RESUMO
Lithium metal anodes offer high theoretical capacities (3,860 milliampere-hours per gram)1, but rechargeable batteries built with such anodes suffer from dendrite growth and low Coulombic efficiency (the ratio of charge output to charge input), preventing their commercial adoption2,3. The formation of inactive ('dead') lithium- which consists of both (electro)chemically formed Li+ compounds in the solid electrolyte interphase and electrically isolated unreacted metallic Li0 (refs 4,5)-causes capacity loss and safety hazards. Quantitatively distinguishing between Li+ in components of the solid electrolyte interphase and unreacted metallic Li0 has not been possible, owing to the lack of effective diagnostic tools. Optical microscopy6, in situ environmental transmission electron microscopy7,8, X-ray microtomography9 and magnetic resonance imaging10 provide a morphological perspective with little chemical information. Nuclear magnetic resonance11, X-ray photoelectron spectroscopy12 and cryogenic transmission electron microscopy13,14 can distinguish between Li+ in the solid electrolyte interphase and metallic Li0, but their detection ranges are limited to surfaces or local regions. Here we establish the analytical method of titration gas chromatography to quantify the contribution of unreacted metallic Li0 to the total amount of inactive lithium. We identify the unreacted metallic Li0, not the (electro)chemically formed Li+ in the solid electrolyte interphase, as the dominant source of inactive lithium and capacity loss. By coupling the unreacted metallic Li0 content to observations of its local microstructure and nanostructure by cryogenic electron microscopy (both scanning and transmission), we also establish the formation mechanism of inactive lithium in different types of electrolytes and determine the underlying cause of low Coulombic efficiency in plating and stripping (the charge and discharge processes, respectively, in a full cell) of lithium metal anodes. We propose strategies for making lithium plating and stripping more efficient so that lithium metal anodes can be used for next-generation high-energy batteries.
RESUMO
In this work, we investigated the interface between the sodium anode and the sulfide-based solid electrolytes Na3SbS4 (NAS), Na3PS4 (NPS), and Cl-doped NPS (NPSC) in all-solid-state-batteries (ASSBs). Even though these electrolytes have demonstrated high ionic conductivities in the range of 1 mS cm-1 at ambient temperatures, sulfide sold-state electrolytes (SSEs) are known to be unstable with Na metal, though the exact reaction mechanism and kinetics of the reaction remain unclear. We demonstrate that the primary cause of capacity fade and cell failure is a chemical reaction spurred on by electrochemical cycling that takes place at the interface between the Na anode and the SSEs. To investigate the properties of the Na-solid electrolyte interphase (SSEI) and its effect on cell performance, the SSEI was predicted computationally to be composed of Na2S and Na3Sb for NAS and identified experimentally via X-ray photoelectron spectroscopy (XPS). These two compounds give the SSEI mixed ionic- and electronic-conducting properties, which promotes continued SSEI growth, which increases the cell impedance at the expense of cell performance and cycle life. The SSEI for NPS was similarly found to be comprised of Na2S and Na3P, but XPS analysis of Cl-doped NPS (NPSC) showed the presence of an additional compound at the SSEI, NaCl, which was found to mitigate the decomposition of NPS. The methodologies presented in this work can be used to predict and optimize the electrochemical behavior of an all-solid-state cell. Such joint computational and experimental efforts can inform strategies for engineering a stable electrolyte and SSEI to avoid such reactions. Through this work, we call for more emphasis on SSE compatibility with both anodes and cathodes, essential for improving the electrochemical properties, longevity, and practicality of Na-based ASSBs.
RESUMO
Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of lithium-ion (Li-ion) batteries. However, a number of setbacks prevent their integration into commercial devices. The main limiting factor is due to nanoscale phenomena occurring at the electrode/electrolyte interfaces, ultimately leading to degradation of battery operation. These key problems are highly challenging to observe and characterize as these batteries contain multiple buried interfaces. One approach for direct observation of interfacial phenomena in thin film batteries is through the fabrication of electrochemically active nanobatteries by a focused ion beam (FIB). As such, a reliable technique to fabricate nanobatteries was developed and demonstrated in recent work. Herein, a detailed protocol with a step-by-step process is presented to enable the reproduction of this nanobattery fabrication process. In particular, this technique was applied to a thin film battery consisting of LiCoO2/LiPON/a-Si, and has further been previously demonstrated by in situ cycling within a transmission electron microscope.
Assuntos
Fontes de Energia Elétrica , Eletrodos , Íons/química , Lítio/químicaRESUMO
Zn aqueous batteries typically suffer from poor cycle life because water soluble zincate ions are formed during the oxidation of Zn. When Zn is oxidized, most of the Zn2+ ions detach from the current collector and become electrochemically inactive, leaving the battery non-rechargeable. Numerous reports demonstrate the use of Bi2O3 as an electrode additive to enhance electrochemical performance and they attribute this phenomenon to the improvement in electrical conductivity. However, conductivity does not have an effect on the intrinsic solubility of the zincate ion. We conduct a series of characterizations to provide a comprehensive mechanistic role of Bi2O3 in the Zn electrode. We find that upon oxidation, zincate ions are formed but they relax into ZnO on the surface of the bismuth species. This work proposes that the reason for the prolonged cycle life is due to the deposition of ZnO through relaxation and this prevents losing electrochemically active materials. This finding paves the way for further improving the cycle life and understanding the mechanism of the Zn based rechargeable aqueous batteries and possibly other conversion types of rechargeable batteries.
RESUMO
Direct solar-to-fuels conversion can be achieved by coupling a photovoltaic device with water-splitting catalysts. We demonstrate that a solar-to-fuels efficiency (SFE) > 10% can be achieved with nonprecious, low-cost, and commercially ready materials. We present a systems design of a modular photovoltaic (PV)-electrochemical device comprising a crystalline silicon PV minimodule and low-cost hydrogen-evolution reaction and oxygen-evolution reaction catalysts, without power electronics. This approach allows for facile optimization en route to addressing lower-cost devices relying on crystalline silicon at high SFEs for direct solar-to-fuels conversion.