Redox-Active Vertically Aligned Mesoporous Silica Thin Films as Transparent Surfaces for Energy Storage Applications

Organic–inorganic hybrid membranes, made of a high density of redox active moieties covalently bonded to the internal surfaces of vertically aligned mesoporous silica thin films, are relevant for applications in transparent energy storage devices. This is demonstrated here on the basis of functionalized transparent mesoporous silica thin films prepared on the indium–tin oxide electrode from the combination of an electrochemically induced self-assembly method (to generate azide-functionalized silica) and a copper-catalyzed azide–alkyne click reaction (to derivatize the material with electroactive groups). The very small thickness (105 nm) and the uniformly distributed vertical mesochannels with ultranarrow diameter (2 nm) make the hybrid film a promising substrate that not only achieves a transparency of 82% but also provides large surface area to accommodate a high density of redox active species such as ferrocene. In such rigid and insulating porous membranes, the charge transfer reactions take place through a pure electron-hopping mechanism between adjacent redox sites, which are favored by the ordered and oriented mesostructure containing large amounts of uniformly distributed ferrocene functions in the mesochannels. Their performance results from both high charge transfer rates (electron hopping) and easy mass transport (fast diffusion of counter ions). The most effective system is the ferrocene-functionalized silica film prepared from 40% organosilane, which is able to deliver a capacity of 105 C cm–3 (1.10 mC cm–2) at a current density of 0.4 A cm–3 (with up to 48% capacity retention achieved at a charging time as short as 2.8 s). Such an electrode can be associated to an electrodeposited graphene anode in a solid-state battery–capacitor hybrid device, which can deliver 0.74 mC cm–2 at a potential scan rate of 20 mV s–1. The azide-functionalized mesoporous silica film is actually a versatile platform that can be functionalized with different redox molecules, as shown here for cobaltocenium moieties, which may broaden its application field.