Search Results (22)

Lithium borohydride (LiBH₄) has emerged as a promising hydrogen storage material due to its exceptional theoretical hydrogen capacity (18.5 wt.%). However, its practical application is hindered by high dehydrogenation temperature (>400 °C), sluggish kinetics, and limited reversibility due to stable intermediate formation. This review critically analyzes recent advances in LiBH₄ modification through three primary strategies: catalytic enhancement, nanostructure engineering, and reactive composite design. Advanced carbon architectures and metal oxide catalysts demonstrate significant improvements in reaction kinetics and cycling stability through interface engineering and electronic modification. Sophisticated nanostructuring approaches, including mechanochemical processing and infiltration techniques, enable precise control over material architecture and phase distribution, effectively modifying thermodynamic and kinetic properties. The development of reactive hydride composites, particularly LiBH₄-MgH₂ systems, provides promising pathways for thermodynamic destabilization while maintaining high capacity. Despite these advances, challenges persist in maintaining engineered structures and suppressing intermediate phases during cycling. Future developments require integrated approaches combining multiple modification strategies while addressing practical implementation requirements. Full article

By reacting nitrilium derivative of the closo-dodecaborate anion, Bu₄N[B₁₂H₁₁N≡CR] (where R = Me, Et, nPr, iPr, p-tolyl), with lithium aluminum hydride (LiAlH₄), N-alkylammonium derivatives of the closo-dodecaborate anion, and Bu₄N[B₁₂H₁₁NH₂CH₂R], were obtained. The reduction reaction procedure was optimized, achieving yields close to quantitative (90–95%). The structure of the compound Bu₄N[B₁₂H₁₁NH₂CH₂CH₃] was determined using X-ray structural analysis. It was found that substituting lithium aluminum hydride (LiAlH₄) with sodium borohydride (NaBH₄) leads to the same products but only upon heating, while the reaction with LiAlH₄ proceeds at room temperature. Full article

Realizing rapid and stable hydrogen sorption at low temperature is critical for magnesium-based hydrogen storage materials. Herein, liquid channels are built in magnesium hydride by introducing lithium borohydride ion conductors as an efficient route for improving its hydrogen sorption. For instance, the 5 wt% LiBH₄-doped MgH₂ can release about 7.1 wt.% H₂ within 40 min at 300 °C but pure MgH₂ only desorbs less than 0.7 wt.% H₂, and more importantly it delivers faster desorption kinetics with more than 10 times enhancement to pure MgH₂. The hydrogen absorption capacity of LiBH₄-doped MgH₂ can still be well kept at approximately 7.2 wt.% without obvious capacity degradation even after six absorption and desorption cycles. This approach is not only through building ion transfer channels as a hydrogen carrier for kinetic enhancement but also by inhibiting the agglomeration of MgH₂ particles to obtain stable cyclic performance, which brings further insights to promoting the hydrogen ab-/desorption of other metal hydrides. Full article

In the current global energy crisis, the value of hydrogen has become better appreciated. Metal borohydrides attract a lot of attention from researchers because they are rich in hydrogen. In this study, glass microscope slides were coated with nickel as nanorods for use as a catalyst by the magnetron sputtering method, and then catalytic hydrolysis reactions of dimethylamine borane and lithium borohydride were carried out to produce hydrogen. Parameters such as temperature, the amount of catalyst, lithium borohydride, or dimethylamine borane concentration were varied and their effects on the catalytic performances of the catalyst were examined. Moreover, the catalyst was characterized by field emission scanning electron microscopy and X-ray diffraction, and hydrolysis products were analyzed through field emission scanning electron microscopy with energy dispersive spectroscopy analyses. Reaction kinetic parameters were also determined. The activation energy values of dimethylamine borane and lithium borohydride were determined to be 40.0 kJ mol⁻¹ and 63.74 kJ mol⁻¹, respectively. Activation enthalpy values were also calculated as 37.34 kJ mol⁻¹ and 62.45 kJ mol⁻¹ for dimethylamine borane and lithium borohydride, respectively. Initial hydrogen production rates under different conditions were also investigated in the study. For both hydrolysis systems, the fastest hydrogen production rates were calculated as 109 mL g_Ni⁻¹ min⁻¹ and 103 mL g_Ni⁻¹ min⁻¹ for dimethylamine borane and lithium borohydride, respectively, in the experiment performed at 60 °C at 0.2 M substrate concentration and with 1.3 g of catalyst. These hydrolysis systems using this catalyst are good candidates for systems that need hydrogen. Full article

Featuring a high hydrogen storage content of up to 20 wt%, complex metal borohydrides remain promising solid state hydrogen storage materials, with the real prospect of reversible behavior for a zero–emission economy. However, the thermodynamic barriers and sluggish kinetics are still barriers to overcome. In this context, nanoconfinement has provided a reliable method to improve the behavior of hydrogen storage materials. The present work describes the thermodynamic and kinetic enhancements of LiBH₄ nanoconfined in MFe₂O₄ (M=Co, Ni) ferrite-catalyzed graphene host. Composites of LiBH₄-catalysts were prepared by melt infiltration and investigated by X-ray diffraction, TEM, STEM-EDS and TPD. The role of ferrite additives, metal precursor treatment (Ar, Ar/H₂) and the effect on hydrogen storage parameters are discussed. The thermodynamic parameters for the most promising composite LiBH₄-graphene-NiFe₂O₄ (Ar) were investigated by Kissinger plot method, revealing an E_A = 127 kJ/mol, significantly lower than that of neat LiBH₄ (170 kJ/mol). The reversible H₂ content of LiBH₄-graphene-NiFe₂O₄ (Ar) after 5 a/d cycles was ~6.14 wt%, in line with DOE’s target of 5.5 wt% storage capacity, while exhibiting the lowest desorption temperature peak of 349 °C. The composites with catalysts treated in Ar have lower desorption temperature due to better catalyst dispersion than using H₂/Ar. Full article

Limonin is a natural compound which is rich in the fruit of various plants of the Rutaceae family and demonstrated to have a wide range of biological activities. In this work, seven limonin derivatives were successfully synthesized by hydrogenation of limonin, using different reducing agents (sodium cyanoborohydride, lithium aluminum hydride, and sodium borohydride). The chemical structure of the seven derivatives was characterized and identified by a series of techniques, including HR-ESI-MS, 1H-NMR, 13C-NMR, 2D-NMR, and IR. Among the seven limonin derivatives, six limonin derivatives were found to be new compounds which have not been previously reported. Then, the anti-inflammatory activities of the seven synthesized limonin derivatives, as well as the anti-inflammatory activities of eight known natural limonins, were evaluated and compared. Natural limonins, 30-O-Acetylhainangranatumin E and Xylogranatin A, presented significantly better anti-inflammatory activity. Xylogranatin A could inhibit LPS-induced RAW264.7 cell inflammatory factors, with a 90.0% inhibition ratio of TNF-α and 63.77% inhibition ratio of NO release in LPS-induced BV2 cells at 10 μM. Other natural limonins showed poor anti-inflammatory activity. In comparison, all the synthetic limonin derivatives showed decent anti-inflammatory activities, with the highest inhibition ratio of TNF-α of 37.8% and inhibition ratio of NO release of 12.5% in LPS-induced BV2 cells at 10 μM. Full article

In this study, lithium borohydride (LiBH₄) reduction was used to modify the surface chemistry of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) fibers. Although the most common reaction employed in the surface treatment of polyester materials is hydrolysis, it is not suitable for fiber modification of bacterial polyesters, which are highly resistant to this type of reaction. The use of LiBH₄ allowed the formation of surface hydroxyl groups under very mild conditions, which was crucial for maintaining the fibers’ integrity. The presence of these groups resulted in a noticeable improvement in the surface hydrophilicity of PHBV, as revealed by contact angle measurements. After the treatment with a LiBH₄ solution, the electrospun PHBV fibrous mat had a significantly greater number of viable osteoblast-like cells (SaOS-2 cell line) than the untreated mat. Moreover, the results of the cell proliferation measurements correlated well with the observed cell morphology. The most flattened SaOS-2 cells were found on the surface that supported the best cell attachment. Most importantly, the results of our study indicated that the degree of surface modification could be controlled by changing the degradation time and concentration of the borohydride solution. This was of great importance since it allowed optimization of the surface properties to achieve the highest cell-proliferation capacity. Full article

Electrochemical energy storage is considered a remarkable way to bridge the gap between demand and supply due to intermittent renewable energy production. All-solid-state batteries are an excellent alternative and are known to be the safest class of batteries. In the present scenario to accomplish the energy demands, high-capacity and stable anodes are warranted and can play a vital role in technology upgradation. Among the variety of anodes, alloying-type anodes are superior due to their high gravimetric capacity and stability. In the present work, zinc metal was implemented as electrode material in an all-solid-state lithium-ion battery. This anode material was tested with two different solid-state electrolytes, i.e., lithium borohydride (LiBH₄) and halide-stabilized LiBH₄ (i.e., LiBH₄.LiI). In a coin cell, Li foil was placed as a counter electrode. The establishment of a reaction mechanism during the charging and discharging was obtained through X-ray diffraction (XRD) and cyclic voltammetry (CV). Systematic studies using the temperature dependence performance were also conducted. The volumetric density with both electrolytes was found at more than 3000 mAh/cm³. The coulombic efficiency for the electrode material was also observed at ~94%. These impressive numbers present zinc electrodes as a promising material for future electrode material for all-solid-state Li-ion batteries. Full article

Complex hydrides, such as LiBH₄, are a promising class of ion conductors for all-solid-state batteries, but their application is constrained by low ion mobility at room temperature. Mixing with halides or complex hydride anions, i.e., other complex hydrides, is an effective approach to improving the ionic conductivity. In the present study, we report on the reaction of LiBH₄ with LiBF₄, resulting in the formation of conductive composites consisting of LiBH₄, LiF and lithium closo-borates. It is believed that the in-situ formation of closo-borate related species gives rise to highly conductive interfaces in the decomposed LiBH₄ matrix. As a result, the ionic conductivity is improved by orders of magnitude with respect to the Li-ion conductivity of the LiBH₄, up to 0.9 × 10⁻⁵ S cm⁻¹ at 30 °C. The insights gained in this work show that the incorporation of a second compound is a versatile method to improve the ionic conductivity of complex metal hydrides, opening novel synthesis pathways not limited to conventional substituents. Full article

All-solid-state Li-S batteries (use of solid electrolyte LiBH₄) were prepared using cathodes of a homogeneous mixture of graphene oxide (GO) and reduced graphene oxide (rGO) with sulfur (S) and solid electrolyte lithium borohydride (LiBH₄), and their electrochemical performance was reported. The use of LiBH₄ and its compatibility with Li metal permits the utilization of Li anode that improves the vitality of composite electrodes. The GO-S and rGO-S nanocomposites with different proportions have been synthesized. Their structural and morphological characterizations were performed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the results are presented. The electrochemical performance was tested by galvanostatic charge-discharge measurements at a 0.1 C-rate. The results presented here demonstrate the successful implementation of GO-S composites in an all-solid-state battery. Full article

Boron-based materials have been widely studied for hydrogen storage applications. Examples of these compounds are borohydrides and boranes. However, all of these present some disadvantages that have hindered their potential application as hydrogen storage materials in the solid-state. Thus, different strategies have been developed to improve the dehydrogenation properties of these materials. The purpose of this review is to provide an overview of recent advances (for the period 2015–2021) in the destabilization strategies that have been considered for selected boron-based compounds. With this aim, we selected seven of the most investigated boron-based compounds for hydrogen storage applications: lithium borohydride, sodium borohydride, magnesium borohydride, calcium borohydride, ammonia borane, hydrazine borane and hydrazine bisborane. The destabilization strategies include the use of additives, the chemical modification and the nanosizing of these compounds. These approaches were analyzed for each one of the selected boron-based compounds and these are discussed in the present review. Full article

The goal of this article is to highlight crucial breakthroughs in solid-state ionic conduction in borohydrides for battery applications. Borohydrides, M^z+B_xH_y, form in various molecular structures, for example, nido-M⁺BH₄; closo-M²⁺B₁₀H₁₀; closo-M²⁺B₁₂H₁₂; and planar-M⁶⁺B₆H₆ with M = cations such as Li⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺, which can participate in ionic conduction. This overview article will fully explore the phase space of boron–hydrogen chemistry in order to discuss parameters that optimize these materials as solid electrolytes for battery applications. Key properties for effective solid-state electrolytes, including ionic conduction, electrochemical window, high energy density, and resistance to dendrite formation, are also discussed. Because of their open structures (for closo-boranes) leading to rapid ionic conduction, and their ability to undergo phase transition between low conductivity and high conductivity phases, borohydrides deserve a focused discussion and further experimental efforts. One challenge that remains is the low electrochemical stability of borohydrides. This overview article highlights current knowledge and additionally recommends a path towards further computational and experimental research efforts. Full article

Solid electrolytes with high Li-ion conductivity and electrochemical stability are very important for developing high-performance all-solid-state batteries. In this work, Li₂(BH₄)(NH₂) is nanoconfined in the mesoporous silica molecule sieve (SBA-15) using a melting–infiltration approach. This electrolyte exhibits excellent Li-ion conduction properties, achieving a Li-ion conductivity of 5.0 × 10⁻³ S cm⁻¹ at 55 °C, an electrochemical stability window of 0 to 3.2 V and a Li-ion transference number of 0.97. In addition, this electrolyte can enable the stable cycling of Li|Li₂(BH₄)(NH₂)@SBA-15|TiS₂ cells, which exhibit a reversible specific capacity of 150 mAh g⁻¹ with a Coulombic efficiency of 96% after 55 cycles. Full article

Polyhydroborate salts represent the important class of energy materials attracting significant recent attention. Some of these salts exhibit promising hydrogen storage properties and/or high ionic conductivities favorable for applications as solid electrolytes in batteries. Two basic types of thermally activated atomic jump motion are known to exist in these materials: the reorientational (rotational) motion of complex anions and the translational diffusion of cations or complex anions. The present paper reviews recent progress in nuclear magnetic resonance (NMR) studies of both reorientational and diffusive jump motion in polyhydroborate salts. The emphasis is put on sodium and lithium closo-borates exhibiting high ionic conductivity and on borohydride-based systems showing extremely fast reorientational motion down to low temperatures. For these systems, we discuss the effects of order–disorder phase transitions on the parameters of reorientations and diffusive jumps, as well as the mechanism of low-temperature rotational tunneling. Full article

Hydrogen as an energy carrier is very versatile in energy storage applications. Developments in novel, sustainable technologies towards a CO₂-free society are needed and the exploration of all-solid-state batteries (ASSBs) as well as solid-state hydrogen storage applications based on metal hydrides can provide solutions for such technologies. However, there are still many technical challenges for both hydrogen storage material and ASSBs related to designing low-cost materials with low-environmental impact. The current materials considered for all-solid-state batteries should have high conductivities for Na⁺, Mg²⁺ and Ca²⁺, while Al³⁺-based compounds are often marginalised due to the lack of suitable electrode and electrolyte materials. In hydrogen storage materials, the sluggish kinetic behaviour of solid-state hydride materials is one of the key constraints that limit their practical uses. Therefore, it is necessary to overcome the kinetic issues of hydride materials before discussing and considering them on the system level. This review summarizes the achievements of the Marie Skłodowska-Curie Actions (MSCA) innovative training network (ITN) ECOSTORE, the aim of which was the investigation of different aspects of (complex) metal hydride materials. Advances in battery and hydrogen storage materials for the efficient and compact storage of renewable energy production are discussed. Full article