CN110804705A - Oxidation-resistant polyimide-Mg-based composite hydrogen storage material and preparation method thereof - Google Patents
Oxidation-resistant polyimide-Mg-based composite hydrogen storage material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to the technical field of hydrogen storage materials, and discloses an oxidation-resistant polyimide-Mg-based composite hydrogen storage material and a preparation method thereof, wherein the oxidation-resistant polyimide-Mg-based composite hydrogen storage material comprises the following formula raw materials: mg-doped Cr-Ti-V alloy composite material, 2- (4-aminophenyl) -5-aminobenzimidazole, p-phenylenediamine, 3',4,4' -biphenyl tetracarboxylic dianhydride and ammonium persulfate. The radius of Ti atoms in the Cr-Ti-V alloy is larger, the lattice constant of the Cr-Ti-V alloy is increased, H atoms are promoted to be added into the lattice gaps of the alloy, the Cr-Ti-V alloy also has certain hydrogen absorption capacity, the Cr-Ti-V alloy improves the hydrogen release rate of a magnesium-based material, the circulation stability of the magnesium-based material in the hydrogen absorption and release processes is improved, the benzimidazole grafted polyimide coats the magnesium-based hydrogen storage material, the problem that the magnesium-based hydrogen storage material is oxidized due to direct contact with oxygen in the air is solved, and the chemical circulation stability and the service life of the hydrogen storage material substrate are improved.
Description
Technical Field
The invention relates to the field of hydrogen storage materials, in particular to an antioxidant polyimide-Mg-based composite hydrogen storage material and a preparation method thereof.
Background
With the gradual depletion of fossil fuel reserves and the increasing severity of environmental problems caused by the combustion of fossil fuels, the development of green and efficient new energy is urgent, hydrogen energy is a green and efficient secondary energy, and has the advantages of abundant resources, high combustion efficiency and the like, and the hydrogen energy is widely applied to the aspects of hydrogen energy power generation, fused carbonate fuel, phosphate fuel cells and the like.
At present, the problems of hydrogen energy preparation, storage, transportation and the like mainly exist in the development and utilization of hydrogen energy, wherein the storage of hydrogen is a key problem, the hydrogen storage problem relates to the aspects of hydrogen production, transportation, application and the like, if the problem of blocking the storage of hydrogen energy cannot be solved well, the large-scale utilization of hydrogen energy can be blocked, the main hydrogen storage modes at present comprise gas-state hydrogen storage, liquid-state hydrogen storage and solid-state hydrogen storage, the solid-state storage is to store hydrogen in a solid material by utilizing the physical adsorption or chemical reaction of solid to hydrogen and the like, and the solid-state storage has the advantages of high efficiency, safety and the like, so the development of a high-performance hydrogen storage material is the key of hydrogen storage development and.
The solid hydrogen storage material mainly comprises an alloy hydrogen storage material, an organic hydrogen storage material, a carbonaceous material and the like for storing hydrogen, the magnesium-based material has the advantages of high hydrogen storage capacity, good cycle stability, less pollution and the like, and is a hydrogen storage material with great potential, mainly comprises simple substances of magnesium, magnesium-nickel alloy, magnesium-vanadium alloy and the like, but the existing magnesium-based hydrogen storage material has low hydrogen storage content and low hydrogen release rate, and is easy to oxidize in the air, so that the hydrogen storage performance of the magnesium-based material is reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an oxidation-resistant polyimide-Mg-based composite hydrogen storage material and a preparation method thereof, which solve the problems of low hydrogen storage content and low hydrogen release rate of the magnesium-based hydrogen storage material and solve the problem that the magnesium-based hydrogen storage material is easily oxidized in the air.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: an oxidation resistant polyimide-Mg based composite hydrogen storage material and a preparation method thereof, which comprises the following formula raw materials by weight: 91-95 parts of Mg-doped Cr-Ti-V alloy composite material, 0.6-1 part of 2- (4-aminophenyl) -5-aminobenzimidazole, 1-1.5 parts of p-phenylenediamine, 3-5.5 parts of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.4-1 part of ammonium persulfate.
