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. 2021 Dec 14:2021:9819176.
doi: 10.34133/2021/9819176. eCollection 2021.

Titanium Hydride Nanoplates Enable 5 wt% of Reversible Hydrogen Storage by Sodium Alanate below 80°C

Zhuanghe Ren  1 , Xin Zhang  1 , Hai-Wen Li  2 , Zhenguo Huang  3 , Jianjiang Hu  4 , Mingxia Gao  1 , Hongge Pan  1   5 , Yongfeng Liu  1   5
Affiliations

Titanium Hydride Nanoplates Enable 5 wt% of Reversible Hydrogen Storage by Sodium Alanate below 80°C

Zhuanghe Ren et al. Research (Wash D C). .

Abstract

Sodium alanate (NaAlH4) with 5.6 wt% of hydrogen capacity suffers seriously from the sluggish kinetics for reversible hydrogen storage. Ti-based dopants such as TiCl4, TiCl3, TiF3, and TiO2 are prominent in enhancing the dehydrogenation kinetics and hence reducing the operation temperature. The tradeoff, however, is a considerable decrease of the reversible hydrogen capacity, which largely lowers the practical value of NaAlH4. Here, we successfully synthesized a new Ti-dopant, i.e., TiH2 as nanoplates with ~50 nm in lateral size and ~15 nm in thickness by an ultrasound-driven metathesis reaction between TiCl4 and LiH in THF with graphene as supports (denoted as NP-TiH2@G). Doping of 7 wt% NP-TiH2@G enables a full dehydrogenation of NaAlH4 at 80°C and rehydrogenation at 30°C under 100 atm H2 with a reversible hydrogen capacity of 5 wt%, superior to all literature results reported so far. This indicates that nanostructured TiH2 is much more effective than Ti-dopants in improving the hydrogen storage performance of NaAlH4. Our finding not only pushes the practical application of NaAlH4 forward greatly but also opens up new opportunities to tailor the kinetics with the minimal capacity loss.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Comparison of hydrogen desorption (a) and absorption (b) performance of NaAlH4 doped with various Ti-based catalysts.
Figure 2
Figure 2
Schematic illustration for the preparation process of TiH2 nanoplates.
Figure 3
Figure 3
(a) XRD pattern, (b) EDS spectrum, (c) TPD-MS signal, and (d) TGA curve of as-prepared solid products of the sonochemical reaction between TiCl4 and LiH in THF.
Figure 4
Figure 4
(a) TEM image, (b) EDS mapping, (c) HRTEM image, and (d) AFM image of NP-TiH2@G. Inset on (a) is the corresponding particle size distribution.
Figure 5
Figure 5
TEM images of NP-TiH2@G with the ultrasonic time of 1 h (a, b), 2 h (c, d), and 4 h (e, f).
Figure 6
Figure 6
(a) Volumetric release curves of NaAlH4 doped with NP-TiH2@G, (b) nonisothermal hydrogenation curves, and (c, d) SEM and corresponding EDS mapping of NaAlH4 mixed with 7 wt% (c) TiH2 nanoplates and (d) commercial TiH2.
Figure 7
Figure 7
STEM and corresponding EDS mapping of as-milled (a) and activated (b) NaAlH4-7 wt% NP-TiH2@G samples. The rectangular areas in (a) and (b) are taken for composition analysis.
Figure 8
Figure 8
(a) Isothermal dehydrogenation curves, (b) isothermal TG curves, (c) isothermal hydrogenation curves, and (d) Kissinger's plots of activated NaAlH4-7 wt% NP-TiH2@G sample.
Figure 9
Figure 9
(a) Cycling tests operated at 140°C for dehydrogenation and 100°C/100 atm H2 for hydrogenation of NaAlH4-7 wt% NP-TiH2@G, (b) TEM image, (c) STEM and corresponding EDS mapping images, (d) SEM and corresponding images, and (e) Ti 2p XPS spectra of NaAlH4-7 wt% NP-TiH2@G sample after 50 cycles.
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