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At least 109 records · Page 6

Optimization of Extended-Surface PtNi Nanowire Oxygen Reduction Electrocatalysts Produced via Atomic Layer Deposition

Polymer electrolyte membrane fuel cells (PEMFCs) produce electricity with only heat and water as byproducts, but sluggish kinetics of the oxygen reduction reaction (ORR) at the cathode and durability limitations restrict widespread commercialization, motivating the development of advanced catalysts. In this research, extended-surface platinum nickel (PtNi) nanowires (NWs) synthesized using the scalable atomic layer deposition (ALD) technique are investigated with the goal of exploring the durability benefits of high-aspect-ratio electrocatalysts and the tunability of beneficial kinetic properties. The surface and bulk composition and the structure of the PtNi NWs were investigated as a function of a series of postsynthesis modifications. The results from a combination of electron microscopy and X-ray spectroscopy characterization techniques were correlated to electrochemical performance to gain a comprehensive understanding of the structure-property-performance relationships. The robust structure of the ALD-derived NWs enabled additional postsynthesis optimization steps, which were not possible with previous-generation materials synthesized via spontaneous galvanic displacement, resulting in a catalyst with beneficial properties for catalyst kinetics as well as improved durability. Our study demonstrates potential pathways toward further improving the performance of this class of materials through optimization of bulk and surface properties of the catalyst.

30 DIRECT ENERGY CONVERSION↗

Resonant X-ray Diffraction Reveals the Location of Counterions in Doped Organic Mixed Ionic Conductors

Organic mixed ionic–electronic conductors (OMIECs) have the potential to enable diverse new technologies, ranging from novel in situ biosensors to flexible energy storage devices and neuromorphic computing platforms. However, their complex behavior in functional films involving electrolyte-induced swelling, ion ingress, and electrochemical doping inhibits rational material design. Of critical importance is an understanding of the specific location of the ions in the volumetrically doped material, yet this information is not readily available. Here, in this report, we present the use of grazing- incidence resonant X-ray diffraction (RXRD, also known as anomalous diffraction) at S and Cl K-edges to determine the structure of a doped, prototypical, semicrystalline polymer OMIEC based on oligo(ethylene glycol) substitution of regioregular polythiophene. The RXRD measurement provides two key insights. Quantitative analysis of the RXRD allows the determination of the position of the ion relative to the polymer backbone in the crystalline regions. We find that the anion is relatively distant from the backbone, nearer to the lamella mid-plane naively in conflict with expected Coulombic attraction between the ion and the doped polymer polaron. Comparison of RXRD to Cl – fluorescence (total Cl – ) allows determination of the relative order of doping between the crystalline and amorphous regions. We find preferential doping of the crystalline regions. Both insights, the preferential doping of crystals at low potential and the specific location of the counterion with respect to the polymer backbone, are critical to developing a microscopic understanding of transport in OMIECs.

