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At least 181 records · Page 10

Hydrogen production from lignocellulosic hydrolysate in an up-scaled microbial electrolysis cell with stacked bio-electrodes

Hydrogen production from renewable resources via microbial electrolysis cells (MECs) is a promising approach for sustainable energy production. Yet high hydrogen yield from real feedstocks has not been demonstrated in up-scaled MECs. In this study, a 10-L single chamber MEC with a high electrode surface area to volume ratio (66 m 2 /m 3 ) was constructed and electroactive cathodic biofilms were enriched for hydrogen evolution reaction. A high hydrogen yield of 91% was achieved using lignocellulosic hydrolysate with a hydrogen production rate of 0.71 L/L/D at an organic loading rate of 0.4 g/D. The anodic and cathodic microbial communities, with Enterococcus spp. as the known electroactive bacteria, were capable of achieving current densities of 13.7 A/m 2 and 16.5 A/m 2 , respectively. Finally, a machine learning algorithm was used to investigate the correlation between community data and electrochemical performance, and the critical genera on determining current density were identified.

54 ENVIRONMENTAL SCIENCES↗

Scaling-up up-flow microbial electrolysis cells with a compact electrode configuration for continuous hydrogen production

Maintaining high current densities is a key challenge in scaling-up microbial electrolysis cell (MEC) reactors. In this study, a novel 10 L MEC reactor with a total electrode surface area > 1 m 2 was designed and evaluated to maximize the current density and H 2 recovery. Performances of the reactor suggest that the longitudinal structure with parallel vertical orientation of the electrodes encouraged high fluid mixing and the sheet metal electrode frames provided distributed electrical connection. Results also demonstrated that the electrode pairs located next to reactor walls decreased current density, as did separating the electrodes with separators. High volumetric H 2 production rate of 5.9 L/L/d was achieved at a volumetric current density of 970 A/m 3 (34 A/m 2 ). Furthermore, the observed current densities of the large reactor were accurately predicted based on the internal resistance analysis of small scale MECs (0.15 L), demonstrating the scalability of the single chamber MEC design.

08 HYDROGEN↗

Breaking the loop: Tackling homoacetogenesis by chloroform to halt hydrogen production-consumption loop in single chamber microbial electrolysis cells

The presence of homoacetogenesis and hydrogen production-consumption loop significantly hinders the efficient hydrogen recovery in single chamber microbial electrolysis cells (MECs). Furthermore, no effective inhibition method has been proposed against homoacetogens hitherto. In this study, we demonstrated the effectiveness of chloroform as a homoacetogen inhibitor in MECs. In small MECs (320 ml) operated in batch mode, chloroform with concentrations of 0.02% (v/v) and 0.03% (v/v) ceased homoacetogenesis with nonfermentable substrate (acetate), enhancing hydrogen yield and cathodic hydrogen recovery from 21% and 14% to 94% and 90%, respectively. Electrochemical performance was not significantly affected as current density (based on anode surface area) only decreased from 18 A/m 2 to 13 A/m 2 with chloroform concentration increased from 0% (v/v) to 0.03% (v/v). However, when using a fermentable substrate (glucose), the inhibition against homoacetogens by 0.01% (v/v) chloroform led to a significant decrease in current density possibly due to the decreased production of acetate, which reduced the substrate concentration for exoelectrogenesis. Nevertheless, in a larger MEC (10 L), using an immobilized sludge culture and higher glucose concentration (56mM), 0.02% (v/v) chloroform enhanced hydrogen production rate from 0 L/L/D to 4.9 L/L/D and current density from 12-16 A/m 2 to 18-21 A/m 2 . Microbial community analysis revealed that the amount of homoacetogenic Acetobacterium spp. was eliminated in the cathodic biofilms and planktonic cells by chloroform. Future improvement of this method, through reducing the residual chloroform concentration and developing more environment friendly inhibitor using similar mechanisms, may lead to the practical application in MECs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scalable membrane-less microbial electrolysis cell with multiple compact electrode assemblies for high performance hydrogen production

