Engineering LiBH4-Based Materials for Advanced Hydrogen Storage: A Critical Review of Catalysis, Nanoconfinement, and Composite Design

Lithium borohydride (LiBH4) has emerged as a promising hydrogen storage material due to its exceptional theoretical hydrogen capacity (18.5 wt.%). However, its practical application is hindered by high dehydrogenation temperature (>400 °C), sluggish kinetics, and limited reversibility due to stable intermediate formation. This review critically analyzes recent advances in LiBH4 modification through three primary strategies: catalytic enhancement, nanostructure engineering, and reactive composite design. Advanced carbon architectures and metal oxide catalysts demonstrate significant improvements in reaction kinetics and cycling stability through interface engineering and electronic modification. Sophisticated nanostructuring approaches, including mechanochemical processing and infiltration techniques, enable precise control over material architecture and phase distribution, effectively modifying thermodynamic and kinetic properties. The development of reactive hydride composites, particularly LiBH4-MgH2 systems, provides promising pathways for thermodynamic destabilization while maintaining high capacity. Despite these advances, challenges persist in maintaining engineered structures and suppressing intermediate phases during cycling. Future developments require integrated approaches combining multiple modification strategies while addressing practical implementation requirements.