CN107021527B - High-activity chemical-chain hydrogen storage material and preparation method thereof - Google Patents
High-activity chemical-chain hydrogen storage material and preparation method thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 105
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 105
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000011232 storage material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000000694 effects Effects 0.000 title claims abstract description 17
- 238000003860 storage Methods 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- -1 oxygen ions Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011777 magnesium Chemical class 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 150000002500 ions Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract 1
- 150000004692 metal hydroxides Chemical class 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910003023 Mg-Al Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PCIREHBGYFWXKH-UHFFFAOYSA-N iron oxocobalt Chemical compound [Fe].[Co]=O PCIREHBGYFWXKH-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0045—Mixed oxides or hydroxides containing aluminium
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公布了一种高活性化学链储氢材料及其制备方法，该材料采用溶剂热法制备，首先将FeCl2·4H2O，MgCl2·6H2O，AlCl3·6H2O和尿素，按1～3:1:1:7的摩尔比溶于甲醇中，所得溶液在高压釜中溶剂热处理，得到的产物真空干燥，得到具有层状双金属氢氧化物(LDH)结构的高活性化学链储氢材料。该材料采用化学链循环氧储氢原理，通过创造氧空位再由氧空位逆变产氢的方式间接储氢，理论上一个氧空位逆变得到两个氢，储氢密度是传统的氢空位储氢的两倍。该材料具有花瓣状LDH结构，比表面积大，为Fe3+提供更多的附着位点；材料中结晶态含铝层板的吸附作用，使得Mg2+、Fe3+均匀稳定分布的在层板中，使反应物可以充分的与活性中心接触，这些因素都大大提高了材料的反应活性。
The invention discloses a highly active chemical chain hydrogen storage material and a preparation method thereof. The material is prepared by a solvothermal method. First, FeCl 2 ·4H 2 O, MgCl 2 ·6H 2 O, AlCl 3 ·6H 2 O and urea are mixed , dissolved in methanol at a molar ratio of 1 to 3:1:1:7, the resulting solution was solvothermally treated in an autoclave, and the obtained product was vacuum-dried to obtain a layered double metal hydroxide (LDH) structure with high activity Chemical chain hydrogen storage materials. The material adopts the principle of oxygen hydrogen storage in chemical chain cycle, and indirectly stores hydrogen by creating oxygen vacancies and then reversing hydrogen production from oxygen vacancies. In theory, one oxygen vacancy can be reversed to obtain two hydrogens. twice as much hydrogen. The material has a petal-like LDH structure and a large specific surface area, which provides more attachment sites for Fe 3+ ; the adsorption of crystalline aluminum-containing laminates in the material makes Mg 2+ and Fe 3+ evenly and stably distributed in the layer. In the plate, the reactants can be fully contacted with the active center, and these factors greatly improve the reactivity of the material.
Description
Technical Field
The invention relates to the field of material preparation and chemical-looping hydrogen storage, in particular to a high-activity chemical-looping hydrogen storage material and a preparation method thereof.
Background
The hydrogen energy is a renewable energy source with large combustion heat value and no pollution, and is regarded as the clean energy source with the most development potential in the 21 st century. The key to effectively utilize hydrogen energy is to develop a hydrogen storage technology which is efficient and can be applied in a large scale.
Common hydrogen storage technologies at present are classified into physical hydrogen storage and chemical hydrogen storage. High-pressure hydrogen storage and hydraulic hydrogen storage in physical hydrogen storage can realize large-scale commercialized hydrogen energy storage, but potential safety hazards brought by high pressure still restrict the application of the two hydrogen storage technologies, and in addition, the high-pressure hydrogen storage and the hydraulic hydrogen storage also have the defects of high energy consumption, large occupied area and the like; the main implementation modes of chemical hydrogen storage include hydrogen storage alloy, metal hydride, organic hydrogen storage and the like. The chemical hydrogen storage material has the advantages of high hydrogen storage density, mild reaction conditions, good safety and the like. However, due to the high preparation cost, the chemical hydrogen storage material is still in the laboratory research stage and has not been reported commercially. The defects of easy environmental pollution and the like also bring difficulty to the popularization of the chemical hydrogen storage technology.
The chemical chain circulation oxygen hydrogen storage technology is a novel hydrogen storage technology and is innovative in that oxygen vacancies are used for indirectly storing hydrogen, and because one oxygen vacancy corresponds to two hydrogen, the theoretical hydrogen storage density of a circulation oxygen vacancy hydrogen storage material is twice that of the traditional hydrogen vacancy hydrogen storage material. The principle of hydrogen storage is illustrated by taking a cobalt-iron oxygen carrier as an example:
the hydrogen storage process comprises the following steps:
hydrogen release process:
the active ingredient in the oxygen carrier is iron oxide. During the hydrogen storage process, oxygen in the iron oxide is combined with hydrogen to form water, and the iron oxide is reduced into low-valent iron oxide. Every 1 oxygen atom is bonded to 2 hydrogen atoms, corresponding to the creation of an oxygen vacancy. In the hydrogen release process, 1 oxygen vacancy cracks 1 molecule of water, oxygen in water is left in the oxygen vacancy, hydrogen is released in the form of hydrogen, meanwhile, the low-valence iron oxide is oxidized, and the oxygen carrier can be used for storing hydrogen again, so that reversible storage of the hydrogen is realized.
