Solidification of a Silica-Based Solid Composite Electrolyte for Lithium-Ion Batteries Induced By UV Irradiation
Authors: De Sloovere Dries , Vounckx Ulrique , Vranken Thomas , Reekmans Gunter , Adriaensens Peter , Vereecken Philippe M. , Van Bael Marlies K. , Hardy An 
Published: February 2024

The use of solid electrolytes in lithium-ion batteries (LIBs) instead of their liquid counterparts may significantly increase their energy density. Of particular interest are solid composite electrolytes (SCEs) which can be synthesized by incorporating ionic liquids (ILs, salts with a melting point lower than 100 °C) into a solid matrix. This class of SCE can have a wide electrochemical stability window and is typically non-flammable.
Chen et al.1 developed an SCE with excellent ionic conductivity, consisting of a mesoporous silica monolith which encloses an IL electrolyte (solid nanocomposite electrolyte or nano-SCE). It is formed from a precursor solution which does not contain acids such as formic acid or HCl, meaning that it can be impregnated into porous electrodes without causing damage to the latter. However, its gelation process is long and variable (5-9 days), and is considerably affected by its presence within the electrode. As such, the nano-SCE has poor manufacturability and is not compatible with the continuous roll-to-roll processing typically used for LIB manufacturing. The manufacturability of the nano-SCE can be significantly improved by making its solidification process instantaneous upon subjection to an external trigger.
As such, organic modification was used to produce silica-based precursor solutions capable of triggered solidification, for instance by irradiation with UV light. This solidification process takes a few minutes to complete and does not depend on pH, rendering it particularly versatile. The aging of the precursor solutions was studied with 29Si, 1H, and 13C NMR spectroscopy, which revealed that the alkoxysilane precursor molecules condensed into larger soluble structures over the course of five weeks. The aged precursor solutions remained stable over an indefinite period of time. When a photo-initiator is added to these solutions and they are irradiated with UV light, the soluble structures are linked together, resulting in the formation of silica nanoparticles which subsequently aggregate into a porous matrix which encapsulates the ionic liquid electrolyte (ILE).
The adaptation does not compromise the functional properties such as ionic conductivity or electrochemical stability. As determined with Raman spectroscopy, the extent of organic modification and amount of ILE can be optimized to decrease the interaction of lithium ions with the other ions as compared to the neat ILE. The increased Li+ mobility means that the SCE can reach higher ionic conductivity (2.7 mS cm-1 at 20 °C) values than the neat ILE (2.5 mS cm-1). Anodic and cathodic linear sweep voltammetry in three-electrode cells was performed to determine that the SCEs can have an electrochemical stability window exceeding 5 V (i.e. lithium plating < 0 vs Li+/Li and electrolyte oxidation > 5.0 V vs Li+/Li). Electrochemical impedance spectroscopy further confirmed the SCE’s compatibility with lithium metal. As no acids are added to the precursor solution, a good electrode compatibility is expected. As such, the precursor solutions were impregnated into NMC622-based electrodes, solidified, and incorporated in half cells. These cells had an initial discharge capacity of 162 mAh g-1 at 0.1 C, retaining 86.8% of this capacity after 100 cycles.
This work was supported by funding from the European Union’s Horizon 2020 research and innovation program for the Solidify project under grant agreement No. 875557.
(1) Chen, X.; Put, B.; Sagara, A.; Gandrud, K.; Murata, M.; Steele, J. A.; Yabe, H.; Hantschel, T.; Roeffaers, M.; Tomiyama, M.; et al. Silica Gel Solid Nanocomposite Electrolytes with Interfacial Conductivity Promotion Exceeding the Bulk Li-Ion Conductivity of the Ionic Liquid Electrolyte Filler. Sci. Adv.
2020, 6 (2). https://doi.org/10.1126/sciadv.aav3400.