Bioelectrochemical hydrogen production via microbial electrolysis cells (MECs) is a promising method for sustainable energy production and decarbonization of energy systems. However, the application of MECs is limited by the electrochemical performance, scalability, and the cost associated with expensive materials. Here, in this study, a scalable MEC (500 mL) with novel compact electrode assemblies and high electrode surface area to volume ratio (160 m 2 /m 3 ) was designed and constructed. The use of membranes, precious metal catalyst, and current collectors with high costs was avoided. A high current density at the steady state of 49.5 ± 5.3 A/m 2 was achieved using acetate as the substrate with phosphate buffer under the applied voltage of 1.01 V. The corresponding volumetric current density was 3948 ± 422 A/m 3 . The compact electrode assembly design limited methane production rate to 3.9 ± 0.2 L/L/D, while achieving a hydrogen production rate of 33.7 ± 1.7 L/L/D. With the suppression of microbial hydrogen consumption, the hydrogen production rate was 39.8 ± 1.9 L/L/D, higher by almost one order of magnitude than those of MECs with scaling up attempts. The compact electrode configuration reduced internal resistance to 88.5 ± 4.4 Ω cm 2 . The energy efficiency based on input electricity was 146 ± 7 % to 189 ± 9 % within the applied voltage range of 0.71 to 1.05 V. The results in this study demonstrated successful scaling up of high performance small MECs and offered a new possible approach of scaling up MECs by stacking high-performance subunits, with no trade-offs on electrochemical performance.

08 HYDROGEN↗

Porous transport electrodes for oxygen evolution reaction in proton exchange membrane water electrolysis -cells: Materials, designs, and diagnoses

H 2 production using proton exchange membrane (PEM) water electrolysis (PEMWE) cells has received considerable attention because of the high efficiencies of these cells and no harmful emissions from the related process. In PEMWE cells, porous transport electrodes (PTEs) composed of a catalyst layer (CL) comprising O 2 evolution reaction (OER) catalysts, porous transport layer (PTL), and PEM play key roles in the stack performance and lifetime. Herein, Ir-based and non-precious-metal OER catalysts that are highly active and stable at low pH values and high anodic potentials are reviewed to understand their OER mechanisms. Various strategies are proposed for engineering CLs and PTLs to improve the interfacial properties and mass transfers of reactants and products to and from the active sites. Additionally, diagnoses of PTEs is significantly crucial for interpreting electrochemical processes and addressing their current challenges. Therefore, half-cell analyses, including diffusion electrode (DE), floating electrode (FE), and modified rotating disk electrode (MRDE) techniques, are explored, and membrane electrode assembly (MEA)-based analyses, such as the polarization technique, electrochemical impedance spectroscopy, and magnetic field analysis, are established. In conclusion, this study aims to provide an overview of recent technologies used for the engineering and diagnostic tools of PEMWE cells and insights into the advanced components and systems to be developed in this field.

Diagnosis of PEMWE Cells↗

Application of a temporal multiscale method for efficient simulation of degradation in PEM Water Electrolysis under dynamic operating conditions

Hydrogen is emerging as a vital energy carrier, driven by the need to reduce carbon emissions. Proton Electrolyte Membrane Water Electrolysis (PEMWE) enables hydrogen production under fluctuating renewable power conditions but requires improved understanding and stability of the anode catalyst layer under dynamic operating conditions, especially with low noble metal loadings. Long-term degradation experiments are both time-consuming and costly; therefore, a systematic, model-aided approach is essential. In the present work, a temporal multiscale method is applied to reduce the computational effort of simulating long-term degradation processes in PEMWE, with an exemplary focus on catalyst dissolution. A mechanistic model incorporating the oxygen evolution reaction, catalyst dissolution, and hydrogen permeation from the cathode to the anode was hypothesized and implemented. In this way, the local periodicity of transport and reaction processes in dynamic PEMWE operation, which influence the gradual degradation of the catalyst layer, is captured. The temporal multiscale method significantly reduces the computational effort of simulation, decreasing processing time from hours to mere minutes. This efficiency gain is attributed to the limited evolution of Slow-Scale variables during each period of time P of the Fast-Scale variables. Consequently, simulation is required only until local periodicity is achieved within each Slow-Scale time step. Hence, the fully resolved dynamic problem is decoupled into these two scales, employing a heterogeneous multiscale technique. The developed approach effectively accelerates parameter estimation and predictive simulations, supporting systematic modeling of PEMWE degradation under dynamic conditions.

