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At least 91 records · Page 5

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↗

Black-to-Transmissive dual polymer complementary electrochromics with high coloration efficiency

In a complementary electrochromic device (ECD), both the anode and the cathode can synergistically change color in response to an electrical bias, allowing for a high coloration efficiency. Complementary ECD that can switch from black to transmissive state is rare, due to the difficulty of pairing two electrochromic electrodes. In this study, we report the construction of high coloration efficiency complementary ECDs by pairing polyazoisoindigo (PAI), an n-type electrochromic polymer that undergoes green-to-transmissive switching, with p-type magenta (ECP-M) and red (ECP-R) electrochromic polymers to obtain black-to-transmissive ECD. Physical modeling tool, COMSOL, is introduced for complementary color matching. Through balancing the charge densities of two electrochromic electrodes, black-to-transmissive ECDs with record-high coloration efficiencies of 688 cm 2 /C and 437 cm 2 /C have been achieved for PAI|ECP-M and PAI|ECP-R, respectively. This study provides a general protocol for the design and fabrication of complementary ECDs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Construction of Fluorine- and Piperazine-Engineered Covalent Triazine Frameworks Towards Enhanced Dual-Ion Positive Electrode Performance

Organic positive electrodes featuring lightweight, and tunable energy storage modes by molecular structure engineering have promising application prospects in dual-ion batteries. Herein, a series of highly porous covalent triazine frameworks (CTFs) were synthesized under ionothermal conditions using fluorinated aromatic nitrile monomers containing a piperazine ring. Fluorinated monomers can result in more defects in CTFs, leading to a higher surface area up to 2515 m 2 /g and a higher N content of 11.34 wt% compared to the products from the non-fluorinated monomer. The high surface area and abundant redox sites of these CTFs afforded high specific capacities (up to 279 mAh/g at 0.1 A/g), excellent rate performance (89 mAh/g at 5 A/g), and durable cycling performance (92.3% retention rate after 500 cycles at 2.0 A g -1 ) as dual-ion positive electrodes

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Operando Nanoscale Imaging of Electrochemically Induced Strain in a Locally Polarized Pt Grain

Developing new methods that reveal the structure of electrode materials under polarization is key to constructing robust structure-property relationships. However, many existing methods lack the spatial resolution in structural changes and fidelity to electrochemical operating conditions that are needed to probe catalytically relevant structures. Here, we combine a nanopipette electrochemical cell with three-dimensional X-ray Bragg coherent diffractive imaging to study how strain in a single Pt grain evolves in response to applied potential. During polarization, marked changes in surface strain arise from the Coulombic attraction between the surface charge on the electrode and the electrolyte ions in the electrochemical double layers, while the strain in the bulk of the crystal remains unchanged. The concurrent surface redox reactions have a strong influence on the magnitude and nature of the strain changes under polarization. In conclusion, our studies provide a powerful blueprint to understand how structural evolution influences electrochemical performance at the nanoscale.

36 MATERIALS SCIENCE↗

Tailorable multiferroic tunnel junctions from all-van der Waals multilayer stacking

Multiferroic tunnel junctions (MFTJs) represent a class of multistate, non-volatile spintronic devices, in which electron tunnelling can be manipulated by switching long-range lattice and spin orders. In contrast to conventional oxide-based MFTJs, MFTJs constructed from two-dimensional van der Waals (vdW) crystals promise minimal defect concentration in the constituents and at interfaces, which may allow for probing intrinsic tunnelling physics and the development of high-performance devices. Here, in this study, we construct Fe 3 GeTe 2 /CuInP 2 S 6 /Fe 3 GeTe 2 all-vdW MFTJs by assembling multilayer flakes of ferromagnetic Fe 3 GeTe 2 electrodes and a ferroelectric CuInP 2 S 6 spacer. These MFTJs exhibit four non-volatile resistance states featuring sizable tunnelling magnetoresistance of ∼10 2 % and tunnelling electroresistance of ∼10 4 %. To tune the properties of the vdW MFTJ, we make use of the flexibility in material choice offered by vdW heterostructure devices; we use Fe 3 GeTe 2 /Fe 5 GeTe 2 asymmetric electrodes to boost the tunnelling electroresistance by 10 3 %, we integrate In 2 Se 3 as a ferroelectric with a smaller bandgap to enhance the ON-state current density by 10 4 % to 10 4 A cm −2 and we use Fe 3 GaTe 2 electrodes to demonstrate room temperature operation. Furthermore, when we combine the asymmetric ferromagnetic electrodes with the small-bandgap ferroelectric spacer to construct Fe 3 GeTe 2 /In 2 Se 3 /Fe 5 GeTe 2 MFTJs, we simultaneously realized tunnelling electroresistance of 10 6 % and an ON-state current density of 10 4 A cm −2 , both two orders of magnitude higher than the highest values achieved with conventional oxide-based MFTJs. In the future, our all-vdW MFTJs with the tailorability of all functional layers may make it possible to investigate fundamental aspects of interlayer tunnelling and enable the design of functional magnetoelectric nanodevices.

