Low Temperature Water Electrolysis Research Articles

Oxygen 1s X-ray Photoelectron Spectra of Iridium Oxides as a Descriptor of the Amorphous-Rutile Character of the Surface.

Characterization of the surface of iridium oxide (IrOx) materials is of crucial importance to understand catalysts for the oxygen evolution reaction (OER) in low-temperature water electrolysis. While much of our current knowledge is based on well-defined single-crystal surfaces, surface-sensitive techniques like X-ray photoelectronic spectroscopy (XPS) are relevant to characterize the nanostructures considered. In this work, we describe a simple approach to use oxygen 1s spectra as an identifier of the amorphous/crystalline characteristics of iridium oxide structures from purely amorphous to purely crystalline. This conceptual approach was validated on seven commercially available materials. The presence of oxygen-associated defects in the surface moieties/species is shown even for purely crystalline materials with defect concentration increasing with greater amorphous character. This methodology provides us with an accessible ex situ descriptor of the catalyst surface as a baseline for further studies of the impact on catalytic properties.

Enhancement of critical current density using micro-porous structure in a low-temperature water electrolysis

The critical current density (CCD), which limits the hydrogen production rate was measured by forming micro-porous structures on the cathode electrode in a low-temperature water electrolysis. Several micro-porous structures were formed by the electrodeposition method varying the current density during the deposition. A maximum 54% enhancement of the CCD was recorded compared to the plain surface. With the micro-porous structures, the superior capillary wicking effect allowed the electrolyte to penetrate the structure, resulting in the increased number of hydrogen nucleation sites. The increased hydrogen nucleation sites led to the decreased hydrogen bubble size and increased departed bubble density, which delayed formation of the hydrogen film leading to the CCD. The surface morphology revealed that the multiple pore layers with the interconnected pores exhibited superior capillary wicking effect compared to the open type single pore layer. It is expected that the results of present work stimulate further research regarding electrode surface design in the low-temperature water electrolysis.

One-pot synthesis of FeNi3/FeNiOx nanoparticles for PGM-free anion exchange membrane water electrolysis

Low-temperature anion exchange membrane water electrolysis (AEMWE) is one of the most promising technologies to produce green hydrogen. To date, membrane-electrode assembly (MEA) based on platinum group metal (PGM) electrocatalysts shows higher performance than PGM-free ones. Here, a single and easy synthesis for non-noble metal electrocatalysts (PGM-free) for both hydrogen and oxygen evolution reactions (HER and OER) was developed. Both electrocatalysts consist of FeNi3/FeNiOx nanoparticles obtained through chemical reduction using hydrazine. The electrocatalyst exhibits an overpotential of 210 mV and 234 mV for HER and OER respectively, at a current density of 10 mA cm−2 in 1 M KOH electrolyte, allowing a comparison between mass activity and geometric activity compared to PGM catalysts. In addition to a preliminary electrochemical characterization of the FeNi3/FeNiOx, the electrocatalyst were integrated into a pilot-scale AEMWE at both anode and cathode, which reaches (without iR-correction) 1.72 V and 1.94 V at a current density of 0.4 A cm−2 and 1 A cm−2 respectively at 60 °C. This PGM-free MEA outperforms the one based on Pt/C at cathode and RuO2 at anode with a voltage gap of 284 mV at 1 A cm−2. The aforementioned MEA was tested for 150 h with a discontinuous power profile, in order to get an idea of the possible degradation trends for a future industrial application, the reversible and irreversible voltage losses were calculated resulting in a degradation rate of 886 µV/h. This work demonstrates a simple and scalable synthesis of earth-abundant electrocatalytic materials for high-efficiency AEM water electrolysis.

Model-based evaluation of ammonia energy storage concepts at high technological readiness level

Ammonia is a promising carbon-free energy carrier since it can be stored as a liquid at mild conditions and its production process from hydrogen and nitrogen is established and efficient. Several Ammonia-to-Power concepts have been proposed in the literature, many of which employ not-yet-mature electrochemical technologies. We model the charging and discharging phases of three ammonia energy storage concepts in Aspen Plus seeking a compromise between efficient concepts and mature technologies. In the charging phase, ammonia is produced via the Haber–Bosch process using hydrogen from low-temperature water electrolysis for all the considered concepts. For the discharging phase, three ammonia conversion processes are modeled: (i) ammonia is thermally decomposed into nitrogen and hydrogen by using thermal energy from storage, and hydrogen is converted into electricity in a fuel cell; (ii) ammonia is thermally decomposed by using heat generated through the combustion of a fraction of the ammonia stream, and the produced hydrogen is supplied to a fuel cell; (iii) ammonia is used as a fuel in a combined power cycle. We compare these concepts with respect to roundtrip efficiency and levelized cost of electricity. The roundtrip efficiency and the levelized cost of electricity of the modeled concepts are ca. 30–34 % and 0.28–0.31 €kWh−1 (for an electricity purchase price of 0.03 €kWh−1). Concept (i) has both the highest roundtrip efficiency and the lowest levelized cost of electricity. We identify the process bottlenecks via an exergy analysis.

Low-Temperature Water Electrolysis Under a Sustained pH-Gradient for Electrochemically-Induced Decarbonation of Limestone into Hydrated Lime

Lime holds considerable potential in diverse environmental applications. However, its current production remains highly carbon-intensive, emitting more than one ton of CO2 per ton of lime. To address this issue, recent studies have explored the concept of electrifying the decarbonation of limestone to produce hydrated lime. In this work, a two-compartment electrolysis cell capable of producing Ca(OH)2 has been tested at different currents. Precise pH and Ca2+ concentration measurements demonstrate that the electrolysis setup is able to dissolve CaCO3 and precipitate Ca(OH)2 with near-perfect efficiencies. Notably, it highlights that Faraday’s law and the concept of transport number can be applied to predict both the equilibrium and kinetic behavior of each step of the process in each of the two cell compartments. Moreover, the use of controlled batch additions of CaCO3 in the system, as opposed to one-time excess addition, was assessed to mitigate the fouling of the cationic exchange membrane used to separate the compartments. Finally, based on the experimental findings, key guidelines are proposed to achieve a perfect reaction stoichiometry for each step. These findings pave the way for a more sustainable and environmentally friendly approach to lime production.