08 HYDROGEN↗

Impact of reactor architecture and design parameters on the performance of microbial electrolysis cells revealed by the electrode potential slope analysis

Microbial electrolysis cells (MECs) are appealing for recovering the chemical energy contained in domestic and industrial liquid wastes as hydrogen gas. Despite several years of research in the field, there is still a lack of critical analysis of how the reactor architecture dictates the electrochemical performance of the cell. In this study, internal resistance and onset voltage from the electrode potential slope analysis (EPS) were used in combination with current density, hydrogen production rate, reactor packing density, electrode spacing, membrane type and composition from 23 different studies to identify the reactor design parameters that primarily govern electrochemical performance of MECs. Using anion exchange membranes resulted in smaller internal resistances (AEM R int = 41± 40 mΩ m 2 ) and larger current density (18 ± 14 A m −2 ) compared to single chamber reactors (SC R int = 68 ± 58 mΩ m 2 ; 22 ± 16 A m −2 ) or MECs with cation exchange membranes (CEM R int = 376 ± 280 mΩ m 2 ; 3.0 ± 2.1 A m −2 ). Higher electrochemical performance for AEM- and SC-MECs translated in larger hydrogen gas production rates (0.122 mL H 2 C −1 for AEM vs 0.117 mL H 2 C −1 for SC), but only when inhibitors against hydrogen scavengers were added in single chamber systems (0.080 mL H 2 C −1 for SC without inhibitors). Following membrane type and composition, maintaining a small electrode spacing was the most critical parameter to improve MEC performance, indicating that the low conductivity of the media primarily limit performance by increasing ohmic resistance. Here, reactor volume and electrode surface area negatively correlated with internal resistance and current density, indicating that better performance of scaled-up reactors can likely be obtained by stacking multiple smaller units rather than just increasing reactor size. Although challenges remain in the implementation of MECs for hydrogen production from liquid wastes, advances in electrochemical engineering of the reactors can facilitate scale up and performance prediction at scale.

Electrochemistry↗

A real-time multiphysics model of a pressurized solid oxide electrolysis cell (SOEC) for cyber-physical simulation

Solid oxide electrolysis cells (SOEC) can play important roles in integrated energy systems (IES) as the hydrogen production hub and the resilience energy hub. When tied to a microgrid with high renewable penetration, the SOEC is subjected to rapid load transitions in response to the intermittent renewable generations that occur not only in diurnal cycles but also in short timeframes (e.g., sub-minute). The cyber-physical simulation approach can derisk operability research but requires a real-time dynamic SOEC model. In the present work, a real-time multiphysics model for pressurized SOEC is developed and validated in the pressure range from 1.4 to 8bar. Further, the accuracy of the single repeating unit (SRU) assumption in SOEC stack simulation is quantified. A guidance of more than 45 cells in one SOEC stack is recommended to safely apply the SRU assumption. Modeling results suggest that at a given current density, more power is consumed by SOEC at elevated operating pressures. The anode air and cathode stream have major impacts on thermal management, highlighting the potential benefit of integrating SOEC with other thermal processes in IES. To achieve high hydrogen production efficiency, the SOEC could operate at the maximum endothermic point to maximize the use of thermal energy. The real-time execution of the developed SOEC model is also demonstrated, which only takes 0.1% of the fixed time step of 5ms. The developed model establishes the basis for cyber-physical simulation of SOEC hybrid systems.