36 MATERIALS SCIENCE↗

Electrochemical Random-Access Memory: Progress, Perspectives, and Opportunities

Non-von Neumann computing using neuromorphic systems based on analogue synaptic and neuronal elements has emerged as a potential solution to tackle the growing need for more efficient data processing, but progress toward practical systems has been stymied due to a lack of materials and devices with the appropriate attributes. Recently, solid state electrochemical ion-insertion, also known as electrochemical random access memory (ECRAM) has emerged as a promising approach to realize the needed device characteristics. ECRAM is a three terminal device that operates by tuning electronic conductance in functional materials through solid-state electrochemical redox reactions. This mechanism can be considered as a gate-controlled bulk modulation of dopants and/or phases in the channel. Early work demonstrating that ECRAM can achieve nearly ideal analogue synaptic characteristics has sparked tremendous interest in this approach. More recently, the realization that electrochemical ion insertion can be used to tune the electronic properties of many types of materials including transition metal oxides, layered two-dimensional materials, organic and coordination polymers, and that the changes in conductance can span orders of magnitude has further attracted interest in ECRAM as the basis for analogue synaptic elements for inference accelerators as well as for dynamical devices that can emulate a wide range of neuronal characteristics for implementation in analogue spiking neural networks. At its core, ECRAM shares many fundamental aspects with rechargeable batteries, where ion insertion materials are used extensively for their ability to reversibly store charge and energy. Computing applications, however, present drastically different requirements: systems will require many millions of devices, scaled down to tens of nanometers, all while achieving reliable electronic-state tuning at scaled-up rates and endurances, and with minimal energy dissipation and noise. Further, in this review, we discuss the history, basic concepts, recent progress, as well as the challenges and opportunities for different types of ECRAM, broadly grouped by their primary mobile ionic charge carrier, including Li, protons, and oxygen vacancies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Additive-Induced Morphology Change of Polymer Film Enables Enhanced Charge Mobility and Faster Organic Electrochemical Transistor Switching

Conjugated polymers (CPs) play an important role in organic electrochemical transistors (OECTs) for bioelectronics and related applications, where they serve as channel materials. Currently, most successful polymers for CPs are re-engineered from traditional CPs by replacing hydrophobic alkyl side chains with hydrophilic ethylene glycol or ionic groups. Frustratingly, the enhanced ion transport often compromises the charge mobility of the original CP. In this work, we present an additive-mediated method to construct a modified poly(3-hexylthiophene) (P3HT) film to enable efficient ion migration. The additive is designed with a cleavable diazo group that releases nitrogen and 2-methoxyethanol, a volatile compound, to alter the P3HT film morphology. OECTs based on the film exhibit improved response times. Interestingly, the process also enhances the crystallinity of P3HT, leading to higher hole mobility compared with pristine P3HT. This study proposes an in situ strategy to achieve the functionality of the OMIEC via morphological regulation, offering a promising route to simultaneously enhance both ion accessibility and charge mobility.

Organic polymers↗

Self-adhesive ionomers for durable low-temperature anion exchange membrane electrolysis

Low-temperature water electrolysis using an anion conductive polymer electrolyte has several potential advantages over other technologies, however, the fabrication of durable alkaline electrodes remains a challenge. Detachment of catalysts results in the loss of electrochemical surface area. Simple mixtures of ionomer and catalyst can suffer from poor catalyst adhesion because only physical adhesion is used to bind the components together. A family of chemically bonded, self-adherent, hydroxide conducting ionomers were synthesized and tested under alkaline electrolysis conditions with nickel ferrite anode electrocatalysts and platinum-nickel cathode catalyst. The ionomers are based on hydroxide conducting poly(norbornene) polymers used as the solid polymer electrolyte in alkaline fuel cells and electrolyzers. The synthesized terpolymer ionomers have been functionalized to provide pendant sites for covalent chemical bonding of bis(phenyl)-A-diglycidyl ether to the ionomer, catalyst, and porous transport layer. The electrodes show excellent adhesion between the catalyst particles, porous transport layer and ionomer, as determined by adhesion measurements and electrolysis performance. As a result, the AEM electrolyzer had stable voltage performance under high current density (1 A/ cm 2 at 1.83 V (67% voltage efficiency)) for extended time periods (>600 h) without degradation.

08 HYDROGEN↗

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↗

Porin-Inspired Ionomers with sub-nm Gated Ion Channels for High Ion Conductivity and Selectivity (Final Project Report (2026))

The physiological functions of living systems heavily rely on biological ion channels, whose malfunction can lead to disease. These channels enable selective and regulated transport of water, ions, or small molecules across membranes. Analogously, ionomers used in energy conversion and storage technologies govern ion transport within membrane separators and catalyst binder layers. This DOE Office of Science Early CAREER project aimed to achieve molecular-level control over ionic conductivity and ion permselectivity by translating the functionalities of biological, gated ion channels into a novel class of ion-conducting polymers (ionomers) incorporating macrocyclic calix[4]arene-based repeat units. The overarching goal was to establish fundamental design principles and elucidate proton conduction mechanisms through strategic design of macrocyclic calix[4]arene-containing ionomers, with close relevance to energy conversion and storage devices, including proton exchange membrane fuel cells (PEMFCs). The project leveraged sub-nm-sized macrocyclic pores to facilitate exceptionally fast ion transport (beneficial to addressing sluggish ORR kinetics of PEMFC electrodes) and achieve functionalities of ionic diodes under applied electrochemical fields, beneficial for selective transport/separation.

