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At least 307 records · Page 17

Oxygen-Plasma-Induced Hetero-Interface NiFe2O4/NiMoO4 Catalyst for Enhanced Electrochemical Oxygen Evolution

The electrolysis of water to produce hydrogen is an effective method for solving the rapid consumption of fossil fuel resources and the problem of global warming. The key to its success is to design an oxygen evolution reaction (OER) electrocatalyst with efficient conversion and reliable stability. Interface engineering is one of the most effective approaches for adjusting local electronic configurations. Adding other metal elements is also an effective way to enrich active sites and improve catalytic activity. Herein, high-valence iron in a heterogeneous interface of NiFe 2 O 4 /NiMoO 4 composite was obtained through oxygen plasma to achieve excellent electrocatalytic activity and stability. In particular, 270 mV of overpotential is required to reach a current density of 50 mA cm -2 , and the overpotential required to reach 500 mA cm -2 is only 309 mV. The electron transfer effect for high-valence iron was determined by X-ray photoelectron spectroscopy (XPS). The fast and irreversible reconstruction and the true active species in the catalytic process were identified by in situ Raman, ex situ XPS, and ex situ transmission electron microscopy (TEM) measurements. This work provides a feasible design guideline to modify electronic structures, promote a metal to an active oxidation state, and thus develop an electrocatalyst with enhanced OER performance.

36 MATERIALS SCIENCE↗

Photocatalytic water splitting—The untamed dream: A review of recent advances

Here, photocatalytic water splitting using sunlight is a promising technology capable of providing high energy yield without pollutant byproducts. Herein, we review various aspects of this technology including chemical reactions, physiochemical conditions and photocatalyst types such as metal oxides, sulfides, nitrides, nanocomposites, and doped materials followed by recent advances in computational modeling of photoactive materials. As the best-known catalyst for photocatalytic hydrogen and oxygen evolution, TiO 2 is discussed in a separate section, along with its challenges such as the wide band gap, large overpotential for hydrogen evolution, and rapid recombination of produced electron-hole pairs. Various approaches are addressed to overcome these shortcomings, such as doping with different elements, heterojunction catalysts, noble metal deposition, and surface modification. Development of a photocatalytic corrosion resistant, visible light absorbing, defect-tuned material with small particle size is the key to complete the sunlight to hydrogen cycle efficiently. Computational studies have opened new avenues to understand and predict the electronic density of states and band structure of advanced materials and could pave the way for the rational design of efficient photocatalysts for water splitting. Future directions are focused on developing innovative junction architectures, novel synthesis methods and optimizing the existing active materials to enhance charge transfer, visible light absorption, reducing the gas evolution overpotential and maintaining chemical and physical stability

36 MATERIALS SCIENCE↗

Carbon Nanotube Supported Amorphous MoS 2 via Microwave Heating Synthesis for Enhanced Performance of Hydrogen Evolution Reaction

Amorphous molybdenum disulfide (MoS 2 ) is a promising electrochemical catalyst for hydrogen evolution reaction (HER) due to more active sites exposed on the surface compared to its crystalline counterpart. In this study, a novel fast three-minute one-pot method is proposed to prepare the single-wall carbon nanotube- (SWCNT-) supported amorphous MoS 2 via a microwave heating process. Compared to traditional hydro- or solvent thermal methods to prepare MoS 2 which usually consume more than 10 hours, it is more promising for fast production. An overpotential at 10 mA/cm 2 of amorphous MoS 2 @SWCNT is 178 mV, which is 99 mV and 22 mV lower than crystalline MoS 2 @SWCNT and pure amorphous MoS 2 , respectively. After running 1000 cycles of polarization, ~2% increase in overpotential is observed, indicating its good stability. The enhanced performance results from the beneficial combination of the SWCNT substrate and the amorphous microstructures. The introduction of SWCNT increases catalyst conductivity and prevents MoS 2 aggregation. The amorphous microstructures of MoS 2 prepared by a microwave heating method lead to more Mo edges or active sites exposed.

