Nanocomposite system for solid hydrogen storage
10364148 ยท 2019-07-30
Assignee
Inventors
- Mohamed Sherif Mohamed Mostafa El-Eskandarany (Salmya, KW)
- Fahad Talal Mohammed Ali Salem Alajmi (Hadiya, KW)
- Mohammad E. A. A. Banyan (Abdullah Al-Mubarak, KW)
Cpc classification
C01B3/0078
CHEMISTRY; METALLURGY
B22F1/07
PERFORMING OPERATIONS; TRANSPORTING
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
C01P2002/72
CHEMISTRY; METALLURGY
Y02E60/32
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B22F9/04
PERFORMING OPERATIONS; TRANSPORTING
International classification
C01B3/00
CHEMISTRY; METALLURGY
B22F9/04
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The nanocomposite system for hydrogen storage is a composite of MgH.sub.2 powder with ZrNi.sub.5 powder and a combination of Nb.sub.2O.sub.5, TiC and VC. Preferably, the MgH.sub.2 is in nanocrystalline form and the ZrNi.sub.5 is significantly in a Friauf-Laves phase. The nanocomposite system is formed by combining the MgH.sub.2 powder with the ZrNi.sub.5, Nb.sub.2O.sub.5, TiC and VC, preferably in amounts of 4 wt. % ZrNi.sub.5+1 wt. % Nb.sub.2O.sub.5+0.5 wt. % TiC+0.5 wt. % VC, to form a mixture, and then performing reactive ball milling on the mixture. Preferably, the reactive ball milling is performed for a period of 50 hours.
Claims
1. A nanocomposite system for solid hydrogen storage, comprising a nanocrystalline powder mixture of magnesium hydride (MgH.sub.2) doped with a catalyst for improving hydrogenation and dehydrogenation properties of the MgH.sub.2, the catalyst including ZrNi.sub.5, Nb.sub.2O.sub.5, titanium carbide (TiC) and vanadium carbide (VC).
2. The nanocomposite system for solid hydrogen storage as recited in claim 1, wherein the nanocrystalline powder mixture comprises: 4 wt % ZrNi.sub.5; 1 wt % Nb.sub.2O.sub.5; 0.5 wt % TiC; 0.5 wt % VC; the balance being MgH.sub.2.
3. The nanocomposite system for solid hydrogen storage as recited in claim 1, wherein the magnesium hydride and the catalyst are mixed mechanically by reactive ball milling to form the nanocrystalline powder.
4. The nanocomposite system for solid hydrogen storage as recited in claim 1, wherein the MgH.sub.2 comprises nanocrystalline -MgH.sub.2 powder.
5. The nanocomposite system for solid hydrogen storage as recited in claim 1, wherein the ZrNi.sub.5 powder comprises ZrNi.sub.5 in Friauf-Laves phase crystalline structure.
6. The nanocomposite system for solid hydrogen storage as recited in claim 1, wherein nanocrystalline powder mixture have a particle size between 5-12 nm.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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(15) Similar reference characters denote corresponding features consistently throughout the attached drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(16) The nanocomposite system for solid hydrogen storage includes MgH.sub.2 powder and a combination of ZrNi.sub.5, Nb.sub.2O.sub.5, TiC and VC powders. The ZrNi.sub.5 powder can be a Friauf-Laves phase powder. Preferably, the ZrNi.sub.5 powder forms about 4 wt. % of the nanocomposite system for hydrogen storage. The Nb.sub.2O.sub.5, TiC, and VC powders preferably form about 1 wt. %, 0.5 wt. % and 0.5 wt. %, respectively. As will be described in greater detail below, the nanocomposite system for hydrogen storage is prepared by producing nanocrystalline MgH.sub.2 powder using a reactive ball milling (RBM) technique. ZrNi.sub.5 powder, preferably a Friauf-Laves phase powder, is formed and combined with the nanocrystalline MgH.sub.2 powder using RBM, along with a preferred combination of Nb.sub.2O.sub.5, TiC and VC, to form the nanocomposite system. Preferably, the reactive ball milling is performed at room temperature at 250 rpm for a period of 50 hours.