59 BASIC BIOLOGICAL SCIENCES↗

Electronic interactions and stability issues at the copper-graphene interface in air and in alkaline solution under electrochemical control

A micro-electrochemical cell is sealed with a polymer-free single-layer graphene (SLG) membrane to monitor the stability of Cu nanoparticles (NPs) attached to SLG, as well as the interfacial electronic interactions between Cu NPs and SLG both in air and in a mildly alkaline aqueous solution under electrochemical control. A combination of techniques, including in-situ Kelvin probe force microscopy (KPFM) and ex-situ electron microscopy, are applied. When Cu NPs are metallic at cathodic potentials, there is a relatively bias-independent offset in the SLG work function due to charge transfer at the Cu-SLG contact. When Cu NPs are oxidized at anodic potentials, on the other hand, the work function of SLG also depends on the applied bias in a quasi-linear fashion due to electrochemical gating, in addition to charge transfer at the CuOx-SLG contact. Furthermore, Cu NPs were found to oxidize and detach from SLG when kept under anodic potentials for a few hours, whereas they remain adhered to SLG at cathodic potentials. This is attributed to water intercalation at the CuO-SLG interface associated with the enhanced hydrophilicity of positively polarized graphene, as supported by the absence of Cu detachment following oxidation by galvanic corrosion in air.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Linking Perfluorosulfonic Acid Ionomer Chemistry and High-Current Density Performance in Fuel-Cell Electrodes

Transport phenomena are key in controlling the performance of electrochemical energy-conversion technologies and can be highly complex, involving multiple length scales and materials/phases. Material designs optimized for one reactant species transport however may inhibit other transport processes. We explore such trade-offs in the context of polymer-electrolyte fuel-cell electrodes, where ionomer thin films provide the necessary proton conductivity but retard oxygen transport to the Pt reaction site and cause interfacial resistance due to sulfonate/Pt interactions. We examine the electrode overall gas-transport resistance and its components as a function of ionomer content and chemistry. Low-equivalent-weight ionomers allow better dissolved-gas and proton transport due to greater water uptake and low crystallinity but also cause significant interfacial resistance due to the high density of sulfonic acid groups. These effects of equivalent weight are also observed via in situ ionic conductivity and CO displacement measurements. Of critical importance, the results are supported by ex situ ellipsometry and X-ray scattering of model thin-film systems, thereby providing direct linkages and applicability of model studies to probe complex heterogeneous structures. Structural and resultant performance changes in the electrode are shown to occur above a threshold sulfonic-group loading, highlighting the significance of ink-based interactions. Furthermore, our findings and methodologies are applicable to a variety of solid-state energy-conversion devices and material designs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fe–N–C Boosts the Stability of Supported Platinum Nanoparticles for Fuel Cells

The poor durability of Pt-based nanoparticles dispersed on carbon black is the challenge for the application of long-life polymer electrolyte fuel cells. Recent work suggests that Fe- and N-codoped carbon (Fe-N-C) might be a better support than conventional high-surface-area carbon. In this work, we find that the electrochemical surface area retention of Pt/Fe-N-C is much better than that of commercial Pt/C during potential cycling in both acidic and basic media. In situ inductively coupled plasma mass spectrometry studies indicate that the Pt dissolution rate of Pt/Fe-N-C is 3 times smaller than that of Pt/C during cycling. Density functional theory calculations further illustrate that the Fe-N-C substrate can provide strong and stable support to the Pt nanoparticles and alleviate the oxide formation by adjusting the electronic structure. The strong metal-substrate interaction, together with a lower metal dissolution rate and highly stable support, may be the reason for the significantly enhanced stability of Pt/Fe-N-C. In conclusion, this finding highlights the importance of carbon support selection to achieve a more durable Pt-based electrocatalyst for fuel cells.

