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At least 469 records · Page 26

Improving Lithium Metal Composite Anodes with Seeding and Pillaring Effects of Silicon Nanoparticles

Metallic lithium (Li) anodes are crucial for the development of high specific energy batteries yet plagued by their poor cycling efficiency. Electrode architecture engineering is vital for maintaining a stable anode volume and suppress Li corrosion during cycling. In this paper, a reduced graphene oxide “host” framework for Li metal anodes is further optimized by embedding silicon (Si) nanoparticles between the graphene layers. They serve as Li nucleation seeds to promote Li deposition within the framework even without pre-stored Li. Meanwhile, the LixSi alloy particles serve as supporting “pillars” between the graphene layers, enabling a minimized thickness shrinkage after full stripping of metallic Li. Combined with a Li compatible electrolyte, 99.4% Coulombic efficiency over ~600 cycles is achieved, and stable cycling of a Li||NMC532 full cell for ~380 cycles with negligible capacity decay is realized.

Wang, Hansen↗

Photo-driven growth of a monolayer of platinum spherical-nanocrowns uniformly coated on a membrane toward fuel cell applications

Membrane electrode assemblies (MEAs) serve as the core units of polymer electrolyte membrane fuel cells (PEMFCs) and are regularly fabricated by painting a slurry of commercial Pt/C onto a membrane, leading to thick and disordered electrocatalyst layers (CLs). Herein, we report a photo-driven fabrication of MEAs with ultra-thin and ordered CLs by growing a monolayer of dendritic platinum spherical nanocrowns onto each side of a photocatalyst-modified membrane. This approach allows us to control the thickness and platinum loading of ordered CLs by simply varying the concentration of the platinum precursor under tungsten light irradiation. The resultant MEAs exhibit an excellent fuel cell power density of 1.01 ± 0.05 W cm –2 at a platinum loading of 53 ± 1.5 μg cm cathode –2 . Furthermore, this exceptional activity likely arises from the nanostructured platinum crowns, efficient mass transport, and uniform reaction rate in the ultrathin (59 ± 12 nm thick) and ordered CLs according to electrochemical and theoretical investigations.

25 ENERGY STORAGE↗

Fast Electromechanical Switches Based on Carbon Nanotubes

Electrostatically actuated nanoelectromechanical switches based on carbon nanotubes have been fabricated and tested in a continuing effort to develop high-speed switches for a variety of stationary and portable electronic equipment. As explained below, these devices offer advantages over electrostatically actuated microelectromechanical switches, which, heretofore, have represented the state of the art of rapid, highly miniaturized electromechanical switches. Potential applications for these devices include computer memories, cellular telephones, communication networks, scientific instrumentation, and general radiation-hard electronic equipment. A representative device of the present type includes a single-wall carbon nanotube suspended over a trench about 130 nm wide and 20 nm deep in an electrically insulating material. The ends of the carbon nanotube are connected to metal electrodes, denoted the source and drain electrodes. At bottom of the trench is another metal electrode, denoted the pull electrode (see figure). In the off or open switch state, no voltage is applied, and the nanotube remains out of contact with the pull electrode. When a sufficiently large electric potential (switching potential) is applied between the pull electrode and either or both of the source and drain electrodes, the resulting electrostatic attraction bends and stretches the nanotube into contact with the pull electrode, thereby putting the switch into the "on" or "closed" state, in which substantial current (typically as much as hundreds of nanoamperes) is conducted. Devices of this type for use in initial experiments were fabricated on a thermally oxidized Si wafer, onto which Nb was sputter-deposited for use as the pull-electrode layer. Nb was chosen because its refractory nature would enable it to withstand the chemical and thermal conditions to be subsequently imposed for growing carbon nanotubes. A 200- nm-thick layer of SiO2 was formed on top of the Nb layer by plasma-enhanced chemical vapor deposition. In the device regions, the SiO2 layer was patterned to thin it to the 20-nm trench depth. The trenches were then patterned by electron- beam lithography and formed by reactive- ion etching of the pattern through the 20-nm-thick SiO2 to the Nb layer.

