LAUSR

Abstract Alkali metal borohydrides are promising candidates for large‐scale hydrogen storage. They react spontaneously with water, generating dihydrogen and metaborate salts. While sodium borohydride is the most studied, potassium has the best chance of commercial application. Here we examine the physical and chemical properties of such self‐hydrolysis solutions. We do this by following the hydrogen evolution, the pH changes, and monitoring the reaction intermediates using NMR. Most studies on such systems are done using dilute solutions, but real‐life applications require high concentrations. We show that increasing the borohydride concentration radically changes the system's microstructure and rheology. The changes are seen already at concentrations as low as 5 w/w%, and are critical above 10 w/w%. While dilute solutions are Newtonian, concentrated reaction solutions display non‐Newtonian behaviour, that we attribute to the formation and (dis)entanglement of metaborate oligomers. The implications of these findings towards using borohydride salts for hydrogen storage are discussed.