Preferably, the preparation method of the Mg-doped Cr-Ti-V alloy composite material comprises the following steps:
(1) sequentially adding high-purity elementary substance Cr, high-purity elementary substance Ti and high-purity elementary substance V into a planetary ball mill, wherein the revolution speed of the ball mill is 40-60 rpm, the rotation speed is 600-plus-640 rpm, carrying out ball milling until all materials pass through a 400-plus-600-mesh sieve, passing a solid mixture through a discharge plasma sintering furnace, repeatedly smelting, carrying out ball milling on a solid alloy through the planetary ball mill until all solids pass through a 300-plus-500-mesh sieve, placing a solid product in a nitrogen vacuum drying box, heating to 350-plus-380 ℃, and carrying out N-phase sintering2Drying for 1-2 h in the atmosphere to obtain the Cr-Ti-V alloy.
(2) Sequentially weighing Cr-Ti-V alloy and high-purity simple substance Mg, adding into a planetary ball mill, and introducing high-purity H2In the ball mill tank H2The pressure is 4-6 MPa, the revolution speed of the ball mill is 80-120 rpm, the rotation speed is 600-640 rpm, and the hydrogenation ball milling is carried out for 6-8 h, and the ball milling product is the Mg-doped Cr-Ti-V alloy composite material.
Preferably, the molar ratio of the simple substance Cr to the simple substance Ti to the simple substance V is 1-2.5:1.5-3:1, and the chemical expression of the Cr-Ti-V alloy is Cr1-2.5Ti1.5-3V1。
Preferably, the mass ratio of the Cr-Ti-V alloy to the high-purity simple substance Mg is 1: 4.5-5.5.
Preferably, the preparation method of the oxidation-resistant polyimide-Mg-based composite hydrogen storage material comprises the following steps:
(1) toluene solvent was added to the reaction flask and passed through N2Discharging air, sequentially adding 0.6-1 part of 2- (4-aminophenyl) -5-aminobenzimidazole and 1-1.5 parts of p-phenylenediamine, placing a reaction bottle in a low-temperature cooling instrument, uniformly stirring and reacting for 15-20 h at 0-5 ℃, adding 3-5.5 parts of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.4-1 part of ammonium persulfate, uniformly stirring and reacting for 5-8 h, raising the temperature to 65-75 ℃, uniformly stirring and reacting for 2-3 h, removing the solvent from the solution through reduced pressure concentration, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the benzimidazole grafted polyimide.
(2) Adding proper amount of the mixture into a reaction bottleN,NA dimethylformamide solvent, adding 91-95 parts of Mg-doped Cr-Ti-V alloy composite material and the benzimidazole grafted polyimide prepared in the step (1), placing a reaction bottle in an ultrasonic treatment instrument, heating to 110 ℃ and the ultrasonic frequency of 22-28 KHz, performing ultrasonic dispersion treatment for 4-6 h, pouring the solution into a film forming device, naturally casting to form a film, placing the film in a nitrogen vacuum drying box, heating to 80-100 ℃, and performing N-phase vacuum drying in a vacuum drying box at the temperature of N2And fully drying the solvent in the atmosphere to prepare the polyimide-Mg based composite hydrogen storage material with the oxidation resistance.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the oxidation-resistant polyimide-Mg-based composite hydrogen storage material and the preparation method thereof have the advantages that the hydrogen release rate of the magnesium-based material is improved by using the Cr-Ti-V alloy, the circulation stability in the hydrogen absorption and release processes of the magnesium-based material is improved, the practicability and the service life of the magnesium-based hydrogen storage material are improved, the radius of Ti atoms is larger, the lattice constant of the Cr-Ti-V alloy is increased, and the addition of H atoms into the lattice gaps of the alloy is promoted, so that the Cr-Ti-V alloy also has certain hydrogen absorption capacity, the hydrogen storage performance of the composite material is improved, and the Cr-Ti-V alloy and a magnesium hydrogen absorption product MgH are obtained2The thermal stability of the MgH is similar, and the MgH is made by in-situ hydrogenation ball milling2Forming good synergistic effect with Cr-Ti-V alloy and reducing MgH2Thereby improving the thermodynamic stability of the composite hydrogen storage material.
