Improved dehydrogenation/rehydrogenation performance of LiBH4 by doping mesoporous Fe2O3 or/and TiF3

Zhang, Hui; Cao, Zhong; Sun, Lin; Sun, Yujia; Xu, Fen; Liu, Hui; Zhang, Jian; Huang, Ziqiang; Jiang, Xia; Li, Zhibao; Liu, Shuang; Wang, Shuang; Jiao, Chengli; Zhou, Huaiying; Sawada, Yutaka

doi:10.1007/s10973-012-2721-8

Cited by 10 publications

(3 citation statements)

References 47 publications

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“…63 The cyclic stability of bulk LiBH 4 −CaH 2 has also been reported by Li. 64 Bulk LiBH 4 −CaH 2 decreases in capacity by 66% during 10 desorption cycles with rehydrogenation conditions of 450 °C under 8 MPa for 16 h and with dehydrogenation performed at 450 °C under 0.1 MPa H 2 pressure. In comparison to our results, 450 °C is insufficient to obtain stable reversibility of LiBH 4 .…”

Section: ■ Results and Discussionmentioning

confidence: 95%

Reversibility of LiBH₄ Facilitated by the LiBH₄–Ca(BH₄)₂ Eutectic

Javadian

Payandeh

et al. 2017

J. Phys. Chem. C

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The hydrogen storage properties of eutectic melting 0.68LiBH4–0.32Ca(BH4)2 (LiCa) as bulk and nanoconfined into a high surface area, S BET = 2421 ± 189 m2/g, carbon aerogel scaffold, with an average pore size of 13 nm and pore volume of V tot = 2.46 ± 0.46 mL/g, is investigated. Hydrogen desorption and absorption data were collected in the temperature range of RT to 500 °C (ΔT/Δt = 5 °C/min) with the temperature then kept constant at 500 °C for 10 h at hydrogen pressures in the range of 1–8 and 134–144 bar, respectively. The difference in the maximum H2 release rate temperature, T max, between bulk and nanoconfined LiCa during the second cycle is ΔT max ≈ 40 °C, which over five cycles becomes smaller, ΔT max ≈ 10 °C. The high temperature, T max ≈ 455 °C, explains the need for high temperatures for rehydrogenation in order to obtain sufficiently fast reaction kinetics. This work also reveals that nanoconfinement has little effect on the later cycles and that nanoconfinement of pure LiBH4 has a strong effect in only the first cycle of H2 release. The hydrogen storage capacity is stable for bulk and nanoconfined LiCa in the second to the fifth cycle, which contrasts to nanoconfined LiBH4 where the H2 storage capacity continuously decreases. Bulk and nanoconfined LiCa have hydrogen storage capacities of 5.4 and 3.7 wt % H2 in the fifth H2 release, which compare well with the calculated hydrogen contents of LiBH4 only and in LiCa, which are 5.43 and 3.69 wt % H2, respectively. Thus, decomposition products of Ca(BH4)2 appear to facilitate the full reversibility of the LiBH4, and this approach may lead to new hydrogen storage systems with stable energy storage capacity over multiple cycles of hydrogen release and uptake.

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Section: ■ Results and Discussionmentioning

confidence: 95%

Reversibility of LiBH₄ Facilitated by the LiBH₄–Ca(BH₄)₂ Eutectic

Javadian

Payandeh

et al. 2017

J. Phys. Chem. C

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“…To our knowledge, no studies have been reported on LiAlH 4 doped with Fe 2 O 3 and Co 2 O 3 . According to Zhang et al, mesoporous Fe 2 O 3 exhibits a prominent effect on improving the dehydrogenation properties of LiBH 4 . Recently, it has also been reported that Fe 3+ and Fe could provide favorable effect on enhancing the dehydrogenation properties of LiAlH 4 . − , Thus, Fe 2 O 3 could be selected as catalyst precursor to investigate its effect on the dehydrogenation properties of LiAlH 4 .…”

