Boosting Hydrogen Storage Performance of MgH2 by Oxygen Vacancy-Rich H-V2O5 Nanosheet as an Excited H-Pump

doi:10.1007/s40820-024-01375-8

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Abstract

MgH₂ is a promising high-capacity solid-state hydrogen storage material, while its application is greatly hindered by the high desorption temperature and sluggish kinetics. Herein, intertwined 2D oxygen vacancy-rich V₂O₅ nanosheets (H-V₂O₅) are specifically designed and used as catalysts to improve the hydrogen storage properties of MgH₂. The as-prepared MgH₂-H-V₂O₅ composites exhibit low desorption temperatures (T_onset = 185 °C) with a hydrogen capacity of 6.54 wt%, fast kinetics (E_a = 84.55 ± 1.37 kJ mol⁻¹ H₂ for desorption), and long cycling stability. Impressively, hydrogen absorption can be achieved at a temperature as low as 30 °C with a capacity of 2.38 wt% within 60 min. Moreover, the composites maintain a capacity retention rate of ~ 99% after 100 cycles at 275 °C. Experimental studies and theoretical calculations demonstrate that the in-situ formed VH₂/V catalysts, unique 2D structure of H-V₂O₅ nanosheets, and abundant oxygen vacancies positively contribute to the improved hydrogen sorption properties. Notably, the existence of oxygen vacancies plays a double role, which could not only directly accelerate the hydrogen ab/de-sorption rate of MgH₂, but also indirectly affect the activity of the catalytic phase VH₂/V, thereby further boosting the hydrogen storage performance of MgH₂. This work highlights an oxygen vacancy excited “hydrogen pump” effect of VH₂/V on the hydrogen sorption of Mg/MgH₂. The strategy developed here may pave a new way toward the development of oxygen vacancy-rich transition metal oxides catalyzed hydride systems.

Key words： Hydrogen storage MgH₂ V₂O₅ nanosheets Oxygen vacancies VH₂

Received: 04 December 2023 Published: 21 March 2024

Corresponding Authors: Jianxin Zou

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	Li Ren
	Yinghui Li
	Zi Li
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	Wenjiang Ding
	Jianxin Zou

Cite this article:

Li Ren,Yinghui Li,Zi Li, et al. Boosting Hydrogen Storage Performance of MgH₂ by Oxygen Vacancy-Rich H-V₂O₅ Nanosheet as an Excited H-Pump[J]. Nano-Micro Letters, 2024, 16(1): 160-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01375-8 OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/160

Fig. 1 a Schematic illustration of the synthetic process of the H-V2O5 nanosheets. Typical SEM images of b, c pristine V2O5·xH2O and d, e H-V2O5 nanosheets. f Typical TEM and HRTEM images of pristine V2O5·xH2O nanosheets. g HAADF image and the corresponding elemental mapping of pristine V2O5·xH2O nanosheets. h Typical TEM image of H-V2O5 nanosheets

Fig. 2 a XRD patterns of V2O5 nanosheets with different states. (The enlarged image shows the peak shift observed from different samples.) b N2 ad/de-sorption isotherms and corresponding specific surface areas of V2O5·xH2O and commercial V2O5. c High-resolution V 2p XPS spectra acquired from the V2O5·xH2O, V2O5-350air, and H-V2O5-300. d TG curve of H-V2O5-300 in air. e Raman spectra obtained from different samples

Fig. 3 a TPD results of H-V2O5-doped MgH2 samples and pristine MgH2-BM. b DSC curves of MgH2 doped with different catalysts and c MgH2-10 wt% H-V2O5 with different heating rates. d Isothermal H2 absorption curves of MgH2-10 wt% H-V2O5 at various temperatures. e Isothermal H2 desorption curves of MgH2-10 wt% H-V2O5 at various temperatures (including the desorption curves of pristine MgH2-BM at 275 °C for comparison)

Fig. 4 a The extent of reaction curves of MgH2-10 wt% H-V2O5 composites at 225, 250, and 275 °C. b (t/t0.5)theo vs. (t/t0.5)exp of composites at 225 °C for various kinetic models. c Time dependence of kinetic modeling equations g(α) for composites with 0.2 < α < 0.7 at different temperatures. d Calculation of the apparent activation energies according to the Arrhenius equation

Fig. 5 a De/re-hydrogenation cycle curves of MgH2-10 wt% H-V2O5. b TPD results of MgH2-10 wt% H-V2O5 upon cycling

Fig. 6 a XRD patterns and b high-resolution V 2p XPS spectra of MgH2 under the catalysis of H-V2O5 nanosheets at various states

Fig. 7 a-c The typical bright field TEM images, the HAADF images, the corresponding elemental mapping, and d-f the relative HRTEM images of MgH2-H-V2O5 composites at various states (The inset in a-c shows the corresponding SAED patterns)

Fig. 8 Schematic illustration of the H2 desorption process of a MgH2 on the V2O5 (001) plane and b MgH2 on the V2O5-x (001) plane. Calculated energy profiles for the c H2 desorption and d absorption of MgH2

Fig. 9 DOS of the a MgH2-V2O5/V2O5-x system and b VH2-V2O5/V2O5-x system

Fig. 10 Schematic diagram showing the mechanisms of enhanced hydrogen storage performances of the MgH2-H-V2O5 composites

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