Tang, Wei↗

Rational Electrolyte Formulation for Sodium Metal Batteries Operating in Extremely Cold Environments

Sodium metal batteries have shown considerable potential when operated at ambient temperatures. However, their performance in cold environments is constrained by increased electrolyte resistance with decreasing temperature and dendritic sodium plating associated with unstable solid electrolyte interphase (SEI), which are primarily influenced by the electrolyte composition. In this study, we present an electrolyte formulation that remains thermally stable down to −150 °C, which not only facilitates low internal resistance but also contributes to the formation of a protective SEI under cryogenic conditions. When cycled at −40 °C at 1 mA cm −2 , the sodium metal electrode exhibits a low overpotential of only 16 mV over 750 h; even at an ultra-low temperature of −80 °C, the electrode demonstrates remarkable long-term stability with a low overpotential of 54 mV sustained over 1500 h at 0.5 mA cm −2 . Furthermore, full cell evaluations when paring with Na 3 V 2 (PO 4 ) 3 cathode reveal a high average Coulombic efficiency exceeding 99.1% and a capacity retention over 83% after 100 cycles at both −40 °C and −80 °C.

Electrolyte↗

The molten carbonate carbon dioxide concentrator - Cathode performance at high CO2 utilization

An experimental study of the cathode performance of the molten carbonate carbon dioxide concentrator (MCCDC) at typical gas concentrations is reported, and the behavior is described in terms of standard electrochemical kinetic analysis. Theoretical aspects of the MCCDC are discussed, including the current-generating processes, the overpotential, and the reaction kinetics. A final working equation is derived, and the electrochemical cell is described. The parameters determined by the experiments include cathode overpotentials and removal and current efficiency as a function of current density, as well as carbon dioxide removal rate as a function of flow rate. The results are compared with data for other cells; the agreement with data for the molten carbonate fuel cell suggests that the major difference between the two cells is in the wetting characteristics. The MCCDC achieves high removal efficiencies at high current efficiencies. The lowest current efficiency recorded was 80 percent, and at most current densities, current efficiencies were above 100 percent.

Weaver, J. L.↗

A High Performance H2-Cl2 Fuel Cell for Space Power Applications

NASA has numerous airborne/spaceborne applications for which high power and energy density power sources are needed. The proton exchange membrane fuel cell (PEMFC) is an attractive candidate for such a power source. PEMFC's offer many advantages for airborne/spaceborne applications. They have high power and energy densities, convert fuel to electrical power with high efficiency at both part and full load, and can rapidly startup and shutdown. In addition, PEMFC's are lightweight and operate silently. A significant impediment to the attainment of very high power and energy densities by PEMFC's is their current exclusive reliance on oxygen as the oxidant. Conventional PEMFC's oxidize hydrogen at the anode and reduce oxygen at the cathode. The electrode kinetics of oxygen reduction are known to be highly irreversible, incurring large overpotential losses. In addition, the modest open circuit potential of 1.2V for the H2-O2 fuel cell is unattainable due to mixed potential effects at the oxygen electrode. Because of the high overpotential losses, cells using H2 and O2 are capable of achieving high current densities only at very low cell voltages, greatly curtailing their power output. Based on experimental work on chlorine reduction in a gas diffusion electrode, we believe significant increases in both the energy and power densities of PEMFC systems can be achieved by employing chlorine as an alternative oxidant.