Tuning Oxygen Evolving Catalytic Activity of a Precious Metal-Free Nickel Boride by a Cost-Effective Method

The production of hydrogen (H2) by electrochemical water splitting [Green Hydrogen (Green H2)], if driven by green electricity, has attracted considerable interest as an alternative sustainable energy carrier, e.g., in fuel cells for electricity or power and heat generation [1]. However, the lack of satisfactory and cheap electrocatalysts (ECs) to drive the vital electrochemical reactions of hydrogen evolution (HER) and oxygen evolution (OER) in water splitting is the biggest challenge for this technology.Currently, the most advanced electrocatalysts for the two half-reactions of water electrolysis (HER and OER) are noble metal-based materials [2]. Despite the excellent catalytic properties of these noble metal catalysts, their high cost, and scarcity make their commercial use both uneconomical and impractical in low temperature water electrolysis (LT-WE) systems at industrial scale for green H2 as a clean energy alternative to cheaper fossil fuels[3]. In addition to addressing this issue by the development of precious-material-based with a low-loading of precious metal elements, the development of desirable and high-efficiency electrocatalysts (ECs) based on earth-abundant metal elements materials is paramount. However, their catalytic activity is often limited by poor electron transfer, low conductivity, low stability, and small surface area of these materials. Thus, it is crucial to develop earth-abundant metal elements-based materials that are more cost-effective to reduce the high cost of active catalysts for water electrolysis. Although several low-cost materials have already been designed, the potential required for the practical application of water splitting is still very high compared to the theoretical potential (1.23 V), which means that much energy is consumed, which theoretically could be reduced. Due to their remarkable advanced charge transfer and durability for water oxidation in alkaline media, electrocatalysts derived from metal borides-based materials have received a lot of attention as new high-performance catalysts for water oxidation.[4] These properties stem from the multi-dimensional covalent bonding of the metalloid with the surrounding metal atoms.We present here an approach to tune the OER of transition metal borides (TMBs) using the cost-effective and less energy-consuming method that is nevertheless a highly efficient material for OER (Fig. 1). We have developed a low-cost, rational and easily scalable method to enhance the catalytic activity of nickel boride (Ni–B), which requires an annealing process to optimize the catalytic activity. However, this method may have limited applicability on a large scale as it requires a highly inert environment and high-temperature treatment of Ni–B catalysts. We also elucidate a structure-activity relationship using scale-bridging techniques such as TEM and electrochemical characterization. The developed based on non-noble electrocatalysts are prepared by a simple method of chemical reduction of transition metal elements with boron in aqueous solution. The production is a one-step process and the material does not require any further treatment, yet this material shows comparable activity to the state of the art (precious metal-based materials) for OER in alkaline solution at a selected current density. This improved catalytic performance is further corroborated by the microstructural investigations in the TEM. The nanoparticles obtained have an improved porous structure compared to Ni–B and thus provide more available sites for the surface reactions and hence for the catalytic performance of the material. Furthermore, it is shown that activation enables the morphological and structural changes, while some transition metal elements act as sacrificial elements to provide more accessible and stable sites for oxygen-forming centers. This paves the way for a better understanding of metal boride-derived electrocatalysts for water oxidation, a crucial chemical reaction in water electrolysis and other electrochemical energy technologies. Acknowledgements: This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No 945422. We acknowledge the use of the DFG-funded Micro-and Nanoanalytics Facility (MNaF) at the University of Siegen (INST 221/131-1).

(Invited) Cost Reduction Strategies in Low Temperature Water Electrolysis with Improved Catalytic Activity

