Synergistic hydrogen generation from AlLi alloy and solid-state NaBH4 activated by CoCl2 in water for portable fuel cell

Solid-state AlLi/NaBH₄ mixture activated by CoCl₂ salt is fabricated for hydrogen generation via a milling process, providing uniform dispersion of AlLi alloy and CoCl₂ salt among pulverized NaBH₄ particles in order to improve NaBH₄ hydrolysis through the contact of NaBH₄ with active catalytic sites. The active catalytic sites come from Co₂B loaded in Al(OH)₃ (Bayerite) or LiAl₂(OH)₇ hydrate, generated from the reaction of CoCl₂, AlLi alloy, and NaBH₄ in water. The results show that the gravimetric hydrogen storage capacity is as high as 6.4 wt.% and an efficiency of above 90% in 30-min hydrolysis at 323 K could be achieved using the limited amount of water. The hydrogen generation amount and rate could be regulated by changing the composition, mixing style, mixture/water weight ratio, and hydrolysis temperature. The relative mechanism is explored.     

Hydrogen generation from Al/NaBH4 hydrolysis promoted by Li-NiCl2 additives

On-demand hydrogen generation from solid-state Al/NaBH₄ hydrolysis activated by Li-NiCl₂ additives are elaborated in the present paper. Hydrogen generation amount and rate can be regulated by changing Al/NaBH₄ weight ratio, Li and NiCl₂ amount, hydrolytic temperature, etc. The optimized Al−10 wt.% Li−15 wt.% NiCl₂/NaBH₄ mixture (weight ratio of 1:1) yields 1778 ml hydrogen/1 g mixture with 100% efficiency within 50 min at 323 K. The improved hydrolytic performance comes from the effect of Li-NiCl₂ additives, which decrease aluminum particle size in the milling process and produce the catalytic promoter BNi₂/Al(OH)₃ in the hydrolytic process. Compared with the conventional reaction of Al and NaBH₄ in water, there is an interaction of Al/NaBH₄ hydrolysis which improves the hydrolytic kinetics of Al/NaBH₄ via the catalytic effect of hydrolysis by-products Al(OH)₃, BNi₂, and NaBO₂. The Al/NaBH₄ mixture may be applied as a portable hydrogen generation material. Our experimental data lay a foundation for designing practical hydrogen generators.     

Preparation and catalytic activity of PVP-protected Au/Ni bimetallic nanoparticles for hydrogen generation from hydrolysis of basic NaBH4 solution

Poly(N-vinyl-2-pyrrolidone)(PVP)-protected Au/Ni bimetallic nanoparticles (BNPs) were prepared in one-vessel via chemical reduction of the corresponding ions with dropwise addition of NaBH₄, and their catalytic activity in the hydrogen generation from hydrolysis of a basic NaBH₄ solution was examined. The structure, particle size, and chemical composition of the resultant BNPs were characterized by Ultraviolet–visible spectrophotometry (UV–Vis), X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM) and High-resolution transmission electron microscopy (HR-TEM). The effects of processing parameters such as metal composition, metal ion concentration, and mole ratio of PVP to metal ion on the hydrolysis of a basic NaBH₄ solution were studied in detail. The results indicated that as-prepared Au/Ni BNPs showed a higher catalytic activity than corresponding monometallic NPs (MNPs) in the hydrogen generation from the hydrolysis reaction of a basic NaBH₄ solution. Among all the MNPs and BNPs, Au/Ni BNPs with the atomic ratio of 50/50 exhibited the highest catalytic activity, showing a hydrogen generation rate as high as 2597 mL-H₂ min⁻¹ g-catalyst⁻¹ at 30 °C, which can be ascribed to the presence of negatively charged Au atoms and positively charged Ni atoms. Based on the kinetic study of the hydrogen generation from the hydrolysis reaction of a basic NaBH₄ solution over the PVP-protected Au/Ni BNPs, the corresponding apparent activation energy was determined as 30.3 kJ/mol for the BNPs with the atomic ratio of 50/50.     

Alkaline sodium borohydride gel as a hydrogen source for PEMFC or an energy carrier for NaBH4-air battery

In this preliminary study, we tried to use sodium polyacrylate as the super absorbent polymer to form alkaline NaBH₄ gel and explored its possibilities for borohydride hydrolysis and borohydride electro-oxidation. It was found that the absorption capacity of sodium polyacrylate decreased with increasing NaBH₄ concentration. The formed gel was rather stable in the sealed vessel but tended to slowly decompose in open air. Hydrogen generation from the gel was carried out using CoCl₂ catalyst precursor solutions. Hydrogen generation rate from the alkaline NaBH₄ gel was found to be higher and impurities in hydrogen were less than that from the alkaline NaBH₄ solution. The NaBH₄ gel also successfully powered a NaBH₄-air battery.     

Effects of alkaline treatment of hydrogen storage alloy on electrocatalytic activity for NaBH4 oxidation

Activation of the MmNi_4.03Co_0.42Mn_0.31Al_0.24 hydrogen storage alloy electrode is performed by immersing the electrode in a solution containing 6.0 mol dm⁻³ NaOH and 0.1 mol dm⁻³ NaBH_4. The effects of activation on the electrocatalytic activity of the electrode for NaBH₄ oxidation are investigated by cyclic voltammetry and chronoamperometry. Immersion activation greatly improves the electrocatalytic activity of the alloy electrode. Hydrogen was absorbed in the alloy during the immersion activation treatment and its electrooxidation is responsible for the high initial oxidation current. The stabilized current mainly results from the direct oxidation starting from the borohydride species. The effects of activation on structure and surface chemistry of the alloy are also discussed.     

Study on reversible hydrogen sorption behaviors of a 3NaBH4/HoF3 composite

In this work, the complex hydrogen sorption behaviors in a 3NaBH₄/HoF₃ composite prepared through mechanical milling were carefully investigated, including the reactions occurred during ball milling and de-/rehydrogenation processes. Different from other rear earth fluorides, the HoF₃ can react with NaBH₄ during ball milling, leading to the formations of Na–Ho–F and Na–Ho–BH₄ complex compounds. The first dehydriding of the 3NaBH₄/HoF₃ composite can be divided into 4 steps, including the ion exchange between H⁻ and F⁻, the formation of NaHo(BH₄)₄, the decomposition of NaHo(BH₄)₄ and reaction of NaBH₄ with Na–Ho–F compounds. The final products, HoB₄, HoH₃ and NaF, can be rehydrogenated to generate NaBH₄ and NaHoF₄ with an absorption capacity of 2.3 wt% obtained at 400 °C. Based on the Pressure–Composition–Temperature measurements, the de-/rehydrogenation enthalpies of the 3NaBH₄/HoF₃ composite are determined to be 88.3 kJ mol⁻¹ H₂ and −27.1 kJ mol⁻¹ H₂, respectively.     

Hydrolysis of AlLi/NaBH4 system promoted by Co powder with different particle size and amount as synergistic hydrogen generation for portable fuel cell

Hydrogen generation from the hydrolysis of aluminum lithium/sodium borohydride (referred to as AlLi/NaBH₄) system activated by Co powder with different particle size and amount was evaluated in this paper. The designed aluminum–lithium–cobalt (referred to as Al–Li–Co/NaBH₄) systems including Al-5 wt% Li-50 wt% nano Co, Al-7.5 wt% Li-25 wt% nano Co, Al-5 wt% Li-50 wt% micro Co, and Al-7.5 wt% Li-25 wt% micro Co had 100% hydrogen yield at 323 K. The hydrogen generation rates of these systems were regulated by Co species, Co amount, as well as consecutive runs of NaBH₄ hydrolysis. The underlying activation mechanism, including the formation of Al_0.94Co_1.06 alloy and highly active and stable Co-based catalyst has been elaborated in this study. Experimental data present an inexpensive and highly efficient hydrogen source for portable fuel cell.     

Synthesis of solid-state NaBH4/Co-based catalyst composite for hydrogen storage through a high-energy ball-milling process

Solid-state composites of NaBH₄ and Co-based catalyst have been fabricated for hydrogen generation via a novel mechanochemical technique, i.e. the high-energy ball milling, in which the gravimetric storage capacity of hydrogen has reached 6.7 wt%, meeting the 2010 target of at least 0.06 kg H₂/kg set by the U.S. Department of Energy (DOE). The active catalysts used in the hydrolysis reaction of sodium borohydride for hydrogen generation are mainly cobalt oxides. Controlled addition of water, namely water used as a limiting agent, to the solid composites of NaBH₄ and Co-based catalyst greatly improves the H₂ storage capacity and resolved the issues of low gravimetric H₂ storage in conventional aqueous system of sodium borohydride. Factors influencing the performance of hydrogen production such as amounts of H₂O added, catalyst loadings and durations of ball-milling processes are investigated. Moreover the hydrolyzed products of NaBH₄ and spent catalysts are analyzed as well.     

Solution combustion synthesized cobalt oxide catalyst precursor for NaBH4 hydrolysis

In this paper we report the solution combustion synthesis of cobalt oxide nanofoam from solutions of cobalt nitrate and glycine and subsequent use as an effective catalyst precursor for NaBH₄ hydrolysis. The catalytic activity results show that the hydrogen generation rate (HGR) at room temperature was much higher for the solution combustion synthesized material than for commercial Co₃O₄ nanopowder, though their specific surface areas were comparable (∼26–32 m²/g). Using a 0.6 wt.% aqueous solution of NaBH₄ at 20 °C and a 5 wt.% catalyst precursor loading, a HGR of 1.93 L min⁻¹ g_cat⁻¹ was achieved for solution combustion synthesized Co₃O₄. In contrast, at the same conditions, for commercial Co₃O₄ and elemental Co powders HGRs of 0.98 and 0.49 L min⁻¹ g_cat⁻¹ were achieved respectively. This type of synthesis is amenable to many complex metal oxide catalysts as well, such as LiCoO₂, which have also been shown to be good catalyst precursors for hydrolysis of NaBH₄.     

Hydrogen sorption properties of MgH2/NaBH4 composites

The hydrogen sorption properties of magnesium hydride–sodium borohydride composites prepared by means of high-energy ball milling under Ar atmosphere were investigated. Mutual influence of milling time and the content of NaBH₄ were studied. Microstructural and morphological analyses were carried out using X-ray Diffraction (XRD), laser scattering measurements and Scanning Electron Microscopy (SEM), while kinetic analysis and cycling were performed in a Sievert's volumetric apparatus. It has been shown that low content of NaBH₄ and short milling time are beneficial for hydrogen sorption kinetics.     

Novel fabrication of solid-state NaBH4/Ru-based catalyst composites for hydrogen evolution using a high-energy ball-milling process

Solid-state NaBH₄/Ru-based catalyst composites have been fabricated for hydrogen generation through a high-energy ball-milling process, providing uniform dispersion of resin-supported Ru³⁺ catalysts among pulverized NaBH₄ (SBH) particles, so as to increase the contacts of SBH with active catalytic sites. Consequently, the gravimetric hydrogen storage capacity as high as 7.3 wt% could be achieved by utilizing water as a limiting reagent to overcome the issue of deactivated catalysts whose active sites are often blocked by precipitates caused by limited NaBO₂ solubility occurring in conventional aqueous SBH systems for hydrogen productions. Products of hydrolyzed SBH that greatly influence the gravimetric H₂ storage capacity are found to be most likely NaBO₂·2H₂O and NaBO₂·4H₂O from SBH/H₂O reacting systems with initial weight ratios, SBH/H₂O = 1/2 and 1/10, respectively, according to the TGA and XRD analyses.     

New insights into the mechanism of H2 generation through NaBH4 hydrolysis on Co-based nanocatalysts studied by differential reaction calorimetry

To our knowledge, the present study is the first investigation by liquid-phase calorimetry of the mechanism of hydrogen generation by hydrolysis of sodium borohydride catalyzed by Co₂B nanoparticles generated in situ. The differential reaction calorimeter was coupled with a volumetric hydrogen measurement, allowing a simultaneous thermodynamic and kinetic study of the reaction. At the end of the reaction, the catalyst was characterized ex situ by TEM, XRD, magnetism, N₂ adsorption, TGA–DTA, and the liquid hydrolysis products were analyzed by Wet-STEM and ¹¹B-NMR. The in situ preparation method made it possible to form nanoparticles (<12 nm) of Co₂B which are the active phase for the hydrolysis reaction. In semi-batch conditions, the Co₂B catalyst formed in situ is subsequently reduced by each borohydride addition and oxidized at the end of the hydrolysis reaction by OH⁻ in the presence of metaborate. A coating of the nanoparticles has been observed by calorimetry and physico-chemical characterization, corresponding to the formation of a 2–3 nm layer of cobalt oxide or hydroxide species.     

Comparative XPS study of Rh/Al2O3 and Rh/TiO2 as catalysts for NaBH4 hydrolysis

The catalysts Rh/Al₂O₃ and Rh/TiO₂ for hydrogen production from NaBH₄ were prepared by deposition technique from RhCl₃ reduced by NaBH₄ and were studied by XPS and TEM. It was found that the RhCl₃/Al₂O₃ system is more stable comparing to RhCl₃/TiO₂ which starts to decompose by weak heat treatment. It was shown that NaBH₄ reduced RhCl₃/TiO₂ (Al₂O₃) to supported metal Rh nanoparticles in both cases. In the case of Rh/TiO₂ SMSI effect it was found after RT reduction. The SMSI (Strong Metal-Support Interaction) effect gave an explanation for the difference of activity between Rh/TiO₂ and Rh/Al₂O₃ catalysts in hydrolysis reaction of NaBH₄.     

