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At least 613 records · Page 34

The Promise of Alloy Anodes for Solid-State Batteries

Solid-state batteries are anext-generation technology that could featureimproved safety and energy density, but reliably integrating high-capacity electrode materials to enable high energy while retaining stablelong-termcycling remains a challenge. Anode materials that alloy with lithium, such as silicon, tin, and aluminum,offer high capacity that canyield high-energy battery cells. The use of alloy anodes in solid-state batteries potentially offers major mechanistic benefits compared to other anode contendersand battery systems, such as lithium metal in solid-state architectures or alloys in liquid-electrolyte batteries. This perspective discusseskey advantagesof alloy anode materials for solid-state batteries, including the avoidance of the short circuiting observed with lithium metal and the chemo-mechanical stabilization of the solid-electrolyte interphase (SEI). We further discuss open research questions and challenges in engineering alloy-anode-based solid-state batteries, with the goal of advancing our understanding and control of alloy anode materialswithin solid-state architectures toward commercial application.

John A Lewis↗

Vertically stacked photovoltaic and thermal solar cell

According to some embodiments, the present invention provides a novel photovoltaic solar cell system from photovoltaic modules that are vertically arrayed in a stack format using thin film semiconductors selected from among organic and inorganic thin film semiconductors. The stack cells may be cells that are produced in a planar manner, then vertically oriented in an angular form, also termed herein tilted, to maximize the light capturing aspects. The use of a stack configuration system as described herein allows for the use of a variety of electrode materials, such as transparent materials or semitransparent metals. Light concentration can be achieved by using fresnel lens, parabolic mirrors or derivatives of such structures. The light capturing can be controlled by being reflected back and forth in the photovoltaic system until significant quantities of the resonant light is absorbed. Light that passes to the very end and can be reflected back through the device by beveling or capping the end of the device with a different refractive index material, or alternatively using a reflective surface. The contacting between stacked cells can be done in series or parallel. According to some embodiments, the present invention uses a concentrator architecture where the light is channeled into the cells that contain thermal fluid channels (using a transparent fluid such as water) to absorb and hence reduce the thermal energy generation.

14 SOLAR ENERGY↗

Large-volume-change lithium battery electrodes

A battery electrode material includes: 1) primary particles formed of an electrochemically active material; and 2) a secondary particle defining multiple, discrete internal volumes, wherein the primary particles are disposed within respective ones of the internal volumes.

Cui, Yi↗

Coated semiconductor particles and methods of making the same

The present disclosure relates to an electrode material that includes a solid core particle having an outer surface and including at least one of a Group II element, a Group III element, a Group IV element, a Group V element, and/or a Group VI element, and a layer including a polymer, where the solid core particle has a characteristic length between greater than zero nanometers and 1000 nm, the layer substantially covers all of the outer surface, the layer has a thickness between greater than zero nanometers 100 nm, and the layer is capable of elastically stretching as a result of expansion and contraction by the solid core.

Ban, Chunmei↗

Wet chemical synthesis and properties of argyrodite sulfide solid electrolytes for solid state lithium batteries

The commercialization of the lithium-ion battery (LIB) in 1991 was responsible for the explosion in portable electronic technologies that has been seen over the past 30 years. With the advent of electric vehicles and other high-powered technologies, there is tremendous demand for LIBs with higher energy density and high safety. To achieve this, new electrode materials must be explored. The obvious choice of anode material would be pure metal lithium, which has a theoretical specific capacity of 3860 mAh g-1 . Unfortunately, metal lithium anodes have not been widely commercialized due to their tendency to react violently with the flammable liquid electrolytes used in today’s batteries. Battery safety can best be achieved by adopting solid electrolytes in place of liquid electrolytes. Solid electrolytes are nonvolatile and nonflammable, safely allowing for the combination of high-capacity cathode materials with a Li metal anode. Argyrodite sulfide solid electrolytes such as halogen-doped Li6PS5X (X = Cl, Br, I) are noted for their high ionic conductivity. But before sulfides can be commercially adopted, they possess several disadvantages which must be addressed, including time- and energy-consuming synthesis processes, poor electrochemical stability, and intrinsically poor air stability. This dissertation seeks to address each of these challenges through materials design an synthesis strategies. In this work, we pioneer a solvent-based approach for the synthesis of argyrodite solid electrolytes Li7PS6 and Li6PS5Xinstead of a stringent solid-state synthesis. Nontoxic ethanol is employed as the solvent, enabling a rapid synthetic approach to produce argyrodite solid electrolytes with high phase purity and compositional flexibility. Compared with Li7PS6, halogen doping (i.e. X = F, Cl, Br, I) not only increases the ionic conductivity, but also enhances the electrochemical stability at the interface towards Li metal. Specifically, F-doped argyrodites produce a robust SEI layer containing LiF, contributing to enhanced interfacial stability. Finally, to address the air instability challenge, argyrodite-incorporated composite solid electrolytes (CSEs) are designed and prepared to produce stable and flexible membranes that are demonstrated in solid-state Li metal batteries. These advances push argyrodite sulfide solid electrolyte research further and pave the way for the proliferation of next generation lithium metal batteries.

