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At least 1,099 records · Page 61

Ionomer-free and recyclable porous-transport electrode for high-performing proton-exchange-membrane water electrolysis

Abstract Clean hydrogen production requires large-scale deployment of water-electrolysis technologies, particularly proton-exchange-membrane water electrolyzers (PEMWEs). However, as iridium-based electrocatalysts remain the only practical option for PEMWEs, their low abundance will become a bottleneck for a sustainable hydrogen economy. Herein, we propose high-performing and durable ionomer-free porous transport electrodes (PTEs) with facile recycling features enabling Ir thrifting and reclamation. The ionomer-free porous transport electrodes offer a practical pathway to investigate the role of ionomer in the catalyst layer and, from microelectrode measurements, point to an ionomer poisoning effect for the oxygen evolution reaction. The ionomer-free porous transport electrodes demonstrate a voltage reduction of > 600 mV compared to conventional ionomer-coated porous transport electrodes at 1.8 A cm −2 and <0.1 mg Ir cm −2 , and a voltage degradation of 29 mV at average rate of 0.58 mV per 1000-cycles after 50k cycles of accelerated-stress tests at 4 A cm −2 . Moreover, the ionomer-free feature enables facile recycling of multiple components of PEMWEs, which is critical to a circular clean hydrogen economy.

08 HYDROGEN↗

A layered Prussian blue analogue as fast-charging negative electrode material for lithium-ion batteries

The simultaneous achievement of fast-charging and high specific capacity remains a critical challenge for lithium-ion battery negative electrodes. Here we report a layered manganese-based Prussian blue analogue, synthesized through vacancy control and subsequent thermal transformation. As a conversion-type negative electrode, this material exhibits high-rate performance, delivering a specific capacity of 510 mAh g −1 at a specific current of 8 A g −1 , and operates at a moderate average voltage of approximately 1.2 V vs. Li/Li + , which mitigates lithium plating risks. This high-rate capability stems from the analogue’s specific linkage configurations, which facilitate a high content of active transition metal and strong Li+ adsorption at nitrogen sites. The high transition metal content enables a high reversible capacity, while strong Li + adsorption promotes an efficient initial crystalline-to-amorphous transformation. This process induces dynamically reversible component migration during subsequent cycling, thereby enhancing conversion reaction kinetics. Our findings provide insights into the application of Prussian blue analogues as fast-charging negative electrode materials. The development of fast-charging and high-capacity negative electrodes is critical for advanced lithium-ion batteries. Here, authors use a vacancy engineering strategy to develop a layered Prussian blue analogue with competitive rate capability, delivering a specific capacity of 510 mAh g −1 at a specific current of 8 A g −1 .

25 ENERGY STORAGE↗

Electrochemically induced amorphous-to-rock-salt phase transformation in niobium oxide electrode for Li-ion batteries

Intercalation-type metal oxides are promising negative electrode materials for safe rechargeable lithium-ion batteries due to the reduced risk of Li plating at low voltages. Nevertheless, their lower energy and power density along with cycling instability remain bottlenecks for their implementation, especially for fast-charging applications. Here, we report a nanostructured rock-salt Nb 2 O 5 electrode formed through an amorphous-to-crystalline transformation during repeated electrochemical cycling with Li + . This electrode can reversibly cycle three lithiums per Nb 2 O 5 , corresponding to a capacity of 269 mAh g –1 at 20 mA g –1 , and retains a capacity of 191 mAh g –1 at a high rate of 1 A g –1 . Further, it exhibits superb cycling stability with a capacity of 225 mAh g –1 at 200 mA g –1 for 400 cycles, and a Coulombic efficiency of 99.93%. We attribute the enhanced performance to the cubic rock-salt framework, which promotes low-energy migration paths. Our work suggests that inducing crystallization of amorphous nanomaterials through electrochemical cycling is a promising avenue for creating unconventional high-performance metal oxide electrode materials.