Microstructural control of catalyst-loaded PVDF microcapsule membrane for hydrogen generation by NaBH4 hydrolysis

Polymer microcapsules were prepared and used as catalyst support for hydrogen generation from sodium borohydride. Polyvinylidene fluoride (PVDF) porous microcapsule membranes immobilized with metal salt (cobalt (II) chloride hexahydrate) catalyst and cobalt–boron catalyst were prepared, denoting them as MS and MP method respectively. Non-solvent coagulation bath consisting of a mixture of water and isopropanol (IPA) were used to prepare the microcapsules. The compositions of the non-solvents were changed with a ratio of 10:90 (v/v%)–50:50 (v/v%) with 1 wt% NaOH and 0.5 wt% NaBH₄. The effects of a number of parameters such as the kinds of additives, the size and morphology of the resulting microcapsules were studied on hydrogen generation. The structures and physical–chemical properties of the metal catalyst-loaded microcapsule membranes were characterized using SEM and EDX. The MS method used in preparing the microcapsule showed good performance in hydrogen generation from sodium borohydride. There was also improved performance in hydrogen generation with increasing IPA composition used in the metal salts loaded microcapsule preparation. The control of three regions inside the microcapsules (hollow region, crust region and skin layer) as well as the specific loading of metal catalysts gave a good hydrogen generation performance. The catalyst-loaded microcapsule also maintained an appreciable performance and stability after many runs of hydrolysis reaction for the hydrogen generation.     

Thermochemical recycling of hydrolyzed NaBH4. Part II: Systematical study of parameters dependencies

This paper focuses on the yields of both main product NaBH₄ and byproduct MgH₂ of the thermochemical process. The influence of parameters such as i) the isothermal reaction temperature in the range 480 °C–660 °C, ii) the stoichiometric ratio of solid reactants NaBO₂:Mg prepared from 1:2 to 1:8, iii) H₂ pressure supplied from 2 to 31 bars and iv) the reaction time kept at isotherm from 0 to 16 h have been systematically investigated. The yields are estimated by in-situ and ex-situ evaluations. Two temperature regimes for MgH₂ and NaBH₄ formation are recognized from 370 °C to 450 °C and above 500 °C respectively. With regard to NaBH₄ regeneration, temperature is the most important factor that positively accelerates the apparent reaction rate between 500 °C and 650 °C providing a sufficient H₂ pressure. To efficiently obtain high NaBH₄ yield mixtures with molar stoichiometric ratio between solid reactants not less than 1:4 is suggested. Experimental results also reveal that at 12 bars of H₂ pressure high NaBH₄ yield is obtained. Hence, more efficient way to improve mass transfer of solid reactants (e.g. advance reactor enhances mobility of reactants) rather than increasing H₂ pressures is advised. Under optimized condition, 100% conversion of NaBO₂ can be achieved within 1.5 h.     

Enhanced hydrogen storage performance of LiAlH4-MgH2-TiF3 composite

The mutual destabilization of LiAlH₄ and MgH₂ in the reactive hydride composite LiAlH₄-MgH₂ is attributed to the formation of intermediate compounds, including Li-Mg and Mg-Al alloys, upon dehydrogenation. TiF₃ was doped into the composite for promoting this interaction and thus enhancing the hydrogen sorption properties. Experimental analysis on the LiAlH₄-MgH₂-TiF₃ composite was performed via temperature-programmed desorption (TPD), differential scanning calorimetry (DSC), isothermal sorption, pressure-composition isotherms (PCI), and powder X-ray diffraction (XRD). For LiAlH₄-MgH₂-TiF₃ composite (mole ratio 1:1:0.05), the dehydrogenation temperature range starts from about 60 °C, which is 100 °C lower than for LiAlH₄-MgH₂. At 300 °C, the LiAlH₄-MgH₂-TiF₃ composite can desorb 2.48 wt% hydrogen in 10 min during its second stage dehydrogenation, corresponding to the decomposition of MgH₂. In contrast, 20 min was required for the LiAlH₄-MgH₂ sample to release so much hydrogen capacity under the same conditions. The hydrogen absorption properties of the LiAlH₄-MgH₂-TiF₃ composite were also improved significantly as compared to the LiAlH₄-MgH₂ composite. A hydrogen absorption capacity of 2.68 wt% under 300 °C and 20 atm H₂ pressure was reached after 5 min in the LiAlH₄-MgH₂-TiF₃ composite, which is larger than that of LiAlH₄-MgH₂ (1.75 wt%). XRD results show that the MgH₂ and LiH were reformed after rehydrogenation.     

