Electrode Kinetics Research Articles

In–Li Counter Electrodes in Solid‐State Batteries – A Comparative Approach on Kinetics, Microstructure, and Chemomechanics

AbstractA key challenge for solid‐state batteries is the fabrication of high‐capacity cathodes with high area loading and good rate performance. To reliably quantify the performance of high‐capacity cathodes, electrochemically stable, and high‐rate counter electrodes are essential. Otherwise, a three‐electrode setup is required. In–Li alloy electrodes are used for years in a kind of standard approach, since these seem to offer stable operation. In this comparative study, seven preparation methods for In–Li electrodes are examined, determining their suitability for cathode testing. The microstructure of a planar (i.e., foil) and a particle‐based (i.e., composite) anode configuration is analyzed in more detail. Their rate‐dependent electrode performance as well as electrochemical and chemomechanical reversibility in full‐cell configuration are analyzed. The combined results demonstrate the limitations of In–Li electrodes for high‐capacity testing, especially at high rates, while confirming their suitability for simple lab‐scale testing. Preparation significantly influences the electrode microstructure and kinetics, consequently impacting the performance benchmarks of cathodes. These findings underscore both the challenges involved in applying In–Li counter electrodes and the resulting limited comparability of results from different laboratories.

High-Na-Content Birnessite via P'3-Stacking with Tunable Active Facets for Advanced Aqueous Sodium-Ion Batteries.

Layered Na-birnessites are promising cathode materials for aqueous sodium-ion batteries due to their high theoretical capacity, low cost, and environmental benignity. However, the general O'3 Na-birnessites possess low Na content and dominant inactive {001} exposed facets, which compromise their Na storage capability and cycling stability. Herein, we develop a high-Na-content P'3-Na0.71MnO2·0.15H2O with highly enriched {010} active facets by a hydrothermal conversion method. In comparison with the O'3 Na-birnessite, the P'3 Na-birnessite with a high ratio of {010}/{001} exposed facets provides greatly increased open channels for Na+ diffusion, while the P'3 stacking affords a lower Na+ diffusion barrier, resulting in improved electrode kinetics with a large specific capacity of 176 mAh g-1 at 0.2 A g-1. More importantly, the P'3 Na-birnessite manifests solo Na+ intercalation/deintercalation with extraordinary cycling stability in an aqueous electrolyte, achieving 90.5% capacity retention after 60,000 cycles. When coupled with the NaTi2(PO4)3 anode, the P'3 Na-birnessite-based full cell delivers both high energy density and long cycle life, demonstrating the potential application in aqueous sodium-ion batteries. This study demonstrates an efficient method to prepare high-Na-content P'3 birnessite with tunable exposed facets and provides important insights into developing highly stable layered cathodes for sustainable aqueous sodium-ion batteries.

Metal organic framework derived heteroatom doped porous carbon nanocubes enable efficient charge storage in a lithium-ion capacitor

Lithium-ion capacitors (LICs) are regarded as one of the promising technologies towards realizing energy & power dense energy storage systems. However, their energy densities at higher power densities are still limited due to the discrepancy between electrode kinetics of capacitor-like cathode and battery-like anode. Developing carbon materials with well-defined structures, porosity to match the chemical kinetics between electrodes are the major challenges to overcome. In the present work, we have devised a strategy to fabricate S, N dual-doped porous carbon nanocubes (S, N-PCNs) using zeolitic imidazole framework (ZIF)-8 precursors, and employed the PCNs as anode material in LICs. With its well-defined structure, hierarchical porous nature, and abundant heteroatom presence (1.9 % S, 16.2 % N), the pre-lithiated S, N-PCNs based anode has offered a greatly improved reversible storage capacity of ∼930 mAh g−1 at 0.1 A g−1 along with an impressive rate capability and cycling life. When S, N-PCNs anode is paired with activated carbon cathode, the 4 V dual-carbon LIC yields an energy density as high as 120.24 Wh kg−1 and 10.2 kW kg−1 of power density with a good cycle stability of 90.6 % after 5000 charge-discharge cycles. This work would open new scopes of exploring metal-organic framework derived heteroatom-doped porous carbons to make metal-ion capacitors more efficient.