The polyimide-Mg based composite hydrogen storage material with oxidation resistance and the preparation method thereof, the benzimidazole grafted polyimide is used for coating the magnesium based hydrogen storage material, the polyimide is a good gas selective permeation membrane, hydrogen atoms can pass through the polyimide and oxygen atoms are blocked from passing through the polyimide, the benzimidazole grafted polyimide and the benzimidazole branched chain enlarge the distance between polyimide molecules to form rich pore structures, and the magnesium based hydrogen storage material can be better coated, thereby avoiding the problem that the magnesium material is oxidized because the magnesium based hydrogen storage material is directly contacted with oxygen in the air, ensuring the chemical cycle stability and the service life of the base body of the hydrogen storage material, and among the benzimidazole grafted polyimide molecules, the imino group of imidazole and the carbonyl group in the polyimide form a hydrogen bond, enhancing the acting force among molecules and limiting the movement of the molecular chain of the polyimide, the polyimide is made to be chemically inert, so that the chemical stability and the thermal stability of the polyimide are improved, and the service life of the composite hydrogen storage material is prolonged.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: an oxidation resistant polyimide-Mg based composite hydrogen storage material and a preparation method thereof, which comprises the following formula raw materials by weight: 91-95 parts of Mg-doped Cr-Ti-V alloy composite material, 0.6-1 part of 2- (4-aminophenyl) -5-aminobenzimidazole, 1-1.5 parts of p-phenylenediamine, 3-5.5 parts of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.4-1 part of ammonium persulfate.
The preparation method of the Mg-doped Cr-Ti-V alloy composite material comprises the following steps:
(1) sequentially adding high-purity elementary substance Cr, high-purity elementary substance Ti and high-purity elementary substance V into a planetary ball mill, wherein the mass molar ratio of the three substances is 1-2.5:1.5-3:1, the revolution speed of the ball mill is 40-60 rpm, the rotation speed of the ball mill is 600-640 rpm, carrying out ball milling until all the materials pass through a 400-mesh sieve, repeatedly smelting the solid mixture in a discharge plasma sintering furnace, carrying out ball milling on the solid alloy in the planetary ball mill until all the solids pass through a 300-mesh sieve and a 500-mesh sieve, placing the solid product in a nitrogen vacuum drying box, heating to 350-mesh 380 ℃, and carrying out N-mesh drying at the temperature of 350-mesh and 380 DEG2Drying for 1-2 h in the atmosphere to obtain the Cr-Ti-V alloy.
(2) Sequentially weighing Cr-Ti-V alloy and high-purity simple substance Mg, adding the Cr-Ti-V alloy and the high-purity simple substance Mg into a planetary ball mill in a mass ratio of 1:4.5-5.5, and introducing high-purity H2In the ball mill tank H2The pressure is 4-6 MPa, the revolution speed of the ball mill is 80-120 rpm, the rotation speed is 600-640 rpm, and the hydrogenation ball milling is carried out for 6-8 h, and the ball milling product is the Mg-doped Cr-Ti-V alloy composite material.
The preparation method of the antioxidant polyimide-Mg-based composite hydrogen storage material comprises the following steps:
(1) toluene solvent was added to the reaction flask and passed through N2Discharging air, sequentially adding 0.6-1 part of 2- (4-aminophenyl) -5-aminobenzimidazole and 1-1.5 parts of p-phenylenediamine, placing a reaction bottle in a low-temperature cooling instrument, uniformly stirring and reacting for 15-20 h at 0-5 ℃, adding 3-5.5 parts of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.4-1 part of ammonium persulfate, uniformly stirring and reacting for 5-8 h, raising the temperature to 65-75 ℃, uniformly stirring and reacting for 2-3 h, removing the solvent from the solution through reduced pressure concentration, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the benzimidazole grafted polyimide.
(2) Adding proper amount of the mixture into a reaction bottleN,NA dimethylformamide solvent, adding 91-95 parts of Mg-doped Cr-Ti-V alloy composite material and the benzimidazole grafted polyimide prepared in the step (1), placing a reaction bottle in an ultrasonic treatment instrument, heating to 110 ℃ and the ultrasonic frequency of 22-28 KHz, performing ultrasonic dispersion treatment for 4-6 h, pouring the solution into a film forming device, naturally casting to form a film, placing the film in a nitrogen vacuum drying box, heating to 80-100 ℃, and performing N-phase vacuum drying in a vacuum drying box at the temperature of N2And fully drying the solvent in the atmosphere to prepare the polyimide-Mg based composite hydrogen storage material with the oxidation resistance.