25 ENERGY STORAGE↗

Self-replenishing Ni-rich stainless-steel electrode toward oxygen evolution reaction at ampere-level

In the past few decades, tremendous attention has been devoted to enhancing the activity of oxygen evolution reaction (OER) catalysts for hydrogen production, while the cost and long-term stability of catalysts, which can play an even more important role in industrialization, have been much less emphasized. Herein, we engineered an OER electrode from abundant stainless steel (SS) via facile approaches, and the obtained electrode consists of a Ni-rich oxide surface layer with a Fe-rich metal substrate. An outstanding activity was observed with an overpotential of 316 mV at 100 mA cm −2 in 1 M KOH electrolyte. Additionally, an electrode self-replenishing concept is proposed in which a Ni-rich catalyst layer can be regenerated from a metallic substrate due to the difference in diffusion and dissolution rates of metal oxides/hydroxides, and this regeneration is validated by various characterizations. A recorded degradation rate of 0.012 was observed at 1000 mA cm −2 for 1000 h. The facile engineering of OER electrodes from SS combined with the self-replenishing catalyst can potentially address the cost, activity, and long-term stability barriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metabolic spatial variability in electrode-respiring Geobacter sulfurreducens biofilms

Certain bacteria are capable of transferring electrons derived from respiratory metabolism to solid extracellular electron-accepting materials1-4. This ability allows the organisms to use conductive substrata as their sole electron sink, generating electricity that is available for practical applications5-7. Geobacter is a biofilm-forming genus capable of this extracellular electron transfer8-11. Evidence in the literature suggests that Geobacter cells produce a conductive matrix to gain access to electron-accepting surfaces12,13. It has been hypothesized that cells that are more than tens of microns from the electron-accepting surface cannot respire because of electrical resistance in the matrix and thus remain metabolically inactive14-16. To test this hypothesis, we sought to determine whether the entire biofilm remains metabolically active and able to respire on an electron-accepting surface as the biofilm thickness increases. We developed and used a novel electrochemical-nuclear magnetic resonance (EC-NMR) microimaging system capable of sustaining an electrochemically active biofilm on a polarized electrode inside a superconducting magnet, allowing for simultaneous NMR and electrochemical investigation of a biofilm for the first time. Here, we show that Geobacter biofilms can grow to several hundred microns thick while respiring on an electrode and that the top of the biofilm remains metabolically active. This is only possible if the cells near the top are able to transfer electrons through the initial biofilm matrix to the electrode. We used X-ray absorption spectroscopy to verify electron transfer to uranium ions by metabolically active cells near the top of the biofilm. Our results reveal that extracellular electron transfer is not prevented by electrical resistance, even when the biofilm is hundreds of microns thick. Furthermore, the electron donor may be the limiting factor for respiration and the base of the biofilm may be less active despite being in close proximity to the electrode. Long-range electron transfer across metabolically inactive regions within Geobacter biofilms adds a novel facet to our comprehension of electrochemically active biology.

ANODE↗

Nanomaterials for bio-functionalized electrodes: recent trends

This review intends to highlight the interest of nanomaterials for building biologically-modified electrodes. Rather than giving a comprehensive overview of the topic, the present work intends to give a flavour on the most exciting achievements and most recent approaches to get (and use) nanostructured electrode surfaces (or electrodes modified with nano-objects) comprising biomolecules. It will mainly consider nano-engineered functional polymers, nano-sized objects such as nanoparticles, carbon nanotubes, graphene or related materials, as well as template-based nanostructures, as modifiers for bio-functionalised electrodes.

biosensors↗

Is Cu a stable electrode material in hybrid perovskite solar cells for a 30-year lifetime?

One grand challenge for long-lived perovskite solar cells is that the common electrode materials in solar cells, such as silver and aluminum or even gold, strongly react with hybrid perovskites. Here we report the evaluation of the potential of copper (Cu) as the electrode material in perovskite solar cells for long-term stability. In encapsulated devices which limit exposure to oxygen and moisture, Cu in direct contact with CH 3 NH 3 PbI 3 showed no reaction at laboratory time scales, and is predicted to be stable for almost 170 years at room temperature and over 22 years at the nominal operating cell temperature of 40 °C. No diffusion of Cu into CH 3 NH 3 PbI 3 has been observed after thermal annealing for over 100 hours at 80 °C, nor does Cu cause charge trap states in direct contact with CH 3 NH 3 PbI 3 after long-term thermal annealing or illumination. High performance devices with efficiency above 20% with Cu electrode retains 98% of the initial efficiency after 816 hours storage in ambient environment without encapsulation. Finally, the results indicate Cu is a promising low-cost electrode material for perovskite solar cells for long-term operation.

