A wide variety of metal borohydrides, MBH₄, have been discovered and characterized during the past decade, revealing an extremely rich chemistry including fascinating structural flexibility and a wide range of compositions and physical properties. Metal borohydrides receive increasing interest within the energy storage field due to their extremely high hydrogen density and possible uses in batteries as solid state ion conductors. Recently, new types of physical properties have been explored in lanthanide-bearing borohydrides related to solid state phosphors and magnetic refrigeration. Two major classes of metal borohydride derivatives have also been discovered: anion-substituted compounds where the complex borohydride anion, BH₄ ⁻, is replaced by another anion, i.e. a halide or amide ion; and metal borohydrides modified with neutral molecules, such as NH₃, NH₃BH₃, N₂H₄, etc. Here, we review new synthetic strategies along with structural, physical and chemical properties for metal borohydrides, revealing a number of new trends correlating composition, structure, bonding and thermal properties. These new trends provide general knowledge and may contribute to the design and discovery of new metal borohydrides with tailored properties towards the rational design of novel functional materials. This review also demonstrates that there is still room for discovering new combinations of light elements including boron and hydrogen, leading to complex hydrides with extreme flexibility in composition, structure and properties.

Increased reliance on solar energy conversion technologies will necessarily constitute a major plank of any forward global energy supply strategy. It is possible that solar photovoltaic (PV) technology and concentrating solar thermal (CST) power technology will play roughly equal, but complementary roles by 2050. The ability to increase reliance on CST power technology during this period, however, will be constrained by a number of factors: the large plant sizes dictated by economies of scale, the high associated transmission infrastructure investment cost, and the limitations of current thermal energy storage technologies. Thus, solar technology's main midterm role is seen to be as hybrid solar thermal power plant. The development of low-cost, high-temperature, high-energy density thermal energy storage systems is needed to enable CST plants to be dispatchable and accelerate the deployment of this technology. Thermochemical storage has the best potential to achieve these energy storage requirements and a brief overview of thermochemical energy storage options for CST plants points to high-temperature metal-hydride thermochemical heat energy storage systems. Hydrogen storage systems offer the highest energy storage capacity per volume and are therefore the most likely candidates for achieving the goal of fully dispatchable CST plants. A number of high-temperature metal-hydride thermochemical solar energy storage systems have been proposed and a small number of these systems are currently being investigated and developed. A key component of this work is matching the thermochemical metal-hydride system with a suitable “low-temperature” hydrogen storage material to produce systems that are self-regulating. A summary of the development status of these systems suggests that, despite the technical challenges associated with high-temperature thermochemical energy storage systems, their potential advantages are now seeing development occurring. Although in the early stages, their commercialisation could be fast tracked.