25 ENERGY STORAGE↗

CONVENTIONAL SUPERCAPACITOR ELECTROLYTES: AQUEOUS, ORGANIC, AND IONIC

This chapter thoroughly covers the most recent developments of aqueous and non-aqueous electrolytes for electrochemical supercapacitors (ESs). In more detail, the overview of different types of electrolytes and their featured properties are initially introduced. Thereafter, the conventional aqueous electrolyte was first discussed, summarized, and opened the perspectives of some new salts that can be used to enhance the ionic conductivity and the performance of supercapacitor. The organic electrolytes, including the organic solvents/salt, ionic liquids, and deep eutectic, are the main parts to explore different trends and cutting-edge advances in optimizing electrolyte formulations customized for different electrode materials. Furthermore, the discussion on the current obstacles and prospects of these electrolytes is also underlined.

electrochemical capacitors, aqueous electrolyte, o↗

Examples of X-Ray Characterization Techniques in Energy Storage Research

Lithium-ion batteries have revolutionized the portable electronics and transportation sectors. Their performance is often critically dependent on the crystal structures of the anode and cathode electrode materials, which must enable the transport and reversible storage of lithium ions into and out of the lattice. Because lithium is a low-Z element, characterization of materials for lithium-ion batteries can be particularly challenging. Regardless, X-ray techniques enable analysis of material structures to better understand how battery materials perform and degrade, particularly when combined with other materials characterization and electrochemical characterization techniques. While X-ray techniques are most often used in battery research for phase identification of crystal structures, X-ray characterization techniques are also used for a wide variety of other purposes. I will discuss several examples from my research with various collaborators on several projects that highlight the impact that X-ray characterization techniques can have on battery research. The first example will focus on low-temperature microwave-assisted solvothermal synthesis of vanadium-doped LiFePO4 cathode materials for lithium-ion batteries. (1,2) Through a combination of electrochemical and materials characterization, we determined that low temperature synthesis resulted in metastable phases that enabled incorporation of higher dopant levels than resulting from high-temperature synthesis of thermodynamically stable phases. Rietveld refinement of X-ray diffraction data enabled understanding of how lattice parameters changed with doping levels and synthesis temperature. X-ray absorption near edge spectroscopy enabled understanding of the vanadium and iron oxidation states to confirm how vacancies in the structure caused by doping were charge compensated. This was important to understand because the literature suggests doping can improve LiFePO4 electrical conductivity, which improves battery charge and discharge rates. The second example will focus on understanding residual strain in lithium metal anodes. Lithium-ion batteries typically use graphite anodes, but the charge-storage capacity can be theoretically improved ~10x by using lithium metal as the anode material instead. However, lithium anodes suffer from growth of high-aspect-ratio features, such as dendrites, that can pierce nanoporous polymer separators and lead to short circuits and fires. External pressure is commonly applied to cells to enable better morphological control. We hypothesized that applied pressure may promote strain and possibly work hardening during electrochemical cycling, which motivated us to look for evidence of residual strain in lithium metal cycled under applied pressure using X-ray diffraction and sin2(..psi..) analysis. We found that lithium electrodeposited under high pressure exhibited in-plane compressive strain and that that lithium electrodeposited under low pressure did not. (3) The residual strain that accompanies electrodeposition under high pressure may lead to work hardening, which may explain how a soft metal like lithium can puncture separators and why higher pressure does not always decrease short circuits. (4-6) References: 1) Harrison, K. L.; Manthiram, A. Microwave-Assisted Solvothermal Synthesis and Characterization of Metastable LiFe1- x (VO) x PO4 Cathodes. Inorganic chemistry 2011, 50(8), 3613-3620. 2) Harrison, K. L.; Bridges, C. A.; Paranthaman, M. P.; Segre, C. U.; Katsoudas, J.; Maroni, V. A.; Idrobo, J. C.; Goodenough, J. B.; Manthiram, A. Temperature Dependence of Aliovalent-Vanadium Doping in LiFePO4 Cathodes. Chemistry of Materials 2013, 25(5), 768-781. 3) Rodriguez, M. A.; Harrison, K. L.; Goriparti, S.; Griego, J. J.; Boyce, B. L.; Perdue, B. R. Use of a Be-Dome Holder for Texture and Strain Characterization of Li Metal Thin Films via Sin2 (..psi..) Methodology. Powder Diffraction 2020, 35(2), 89-97. 4) Jungjohann, K. L.; Gannon, R. N.; Goriparti, S.; Randolph, S. J.; Merrill, L. C.; Johnson, D. C.; Zavadil, K. R.; Harris, S. J.; Harrison, K. L. Cryogenic Laser Ablation Reveals Short-Circuit Mechanism in Lithium Metal Batteries. ACS Energy Letters 2021, 6(6), 2138-2144. 5) Harrison, K. L.; Merrill, L. C.; Long, D. M.; Randolph, S. J.; Goriparti, S.; Christian, J.; Warren, B.; Roberts, S. A.; Harris, S. J.; Perry, D. L. Cryogenic Electron Microscopy Reveals That Applied Pressure Promotes Short Circuits in Li Batteries. Iscience 2021, 24(12). 6) Harrison, K. L.; Goriparti, S.; Merrill, L. C.; Long, D. M.; Warren, B.; Roberts, S. A.; Perdue, B. R.; Casias, Z.; Cuillier, P.; Boyce, B. L. Effects of Applied Interfacial Pressure on Li-Metal Cycling Performance and Morphology in 4 M LiFSI in DME. ACS Applied Materials & Interfaces 2021, 13(27), 31668-31679.