25 ENERGY STORAGE↗

Porous carbon derived from aniline-modified fungus for symmetrical supercapacitor electrodes

N incorporated carbon materials are proven to be efficient EDLCs electrode materials. In this work, aniline modified fungus served as a raw material, and N-doped porous activated carbon is prepared via an efficient KOH activation method. A porous network with a high specific surface area of 2339 m 2 g -1 is displayed by the prepared carbon material, resulting in a high accessible surface area and low ion diffusion resistance which is desirable for EDLC electrode materials. In assembled EDLCs, the N–AC based electrode exhibits a specific capacitance of 218 F g -1 at a current density of 0.1 A g -1 . Besides, excellent stability is displayed after 5000 continuous cycles at different current densities ranging from 0.1 to 10 A g -1 . Thus, the present work reveals a promising candidate for electrode materials of EDLCs.

36 MATERIALS SCIENCE↗

Modeling gas-diffusion electrodes for CO 2 reduction

CO 2 reduction conducted in electrochemical cells with planar electrodes immersed in an aqueous electrolyte is severely limited by mass transport across the hydrodynamic boundary layer. This limitation can be minimized by use of vapor-fed, gas-diffusion electrodes (GDEs), enabling current densities that are almost two orders of magnitude greater at the same applied cathode overpotential than what is achievable with planar electrodes in an aqueous electrolyte. The addition of porous cathode layers, however, introduces a number of parameters that need to be tuned in order to optimize the performance of the GDE cell. In this study, we develop a multiphysics model for gas diffusion electrodes for CO 2 reduction and used it to investigate the interplay between species transport and electrochemical reaction kinetics. The model demonstrates how the local environment near the catalyst layer, which is a function of the operating conditions, affects cell performance. Finally, we also examine the effects of catalyst layer hydrophobicity, loading, porosity, and electrolyte flowrate to help guide experimental design of vapor-fed CO 2 reduction cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomically dispersed metal–nitrogen–carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement

The urgent need to address the high-cost issue of proton-exchange membrane fuel cell (PEMFC) technologies, particularly for transportation applications, drives the development of simultaneously highly active and durable platinum group metal-free (PGM-free) catalysts and electrodes. The past decade has witnessed remarkable progress in exploring PGM-free cathode catalysts for the oxygen reduction reaction (ORR) to overcome sluggish kinetics and catalyst instability in acids. Among others, scientists have identified the newly emerging atomically dispersed transition metal (M: Fe, Co, or/and Mn) and nitrogen co-doped carbon (M–N–C) catalysts as the most promising alternative to PGM catalysts. Here, we provide a comprehensive review of significant breakthroughs, remaining challenges, and perspectives regarding the M–N–C catalysts in terms of catalyst activity, stability, and membrane electrode assembly (MEA) performance. A variety of novel synthetic strategies demonstrated effectiveness in improving intrinsic activity, increasing active site density, and attaining optimal porous structures of catalysts. Rationally designing and engineering the coordination environment of single metal MN x sites and their local structures are crucial for enhancing intrinsic activity. Increasing the site density relies on the innovative strategies of restricting the migration and agglomeration of single metal sites into metallic clusters. Relevant understandings provide the correlations among the nature of active sites, nanostructures, and catalytic activity of M–N–C catalysts at the atomic scale through a combination of experimentation and theory. Current knowledge of the transferring catalytic properties of M–N–C catalysts to MEA performance is limited. Rationally designing morphologic features of M–N–C catalysts play a vital role in boosting electrode performance through exposing more accessible active sites, realizing uniform ionomer distribution, and facilitating mass/proton transports. We outline future research directions concerning the comprehensive evaluation of M–N–C catalysts in MEAs. The most considerable challenge of current M–N–C catalysts is the unsatisfied stability and rapid performance degradation in MEAs. Therefore, we further discuss practical methods and strategies to mitigate catalyst and electrode degradation, which is fundamentally essential to make M–N–C catalysts viable in PEMFC technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO 2 electrochemical reduction at thiolate-modified bulk Au electrodes

Electrochemical reduction provides an opportunity to convert atmospheric CO 2 to fuels or chemicals using renewable energy. Here, we demonstrate unexpected influence on the catalytic activity and selectivity of the electrochemical CO 2 reduction reaction (CO 2 RR) through the functionalization of Au with thiols. 2-Phenylethanethiol modified Au electrodes (2-PET-Au) show up to a 2-fold enhancement in both Faradaic efficiency and current density for CO evolution, between –0.6 and –0.9 V vs. the reversible hydrogen electrode. Functionalization with 2-mercaptopropionic acid, which has a readily ionized carboxylate group, leads to hydrogen evolution with up to 100% Faradaic efficiency at the expense of CO evolution. Remarkably, the adsorption of certain thiols on Au does not have a negative impact on the total current density compared to blank Au. We present evidence that it is due to ligand-induced reconstruction of Au surfaces resulting in the creation of structurally and chemically modified local reaction environments. Thus a thiol species such as 2-PET, which does not contain any nitrogen-based heterocycle with a charge transfer center, can induce the formation of active sites on Au that are electrochemically active toward CO 2 RR within the range of electrode potential that most of the ligand concentration remains stable on Au. Our findings suggest a simple, effective, and tunable way to modify the activity and selectivity of Au electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