In situ ammonium formation mediates efficient hydrogen production from natural seawater splitting

Seawater electrolysis using renewable electricity offers an attractive route to sustainable hydrogen production, but the sluggish electrode kinetics and poor durability are two major challenges. We report a molybdenum nitride (Mo2N) catalyst for the hydrogen evolution reaction with activity comparable to commercial platinum on carbon (Pt/C) catalyst in natural seawater. The catalyst operates more than 1000 hours of continuous testing at 100 mA cm−2 without degradation, whereas massive precipitate (mainly magnesium hydroxide) forms on the Pt/C counterpart after 36 hours of operation at 10 mA cm−2. Our investigation reveals that ammonium groups generate in situ at the catalyst surface, which not only improve the connectivity of hydrogen-bond networks but also suppress the local pH increase, enabling the enhanced performances. Moreover, a zero-gap membrane flow electrolyser assembled by this catalyst exhibits a current density of 1 A cm−2 at 1.87 V and 60 oC in simulated seawater and runs steadily over 900 hours.

Biocatalyst for carbon veil anode in microbial fuel cells: The effect of precursor and catalyst loading on overall performance

Biocatalysts in anodes have been crucial in improving microbial fuel cell (MFC) performance. Biocatalysts derived from biomass such as coconut wood sawdust (SD-B) and pepper processing residue (PS-B), were used to improve the electrocatalytic properties of Carbon Veil (CV) electrodes. The amorphous graphitic carbon biocatalyst with a mesoporous structure was found to have a surface area of 889.31 m2/g for SD-B and 763.56 m2/g for PS-B. Surface functional groups such as -OH which imparts hydrophilicity and -C=O and COOH which promotes bacterial compatibility have been revealed to be present in both catalysts. Catalyst loading played a major role and at an optimal loading of 2 mg/cm2, the electrodes exhibited maximum electrocatalytic activity in the case of both biocatalysts. The voltammetric capacitances of SD-B and PS-B modified electrodes were 191.6 mF/cm2 and 106.6 mF/cm2 demonstrating their pseudocapacitive behaviour too. The performance of MFC with SD-B revealed a maximum power density of 10.1 W/m3 (Open Circuit Voltage (OCV) of 850 mV), followed by PS-B at 6.89 W/m3 (OCV of 825 mV) whereas the plain CV was at 0.168 W/m3 (OCV of 760 mV). Anode polarization studies indicated reduced slopes for biocatalyst-modified anodes, signifying improved electrode kinetics, particularly notable in the SD-B modified MFC where the cathode became the limiting electrode. Coulombic efficiencies of the biocatalyst-modified MFCs increased to 54.50%, (SD-B 2 mg/cm2) and 37.78% (PS-B 2 mg/cm2) respectively from 12.74% as noticed in the case of unmodified MFC. This study emphasizes the potential of biocatalysts as a simple and low-cost means of enhancing the anode properties – porosity, conductivity, hydrophilicity, and biocompatibility.

Bifunctional Fluorocarbon Electrode Additive Lowers the Salt Dependence of Aqueous Electrolytes.

The solid electrolyte interphase (SEI) plays a crucial role in extending the life of aqueous batteries. The traditional anion-derived SEI formation in aqueous electrolytes highly depends on high-concentrated organic fluorinating salts, resulting in low forming efficiency and long-term consumption. In response, this study proposes a bifunctional fluorocarbon electrode additive (BFEA) that enables electrochemical pre-reduction instead of TFSI anion to form the LiF-rich SEI and in situ produce conductive graphite inside the anode before the lithiation. The BFEA lowers the salt dependence of aqueous electrolytes, enabling the inorganic LiCl electrolyte to work first, but also successfully achieves a high SEI formation efficiency in the relatively low 10m LiTFSI without mass transfer concerns, suppressing the parasitic hydrogen evolution from 11.24 to 4.35nmol min-1. Besides, BFEA strengthens the intrinsic superiority of Li storage reaction by lowering battery polarization resulting from the in situ production of graphite, promoting charge transfer of electrode kinetics. Compared with the control group, the demonstrated Ah-level pouch cell employing BFEA exhibits better cycle stability above 300 cycles with higher capacity retention of 78.2% and the lower decay of the round-trip efficiency (△RTE = 2%), benefiting for maintaining the high efficiency and reducing heat accumulation in large-scale electric energy storage.