Kaul, Anupama↗

Practically Accessible All-Solid-State Batteries Enabled by Organosulfide Cathodes and Sulfide Electrolytes

The combination of organic electrode materials and sulfide electrolytes is expected to enable the development of all-solid-state organic batteries featuring high energy density and long-term sustainability. In this work, thiuram hexasulfide is reported as a low-cost and high-capacity organic cathode for solid-state batteries based on sulfide electrolytes, delivering a capacity of ~600 mAh g -1 and retaining 80.8 % capacity after 500 cycles. An electrochemically reversible change of the cathode interface was revealed upon cycling. Full cell displays an oscillating stress change up to 0.6 MPa during cycling, predominated by the anode side. The energy density is 1140 Wh kg -1 at the material level and 376 Wh kg -1 at the electrode level, which are among the best-reported organic cathodes to date. A high areal capacity of 10.4 mAh cm -2 is reached with a high mass loading cathode. A dry-film approach is further explored to manufacture sheet-type cells. Free-standing electrolyte film is merely ~48 μm thick and demonstrates an ultralow areal resistance of 3.9 Ω cm 2 , significantly boosts the cell-level energy density and reduces the cell internal resistance.

25 ENERGY STORAGE↗

Superlattice-Structured Films by Magnetron Sputtering as New Era Electrodes for Advanced Lithium-ion Batteries

Sustaining sound structures in Si-based anodes is extremely challenging because of the high volumetric expansion that occurs upon cycling. To maintain high capacities over cycles, new designs rely on engineering-specific hierarchical geometries and/or optimized composite compositions such that at least one of the multiple elements serves as buffer and/or electron conductive pathways in the electrodes. In this paper, we report an innovative design in which alternating layers of periodic atomic structures involving multiple elements form a new anode material for lithium-ion batteries. In this work, a superlattice-structured amorphous film made using Si, Mo, and Cu is fabricated by a simple and scalable magnetron sputtering process for the first time. This continuous and repetitive superlattice formation along the film thickness provides a homogeneous stress-strain distribution. The Mo-Cu layer in the superlattice acts as an inactive-conductive layer and as a backbone to handle the volume expansion of active Si upon cycling. This nano-functional superlattice approach enables harnessing the high energy density of Si while maintaining its structural stability. As a result, the electrode exhibits high specific capacity and capacity retention even at high cycling rates. The possible use of the film in a full cell is also evaluated by cycling it vs. the LiMn 1.5 Ni 0.5 O 4 cathode. The full cell maintains a stable capacity of about 900 mAh g anode -1 over 150 cycles, at ~600 mA g -1 rate. The remarkable performance of this nano-functional superlattice film is found to be promising as anodes for applications that require high energy, long calendar life, and excellent abuse tolerance such as electric vehicle batteries.

25 ENERGY STORAGE↗

Operando video microscopy of Li plating and re-intercalation on graphite anodes during fast charging

Despite the demand for fast-charging lithium (Li)-ion batteries, high-energy-density batteries with thick graphite anodes are limited by Li plating when charging at >4C rates. In this work, plan-view operando video microscopy is applied on >3 mA h cm –2 calendared graphite electrodes to study the dynamic evolution of local state-of-charge (SoC) and Li plating during fast charging. This technique allows for visualization of the spatial heterogeneity in SoC across the electrode, nucleation and growth of Li filaments, Li re-intercalation into graphite, “dead Li” formation, and SoC equilibration. The operando microscopy analysis is complemented by ex situ imaging of through-plane gradients in SoC to gain a three-dimensional visualization of spatial heterogeneity. We demonstrate that (1) Li plating preferentially nucleates on the graphite particles that lithiate fastest during fast charging; (2) the onset of Li plating correlates with the local minimum of the graphite electrode potential; (3) galvanic corrosion currents are responsible for Li re-intercalation, dead Li formation, and SoC re-equilibration after fast charging; and (4) electrochemical signatures during OCV rest or discharge are associated with Li re-intercalation into graphite. Furthermore, this work provides insight into the Li–graphite interactions at the composite electrode level and can be used to inform strategies to diagnose and mitigate Li plating during fast charging.

