ions’ escalator residence time. Compared to the previous generation, the new multilevel SLIM demonstrated a better transmission for a set of phosphazene ions, especially for the low-mobility ions. The new multilevel SLIM achieved better resolving powers than our previous 4-level SLIM. The collision cross-section-based resolving power of the SLIM platform was tested using a pair of singly-charged reverse sequence peptides (SDGRG 1+ , GRGDS 1+ ). We achieved 1100 resolving power using 88 meters of path length (i.e., 8 levels) and 1400 following an additional pass through the eight levels (i.e., 16 levels or 173.5 m). The multilevel SLIM was further evaluated to demonstrate the enhanced separation for a positively and negatively charged brain total lipid extract sample. Finally, the new multilevel SLIM enables much higher resolving powers for a wide range of ion mobilities, improved transmission for low-mobility ions, and the ability to perform even higher resolving power for ions of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resistive Switching Memory Performance of Two-Dimensional Polyimide Covalent Organic Framework Films

Two-dimensional polyimide covalent organic framework (2D PI-NT COF) films were constructed on indium tin oxide-coated glass substrates to fabricate two-terminal sandwiched resistive memory devices. The 2D PI-NT COF films condensated from the reaction between 4,4',4"-triaminotriphenylamine and naphthalene-1,4,5,8-tetracarboxylic dianhydride under solvothermal conditions demonstrated high crystallinity, good orientation preference, tunable thickness, and low surface roughness. The well-aligned electron-donor (triphenylamine unit) and -acceptor (naphthalene diimide unit) arrays rendered the 2D PI-NT COF films a promising candidate for electronic applications. The memory devices based on 2D PI-NT COF films exhibited a typical write-once-read-many-time resistive switching behavior under an operating voltage of +2.30 V on the positive scan and -2.64 V on the negative scan. A high ON/OFF current ratio (>10 6 for the positive scan and 10 4 -10 6 for the negative scan) and long-term retention time indicated the high fidelity, low error, and high stability of the resistive memory devices. The memory behavior was attributed to an electric field-induced intramolecular charge transfer in an ordered donor-acceptor system, which provided the effective charge-transfer channels for injected charge carriers. Furthermore, this work represents the first example that explores the resistive memory properties of 2D PI-COF films, shedding light on the potential application of 2D COFs as information storage media.

2D covalent organic framework film↗

Potential-Controlled Deposition of Multilayer CO 2 Reduction Catalyst Films onto Silicon Photoelectrodes Demonstrates Thickness-Dependent Catalytic Rates

Covalently attaching molecular catalysts to semiconductor surfaces yields promising hybrid photoelectrode architectures for reducing CO 2 to higher-value carbon products. Polymeric molecular catalyst films have higher loading densities than their monolayer counterparts, promising greater rates of solar fuel production. Using photoassisted diazonium electrografting, multilayered films of a Re(apbpy)(CO) 3 Cl CO 2 -reduction catalyst were attached to low-doped p-type Si (pSi). Parallel characterization of the newly formed films with ellipsometry, XPS, and ICP-MS revealed that catalyst loading increased with increasingly negative applied grafting potentials (Vgraft), providing us an experimental test bed to study the effects of film thickness on photocatalytic performance. Controlled-potential electrolysis experiments showed enhanced CO evolution rates on all photoelectrodes with increasingly negative applied potentials (V app ), with thicker films exhibiting the greatest rates of enhancement. Competitive proton reduction reactions at the Si surface were not strongly linked to V app but dependent on film thickness, with thicker films showing increased CO-to-H 2 production ratios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent-Free Melt-Processed Cathode Mitigates Li Anode Instability in Polymer-Based Solid-State Batteries

Solvent-free manufacturing of battery components is a promising alternative to traditional slurry processing for reducing the cost and environmental impact. In this work, we used twin-screw melt extrusion to fabricate a polymer-based high voltage composite cathode. The melt-processed cathode is dense (near zero porosity) and thick (65 μm) and has high active material loading (80 wt %). The active particles are distributed uniformly throughout the melt-processed cathode, unlike the traditional slurry-cast cathode, which exhibits inhomogeneous particle distribution. In the melt-processed cathode, polymer and carbon form separate phases, whereas in the slurry-cast cathode they blend into a single phase. Due to these structural differences, the melt-processed cathode shows smooth charge–discharge profiles, while the slurry-cast cathode shows noisy charging and soft-shorting behavior. In conclusion, this work highlights that twin-screw extrusion as a scalable, solvent-free manufacturing method is advantageous in producing uniform cathodes, which mitigates anode instability.

