Influence of Additives on the Electrochemical and Interfacial Properties of SiOx-Based Anode Materials for Lithium-Sulfur Batteries.

The influence of electrolyte additives on the electrochemical and interfacial properties of SiOx-based anodes for lithium-sulfur batteries (Li-S) was systematically investigated. Four different electrolyte additives, namely, lithium nitrate, vinylene carbonate (VC), vinyl ethylene carbonate, and fluoroethylene carbonate (FEC), were added to the bare electrolyte comprising 1 M LiTFSI in tetraethylene glycol dimethyl ether/1,3 dioxolane in a ratio of 1:1 (v/v). The self-extinguishing time (SET) of the liquid electrolytes was measured. The 2032-type half-cells composed of Li/SiOx/Si/C were assembled, and their charge -discharge studies were analyzed at the 0.1 C-rate. Upon cycling, the electrode materials were subjected to surface morphology and differential scanning calorimetry analyses. The interfacial properties of SiOx-based electrodes were investigated by electrochemical impedance spectroscopy, Fourier transform infrared, and X-ray photoelectron spectroscopy studies. Among the electrolytes examined, FEC-added electrolytes offered the lowest SET and interfacial resistance values. The superior charge-discharge properties of FEC-added electrolytes were attributed to the formation of a stable solid electrolyte interface layer on the electrode surface. The surface chemistry studies revealed the formation of Li2CO3 and ROCO2Li peaks on the electrode surface.

Microporous Metal-Organic Framework (MOF)-Based Composite Polymer Electrolyte (CPE) Mitigating Lithium Dendrite Formation in All-Solid-State-Lithium Batteries.

Poly(ethylene oxide) (PEO)-based composite polymer electrolytes (CPEs) containing the amine-functionalized, zirconium-based metal-organic framework @silica (UiO-66-NH2@SiO2) and lithium, LiN(CF3SO2)2 salt (LiTFSI) are prepared using a simple hot press method. The electrochemical properties such as compatibility of the electrolyte with the Li metal anode, Li transference number, and ionic conductivity are investigated for the different systems containing different relative concentrations of the additives. The incorporation of UiO-66-NH2@SiO2 in the PEO-LiTFSI matrix not only enhanced ionic conductivity by one order of magnitude but also offered better compatibility and suppressed the formation of lithium dendrites appreciably. X-ray photoelectron spectroscopy studies on post-cycled materials revealed the formation of lithium alkoxide (RO-Li) on the cathode and Li2O on the anode. The coin cell (2032-type) consisting of LiFePO4/CPE/Li with UiO-66-NH2@SiO2 as filler provided a discharge capacity of 151 mA h g-1 at 0.1 C-rate at 60 °C, measurably higher than control experiments utilizing SiO2 and UiO-66-NH2. The notable enhancement of electrochemical properties when incorporating the UiO-66-NH2@SiO2 at the CPE was attributed to formation of more uniform ion conduction pockets and channels within the PEO matrix, facilitated by the presence of the microporous UiO-66-NH2@SiO2. The enhanced distribution of microporous channels, where Li ions are assumed to percolate through within the matrix, is assumed to desirably reduce formation of Li dendrites by increasing diffusion channels and therefore reducing crystallization and growth of dendrites at the electrode surface.