Proton exchange membrane water electrolysis (PEMWE) technology is especially advantageous for green H2 production as a clean energy vector. During the water electrolysis process, the oxygen evolution reaction (OER) requires a large amount of iridium (2-3 mgIr cm−2) as catalyst. This material is scarce and expensive, representing a major bottleneck for large-scale deployment of electrolyzers. Recently, Retuerto et al. have synthesized different Ir double perovskites (Sr2CaIrO6) with the Ir atoms in a high oxidation state (Ir6+/5+) 1 and their catalytic activity was extensively investigated. Specifically, a Ca-based double perovskite (Sr2CaIrO6) has showed the highest OER activity similar to those of Ir or Ir oxides-based catalysts while being stable for the OER in half cell measurements. We report the development of a membrane electrode assembly taking advantage of the high activity of the Sr2CaIrO6 catalyst that has only 0.2 mgIr cm−2, around 10 times lower compared to what it is used in the anodes of commercial PEMWE, showing superior performance and stability. The morphology/structure of the developed anode and Sr2CaIrO6 catalyst, before and after operation in PEMWE, were extensively characterized by X-ray diffraction (XRD, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption near edge structure (XANES). We discuss in this contribution how the finding of this work can provide a strategy to lower the Ir content in commercial PEMWE.Anion exchange membrane water electrolysis (AEMWE) combines the advantages of proton exchange membrane water electrolysis (PEMWE), i.e., high current density while maintaining high efficiency and fast dynamic response with the advantages of alkaline water electrolysis (AWE), i.e., low-cost materials. However, AEMWE technology is still depends on a supporting electrolyte and its durability is low. In this regard, the German Aerospace Center (DLR) is developing novel approaches and cell components. Raney-nickel electrodes were developed via vacuum plasma spraying, reaching performance and stability comparable to SoA MW size PEMWE. The electrodes were further refined, switching to lower cost atmospheric plasma spraying while maintaining high performance. Studying the effect of supporting electrolyte concentration it was found, that lowering the ohmic resistance is by far the largest challenge for high performance AEMWE, especially at low KOH concentrations and electrode kinetics are less impactful. Moreover, a 17% efficiency uplift was achieved by applying a carefully tuned, thermally sprayed, nickel-based macro porous layer (MPL) onto a traditional mesh porous transport layer. Both ohmic and mass transport resistances were found to be lowered by the MPL. FIB-SEM and µCT analysis revealed an ideal structure, i.e., 30-40% porosity, almost exclusively open pores, and a broad pore size distribution2. In a fundamental study3, the mechanism of the OER activity was investigated as well as the effect of trace amounts of iron in Ni(OH)2. X-ray diffraction (XRD) and Thermogravimetric analysis (TGA) TGA analysis lead to the conclusion, that iron stabilized the α-Ni(OH)2which is the most active. CV analysis showed that an important redox switching step is also accelerated by Fe-doping. M. Retuerto, L. Pascual, J. Torrero, M. A. Salam, Á. Tolosana-Moranchel, D. Gianolio, P. Ferrer, P. Kayser, V. Wilke, S. Stiber, V. Celorrio, M. Mokthar, A. S. Gago, K. A. Friedrich, M. A. Peña, J. A. Alonso, D. G. Sanchez, S. Rojas, Highly Active and Stable OER Electrocatalysts Derived from Sr2MIrO6 for Proton Exchange Membrane Water Electrolyzers. Nat. Commun. 2022, 13, 7935. Razmjooei, F.; Morawietz, T.; Taghizadeh, E.; Hadjixenophontos, E.; Mues, L.; Gerle, M.; Wood, B. D.; Harms, C.; Gago, A. S.; Ansar, S. A.; Friedrich, K. A., Increasing the performance of an anion-exchange membrane electrolyzer operating in pure water with a nickel-based microporous layer. Joule 2021, 5 (7), 1776-1799. Wang, L.; Saveleva, V. A.; Eslamibidgoli, M. J.; Antipin, D.; Bouillet, C.; Biswas, I.; Gago, A. S.; Hosseiny, S. S.; Gazdzicki, P.; Eikerling, M. H.; Savinova, E. R.; Friedrich, K. A., Deciphering the Exceptional Performance of NiFe Hydroxide for the Oxygen Evolution Reaction in an Anion Exchange Membrane Electrolyzer. ACS Applied Energy Materials 2022, 5 (2), 2221-2230.

Design and Preparation at Scale of Ternary NiFe-M-Ox (M=Co, Mo) Catalysts for OER in Alkaline Media

Due to scarcity of Platinum Group Metals (PGMs) widely used in low temperature water electrolysis as cathodes (Hydrogen Evolution Reaction; HER) and anodes (Oxygen Evolution Reaction; OER) a boosting interest to their substitution to Earth abundant elements is observed. It was successfully demonstrated that elements like iron, nickel, cobalt and other (in their oxide and hydroxide forms) can be effective OER catalysts when operate at high pH ranges from 12 to 14 [1-3].This work is devoted to systematic investigation of influence of third element addition to NiFeOx system on a performance and stability of catalysts in alkaline OER. As a co-catalytic elements Mo and Co were selected, based on our previous experience [4,5]. A systematic study on an effect of NiFe-to-M ratio, concentration of precipitation agent and post-treatment temperature were evaluated in a wide range of parameters. Taking into account that mass loading of PGM-free OER catalysts is substantially higher than iridium/ruthenium once and can be up to several milligrams per cm2 all experiments were designed to be scalable. In a laboratory scale reactor, a fascinating batch size of 25g was achieved, using minimal amount of water-based solvents in order to minimize a waste stream generated. Presentation will discuss characterization of obtained materials by SEM, TEM, XPS, XRD and other methods as well as their performance, stability and durability in alkaline conditions, studying Oxygen Evolution Reaction. Acknowledgements and Statements. The authors acknowledge financial support from H2NEW and ElectroCat consortia. References. [1] X. Lyu, J. Li, J. Yang, A. Serov "Significance of Slight Ambient Temperature Variation on the Electrocatalyst Performance toward Oxygen Evolution Reaction" Journal of Environmental Chemical Engineering (2023).[2] X. lyu, A. Serov “Cutting-edge methods for amplifying the oxygen evolution reaction during seawater electrolysis: a brief synopsis” Ind. Chem. Mater., (2023).[3] X. Lyu, Y. Bai, J. Li, R. Tao, J. Yang, A. Serov "Investigation of oxygen evolution reaction with 316 and 304 stainless-steel mesh electrodes in natural seawater electrolysis" J. of Environmental Chemical Engineering 11 (2023) 109667.[4] A. Serov,N. I. Andersen, A. J. Roy, I. Matanovic, K. Artyushkova, P. Atanassov “CuCo2O4 ORR/OER Bi-Functional Catalyst: Influence of Synthetic Approach on Performance”, J. of The Electrochem. Soc. 162 (4) (2015) F449-F454.[5] N. I. Andersen, A. Serov, P. Atanassov “Metal Oxides/CNT Nano-Composite Catalysts for Oxygen Reduction/Oxygen Evolution in Alkaline Media”, Appl. Catal. B: Environmental 163 (2015) 623-627.