25 ENERGY STORAGE↗

Insights into catalyst degradation during alkaline water electrolysis under variable operation

Energy conversion technologies that are key to decarbonization efforts face significant durability challenges due to variable operation. Understanding the impact of variable operation on catalytic stability and identifying the key variables that dictate degradation is crucial for developing robust technologies. Here, we present a comprehensive investigation of the effects of variable operation on liquid alkaline water electrolysis. Our findings reveal that variable operation induces severe degradation of Ni, Fe, and Co catalytic films that is not observed during steady-state operation. By systematically interrogating the electrode discharge during simulated shutdown tests using Raman spectroscopy and mass spectrometry techniques, we uncover significant alterations caused by reverse currents in real time. These include changes in crystal structure, composition, film thickness, electronic conductivity, and dissolution rates. Lab-scale electrolyzer experiments further highlight the impact of variable operation on catalyst materials under relevant conditions. Finally, we provide guidelines for leveraging these insights to advance electrocatalysis research. This work underscores the importance of integrating realistic stressors into stability testing and offers practical guidelines for catalyst design, performance evaluation, and industrial implementation. Collectively, insights from this study will drive the development of more resilient energy conversion technologies.

Marquez, Raul A. [Univ. of Texas, Austin, TX (Unit↗

How Interface Evolution at the Nanoscale Dictates Protonic Ceramic Cell Behavior

Understanding the effects of heterointerfaces in nanodevices remains a challenge in interface engineering for systems applied in solid oxide fuel cells, catalysis, sensors, and memristors [1]. Previous studies have shown that the presence of interfaces in ceramic oxide nanodevices affects their impedance properties compared to bulk systems [2]. In this work, we analyze a thin-film model system designed to study the interfaces between representative electrode and electrolyte materials employed in protonic ceramic electrochemical cells for the reversible conversion of hydrogen o electricity. The investigated device features a 21-layer architecture that alternates between an electrode material PBSCF (PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+ϵ ) and a proton-conducting electrolyte BZY (BaZr 0.8 Y 0.2 O 3-δ ), with uniform 20 nm thickness for each layer. Here, the device was fabricated using Pulsed Laser Deposition (PLD) and supported on a conductive Nb-doped STO (Nb-SrTiO 3 ) substrate.

dos Santos, Gabriel T. [Northwestern University, E↗

How Selective Transport Layer Improves Efficiency and Durability of Proton Exchange Membrane Fuel Cells

In any electrochemical device, the separator or membrane allows specific ions to transport but blocks electrons and other chemical species, enabling the electrochemical energy to be harvested. However, small amounts of undesired species are known to permeate through the membrane, reducing overall system efficiency and lifetime. An emerging concept called the “Selective Transport Layer” preferentially allows only protons to pass through but reduces the permeance of other species by a meaningful degree. Here, in this study, we demonstrate that a 60 nm thick graphene oxide composite layer can be very effective in reducing gas and ion permeation, even for a gas as small as H 2 , while not noticeably increasing proton transport resistance. In electrode and membrane accelerated stability tests, we show that both electrode and membrane durability are improved by a factor of two. Microscopy and mathematic simulations confirm that the graphene oxide composite is effective in blocking transport of dissolved Pt 2+ . The improved durability and reduced H 2 fuel crossover are expected to substantially reduce initial and operating costs of the fuel cell system. How this technology may affect other membrane-based electrochemical devices is also discussed.