Xie, Ti [University of Maryland, College Park, MD ↗

Fabrication and testing of negative-limited sealed nickel-cadmium cells

Negative-limited sealed nickel-cadmium cells are a possible means toward increasing the life of nickel-cadmium cells to about a decade or more. The purpose of this program is to design, construct, and test 100, 20 Ah and 100, 30 Ah negative-limited sealed cells. The cell design was completed and hardware was ordered during the first quarter. Electrode fabrication was started in the first quarter and carried on through the second quarter. The fabrication and selection of the necessary electrodes has been completed during the third quarter. Cell construction has been completed and the preparatory cell cycling is underway. The preliminary testing to select the initial delivery cell has been started.

Gordy, D. J.↗

Flow Visualization of Low Prandtl Number Fluids using Electrochemical Measurements

It is well established that residual flows exist in contained liquid metal processes. In 1-g processing, buoyancy forces often drive these flows and their magnitudes can be substantial. It is also known that residual flows can exist during microgravity processing, and although greatly reduced in magnitude, they can influence the properties of the processed materials. Unfortunately, there are very few techniques to visualize flows in opaque, high temperature liquid metals, and those available are not easily adapted to flight investigation. In this study, a novel technique is developed that uses liquid tin as the model fluid and solid-state electrochemical cells constructed from Yttria-Stabilized Zirconia (YSZ) to establish and measure dissolved oxygen boundary conditions. The melt serves as a common electrode for each of the electrochemical cells in this design, while independent reference electrodes are maintained at the outside surfaces of the electrolyte. By constructing isolated electrochemical cells at various locations along the container walls, oxygen is introduced or extracted by imposing a known electrical potential or passing a given current between the melt and the reference electrode. This programmed titration then establishes a known oxygen concentration boundary condition at the selected electrolyte-melt interface. Using the other cells, the concentration of oxygen at the electrolyte-melt interface is also monitored by measuring the open-circuit potentials developed between the melt and reference electrodes. Thus the electrochemical cells serve to both establish boundary conditions for the passive tracer and sense its path. Rayleigh-Benard convection was used to validate the electrochemical approach to flow visualization. Thus, a numerical characterization of the second critical Rayleigh numbers in liquid tin was conducted for a variety of Cartesian aspect ratios. The extremely low Prandtl number of tin represents the lowest value studied numerically. Additionally, flow field oscillations are visualized and the effect of tilt on convecting systems is quantified. Experimental studies of the effect of convection in liquid tin are presented. Three geometries are studied: (1) double electrochemical cell with vertical concentration gradients; (2) double cell with horizontal concentration gradients; and (3) multiple cells with vertical temperature gradients. The first critical Rayleigh number transition is detected with geometry (1) and it is concluded that current measurements are not as affected by convection as EMF measurements. The system is compared with numerical simulations in geometry (2), and oscillating convection is detected with geometry (3).