N-Doped carbon nanoparticles on highly porous carbon nanofiber electrodes for sodium ion batteries

Nitrogen doped carbon nanoparticles on highly porous carbon nanofiber electrodes were successfully synthesized via combining centrifugal spinning, chemical polymerization of pyrrole and a two-step heat treatment. Nanoparticle-on-nanofiber morphology with highly porous carbon nanotube like channels were observed from SEM and TEM images. Nitrogen doped carbon nanoparticles on highly porous carbon nanofiber (N-PCNF) electrodes exhibited excellent cycling and C-rate performance with a high reversible capacity of around 280 mA h g -1 in sodium ion batteries. Moreover, at 1000 mA g -1 , a high reversible capacity of 172 mA h g -1 was observed after 300 cycles. The superior electrochemical properties were attributed to a highly porous structure with enlarged d-spacings, enriched defects and active sites due to nitrogen doping. The electrochemical results prove that N-PCNF electrodes are promising electrode materials for high performance sodium ion batteries.

25 ENERGY STORAGE↗

Quantitative local state of charge mapping by operando electrochemical fluorescence microscopy in porous electrodes

We introduce operando quantitative electrochemical fluorescence state of charge mapping (QEFSM), a non-invasive technique to study operating electrochemical systems along with a new design of optically transparent microfluidic redox flow cells compatible with the most demanding optical requirements. QEFSM allows quantitative mappings of the concentration of a particular oxidation state of a redox-active species within a porous electrode during its operation. In this study, we used confocal microscopy to map the fluorescence signal of the reduced form of 2,7-anthraquinone disulfonate (AQDS) in a set of multistep-chronoamperometry experiments. Calibrating these images and incorporating an analytical model of quinhydrone heterodimer formation with no free parameters, and accounting for the emission of each species involved, we determined the local molecular concentration and the state of charge (SOC) fields within a commercial porous electrode during operation. With this method, electrochemical conversion and species advection, reaction and diffusion can be monitored at heretofore unprecedented transverse and axial resolution (1 μm and 25 μm, respectively) at frame rates of 0.5 Hz, opening new routes to understanding local electrochemical processes in porous electrodes. Here, we observed pore-scale SOC inhomogeneities appearing when the fraction of electroactive species converted in a single pass through the electrode becomes large.

42 ENGINEERING↗

Mass spectral molecular mapping shows benefits of thermal evaporation in prelithiated silicon-based electrodes

Silicon based composites have become increasingly popular as potential anodes for lithium-ion batteries due to their large storage capacity and potential ability to generate batteries with energy densities greater than 350 Wh kg −1 . These anodes often see reduced initial columbic efficiency (ICE) due to disruptive volume expansionup to 300% and continuous solid electrolyte interphase (SEI) layer formation. Prelithiation, where an excess reservoir of Li is added to the electrode to compensate for irreversible SEI formation losses during their sample preparation, has proven to solve the issue of immediate capacity loss. Thermal evaporation is a prelithiation technique with limited studies on its effectiveness. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to highlight the benefits of prelithiation via thermal evaporation. ToF-SIMS provides chemical mapping and spatial information in 2D and 3D visualizing the deposition of lithium, identifying Li x Si y alloy and Li x Si y O z silicate formation, and the distribution of lithium passivation into the electrodes. Passivation under different atmospheric conditions, such as inert Argon (Ar) and Ar/ carbon dioxide (CO 2 ), highlights the impact of the environment on the passivation effectiveness and formation of Li x Si y alloy and Li x Si y O z silicate. The ToF-SIMS molecular imaging and depth profiling results indicate that prelithiation via thermal evaporation effectively distributes lithium throughout the depth profile thickness of several hundred nanometers. It induces a greater degree of Li x Si y O z silicate formation over Li x Si y alloy. Our ToF-SIMS characterization results show the effectiveness of thermal evaporation in producing a more stable electrode and an electrode with an effective lithium reserve that can preserve its capacity.