Anderson, Everett B.↗

A Dual Stage Sodium Thermo-Electro-Chemical Converter

The need for reliable and distributable energy sources is evident given the current forecasting of the world’s energy demand [1]. One prominent obstacle is the lack of an efficient direct heat-to-electricity conversion technology. The sodium thermo-electro-chemical converter (Na-TECC) is a highly efficient thermally regenerative electrochemical system (TRES) that can fill this void. The advantage of the Na-TECC over other direct conversion technologies is that it is a closed device (unlike fuel cells) requiring nothing more than a heat input (similar to thermoelectrics). It also has a high power density (> 1 W/cm2) and specific power up to 0.5 kW/kg , with the potential to achieve > 45% heat to electricity conversion efficiencies [2]. Furthermore, the converter rejects heat at a temperature hot enough to make it amenable for cogeneration, potentially under air-cooled operation. This electrochemical technology uses a special ion-selective solid-electrolyte called beta-alumina (Na2O•11Al2O3), that is highly conductive to sodium cations. A more conducting variation of this compound is beta”-alumina (Na2O•MgO•5Al2O3), where the magnesium acts as a stabilizer [3]. In the device, liquid sodium enters an evaporator where it is heated isobarically and vaporizes. The vapor is then oxidized at the interface between the anode and the solid-electrolyte. The Na-TECC generates electric power by allowing the high pressure oxidized sodium vapor ions to expand isothermally through the solid-electrolyte from the anode to the cathode. The liberated electrons are simultaneously conducted through an external load and recombine with the cations at the cathode. The low pressure sodium vapor is subsequently condensed and a wick pumps the liquid into the high pressure plenum to complete the cycle. Previous Na-TECCs have achieved efficiencies of 18% due to practical losses, whereas the potential efficiencies are above 45% [4]. Thermodynamic limitations and design constraints have limited previous devices from attaining these record efficiencies. Specifically, the maximum potential voltage in these previous devices was substantially reduced by the kinetic limitations of the charge transfer in the cathode (referred to as the overpotential) and by Joule heating losses due to the solid-electrolyte resistance, electrode resistance, and current collector resistance. Moreover, previous devices experienced a steady loss in performance throughout their lifetime. The drop in performance has been attributed to the electrolyte undergoing thermal and chemical breakdown due to crack propagation, loss of sodium oxide, and the formation of molten dendrites that create electrical shorts [5]. Finally, previous designs have also had a substantial problem with proper thermal management, with some showing thermal losses as great as 50% of the heat input. To improve the efficiency, a dual stage conversion process is being explored. Rather than using one isothermal expansion step, the dual cycle will employ two separate electrolytes to allow two separate expansion steps: one at the high temperature, and another at an intermediate temperature. This new cycle is thermodynamically favorable as it allows for regeneration from the isobaric cooling of the first expansion step, and reheat to complete the expansion in the second step. This allows the engine to reach a lower condenser temperature than its single stage counterpart, thus increasing the overall efficiency. The temperature drop across each electrolyte in the dual stage device (e.g., ~ 400 K) is smaller than the temperature drop across a comparable single stage device (e.g., ~ 800 K). This is amenable for better thermal management and allows for less heat loss. This will also mitigate the thermal shock across the very thin (< 1 mm) solid electrolytes, reduce crack propagation and limit the percolation of the molten dendrites, and ultimately increase the lifetime of the device. As an additional benefit the dual stage can be designed using planer geometries, rather than tubular geometries used in previous single stage models, which can be manufactured less expensively. This modified geometry can be tailored to improve the thermal management by reducing the radiation losses, which has been the biggest source of thermal losses [2]. A dual stage concept for the Na-TECC has never been demonstrated in literature. In this presentation, the operation of a single stage device will be revisited and, by adopting concepts used for similar converters, the thermodynamic operation of the dual stage will be developed [6]. Using the dual stage approach, the efficiency and power equations have been redefined to include regeneration and reheat. Questions such as what current densities optimize the power output or which intermediate temperature maximizes the efficiency will also be answered. Initial calculations of the dual stage show that the thermal management is the most sensitive parameter. Although the ideal voltage produced by the dual stage can be higher, there are potential drawbacks. For example, by using a lower condenser temperature the dual stage device will have a higher open circuit voltage, but it will also have a larger overpotential due to the limited cathodic kinetics that occur at a lower temperature. In short, there are several trade-offs in this device that need to be balanced. It will be demonstrated that the dual stage device must have lower thermal losses than a single stage device if it is to have a higher efficiency.

14 SOLAR ENERGY↗

Textile Inspired Lithium-Oxygen Battery Cathode with Decoupled Oxygen and Electrolyte Pathways

The lithium–air (Li–O 2 ) battery has been deemed one of the most promising next–generation energy–storage devices due to its ultrahigh energy density. However, in conventional porous carbon–air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile–based air cathode is developed with a triple–phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile–based Li–O 2 cathode exhibits a high discharge capacity of 8.6 mAh cm –2 , a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile–based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. In conclusion, the reported decoupled transport pathway design also spurs potential toward flexible/wearable Li–O 2 batteries.