Benchmark and Roadmap for Low Temperature Water Electrolysis for Green H2 Production and Applications

Water electrolysis has attracted world-wide attention due to its ability to produce green hydrogen when coupled with renewable electricity. Green hydrogen is a viable solution to decarbonizing a variety of industries including fertilizer, metal production, petrochemical, and synthetic fuels. There are three major low temperature water electrolysis technologies, alkaline water electrolyzer (AWE), proton exchange membrane water electrolyzer (PEMWE), and anion exchange membrane water electrolyzer (AEMWE). This work will first provide the status of these three technologies in terms of operating conditions, lifetime, and capital cost. Subsequently, the challenges and constraints for these technologies will be discussed in the scenarios of large-scale manufacturing and integration with intermittent renewables. More efforts will be made to illustrate the trajectory of the next-gen water electrolysis technologies, which feature at ultralow PGM or PGM-free catalysts, thin membranes with reduced hydrogen crossover, high-current high-power operation, long lifetime, and remarkable cost reduction. The work will also address the challenges of automated MEA fabrication and stack manufacturing at scale. Finally, a real example of renewable wind turbine integrated with water electrolyzer to produce green hydrogen and subsequently green ammonia will be demonstrated.

Low-Temperature Water Electrolysis Under a Sustained pH-Gradient for the Electrochemically-Induced Decarbonation of Limestone into Hydrated Lime

Conventional low-temperature water electrolysis processes operate either at high or low pH to enhance conductivity, minimizing electrical resistance. Neutral water electrolysis in a buffer solution is considered non-competitive due to higher energy consumption. Nevertheless, interest in water electrolysis using a salt-based electrolyte has grown due to its ability to generate a pH gradient inside the cell. Electrolysis using a neutral salt-based electrolyte has higher operating costs due to its higher standard equilibrium potential (due to the pH gradient) and lower conductivity. Although this approach incurs higher operating costs, it presents a unique advantage: the production of additional valuable elements thanks to the pH gradient generated.In 2019, Ellis & al. [1] highlighted the possibility to use this pH gradient to electrify the production of hydrated lime (calcium hydroxide). Lime has applications in different areas such as the removal of impurities during steel production and aqueous or gaseous effluent treatments. It can also be used as a precursor of cement. Cement production is accounting for 8% of global CO2 emissions. The acidity generated by water oxidation at the anode dissolves the calcium carbonate inserted. Carbon dioxide from the dissolution is recovered with the oxygen generated. The calcium cations migrate through the cationic membrane towards the cathodic compartment to react with the hydroxide ions generated by water reduction at the cathode. Calcium hydroxide is finally collected after precipitation. Figure 1 compares the conventional process with the electrochemical way and describes more precisely the steps involved in Figure 1. More recently, another way of exploiting this gradient has been proposed by Ni & al. [2] for the recycling of spent Li-ion batteries. With the growing interest in process electrification, other applications may emerge.In this paper, this hybrid electrochemical system for the simultaneous production of hydrogen, oxygen and calcium hydroxide has been intensively studied. Water electrolysis has been performed in a two-compartment cell at different applied currents. Calcium concentration and pH measurement enabled the study of the sub-step efficiencies and equilibria in anodic and cathodic chambers. Perfect faradic efficiencies were obtained with perchlorate salt electrolytes and platinum-free electrodes. The establishment of the pH gradient has been proven and correlated with the transport number of protons through the cationic membrane. Finally, the kinetics of calcium ion migration and calcium hydroxide precipitation have been investigated as well. Continuous addition of calcium carbonate as opposed to a single excess addition was shown to be able to tune the working pH in the anodic compartment and thereby reducing the risk of precipitation on the membrane. Our experimental results lead to the formulation of practical recommendations for achieving optimal reaction stoichiometry in each stage. These findings pave the way for scaling up a promising new sustainable process for lime and cement production.[1] L. D. Ellis, A. F. Badel and M. L. Chiang, "Toward electrochemical synthesis of cement," PNAS, vol. 117, no. 23, pp. 12584-12591, 2019.[2] N. Jihong, Z. Jiayin, B. Jinhong and G. Xiaofei, "Recycling the cathode materials of spent Li-ion batteries in a H-Shaped neutral water electrolysis cell," Separation and Putification Technology , vol. 278, p. 119485, 2022. Figure 1 - Conventional and electrochemical production route of Ca(OH)2 and a simplified scheme of the hybrid electrolyzer used in this work, with the reactions involved. Figure 1

Synergistic Electrocatalysts Impact Efficient and Durable Oxygen Evolution Catalysis for Proton Exchange Membrane Water Splitting