Today, the design and manufacture of high performance chemical-looping hydrogen storage materials is an important issue. The existing chemical chain hydrogen storage material is generally prepared by a sol-gel method, a mechanical mixing method, an immersion method and other methods, and the materials prepared by the methods have low hydrogen charging and discharging speed and long hydrogen storage and releasing time. Therefore, the research and development of a preparation method of the high-activity chemical-chain hydrogen storage material is of great significance.
Disclosure of Invention
The technical problem is as follows: in order to solve the problem of weak reaction activity of the existing chemical-chain hydrogen storage material, the invention provides a high-activity chemical-chain hydrogen storage material and a preparation method thereof.
The technical scheme is as follows: the chemical formula of the high-activity chemical-chain hydrogen storage material is FexMgAlO1.5X+2.5Wherein X is more than or equal to 1 and less than or equal to 3, and the hydrogen storage material has petal-shaped layered bimetalHydroxide compound(LDH) structure, wherein a layered laminate in the hydrogen storage material is formed by combining oxygen ions and metal ions through electrostatic interaction. Under the action of electrostatic force, the metal ions form active centers which are uniformly and stably distributed in the layered laminate.
Wherein:
the metal ion is Fe3+、Mg2+、Al3+。
The specific surface area of the hydrogen storage material is 200-300 m2/g。
The preparation method of the high-activity chemical-chain hydrogen storage material adopts a solvothermal method to prepare the high-activity chemical-chain hydrogen storage material, and the method comprises the following steps of mixing hydrated chloride salts of iron, magnesium and aluminum with urea in a molar ratio of (1-3) to 1:1: dissolving in methanol, treating the mixture with solvent, centrifuging, washing with deionized water and ethanol for several times, and drying.
In the preparation process, the solvothermal treatment step is to transfer the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and heat the mixture in an oil bath for 24 hours at 170-190 ℃.
And centrifuging and washing the product, and drying the product in a drying oven at 70-80 ℃ for 12-14 hours.
Has the advantages that: compared with the prior art, the invention has at least the following beneficial effects:
1. the novel hydrogen storage material prepared by the invention adopts the chemical chain circulation hydrogen storage principle, creates oxygen vacancies in the material and uses the oxygen vacanciesThe hydrogen is indirectly stored by a position inversion hydrogen production mode, theoretically, one oxygen vacancy can be inverted to obtain two hydrogen, and therefore, the hydrogen storage density is twice of that of the traditional hydrogen vacancy. The mass fraction of hydrogen stored in the material can reach more than 4.8 percent, and the volume hydrogen storage density can reach 120kg/m3The above
2. The high-activity chemical chain hydrogen storage material prepared by the invention has a petal-shaped LDH structure and a large specific surface area (200-300 m)2And/g), the active centers are uniformly and stably distributed in the laminate, so that the reaction activity of the material is greatly improved. The hydrogen storage process of the material takes 5-10 min, and the hydrogen release process only takes 25-40% of the common oxygen carrier material and takes 2-3 min.
3. The invention adopts cheap chlorine metal salt as raw material, and the preparation process is simple and can be used for large-scale production.
Drawings
FIG. 1 is an SEM image of a highly active chemical-looping hydrogen storage material prepared in example 1.
Fig. 2 is an XRD pattern of the highly active chemical-looping hydrogen storage material prepared in example 1.
FIG. 3 is an SEM image of the highly active chemical-looping hydrogen storage material prepared in example 2.
Fig. 4 is an XRD pattern of the highly active chemical-looping hydrogen storage material prepared in example 2.
FIG. 5 shows the hydrogen storage density of the material in different Fe-Mg-Al molar ratios during the hydrogen charging and discharging cycle, and the reaction temperature is 900 ℃.
FIG. 6 is a graph of hydrogen release rate of the material in hydrogen release process with different Fe-Mg-Al molar ratios, and the reaction temperature is 900 ℃.
Detailed Description
In order to achieve the aim, the high-activity chemical chain hydrogen storage material adopted by the invention adopts the hydrogen storage principle of chemical chain circulating oxygen hydrogen storage, and adopts the mode of manufacturing oxygen vacancies in the material and then generating hydrogen by oxygen vacancy inversion to indirectly store the hydrogen. The material has a petal-shaped LDH structure and a large specific surface area (200-300 m)2/g) can be Fe3+Provide more attachment sites and allow Mg to adsorb due to the adsorption of the crystalline aluminum-containing layer2+、Fe3+Into a laminar stateIn the laminate, active centers are formed in the laminate in a uniform and stable distribution.
