Superior reversible hydrogen storage in eutectic LiBH4–KBH4 system via Ni–based catalysts synergized with graphene

Shanqing Qu , Yaxiong Yang , Mingxia Gao , Zhenglong Li , Wenping Sun , Chu Liang , Xin Zhang , Xiaoyu Zhang , Lingchao Zhang , Ruizi Wang , Hongge Pan
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Abstract

Light metal borohydrides are promising candidates for solid–state hydrogen storage due to their high hydrogen storage capacities; however, the reversibility and kinetics of de/hydrogenation still require significant improvement. The present work focuses on the improvement of the hydrogen storage properties of the eutectic borohydride system of LiBH4–KBH4 (Li/KBH4). A layered composite of graphene supported with ultrafine Ni3B nanoparticles (Ni3B/G) is designed and synthesized, which acts as catalyst and confinement carrier for Li/KBH4. Assisted with a heating of the mixture of Li/KBH4 and Ni3B/G to 110 °C in the molten state of Li/KBH4, an interlayer structure of graphene dispersed with Ni3B nanoparticles and sheet–like Li/KBH4 is constructed. The graphene effectively disperses Ni3B nanoparticles and confines the Li/KBH4 in its interlayers. The confinement of Li/KBH4 and the catalysis of Ni3B nanoparticles, assisted with the high thermal conductivity of graphene, contribute synergistically the hydrogen storage of Li/KBH4. The main dehydrogenation peak temperature of the system is lowered to 278 °C. The system can release 8.5 wt% H2 within 30 min at 350 °C. The capacity retention achieves 81.2 % after 50 cycles. DFT theoretical analysis shows that there is strong charge transfer interaction between Ni3B and LiBH4/KBH4, which destabilizes the [BH4] structure and promotes the dehydrogenation. This work provides a new approach for the design of new structural LiBH4–based eutectic system with high capacity, low dehydrogenation temperature, high reversibility and long cycling life.
镍基催化剂与石墨烯协同作用在LiBH4-KBH4共晶体系中具有优异的可逆储氢性能
轻金属硼氢化物因其高储氢能力而成为固态储氢的有希望的候选者;然而,脱氢化反应的可逆性和动力学仍有待改进。本文主要研究了LiBH4-KBH4 (Li/KBH4)共晶硼氢化物体系储氢性能的改进。设计并合成了一种层状石墨烯-超细Ni3B纳米颗粒复合材料(Ni3B/G),作为Li/KBH4的催化剂和约束载体。在Li/KBH4熔融状态下,将Li/KBH4和Ni3B/G的混合物加热至110℃,构建了分散有Ni3B纳米粒子和片状Li/KBH4的石墨烯层间结构。石墨烯有效地分散了Ni3B纳米颗粒,并将Li/KBH4限制在其中间层中。Li/KBH4的约束和Ni3B纳米颗粒的催化作用,以及石墨烯的高导热性,协同促进了Li/KBH4的储氢。系统主脱氢峰温度降至278℃。该系统在350℃下可在30 min内释放8.5 wt% H2。循环50次后,容量保持率达到81.2 %。DFT理论分析表明,Ni3B与LiBH4/KBH4之间存在较强的电荷转移相互作用,使[BH4] -结构不稳定,促进了脱氢反应。本工作为设计高容量、低脱氢温度、高可逆性和长循环寿命的新型结构libh4共晶体系提供了新途径。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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