Metal‐Organic Framework Hosted Silicon for Long‐Cycling, Low‐Cost, and Flexible Batteries

AbstractDeveloping biodegradable electrodes is a significant step toward environmental sustainability and cost reduction in battery technology. This paper presents a new approach that utilizes metal‐organic framework (MOF)‐encapsulated silicon nanoparticles (SiNPs) as the active anode material within a cellulose‐based electrode. The electrode is free‐standing, flexible, biodegradable, and significantly reduces the strain experienced by SiNPs during volume expansion, resulting in improved capacity and cycle life stability of SiNPs. The high porosity of the electrode creates efficient lithium (Li+) ion transport channels and enhances electrolyte absorption, thus promoting effective contact between the electrolyte and active material. The outcome is rapid electrode kinetics and a highly reversible discharge capacity of 1744.6 mAh g−1 at 0.5 A g−1 versus Li/Li+ over 1000 cycles. Further, full cell tests are conducted that demonstrate a stable cycle performance exceeding 3400 cycles, with an initial discharge capacity retention of 80.5% at 0.5 A g−1. By employing cellulose and avoiding toxic organic solvents and binders, the proposed approach is promising for a substantial reduction of the production costs of Li‐ion batteries. The scalability of the proposed method further enhances its practical viability, offering intriguing economic implications for the future of battery technology.

Cross-Scale Decoupling Kinetic Processes in Lithium-Ion Batteries Using the Multi-Dimensional Distribution of Relaxation Time.

To non-destructively resolve and diagnose the degradation mechanisms of lithium-ion batteries (LIBs), it is necessary to cross-scale decouple complex kinetic processes through the distribution of relaxation times (DRT). However, LIBs with low interfacial impedance render DRT unreliable without data processing and closed-loop validation. This study proposes a hierarchical analytical framework to enhance timescale resolution and reduce uncertainty, including interfacial impedance reconstruction and multi-dimensional DRT analysis. Interfacial impedance is reconstructed by eliminating simulated inductive and diffusive impedance based on a high-fidelity frequency-domain model. Multi-dimensional DRT decouples solid electrolyte interphase (SEI) and charge transfer (CT) processes by the reversibility of electrochemical reactions with state of charge (SOC) to characterize electrode kinetic evolution driven by SOC and temperature through timescales and peak area. The findings reveal that reconstructed impedance improves the accuracy of identified time constants by ≈20%. Cross-scale DRT results reveal that SOCs below 10% at 25 °C effectively distinguish electrode kinetics due to the high correlation between cathodic CT and SOC. Kinetic metrics characterize that anodic SEI or CT are different control steps limiting the low-temperature performance of different cells. This work underscores the potential of the proposed framework for non-destructive diagnostics of kinetic evolution.

Comparative Analysis of Thermal Activation on Felts and Continuous Carbon Filament Electrodes for Vanadium Redox Flow Batteries

AbstractThermal treatments are commonly used to improve electrode kinetics in vanadium redox flow batteries (VRFB). The impact of the widely adopted thermal treatment—400 °C for least 24 hours—was investigated on polyacrylonitrile (PAN)‐based continuous carbon filaments (tows) and compared to PAN‐based graphite felts. Surface properties were assessed with scanning electron microscopy (SEM), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS) and wettability measurements. The electrode activity was investigated via electrochemical impedance spectroscopy (EIS). Charge‐transfer resistances and the constant phase element parameters related to the electric double layer were determined, revealing a correlation between enhanced electrode activity and increased double layer across all electrodes. An 8‐hour 400 °C thermal treatment was sufficient to improve electrode activity for tows, whereas felts required longer durations, up to 24 hours, attributed to differences in the carbonization process employed for each material, with the tows undergoing continuous processing and the felts following a batch process. Three‐electrode half‐cell EIS measurements were conducted to elucidate positive and negative electrode contributions. Activated continuous carbon filament electrodes exhibited consistent electrode activities in both the catholyte (VO2+/VO2+) and anolyte (V3+/V2+), whereas the electrochemical activity of felts was limited by the electrode deactivation in the anolyte.

Ultra-Low Alginate-Based Multifunctional Composite Binders for Enhanced Mechanical, Electrochemical, and Thermal Performance of Li-S Batteries.