25 ENERGY STORAGE↗

A 3D Lithiophilic Mo 2 N–Modified Carbon Nanofiber Architecture for Dendrite–Free Lithium–Metal Anodes in a Full Cell

The pursuit for high-energy-density batteries has inspired the resurgence of metallic lithium (Li) as a promising anode, yet its practical viability is restricted by the uncontrollable Li dendrite growth and huge volume changes during repeated cycling. Herein, a new 3D framework configured with Mo 2 N-mofidied carbon nanofiber (CNF) architecture is established as a Li host via a facile fabrication method. The lithiophilic Mo 2 N acts as a homogeneously pre-planted seed with ultralow Li nucleation overpotential, thus spatially guiding a uniform Li nucleation and deposition in the matrix. The conductive CNF skeleton effectively homogenizes the current distribution and Li-ion flux, further suppressing Li-dendrite formation. As a result, the 3D hybrid Mo 2 N@CNF structure facilitates a dendrite-free morphology with greatly alleviated volume expansion, delivering a significantly improved Coulombic efficiency of ≈99.2% over 150 cycles at 4 mA cm –2 . Symmetric cells with Mo 2 N@CNF substrates stably operate over 1500 h at 6 mA cm –2 for 6 mA h cm –2 . Furthermore, full cells paired with LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) cathodes in conventional carbonate electrolytes achieve a remarkable capacity retention of 90% over 150 cycles. Finally, this work sheds new light on the facile design of 3D lithiophilic hosts for dendrite-free lithium-metal anodes.

25 ENERGY STORAGE↗

Particle‐Size‐Dependent Lithium‐Ion Transport in PEO/LLZO Composite Electrolytes

Lithium-metal batteries with solid electrolytes can deliver higher energy density and improved safety than conventional Li-ion batteries. Among solid electrolyte candidates, polymer/ceramic composite electrolytes are attractive because they combine polymer flexibility with the high ionic conductivity of ceramics. However, whether ceramic fillers synergistically reduce polarization losses in the polymer matrix remains unclear. A central unknown is the critical polymer/ceramic interfacial resistance (Rint,crit), below which adding ceramics lowers electrolyte overpotential. Here, we present the first macroscale model framework to quantify R int,crit for composite electrolytes based on polyethylene oxide (PEO) and Ta-doped Li 7 La 3 Zr 2 O 12 (LLZO). A 1D model for DC-polarization of tri-layer cells (PEO-LiTFSI/LLZO/PEO-LiTFSI) shows that LLZO surface functionalization reduces the PEO/LLZO interfacial resistance, consistent with electrochemical impedance measurements. Extending to a 2D composite model, we show notably that Rint,crit scales linearly with LLZO particle diameter and shifts toward experimentally accessible values (e.g., 28.8 Ωcm 2 ) as particle size increases. At fixed ceramic volume fraction, larger LLZO particles reduce the number of interfacial crossings, driving more current through the ceramic phase and lowering concentration polarization. In contrast, R int,crit is largely independent of ceramic volume fraction. These results demonstrate that ceramic filler-size engineering can enable synergistic, energy-efficient transport in polymer/ceramic composite electrolytes.

25 ENERGY STORAGE↗

Regulating the product distribution of CO reduction by the atomic-level structural modification of the Cu electrode surface

Here, Cu catalyzes the electrochemical reduction of CO 2 or CO to an assortment of products, a behavior that is a detriment when only one reduced compound is desired. The present article provides an example in which, through the atomic-level control of the structure of the Cu electrode surface, the yield distribution is regulated to generate only one product. The reaction investigated was the preferential reduction of CO to C 2 H 5 OH on Cu at a low overpotential in alkaline solution. Experimental measurements combined electrochemical scanning tunneling microscopy (ECSTM) and differential electrochemical mass spectrometry (DEMS). An atomically ordered Cu(100) surface, prepared from either a single crystal or by Cu(pc)-to-Cu(100) reconstruction, did not produce ethanol. When the surfaces were subjected to monolayer-limited Cu↔Cu 2 O cycles, only the reconstructed surface underwent an additional structural transformation that spawned the selective production of ethanol at a potential 645 mV lower than that which generates multiple products. Quasi-operando ECSTM indicated transformation to an ordered stepped surface, Cu(S) [3(100)×(111)], or Cu(511). The non-selective, multiple-product Cu-catalyzed reduction of CO had thus been regulated to yield only one liquid fuel by an atomic-level structural modification of the electrode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of various parameters of different porous transport layers in proton exchange membrane water electrolysis

