RESUMEN
The full electrification of transportation will require batteries with both 3-5× higher energy densities and a lower cost than what is available in the market today. Energy densities of >1000 W h kg-1 will enable electrification of air transport and are among the very few technologies capable of achieving this energy density. Limetal-O2 or Limetal-air are theoretically able to achieve this energy density and are also capable of reducing the cost of batteries by replacing expensive supply chain constrained cathode materials with "free" air. However, the utilization of liquid electrolytes in the Limetal-O2/Limetal-air battery has presented many obstacles to the optimum performance of this battery including oxidation of the liquid electrolyte and the Limetal anode. In this paper a path towards the development of a Limetal-air battery using a cubic garnet Li7La3Zr2O12 (LLZ) solid-state ceramic electrolyte in a 3D architecture is described including initial cycling results of a Limetal-O2 battery using a recently developed mixed ionic and electronic (MIEC) LLZ in that 3D architecture. This 3D architecture with porous MIEC structures for the O2/air cathode is essentially the same as a solid oxide fuel cell (SOFC) indicating the importance of leveraging SOFC technology in the development of solid-state Limetal-O2/air batteries.
RESUMEN
Nanomaterials have found use in a number of relevant energy applications. In particular, nanoscale motifs of binary metal sulfides can function as conversion materials, similar to that of analogous metal oxides, nitrides, or phosphides, and are characterized by their high theoretical capacity and correspondingly low cost. This review focuses on structure-composition-property relationships of specific relevance to battery applications, emanating from systematic attempts to either (1) vary and alter the dimension of nanoscale architectures or (2) introduce conductive carbon-based entities, such as carbon nanotubes and graphene-derived species. In this study, we will primarily concern ourselves with probing metal sulfide nanostructures generated by a microwave-mediated synthetic approach, which we have explored extensively in recent years. This particular fabrication protocol represents a relatively facile, flexible, and effective means with which to simultaneously control both chemical composition and physical morphology within these systems to tailor them for energy storage applications.
RESUMEN
Herein, zinc vanadium oxide (ZVO) and zinc hydroxy-sulfate (ZHS) formation as discharge products in sodium vanadium oxide (NVO) cathode materials of two distinct morphologies, NVO(300) and NVO(500), is studied with ex situ and operando X-ray diffraction methods. ZHS formation upon discharge is shown to be favored at higher current densities and reversible upon charge, while ZVO formation is found to be favored at lower current densities but persists throughout cycling. Operando synchrotron-based energy dispersive X-ray diffraction (EDXRD) reveals reversible expansion of the NVO lattice due to Zn2+ during discharge, spontaneous ZVO formation following cell assembly, and ZHS formation concomitant with H+ insertion at potentials less than â¼0.8 V vs Zn/Zn2+. With spatially resolved EDXRD, ZVO formation is show to occur near the separator region first, eventually moving to the current collector region as discharge depth increases. ZHS formation, however, is found to originate from the current collector side of the positive electrode and then propagate through the porous electrode network. This study highlights the special benefits of the EDXRD method to gain mechanistic insight into structural evolution within the electrode and at its interface.
RESUMEN
The electrochemical charge storage of sodium vanadate (NaV3O8 or NVO) cathodes in aqueous Zn-ion batteries has been hypothesized to be influenced by the inclusion of structural water for facilitating ion transfer in the material. Materials properties considered important (morphology, crystallite and particle size, surface area) are systematically studied herein through investigation of two NVO materials, NaV3O8·0.34H2O [NVO(300)] and NaV3O8·0.05H2O [NVO(500)], with different water content, acicular morphologies with different size and surface area achieved via post-synthesis heat treatment. The electrochemistry of the two materials was evaluated in aqueous Zn-ion cells with 2 M ZnSO4 electrolyte using cyclic voltammetry, galvanostatic cycling, and rate capability testing. The thinner NVO(300) nanobelts (0.13 µm) demonstrate greater specific capacities and higher effective diffusion coefficients relative to the thicker NVO(500) nanorods. Notably however, while cells containing NVO(500) deliver lower specific capacity, they demonstrate enhanced capacity retention with cycling. The structural changes accompanying oxidation and reduction are elucidated via ex situ X-ray diffraction, transmission electron microscopy, and operando V K-edge X-ray absorption spectroscopy (XAS), where NVO material properties are shown to influence the ion insertion. Operando XAS verified that electron transfer corresponds directly to change in vanadium oxidation state, affirming vanadium redox as the governing electrochemical process.
RESUMEN
One of the inherent challenges with Li-S batteries is polysulfide dissolution, in which soluble polysulfide species can contribute to the active material loss from the cathode and undergo shuttling reactions inhibiting the ability to effectively charge the battery. Prior theoretical studies have proposed the possible benefit of defective 2 D MoS2 materials as polysulfide trapping agents. Herein the synthesis and thorough characterization of hydrothermally prepared MoS2 nanosheets that vary in layer number, morphology, lateral size, and defect content are reported. The materials were incorporated into composite sulfur-based cathodes and studied in Li-S batteries with environmentally benign ether-based electrolytes. Through directed synthesis of the MoS2 additive, the relationship between synthetically induced defects in 2 D MoS2 materials and resultant electrochemistry was elucidated and described.
RESUMEN
Silicon offers high theoretical capacity as a negative electrode material for lithium-ion batteries; however, high irreversible capacity upon initial cycling and poor cycle life have limited commercial adoption. Herein, we report an operando isothermal microcalorimetry (IMC) study of a model system containing lithium metal and silicon composite film electrodes during the first two cycles of (de)lithiation. The total heat flow data are analyzed in terms of polarization, entropic, and parasitic heat flow contributions to quantify and determine the onset of parasitic reactions. These parasitic reactions, which include solid-electrolyte interphase formation, contribute to electrochemical irreversibility. Cycle 1 lithiation demonstrates the highest thermal energy output at 1509 mWh/g, compared to cycle 1 delithiation and cycle 2. To complement the calorimetry, operando X-ray diffraction is used to track the phase evolution of silicon. During cycle 1 lithiation, crystalline Si undergoes transformation to amorphous lithiated silicon and ultimately to crystalline Li15Si4. The solid-state amorphization process is correlated to a decrease in entropic heat flow, suggesting that heat associated with the amorphization contributes significantly to the entropic heat flow term. This study effectively uses IMC to probe the parasitic reactions that occur during lithiation of a silicon electrode, demonstrating an approach that can be broadly applied to quantify parasitic reactions in other complex systems.
