The development of solar energy can potentially meet the growing requirements for a global energy system beyond fossil fuels, but necessitates new scalable technologies for solar energy storage.

No abstract

Discovering physicochemical principles for simultaneous harvesting of multiform energy from the environment will advance current sustainable energy technologies. Here we explore photochemical phase transitionsa photochemistry−thermophysics coupled regimefor coharvesting of solar and thermal energy. In particular, we show that photon energy and ambient heat can be stored together and released on demand as high-temperature heat, enabled by room-temperature photochemical crystal↔liquid transitions of engineered molecular photoswitches. Integrating the two forms of energy in single-component molecular materials is capable of providing energy capacity beyond that of traditional solar or thermal energy storage systems based solely on molecular photoisomerization or phase change, respectively. Significantly, the ambient heat that is harvested during photochemical melting into liquid of the low-melting-point, metastable isomer can be released as high-temperature heat by recrystallization of the high-melting-point, parent isomer. This reveals that photon energy drives the upgrading of thermal energy in such a hybrid energy system. Rationally designed small-molecule azo switches achieve high gravimetric energy densities of 0.3–0.4 MJ/kg with long-term storage stability. Rechargeable solar thermal battery devices are fabricated, which upon light triggering provide gravimetric power density of about 2.7 kW/kg and temperature increases of >20 °C in ambient environment. We further show their use as deicing coatings. Our work demonstrates a new concept of energy utilizationcombining solar energy and low-grade heat into higher-grade heatwhich unlocks the possibility of developing sustainable energy systems powered by a combination of natural sunlight and ambient heat.

Norbornadiene-quadricyclane (NBD-QC) photoswitches are candidates for applications in solar thermal energy storage. Functionally, they rely on an intramolecular [2+2] cycloaddition reaction, which couples the S landscape on the NBD side to the S landscape on the QC side of the reaction and vice-versa. This commonly results in an unfavourable correlation between the first absorption maximum and the barrier for thermal back-conversion. This work demonstrates that this correlation can be counteracted by using steric repulsion to hamper the rotational motion of the side groups along the back-conversion path. It is shown that this modification reduces the correlation between the effective back-conversion barrier and the first absorption maximum and also increases the back-conversion entropy. The resulting molecules exhibit exceptionally long half-lives for their metastable forms without significantly affecting other properties, most notably solar spectrum match and storage density.

Molecular photoswitches can be used for solar thermal energy storage by photoisomerization into high-energy, meta-stable isomers; we present a molecular design strategy leading to photoswitches with high energy densities and long storage times. High measured energy densities of up to 559 kJ kg−1 (155 Wh kg−1), long storage lifetimes up to 48.5 days, and high quantum yields of conversion of up to 94% per subunit are demonstrated in norbornadiene/quadricyclane (NBD/QC) photo-/thermoswitch couples incorporated into dimeric and trimeric structures. By changing the linker unit between the NBD units, we can at the same time fine-tune light-harvesting and energy densities of the dimers and trimers so that they exceed those of their monomeric analogs. These new oligomers thereby meet several of the criteria to be met for an optimum molecule to ultimately enter actual devices being able to undergo closed cycles of solar light-harvesting, energy storage, and heat release.