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At least 523 records · Page 29

Constructing Ultrathin W-Doped NiFe Nanosheets via Facile Electrosynthesis as Bifunctional Electrocatalysts for Efficient Water Splitting

Exploring cost-effective and efficient bifunctional electrocatalysts via simple fabrication strategies is strongly desired for practical water splitting. Herein, an easy and fast one-step electrodeposition process is developed to fabricate W-doped NiFe (NiFeW)-layered double hydroxides with ultrathin nanosheet features at room temperature and ambient pressure as bifunctional catalysts for water splitting. Notably, the NiFeW nanosheets require overpotentials of only 239 and 115 mV for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively, to reach a current density of 10 mA/cm 2 in alkaline media. Their exceptional performance is further demonstrated in a full electrolyzer configuration with the NiFeW as both anode and cathode catalysts, which achieves a low cell voltage of 1.59 V at 10 mA/cm 2 , 110 mV lower than that of the commercial IrO 2 (anode) and Pt (cathode) catalysts. Moreover, the NiFeW nanosheets are superior to various recently reported bifunctional electrocatalysts. Such remarkable performances mainly ascribe to W doping, which not only effectively modulates the electrocatalyst morphology but also engineers the electronic structure of NiFe hydroxides to boost charge-transfer kinetics for both the OER and HER. Hence, the ultrathin NiFeW nanosheets with an efficient fabrication strategy are promising as bifunctional electrodes for alkaline water electrolyzers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scalable Gas Diffusion Electrode Fabrication for Electrochemical CO 2 Reduction Using Physical Vapor Deposition Methods

Electrochemical CO 2 reduction (ECR) promises the replacement of fossil fuels as the source of feedstock chemicals and seasonal storage of renewable energy. While much progress has been made in catalyst development and electrochemical reactor design, few studies have addressed the effect of catalyst integration on device performance. Using a microfluidic gas diffusion electrolyzer, we systematically studied the effect of thickness and the morphology of electron beam (EB) and magnetron-sputtered (MS) Cu catalyst coatings on ECR performance. We observed that EB-Cu outperforms MS-Cu in current density, selectivity, and energy efficiency, with 400 nm thick catalyst coatings performing the best. Additionally, the superior performance of EB-Cu catalysts is assigned to their faceted surface morphology and sharper Cu/gas diffusion layer interface, which increases their hydrophobicity. Tests in a large-scale zero-gap electrolyzer yielded similar product selectivity distributions with an ethylene Faradaic efficiency of 39% at 200 mA/cm 2 , demonstrating the scalability for industrial ECR applications.

36 MATERIALS SCIENCE↗

Synergistic Coupling of Proton Conductors BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ and La 2 Ce 2 O 7 to Create Chemical Stable, Interface Active Electrolyte for Steam Electrolysis Cells

For the first time, proton conductors BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ (BZCYYb) and La 2 Ce 2 O 7 (LCO) are combined to create an interface active and steam-tolerant electrolyte for high-performance proton-conducting solid oxide electrolysis cells. LCO shows good chemical compatibility with BZCYYb. The readily fabricated LCO/BZCYYb bilayer electrolyte can be densified at a temperature of as low as 1300 °C versus ~1600 °C for the benchmark steam-stable BaZr 0.8 Y 0.2 O 3–δ electrolyte. With Pr 2 NiO 4+δ as the anode and Ni as the cathode catalyst, this bilayer electrolyte cell yields a current density of 975 and 300 mA/cm 2 under a 1.3 V applied potential at 700 and 600 °C, respectively. This performance is among the best of all H-SOECs equipped with a chemically stable electrolyte so far. A BZCYYb layer in the bilayer electrolyte promotes the hydrogen evolution reaction at the cathode side, resulting in a 108% improvement over the cell without this layer. The LCO layer, on the other hand, effectively protects this functional BZCYYb layer from the high concentration of steam in a practical SOEC operation condition. The cell without the LCO layer shows degradation in terms of an increased electrolyzing potential from 1.07 to 1.29 V during a constant 400 mA/cm 2 operation at 700 °C. In contrast, the bilayer electrolyte cell maintains the same electrolyzing potential of 1.13 V under the same conduction for a 102 h operation. These findings demonstrate that this synergic bilayer electrolyte design is a vital strategy to overcome the dilemma between performance and stability faced by the current benchmark Zr- or Ce-rich Ba(CeZr)O 3–δ electrolysis cells to achieve excellent performance and stability at the same time.