The practical application of Li-S batteries, which hold great potential as energy storage devices, is impeded by various challenges, such as capacity degradation caused volume change, polysulfide shuttling, poor electrode kinetics, and safety concerns. Binder plays a crucial role in suppressing volume change of cathode side, thereby enhancing the electrochemical performance of Li-S batteries. In this research, a novel network binder (SA-Co-PEDOT) composed of sodium alginate is presented, Co2+ ions as cross-linking agent and PEDOT as an electronic conductor. The theoretical analysis and experimental testing confirm that the SA-Co-PEDOT binder with synergistic combination of catalytic center and electron transfer network effectively mitigates large volumetric changes during cycling while simultaneously enhancing electrode kinetics through controlling the deposition morphology of sulfur end product and its nucleation and dissolution. As a result, it achieves a capacity of 844 mAh g-1 after 150 cycles at 0.2 C. Moreover, the electrode with SA-Co-PEDOT binder subjected a bending test maintains a capacity of 395 mAh g-1 after 500 cycles at 0.5 C, exhibiting an impressively low decay rate of only 0.11%. Even with an ultra-low content of 2 wt.% SA-Co-PEDOT binder, the electrode still maintains a capacity of 999.7 mAh g-1 after 100 cycles at 0.5 C.

KSCN molten salt synthesis of hierarchical MoS2/NPC for rapid and durable sodium storage

MoS2 boasts high capacity but often encounters issues such as poor electrical conductivity, limited cycling stability due to volume expansion, and polysulfide shuttling when applied as the anode in sodium-ion batteries (SIBs). To this end researchers have developed MoS2/carbon composites, which enhance electronic conductivity, ion diffusion, and structural stability. Herein, we develop a new synthesis method using a KSCN molten salt to produce hierarchical MoS2 on nitrogen and phosphorus co-doped carbon (NPC). The molten KSCN acts both as the sulfur source and the reaction medium, facilitating the creation of hierarchical MoS2 structures with a high loading of 85.8 wt%. These structures optimize ion diffusion channels and enhance electrochemical reaction kinetics. Additionally, the NPC framework improves electron transport and reduces polysulfide shuttling. With its superior structural stability and accelerated electrode kinetics, MoS2/NPC exhibits an impressive rate capacity of 468 mAh g−1 at 10 A g−1 and maintains a long lifespan of 1300 cycles at 2 A g−1. Moreover, full cells equipped with a NaNi1/3Fe1/3Mn1/3O2 cathode retain 98 % capacity retention after 400 cycles. This study presents a promising approach for fabricating advanced MoS2/carbon anodes with dedicate nanostructures for SIBs.

Advances in Functional Organosulfur-Based Mediators for Regulating Performance of Lithium Metal Batteries.

Rechargeable lithium metal batteries (LMBs) are promising next-generation energy storage systems due to their high theoretical energy density. However, their practical applications are hindered by lithium dendrite growth and various intricate issues associated with the cathodes. These challenges can be mitigated by using organosulfur-based mediators (OSMs), which offer the advantages of abundance, tailorable structures, and unique functional adaptability. These features enable the rational design of targeted functionalities, enhance the interfacial stability of the lithium anode and cathode, and accelerate the redox kinetics of electrodes via alternative reaction pathways, thereby effectively improving the performance of LMBs. Unlike the extensively explored field of organosulfur cathode materials, OSMs have garnered little attention. This review systematically summarizes recent advancements in OSMs for various LMB systems, including lithium-sulfur, lithium-selenium, lithium-oxygen, lithium-intercalation cathode batteries, and other LMB systems. It briefly elucidates the operating principles of these LMB systems, the regulatory mechanisms of the corresponding OSMs, and the fundamentals of OSMs activity. Ultimately, strategic optimizations are proposed for designing novel OSMs, advanced mechanism investigation, expanded applications, and the development of safe battery systems, thereby providing directions to narrow the gap between rational modulation of organosulfur compounds and their practical implementation in batteries.

Controlling coating thickness distribution for a complex geometry with the help of simulation

This paper aims to develop a proper and valid simulation model for electroplating complex geometries. Since many variables influence the quality of the deposited coating and its thickness distribution, it is challenging to conduct efficient research only through experiments. In contrast, simulation can be an efficient way to optimize the electroplating experiments. Despite its potential, simulation has seen limited commercial use in the electroplating industry due to its inherent complexity and difficulty in achieving accurate precision for intricate geometries. The present study addresses the aspects that can enhance the electroplating simulation’s accuracy, which has been typically overlooked in the literature, such as the effect of current efficiency and its dependency on the current density, the input data for the electrode kinetics, the surface topology changes, and the differences between 2 and 3D simulations. The simulation model was validated by experimental results related to the coating thickness of Ni plating on a T-joint geometry. The results showed good agreement with the experimental ones, confirming the model’s ability to precisely predict the coating thickness and distribution and promote its broader utilization in the industry. Finally, the developed model was used to determine the optimal current density regime for achieving uniform coating thickness distribution on a T-joint sample.

