We have investigated the decomposition path and reversibility of Ca(BH4)2 and Ca(BH4)2 + MgH2 composite using X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and Raman spectroscopy. Formation of CaB6 during dehydrogenation of both systems was confirmed for the first time. CaB6 appears as broad peaks in X-ray diffraction data, but Raman spectroscopy unambiguously captures the existence of CaB6. Reversibility of catalyzed Ca(BH4)2 was previously reported, and here we demonstrate reversibility of Ca(BH4)2 + MgH2 composite. Dehydrogenated product of Ca(BH4)2 + MgH2 is composed of CaH2, CaB6, and Mg. About 60% reversibility was achieved after rehydrogenation for 24 h under 90 bar of hydrogen pressure at 350 °C even without the help of catalysts, which makes a good contrast with the case of pure Ca(BH4)2 where almost negligible rehydrogenation occurs under the same conditions. To understand the difference, the role of Mg in rehydrogenation is worth further investigation. Formation of CaB6 seems critical in the reversibility of Ca(BH4)2 containing systems; the case of other borohydrides is compared.
O3-type layered oxide materials are considered to be a highly suitable cathode for sodium-ion batteries (NIBs) due to their appreciable specific capacity and energy density. However, rapid capacity fading caused by serious structural changes and interfacial degradation hampers their use. A novel Sn-modified O3-type layered NaNi 1/3 Fe 1/3 Mn 1/3 O 2 cathode is presented, with improved high-voltage stability through simultaneous bulk Sn doping and surface coating in a scalable one-step process. The bulk substitution of Sn 4+ stabilizes the crystal structure by alleviating the irreversible phase transition and lattice structure degradation and increases the observed average voltage. In the meantime, the nanolayer Sn/Na/O composite on the surface effectively inhibits surface parasitic reactions and improves the interfacial stability during cycling. A series of Sn-modified materials are reported. An 8%-Sn-modified NaNi 1/3 Fe 1/3 Mn 1/3 O 2 cathode exhibits a doubling in capacity retention increase after 150 cycles in the wide voltage range of 2.0–4.1 V vs Na/Na + compared to none, and 81% capacity retention is observed after 200 cycles in a full cell vs hard carbon. This work offers a facile process to simultaneously stabilize the bulk structure and interface for the O3-type layered cathodes for sodium-ion batteries and raises the possibility of similar effective strategies to be employed for other energy storage materials.
KZn(BH4)Cl2, synthesized for the first time, contains a heteroleptic complex anion [Zn(BH4)Cl2]–, extending the structural diversity of metal borohydrides. In‐situ synchrotron powder diffraction, NMR and Raman spectroscopy were used to characterize KZn(BH4)Cl2 and to evaluate the mechanism for its thermal decomposition. The title compound decomposes at a significantly lower temperature than KBH4 and may be used for inspiration for the design of novel hydrogen storage materials. Combining different ligands in modified metal borohydrides is proposed as a way to adjust stability with respect to hydrogen desorption.
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