Boron Hydrogen Compounds: Hydrogen Storage and Battery Applications

About 25 years ago, Bogdanovic and Schwickardi (B. Bogdanovic, M. Schwickardi: J. Alloys Compd. 1–9, 253 (1997) discovered the catalyzed release of hydrogen from NaAlH(4). This discovery stimulated a vast research effort on light hydrides as hydrogen storage materials, in particular boron hydrogen compounds. Mg(BH(4))(2), with a hydrogen content of 14.9 wt %, has been extensively studied, and recent results shed new light on intermediate species formed during dehydrogenation. The chemistry of B(3)H(8)(−), which is an important intermediate between BH(4)(−) and B(12)H(12)(2−), is presented in detail. The discovery of high ionic conductivity in the high-temperature phases of LiBH(4) and Na(2)B(12)H(12) opened a new research direction. The high chemical and electrochemical stability of closo-hydroborates has stimulated new research for their applications in batteries. Very recently, an all-solid-state 4 V Na battery prototype using a Na(4)(CB(11)H(12))(2)(B(12)H(12)) solid electrolyte has been demonstrated. In this review, we present the current knowledge of possible reaction pathways involved in the successive hydrogen release reactions from BH(4)(−) to B(12)H(12)(2−), and a discussion of relevant necessary properties for high-ionic-conduction materials.