25 ENERGY STORAGE↗

Optimal operation of solid-oxide electrolysis cells considering long-term chemical degradation

Optimizing the performance of solid oxide electrolysis cells (SOECs) for long-term hydrogen (H 2 ) production at high temperatures is crucial, as prolonged operation leads to efficiency losses and shorter cell lifespans due to chemical degradation. Here, in this work, we adopt a quasi-steady state approach for dynamic optimization over extended operational periods to address the disparity in timescales between cell operation and degradation. Integrating a 2-D non-isothermal SOEC model with balance-of-plant (BOP) equipment, we explore three optimization objectives: minimizing terminal degradation, maximizing integral efficiency, and minimizing the levelized cost of H 2 (LCOH). Our dynamic optimization algorithm reduces LCOH by 9.5% and 16% compared to strategies focusing solely on terminal degradation and integral efficiency, respectively. For electricity prices of 0.03 $\$$/mWh and 0.3 $\$$ mWh optimal replacement schedules range from 5 to 2 years, depending on the operational mode. Furthermore, a flexible operational mode yields additional improvements in LCOH over traditional galvanostatic and potentiostatic modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental studies on the effects of sheet resistance and wettability of catalyst layer on electro-catalytic activities for oxygen evolution reaction in proton exchange membrane electrolysis cells

As the most important part of electrochemical reaction in proton exchange membrane electrolysis cells (PEMECs) for water splitting, oxygen evolution reaction (OER) occurs at the anode catalyst layer (CL). The distribution of the OER site is affected by many factors, such as properties of CL, operation parameters, procedures, etc. To study the effects of properties of CLs on the distribution of OER site on the CL, and consequently affect the performance of PEMECs, CLs with different sheet resistances are tested under different operation conditions. Furthermore, the phenomena of OER on CLs are captured by a high-speed and micro-scale visualization system in-situ and analysed coupled with electrochemical results. The results in this work show that both sheet resistance and wettability of CLs have significant impact on the distribution of the OER site, which can help optimize the design of membrane electrode assembly and improve the operating parameters for electrochemical devices.

08 HYDROGEN↗

Modeling the performance and faradaic efficiency of solid oxide electrolysis cells using doped barium zirconate perovskite electrolytes

Y-doped BaZrO 3 (BaZr 1 x Y x O 3 δ , or “BZY”), a proton-conducting ceramic featuring high bulk conductivity and good chemical stability, is a promising electrolyte material for solid oxide electrolysis cells. Further doping with Ce and/or Yb (creating materials “BCZY” and “BCZYYb”) can improve conductivity and sintering properties, but at significant penalty to cells’ faradaic efficiency (FE). Studies have proposed that reduction of lattice Ce can occur in the hydrogen electrode, which consumes some hydrogen produced by the hydrogen evolution reaction, leading to decreased FE. Despite studies suggesting this phenomenon, the mechanism is largely unknown. In this work, we developed a multiphysics model to study the transport of multiple defect species and the performance of BZY, BCZY, and BCZYYb, capturing the tradeoff between enhanced performance at the cost of FE for BCZY and BCZYYb electrolytes compared to BZY. We also found that increasing the water content of the anode gas supply lowers the current output of the cell but results in better FE. The model, which uses several parameters previously unavailable in the literature, was validated to experiments varying temperature, steam water content, and electrolyte material, as well as two performance metrics (performance curves and FE). Results verify and explain observed trends, informing future work on Ce-doped BZY electrolytes.