25 ENERGY STORAGE↗

Engineering Solid Electrolyte Interphase Composition by Assessing Decomposition Pathways of Fluorinated Organic Solvents in Lithium Metal Batteries

Studies have shown fluorinated electrolyte solvents can form desirable solid electrolyte interphase (SEI) in lithium metal batteries. In this study, we develop a detailed mechanistic understanding of two high performing electrolytes, Fluoroethylene Carbonate (FEC) and Difluoroethylene Carbonate (DFEC) to demonstrate minimal structural variations can lead to different decomposition products, and thereby the nature of the SEI. Using density functional theory (DFT) calculations, we find different initial bond-breaking mechanisms between FEC and DFEC. We develop free energy diagrams for the decomposition pathways including both electrochemical and chemical steps. Using the computational Li electrode, we identify the largest limiting potential of 1.77 V for FEC decomposition, associated with the formation of lithium fluoride, lithium oxide and FEC oligomers, and 1.53 V for DFEC, which correspond to the formation of polymerized vinylene carbonate and lithium fluoride. We suggest the formation of oligomers in the case of FEC instead of long polymers may lead to better SEI compactness. We also demonstrate the SEI components of FEC and DFEC are not stable on typical cathode voltage (3.87 V). This study presents a unified electrocatalytic perspective on SEI formation and decomposition.

25 ENERGY STORAGE↗

Photoluminescence Probes Ion Insertion into Amorphous and Crystalline Regions of Organic Mixed Conductors

Abstract Organic mixed ionic‐electronic conductors (OMIECs) have emerged as promising materials for a wide range of next‐generation technologies, including bioelectronics and neuromorphic computing. The performance of these materials depends on the transport of ions through the polycrystalline polymer matrix as well as how the distribution of ions and polarons in crystalline and amorphous regions impacts electronic transport. However, it is often challenging to distinguish whether ions enter crystalline or amorphous regions. In this work, steady‐state and time‐resolved photoluminescence (PL) spectroelectrochemistry is used to probe initial ion insertion in crystalline and amorphous regions of the OMIEC material poly(3‐[2‐[2‐(2‐methoxyethoxy)ethoxy]ethyl]thiophene ‐2,5‐diyl) (P3MEEET) as a function of applied voltage. It is found that PL spectroelectrochemistry reports on the initial stages of electrochemical doping through the quenching of PL emission. By distinguishing between amorphous and crystalline contributions to the PL spectrum, ion insertion in crystalline and amorphous regions as a function of voltage is tracked. It is found that PL spectroelectrochemistry is much more sensitive to the initial injection of ions than complementary methods, highlighting its potential as a sensitive tool for interrogating ion injection in OMIECs.

