4.7 Article

In-situ introduction of highly active TiO for enhancing hydrogen storage performance of LiBH4

Journal

CHEMICAL ENGINEERING JOURNAL
Volume 433, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2021.134485

Keywords

TiO additive; In-situ introduction strategy; Kinetics; Reversibility; LiBH4 hydrogen storage

Funding

  1. National Key Research and Develop-ment Program of the Ministry of Science and Technology of PR China [2018YFB1502103]
  2. National Natural Science Foundation of PR China [52071287, 51571175, U1601212, 52001277, 51901168]
  3. Natural Science Basic Research Plan in Shaanxi Province of P. R. China [2020JQ-809]
  4. Special Fund Project of Education Department of Shaanxi Province of P. R. China [20200428]

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In this study, a novel synthetic strategy of heat treating a LiBH4 and Ti(OEt)(4) mixture is used to introduce TiO into LiBH4. The optimized LiBH4-0.06TiO system exhibits lower onset and peak dehydrogenation temperatures, rapid hydrogen release, and good cycling stability.
LiBH4 is a promising candidate for solid state hydrogen storage, however, it still suffers from high hydrogen desorption temperature, harsh hydrogen absorption conditions, and poor reversibility, which hinder its practical development. In this paper, a novel synthetic strategy of heat treating a LiBH4 and Ti(OEt)(4) mixture is employed to prepare LiBH4 system with TiO in-situ introduced. With an optimized TiO content of 0.06 in molar fraction, the LiBH4-0.06TiO system shows onset and peak dehydrogenation temperatures of 240 & DEG;C and 340 & DEG;C, respectively, which are 140 & DEG;C and 90 & DEG;C lower than those of the pure LiBH4. The LiBH4-0.06TiO system can rapidly release 9 wt% H-2 after dwelling at 400 & DEG;C for 10 min. The hydrogenation of the dehydrogenation product initiates at 150 & DEG;C, and a capacity of 9 wt% is reached after isothermal dwelling at 500 & DEG;C under 50 bar of H-2 for 100 min. The capacity retention of the system can reach 74.4% after 10 cycles, indicating a favorable reversibility. With the introduction of TiO, the apparent dehydrogenation activation energy of the system is evidently reduced, and the formation of Li2B12H12, a highly thermal stable intermediate phase, is greatly suppressed. In addition, the aggregation is evidently alleviated. All of these contribute to the enhanced dehydrogenation kinetics and reversibility. TiO reacts with LiBH4, forming Li3BO3 and TiH2 after the initial dehydrogenation, which play significant catalytic effect to LiBH4.

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