Cobalt nanoparticles supported on magnetic core-shell structured carbon as a highly efficient catalyst for hydrogen generation from NaBH4 hydrolysis

A novel recyclable cobalt nanocatalyst, supported on magnetic carbon with core-shell structure, was successfully synthesized by using wetness impregnation-chemical reduction method for hydrogen generation from hydrolysis of NaBH₄. The resultant nanocomposite was characterized to determine the structural and physical-chemical properties by a series of analytical techniques such as FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscope), EDX (energy-dispersive X-ray spectroscopy), TEM (transmission electron microscopy), etc. The results demonstrated that amorphous cobalt nanoparticles were homogeneously surrounded on the surface of the support due to having abundant hydrophilic groups (such as aldehyde and hydroxyl groups) on the surface of carbon layer for the effective immobilization of metal ions. The supported catalyst showed superior catalytic performance towards the hydrolysis reaction of NaBH₄ at room temperature. The total rate of hydrogen generation and activation energy were calculated to be 1403 ml H₂ g_cat^?1 min^?1 and 49.2 kJ mol^?1, respectively, which were comparable to the values of most cobalt-based catalyst reported for hydrogen production from hydrolysis of NaBH₄. Additionally, reusability test revealed that the hydrogen in NaBH₄ substrate could be completely released within 25 min with a minimum hydrogen generation rate of 832 ml H₂ g_cat^?1 min^?1 even after five runs of hydrolytic reaction, implying the as-prepared Co/Fe₃O₄@C composite could be considered as a promising candidate catalyst for portable hydrogen fuel system such as PEMFC (proton exchange membrane fuel cells).     

A novel design of solid-state NaBH4 composite as a hydrogen source for 2 W PEMFC applications

Hydrolysis of sodium borohydride (NaBH₄) is a promising method for on-board hydrogen supply to polymer electrolyte membrane fuel cells (PEMFC). This article presents an attempt to design a novel solid-state NaBH₄ composite, which is made up of NaBH₄ powder, Co²⁺/IR-120 catalyst and silicone rubber, for hydrogen generator. The silicone rubber can act as a stabilizer in the solid-state NaBH₄ composite because of its surface hydrophobicity leading to reduced diffusion rate of water into the composite. The solid-state NaBH₄ composite can produce hydrogen stably near 25 mL min⁻¹ for at least 2 h without employment of any mechanical control system. Using the hydrogen generated from the solid-state NaBH₄ composite, a 2 W PEMFC stack is successfully operated to power a cellular phone.     

Hydrogen generation from the ball milled composites of sodium and lithium borohydride (NaBH4/LiBH4) and magnesium hydroxide (Mg(OH)2) without and with the nanometric nickel (Ni) additive

The composites of (NaBH₄+2Mg(OH)₂) and (LiBH₄+2Mg(OH)₂) without and with nanometric Ni (n-Ni) added as a potential catalyst were synthesized by high energy ball milling. The ball milled NaBH₄-based composite desorbs hydrogen in one exothermic reaction in contrast to its LiBH₄-based counterpart which dehydrogenates in two reactions: an exothermic and endothermic. The NaBH₄-based composite starts desorbing hydrogen at 240 °C. Its ball milled LiBH₄-based counterpart starts desorbing at 200 °C. The latter initially desorbs hydrogen rapidly but then the rate of desorption suddenly decelerates. The estimated apparent activation energy for the NaBH₄-based composite without and with n-Ni is equal to 152 ± 2.2 and 157 ± 0.9 kJ/mol, respectively. In contrast, the apparent activation energy for the initial rapid dehydrogenation for the LiBH₄-based composite is very low being equal to 47 ± 2 and 38 ± 9 kJ/mol for the composite without and with the n-Ni additive, respectively. XRD phase studies after volumetric isothermal dehydrogenation tests show the presence of NaBO₂ and MgO for the NaBH₄-based composite. For the LiBH₄-based composite phases such as MgO, Li₃BO₃, MgB₂, MgB₆ are the products of the first exothermic reaction which has a theoretical H₂ capacity of 8.1 wt.%. However, for reasons which are not quite clear, the first reaction never goes to full completion even at 300 °C desorbing ∼4.5 wt.% H₂ at this temperature. The products of the second endothermic reaction for the LiBH₄-based composite are MgO, MgB₆, B and LiMgBO₃ and the reaction has a theoretical H₂ capacity of 2.26 wt.%. The effect of the addition of 5 wt.% nanometric Ni on the dehydrogenation behavior of both the NaBH₄-and LiBH₄-based composites is rather negligible. The n-Ni additive may not be the optimal catalyst for these hydride composite systems although more tests are required since only one n-Ni content was examined.