36 MATERIALS SCIENCE↗

Engineering CoO x ‑Based Self-Supported Anodes for Pure-Water-Fed Anion-Exchange-Membrane Electrolysis

Commercial membrane electrolyzers rely on acidic fluorocarbon membranes and ionomers, requiring the use of expensive IrO x -based oxygen-evolution catalysts. Anion-exchange-membrane water electrolyzers (AEMWEs) operate in an alkaline environment, enabling the use of non-precious-metal catalysts. Here, we study and engineer CoO x -based catalyst-coated anodes deposited via hydrothermal synthesis directly onto porous transport layers both with and without thermal annealing. The self-supported, nanoneedle-structured Co3O4 anode, formed by annealing the as-synthesized cobalt carbonate hydroxide, Co­(CO3) x (OH) y , outperforms the baseline Co3O4 nanoparticle ink-based anode in pure-water-fed AEMWE due to the improved catalyst-layer continuity and thus number of electroactive Co species. The as-synthesized and unannealed Co­(CO3) x (OH) y , however, appears to undergo substantial conversion to a more-active CoO x (OH) y phase predominantly at the surface, with nominal Co3+ present and higher electrical conductivity, lowering the cell voltage to ∼200 mV at 1.0 A·cm–2 in pure-water-fed AEMWE compared to the conventional Co3O4 nanoparticle anodes. We analyze the differences in electrode electrochemical response between pure-water and KOH feed modes, finding distinct activation and degradation modes. The Co­(CO3) x (OH) y anode shows significant activation and slower degradation linked to the conversion to oxyhydroxide. We propose catalyst layer designs that promote both hydroxide and electron transport, alongside interfacial engineering strategies to obtain high performance while mitigating anode degradation.

anion-exchange-membrane water electrolysis↗

Membrane Strategies for Water Electrolysis

Hydrogen holds great promise as a clean energy resource to help the global carbon-free energy goal. Here, green hydrogen production from renewable energy-powered water electrolysis can decarbonize hard-to-abate industries and transport applications. Ion-exchange membranes are an essential component of membrane-based water electrolysis, enabling high hydrogen production efficiency through a zero-gap configuration. While perfluorosulfonic acids are the standard polymer electrolyte membrane material, research efforts for membrane alternatives have increased over the years to drive down the cost of electrolyzers and improve devices’ durability without sacrificing performance and efficiency. Here we present our perspectives on acidic, alkaline, and bipolar membranes for water electrolyzers and discuss future research directions to develop advanced membranes for green hydrogen production technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanovoid Incorporated IrxCu Metallic Aerogels for Oxygen Evolution Reaction Catalysis

Ir-based nanomaterials are regarded as state-of-the-art cathode electrocatalysts in proton exchange membrane water electrolyzers (PEMWEs). Engineering the morphology of Ir-based three-dimensional architectures as electrocatalysts toward oxygen evolution reaction (OER) has been rarely studied. Here, we report the gelation of IrxCu metallic hydrogels self-assembled with ultrafine and nanovoid incorporated building blocks for enhancing the electrocatalytic performance toward OER. The composition-optimized Ir3Cu metallic aerogels exhibited improved catalytic activity and durability toward OER. The mesosized voids generated through the in situ galvanic replacement reaction and the macrosized porous systems make a great contribution to the increased number of active sites. First-principle calculations revealed the intrinsic optimized binding energy of Ir by alloying with Cu. The best catalytic performance necessities a balance of the adsorption and desorption energy. The well-defined morphology and enhanced OER electrochemical performances of nanovoid incorporated IrxCu metallic aerogels hold great promise in further applications in PEMWEs.