Collins, Garrett W.↗

NASA Tech Briefs, July 2007

Topics covered include: Miniature Intelligent Sensor Module; "Smart" Sensor Module; Portable Apparatus for Electrochemical Sensing of Ethylene; Increasing Linear Dynamic Range of a CMOS Image Sensor; Flight Qualified Micro Sun Sensor; Norbornene-Based Polymer Electrolytes for Lithium Cells; Making Single-Source Precursors of Ternary Semiconductors; Water-Free Proton-Conducting Membranes for Fuel Cells; Mo/Ti Diffusion Bonding for Making Thermoelectric Devices; Photodetectors on Coronagraph Mask for Pointing Control; High-Energy-Density, Low-Temperature Li/CFx Primary Cells; G4-FETs as Universal and Programmable Logic Gates; Fabrication of Buried Nanochannels From Nanowire Patterns; Diamond Smoothing Tools; Infrared Imaging System for Studying Brain Function; Rarefying Spectra of Whispering-Gallery-Mode Resonators; Large-Area Permanent-Magnet ECR Plasma Source; Slot-Antenna/Permanent-Magnet Device for Generating Plasma; Fiber-Optic Strain Gauge With High Resolution And Update Rate; Broadband Achromatic Telecentric Lens; Temperature-Corrected Model of Turbulence in Hot Jet Flows; Enhanced Elliptic Grid Generation; Automated Knowledge Discovery From Simulators; Electro-Optical Modulator Bias Control Using Bipolar Pulses; Generative Representations for Automated Design of Robots; Mars-Approach Navigation Using In Situ Orbiters; Efficient Optimization of Low-Thrust Spacecraft Trajectories; Cylindrical Asymmetrical Capacitors for Use in Outer Space; Protecting Against Faults in JPL Spacecraft; Algorithm Optimally Allocates Actuation of a Spacecraft; and Radar Interferometer for Topographic Mapping of Glaciers and Ice Sheets.

Source record↗

Interphase Engineering Enabled by Using a Separator with Electrochemically Active Carbazole Polymers for Lithium-Ion Batteries

Separators are generally considered inert components in lithium-ion batteries. In the past, some electroactive polymers have been successfully applied in separator modifications for overcharge protection or as acid scavengers. This study highlights the first use of two “electroactive” carbazole polymers (copolymer 9-phenyl-9H-carbazole-phenyl [PCP] and poly(9-vinylcarbazole) [PVC]), which were each applied separately as coatings on the cathode-facing side of commercial Celgard 2325 separators, respectively, to enhance the cycling performance of 0.3Li 2 MnO 3 ·0.7LiMn 0.5 Ni 0.5 O 2 //graphite (LMR-NM//Gr) full cells through interphase engineering. The team observed an irreversible polymer oxidation process of the carbazole-functionalized polymers—occurring only during the first charge—for the modified separator cells, and the results were confirmed by dQ/dV analysis, cyclic voltammetry measurements, and nuclear magnetic resonance characterizations. During this oxidation, carbazole polymers participate in the process of interphase formation, contributing to the improved cycling performance of LMR-NM//Gr batteries. Particularly, oxidation takes place at voltages of ~4.0 and ~3.5 V when PCP and PVC are used as separator coatings, which is highly irreversible. Further postmortem examinations suggest that the improvements using these modified separators arise from the formation of higher-quality and more inorganic SEI, as well as the beneficial CEI enriched in LixPOyFz. These interphases effectively inhibit the crosstalk effect by reducing TM dissolution.

carbazole↗

Glass-fiber-reinforced polymeric film as an efficient protecting layer for stable Li metal electrodes

With numerous reports on protecting films for stable lithium (Li) metal electrodes, the key attributes for how to construct these efficient layers have rarely been fully investigated. Here, we report a rationally designed hybrid protective layer (HPL) with each component aligning with one key attribute; i.e., cross-linked poly(dimethylsiloxane) (PDMS) enhances flexibility, polyethylene glycol (PEG) provides homogeneous ion-conducting channels, and glass fiber (GF) affords mechanical robustness. A significant improvement of the electrochemical performance of HPL-modified electrodes can be achieved in Li/HPL@Cu half cells, HPL@Li/HPL@Li symmetric cells, and HPL@Li/LiFePO 4 full cells. Even with an industrial standard LiFePO 4 cathode (96.8 wt % active material), the assembled cell still exhibits a capacity retention of 90% after 100 cycles at 1 C. More importantly, the functionality of each component has been studied comprehensively via electrochemical and physical experiments and simulations, which will provide useful guidance on how to construct efficient protective layers for next-generation energy storage devices.