Parker, Gabriel D. [Oak Ridge National Laboratory ↗

Optimized electrode placement along the channel of a Hall thruster for ion focusing

An optimal placement of the segmented electrode for increasing the lifetime of the Aton-type Hall thruster, i.e., reducing the plume divergence, is demonstrated using a 2D3V fully kinetic Particle-in-Cell method. Segmented electrodes, embedded near the ionization region of non-segmented case and biased above anode potential, lead to an increased separation between the ionization and acceleration regions and the formation of an efficient acceleration electric field configuration as potential lens. Due to this electrode placement, the sheath near the ceramic walls of the acceleration region is collapsed and an excellent ion beam focusing is demonstrated. The potential contour pockets around the electrodes and the sheath collapse phenomenon are also discussed.

43 PARTICLE ACCELERATORS↗

Indium tin oxide-free transparent and conductive electrode based on SnO{sub x} | Ag | SnO{sub x} for organic solar cells

A SnO{sub x} | Ag | SnO{sub x} multilayer deposited by E-beam evaporation is proposed as transparent anode for a (poly-3-hexylthiophene):[6,6]-phenyl-C{sub 61}-butyric acid methyl ester (P3HT:PCBM) bulk heterojunction based Organic Solar Cell (OSC). Such multilayers are studied and manufactured with the objective to give to the electrode its best conductivity and transparency in the visible spectral range. A transfer matrix method numerical optimization of the thicknesses of each layer of the electrode is developed to limit the number of test samples which would have been manufactured whether an empirical method was chosen. Optical characterization of the deposited SnO{sub x} and Ag thin films is performed to determine the dispersion of the complex refractive indices which are used as input parameters in the model. A satisfying agreement between numerical and experimental optical properties is found. The bare tri-layer electrodes show low sheet resistance (as low as 6.7 Ω/□) and the whole Glass | SnO{sub x} | Ag | SnO{sub x} structure presents a mean transparency on 400–700 nm spectral band as high as 67%. The multilayer is then numerically studied as anode for a P3HT:PCBM bulk heterojunction based OSC. Intrinsic absorption inside the sole active layer is calculated giving the possibility to perform optical optimization on the intrinsic absorption efficiency inside the active area by considering the media embedding the electrodes. An additional study using the morphology of the silver inserted between both oxide layers as input data is performed with a finite difference time domain 3D-method to improve the accordance between optical measurements and numerical results.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Solvothermal synthesis of NiAl double hydroxide microspheres on a nickel foam-graphene as an electrode material for pseudo-capacitors

In this paper, we demonstrate excellent pseudo-capacitance behavior of nickel-aluminum double hydroxide microspheres (NiAl DHM) synthesized by a facile solvothermal technique using tertbutanol as a structure-directing agent on nickel foam-graphene (NF-G) current collector as compared to use of nickel foam current collector alone. The structure and surface morphology were studied by X-ray diffraction analysis, Raman spectroscopy and scanning and transmission electron microscopies respectively. NF-G current collector was fabricated by chemical vapor deposition followed by an ex situ coating method of NiAl DHM active material which forms a composite electrode. The pseudocapacitive performance of the composite electrode was investigated by cyclic voltammetry, constant charge–discharge and electrochemical impedance spectroscopy measurements. The composite electrode with the NF-G current collector exhibits an enhanced electrochemical performance due to the presence of the conductive graphene layer on the nickel foam and gives a specific capacitance of 1252 F g{sup −1} at a current density of 1 A g{sup −1} and a capacitive retention of about 97% after 1000 charge–discharge cycles. This shows that these composites are promising electrode materials for energy storage devices.

36 MATERIALS SCIENCE↗

White organic light-emitting diodes with 4 nm metal electrode

We investigate metal layers with a thickness of only a few nanometers as anode replacement for indium tin oxide (ITO) in white organic light-emitting diodes (OLEDs). The ultrathin metal electrodes prove to be an excellent alternative that can, with regard to the angular dependence and efficiency of the OLED devices, outperform the ITO reference. Furthermore, unlike ITO, the thin composite metal electrodes are readily compatible with demanding architectures (e.g., top-emission or transparent OLEDs, device unit stacking, etc.) and flexible substrates. Here, we compare the sheet resistance of both types of electrodes on polyethylene terephthalate for different bending radii. The electrical performance of ITO breaks down at a radius of 10 mm, while the metal electrode remains intact even at radii smaller than 1 mm.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