Example 1:
(1) preparation of Cr2.5Ti1.5V1Alloy component 1: sequentially adding high-purity elementary substance Cr, high-purity elementary substance Ti and high-purity elementary substance V into a planetary ball mill, wherein the mass molar ratio of the three substances is 2.5:1.5:1, the revolution speed of the ball mill is 40rpm, the rotation speed of the ball mill is 600rpm, carrying out ball milling until all the materials pass through a 400-mesh sieve, passing a solid mixture through a discharge plasma sintering furnace, repeatedly smelting, carrying out ball milling on a solid alloy through the planetary ball mill until all the solids pass through a 300-mesh sieve, placing a solid product in a nitrogen vacuum drying box, heating to 350 ℃, and carrying out N-phase vacuum drying2Drying for 1 h in atmosphere to prepare Cr2.5Ti1.5V1And (3) component 1.
(2) Preparation of Mg-doped Cr2.5Ti1.5V1Alloy composite material 1: weighing Cr in sequence2.5Ti1.5V1Adding alloy component 1 and high-purity simple substance Mg into a planetary ball mill in a mass ratio of 1:4.5, and introducing high-purity H2In the ball mill tank H2Performing hydrogenation ball milling for 6 hours under the conditions that the pressure is 4 MPa, the revolution speed of the ball mill is 80 rpm and the rotation speed is 600rpm, and the ball milling product is Mg-doped Cr2.5Ti1.5V1An alloy composite material 1.
(3) Preparation of benzimidazole grafted polyimide component 1: toluene solvent was added to the reaction flask and passed through N2Discharging air, sequentially adding 0.6 part of 2- (4-aminophenyl) -5-aminobenzimidazole and 1 part of p-phenylenediamine, placing a reaction bottle in a low-temperature cooling instrument, uniformly stirring and reacting for 15 hours at 5 ℃, then adding 3 parts of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 0.4 part of ammonium persulfate, uniformly stirring and reacting for 5 hours, raising the temperature to 65 ℃, uniformly stirring and reacting for 2 hours, removing the solvent from the solution through reduced pressure concentration, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the benzimidazole grafted polyamide component 1.
(4) Preparing an oxidation-resistant polyimide-Mg-based composite hydrogen storage material 1: adding proper amount of the mixture into a reaction bottleN,N-dimethylformamide solvent, 95 parts of Mg doped Cr2.5Ti1.5V1Placing a reaction bottle in an ultrasonic treatment instrument, heating to 100 ℃, carrying out ultrasonic dispersion treatment for 4 hours at the ultrasonic frequency of 22KHz, pouring the solution into a film forming device, naturally casting to form a film, placing the film in a nitrogen vacuum drying oven, heating to 80 ℃, and carrying out N-phase vacuum drying on the film in a nitrogen vacuum drying oven2And fully drying the solvent in the atmosphere to prepare the polyimide-Mg based composite hydrogen storage material 1 with oxidation resistance.
Example 2:
(1) preparation of Cr2.2Ti1.8V1Alloy component 2: sequentially adding high-purity elementary substance Cr, high-purity elementary substance Ti and high-purity elementary substance V into a planetary ball mill, wherein the mass molar ratio of the three substances is 2.2:1.8:1, the revolution speed of the ball mill is 60 rpm, the rotation speed of the ball mill is 600rpm, carrying out ball milling until all the materials pass through a 600-mesh screen, and enabling a solid mixture to pass through the 600-mesh screenRepeatedly smelting in a discharge plasma sintering furnace, ball-milling the solid alloy by a planetary ball mill until all the solid passes through a 500-mesh sieve, placing the solid product in a nitrogen vacuum drying oven, heating to 350 ℃, and performing N reaction in the vacuum drying oven2Drying for 2 h in atmosphere to prepare Cr2.2Ti1.8V1Alloy composition 2.
