Effective nanoconfinement of 2LiBH4–MgH2 via simply MgH2 premilling for reversible hydrogen storages


To improve nanoconfinement of LiBH4 and MgH2 in carbon aerogel scaffold (CAS), particle size reduction of MgH2 by premilling technique before melt infiltration is proposed. MgH2 is premilled for 5 h prior to milling with LiBH4 and nanoconfinement in CAS to obtained nanoconfined 2LiBH4–premilled MgH2. Significant confinement of both LiBH4 and MgH2 in CAS, confirmed by SEM–EDS–mapping results, is achieved due to MgH2 premilling. Due to effective nanoconfinement, enhancement of CAS:hydride composite weight ratio to 1:1, resulting in increase of hydrogen storage capacity, is possible. Nanoconfined 2LiBH4–premilled MgH2 reveals a single–step dehydrogenation at 345 °C with no B2H6 release, while dehydrogenation of nanoconfined sample without MgH2 premilling performs in multiple steps at elevated temperatures (up to 430 °C) together with considerable amount of B2H6 release. Activation energy (EA) for the main dehydrogenation of nanoconfined 2LiBH4–premilled MgH2 is considerably lower than those of LiBH4 and MgH2 of bulk 2LiBH4–MgH2 (ΔEA = 31.9 and 55.8 kJ/mol with respect to LiBH4 and MgH2, respectively). Approximately twice faster dehydrogenation rate are accomplished after MgH2 premilling. Three hydrogen release (T = 320 °C, P(H2) = 3–4 bar) and uptake (T = 320–325 °C, P(H2) = 84 bar) cycles of nanoconfined 2LiBH4–premilled MgH2 reveal up to 4.96 wt. % H2 (10 wt. % H2 with respect to hydride composite content), while the 1st desorption of nanoconfined sample without MgH2 premilling gives 4.30 wt. % of combined B2H6 and H2 gases. It should be remarked that not only kinetic improvement and B2H6 suppression are obtained by MgH2 premilling, but also the lowest dehydrogenation temperature (T = 320 °C) among other modified 2LiBH4–MgH2 systems is acquired.
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