Porous transport layers (PTLs) play an important role in proton exchange membrane water electrolysis (PEMWE) cells. The PTL facilitates water and gas transport, as well as thermal and electrical conduction, and is required to sustain good contact with adjacent components. It is expected that using PTLs with variations in material properties such as structure, composition, thickness and wettability results in performance changes of the PEMWE. Here, a general mathematical PEMWE model is developed that separates and analyzes the contributions of ohmic, activation, diffusion and Nernst potentials. For model validation, three inherently different anode PTL structures (carbon paper, sintered titanium particles, and titanium felt) are operated over a range of conditions. Additionally, the effects of PTL wettability were used to verify the model using Polytetrafluoroethylene (PTFE) treated Toray papers with PTFE loading ranging from 0% to 20%. The modeling results of both PTFE treated and untreated materials show good agreement with the experimental data. Mass transport or diffusion loss is the primary reason for performance differences between PTFE treated and untreated PTLs. Sintered titanium PTLs with thicknesses above 1 mm suffer from up to 33% increased ohmic losses without indicating any obvious changes in activation and diffusion losses when compared to untreated PTLs. The losses of the cell increase when using PTFE treated Toray paper. Individual contributions are quantified and assigned to increased ohmic, activation, and diffusion losses. In conclusion, the proposed model offers insights into the overpotential contributions of a PEMWE. It is a useful tool for predicting performance of various PTL materials and can be applied for PTL development and optimization efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Retrofitting of carbon-supported bimetallic Ni-based catalysts by phosphorization for hydrogen evolution reaction in acidic media

Commercial bimetallic Ni–Mo and Ni–Re electrocatalysts supported on advanced conductive carbon are high-performing materials for H 2 evolution reaction in alkaline medium, but they cannot be applied in acidic medium due to the rapid dissolution of metals. Here, in this work, we solve this issue by introducing a convenient phosphorization protocol to convert these commercial metallic electrocatalysts into the respective phosphides, rendering them stable under acidic conditions, and thus providing a pathway to electrocatalysts for water reduction in acidic electrolyte. The novel materials demonstrate high performance, as reflected by the measured low overpotentials, shallow Tafel slopes, fast kinetics, as well as excellent stability and durability. This work opens the possibility to expand the applicability of commercial supported metallic catalysts and electrocatalysts through retrofitting via phosphorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Durability evaluation of a Fe–N–C catalyst in polymer electrolyte fuel cell environment via accelerated stress tests

In this work, an “atomically-dispersed” iron-nitrogen-carbon (Fe–N–C) catalyst was used to provide a systematic comparison of platinum group metal (PGM)-free electrocatalyst degradation as a function of accelerated stress tests (ASTs) in an acidic polymer electrolyte fuel cell (PEFC). It was determined that the majority of catalyst degradation was caused by cell operation in presence of O 2 . In contrast, potential cycling of the Fe–N–C-containing cathode under inert atmosphere over typical PEFC cathode operation from 0.95 to 0.6 V had little to no effect. The increase in kinetic overpotential is shown to be the major source of the PEFC performance decrease during the ASTs. These results continue to showcase the need for development of robust PGM-free electrocatalysts in concert with improved electrochemical performance.

25 ENERGY STORAGE↗

Charge Transport Properties of Lithium Superoxide in Li–O 2 Batteries

The theoretical energy density of lithium–oxygen (Li–O 2 ) batteries is extremely high, although there are many challenges that must be overcome to achieve high energy density in a manufactured cell. For example, little is known about the properties of one of the key intermediates, lithium superoxide (LiO 2 ), which until recently had not been stabilized in bulk form. In this work, lithium superoxide was deposited onto iridium–reduced graphene oxide (Ir–rGO) cathodes in a Li–O 2 system under a flow of O 2 . Lithium peroxide (Li 2 O 2 ) was subsequently produced on the cathode surface in an inert Ar atmosphere. Based on a detailed analysis of electrochemical impedance spectroscopy data, it was demonstrated experimentally for the first time that the charge transport resistance through LiO 2 was much lower than for Li 2 O 2 and correlated with lower LiO 2 charge overpotentials. We report this result indicates that LiO 2 has good electronic conductivity and confirms previous theoretical predictions that bulk LiO 2 has better charge transport properties than Li 2 O 2 . In addition, impedance and other characterization of Li 2 O 2 formation from LiO 2 in an Ar atmosphere revealed that when surface-mediated Li 2 O 2 formation occurs, it has a significantly lower discharge potential than when it forms through a solution-phase-mediated process. These significant findings will contribute to the development of Li–O 2 batteries through better understanding of LiO 2 properties and formation mechanisms.