(2) Preparation of Mg-doped Cr2.2Ti1.8V1Alloy composite 2: weighing Cr in sequence2.2Ti1.8V1Adding alloy component 2 and high-purity simple substance Mg into a planetary ball mill in a mass ratio of 1:4.5, and introducing high-purity H2In the ball mill tank H2Performing hydrogenation ball milling for 8 hours under the conditions that the pressure is 4 MPa, the revolution speed of the ball mill is 80 rpm and the rotation speed is 600rpm, and the ball milling product is Mg-doped Cr2.2Ti1.8V1An alloy composite 2.
(3) Preparation of benzimidazole grafted polyimide component 2: toluene solvent was added to the reaction flask and passed through N2Discharging air, sequentially adding 0.7 part of 2- (4-aminophenyl) -5-aminobenzimidazole and 1.2 parts of p-phenylenediamine, placing a reaction bottle in a low-temperature cooler, uniformly stirring and reacting for 15 hours at 5 ℃, then adding 3.6 parts of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.5 part of ammonium persulfate, uniformly stirring and reacting for 8 hours, heating to 65 ℃, uniformly stirring and reacting for 3 hours, removing the solvent from the solution through reduced pressure concentration, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the benzimidazole grafted polyimide component 2.
(4) Preparing an oxidation-resistant polyimide-Mg-based composite hydrogen storage material 2: adding proper amount of the mixture into a reaction bottleN,N-dimethylformamide solvent, further 94 parts of Mg-doped Cr2.2Ti1.8V1Placing the alloy composite material 2 and the benzimidazole grafted polyimide component 2 prepared in the step (3) in an ultrasonic treatment instrument, heating to 100 ℃, carrying out ultrasonic dispersion treatment for 6 hours at the ultrasonic frequency of 28KHz, pouring the solution into a film forming device, naturally casting to form a film, placing the film in a nitrogen vacuum drying oven, heating to 80 ℃, and carrying out N-phase vacuum drying in a nitrogen vacuum drying oven2Fully drying solvent in atmosphereAnd preparing the polyimide-Mg based composite hydrogen storage material 2 with oxidation resistance.
Example 3:
(1) preparation of Cr1.8Ti2.2V1Alloy component 3: sequentially adding high-purity elementary substance Cr, high-purity elementary substance Ti and high-purity elementary substance V into a planetary ball mill, wherein the mass molar ratio of the three substances is 1.8:2.2:1, the revolution speed of the ball mill is 50 rpm, the rotation speed of the ball mill is 620rpm, carrying out ball milling until all the materials pass through a 500-mesh sieve, repeatedly smelting a solid mixture in a discharge plasma sintering furnace, carrying out ball milling on a solid alloy through the planetary ball mill until all the solids pass through a 400-mesh sieve, placing a solid product in a nitrogen vacuum drying box, heating to 360 ℃, and carrying out N-phase vacuum drying2Drying for 1 h in atmosphere to prepare Cr1.8Ti2.2V1Alloy component 3.
(2) Preparation of Mg-doped Cr1.8Ti2.2V1Alloy composite material 3: weighing Cr in sequence1.8Ti2.2V1Adding alloy component 3 and high-purity simple substance Mg into a planetary ball mill in a mass ratio of 1:4.5, and introducing high-purity H2In the ball mill tank H2Carrying out hydrogenation ball milling for 7 hours under the conditions that the pressure is 4 MPa, the revolution speed of the ball mill is 110 rpm and the rotation speed is 620rpm, and the ball milling product is Mg-doped Cr1.8Ti2.2V1An alloy composite 3.
(3) Preparation of benzimidazole grafted polyimide component 3: toluene solvent was added to the reaction flask and passed through N2Discharging air, sequentially adding 0.8 part of 2- (4-aminophenyl) -5-aminobenzimidazole and 1.3 parts of p-phenylenediamine, placing a reaction bottle in a low-temperature cooler, uniformly stirring and reacting at 5 ℃ for 18 h, then adding 4.2 parts of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.7 part of ammonium persulfate, uniformly stirring and reacting for 6 h, heating to 70 ℃, uniformly stirring and reacting for 2.5 h, removing the solvent from the solution through reduced pressure concentration, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the benzimidazole grafted polyimide component 3.
