The
rechargeable magnesium (Mg) battery has been considered a promising
candidate for future battery generations due to unique advantages
of the Mg metal anode. The combination of Mg with a sulfur cathode
is one of the attractive electrochemical energy storage systems that
use safe, low-cost, and sustainable materials and could potentially
provide a high energy density. To develop a suitable electrolyte remains
the key challenge for realization of a magnesium sulfur (Mg–S)
battery. Herein, we demonstrate that magnesium tetrakis(hexafluoroisopropyloxy)
borate Mg[B(hfip)4]2 (hfip = OC(H)(CF3)2) satisfies a multitude of requirements for an efficient
and practical electrolyte, including high anodic stability (>4.5
V),
high ionic conductivity (∼11 mS cm–1), and
excellent long-term Mg cycling stability with a low polarization.
Insightful mechanistic studies verify the reversible redox processes
of Mg–S chemistry by utilizing Mg[B(hfip)4]2 electroylte and also unveil the origin of the voltage hysteresis
in Mg–S batteries.
The decomposition pathway in LiBH4−MgH2 reactive hydride composites was investigated systematically as a function of pressure and temperature. Individual decomposition of MgH2 and LiBH4 is observed at higher temperatures and low pressures (T ≥ 450 °C and p(H2) ≤ 3 bar), whereas simultaneous desorption of H2 from LiBH4 and formation of MgB2 was observed at 400 °C and a hydrogen backpressure of p(H2) = 5 bar. The simultaneous desorption of H2 from LiBH4 and MgH2 without intermediate formation of metallic Mg could not be observed. In situ X-ray diffraction (XRD) and infrared (IR) spectroscopy reveal the present crystalline and amorphous phases
Nowadays, the technological utilization of reactive hydride composites (RHC) as hydrogen storage materials is limited by their reaction kinetics. However, addition of transition-metal-based additives, for instance titanium isopropoxide (Ti-iso), to the 2LiBH4+MgH2 system, results in a significant improvement of sorption kinetics. In this work, the evolution of chemical state and local structure of the Ti-based additive has been investigated by means of X-ray absorption (XAS) and photoemission (XPS) spectroscopy. X-ray absorption near-edge structure (XANES) as well as extended X-ray absorption fine structure (EXAFS) analysis have been undertaken at the Ti K-edge. The measurements reveal the formation of a highly dispersed and disordered TiO2-like phase during ball milling. During first desorption reduced titanium oxide and titanium boride are formed and remain stable upon cycling. The surface analysis performed by XPS shows that the reduction processes of the Ti-based additive during first desorption is coupled to the migration of the Ti species from the surface to the bulk of the material. Several factors, related to favoring heterogeneous nucleation of MgB2 and the increase of interfacial area through grain refinement are proposed as potential driving force, among other effects, for the observed kinetic improvement.
An exhaustive microstructural characterization is reported for the LiBH 4-MgH 2 reactive hydride composite (RHC) system with and without the Ti-isopropoxide additive. X-ray diffraction (XRD) with Rietveld analysis, transmission electron microscopy (TEM) coupled to energy dispersive X-ray analysis (EDX), selected area electron diffraction (SAED) and electron energy loss spectroscopy (EELS) are presented in this paper as the first time for this system in all sorption steps. New data are reported regarding average crystallite and grain size, microstrain, phase formation and morphology that contribute to the understanding of the reaction mechanism and the influence of the additives on the kinetics. Microstructural effects, related to the high dispersion of titanium based additives, results in a distinct grain refinement of MgB 2 and an increase of reaction sites which causes acceleration of desorption and absorption reactions. Considerations on stability of phases under e-beam irradiation have been also reported.
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