Ngo, Phuong Quynh [General Motors, Pontiac, MI (Un↗

Distributed Capacitive Sensor for Sample Mass Measurement

Previous robotic sample return missions lacked in situ sample verification/ quantity measurement instruments. Therefore, the outcome of the mission remained unclear until spacecraft return. In situ sample verification systems such as this Distributed Capacitive (DisC) sensor would enable an unmanned spacecraft system to re-attempt the sample acquisition procedures until the capture of desired sample quantity is positively confirmed, thereby maximizing the prospect for scientific reward. The DisC device contains a 10-cm-diameter pressure-sensitive elastic membrane placed at the bottom of a sample canister. The membrane deforms under the weight of accumulating planetary sample. The membrane is positioned in close proximity to an opposing rigid substrate with a narrow gap. The deformation of the membrane makes the gap narrower, resulting in increased capacitance between the two parallel plates (elastic membrane and rigid substrate). C-V conversion circuits on a nearby PCB (printed circuit board) provide capacitance readout via LVDS (low-voltage differential signaling) interface. The capacitance method was chosen over other potential approaches such as the piezoelectric method because of its inherent temperature stability advantage. A reference capacitor and temperature sensor are embedded in the system to compensate for temperature effects. The pressure-sensitive membranes are aluminum 6061, stainless steel (SUS) 403, and metal-coated polyimide plates. The thicknesses of these membranes range from 250 to 500 m. The rigid substrate is made with a 1- to 2-mm-thick wafer of one of the following materials depending on the application requirements glass, silicon, polyimide, PCB substrate. The glass substrate is fabricated by a microelectromechanical systems (MEMS) fabrication approach. Several concentric electrode patterns are printed on the substrate. The initial gap between the two plates, 100 m, is defined by a silicon spacer ring that is anodically bonded to the glass substrate. The fabricated proof-of-concept devices have successfully demonstrated tens to hundreds of picofarads of capacitance change when a simulated sample (100 g to 500 g) is placed on the membrane.

Toda, Risaku↗

Electrochemical carbon deposition from CO 2 in molten carbonates: substrate-dependent growth

Electrochemical carbon deposition from molten carbonate salts using inert electrodes and no additional catalyst is systematically examined. At sufficiently cathodic potentials, carbon formation occurs within 30 min and transitions from substrate-dependent nucleation to carbon-on-carbon growth. Although deposits formed on either mild-steel or graphite cathodes exhibit comparable thicknesses and salt contents, their macrostructures differ, reflecting differences in early-stage growth rates and surface chemistry. Characterization by ICP-OES, Raman spectroscopy, SEM/EDS, synchrotron powder X-ray diffraction, and C K-edge X-ray absorption near edge structure reveals that the as-deposited carbon is predominantly disordered sp 2 -bonded material. However, post-treatment reveals latent turbostratic ordering in select samples, indicating that short-range order is established during deposition but is obscured by an entrained electrolyte and kinetically formed amorphous phases. No anode-derived contamination is detected, and carbon grown on graphite cathodes shows minimal metallic impurities. These results clarify the role of cathode surface chemistry and provide pathways for controlling electrode-derived impurity incorporation and carbon structure in catalyst-free molten carbonate systems.

36 MATERIALS SCIENCE↗

Two-Dimensional Siloxene Nanosheets: Impact of Morphology and Purity on Electrochemistry

Two-dimensional (2D) siloxene (Si 6 O 3 H 6 ) has shown promise as a negative electrode material for Li-ion batteries due to its high gravimetric capacity and superior mechanical properties under (de)lithiation compared to bulk Si. Here, in this work, we prepare purified siloxene nanosheets through the removal of bulk Si contaminants, use ultrasonication to control the lateral size and thickness of the nanosheets, and probe the effects of the resulting morphology and purity on the electrochemistry. The thin siloxene nanosheets formed after 4 h of ultrasonication deliver an average capacity of 810 mA h/g under a 1000 mA/g rate over 200 cycles with a capacity retention of 76%. Interestingly, the purified siloxene shows lower initial capacity but superior capacity retention over extended cycling. The 2D morphology benefit is illustrated where the parent siloxene nanosheet morphology and structure were largely maintained based on operando optoelectrochemistry, in situ Raman, ex situ scanning electron microscopy, and ex situ transmission electron microscopy. Furthermore, the purified siloxene-based electrode free from crystalline Si impurity experiences the least expansion upon (de)lithiation as visualized by cross-section electron microscopy of samples recovered post-cycling.