batteries↗

Project Development of an Electrochemical Denitration and Caustic Generation System for HLW Pretreatment at Hanford - 26350

An engineering-scale electrochemical processing skid is proposed to perform the denitration of Hanford tank waste, which would help to mitigate a key process concern with the direct feed processing of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The reduction of nitrates and organic compounds in the waste feed will directly reduce hazardous NOx and ammonia gases generated during the vitrification process, which in turn will aid in addressing potential regulatory and safety challenges associated with processing large volumes of tank waste. This paper highlights the past legacy work, project layout, accomplishments from Phase 1 and research and development envisioned for Phase 2. An innovative electrochemical denitration and caustic generation (EDCGe) process was demonstrated for the pretreatment of tank waste at the Savannah River Site (SRS) in the early 2000s. The denitration electrolyzer, off-gas abatement system, and caustic generator electrolyzer are being developed with the intent that the denitration electrolyzer will convert nitrate and nitrite anions to nitrogen gas while also yielding other gaseous byproducts, which may include N2O, NH3, VOCs, and H2. The gaseous byproducts will be managed via a tandem off-gas catalyst-bed treatment system. The caustic generation electrolyzer will recycle NaOH from the feed to produce a clean caustic stream for use within the batching tanks at Hanford, aiding in the preparation of waste for WTP. The reduction in hazardous emissions and improved waste treatment processes provides a robust solution for nuclear waste management, contributing to environmental safety and regulatory compliance. The EDCGe technology is being adapted, modified, and updated for the preparation of the Direct Feed-High Level Waste (DF-HLW) flowsheet at Hanford. Phase 1 demonstrated a bench-scale proof-of-concept for reactions involving the denitration electrolyzer and gas phase abatement of ammonia. The electrochemical technology is drawing on the scientific outcomes that were reported in the legacy work. The results from Phase 1 demonstrated the viability of the EDCGe system in reducing the nitrogen species of simple non-radioactive waste simulants. Commercially available alloys used as electrode materials and membranes are being studied for the denitration and caustic generation electrolyzers. The continuation of this project holds promise for broader applications, such as energy-efficient ammonia production, and contributes significant advancements in nuclear waste management. Additional material discovery has been investigated into ceramic Na super ion conductive (NaSICON) materials and off-gas abatement catalyst discovery. NaSICON is of interest for selective transport of Na within the electrolyzers to make a clean caustic stream. Future integration and optimization efforts, informed by Phase 1 results and ongoing research, will continue to drive advancements in nuclear waste management technology. The technology developed for the EDCGe treatment of tank waste will also have broader potential to inform other fields, such as energy-efficient ammonia production, as well as ammonia abatement catalysis through the lessons learned in electrochemical nitrate reduction. The applications and benefits of this research extend beyond Hanford and the Savannah River Site, supported by a collaborative team of scientists and engineers from national labs, academia, and industry, ensuring a comprehensive approach to solving complex waste treatment challenges. The team is leveraging advanced electrochemical technologies, machine learning, novel catalysts tailored for gaseous nitrogen species, and cutting-edge reactor systems to enhance the process efficiency and effectiveness of the denitration process.