High-energy bimetallic substituted Na3V2(PO4)3 cathode for advanced sodium-ion batteries

NASICON-type cathodes have attracted great attention due to their open three-dimensional (3D) frame structure and excellent ion transport properties. Accordingly, how to improve the stability and energy density of materials is a hot topic of research. In this study, the significant effects of aluminum-zirconium bimetallic substitution on electrode kinetics and structural stability are reported. The designed Na2.9V1.8Al0.1Zr0.1(PO4)3 cathode exhibits a highly reversible capacity of 107 mAh g-1 at 1C and decent cyclic stability (75 mAh g-1 capacity after 2000 cycles at 20C). These excellent electrochemical properties can be attributed to expanding the lattice structure and activating part of V4+, which facilitates the migration of Na+ and increases the reversible capacity. The cyclic voltammetry, electrochemical impedance spectra and galvanostatic intermittent titration technique tests analyze the diffusion kinetics of sodium ions and confirm the desired sodium ion diffusion coefficients (DNa+). In situ X-ray diffraction reveals reversible structural changes during the electrochemical reaction, which confirms that the bimetallic doping strategy slows down material volume change. This work provides a new perspective for the construction of high-performance NASICON cathode materials.

Electrocatalysis of hydrogen and oxygen electrode reactions in alkaline media by Rh-modified polycrystalline Ni electrode

Developing novel electrocatalysts for energy conversion applications is of utmost importance for reaching the energy security of modern society. Here we present a comprehensive investigation of rhodium-modified polycrystalline nickel as an electrocatalyst for hydrogen and oxygen electrode reactions in alkaline media. The surface modification of nickel electrodes was achieved by facile galvanic displacement (up to 30 s) from a highly concentrated acidic Rh3+ solution. The results demonstrate a significant enhancement in the electrocatalytic activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) on the Rh-modified Ni electrodes, positioning galvanic displacement as a viable approach to engineering advanced electrocatalysts for clean energy applications. On the other hand, the hydrogen oxidation (HOR) and oxygen reduction reaction (ORR) activities of the Rh-modified electrodes are lower compared to polycrystalline platinum. It is suggested that semiconducting Rh2O3 has a detrimental role on the HOR and ORR performance, while the activities of HER and OER, dominantly taking place on metallic Rh and conductive RhO2, are very high. This research sheds light on the mechanisms underlying the enhanced electrode kinetics on Rh-modified Ni electrodes and provides insights into the development of efficient and cost-effective electrocatalysts for renewable energy technologies.

Thermal vapor sulfurization of Ti3C2TX MXene to TiS2/carbon nanosheet cathode for long-life and high-loading all-solid-state lithium batteries

Stable and fast operation of all-solid-state lithium batteries (ASSBs) depends on durable and sufficient interfacial contacts between electrode components, especially when the loading and content of electrode active materials are high. Here, we propose promoting ionic/electronic transportations and contacts in sulfide electrolyte-based ASSBs by using TiS2/carbon nanosheets (TiS2/C-s) with large area-to-thickness aspect ratios as the cathode, which are prepared by simple thermal vapor sulfurization of exfoliated Ti3C2Tx MXene. The elastic 2D structure of the TiS2/C-s material can substantially improve interfacial contact with the solid electrolyte, minimize the diffusion distance of lithium ions, and buffer volume/stress changes during cycling, thereby ensuring the electro-chemo-mechanical stability and fast reaction kinetics of electrodes. Consequently, a 50 wt% TiS2/C-s cathode without any conductive carbon additives demonstrates a high discharge capacity (295 mAh g−1), long-term cyclic stability (94.7 and 74.7 % capacity retention after 250 cycles at 0.1 mA cm−2 and after 2300 cycles at 1 mA cm−2, respectively), and decent rate capability (126.0 mAh g−1 at 3 mA cm−2). Moreover, stable cycling with a high areal capacity (5.95 mAh cm−2) can also be achieved.

Enhancing Heavy Metal Detection through Electrochemical Polishing of Carbon Electrodes.

Our research addresses the pressing need for environmental sensors capable of large-scale, on-site detection of a wide array of heavy metals with highly accurate sensor metrics. We present a novel approach using electrochemically polished (ECP) carbon screen-printed electrodes (cSPEs) for high-sensitivity detection of cadmium and lead. By applying a range of techniques, including scanning electron microscopy, energy-dispersive spectroscopy, Raman spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry, we investigated the impact of the electrochemical potential scan range, scan rate, and the number of cycles on electrode response and its ability to detect cadmium and lead. Our findings reveal a 41 ± 1.2% increase in voltammogram currents and a 51 ± 1.6% decrease in potential separations (n = 3), indicating a significantly improved active electrode area and kinetics. The impedance model elucidates the microstructural and electrochemical property changes in the ECP-treated electrodes, showing an 88 ± 2% (n = 3) decrease in the charge transfer resistance, leading to enhanced electrode electrical conductivity. A bismuth-reduced graphene oxide nanocomposite-modified, ECP-treated electrode demonstrated a higher cadmium and lead sensitivity of up to 5 ± 0.1 μAppb-1cm-2 and 2.7 ± 0.1 μAppb-1cm-2 (n = 3), respectively, resulting in sub-ppb limits of detection in spiked deionized water samples. Our study underscores the potential of optimally ECP-activated electrodes as a foundation for designing ultrasensitive heavy metal sensors for a wide range of real-world heavy metal-contaminated waters.

DMSO/DMF co-solvent precipitated nano-sulfur cathode for highly loading lithium-sulfur pouch cells

We employ a simple anti-solvent precipitation method to prepare sulfur nanoparticles. Dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) are chosen as co-solvents, and cetyltrimethylammonium bromide (CTAB) is used as a stabilizer. By adjusting parameters such as the ratio of solvents and concentration, we precisely control the supersaturation, finely tuning the size of the sulfur particles. To enhance the electrical conductivity of the electrode materials, we uniformly composite sulfur with reduced graphene oxide (rGO). As the sulfur particle size decreases, the charge transfer resistance of the S@rGO cathode rapidly decreases, demonstrating excellent electrode kinetics. A lithium-sulfur coin cell assembled with S@rGO-75 exhibits a discharge specific capacity of 1272 mAh g−1. After 180 cycles, the capacity retention remains at 89.1 %, with a Coulombic efficiency of 98.9 %. Additionally, a pouch cell (PC-75) achieves stable charge–discharge behavior at a total sulfur loading of 300 mg, with an initial discharge specific capacity of 1047 mAh g−1 and a capacity retention of 63.7 % after 80 cycles. Under lean electrolyte conditions (E/S = 1.5 μl mg−1), PC-75 maintains outstanding energy density (392.3 Wh kg−1). Based on PC-75, a drone achieves an ultra-long flight time of 255 s, providing preliminary evidence of the practical application potential of PC-75.

(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.

Enhancing Direct Eectrochemical CO2 Electrolysis By Introducing a-Site Deficiency for Dual-Phase Pr(Ca)Fe(Ni)O3-Δ Cathode

High-temperature CO2 electrolysis via solid oxide electrolysis cells (CO2-SOECs) has drawn special attention due to the high energy convention efficiency, fast electrode kinetics, and great potential in carbon cycling. However, the development of cathode materials with high catalytic activity and chemical stability for pure CO2 electrolysis is still a great challenge. In this work, A-site cation deficient dual-phase material, namely (Pr0.4Ca0.6)xFe0.8Ni0.2O3- δ (PCFN, x=1, 0.95, and 0.9), has been designed as the fuel electrode for a pure CO2-SOEC which presents superior electrochemical performance. Among all these compositions, (Pr0.4Ca0.6)0.95Fe0.8Ni0.2O3- δ (PCFN95) exhibited the lowest polarization resistance of 0.458 Ω cm2 at open circuit voltage and 800℃. The application of PCFN95 as the cathode in a single cell yields an impressive electrolysis current density of 1.76 A cm-2 at 1.5 V and 800℃, which is 76% higher than that of single cells with stoichiometric Pr0.4Ca0.6Fe0.8Ni0.2O3- δ (PCFN100) cathode. The effects of A-site deficiency on materials’ phase structure and physicochemical properties are also systematically investigated. Such an enhancement in electrochemical performance is attributed to the promotion of effective CO2 adsorption, as well as the improved electrode kinetics resulting from A-site deficiency.