Low-temperature water electrolysis can rapidly produce environmentally sustainable or green hydrogen, and is a prospective means of storing energy from renewable but intermittent power sources, such as wind and solar, in future clean energy infrastructure (1-4). Commercial water electrolysis either use liquid alkaline electrolyte or proton exchange membrane electrolyte (1). The proton exchange membrane water electrolysis (PEMWE) offers more advantages than the alkaline counterpart, such as higher purity of H2, lower resistance losses, more compact design, and what the most important is the compatible with the intermittent of the renewable energy (1-2). The grant challenge remaining in PEMWE is the development of the highly active, cost effective and stable catalysts for oxygen evolution reaction (OER), which is very sluggish requiring large amounts of precious metal as the catalysts, such as Ir, Ru and their oxides (1).In PEM water electrolysis cells, the catalysts should have high surface areas and high porosities that exposit sufficient active sites available to the reactants and electrolyte, as well as transferring the bubble out of the catalyst surface to ensure a fast mass transfer (5). Also, the OER is dependent on the inherent conductivity of the catalysts or the supports (1). For example, poor electronic conductivity within the catalyst layer will result in poor lateral conductivity across the catalyst layer, thus catalyst not in the vicinity of the porous transport layer will not participate in the reaction. To enable the widespread penetration of the PEMWE technologies, it is urgently to reduce the Ir loading to the sustainable level (~ 0.3 mg/cm2) compared with the current commercial usage (2-6 mg/cm2). Alternatively, to develop precious metal free catalyst with high efficiency and sustained durability (5).In this presentation, we will describe a method of preparing highly active yet stable synergistic electrocatalysts for oxygen evolution reaction for PEMWE. The new catalysts contain IrCoOx/ RuCoOx cluster and La&Li co-doped Co3O4 fiber which was derived from cobalt zeolitic imidazolate framework as precursor. The OER activities of the catalysts were first tested in O2 saturated acidic electrolyte by ring disk electrode (RDE), which displayed high mass activity 26-50 times that of commercial Ir and RuO2. The catalysts were fabricated into membrane electrode assemble and measured under real PEM water electrolysis condition. The cells demonstrated 2 A/cm2@1.76 V @0.25 ± 0.05 mgIr/cm2 loading, and negligible degradation after ~250 h chronoamperometric measurements at 2 A/cm2 (6), which meets the target set by US DOE for OER catalysts for PEMWE.The characterizations of the fresh and post-electrochemical samples were investigated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), transmission electron microscopy (TEM), Raman spectroscopy and BET surface analysis. We also performed DFT simulation on the OER reaction pathways over Ir and Co sites of different facets parallelly on basis of the TEM results. The result reveals the synergy between Ir/Ru and Co resulting in the enhanced catalytic activities of both IrCoOx /RuCoOx and LaLi@Co3O4 toward OER.Acknowledgments:This work was supported by Overseas Outstanding Youth Fund project, shanghai Jiao Tong university, Shanghai, China; Shanghai Pujiang talent Plan, Shanghai, China; Argonne National Laboratory through Maria Goeppert Mayer Fellowship, US; State Key Laboratory of Metal Matrix Composites, shanghai Jiao Tong university, Shanghai, China. The works performed at Hydrogen research center, shanghai Jiao Tong university, and Argonne National Laboratory’s Center for Nanoscale Materials and Advanced Photo Source.Reference: K. Ayers et al., Annu. Rev. Chem. Biomol. Eng. 10, 219–239 (2019).M. Carmo, D. L. Fritz, J. Mergel, D. Stolten, Int. J. Hydrogen Energy 38, 4901–4934 (2013).M. T. M. Koper, J. Electroanal. Chem. 660, 254–260 (2011).R. D. L. Smith et al., Science 340, 60–63 (2013).Chong et al., Science 380, 609–616 (2023).Chong et al., Adv. Energy Mater. 2023, 2302306.

A Guide to Electrocatalyst Stability Using Lab-Scale Alkaline Water Electrolyzers

Green hydrogen from low-temperature water electrolysis has received significant attention with a projected thousand-fold global capacity expansion by 2030.1 Electrocatalyst research is crucial for water electrolysis technologies and has garnered substantial attention. However, despite a surge in publications centered on promising electrocatalytic materials, often claiming "outstanding" performance, few studies have scaled these materials to more realistic setups. This gap primarily stems from the inadequacy of testing environments and operating conditions in academic research. The prevalent use of three-electrode cell configurations fails to mimic practical electrolyzer conditions accurately.2,3 Electrocatalytic performance in these setups does not effectively represent real electrolysis devices operating in zero-gap configurations. Therefore, implementing stability tests in realistic device configurations is essential to assess compounded instability from all components, including the catalyst.2,4 Our group has developed and optimized a lab-scale electrochemical flow cell for alkaline water electrolysis (AWE), refined over four years of dedicated research (Figure 1a).4–7 This work outlines the operation of this device in a laboratory environment, focusing on accelerating the evaluation of electrocatalytic materials and their durability in alkaline conditions. We examined the performance of this lab-scale electrolyzer under industrially relevant conditions, including varying temperatures (Figure 1b). We examined the stability of three standard electrocatalytic materials to demonstrate the electrolyzer performance under fluctuating current conditions, including a benchmark NiFe anode for the oxygen evolution reaction (Figure 1c) and nickel nitride (Ni3N) precatalyst (Figure 1d). Furthermore, we propose a standardized protocol for assessing electrocatalysts under fluctuating and reverse currents, contributing to the understanding of catalyst deactivation. This initiative marks a significant advancement in AWE electrocatalysis research. Our goal is to establish an effective and straightforward protocol for evaluating and validating electrocatalysts in AWE, fostering accurate performance comparisons.

Investigating the Effects of Anode Catalyst Conductivity and Loading on Performance for Anion Exchange Membrane Water Electrolysis

Water electrolysis (WE) is a promising route for carbon-free production of green hydrogen, which is increasingly considered to be an important energy carrier. Among the low-temperature WE technologies, anion exchange membrane water electrolysis (AEMWE) has the potential advantages of high operating current densities and low cost due to the use of zero-gap assembly and platinum group metal (PGM)-free components, respectively [1]. However, significant challenges remain for this technology, including low efficiency, insufficient durability, and poor performance in pure water operation. Recent efforts have yielded improvements in the individual components, particularly the oxygen evolution reaction (OER) catalysts and anion exchange polymers; however, to further improve the performance of the AEMWE, it is also necessary to understand and improve the integration of these materials into the membrane electrode assembly (MEA). Within the MEA, the anode and cathode catalyst layers (CLs) incorporate catalyst and ion-conducting and/or binding polymers, which are deposited onto either the membrane or the porous transport layer. The material properties of each component, as well as the loadings of the catalyst and ionomer and methods of dispersion and deposition, have significant impact on the catalyst layer morphology and uniformity [2]. These CL properties affect the transport of electrons, hydroxide ions, and evolved gases, ultimately controlling the accessibility and utilization of catalyst active sites, with significant consequences for both the performance and durability of AEMWEs.Most of the effort in catalyst development for AEMWE has focused on the OER, aiming to improve sluggish kinetics and improve stability at the highly oxidizing operating potentials. A number of PGM-free catalysts have shown promising activity in rotating disk electrode (RDE) tests, particularly oxides with varying ratios of Ni, Fe, and Co. The activity improvements with tuning the composition are often attributed to the increase in surface area and shift in redox potentials for the in-situ conversion to higher valence sites with higher intrinsic OER activity. However, these activity trends do not always translate into device-level performance because of differences in the operating environment, e.g. hydroxide concentration, reaction rates, etc. In the AEMWE, where typically an order of magnitude higher loadings and current densities are required, the challenges of conductivity and mass transport to allow for full site access are exacerbated. Electrochemical impedance spectroscopy (EIS) is a valuable tool for understanding the origin of voltage losses in the AEMWE, typically broken down into ohmic, kinetic, and mass transport losses. Recently, a transmission line model has been applied to non-Faradaic EIS to isolate another contribution to voltage loss: the catalyst layer resistance (CLR), which corresponds to in-plane and through-plane electronic and ionic resistances in the catalyst layer [3]. Using this approach, the roles of intrinsic catalyst activity and catalyst layer properties can be decoupled, helping to guide materials integration efforts.In this study, we investigate two types of OER catalyst materials, NiFe- and Co-based oxides. Within each composition, the catalysts have similar active sites but vary in electronic conductivity, crystal structure, and surface area. By comparing the AEMWE performance at different catalyst loadings, we are able to determine the role of catalyst properties in determining active site utilization and electronic resistance within the catalyst layer. Figure 1 shows the trends in performance and ohmic and catalyst layer resistance as a function of loading for high-conductivity (Co@Co3O4) and low-conductivity (Co3O4) catalysts. Despite nominally having the same surface chemistry and similar particle morphology, they display both different performance and different trends with loading. Using in-situ EIS diagnostics and ex-situ characterization of the catalyst layer morphology, the relationship between catalyst utilization, CLR, and the physical properties of the catalyst and catalyst layer is elucidated. This work provides insight into the catalyst properties that most strongly affect AEMWE performance, as well as how materials integration strategies must be tailored based on these properties.