The preparation method of the high-activity chemical-chain hydrogen storage material adopts a solvothermal method for preparation, and the preparation method comprises the steps of2·4H2O，MgCl2·6H2O，AlCl3·6H2Dissolving O and urea in methanol according to the stoichiometric ratio of (1-3) to 1:1:7, uniformly stirring, transferring to a high-pressure reaction kettle with a polytetrafluoroethylene lining, and heating in an oil bath at 170-190 ℃ for 24 hours under a sealed condition. And centrifuging the product, washing the product with deionized water and ethanol for several times, and drying the product in a drying oven at 70-80 ℃ for 12-14 hours to obtain the target material.
The material was prepared at different reactant concentrations:
example 1:
0.2mol/L FeCl with the solution amount of 0.03L2·4H2O, 0.1mol/l MgCl2·6H2O, 0.1mol/l AlCl3·6H2O and 0.7mol/l urea were dissolved in 30mL of methanol. The mixture was stirred and then transferred to a teflon lined autoclave, heated at 180 ℃ for 24 hours under closed conditions, the product centrifuged, washed several times with deionized water and ethanol, and dried in an electric oven at 70 ℃ for 12 hours. Obtaining the flower-shaped FeMgAl-LDH ball.
Example 2:
FeCl with the molar concentration of 0.1mol/L and the solution amount of 0.03L2·4H2O, 0.05mol/l MgCl2·6H2O, 0.05mol/l AlCl3·6H2O and 0.35mol/l urea were dissolved in 30mL of methanol. The mixture was stirred and then transferred to a teflon lined autoclave, heated at 180 ℃ for 24 hours under closed conditions, the product centrifuged, washed several times with deionized water and ethanol, and dried in an electric oven at 70 ℃ for 12 hours. Obtaining the flower-shaped FeMgAl-LDH ball.
As can be seen from the XRD and SEM characterization results of example 1 and example 2, under both the working conditions, the material forms obvious petal-shaped LDH structures, and the XRD characterization results also show characteristic peaks of the LDH structures.
FIG. 5 shows the hydrogen storage density of the material in different Fe-Mg-Al molar ratios during the hydrogen charging and discharging cycle. It can be seen that the hydrogen storage density of the material after 20 cycles is basically kept stable, wherein the hydrogen storage density of the three materials with the molar ratio of 3:1:1,5:1:1 and 7:1:1 is basically stabilized at 5000umol g-1。
FIG. 6 is a graph showing the change of hydrogen release rate of the material in hydrogen release process when the hydrogen release rate is less than 10umol g for different Fe-Mg-Al molar ratios-1·s-1When the reaction is considered to be complete, the time consumed for hydrogen release of the three materials is about 2min, and the time consumed in the hydrogen release process is far lower than that of the conventional hydrogen storage material.
The above detailed description of the embodiments of the present invention and the description of the product phenomena of the different embodiments are only examples, and the present invention is not limited to the above described embodiments. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (3)
1. A high-activity chemical-chain hydrogen storage material is characterized in that the chemical formula of the hydrogen storage material is FexMgAlO1.5X+2.5Wherein X is more than or equal to 1 and less than or equal to 3, and the hydrogen storage material has petal-shaped layered bimetalHydroxide compoundThe structure is that the layered laminate in the hydrogen storage material is formed by combining oxygen ions and metal ions through electrostatic force, and the metal ions form active centers which are uniformly and stably distributed in the layered laminate under the action of the electrostatic force; the specific surface area of the material is 200-300 m2The hydrogen storage process takes 5-10 min, and the hydrogen release process takes 2-3 min; the metal ion is Fe3+、Mg2+、Al3+。
2. The preparation method of the high-activity chemical-looping hydrogen storage material as claimed in claim 1, characterized in that the preparation method is a solvothermal method, and the preparation method is characterized in that the molar ratio of hydrated chloride salts of iron, magnesium and aluminum to urea is (1-3): 1:1:7 dissolving in methanol, treating the mixture by solvothermal method, centrifuging the product, washing with deionized water and ethanol for several times, and drying;
in the preparation process, the solvothermal treatment step is to transfer the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and heat the mixture in an oil bath for 24 hours at 170-190 ℃.
3. The method for preparing a high-activity chemical-looping hydrogen storage material according to claim 2, wherein the method comprises the following steps: and centrifuging and washing the product, and drying the product in a drying oven at 70-80 ℃ for 12-14 hours.
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| CN109208030B (en) * | 2018-11-16 | 2020-04-17 | 北京师范大学 | Metal hydroxide-metal organic framework composite material and preparation method thereof |
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