Section: Introductionmentioning

confidence: 99%

Dehydrogenation Improvement of LiAlH₄ Catalyzed by Fe₂O₃ and Co₂O₃ Nanoparticles

Wan

et al. 2013

J. Phys. Chem. C

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The catalytic effect of two nanoscale transition metal oxides, Fe 2 O 3 and Co 2 O 3 , as additives on the dehydrogenation properties of LiAlH 4 after milling are investigated. The onset dehydrogenation temperature for the 5 mol % Fe 2 O 3 -doped and 5 mol % Co 2 O 3 -doped samples are 85 and 79 °C lower for the first-stage and 60 and 45 °C lower for the second-stage, respectively, compared with the asreceived LiAlH 4 . The isothermal dehydriding kinetics reveals that the 5 mol % Fe 2 O 3 -doped sample can release about 7.1 wt % hydrogen in 70 min at 120 °C, whereas as-received LiAlH 4 only releases 0.3 wt % hydrogen under the same conditions. From differential scanning calorimetry (DSC) and Kissinger desorption kinetics analyses, the apparent activation energies (E a ) of the 5 mol % Fe 2 O 3 -doped sample are 54.2 and 86.4 kJ/mol for the first two dehydrogenation stages, resulting in decreases of 42.8 and 50% compared with those of as-received LiAlH 4 , respectively, which are considerably lowered compared with LiAlH 4 doped with other reported catalysts calculated by Kissinger method. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) analyses demonstrate that these finely dispersed Li 2 Fe 2.4 O 4.6 , Fe 0.957 O, and various Co oxides contribute to kinetics improvement by serving as active sites for nucleation and growth of dehydrogenated products.

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“…Some experimental studies involving LiBH 4 with transition metal oxides have been reported for hydrogen storage applications. 27–29 Zhang and his co-workers 30 reported that the re-hydrogenated (at 400 °C under 4.5 MPa) LiBH 4 /M-Fe 2 O 3 /TiF 3 system absorbed ∼4.27 wt% of hydrogen within 60 minutes. In a previous study, ∼1.7 wt% hydrogen uptake capacity for LiBH 4 –2LiNH 2 -0.05/3Co 3 O 4 systems was found under rehydrogenation conditions of 25–220 °C and 110 bar H 2 pressure.…”

Section: Introductionmentioning

confidence: 99%

Effect of a mesoporous NiCo₂O₄ urchin-like structure catalyzed with a surface oxidized LiBH₄ system for reversible hydrogen storage applications

Kaliyaperumal,

Periyasamy,

Kombiah

et al. 2024

RSC Adv.

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Improved dehydrogenation/rehydrogenation performance of LiBH4 by doping mesoporous Fe2O3 or/and TiF3

Cited by 10 publications

References 47 publications

Reversibility of LiBH₄ Facilitated by the LiBH₄–Ca(BH₄)₂ Eutectic

Reversibility of LiBH₄ Facilitated by the LiBH₄–Ca(BH₄)₂ Eutectic

Dehydrogenation Improvement of LiAlH₄ Catalyzed by Fe₂O₃ and Co₂O₃ Nanoparticles

Effect of a mesoporous NiCo₂O₄ urchin-like structure catalyzed with a surface oxidized LiBH₄ system for reversible hydrogen storage applications

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Improved dehydrogenation/rehydrogenation performance of LiBH4 by doping mesoporous Fe2O3 or/and TiF3

Cited by 10 publications

References 47 publications

Reversibility of LiBH4 Facilitated by the LiBH4–Ca(BH4)2 Eutectic

Reversibility of LiBH4 Facilitated by the LiBH4–Ca(BH4)2 Eutectic

Dehydrogenation Improvement of LiAlH4 Catalyzed by Fe2O3 and Co2O3 Nanoparticles

Effect of a mesoporous NiCo2O4 urchin-like structure catalyzed with a surface oxidized LiBH4 system for reversible hydrogen storage applications

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Reversibility of LiBH₄ Facilitated by the LiBH₄–Ca(BH₄)₂ Eutectic

Reversibility of LiBH₄ Facilitated by the LiBH₄–Ca(BH₄)₂ Eutectic

Dehydrogenation Improvement of LiAlH₄ Catalyzed by Fe₂O₃ and Co₂O₃ Nanoparticles

Effect of a mesoporous NiCo₂O₄ urchin-like structure catalyzed with a surface oxidized LiBH₄ system for reversible hydrogen storage applications