Shi, Qiurong↗

Activating Layered Double Hydroxide with Multivacancies by Memory Effect for Energy-Efficient Hydrogen Production at Neutral pH

Sustainable water-splitting hydrogen production has long been considered one of the most promising energy conversion technologies, but enormous challenges remain: for instance, water electrolysis suffers from high overpotential and over energy consumption under neutral pH conditions. Furthermore, taking advantage of the memory effect of layered double hydroxide (LDH), we report an energy-efficient neutral water electrolyzer material based on LDH with multiple vacancy defects. Benefiting from the improved electrical conductivity, larger electrochemical surface area (ECSA), and faster charge transfer, the NiFe LDH with O, Ni, and Fe vacancies exhibits a low overpotential of 87 mV at 10 mA/cm 2 for hydrogen evolution reaction (HER) in a pH 7 buffer electrolyte. Impressively, the as-fabricated vacancy-containing NiFe LDH (v-NiFe LDH) splits water with a current density of 10 mA/cm 2 at ~1.60 V in a two-electrode device, outperforming most other water-splitting catalysts in neutral media. Such an electrolyzer setup could be powered by a commercial 2.0 V solar cell, producing hydrogen at a current density as high as 100 mA/cm 2 .

25 ENERGY STORAGE↗

Nanoscopic Plugs Block Hydrogen Crossover in Submicron Thick Proton-Conducting SiO 2 Membranes for Water Electrolysis

Zero-gap electrolyzers based on submicron thick proton-conducting oxide membranes (POMs) represent a promising approach to increasing the efficiency of H 2 production from water electrolysis while moving away from conventional perfluorosulfonic acid (PFSA) membranes. A critical barrier to the commercialization of such electrolyzers is that the ultrathin nature of POMs, which is necessary to achieve low cell resistance, makes them more susceptible to defects that can lead to unacceptably high rates of H 2 crossover. Herein, we demonstrate an approach to mitigate this problem through selective deposition of carbon-containing silicon oxide (SiO x C y ) “nanoplugs” into the defects of submicron thick SiO 2 membranes using a facile electrochemically mediated deposition process. Selective deposition of nanoplugs within the defects was verified by multiple characterization techniques, while scanning electrochemical microscopy (SECM) was used to confirm selective plugging of H 2 -crossover hotspots associated with defects at identical locations. Thanks to the use of nanoplugs, the H 2 permeance of 250 nm thick SiO 2 membranes was reduced by 5 to 6 orders of magnitude compared to the unmodified atomic layer deposition (ALD) SiO 2 membranes while having negligible impact on the ionic resistance of the membrane. These plug-modified membranes also enabled safe and stable operation of a zero-gap full cell electrolysis cell, in contrast to cells lacking nanoplugs that produced anode effluent streams having H 2 concentrations near or exceeding the lower flammability limit (LFL) of H 2 . Furthermore, beyond water electrolysis, this defect-sealing strategy has the potential to be broadly implemented in other applications, such as fuel cells and flow batteries, offering a versatile solution to mitigate crossover-related performance losses.

