2LiBH₄-MgH₂ System Catalytically Modified with a 2D TiNb₂O₇ Nanoflake for High-Capacity, Fast-Response, and Long-Life Hydrogen Energy Storage

To achieve large-scale hydrogen storage for growing high energy density and long-life demands in end application, the 2LiBH₄-MgH₂ (LMBH) reactive hydride system attracts huge interest owing to its high hydrogen capacity and thermodynamically favorable reversibility. The sluggish dehydrogenation kinetics and unsatisfactory cycle life, however, remain two challenges. Herein, a bimetallic titanium-niobium oxide with a two-dimensional nanoflake structure (2D TiNb₂O₇) is selected elaborately as an active precursor that <i>in situ</i> transforms into TiB₂ and NbB₂ with ultrafine size and good dispersion in the LMBH system as highly efficient catalysts, giving rise to excellent kinetic properties with long-term cycling stability. For the LMBH system added with 5 wt% 2D TiNb₂O₇, 9.8 wt% H₂ can be released within 20 min at 400 °C, after which the system can be fully hydrogenated in less than 5 min at 350 °C and 10 MPa H₂. Moreover, a dehydrogenation capacity of 9.4 wt% can be maintained after 50 cycles corresponding to a retention of 96%, being the highest reported to date. The positive roles of TiB₂ and NbB₂ for kinetics and recyclability are from their catalytic nucleation effects for MgB₂, a main dehydrogenation phase of LMBH, thus reducing the apparent activation energy, suppressing the formation of thermostable Li₂B₁₂H₁₂ byproducts, and inhibiting the hydride coarsening. This work develops an advanced LMBH system, bringing hope for high-capacity, fast-response, and long-life hydrogen energy storage.