Water-Soluble Azobenzene-Based Solar Thermal Fuels with Improved Long-Term Energy Storage and Energy Density.

Azobenzene (azo)-based solar thermal fuels (STFs) have been developed to harvest and store solar energy. However, due to the lipophilicity and low energy density of azo-based STFs, the derived devices demand a large amount of toxic organic solvents for continuous and scalable energy storage. Herein, we report an ionic strategy to prepare water-soluble azo-based STFs (WASTFs) with improved energy storage performance, which can be realized through a facile quaternization reaction using commercial reagents. A family of WASTFs were synthesized, and all of them showed good water solubility, long-term thermal half-life (>30 days), and high energy storage density (a highest energy density of ∼143.6 J g^-1 corresponding to an energy storage enthalpy of ∼111.8 kJ mol^-1). Compared to the electrically neutral azo-based STFs with similar chemical structures, ΔH and thermal half-life (τ_1/2) of the WASTFs are 2.5 times higher and 7.3 times longer, respectively. Cation-π interactions between the quaternized moieties [N⁺(CH_x)₄] and benzene moieties of azo were confirmed, which could account for their improvement of the energy storage performance. Macroscale heat release with an average temperature difference of ∼2 °C was achieved for the WASTFs prepared in this work. Generally, a novel family of WASTFs are synthesized and show great applicable prospects in fabricating advanced solar energy storage devices.