ALD SiO2↗

Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts [Balancing activity, stability and conductivity of nanoporous core-shell Ir/IrO 2 oxygen evolution catalysts]

The selection of oxide materials for catalyzing the Oxygen Evolution Reaction in acid-based electrolyzers must be guided by the proper balance between activity, stability and conductivity – a challenging mission of great importance for delivering affordable and environmentally friendly hydrogen. Here we report that the highly conductive nanoporous architecture of an iridium oxide shell on a metallic iridium core, formed through the fast dealloying of osmium from an Ir 25 Os 75 alloy, exhibits an exceptional balance between oxygen evolution activity and stability as quantified by the Activity-Stability FactorASF. Based on this metric, the nanoporous Ir/IrO 2 morphology of dealloyed Ir 25 Os 75 shows a factor of ~30 improvement ASFrelative to conventional Ir-based oxide materials and a ~8 times improvement over dealloyed Ir 25 Os 75 nanoparticles due to optimized stability and conductivity, respectively. Here, we propose that the Activity-Stability FactorASF is the key “metric” for determining the technological relevance of oxide-based anodic water electrolyzer catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High current density electroreduction of CO 2 into formate with tin oxide nanospheres

In this study, we demonstrate three-dimensional (3D) hollow nanosphere electrocatalysts for CO 2 conversion into formate with excellent H-Cell performance and industrially-relevant current density in a 25 cm 2 membrane electrode assembly electrolyzer device. Varying calcination temperature maximized formate production via optimizing the crystallinity and particle size of the constituent SnO 2 nanoparticles. The best performing SnO 2 nanosphere catalysts contained ~ 7.5 nm nanocrystals and produced 71–81% formate Faradaic efficiency (FE) between -0.9 V and -1.3 V vs. the reversible hydrogen electrode (RHE) at a maximum formate partial current density of 73 ± 2 mA cm geo -2 at -1.3 V vs. RHE. The higher performance of nanosphere catalysts over SnO 2 nanoparticles and commercially-available catalyst could be ascribed to their initial structure providing higher electrochemical surface area and preventing extensive nanocrystal growth during CO 2 reduction. Our results are among the highest performance reported for SnO 2 electrocatalysts in aqueous H-cells. We observed an average 68 ± 8% FE over 35 h of operation with multiple on/off cycles. In situ Raman and time-dependent X-ray diffraction measurements identified metallic Sn as electrocatalytic active sites during long-term operation. Further evaluation in a 25 cm 2 electrolyzer cell demonstrated impressive performance with a sustained current density of 500 mA cm geo -2 and an average 75 ± 6% formate FE over 24 h of operation. Our results provide additional design concepts for boosting the performance of formate-producing catalysts.

36 MATERIALS SCIENCE↗

High performing triple-conductive Pr 2 NiO 4+δ anode for proton-conducting steam solid oxide electrolysis cell

The development of proton-conducting solid oxide electrolysis cells for the intermediate-temperature range application is largely hindered by the limited choice of adequate anode materials. In this study, the popular solid oxide fuel cell cathode material Pr 2 NiO 4+δ (PNO) is investigated as the anode for the electrolysis cell, considering its proton-conducting ability. The introduction of protons into the PNO lattice is confirmed through insertion-induced conductivity variation measurements. Good chemical compatibility is verified between PNO and BaZr 0.2 Ce 0.6 Y 0.2 O 3–δ (BZCY) proton-conducting electrolyte. Excellent catalytic activity towards water splitting is observed for the PNO–BZCY composite anode, 0.52 Ω cm 2 for 550 °C, 0.057 Ω cm 2 for 700 °C. The water-splitting process is disclosed by impedance spectroscopy measured under different conditions. Due to proton conduction in PNO, the PNO surface is activated for electrochemical reactions. The non-charge transfer processes account little to the electrode resistance. The performance of the PNO–BZCY anode is determined by two charge transfer processes whose kinetics are governed the electrolyzing potential. This charge transfer-limiting nature is relatively benign since the electrode resistance has been found to exponentially reduce with increasing overpotential. Cathode-supported Ni–BZCY//BZCY//PNO–BZCY thin film electrolyte single cells are fabricated and characterized. ~95% current efficiency is confirmed. At 700 °C, a current density of 977 mA cm –2 is achieved at a 1.3 V electrolyzing potential, e.g. 0.37 V overpotential, which is one of the best performances of proton-conducting steam electrolysis cells so far. The PNO–BZCY anode accounts only for 16% of the overall polarization resistance at 700 °C. Furthermore, these findings prove that the triple-conductive PNO is a promising anode material for proton-based steam electrolysis cells.