Rodene, Dylan [Savannah River National Laboratory ↗

Defect Thermodynamics and Transport Properties of Proton Conducting Perovskite Electrode and Electrolyte Materials Evaluated Based on Density Functional Theory Modeling

Both electron-rich and electron-poor perovskite oxides have been used in solid oxide cell applications as electrode and electrolyte materials. The rich oxygen defect chemistry and its coupling to temperature, hydrogen-steam or oxygen-steam gas pressure, or to the applied potentials creates enormous complexities for modeling performance and degradation of the materials. Herein, density functional theory-based thermodynamic modeling was carried out to describe the defect chemistry and transport properties of the proton-conducting electrolyte BaZr1-xYxO3-δ (x≤0.1) and of the triple-conducting perovskite (La,Ba)(Fe,M)O3-δ (M=Y and Zr). The defect thermodynamics of intrinsic point defects and the hydrogen-related defect reactions were solved in integrated defect models and further used to predict the Brouwer diagram and the transport properties of the functional perovskites. For the electron-poor electrolytes BaZr0.9Y0.1O3-δ, the developed model has been used to describe the experimental transport properties in the SOC operating conditions. Specifically, the roles played by the acceptor-bound holes and the intrinsic and hydrogen point defects upon the conductivities of holes, protons, and oxygen vacancies under the hydrogen-rich and oxygen-rich conditions at various humidity levels were demonstrated. A defect modeling tool was also developed for the triple-conducting perovskite (La,Ba)(Fe,M)O3-δ (M=Y and Zr) to examine magnetic effects and hydride defects in defect equilibria.

defect thermodynamics↗

Low-Tortuosity Thick Electrodes with Active Materials Gradient Design for Enhanced Energy Storage

The ever-growing energy demand of modern society calls for the development of high-loading and high-energy-density batteries, and substantial research efforts are required to optimize electrode microstructures for improved energy storage. Low-tortuosity architecture proves effective in promoting charge transport kinetics in thick electrodes; however, heterogeneous electrochemical mass transport along the depth direction is inevitable, especially at high C-rates. In this work, we create an active material gradient in low-tortuosity electrodes along ion-transport direction to compensate for uneven reaction kinetics and the nonuniform lithiation/delithiation process in thick electrodes. The gradual decrease of active material concentration from the separator to the current collector reduces the integrated ion diffusion distance and accelerates the electrochemical reaction kinetics, leading to improved rate capabilities. Further, the structure advantages combining low-tortuosity pores and active material gradient offer high mass loading (60 mg cm –2 ) and enhanced performance. Comprehensive understanding of the effect of active material gradient architecture on electrode kinetics has been elucidated by electrochemical characterization and simulations, which can be useful for development of batteries with high-energy/power densities.

25 ENERGY STORAGE↗

Amorphous Iridium Oxide-Integrated Anode Electrodes with Ultrahigh Material Utilization for Hydrogen Production at Industrial Current Densities

Herein, ionomer-free amorphous iridium oxide (IrO x ) thin electrodes are first developed as highly active anodes for proton exchange membrane electrolyzer cells (PEMECs) via low-cost, environmentally friendly, and easily scalable electrodeposition at room temperature. Combined with a Nafion 117 membrane, the IrO x -integrated electrode with an ultralow loading of 0.075 mg cm –2 delivers a high cell efficiency of about 90%, achieving more than 96% catalyst savings and 42-fold higher catalyst utilization compared to commercial catalyst-coated membrane (2 mg cm –2 ). Additionally, the IrO x electrode demonstrates superior performance, higher catalyst utilization and significantly simplified fabrication with easy scalability compared with the most previously reported anodes. Notably, the remarkable performance could be mainly due to the amorphous phase property, sufficient Ir 3+ content, and rich surface hydroxide groups in catalysts. Overall, due to the high activity, high cell efficiency, an economical, greatly simplified and easily scalable fabrication process, and ultrahigh material utilization, the IrO x electrode shows great potential to be applied in industry and accelerates the commercialization of PEMECs and renewable energy evolution.

08 HYDROGEN↗

Plasma confinement system with outer electrode having liquifiable material and methods for use

An example plasma confinement system includes an inner electrode having a rounded first end that is disposed on a longitudinal axis of the plasma confinement system and an outer electrode that at least partially surrounds the inner electrode. The outer electrode includes a solid conductive shell and an electrically conductive material disposed on the solid conductive shell and on the longitudinal axis of the plasma confinement system. The electrically conductive material has a melting point within a range of 170° C. to 800° C. at 1 atmosphere of pressure. Related plasma confinement systems and methods are also disclosed herein.

