RESUMO
The solid electrolyte interphase (SEI) in lithium-ion batteries separates the highly reductive lithiated graphite from reducible electrolyte components. It is critical for the performance, durability, and safe operation of batteries. Inâ situ imaging of the SEI is demonstrated using the feedback mode of scanning electrochemical microscopy (SECM) with 2,5-di-tert-butyl-1,4-dimethoxy benzene as mediator. The formation of the SEI is indicated by a decrease of the mediator regeneration rate. Prolonged imaging of the same region revealed fluctuation of the passivating properties on time scales between 2â min and 20â h with an inhomogeneous distribution over the sample. The implications of the approach for inâ situ assessment of local SEI properties on graphite electrodes are discussed with respect to studying the influence of mechanical stress on SEI reliability and the mode of action of electrolyte additives aiming at improving SEI properties.
RESUMO
Fluoride shuttle batteries (FSBs), which utilize defluorination of metal fluorides and fluorination of the resultant metals, are expected to have high energy densities. Inâ situ Raman microscopy was conducted during FSB reactions of a nearly-2D cluster of orthorhombic BiF3 microparticles partly embedded in a gold-plated film (o-BiF3 /gold). At a high overpotential, defluorination of the surface of an o-BiF3 particle (or cluster) was almost completed within approximately 120â s. At a low over potential, defluorination proceeded from the contours of the cluster that was in contact with the gold to the center of the cluster, suggesting that the rate-limiting process was electronic diffusion. Conversely, fluorination proceeded uniformly at the surface of the cluster to form BiF3 with a cubic structure (c-BiF3 ). The results will lead to the establishment of a strategy for efficient use of active materials with low electronic and ionic conductivities.
RESUMO
Lithium-ion batteries have attracted considerable attention due to their high power density. The change in concentration of salt in the electrolyte solution in lithium-ion batteries during operation causes serious degradation of battery performance. Herein, a new method of inâ situ Raman spectroscopy with ultrafine multifiber probes was developed to simultaneously study the concentrations of ions at several different positions in the electrolyte solution in deep narrow spaces between the electrodes in batteries. The total amount of ions in the electrolyte solution clearly changed during operation due to the low permeability of the solid-electrolyte interphase (SEI) at the anode for Li+ permeation. The permeability, which is a key factor to achieve high battery performance, was improved (enhanced) by adding film-forming additives to the electrolyte solution to modify the properties of the SEI. The results provide important information for understanding and predicting phenomena occurring in a battery and for designing a superior battery. The present method is useful for analysis in deep narrow spaces in other electrochemical devices, such as capacitors.
Assuntos
Fontes de Energia Elétrica , Lítio/química , Sais/química , Eletrodos , Análise Espectral RamanRESUMO
Complementary analytical methods have been used to study the effect of potassium on the pyrolysis mechanisms of cellulose and lignocellulosic biomasses. Thermogravimetry, calorimetry, high-temperature (1) Hâ NMR spectroscopy (inâ situ and real-time analysis of the fluid phase formed during pyrolysis), and water extraction of quenched char followed by size-exclusion chromatography coupled with mass spectrometry have been combined. Potassium impregnated in cellulose suppresses the formation of anhydrosugars, reduces the formation of mobile protons, and gives rise to a mainly exothermic signal. The evolution of mobile protons formed from K-impregnated cellulose has a very similar pattern to the evolution of the mass loss rate. This methodology has been also applied to analyze miscanthus, demineralized miscanthus, miscanthus re-impregnated with potassium after demineralization, raw oak, and Douglas fir. Hydrogen mobility and transfer are of high importance in the mechanisms of biomass pyrolysis.
Assuntos
Biomassa , Potássio/química , Abies , Varredura Diferencial de Calorimetria , Celulose/química , Cromatografia em Gel , Temperatura Alta , Espectrometria de Massas , Poaceae , Espectroscopia de Prótons por Ressonância Magnética , Quercus , TermogravimetriaRESUMO
The ability to directly track the charge carrier in a battery as it inserts/extracts from an electrode during charge/discharge provides unparalleled insight for researchers into the working mechanism of the device. This crystallographic-electrochemical information can be used to design new materials or modify electrochemical conditions to improve battery performance characteristics, such as lifetime. Critical to collecting operando data used to obtain such information inâ situ while a battery functions are X-ray and neutron diffractometers with sufficient spatial and temporal resolution to capture complex and subtle structural changes. The number of operando battery experiments has dramatically increased in recent years, particularly those involving neutron powder diffraction. Herein, the importance of structure-property relationships to understanding battery function, why inâ situ experimentation is critical to this, and the types of experiments and electrochemical cells required to obtain such information are described. For each battery type, selected research that showcases the power of inâ situ and operando diffraction experiments to understand battery function is highlighted and future opportunities for such experiments are discussed. The intention is to encourage researchers to use inâ situ and operando techniques and to provide a concise overview of this area of research.