(4) Preparing an oxidation-resistant polyimide-Mg-based composite hydrogen storage material 3: is turned to the reverse directionAdding proper amount of the mixture into a bottleN,N-dimethylformamide solvent, further 93 parts of Mg doped Cr1.8Ti2.2V1Placing a reaction bottle in an ultrasonic treatment instrument, heating to 105 ℃, wherein the ultrasonic frequency is 25KHz, performing ultrasonic dispersion treatment for 5 hours, pouring the solution into a film forming device, naturally casting to form a film, placing the film in a nitrogen vacuum drying oven, heating to 90 ℃, and performing N-phase vacuum drying on the film in a nitrogen vacuum drying oven2And fully drying the solvent in the atmosphere to prepare the polyimide-Mg based composite hydrogen storage material 3 with oxidation resistance.
Example 4:
(1) preparation of Cr1.4Ti2.6V1Alloy component 4: sequentially adding high-purity elementary substance Cr, high-purity elementary substance Ti and high-purity elementary substance V into a planetary ball mill, wherein the mass molar ratio of the three substances is 1.4:2.6:1, the revolution speed of the ball mill is 60 rpm, the rotation speed of the ball mill is 640rpm, carrying out ball milling until all the materials pass through a 400-mesh sieve, passing a solid mixture through a discharge plasma sintering furnace, repeatedly smelting, carrying out ball milling on a solid alloy through the planetary ball mill until all the solids pass through a 500-mesh sieve, placing a solid product in a nitrogen vacuum drying box, heating to 350 ℃, and carrying out N-phase vacuum drying2Drying for 2 h in atmosphere to prepare Cr1.4Ti2.6V1Alloy composition 4.
(2) Preparation of Mg-doped Cr1.4Ti2.6V1Alloy composite 4: weighing Cr in sequence1.4Ti2.6V1Adding alloy component 4 and high-purity simple substance Mg into a planetary ball mill in a mass ratio of 1:5.5, and introducing high-purity H2In the ball mill tank H2Performing hydrogenation ball milling for 6 hours under the pressure of 6 MPa and the revolution speed and rotation speed of 80 rpm and 640rpm of the ball mill to obtain a ball milling product, namely Mg-doped Cr1.4Ti2.6V1An alloy composite 4.
(3) Preparation of benzimidazole grafted polyimide component 4: toluene solvent was added to the reaction flask and passed through N2Discharging air, adding 0.9 part of 2- (4-aminophenyl) -5-aminobenzimidazole and 1.4 parts of p-phenylenediamine in sequence, and reactingPlacing the bottle in a low-temperature cooling instrument, reacting for 20 hours at 0 ℃ under uniform stirring, adding 4.9 parts of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 0.8 part of ammonium persulfate, reacting for 8 hours under uniform stirring, raising the temperature to 75 ℃, reacting for 3 hours under uniform stirring, removing the solvent from the solution through reduced pressure concentration, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the benzimidazole grafted polyimide component 4.
(4) Preparing an oxidation-resistant polyimide-Mg-based composite hydrogen storage material 4: adding proper amount of the mixture into a reaction bottleN,N-dimethylformamide solvent, further addition of 92 parts of Mg-doped Cr1.4Ti2.6V1Placing the alloy composite material 4 and the benzimidazole grafted polyimide component 4 prepared in the step (3) in an ultrasonic treatment instrument, heating to 110 ℃, carrying out ultrasonic dispersion treatment for 6 hours at the ultrasonic frequency of 22KHz, pouring the solution into a film forming device, naturally casting to form a film, placing the film in a nitrogen vacuum drying oven, heating to 80 ℃, and carrying out N-phase vacuum drying in a nitrogen vacuum drying oven2And fully drying the solvent in the atmosphere to prepare the polyimide-Mg based composite hydrogen storage material 4 with oxidation resistance.
Example 5:
(1) preparation of Cr1Ti3V1Alloy component 5: sequentially adding high-purity elementary substance Cr, high-purity elementary substance Ti and high-purity elementary substance V into a planetary ball mill, wherein the mass molar ratio of the three substances is 1:3:1, the revolution speed of the ball mill is 40rpm, the rotation speed of the ball mill is 640rpm, carrying out ball milling until all the materials pass through a 600-mesh sieve, passing a solid mixture through a discharge plasma sintering furnace, repeatedly smelting, carrying out ball milling on a solid alloy through the planetary ball mill until all the solids pass through a 500-mesh sieve, placing a solid product in a nitrogen vacuum drying box, heating to 380 ℃, and carrying out N-phase sintering at the temperature of 380 DEG C2Drying for 2 h in atmosphere to prepare Cr1Ti3V1Alloy composition 5.