Crunkleton, D.↗

Boosting Superior Lithium Storage Performance of Alloy-Based Anode Materials via Ultraconformal Sb Coating–Derived Favorable Solid-Electrolyte Interphase

Alloy materials such as Si and Ge are attractive as high-capacity anodes for rechargeable batteries, but such anodes undergo severe capacity degradation during discharge-charge processes. Compared to the over-emphasized efforts on the electrode structure design to mitigate the volume changes, understanding and engineering of the solid-electrolyte interphase (SEI) are significantly lacking. This work demonstrates that modifying the surface of alloy-based anode materials by building an ultraconformal layer of Sb can significantly enhance their structural and interfacial stability during cycling. Combined experimental and theoretical studies consistently reveal that the ultraconformal Sb layer is dynamically converted to Li 3 Sb during cycling, which can selectively adsorb and catalytically decompose electrolyte additives to form a robust, thin, and dense LiF-dominated SEI, and simultaneously restrain the decomposition of electrolyte solvents. Hence, the Sb-coated porous Ge electrode delivers much higher initial Coulombic efficiency of 85% and higher reversible capacity of 1046 mAh g -1 after 200 cycles at 500 mA g -1 , compared to only 72% and 170 mAh g -1 for bare porous Ge. The present finding has indicated that tailoring surface structures of electrode materials is an appealing approach to construct a robust SEI and achieve long-term cycling stability for alloy-based anode materials.

25 ENERGY STORAGE↗

Atomically dispersed Pt single sites and nanoengineered structural defects enable a high electrocatalytic activity and durability for hydrogen evolution reaction and overall urea electrolysis

The scarcity and high cost of PGM electrocatalysts are the key bottleneck in the mass-scale commercialization of many electrolysis technologies. Bifunctional single-atom electrocatalysts (SACs) are promising alternatives for PGM electrocatalysts in next-generation electrolysis technologies because of their superior intrinsic activity and perfect atom utilization. Regulating the coordination environment of platinum atomic sites identifies their electrocatalytic performance. Therefore, exploring more appropriate supports could facilitate the construction of active and durable electrocatalysts with ultralow noble metal content. Herein, we report on a reliable approach for producing a novel type of SACs composed of atomically dispersed Pt active sites stabilized on defective NiCo layered double hydroxide (Pt/D-NiCo LDH) nanosheets as an ultralow-Pt hybrid electrocatalyst for hydrogen evolution reaction (HER), urea oxidation reaction (UOR), and full urea-water electrolysis. The optimized Pt 1 /D NiCo LDH-24 SAC displays a remarkable HER and UOR performance where it yields a current density of 10 mA cm -2 at 37 mV and 1.25 V vs. RHE for HER and UOR, respectively. Finally, symmetrical urea electrolyzer constructed of Pt 1 /D-NiCo LDH-24 electrodes attains 10 mA cm -2 at a cell voltage of 1.32 V vs. RHE, demonstrating superior activity and durability over 60 h operation when compared to commercial Pt/C( + )||RuO 2 ( - ) system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanostructured C@CuS Core–Shell Framework with High Lithium-Ion Storage Performance

In this study, we have synthesized a nanostructured core–shell framework of carbon-coated copper sulfide (C@CuS) through a one-step precipitation technique. The carbon sphere template facilitated the nucleation of CuS nanostructures. The synthesized nanocomposites have demonstrated remarkable lithium-ion storage capabilities when utilized as an anode in lithium-ion batteries. Notably, they exhibit an impressive rate capability of 314 mAh g -1 at a high current density of 5000 mA g -1 , along with excellent long-term cycle stability, maintaining 463 mAh g -1 at 1000 mA g -1 after 800 cycles. This superior performance is due to the core–shell architecture of the composite, where the carbon core enhances the conductivity of CuS nanoparticles and mitigates volume expansion, thus preventing capacity loss. Our study not only elucidates the significance of carbon in the construction of nano-heterojunctions or composite electrodes but also presents a practical approach to significantly boost the electrochemical performance of CuS and other metal sulfides.