25 ENERGY STORAGE↗

Nickel Sulfide-Nanowire-Filled Carbon Nanotubes as an Efficient Overall Water Splitting Electrocatalyst

Pursuing stable, efficient, and cost-effective nanostructured bifunctional electrocatalysts is crucial for advancing the electrochemical water splitting process and enabling clean hydrogen energy production. In recent years, considerable efforts have focused on developing highly efficient and durable commercial electrocatalysts for the oxygen evolution reaction (OER) and overall water splitting (OWS). This research introduces an OWS electrocatalyst-nickel sulfide-filled carbon nanotubes grown on a carbon cloth substrate (Ni 3 S 2 @CNTs/CC), synthesized via a one-step in-situ process. The synergistic integration of metal sulfide (Ni 3 S 2 ) and carbon nanotubes provides abundant active sites for catalytic reactions, ensuring a robust composite nanostructure with enhanced durability. Furthermore, the electrocatalytic performance for OER and OWS has been significantly improved by a simple acid treatment to the electrocatalysts, which introduces physical and chemical defects, particularly oxygen functional groups (the acid-treated sample is termed as Ni 3 S 2 @CNTs/CC-AT). As OER electrocatalysts, Ni 3 S 2 @CNTs/CC and Ni 3 S 2 @CNTs/CC-AT present overpotentials of 304 and 200 mV, respectively, for achieving a current density of 10 mA/cm 2 in the OER process. Furthermore, for complete water splitting in 1.0 M KOH electrolyte, Ni 3 S 2 @CNTs/CC and Ni 3 S 2 @CNTs/CC-AT exhibit potentials of 1.63 and 1.44 V, respectively, to achieve a current density of 10 mA/cm 2 when employed as both anode and cathode. Moreover, Ni 3 S 2 @CNTs/CC and Ni 3 S 2 @CNTs/CC-AT demonstrate durable nature for 22 and 20 h durability in the OER and OWS processes, respectively, offering a promising alternative to ruthenium- and iridium-based electrocatalysts for electrochemical hydrogen production through water splitting. In conclusion, the in-situ synthesis method and acid treatment strategy described in this research are promising approaches to fabricating high-performance encapsulated carbon-nanotube-based electrocatalysts.

36 MATERIALS SCIENCE↗

Along the Channel Gradients Impact on the Spatioactivity of Gas Diffusion Electrodes at High Conversions during CO 2 Electroreduction

Results of a 2-D transport model for a gas diffusion electrode performing CO 2 reduction to CO with a flowing catholyte are presented, including the concentration gradients along the flow cell, spatial distribution of the current density and local pH in the catalyst layer. The model predicts that both the concentration of CO 2 and the buffer electrolyte gradually diminish along the channels for a parallel flow of gas and electrolyte as a result of electrochemical conversion and nonelectrochemical consumption. At high single-pass conversions, significant concentration gradients exist along the flow channels leading to large local variations in the current density (>150 mA/cm 2 ), which becomes prominent when compared to ohmic losses. In addition, concentration overpotentials change dramatically with CO 2 flow rate, which results in significant differences in outlet concentrations at high conversions. The outlet concentration of CO attains a maximum of 80% along with 5% CO 2 and 15% H 2 , although the maximum single-pass conversion is limited to below 60% due to homogeneous consumption by the electrolyte. Fundamental and practical implications of our findings on electrochemical CO 2 reduction are discussed with a focus on the trade-off between high current density operation and high single-pass conversion efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of ionic blockades in controlling the efficiency of energy recovery in forward bias bipolar membranes

Limited understanding exists about the operation of bipolar membranes (BPMs) in forward bias to convert protonic gradients into electrical work, despite their emerging role in many electrochemical devices. In these device contexts, the BPM is typically exposed to complex electrolyte mixtures, but their impact on polarization remains poorly understood. Here, for this work, we develop a mechanistic model explaining the forward bias polarization behaviour of BPMs in mixed electrolytes with different acidities/basicities. This model invokes that weak acids/bases accumulate in the BPM and impose an ionic blockade that inhibits the recombination of stronger acids/bases, resulting in a substantial neutralization overpotential. We demonstrate the utility of our model for fuel cells and redox flow batteries and introduce two materials design strategies for mitigating this inhibition. Lastly, we apply our findings to enhance the energy efficiency of carbonate management in CO 2 electrolysers. This work highlights how non-equilibrium local environments at membrane–membrane interfaces can define the efficiency of protonic-to-electrical energy conversion.

25 ENERGY STORAGE↗