25 ENERGY STORAGE↗

A low temperature unitized regenerative fuel cell realizing 60% round trip efficiency and 10 000 cycles of durability for energy storage applications

Unitized regenerative fuel cells (URFC) convert electrical energy to and from chemical bonds in hydrogen. URFCs have the potential to provide economical means for efficient long-term, seasonal, energy storage and on-demand conversion back to electrical energy. We first optimize the catalyst layer for discrete electrolyzer and fuel cell and then configure the URFC. The goal is to identify a cost competitive configuration for URFCs, and demonstrate it in terms of upper limit of round trip efficiencies (RTEs). Two possible configurations of URFCs are compared via experiments and techno-economic analysis (TEA), which emphasize the advantages of the unconventional constant-electrode (CE) URFC over the traditional constant-gas (CG) configuration. We also study the stability via accelerated stress tests (ASTs) and demonstrate steady state operation in a daily cycle for day to night energy shifting. From the investigations, the optimum composition of the URFC anode catalyst layer is 90 at% Ir-black balanced by Pt-black for both CE and CG configurations. At 80 °C and 1 A cm -2 , the optimized CE URFC achieves 57% and 60% RTE with air and O 2 as the reductant gases, respectively. We then evaluated the differences in durability using an AST over 10k charge–discharge cycles; the results reveal that the wider potential window at the anode in CE (0.05–1.55 V) has minimal effect on catalyst layer stability compared to CG (0.55–1.55 V). Furthermore, there was no degradation up to the range of 2k–5k cycles; beyond that the fuel cell (discharge) performance degraded while the electrolyzer (charge) performance was still stable. Finally, the observations here indicate substantial potential to employ URFCs as efficient and cost-effective bidirectional energy-conversion devices within energy storage and utilization systems after appropriate technological and operational optimizations.

25 ENERGY STORAGE↗

Synergistic effect of polyaniline on stabilizing Pt nanoparticles in PEMFCs†

The stability of Pt nanoparticles on a carbon support is crucial for the lifespan of polymer electrolyte membrane fuel cells as well as other electrocatalysis systems such as electrolyzers. Here we took the approach of utilizing the covalently grafted polyaniline on carbon to stabilize Pt nanoparticles by simultaneously alleviating the particle migration and mitigating the Ostwald ripening, which are two major mechanisms for loss of the catalyst stability. A comprehensive investigation of the stability and performance of Pt catalyst nanoparticles on these supports reveals that the polyaniline can shift the Pt L edge binding energy and the Pt 4f peak energy, leading to the increased redox potential of the Pt nanoparticles and making them more resistant to oxidation. Interestingly, the highest polyaniline density (50 wt%) does not show the best catalyst stability, rather, the second (33 wt%) demonstrates the best catalyst stability among these catalysts. Combining the XPS, XAS and fuel cell stability studies, we concluded that the locations of the Pt nanoparticles over the polyaniline layer on the carbon surface depend on the surface density of the polyaniline over the carbon surface. The Pt nanoparticles in the 50 wt% polyaniline catalyst are wrapped by the polyaniline polymer but do not sit directly on the carbon surface, while Pt nanoparticles in the 33 wt% polyaniline catalyst sit on the carbon surface and are densely surrounded by the polyaniline polymer. The results show that the mass activity loss is 12.5% while the ECSA (electrochemically active surface area) loss is 37.1% after 30k cycles of accelerating stress test for the 33 wt% polyaniline catalyst, far exceeding the DOE 2020 target for MEA (i.e., mass activity loss < 50%, and ECSA loss < 40%). Overall, the polyaniline has a synergistic effect on mitigating the surface migration and slowing down the Ostwald ripening to stabilize the Pt nanoparticles in fuel cells. The novel strategy to stabilize Pt nanoparticles using polyaniline opens a new pathway in the development of highly stable catalysts: relying on the functionalization group on the carbon support, instead of just focusing on the catalyst itself.