25 ENERGY STORAGE↗

The Role of Secondary Particle Structures in Surface Phase Transitions of Ni-Rich Cathodes

Nanometer-thick reconstruction layers on layered cathode surfaces have been widely observed on both pristine and cycled materials. However, the mechanisms of reconstruction and the role that these structures play in electrochemical performance are not fully understood. From a crystallographic perspective, such surface reconstruction layers result from cation site-mixing between Li and transition-metal ions, but it remains far from clear as to what the critical factors are that control such cation mixing for various cathode chemistries. In this paper, we report observations on surface transformations during cycling of a Ni-rich cathode-oxide that are governed by direct contact with the liquid electrolyte. Specifically, within a secondary particle, the three-dimensional hierarchical aggregate of primary particles leads to the formation of grain boundaries of different characteristics, including open grain boundaries that allow the permeation of liquid electrolyte, and closed grain boundaries that exclude liquid electrolyte penetration. Upon battery cycling, surfaces in direct contact with the liquid electrolyte showed a surface reconstruction layer while the surfaces that did not have contact with the electrolyte showed no such reconstructions. In addition, the critical role of oxygen in reconstruction of grain boundaries is demonstrated, and the unexpected oxygen depletion at twin boundaries result in severe phase transitions. The present work provides further insights into phase transitions at solid-solid and solid-liquid interfaces within secondary cathode particles and suggests strategies for mitigating surface/interfacial degradation.

36 MATERIALS SCIENCE↗

Oxygen Electrocatalysis on Mixed-Metal Oxides/Oxyhydroxides: From Fundamentals to Membrane Electrolyzer Technology

Catalyzing the oxygen evolution reaction (OER) is important for key energy-storage technologies, particularly water electrolysis and photoelectrolysis for hydrogen fuel production. Under neutral-to-alkaline conditions, first-row transition-metal oxides/(oxy)hydroxides are the fastest-known OER catalysts and have been the subject of intense study for the past decade. Critical to their high performance is the intentional or accidental addition of Fe to Ni/Co oxides that convert to layered (oxy)hydroxide structures during the OER. Unraveling the role that Fe plays in the catalysis and the molecular identity of the true “active site” has proved challenging, however, due to the dynamics of the host structure and absorbed Fe sites as well as the diversity of local structures in these disordered active phases. In this Account, we highlight our work to understand the role of Fe in Ni/Co (oxy)hydroxide OER catalysts. We first discuss how we characterize the intrinsic activity of the first-row transition-metal (oxy)hydroxide catalysts as thin films by accounting for the contributions of the catalyst-layer thickness (mass loading) and electrical conductivity as well as the underlying substrate’s chemical interactions with the catalyst and the presence of Fe species in the electrolyte. We show how Fe-doped Ni/Co (oxy)hydroxides restructure during catalysis, absorb/desorb Fe, and in some cases degrade or regenerate their activity during electrochemical testing. We highlight the relevant techniques and procedures that allowed us to better understand the role of Fe in activating other first-row transition metals for OER. We find several modes of Fe incorporation in Ni/Co (oxy)hydroxides and show how those modes correlate with activity and durability. We also discuss how this understanding informs the incorporation of earth-abundant transition-metal OER catalysts in anion-exchange-membrane water electrolyzers (AEMWE) that provide a locally basic anode environment but run on pure water and have advantages over the more-developed proton-exchange-membrane water electrolyzers (PEMWE) that use platinum-group-metal (PGM) catalysts. We outline the key issues of introducing Fe-doped Ni/Co (oxy)hydroxide catalysts at the anode of the AEMWE, such as the oxidative processes triggered by Fe species traveling through the polymer membrane, pH-gradient effects on the catalyst stability, and possibly limited catalyst utilization in the compressed stack configuration. We also suggest possible mitigation strategies for these issues. Lastly, we summarize remaining challenges including the long-term stability of Fe-doped Ni/Co (oxy)hydroxides under OER conditions and the lack of accurate models of the dynamic active surface that hinder our understanding of, and thus ability to design, these catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Throughput In-Line Coating Metrology Development for Solid Oxide Fuel Cell Manufacturing