25 ENERGY STORAGE↗

A figure of merit for AMTEC electrodes

As a method to compare the results of alkali metal thermoelectric converter (AMTEC) electrode performance measured under different conditions, an AMTEC figure of merit called ZA is proposed. This figure of merit is the ratio of the experimental maximum power for an electrode to a calculated maximum power density as determined from a recently published electrode performance model. The calculation of a maximum power density assumes that certain loss terms in the electrode can be reduced to essentially zero by improved cell design and construction, and that the electrochemical exchange current is determined from a standard value. Other losses in the electrode are considered inherent to the electrode performance. Thus, these terms remain in the determination of the calculated maximum power. A value of ZA near one, then, indicates an electrode performance near the maximum possible performance. The primary limitation of this calculation is that the small electrode effect cannot be included. This effect leads to anomalously high values of ZA. Thus, the electrode area should be reported along with the figure of merit.

Underwood, M. L.↗

Wireless Electrical Device Using Open-Circuit Elements Having No Electrical Connections

A wireless electrical device includes an electrically unconnected electrical conductor and at least one electrically unconnected electrode spaced apart from the electrical conductor. The electrical conductor is shaped for storage of an electric field and a magnetic field. In the presence of a time-varying magnetic field, the electrical conductor so-shaped resonates to generate harmonic electric and magnetic field responses. Each electrode is at a location lying within the magnetic field response so-generated and is constructed such that a linear movement of electric charges is generated in each electrode due to the magnetic field response so-generated.

Woodard, Stanley E.↗

Long Life Nickel Electrodes for Nickel-Hydrogen Cells: Fiber Substrates Nickel Electrodes

Samples of nickel fiber mat electrodes were investigated over a wide range of fiber diameters, electrode thickness, porosity and active material loading levels. Thickness' were 0.040, 0.060 and 0.080 inches for the plaque: fiber diameters were primarily 2, 4, and 8 micron and porosity was 85, 90, and 95%. Capacities of 3.5 in. diameter electrodes were determined in the flooded condition with both 26 and 31% potassium hydroxide solution. These capacity tests indicated that the highest capacities per unit weight were obtained at the 90% porosity level with a 4 micron diameter fiber plaque. It appeared that the thinner electrodes had somewhat better performance, consistent with sintered electrode history. Limited testing with two-positive-electrode boiler plate cells was also carried out. Considerable difficulty with constructing the cells was encountered with short circuits the major problem. Nevertheless, four cells were tested. The cell with 95% porosity electrodes failed during conditioning cycling due to high voltage during charge. Discharge showed that this cell had lost nearly all of its capacity. The other three cells after 20 conditioning cycles showed capacities consistent with the flooded capacities of the electrodes. Positive electrodes made from fiber substrates may well show a weight advantage of standard sintered electrodes, but need considerably more work to prove this statement. A major problem to be investigated is the lower strength of the substrate compared to standard sintered electrodes. Problems with welding of leads were significant and implications that the electrodes would expand more than sintered electrodes need to be investigated. Loading levels were lower than had been expected based on sintered electrode experiences and the lower loading led to lower capacity values. However, lower loading causes less expansion and contraction during cycling so that stress on the substrate is reduced.

Rogers, Howard H.↗

Manipulating the diffusion energy barrier at the lithium metal electrolyte interface for dendrite-free long-life batteries

Abstract Constructing an artificial solid electrolyte interphase (SEI) on lithium metal electrodes is a promising approach to address the rampant growth of dangerous lithium morphologies (dendritic and dead Li 0 ) and low Coulombic efficiency that plague development of lithium metal batteries, but how Li + transport behavior in the SEI is coupled with mechanical properties remains unknown. We demonstrate here a facile and scalable solution-processed approach to form a Li 3 N-rich SEI with a phase-pure crystalline structure that minimizes the diffusion energy barrier of Li + across the SEI. Compared with a polycrystalline Li 3 N SEI obtained from conventional practice, the phase-pure/single crystalline Li 3 N-rich SEI constitutes an interphase of high mechanical strength and low Li + diffusion barrier. We elucidate the correlation among Li + transference number, diffusion behavior, concentration gradient, and the stability of the lithium metal electrode by integrating phase field simulations with experiments. We demonstrate improved reversibility and charge/discharge cycling behaviors for both symmetric cells and full lithium-metal batteries constructed with this Li 3 N-rich SEI. These studies may cast new insight into the design and engineering of an ideal artificial SEI for stable and high-performance lithium metal batteries.