Durability and Performance of Poly(norbornene) Anion Exchange Membrane Alkaline Electrolyzer with High Ionic Strength Anolyte

Anion exchange polymer electrolytes enable low-temperature alkaline water electrolysis for reliable green hydrogen production. Anion exchange membrane water electrolysis (AEMWE) with alkaline electrolytes has several advantages over the proton exchange membrane water electrolysis using acid-based polymer electrolytes. The advantages include low-cost catalysts, all hydrocarbon non-fluorinated polymer membrane, and low-cost cell components. Long-term durability of AEMWEs in high pH operation has been challenging, although there have been significant performance improvements. AEMWE operated at low hydroxide anolyte provides improved chemical stability.In this study, an understanding of the high ionic-strength anolyte is provided along with demonstration of the AEMWE performance and durability. Anion exchange poly(norbornene) solid polymer electrolytes show high-performance, durable membrane electrode assemblies for alkaline electrolysis. Covalently bonded, self-adhesive solid polymer ionomers were used in electrodes for durable electrolysis. Hydration problem with the low pH alkaline anolyte in dry-cathode AEMWE is presented. The effect of anolyte concentration and mobile cations on the cathode electrolysis performance using a low hydroxide anolyte was investigated. High ionic strength anolyte was prepared by changing the mobile cation concentration while maintaining a constant anolyte pH. The mechanism of cathode hydration improvement through use of a high ionic strength anolyte is presented. Long-term durability with the optimal high ionic strength electrolyte is discussed.

Finding the Fingerprint of an PEMWE Electrolyzer Using Applied Machine Learning Techniques

The energy transition is picking up pace and renewable energy sources are playing an increasing role in our energy supply. The use of green hydrogen is considered an important energy carrier, to store renewable energy and allow many industries to decarbonize. There are different ways to produce hydrogen, whereas low-temperature proton exchange membrane water electrolysis (PEMWE) is one of the more mature electrolysis technologies. The benefits of proton exchange membrane water electrolysis (PEMWE) include the ability to deliver pressurized hydrogen and/or oxygen, operate using intermittent and renewable power sources, and have a reduced footprint. To evaluate the characteristic performance of PEMWE, the voltage/current relation is an important metric. The voltage/current relation is commonly represented in jV-curves. jV-curves contain relevant information, and any issues or out-of-specification performance can be observed immediately. The shape of the curve, and indicated values allow to interpret the performance of the PEWME cell. Nevertheless, proper interpretation of jV-curves and understanding of the source leading to the out-of-specification performance requires expertise.This study aims to evaluate jV-curves and identify faults by applying machine learning (ML) techniques. A conventional approach has been used to create the model. In the model the Nernst voltage, activation voltage on the anode, and the voltage losses due to ohmic resistance are modeled. Implementation of optimization algorithms allow to fit measured jV-curve to the model. Literature has shown relevant techniques to apply these kinds of ML techniques to electrolysis data, for example Particle Swarm Optimization and a modified Honer Badger algorithm. The application of ML to electrolysis data enables the opportunity to develop online monitoring and automated interpretation of data. In this study particle Swarm Optimization (PSO) has been implemented to fit the model to the jV-curve and find the unknown parameters. Those parameters are unique, depending on the performance of the electrochemical cell, and can be interpreted at the fingerprint thereof.The data shown in the figure has been measured on a single-cell material screener using Nafion 117 CCMs. Although both CCMs have been produced in the same batch, a difference between the measurements can be observed. The jV-curve of sample 1 shows performance as expected. This expected performance is characterized by its linear behavior above 0.5 A/cm2. Observing sample 2 shows an increase in voltage at increasing current densities compared to sample 1. This increase in voltage results in increased energy consumption and therefore a less efficient electrolysis process. Both CCMs are measured under comparable conditions. The anode and cathode pressure were during the both tests close to atmospheric, and the average cell temperature was kept constant at 333.15 K.Despite high volume production processes for coating and manufacturing, the origin of the difference in performance remains unknown. The application of automated data analysis allows for the immediate evaluation of the parameters at fault. The preliminary results show a discrepancy in the modeling parameters relevant to the sub-model describing ohmic losses. Furthermore, ML allows for the creation of data sets that contain experiences from the past. This can help to develop faster performance evaluation protocols by reducing testing activities. For future work, alternative algorithms have to be considered as well. Utilizing ML can enable the opportunity for online monitoring, predictive maintenance, and optimizing control strategies. Figure 1