(17) The present inventors have found that combining ZrNi.sub.5, Nb.sub.2O.sub.5, TiC and VC powders with MgH.sub.2 powder as described herein improves the hydrogenation/dehydrogenation behavior of MgH.sub.2. For example, the decomposition temperature at 1 bar in He of MgH.sub.2 can be lowered from 60 C. when used in combination with ZrNi.sub.5, Nb.sub.2O.sub.5, TiC and VC powders, as described herein (see
(18) The following is a list of the starting materials and equipment used in the subsequent exemplary procedures. The Starting Materials include commercial magnesium (Mg) powder about 50 m in diameter and 99.5 wt. % purity; sponge zirconium (Zr) metal with 99.5 wt. % purity; nickel (Ni) wires with 99.99 wt % purity; niobium pentoxide (Nb.sub.2O.sub.3) powders with 20 pm particle size and 99.9 wt. % purity; titanium carbide (TiC) powder with 10 m particle size and 99.9 wt. % purity; vanadium carbide (VC) powder with 10 m particle size and 99.9 wt. % purity; helium gas (He) cylinders having 99.999% purity (provided by a local gas company in Kuwait); and hydrogen gas (H.sub.2) cylinders having 99.999% purity, (provided by a local gas company in Kuwait). The Equipment, Devices, and Tools include He-gas atmosphere-glove box (UNILAB Pro Glove Box Workstation, provided by mBRAUN, Germany); FeCr balls (11 mm in diameter) provided by Evico Inc, Germany; 220 ml volume hardened steel high pressure milling vial, provided by Evico Inc, Germany; Gas-Temperature-Monitoring System, provided by Evico Inc, Germany; and Planetary Ball Mill PM400, provided by Retsch, Germany.
Example 1
Synthesis of Nanocomposite System
(19) MgH.sub.2 powder was prepared by sealing 5 g of magnesium (Mg) inside a hardened steel vial (220 mL volume) with 50 FeCr balls (11 mm in diameter). The ball-to-powder weight ratio was 38:1. The atmosphere in the vial was evacuated to 10.sup.3 bar pressure before introducing H.sub.2 gas. The vial was filled with H.sub.2 gas to reach a pressure of 50 bar. Reactive ball milling was then carried out at room temperature using a the PM400 high energy ball mill. After 6, 12.5, 25, 50, 100 and 200 hours of reactive ball milling, the reaction was halted and a small amount (50 mg) of MgH.sub.2 powder was then extracted in the glove box and sealed in vials. The as-reacted ball-milled powders obtained after different milling times were discharged into 8 Pyrex vials and kept under vacuum in a desiccator for further analysis.
(20) To prepare ZrNi.sub.5 Friauf-Laves phase powder, sponge Zr lumps with purity of 99.5% were purified by re-melting several times in He gas atmosphere in an arc-melter (AM type provided by Edmund Buhler GmbH, Germany) using an electric current of 450 A. The recovered Zr billets had purity of 99.999% and were rinsed with pure acetone and then ethanol before drying in an electric oven at 220 C. overnight. Proper amounts of Zr and Ni wires (provided by Alfa AesarUSA, with purity of 99.99% and diameter of about 3 mm) were measured out to give the nominal composition of ZrNi.sub.5, and then placed into a Cu-hearse mounted in the arc-melter. The Zr and Ni were melted under He gas atmosphere (99.999%). The melting process was preceded melting of pure Zr getter to remove the residual gas from the arc-melter's chamber. To ensure the compositional homogeneity of the obtained alloy, the pre-alloyed button was overturned, and the composition was re-melted six times at an electric current ranging between 300 A to 350 A, resulting in a final alloy button.
(21) The alloy button was polished by a SiC abrasive (grade P-80), rinsed with diluted acetone solution, and then dried at 220 C. for about 12 h in a drying furnace to give a master alloy. The master alloy was crushed into irregular small pieces (10 mm-60 mm) by a 60-ton cold press and then disintegrated into coarse particles (50 m) using a vibratory disc mill (RS-200, provided by RETSCH, Germany) at a speed of 1500 rpm for 30 s. The disintegrated material particles were then sieved to separate fine powder particles (under 75 m) from coarse granular materials (above 75 m). The size of the as-synthesized ZrNi.sub.5 particles was reduced by subjecting them to a continuous high-energy ball milling for 10 h (SPEX 8000 Shaker/Mill provided by SPEX SamplePrep Company, USA). The as-milled ZrNi.sub.5 powder consisted of fine nanocrystals less than approximately 200 nm in diameter.