08 HYDROGEN↗

Hydroxide melt induced corrosion of Ni at elevated temperatures under steam electrolysis conditions

Molten alkali electrolyte based high temperature water electrolysis (HTWE) process offers an efficient pathway to integrate renewable energy resources for large scale and economic hydrogen production. Long term and stable operation of these systems require an in-depth understanding of materials stability under anodic and cathodic exposure conditions of the cell and cell stacks. In the present study, we report our findings on the corrosion of Ni in the presence and absence of (LieNa) hydroxide melt at 600 °C under oxidizing and reducing conditions representative of HTWE. While the Ni electrode was found to remain thermodynamically stable in metallic form under cathodic (reducing) exposure conditions, the corrosion rate in molten hydroxide under oxidizing conditions was found to be nonparabolic in nature. A cyclic voltammetry study provides the breakdown of the passive metal-oxide surface layer at the anodic overpotential region between 0.45 V and 2 V in molten hydroxide under oxidizing conditions. As a result, a thermochemical process for accelerated corrosion based on the oxide scale fluxing in hydroxide melt has been developed.

08 HYDROGEN↗

Oxidation of porous stainless steel supports for metal-supported solid oxide electrolysis cells

Oxidation behavior of porous P434L ferritic stainless steel, used for the fabrication of metal-supported solid oxide electrolysis cells (MS-SOEC), is studied under oxygen-side and steam-side conditions. The impact of oxygen content on the oxygen side and steam:hydrogen ratio on the steam side is determined at 700°C for bare, as-sintered samples. For these conditions, oxidation is more aggressive in the steam-side atmosphere. Oxygen with 3% humidification and steam:hydrogen ratio of 90:10 are selected for further assessment with pre-oxidized, catalyst-coated, and CuMn1·8O4-coated samples. The rapid oxidation at 700°C and breakaway oxidation at 600 °C observed for bare stainless steel in 90:10 steam:hydrogen is mitigated by pre-oxidizing the sample in air before exposure. In oxygen, addition of the catalyst or CuMn 1·8 O 4 coatings moderately increases the oxidation rate, due to consumption of Cr via reaction between the coatings and Cr-oxide scale. In conclusion, the results for ex-situ controlled oxidation are similar to oxidation observed after 1000h operation of a full MS-SOEC. In general, the oxidation behavior at 700°C is found to be acceptable.

08 HYDROGEN↗

Linking structure to performance: Characterization of porous transport layers for high-pressure water electrolysis

Proton exchange membrane (PEM) water electrolysis is a promising technology to produce cost-efficient hydrogen. PEM electrolyzers offer a large current density range and the ability to operate at differential pressure which can be used to minimize both capital and operational expenditures. However, directly producing pressurized hydrogen at the cathode results in pushing the membrane against the anode porous transport layer (PTL). This can lead to detrimental effects, such as membrane deformation or ruptures, which depend on membrane properties as well as PTL material properties such as pore size, structure, and morphology. In this work, a range of sinter and felt-based commercial PTLs are evaluated for their contributions to the cell's electrochemical and H 2 crossover performance at cathode pressures up to 30 bar. X-ray tomography and post-operando optical microscopy are used to assess the morphology of the PTLs, and the PTL induced deformation experienced by the catalyst coated membrane (CCM), respectively. PTL samples with lower porosity were found to reduce both the cell voltage and the amount of H 2 permeating from the cathode to the anode exhaust, which was ascribed to improved catalyst layer contact and reduced membrane deformation, respectively. The best performing PTLs improved electrolyzer efficiency by ~1.5 kWh/kg H2 . Specifically, 1 kWh/kg H2 was gained due to reducing membrane deformation and decreasing H 2 crossover. The remainder 0.5 kWh/kg H2 were achieved by improving the electrical contact at the electrode/PTL interface which decreased cell voltage.

08 HYDROGEN↗

High-Throughput Uniformity and Defect Monitoring in Low-Temperature Electrolysis Porous Transport Layers Using X-Ray Radiography

Effective quality control (QC) for manufacturing proton exchange membrane water electrolysis (PEMWE) components is critical to enabling widespread adoption of the technology for hydrogen generation. This study investigates X-ray radiography as a novel, high-throughput, potentially in-line QC technique for detecting defects and assessing material property distributions in titanium-based porous transport layers (PTLs) which constitute a crucial component of low temperature PEMWE stacks. We obtain radiographs of a set of fifteen PTLs and model their absorbance of the broadband radiation as a second-order polynomial to account for the non-monoenergetic radiation source used in this study. The resulting model serves as a basis for predicting the areal density and porosity distributions of the PTLs. We find radiography successful in detecting multiple instances of defects, including holes/depressions, cracks, and excess material on the surface or in the pores of the material, demonstrating its potential as a robust in-line QC tool for PTL manufacturing.