Kinetics of Oxygen Catalyst Based on Pyrochlore Oxide Nano-Particles for Low Temperature Water Electrolysis

Alkaline water electrolysis is carried out at 60 to 80 oC using nickel-based electrode materials and highly concentrated KOH solutions, which make highly corrosive environment against the electrodes, the separator, the current collector, and the others of the cell. Reduction in operating temperature would be preferable to suppress corrosion, although it would also make the catalytic activity for OER and HER down, making the cell voltage up. Since oxygen evolution is known as a high overpotential reaction which is more than 400 mV with nickel-based oxides at 60 oC or more, and alternative materials with lower overpotential and higher stability for OER in AWE have been needed. This paper presents a novel oxygen catalyst nano-particles based on bismuth ruthenium oxide, in which ruthenium at the B site in the pyrochlore structure is partly replaced with manganese1).Mn-doped bismuth ruthenium oxide (MBRO) was prepared by precipitation of metal hydroxide precursor, which had been obtained by addition of NaOH solution into the metal salt solution containing Bi(III) and Ru(III) with Mn(II), followed by calcination at 600 oC. XRD, EDX, EXAFS, ICP-AES, and RBS were used for structural and compositional analyses of MBRO. The obtained oxide was added into distilled water and the solution was treated by ultrasonic vibration to make a suspension, which was then dropped on a titanium disk (4 mm diam.) and dried at RT for 24 h, resulting in oxide particles-coated titanium disk, in which no binders or ionomers were used in the process. The disk was mounted in a commercial rotating disk electrode and was used as the working electrode with a platinum counter electrode, an Hg/HgO reference electrode, and 0.1 mol/L KOH solution. Polarization curves were measured by LSV for OER, of which the results were analyzed to obtain the onset potential, Tafel slope, exchange current density. All measurements were performed at RT (25 oC).EDX and EXAFS studies of MBRO showed that Ru(IV) was replaced with Mn(IV) at the B-site of pyrochlore structure, and this doping made a single phase of pyrochlore structure oxide without sub-product up to 30 at% replacement . Linear sweep voltammetry revealed the overpotential of MBRO for OER was less than 200 mV and the Tafel slope analysis of the LSV curve gave 40 mV/dec or less. The onset potential and the Tafel slope were almost the same when Ru:Mn atomic ratio of MBRO was changed from 100:0 to 70:30 at%. Further analysis of the polarization curve indicated the exchange current density slightly decreased with increasing Mn ratio. These results suggest that Ru is the active site for OER but Mn is as well. The Tafel slope of OER catalysts reported in literatures is mostly 60 mV/dec or more, including more than 200 mV/dec of nickel-based oxides2,3). Therefore, MBRO is a hyper catalytic oxide for OER in alkaline media and can significantly reduce the overpotential of the anode in AWE even at ambient temperature.Ref.1) M. Morimitsu, Patent US.2022085387.A1.2) T. Shinagawa, A. T. Garcia-Esparza, K. Takanabe, Scientific Reports, Vol. 5, Article No.13801 (2015).3) S. Yagi, et al., Nature Communications, Vol. 6, Article No. 8249 (2015).

Non-Stationary Effects of Current-Load on Electrochemical Behavior of La0.8Sr0.2MnO3- δ in Solid Oxide Electrolysis Cell

High-temperature solid oxide water electrolysis is a highly efficient and carbon-free technology employed for energy conversion, offering numerous advantages over traditional low-temperature water electrolysis methods. These benefits include fast electrode kinetics without the need for Pt group metals and the potential to operate in reversible regimes (fuel cell/steam electrolysis), attributed to the elevated operating temperature (i.e., 600-800 °C). However, the high operating temperature imposes stringent material requirements.While recent attention has been directed towards developing and characterizing new materials for both electrodes and electrolytes, a comprehensive understanding of the underlying reaction mechanisms remains incomplete, hindering the further advancement of the solid oxide cells.Despite the emergence of more advanced materials in recent years, the lanthanum-strontium-manganite La1-xSrxMnO3-δ (LSM) remains to be widely used for an oxygen electrode construction. This preference is due to its cost-effectiveness, high electrical conductivity, thermal and chemical stability, and compatibility with various solid electrolytes. Although LSM has been known for several decades, the reaction mechanism occurring on this oxygen electrode in a broad range of electrode potentials is inadequately described, with discrepancies arising among different authors. These inconsistencies are often linked to the evolving understanding of the non-stationary properties of the LSM lattice – the inner defect chemistry of LSM.Contemporary studies increasingly adopt the concept of ionic conductivity of LSM enabled by cathodic polarization to describe the oxygen reduction reaction. This shift from exclusive electron to ionic-electron conductivity enhances the performance of the LSM electrode, potentially causing discrepancies in the literature as experimental data may not align with theoretical descriptions. Conversely, for the oxygen evolution reaction during anodic polarization, a reversed reaction mechanism is considered without accounting for ionic conductivity of LSM under either stationary or non-stationary conditions. This approach may oversimplify the defect chemistry of LSM, particularly during transitions between operational regimes (i.e., fuel cell and electrolyser regimes). However, such changes are difficult to describe only by experimental approach. Here a combination with mathematical modelling seems to be promising approach allowing to gain deeper understanding.The primary objective of this study is to further investigate the impact of LSM defect chemistry on electrode performance, proposing a reaction scheme during both operating regimes and, crucially, during transitions between them.To address this goal, a series of experiments were conducted under both current-less and current-load conditions using laboratory button single cells. Various gas compositions and operating temperatures were used to determine whether LSM becomes a mixed ionic-electron conductor. Potentiostatic or potentiodynamic methods were used to clarify how this altered property influences individual operating regimes. The results indicate that cathodic polarization leads to a partial reduction of Mn4+ to Mn2+ in the crystalline lattice of LSM, creating oxygen vacancies through which oxide ions can be transported. Additionally, these lattice changes, though temporary, impact the oxygen evolution reaction region under certain conditions. A mathematical model incorporating parallel reaction pathways for both operating regimes supports these experimental results, predicting a cathodic potential at which ionic conductivity becomes viable and identifying conditions where partial reduction of Mn ions is no longer possible.This work contributes to understanding solid oxide cells, providing a solid foundation for more complex mathematical modeling of electrolysis cells. It underscores the necessity to fully comprehend the electrochemical behavior of electrode materials for the continued development of this technology.This work was supported by the Technology Agency of the Czech Republic under project no. TK04030143 (Advanced reversible system for hydrogen production on base of the high temperature solid oxide cell).