25 ENERGY STORAGE↗

Ca Metal Batteries and Sn Anode Alloying: Resolving Misconceptions in Ca–Sn Alloy Formation

Ca metal anode suffers from surface passivation and struggles to effectively plate and strip in conventional Ca electrolytes, making the development of alloy anode for calcium metal battery essential. This work systematically and carefully evaluates the electrochemical formation and feasibility of the Sn anode and its possibility of alloying with Ca using a combination of cyclic voltammetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDS), X-ray diffraction (XRD), and synchrotron transmission X-ray microscopy (TXM). Electrochemical measurements and SEM/EDS analyses indicate apparent Ca alloy formation. However, detailed XRD and TXM characterization reveal substantial lithium-ion involvement when lithium metal is employed as the reference electrode, even in electrolytes with high Ca salt concentrations. These findings highlight a significant risk of misinterpretation: Although limited Ca–Sn alloying may occur, the faster kinetics of Li + can dominate the alloying process, leading to a Li-driven reactions at the Sn anode. In contrast, cells constructed with Ca metal as both reference and counter electrodes exhibit distinct redox features only during the initial cycles, followed by rapid cell failure. The high oxidation currents induce severe Ca passivation, occurring nearly concurrently with Sn dealloying. Overall, this study provides critical insight into the practical limitations and common experimental artifacts associated with Ca metal battery systems and underscores the necessity for rigorous cell design and cautious interpretation when evaluating alloy chemistry in multivalent Ca-based batteries.

36 MATERIALS SCIENCE↗

Electronic Tongue for Quantitation of Contaminants in Water

An assembly of sensors, denoted an electronic tongue, is undergoing development as a prototype of compact devices for use in measuring concentrations of contaminants in water. Thus far, the electronic tongue has been tested on ions of Cu, Zn, Pb, and Fe and shown to respond to concentrations as low as about 10 parts per million. This electronic tongue is expected to be capable of measuring concentrations of other metal ions and organic compounds. Potential uses for electronic tongues include monitoring the chemical quality of water in a variety of natural, industrial, and laboratory settings; detecting micro-organisms indirectly by measuring microbially influenced corrosion; and characterizing compounds of interest to the pharmaceutical and food industries. This version of the electronic tongue includes a heater, a temperature sensor, an array of ion-specific electrodes, an oxidation/ reduction sensor pair, an electrical-conductivity sensor, and an array of galvanic cells, all on one compact ceramic substrate. Special-purpose electronic excitation and readout circuitry for the sensors has also been constructed. The main advantage of the electronic tongue, relative to electrodes of this type used traditionally to assess water quality, is extreme ruggedness. The types of measurements that can be performed by use of the sensors on the electronic tongue are quite varied. The best combination of types of measurements for a given application depends on the specific contaminants that one seeks to detect. Experimental studies to identify such combinations were in progress at the time of reporting the information for this article.

Buehler, Marlin↗

Fabrication and testing of large size nickel-zinc cells

The design and construction of nickel zinc cells, containing sintered nickel electrodes and asbestos coated inorganic separator materials, were outlined. Negative electrodes were prepared by a dry pressing process while various inter-separators were utilized on the positive electrodes, consisting of non-woven nylon, non-woven polypropylene, and asbestos.

Klein, M.↗

Study of radiatively sustained cesium plasmas for solar energy conversion

The results of a study aimed at developing a high temperature solar electric converter are reported. The converter concept is based on the use of an alkali plasma to serve as both an efficient high temperature collector of solar radiation as well as the working fluid for a high temperature working cycle. The working cycle is a simple magnetohydrodynamic (MHD) Rankine cycle employing a solid electrode Faraday MHD channel. Research milestones include the construction of a theoretical model for coupling sunlight in a cesium plasma and the experimental demonstration of cesium plasma heating with a solar simulator in excellent agreement with the theory. Analysis of a solar MHD working cycle in which excimer laser power rather than electric power is extracted is also presented. The analysis predicts a positive gain coefficient on the cesium-xenon excimer laser transition.

Palmer, A. J.↗