Coatings play key roles in solid oxide fuel cell (SOFC) stack durability. For example, diffusion barrier coatings on Cr-containing interconnect and balance of plant (BOP) components protect electrodes from Cr poisoning over the long operational lifetimes (>10,000 hours) of the fuel cell stack. Common defects in coatings, such as cracks, pinholes, and porosity, result in a failure to protect the electrodes, resulting in shorter operational lifetime and thus higher cost. It is very unlikely, even in the best coating process, that all these defects can be mitigated, hence identifying critical defects in parts, and removing defective parts from production before they can damage the stack, becomes paramount. Furthermore, these quality control techniques must be operational in the production/assembly line (in-line), i.e., high throughput and non-destructive, and cost effective. Redox Power Systems, LLC (Redox) together with the National Renewable Energy Laboratory (NREL) developed much needed high throughput, in-line metrology techniques for protective coatings. The overall goal of the project is to lower cost while increasing robustness, reliability, and endurance of SOFC stacks. To accomplish this, we had several objectives, including: to identify key coating and substrate defects that lead to coating failure through the use of detailed characterization methods (e.g., microscopy, XRD, EDS, electrochemistry); to assess capabilities of in-line metrology techniques, e.g., optical profilometry (Redox) and thermography (NREL), to probe these defects, or evidence thereof; demonstrate long-term performance of “defect-free” protective coatings, as identified by in-line metrology, in solid oxide fuel cell (SOFC) stack operation. In the first part of this project, the ability to identify key defects expected to lead to coating and SOFC degradation using in-line metrology tools were evaluated. Coated interconnect samples with controlled defect types and populations were tested under conditions similar to SOFC operation, followed by detailed post-test analysis to reveal the defects responsible for observed degradation. In the second part of the project, the optimal in-line metrology techniques and methodologies were used to map the defect distribution in full-size interconnects with critical defects intentionally allowed to exist in some cases. These interconnects underwent SOFC testing for extended periods (up to ~3,000 hours) followed by post-test analysis to evaluate the effectiveness of in-line metrology techniques in mitigating MCO coating related degradation. Key accomplishments in this project included the following: Demonstrated ASR of < 0.05 ohm-cm 2 at 650 °C for 1,000 hours with low defect (determined by in-line metrology) interconnect samples (average ASR=37 milliohms-cm 2 after over 1,000 hours). Demonstrated that low defect coatings on interconnects (as screened using in-line metrology) have low volatilization of chromium at ~650 °C for 1,000 hours as detected using Cr-getter material (< 5 at% increase above baseline); 1022 hour duration tests under humidified, elevated temperature (750 °C rather than 650 °C) compared a base case against different coating thicknesses. Demonstrated capability to identify initial key defects of interest with in-line metrology techniques using up to 8 cm by 10 cm having coatings with and without intentional defects of interest using thermal imaging and optical profilometry. Correlated key defects identified using metrology techniques with observed coating performance (e.g., ASR and Cr volatility). Conducted several 4 cm by 4 cm cell tests using MCO-interconnects that were pre-screened using some of the metrology techniques developed in the project (e.g., optical profilometry). An analysis of ASR measurements were able to show that defect-free coatings resulted in the anticipated performance in the cell tests.

01 COAL, LIGNITE, AND PEAT↗

Scalable Nano-Scaffold SOFC Anode Architecture Enabling Direct Hydrocarbon Utilization