(Invited) Dynamic Modeling of Liquid Alkaline Water Electrolyzers: From Laboratory Cells to Industrial-Sized Stacks

The transition of the energy system towards renewable energies creates an enormous demand for green hydrogen produced by water electrolysis [1]. Among the available processes, alkaline water electrolysis (AEL) is already well-developed and cost-effective, as it does not require expensive or critical membrane and electrode materials [2]. If the liquid alkaline electrolyte is maintained at sufficient reaction temperature (60-90 °C), efficient operation of AEL systems is possible with rapid response to fluctuating renewable power supply [3]. However, a critical phenomenon for all low-temperature water electrolysis technologies is the increased gas impurity – especially for hydrogen in oxygen – during part-load operation [4]. This decreases the process efficiency and is safety-relevant as electrolysis systems must shut down when exceeding 50% of the lower explosive limit. These impurities become dominant at low current density since gas production decreases while the contamination mechanisms (diffusion through the separator and convective transport through electrolyte cycles mixing) are almost load-independent. We have developed a comprehensive dynamic model to properly describe the performance of an AEL system, including cell voltage, electrolyte temperature, electrolyte concentration, and gas purity [5]. With this model, it is possible to describe the dynamic operation of a laboratory AEL system with high accuracy. However, if this model is employed for an industry-sized shortstack with more than 1 m2 cell size, predictions and experimental results are in lesser agreement. This is most probably because the present model assumption of perfectly mixed half-cells no longer holds in large cells with a pronounced dependency of the gas fraction over the cell height. Thus, an improved model including this height dependence must be developed.[1] M. Wappler, D. Unguder, X. Lu, H. Ohlmeyer, H. Teschke, W. Lueke, Int. J. Hydrogen Energ. 47 (2022) 33551[2] J. Brauns, T. Turek, Processes 8 (2020) 248[3] J. Brauns, T. Turek, Electrochim. Acta 404 (2022) 139715[4] P. Trinke, P. Haug, J. Brauns, B. Bensmann, R. Hanke-Rauschenbach, T. Turek, J. Electrochem. Soc. 165 (2018) F502[5] J. Brauns, T. Turek, J. Electrochem. Soc. 170 (2023) 064510

Recent Advances and Challenges in Anion Exchange Membranes Development/Application for Water Electrolysis: A Review.

In recent years, anion exchange membranes (AEMs) have aroused widespread interest in hydrogen production via water electrolysis using renewable energy sources. The two current commercial low-temperature water electrolysis technologies used are alkaline water electrolysis (AWE) and proton exchange membrane (PEM) water electrolysis. The AWE technology exhibited the advantages of high stability and increased cost-effectiveness with low hydrogen production efficiency. In contrast, PEM water electrolysis exhibited high hydrogen efficiency with low stability and cost-effectiveness, respectively. Unfortunately, the major challenges that AEMs, as well as the corresponding ion transportation membranes, including alkaline hydrogen separator and proton exchange membranes, still face are hydrogen production efficiency, long-term stability, and cost-effectiveness under working conditions, which exhibited critical issues that need to be addressed as a top priority. This review comprehensively presented research progress on AEMs in recent years, providing a thorough understanding of academic studies and industrial applications. It focused on analyzing the chemical structure of polymers and the performance of AEMs and established the relationship between the structure and efficiency of the membranes. This review aimed to identify approaches for improving AEM ion conductivity and alkaline stability. Additionally, future research directions for the commercialization of anion exchange membranes were discussed based on the analysis and assessment of the current applications of AEMs in patents.

Design of an integrated system for electrofuels production through Fischer-tropsch process

There has been a growing recognition in recent years that Electrofuels (e-fuels), also known as renewable and sustainable fuels, which are produced from hydrogen and carbon dioxide as the primary feedstocks, have great potential to reduce carbon footprint and address climate change. In the present study, contrary to most previous studies in which the sources of feedstock's preparation were considered as block boxes, two stand-alone processes are taken into account and incorporated into the e-fuels production system. H2 is obtained by a high-temperature electrolysis system having an overall efficiency nearly twice that of a low-temperature electrolysis system. CO2 is captured from a power plant flue gas stream with a purity of 99.81%. Investigating heat integration potential in such an integrated plant is an up-to-date and interesting topic and has not yet been well explored. Therefore, a heat integration within the three individual processes is implemented to reduce energy consumption. The design of the process-to-process heat transfer section is carried out using pinch design rules. By integrating individual units, approximately 42% of the required cold utility, traditionally supplied by chilled water and refrigerants, is allocated to generate high and medium-pressure steams. Having used the high-temperature steam electrolysis for H2 production, a process that requires less external electricity compared to low-temperature water electrolysis, a power-to-liquid efficiency of 70% is achieved. Furthermore, the results reveal a carbon conversion ratio of 98.6%, indicating the effective converting the carbon from the feedstock into liquid hydrocarbons.