Shumlak, Uri↗

Rechargeable alkaline battery using organic materials as negative electrodes

An energy storage device may provide a positive electrode, an electrolyte, and a negative electrode. The energy storage device may utilize an aqueous alkaline electrolyte, which may be nonflammable. The energy storage device may utilize organic material(s) as the negative electrode, such as, but not limited to, poly(anthraquinonyl sulfide) (PAQS), organic carbonyl compounds, organosulfur compounds, redox polymers, or radical polymers.

25 ENERGY STORAGE↗

Significance of a Solid Electrolyte Interphase on Separation of Anode and Cathode Materials from Spent Li-Ion Batteries by Froth Flotation

The separation of electrode active materials from spent Li-ion batteries (LIBs) by froth flotation is challenging due to the changes in surface properties of electrode active materials from cycling as well as the presence of organic binders. In this work, the froth flotation separation of aged anode and cathode composite materials from spent LIBs was systematically investigated after the materials were heat treated. The results show that aged anode and cathode materials from spent LIBs can be well separated from each other after a heating process in air at 400 degrees C and at which some of the PVDF binder remains intact. The underlying mechanism was investigated by X-ray photoelectron spectroscopy (XPS), contact angle measurements, and scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray spectroscopy (EDX). The results from the XPS and contact angle measurements show that there is a hydrophilic and oxygen-rich layer on the surface of aged anode materials. This hydrophilic surface, associated with the solid electrolyte interface (SEI) layer, impacts the froth flotation process significantly. The results also show that both the SEI layers and PVDF binder residues on the surface are removed at 400 degrees C for an hour, restoring the hydrophobicity of the anode materials, which, in turn, benefits the separation of anode and cathode materials. The STEM/EDX elemental analysis data confirms that there are 20 nm-thick oxygen-rich SEI layers on the surfaces, which can be removed after a heating process. The present result illustrates the significance of the SEI layers in flotation separation of electrode materials and sheds new lights into the future development of the recycling processes for the separation of anode and cathode composite materials from spent Li-ion batteries.

25 ENERGY STORAGE↗

Recent advancements in high performance polymer electrolyte fuel cell electrode fabrication – Novel materials and manufacturing processes

The global effort to introduce polymer electrolyte fuel cells for clean and renewable energy to the market is increasing the demand for high performance, robust and affordable membrane electrode assemblies (MEAs). There is not yet a standard method for large scale production of MEAs, or the methods employed are generally unsatisfactory in terms of quality and performance. A large number of published data of newly developed catalyst and electrolyte materials, claim to improve the state of the art, but are often not fully comparable due to different experimental studies and experimental designs. This article summarizes the trends in material developments and emerging MEA-manufacturing techniques. The materials and techniques are systematically compared in terms of cell performance and scalability. Current and future scientific challenges are identified and analysed based on published findings over the past five years. Finally, the results of the cited papers have been quantitatively compared to each other and to the internal benchmarks used in each cited work to provide a complete picture of the state of the art in PEFC MEA manufacturing.

25 ENERGY STORAGE↗

Design and Materials of Reference Electrodes for Radioactive Waste Tank Service – A Literature Review

The Hanford site stores approximately 55 million gallons of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground, carbon steel storage tanks, 149 of these are single shell tanks (SSTs) and 28 of these are double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The DSTs have been in service for 38 to 56 years and current plans indicate that WTP operations will be completed in 2075. Thus, the tanks will need to remain in service far beyond the initial 40-year life expectancy. For life extension of the tanks, effective corrosion control practices must remain in force. This effort includes direct measurements of the extent of corrosion (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Lead-lead oxide-carbon nanocomposite for energy storage cells and method of preparation

Lead/lead oxide/carbon (“Pb—O—C”) nanocomposite materials are useful as electrode active materials for electrodes in lithium and sodium batteries. A Pb—O—C nanocomposite as described herein comprises Pb and lead oxide nanoparticles homogeneously dispersed in a carbon nanoparticle matrix. In the nanocomposite, the other element or elements (e.g., transition metals, Al, Si, P, Sn, Sb, and Bi) can be alloyed with the Pb nanoparticles, incorporated as a mixed oxide with the lead oxide nanoparticles, or can be present as distinct elemental or oxide nanoparticles within the carbon nanoparticle matrix. In some embodiments, the additional element or elements are present as alloys and mixed oxides with the Pb materials and as distinct elemental and/or oxide nanoparticles. In a preferred embodiment the Pb nanoparticles surface is oxidized to lead oxide thus creating a shell on core nanostructure.

Johnson, Christopher S.↗