(2) Preparation of Mg-doped Cr1Ti3V1Alloy composite material 5: weighing Cr in sequence1Ti3V1Adding alloy component 5 and high-purity simple substance Mg into a planetary ball mill in a mass ratio of 1:5.5, and introducing high-purity H2Ball millingIn pot H2Performing hydrogenation ball milling for 8 hours under the conditions that the pressure is 6 MPa, the revolution speed of the ball mill is 120 rpm and the rotation speed is 640rpm, wherein the ball milling product is Mg-doped Cr1Ti3V1An alloy composite 5.
(3) Preparation of benzimidazole grafted polyimide component 5: toluene solvent was added to the reaction flask and passed through N2Discharging air, sequentially adding 1 part of 2- (4-aminophenyl) -5-aminobenzimidazole and 1.5 parts of p-phenylenediamine, placing a reaction bottle in a low-temperature cooling instrument, uniformly stirring and reacting for 20 hours at 0 ℃, then adding 5.5 parts of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 1 part of ammonium persulfate, uniformly stirring and reacting for 8 hours, raising the temperature to 75 ℃, uniformly stirring and reacting for 3 hours, removing the solvent from the solution through reduced pressure concentration, washing the solid product by using a proper amount of ether solvent, and fully drying to prepare the benzimidazole grafted polyamide component 5.
(4) Preparing an oxidation-resistant polyimide-Mg-based composite hydrogen storage material 5: adding proper amount of the mixture into a reaction bottleN,N-dimethylformamide solvent, 91 parts of Mg doped Cr1Ti3V1Placing the alloy composite material 5 and the benzimidazole grafted polyimide component 5 prepared in the step (3) in an ultrasonic treatment instrument, heating to 110 ℃, carrying out ultrasonic dispersion treatment for 6 hours at the ultrasonic frequency of 28KHz, pouring the solution into a film forming device, naturally casting to form a film, placing the film in a nitrogen vacuum drying oven, heating to 100 ℃, and carrying out N-phase vacuum drying in a nitrogen vacuum drying oven2And fully drying the solvent in the atmosphere to prepare the polyimide-Mg based composite hydrogen storage material 5 with oxidation resistance.
In summary, the oxidation-resistant polyimide-Mg-based composite hydrogen storage material and the preparation method thereof have the advantages that the Cr-Ti-V alloy is used for improving the hydrogen desorption rate of the magnesium-based material, improving the circulation stability of the magnesium-based material in the hydrogen absorption and desorption processes, improving the practicability and the service life of the magnesium-based hydrogen storage material, increasing the lattice constant of the Cr-Ti-V alloy due to the larger radius of Ti atoms and promoting the addition of H atoms into the lattice gaps of the alloy, so that the Cr-Ti-V alloy also has certain hydrogen absorption capacity and the hydrogen storage performance of the composite material is improved, and the Cr-Ti-V alloy and the magnesium hydrogen absorption product are obtainedMgH2The thermal stability of the MgH is similar, and the MgH is made by in-situ hydrogenation ball milling2Forming good synergistic effect with Cr-Ti-V alloy and reducing MgH2Thereby improving the thermodynamic stability of the composite hydrogen storage material.
The benzimidazole grafted polyimide is used for coating the magnesium-based hydrogen storage material, the polyimide is a good gas selective permeation membrane, hydrogen atoms can pass through the benzimidazole grafted polyimide, the distance between polyimide molecules is enlarged through benzimidazole branched chains, rich pore structures are formed, and the magnesium-based hydrogen storage material can be better coated, so that the problem that the magnesium-based hydrogen storage material is directly contacted with oxygen in the air to cause oxidation of the magnesium material is solved, the chemical cycle stability and the service life of a hydrogen storage material matrix are ensured, hydrogen bonds are formed between benzimidazole grafted polyimide molecules and carbonyl in the polyimide, the intermolecular force is enhanced, the movement of a polyimide molecular chain is limited, the polyimide becomes chemically inert, and the chemical stability and the thermal stability of the polyimide are improved, the service life of the composite hydrogen storage material is prolonged.