This project is based on WVU’s pending patents, technology and aims to design and modify the internal surfaces of the Ni/YSZ anode from currently commercially viable Solid Oxide Fuel Cells (SOFCs) using the additive manufacturing process of Atomic Layer Deposition (ALD). The surface architecture/scaffold added onto the internal surface of the anode possesses an engineered nanostructure but it features only commonly-used oxide conductors and electro-catalyst materials. The surface layer possesses a minimum thickness of ~2-40 nm and is solely designed to control the surface reforming reactions and to increase catalytic activity. Three-dimensional (3D) nano scaffold architectures with the noble metal nano-catalyst, low-cost bimetallic catalytic alloys, and nano-scale ionic conducting oxide fully compatible with the state-of-the-art Ni/YSZ anode, were applied to the internal surface of the entire porous SOFC anode using ALD. In the present work, the surface scaffold architecture is essentially multi-functional at the nano-scale, facilitated by the multiple heterostructured interfaces. It will significantly enhance the power density and cell durability for direct hydrocarbon utilization by (1) increasing the number of electrochemical reaction sites to enhance the hydrogen/hydrocarbon oxidation reactions; (2) reducing carbon formation; (3) mitigating the coarsening of backbone Ni phase and the oxidation attack of Ni from oxidants (e.g., H2O, CO2); and (4) promoting the internal reforming capabilities, especially for natural gas applications. ALD is employed to generate stable anode surface architectures that are uniform, precisely controllable at the atomic scale, and accurately repeatable for processing. The engineered anode surface nano-scaffold architecture was cataloged and analyzed using High-resolution Transmission Electron Microscopy (TEM), and cell power/durability performance assessed via comprehensive electrochemical performance testing with commercial specimens and relevant environments using hydrocarbon fuels. To the best of our knowledge, this project is the First Report on ALD of Ni/YSZ. The actual achievement of this Project includes (1). Successful demonstration of 7 types of ALD layers on Ni/YSZ anode, including Co, Ni, Mn, Pt, Ru, ZrOx and multi-functional nano-composite. (1). Conformal coating and subsequently spontaneously pinning the discrete nano-catalyst, including the precious metal nano-catalyst and the Ni and Co catalysts, on the YSZ surface upon the electrochemical operation in the reduced atmosphere. Those nano-catalysts on the ionic-conducting YSZ provided excellent sites for promoting internal reforming; (2). Demonstrated ALD coating increased both catalytic activity and conductivity of Ni/YSZ. Conformal coating provided dopants and introduced additional electrical conducting pathways on the YSZ ionic conductor. The doped surface layer of YSZ with mixed conductivity thus further introduces the active triple phase boundaries adjacent to the ALD-coated nano-catalysts such as Pt, Co, and Ni that are pinned on the YSZ surface. The nano-composite ALD coating on Ni/YSZ anode has significantly increased cell durability; and (3). ALD coating of Ni/YSZ anode increased the power density of the entire cell by 300%. For a long time, the SOFC performance, such as the power density, was deemed hindered by the cathode. The sluggish oxygen reduction reaction (ORR) in the cathode was deemed as hindering the power density of the SOFCs. For the anode-supported commercial SOFCs, the cell performance is considered to be limited by the cathode's performance. For the first time in the field of SOFC, this project has demonstrated that (1). the performance of commercial SOFCs can be further increased by the ALD coating on Ni/YSZ anode backbone. (2). ALD coating on Ni/YSZ fuel electrodes results in the enhancement of power density, and increased reliability, robustness, and endurance of SOFCs, for their application using both hydrogen and hydrocarbon fuels over the entire operating temperature range of 650-800ºC for the inherently functional commercial cells. (3). ALD coating provides alternative approaches of exsolutions for introducing the stable catalyst onto the internal surface of the Ni/YSZ electrode. ALD coating could be much more versatile than exsolution in employing the catalysts with various chemistries onto the various backbones. (4). Due to the negligible amount of ALD materials coated onto the internal surface of the porous cathode of the as-fabricated cells, a peak power density increase up to 300 % induced by ALD coating was simultaneously achieved in terms of both power density and specific power. (5). The ALD coating developed through this project was applied to both the SOFC and Solid Oxide Electrolysis Cells (SOEC). SOEC’s face a similar but more demanding need to improve the fuel electrode's performance. It opens further research directions for electrocatalytic surface nanoionics with a wide range of chemistry. It will revolutionize our ability to render the formation of a nanostructured electrode that has been constantly pursued yet barely achieved for practical SOFC/SOEC applications. The research is also immediately transformative since both the preliminary data and the proposed work are on the direct implantation of nanoionics into the state-of-the-art inherently functional SOCs. It represents an immediate impact on the commercial sectors in SOC technology since the applied ALD processing is computer-controlled ALD coating using the commercial ALD systems, and it is scalable to both the single cells and SOC stacks.

36 MATERIALS SCIENCE↗