25 ENERGY STORAGE↗

Assessment of Blocking Contacts in Suppressing Polarization Effects in CsPbBr 3 Perovskite Detectors

The CsPbBr 3 perovskite has garnered significant attention as a room-temperature semiconductor for hard radiation detection due to straightforward synthesis, scalable crystal growth, low cost, and excellent energy resolution. However, despite these advantages, at ambient temperature, CsPbBr 3 devices may experience performance deterioration and irreversible failure due to “polarization” induced by electromigration of ions to electrical connections on the device. In this study, we tested several contact materials and their optimization deposition techniques to assess the stability of high-performance CsPbBr 3 γ-ray detectors. Metals, with low work functions (Ti, In, Sn, Sb, Pb, Bi, Al, Au, and TiC) and high-work-function (Au or Pt) contacts, were used to form different Schottky junctions using vacuum thermal evaporation, electron-beam evaporation, and sputtering methods. These detectors were tested in intermittent and continuous modes to assess their stability. Among the tested detectors, the Bi/CLB/Pt electrode configuration demonstrated superior stability, operating effectively for 11 months under periodic testing and 16 days under continuous testing. In contrast, other configurations functioned only for a few months under intermittent conditions. Upon incorporating a ~40-nm-thick TiC passivation layer on the anode side (Bi/TiC/CLB/Pt), the CLB device operated continuously for 36 days without degradation. In many cases, the failure mode of the devices was due to the degradation of the anode. Here, the chemical changes in the fresh and deteriorated anodes were characterized using scanning electron microscopy and energydispersive X-ray spectroscopy

CsPbBr3 perovskite↗

Automated assembly of Gallium Arsenide and 50-micron thick silicon solar cell modules

The TRW automated solar array assembly equipment was used for the module assembly of 300 GaAs solar cells and 300 50 micron thick silicon solar cells (2 x 4 cm in size). These cells were interconnected with silver plated Invar tabs by means of welding. The GaAs cells were bonded to Kapton graphite aluminum honeycomb graphite substrates and the thin silicon cells were bonded to 0.002 inch thick single layer Kapton substrates. The GaAs solar cell module assembly resulted in a yield of 86% and the thin cell assembly produced a yield of 46% due to intermittent sticking of weld electrodes during the front cell contact welding operation. (Previously assembled thin cell solar modules produced an overall assembly yield of greater than 80%).

Mesch, H. G.↗

Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

Rosario-Castro, Belinda I.↗

Ultrahigh Mass Loading Batteries with Holey Graphene-Enabled Dry-Pressed Cathode Architectures

Holey graphene is a structural derivative of graphene with arrays of nanometer-sized, through-thickness holes across the lateral surface of the atomically thin nanosheet. It has been widely acknowledged that the presence of holes improves ion transport through the graphene planes, making holey graphene an ideal electrode material for electrochemical energy storage. We recently discovered another unique attribute of holey graphene in that it can be directly compressed from powder into electrode in a single step without the use of solvent or binder. In addition to neat holey graphene electrodes, composite electrodes with holey graphene as an ultralightweight scaffold host filled with various active materials can also be readily prepared in a similar solvent-free and binder-free fashion. The active materials can be metal-containing catalysts for lithium-oxygen batteries, lithium-ion battery electrode materials, or high energy density components such as sulfur. Compared to the conventional slurry-based process, the dry-press method is comparably much more suitable toward the facile and scalable preparation of ultrahigh mass loading electrodes with ultrahigh areal capacities.

holey graphene, cathode scaffold, lithium metal, h↗

Opposed arcs permit deep weld penetration with only one pass

Arc welding technique uses opposed electrodes on either side of the workpiece, operated in right angles, out-of-phase, pulsating direct current. complete penetration has been obtained with this technique in metals ranging from 0.062 to 1.0 inch thickness.

Budds, L. E.↗