(22) To prepare the nanocomposite powder, the prepared MgH.sub.2 powder was mixed with the ZrNi.sub.5, Nb.sub.2O.sub.5, TiC and VC powders in the helium gas atmosphere glove box using an agate mortar and pestle. Specifically, the following data reflects the nanocomposite formed by mixing about 4.70 g MgH.sub.2, 0.2 g ZrNi.sub.5, 0.05 g Nb.sub.2O.sub.5, 0.025 g TiC and 0.025 g VC. The mixture was then sealed in a hardened steel vial with 50 hardened steel balls under a helium gas atmosphere. The milling process was carried out at room temperature using the high energy planetary ball mill (RETSCH, PM400, Germany) operated at a rotation speed of 250 rpm. In order to investigate the effect of the ball milling time on the morphological properties of the powders, the milling procedure was interrupted after selected times of 12.5 h, 25 h, 37.5 h and 50 h), at which point a small amount (250-300 mg) of the powder was discharged in the He gas glove box.
Example 2
Structural Characterization of the Nanocomposite Powder
(23) The crystal structure of each sample was investigated by X-ray diffraction (XRD) with CuK radiation using a 9 kW X-ray diffraction system (Smartlab-Rigaku, Japan). The local structure of the synthesized material powders was studied by 200 kV-field emission high resolution transmission electron microscopy/scanning transmission electron microscopy (HRTEM/STEM; JEOL-2100F, Japan). Energy-dispersive X-ray spectroscopy (EDS) was performed using a system supplied by Oxford Instruments, UK. Thermal analysis was performed by differential scanning calorimetry (Shimadzu Thermal Analysis System/TA-60WS) to investigate the decomposition temperatures of the nanocomposite powder (with a heating rate of 20 C./min).
(24) Different DSC experimental sets were performed for different heating rates of 2 C./min, 5 C./min, 10 C./min, 20 C./min and 30 C./min, and the activation energy (Ea) of decomposition was calculated using the Arrhenius equation (Eq. 1):
E.sub.a=RT ln(k)(1)
where k is a temperature-dependent reaction rate constant, R is the gas constant, and T is the absolute temperature. The value E.sub.a of the reaction was determined by measuring the decomposition peak temperature (Tp) corresponding to the respective heating rates and then plotting ln(k) versus 1/Tp. The high pressure DSC (HPDSC) (Setaram Instrumentation, France) was employed using 30 bar of hydrogen gas atmosphere for the different heating rates in order to determine the activation energy of hydrogenation.
(25) Hydrogen absorption/desorption kinetics were investigated using Sievert's method under a hydrogen gas pressure ranging between 200 mbar and 8 bar. Samples were examined at differing temperatures of 50 C., 100 C., 150 C., 250 C., and 275 C.
Example 3
Results of Exemplary Procedures and Analyses
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(28) A high resolution transmission electron microscopy (HRTEM) image of the exemplary nanocomposite powder obtained after ball milling a mixture 50 hours using a high-energy ball mill exhibited Moire-like fringes with nanocrystalline-structure containing crystallites ranging in size from approximately 5-12 nm. The lattice-fringe images reflect components of the nanocomposite powder matrix consistent with those discussed above, i.e., -MgH.sub.2 (101), ZrNi.sub.5 (222), Nb.sub.2O.sub.5 (181), TiC (111) and VC (111).
(29) The nanocomposite powder prepared after 50 hours of RBM was imaged by dark field image (DFI). Fourteen zones of the imaged sample were further imaged by FE-HRTEM and subjected to EDS analysis using a beam 2 nm in diameter. The corresponding elemental results are shown in Table 1.