08 HYDROGEN↗

Degradation of solid oxide electrolysis cells: Phenomena, mechanisms, and emerging mitigation strategies—A review

Solid oxide electrolysis cell (SOEC) is a promising electrochemical device with high efficiency for energy storage and conversion. However, the degradation of SOEC is a significant barrier to commercial viability. In this review article, the typical degradation phenomena of SOEC are summarized, with great attention into the anodes/oxygen electrodes, including the commonly used and newly developed anode materials. Meanwhile, mechanistic investigations on the electrode/electrolyte interfaces are provided to unveil how the intrinsic factor, oxygen partial pressure , and the electrochemical operation conditions, affect the interfacial stability of SOEC. At last, this paper also presents some emerging mitigation strategies to circumvent long-term degradation, which include novel infiltration method, development of new anode materials and engineering of the microstructure.

36 MATERIALS SCIENCE↗

Layer-structured triple-conducting electrocatalyst for water-splitting in protonic ceramic electrolysis cells: Conductivities vs. activity

Electron, proton and oxygen-triple-conducting materials are becoming the dominant steam electrode candidate to break the rate limit on the water-splitting reaction that throttles the performance of protonic ceramic electrolysis cells (PCECs). In this study, based on Pr 2 NiO 4+δ Ruddlesden-Popper phase, we manipulate these conductivities by Pr-site Ba substitution to probe the correlation of each conductivity with the kinetics of the elementary reaction steps. It is found that the proton conductivity is vital to sustain an extended active surface area for faster adsorption of reactants and desorption of products. The effect of oxygen conductivity is surprisingly found insignificant in the water-splitting reaction. On the contrary, surface oxygen removal is discovered as the most rate-limiting process. The electronic conductivity is not a direct limiting factor. However, an electron transfer process between the current collector and the electrode junction could introduce extra resistance that is perceptible at a high operating temperature range. The best water-splitting activity is obtained on a proton conductivity/oxygen surface desorption capability well-balanced sample after Ba substitution. As a result, a water-splitting reaction resistance of 0.022 Ωcm 2 , a current density of 1.96 A/cm 2 at 700 °C is achieved on Pr 1.7 Ba 0.3 NiO 4+δ , one of the best performances for PCECs.

25 ENERGY STORAGE↗

Using nickel-molybdenum cathode catalysts for efficient hydrogen gas production in microbial electrolysis cells

A low-cost cathode catalyst based on a NiMo alloy was examined here to replace noble metals for the hydrogen production in microbial electrolysis cells (MECs). Two NiMo catalysts were synthesized through either an electrochemical assisted (NiMo Elec) or a hydrothermal (NiMo Ht) approach. The NiMo Ht method enriched the electrocatalyst with Mo atoms compared to the NiMo Elec approach, producing a similar current density with a minimal overpotential of 50mV compared to Pt. Further, in MEC tests using the NiMo Ht catalyst, H 2 was generated at a highest rate of 81±3 L H2 /L-d (current density of 44.4 ± 0.9 A/m 2 ) at a cell voltage of -0.86 V, and a Coulombic efficiency of >97%. Modifying the closely stacked MEC design to include a reference electrode, and analysis of the electrode potentials using the electrode potential slope method, revealed a large contribution of the cathode resistance (5.3±0.5mΩm 2 ) compared to the anode (1.4±0.2mΩm 2 ) and ohmic resistance (0.83mΩm 2 ) for a total internal resistance of 7.6±0.5mΩm 2 . The high performance of the NiMo Ht catalyst coupled with its low cost provides an economically viable approach to advance the generation of biohydrogen in MECs.

25 ENERGY STORAGE↗