随着燃料电池、燃料电池汽车的快速发展,LiBH4被认为是最具应用前景的储氢材料之一.然而,LiBH4吸放氢温度高以及吸放氢速率相对缓慢限制了其广泛应用.为改善LiBH4吸放氢性能,在LiBH4中添加少量Al,采用基于密度泛函理论的第一原理赝势平面波方法,计算了LiBH4合金化前后体系的氢化物形成热、H原子解离能,体系的晶体与电子结构.氢化物形成热、H原子解离能计算结果发现:Al合金化后体系相结构稳定性变差,体系解氢过程中所吸收的热量减少,H原子解离能减小,体系解氢能力增强.电子态密度(DOS)、电子密度和Mulliken电子占据数的结果表明:LiBH4结构稳定、解氢困难的电子结构原因是B-H之间较强的共价键,Al对LiBH4体系解氢性能增强主要是Al-LiBH4体系Fermi能级附近能隙值发生变化以及Li-BH,B-H间成键作用减弱.理论上揭示Al添加改善LiBH4体系解氢性能的微观机制,为LiBH4实际应用提供理论指导.
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