Claims (5)
1. An oxidation-resistant polyimide-Mg-based composite hydrogen storage material comprises the following formula raw materials in parts by weight, and is characterized in that: 91-95 parts of Mg-doped Cr-Ti-V alloy composite material, 0.6-1 part of 2- (4-aminophenyl) -5-aminobenzimidazole, 1-1.5 parts of p-phenylenediamine, 3-5.5 parts of 3,3',4,4' -biphenyl tetracarboxylic dianhydride and 0.4-1 part of ammonium persulfate.
2. The oxidation resistant polyimide-Mg based composite hydrogen storage material of claim 1, wherein: the preparation method of the Mg-doped Cr-Ti-V alloy composite material comprises the following steps:
(1) sequentially adding high-purity elementary substance Cr, high-purity elementary substance Ti and high-purity elementary substance V into a planetary ball mill, wherein the revolution speed of the ball mill is 40-60 rpm, the rotation speed is 600-640 rpm, carrying out ball milling until the materials completely pass through a 400-mesh 600-mesh sieve, and enabling the solid mixture to pass through a sieveSmelting in a discharge plasma sintering furnace, ball-milling the solid alloy by a planetary ball mill until the solid completely passes through a 300-mesh sieve with 500 meshes, placing the solid product in a nitrogen vacuum drying box, heating to the temperature of 350-mesh 380 ℃, and carrying out N-mesh roasting in a nitrogen vacuum drying box2Drying for 1-2 h in the atmosphere to prepare Cr-Ti-V alloy;
(2) sequentially weighing Cr-Ti-V alloy and high-purity simple substance Mg, adding into a planetary ball mill, and introducing high-purity H2In the ball mill tank H2The pressure is 4-6 MPa, the revolution speed of the ball mill is 80-120 rpm, the rotation speed is 600-640 rpm, and the hydrogenation ball milling is carried out for 6-8 h, and the ball milling product is the Mg-doped Cr-Ti-V alloy composite material.
3. The Mg doped Cr-Ti-V alloy composite material according to claim 2, characterized in that: the weight mol ratio of the elementary substance Cr, the elementary substance Ti and the elementary substance V is 1-2.5:1.5-3:1, and the chemical expression of the Cr-Ti-V alloy is Cr1- 2.5Ti1.5-3V1。
4. The Mg doped Cr-Ti-V alloy composite material according to claim 2, characterized in that: the mass ratio of the Cr-Ti-V alloy to the high-purity simple substance Mg is 1: 4.5-5.5.
5. The oxidation resistant polyimide-Mg based composite hydrogen storage material of claim 1, wherein: the preparation method of the oxidation-resistant polyimide-Mg-based composite hydrogen storage material comprises the following steps:
(1) toluene solvent was added to the reaction flask and passed through N2Sequentially adding 0.6-1 part of 2- (4-aminophenyl) -5-aminobenzimidazole and 1-1.5 parts of p-phenylenediamine, reacting for 15-20 h at 0-5 ℃, then adding 3-5.5 parts of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 0.4-1 part of ammonium persulfate, reacting for 5-8 h, heating to 65-75 ℃, reacting for 2-3 h, removing the solvent from the solution, washing the solid product, and drying to prepare the benzimidazole grafted polyimide;
(2) to the direction ofN,NAdding 91-95 parts of Mg-doped Cr-Ti-V alloy into a dimethylformamide solvent for compoundingThe material and the benzimidazole graft polyimide prepared in the step (1) are subject to ultrasonic dispersion treatment for 4-6 h at the temperature of 100-110 ℃, the ultrasonic frequency is 22-28 KHz, the solution is poured into a film forming device, natural flow casting is carried out to form a film, the film is placed in a nitrogen vacuum drying box, the temperature is heated to 80-100 ℃, and the temperature is N2And drying the solvent in the atmosphere to prepare the antioxidant polyimide-Mg-based composite hydrogen storage material.
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