25 ENERGY STORAGE↗

Truncating 2D Framework Materials Down to a Single Pore: Synthetic Approaches and Opportunities

Here, in this Accounts article, we summarize our recent work on truncating conjugated two-dimensional framework materials down to a single pore, or a single macrocycle. Conjugated 2D architectures have emerged as one of the most synthetically adaptable motifs for coupling semiconductivity and porosity in metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). However, despite their prevalence, 2D architectures have several limitations. In particular, the strong interlayer π–π stacking can limit both processability and the accessibility of internal active sites. We have found that simple macrocycles preserve key aspects of 2D framework structure and function, including porosity and out-of-plane electrical conductivity, while providing improved processability, surface tunability, and mass transport properties. In this article, we first describe our synthetic approach and general design considerations. Specifically, we show how ditopic analogues of the tritopic ligands commonly found in the synthesis of 2D MOFs and COFs can be used to achieve a diverse library of conjugated macrocycles that resemble fragments of semiconducting frameworks in both form and function. The length of the peripheral side chains, the size of the aromatic core, and the solubility of intermediates are all key variables in favoring selective macrocycle formation over undesired linear polymers and oligomers. Next, we highlight the unique advantages that macrocycles provide, including improved processability, atomically precise surface tunability, and greater active site accessibility. In particular, the identity of the peripheral side chains dramatically impacts both solubility and colloidal stability as well as crystal size and morphology. We further show how the solution processability and nanoscale dimensions of macrocycles can simplify electronic device fabrication and improve electrochemical performance. Finally, we end with a forward-looking discussion on how macrocycles offer a unique bridge between conjugated molecules and extended frameworks, enabling new application areas and fundamental science.

charge transport↗

Relative-Humidity Dependence of Electrochemically Active Surface Area in Porous Carbon Catalyst Layers

Polymer-electrolyte fuel cells (PEFCs) utilize porous catalyst layers (CLs) formed of carbon supports on which Pt particles are deposited and ionomer films are distributed. Carbon supports themselves have varying degrees of porosity, where high-surface-area carbon (HSC) supports possess nanometer-sized interior pores that are suitable for Pt nanoparticle deposition but prevent deleterious ionomer penetration. However, this requires protons to transport through water pathways inside the pores. To understand the generation of such pathways, we examine the various mechanisms of water uptake by PEFC CLs, and the subsequent impact of water uptake on Pt utilization through developing a multiphysics model of the water wetting phenomena as a function of relative humidity. The model details water uptake via ionomer absorption, capillary condensation in the hydrophilic pores, and surface adsorption using molecular potential that account for various water and surface dipole interactions. The results quantify how mesoporous carbons with highly hydrophilic pores increase Pt utilization through the development of wetted layers, which at the same time enable optimized gas-transport pathways. It also demonstrates the impact of pore-size distribution (PSD) and physical and chemical parameters on the water uptake phenomena, allowing for future CL particle and structure optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of hyperbranched polymer films via electrodeposition and oxygen-tolerant surface-initiated photoinduced polymerization

Hypothesis Hyperbranched polymers, not only possess higher functionality, but are also easier to prepare compared to dendrimers and dendric polymers. Combining electrodeposition and surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization is hypothesized to be a novel strategy for preparing hyperbranched polymer films on conductive surfaces without degassing. Experiments In this study, polymer brush grafted films with four different architectures (i.e. linear, branched, linear- block -branched, and branched- block -linear) were prepared on gold-coated glass substrates using electrodeposition, followed by SI-PET-RAFT polymerization. The resulting film structure and thickness, surface topology, absorption property, and electrochemical behavior were confirmed by spectroscopy, microscopy, microbalance technique, and impedance measurement. Findings These hyperbranched polymer brushes were capable of forming a thicker but more uniformly covered films compared to linear polymer brush films, demonstrating that hyperbranched polymer films can be potentially useful for fabricating protective polymer coatings on various conductive surfaces.

36 MATERIALS SCIENCE↗