A thermodynamic assessment of LiBH4

Kharbachi, Abdel El; Pinatel, Eugenio Riccardo; Nuta, Ioana; Baricco, Marcello

doi:10.1016/j.calphad.2012.08.005

Cited by 52 publications

(47 citation statements)

References 53 publications

(130 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the 2nd cycle ( Figure 2b, 2nd cycle), after the polymorphic transition of LiBH 4 , also the polymorphic phase transition of Mg 2 NiH 4 is observed as a broad peak around 245 • C. Both DSC signals can be observed also on cooling. Furthermore, in the 3rd cycle ( Figure 2b, 3rd cycle), after the polymorphic transition peaks, the melting of LiBH 4 can be detected at T peak = 279 • C. All transitions are reversible and well visible during the cooling process and temperature values are in good agreement with the literature [3,4,35]. In the 4th cycle ( Figure 2b, 4th cycle), after the polymorphic transition peaks and LiBH 4 melting, at T peak = 308 • C a broad endothermic peak due to hydrogen release from LiBH 4 can be observed under 2.7 bar H 2 .…”

Section: Mg 2 Nih 4 -Libhsupporting

confidence: 76%

Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures

et al. 2018

Self Cite

View full text Add to dashboard Cite

Abstract:The development of materials showing hydrogen sorption reactions close to room temperature and ambient pressure will promote the use of hydrogen as energy carrier for mobile and stationary large-scale applications. In the present study, in order to reduce the thermodynamic stability of MgH 2 , Ni has been added to form Mg 2 NiH 4 , which has been mixed with various borohydrides to further tune hydrogen release reactions. De-hydrogenation/re-hydrogenation properties of Mg 2 NiH 4 -LiBH 4 -M(BH 4 ) x (M = Na, K, Mg, Ca) systems have been investigated. Mixtures of borohydrides have been selected to form eutectics, which provide a liquid phase at low temperatures, from 110 • C up to 216 • C. The presence of a liquid borohydride phase decreases the temperature of hydrogen release of Mg 2 NiH 4 but only slight differences have been detected by changing the borohydrides in the eutectic mixture.

show abstract

Section: Mg 2 Nih 4 -Libhsupporting

confidence: 76%

Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…For the first time, a ternary hexagonal solid solution containing chloride in the LiBH 4 structure was stabilized at RT lowering the weight of the electrolyte, therefore increasing the energy density. In addition, the solid solution appears more thermally stable than pure LiBH 4 (T m = 280 °C), 82 In summary, the stabilisation at lower temperature of the conductive phase of LiBH 4 in this system, not only mitigates the operational temperature of an all-solid-state cell, i.e. increasing the Li ion conductivity at RT, but also enables the use of high-voltage positive electrodes, thus increasing the overall amount of energy stored in the battery.…”

Section: Discussionmentioning

confidence: 97%

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution

et al. 2019

Self Cite

View full text Add to dashboard Cite

This study shows a flexible system that offers promising candidates for Li-based solid state electrolyte. The Brsubstitution for BH 4 stabilizes the hexagonal structure of LiBH 4 at room temperature, whereas Clis soluble only at higher temperatures. Incorporate chloride in hexagonal solid solution lead to increase the energy density of the system. For the first time, a stable hexagonal solid solution of LiBH 4 containing both Cland Br-halide anions has been obtained at room temperature (RT). The LiBH 4 -LiBr-LiCl ternary phase diagram has been determined at RT by X-ray diffraction coupled with a Rietveld refinement. A solubility of up to 30% of Clin the solid solution has been established. The effect of the halogenation on the Li-ion conductivity and electrochemical stability has been investigated by Electrochemical Impedance Spectroscopy and Cyclic Voltammetry. Considering the ternary samples, h-Li(BH 4 ) 0.7 (Br) 0.2 (Cl) 0.1 compositionshowed the highest value for conductivity (1.3 × 10 −5 S/cm at 30 °C), which is about three order of magnitude higher than that for pure LiBH 4 in the orthorhombic structure. The values of Li-ion conductivity at room temperature depend only on the BH 4 content in the solid solution, suggesting that the Br/Cl ratio does not affect the defect formation energy in the structure. The chloride anion substitution in the hexagonal structure increases the activation energy, moving from about 0.45 eV for samples without Clions in the structure, up to about 0.63 eV for h-Li(BH 4 ) 0.6 (Br) 0.2 (Cl) 0.2 compositions, according with the Meyer-Neldel rule. In addition to increasing Li ion conductivity, the halogenation increase also the thermal stability of the system.Unlike for the Li-ion conductivity, Br/Cl ratio influences the electrochemical stability: a wide oxidative window of 4.04 V vs. Li + /Li is reached in the Li-Br system, while further addition of Cl is a trade-off between oxidative stability and weight reduction. The halogenation allow both binary and ternary systems operating below 120 °C, thus suggesting possible applications of these fast ion conductors as solid-state electrolyte in Li-ion batteries. Graphical AbstractKeywords: complex hydride, solid state electrolyte, Li-ion batteries

show abstract

“…The suggested approach, including a combination of CAL-PHAD and ab initio modelling, has been recently applied to complex hydrides. As an example, equilibrium pressuretemperature (P-T) phase diagrams for NaBH 4 [99], LiBH 4 [100] and Mg(BH 4 ) 2 [101] are shown in Fig. 2.…”

Section: Modellingmentioning

confidence: 99%

Complex and liquid hydrides for energy storage

et al. 2016

Self Cite

View full text Add to dashboard Cite

The research on complex hydrides for hydrogen storage was initiated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH 4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized, and the knowledge regarding the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant portion of the research groups active in the field of complex hydrides is collaborators in the International Energy Agreement Task 32. This paper reports about the important issues in the field of complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and is an excellent summary of the recent achievements.

show abstract

A thermodynamic assessment of LiBH4

Cited by 52 publications

References 53 publications

Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures

Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution

Complex and liquid hydrides for energy storage

Contact Info

Product

Resources

About

A thermodynamic assessment of LiBH4

Cited by 52 publications

References 53 publications

Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures

Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH4–LiBr–LiCl Solid Solution

Complex and liquid hydrides for energy storage

Contact Info

Product

Resources

About

Phase Stability and Fast Ion Conductivity in the Hexagonal LiBH₄–LiBr–LiCl Solid Solution