Li, Chenzhao↗

Wind Turbine Design Optimization for Hydrogen Production

To help meet the need for inexpensive green fuels, we are working on wind turbine design optimization specifically for hydrogen production. We have thus far achieved a 1.53% decrease in LCOH as compared to a turbine optimized for LCOE using the same code, design variables, and models. We accomplished this by optimizing some components of the wind turbine tower, rotor, and drivetrain design with hydrogen production and costs in the design loop.

hydrogen↗

Hybrid power plant design for low-carbon hydrogen in the United States

In this study, we provide a nationwide techno-economic analysis of clean hydrogen production powered by a hybrid renewable energy plant for over 50,000 locations in the United States. We leverage the open-source Hybrid Optimization Performance Platform (HOPP) tool to simulate the hourly performance of an off-grid wind-solar plant integrated with a 1-GW polymer exchange membrane electrolyzer system. The levelized cost of hydrogen is calculated for varying technology costs, and tax credits to explore cost sensitivities independent of plant design, performance, and site selection. Our findings suggest that strategies for cost reduction include selecting sites with abundant wind resources, complementary wind and solar resources, and optimizing the sizing of wind and solar assets to maximize the hybrid plant capacity factor. These strategies are linked to increased hydrogen production and reduced electrolyzer stack replacements, thereby lowering the overall cost of hydrogen.

08 HYDROGEN↗

Hydrogen and Battery Storage Technologies for Low-Cost Energy Decarbonization in Distribution Networks

Deep energy decarbonization cannot be achieved without high penetration of renewables. At higher renewable energy penetrations, the variability and intermittent nature of solar photovoltaic (PV) electricity can cause ramping issues with existing fossil fuel generation, requiring longer term energy storage to increase the reliability of grid operation. Here, a proton exchange membrane electrolyzer can produce H 2 and serves as a utility controllable load. The produced H 2 can then be stored and converted back into electricity, or mixed with natural gas, or used as transportation fuel, or chemical feedstock. This paper considers the perspective of the distribution system operator that operates the distributed energy resources on a standard IEEE 33-node distribution network considering the technical and physical constraints with the goal of minimizing total investment and operation cost. Different case studies, at very high PV penetrations are considered to show the challenges and path to net-zero emission energy production using H 2 energy. Sensitivity of utility PV costs and electrolyzer capital costs on producing H 2 at $\$1$ /kg are presented showing that the distribution network could produce 100% renewable electricity and H 2 could be produced at a cost of $\$1$ /kg by 2050 with conservative cost estimates and by 2030 with accelerated cost declines.

25 ENERGY STORAGE↗

Modeling the Effect of Material Properties on Liquid-Alkaline Water Electrolysis

Liquid-alkaline water electrolyzers (LAWEs) use electricity to drive the conversion of water to H 2 and O 2 gas. These devices benefit from the use of low-cost nickel electrodes and metal-oxide separators, but suffer from lower current densities and higher cell voltages than proton-exchange-membrane water electrolyzers. Identifying the inefficiencies that result in this poor performance is key to mitigating losses and optimizing LAWEs. Here, we report an experimentally-validated 1-D continuum model of a LAWE that elucidates the gradients within the cell, simulates H 2 crossover, and projects the energy improvements made possible by modulating the properties of the electrodes and separator. The model captures the Nernstian polarization losses and the distribution of gas- and liquid-phases within the electrodes, enabling quantification of energy losses associated with kinetic, ohmic, and bubble-induced (mass-transport) resistances. Simulations demonstrate that LAWE can achieve energy intensities of 50 kWh kg −1 of H 2 at 1 A cm −2 using improved electrode and separator properties.

08 HYDROGEN↗