SiO2 Nanoparticle Coating to Enable Polyethylene-Based Na-Ion Battery Separators

Abstract

The increasing demand for Li-ion batteries (LIBs), pushed even more by the electrical vehicle industry, has highlighted the concern with the scarcity and uneven distribution of LIB raw materials. Electrochemical energy storage based on alternative chemistries, once properly developed, may provide sufficient energy density to partly supply that demand, reducing the dependence on Li natural reserves. Among the studied chemistries, Na-ion-based storage is currently attracting a lot of research attention. This is partly due to the similarities between Li and Na, which allow for the utilisation of analogous materials and methods already in place for LIBs. However, not every component of LIBs can be directly applied to Na-ion batteries (SIB).[1] This is the case for battery separators, the membranes used to avoid physical contact between the two battery electrodes to prevent short circuiting while conducting ions from one battery pole to the other. Porous polyolefin films, such as polyethylene (PE) and polypropylene (PP), have been successfully used in LIBs, but are not compatible with SIB electrolytes. In the latter case, issues arise from the poor wettability of the separator with the electrolyte, which leads to low ionic conductivity, and creates an uneven flux of ions that can cause cell failure. To address this issue, previous reports have shown that the presence of inorganic oxides such as ZrO2 [2] and SiO2 [3] on polyolefin films can increase the affinity of the separator with commonly used LIB and SIB electrolytes. Moreover, ceramic-modified films also show higher thermal stability and hindered thermal shrinkage, which improves battery safety.In this work, we investigated PE coated with spherical SiO2 particles (designed by Glantreo, Ireland) with different sizes of 85 and 200 nm. The coatings were made by tape casting both sides of a PE film with slurries containing SiO2 particles and a binder. Binder type, SiO2 concentration and SiO2/binder ratio were optimized for each particle size. The obtained films were characterized by scanning electron microscopy and infrared spectroscopy, and were compared regarding their wettability, thermal stability, and ionic conductivity. The films were tested as separators in hard-carbon half-cells with 1 mol/L NaClO4 in either diethylene glycol dimethyl ether (DEGDME) or ethylene carbonate (EC)/ propylene carbonate (PC) electrolyte. With carbonate-based electrolyte, PE has very low wettability and cells short circuit within the first cycle. However, SiO2-PE samples showed higher wettability, which allowed for cycling at low current densities. In DEGDME-based electrolyte, cells with PE separator presented capacity fade, with 50% capacity loss after 250 cycles at 400 mA/g. On the other hand, cells with SiO2-PE separator had stable cycling for more than 300 cycles and no short-circuiting was observed, even when high active mass loading electrodes (8 mg/cm2) were used. These are promising results showing that a surface layer of SiO2 particles can make PE a viable option for SIB separators.