(30) TABLE-US-00001 TABLE 1 EDS analysis of nanocomposite powder at 14 zones selected from DFI image Composition (wt. %) Point Mg ZiNi.sub.5 Nb.sub.2O.sub.5 TiC VC 1 94.1 4.3 .9 .4 .3 2 93.2 4.4 1.3 .6 .5 3 94.5 3.8 .8 .5 .4 4 94.4 3.9 1.2 .3 .2 5 94.9 3.4 .9 .3 .5 6 94.8 3.8 1.0 .1 .3 7 95.0 4.1 .7 .1 8 94.6 3.7 .8 .6 .3 9 94.8 3.8 .9 .2 .3 10 95.1 3.7 1.0 .2 11 94.8 3.6 .9 .4 .3 12 94.9 3.9 .7 .3 .2 13 95.1 3.7 .8 .2 .2 14 94.6 3.8 .9 .3 .4
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(32) The peak height of the exothermic and endothermic peaks increased proportionally with increasing heating rates, but the peak temperatures (Tp) were also significantly increased with increasing heating rates, as shown in
(33) The thermal stabilities and apparent E.sub.a of decomposition for nanocomposite powders obtained after different RBM times were investigated by DSC performed at 1 bar atmospheric pressure of helium gas for different heating rates.
(34) In
(35) Lattice defects and imperfections lower the E.sub.a of decomposition, as indicated by the significant decrease of E.sub.a with increasing RBM time, as shown in
(36) The hydrogenation kinetics behavior of MgH.sub.2 powder obtained after 200 h of RBM time is shown in
(37) Doping the MgH.sub.2 powders with the mixed catalytic agent powders and milling for 50 h led to outstanding improvements in the kinetics of hydrogenation, as shown in
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(39) Cycle-life-time characterizes the capability of metal hydrides to achieve continuous cyclic hydrogenation/dehydrogenation processes. The cycle-life-time is a measure of the number of times that hydride materials can be charged and discharged with hydrogen. Preferably, to be useful in hydrogen storage applications, a metal hydride should maintain hydrogen storage capacity over a cycle-life-time test. In addition, the powder should show stable hydrogenation/dehydrogenation kinetics without significant degradation.
(40) Apart from improved hydrogenation/dehydrogenation kinetics discussed previously, the nanocomposite powder synthesized as described in Example 1 showed favorable cyclic-reversibility when examined at 275 C. under repeated hydrogenation/dehydrogenation pressure of 100 mbar/8 bar. The cycle-life-time at 275 C. for the nanocomposite powders obtained after 50 h of RBM time were tested as follows. First, the powders were activated by applying cyclic hydrogen gas sorption/desorption under pressure of 35 bar at 350 C. for 10 continuous cycles. This treatment is necessary for surface cleaning of the powders and to break down the oxide phase (Mg) formed on the powder surfaces. The nanocomposite powder then exhibited excellent cyclic-reversible behavior, in particular, high cyclic stability without failure or degradation of kinetics and hydrogen storage, even after about 300 h.
(41) During the first few hydration/dehydration cycles (<25 h), the ductile Mg powder presumably overcame permanent expansion and size change upon removal of the applied pressure, which dropped from 8 bar (absorption mode) to 100 mbar (desorption mode) for each cycle. Cyclic repetitions of the load at an applied temperature of 275 C. (0.42 of the Mg melting point) led to softening of Mg powder particles and a decrease in hardness, resulting in permanent deformation (expansion) of the powders. Accordingly, after about 300 h of the cycle-life-time, the powders tended to lose their original hydrogen storage capacity (i.e., to absorb/desorb hydrogen), which was about 5.0 wt. % H.sub.2. Marginal degradation in the hydrogen storage capacity was detected when the cyclic time reached around 300 h.
(42) Comparing the number of cycles achieved at 275 C. by the present nanocomposite system with existing systems, including MgH.sub.2/Mn.sub.3.6Ti.sub.2.4, 1000 cycles/275 C. (Calka, 1991), MgH.sub.2/10 big-cube Zr.sub.2Ni, 2546 cycles/250 C. (Sorensen, 2005) and MgH.sub.2/5Fe, 47 cycles/300 C. (Principi et al., 2009) systems, the present system is among the most reliable and capable MgH.sub.2-based nanocomposite systems for use in hydrogen storage applications.
(43) In summary, the presently disclosed nanocomposite system and method of fabricating the nanocomposite powder allow for decreasing the high temperature (350-400 C.) required for hydrogenation/dehydrogenation processes by other MgH.sub.2 systems, for improving the kinetics of hydrogen gas absorption/desorption, for ensuring a high performance of cycle-life-time of at least 300 h, and for limiting the tendency of Mg grains from growing upon experiencing several tens of cycle-life-time under high pressure and temperature.
(44) It is to be understood that the present invention is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims.