CN115417375A - Silicon/metal hydride composite material for rapid hydrolysis hydrogen production and preparation method thereof - Google Patents
Silicon/metal hydride composite material for rapid hydrolysis hydrogen production and preparation method thereof Download PDFInfo
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- CN115417375A CN115417375A CN202211215363.8A CN202211215363A CN115417375A CN 115417375 A CN115417375 A CN 115417375A CN 202211215363 A CN202211215363 A CN 202211215363A CN 115417375 A CN115417375 A CN 115417375A
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- C—CHEMISTRY; METALLURGY
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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- C—CHEMISTRY; METALLURGY
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a silicon/metal hydride composite material for hydrogen production by hydrolysis and a preparation method thereof. The composite material takes silicon and metal hydride as raw materials, and the metal hydride is one of calcium hydride, magnesium hydride and sodium hydride; wherein, the mole ratio of the silicon content is 0.3-0.5, and the preparation method mainly comprises the following steps: 1) Weighing a certain amount of silicon powder and metal hydride powder according to a proportion, placing the silicon powder and the metal hydride powder in a ball milling tank, and decompressing and exhausting to a vacuum state; 2) And carrying out ball milling in a hydrogen atmosphere to obtain the solid composite material. The composite material does not consume electric energy and heat energy when hydrogen is discharged, and has higher reaction rate, conversion rate and hydrogen discharge capacity; the raw materials are wide in source and low in cost; the reaction with water does not need an additional strong alkali environment, so that the safety is higher; the byproduct is environment-friendly, no toxic and harmful gas is generated, and the method has good application prospect in the field of portable hydrogen sources.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by hydrolysis, and particularly relates to a silicon/metal hydride composite material for rapid hydrogen production by hydrolysis and a preparation method thereof.
Background
The hydrogen has the advantages of wide raw materials, no pollution of combustion products, high dissipation speed, high heat value and the like, and can undoubtedly become a novel secondary energy for replacing fossil energy under the background of ecological destruction and energy crisis. With the continuous breakthrough of fuel cell technology and the increasing application of fuel cell technology in the fields of electronic products, new energy automobiles and the like, the portable hydrogen production method is increasingly and widely concerned.
The silicon element accounts for 26.4 percent of the mass of the earth crust, has rich content, low economic cost, large theoretical hydrogen capacity (14.3 weight percent), generates no harmful substances in the hydrolysis process, and is considered as a promising material for hydrolysis hydrogen production. In recent years, the service life of a solar cell using silicon as a main photovoltaic material reaches the limit, and tens of thousands of waste elemental silicon materials have great practical significance for improving the current energy situation if the elemental silicon materials can be recycled and used as a portable hydrogen source of a fuel cell.
The hydrolysis of silicon proceeds spontaneously from a thermodynamic perspective, but since the activity of silicon is low and SiO is formed during the reaction 2 It can coat the surface of the material, resulting in an extremely slow or even stop hydrolysis process. The current approaches to solve this problem are mainly: 1) Silicon is hydrolyzed in a high-concentration alkaline environment, so that the reaction conversion rate and the hydrolysis rate can be improved; 2) The composite material is compounded with other high-activity metals, so that the hydrolysis kinetics are improved; 3) Increase the specific surface area of silicon, such as nanocrystallization or preparation of porous silicon. However, the above method is complicated to operate, and the high-concentration alkali solution has extremely strong corrosivity and a large risk coefficient, and is not suitable for practical application.
Disclosure of Invention
Aiming at the defects of the prior art scheme, the invention provides a silicon/metal hydride composite material and a preparation scheme thereof, so as to improve the conversion rate and the dynamic performance of hydrogen production by silicon hydrolysis.
A silicon/metal hydride composite material for preparing hydrogen by fast hydrolysis is prepared from silicon and metal hydride as raw materials, and the metal hydride is one or more of calcium hydride, magnesium hydride and sodium hydride. Wherein the mol ratio of the silicon in the composite material is 0.3-0.5.
In the hydrolysis process of the composite material, the metal hydride reacts with water to generate hydroxide, a local high-concentration alkaline environment is formed around the fine silicon particles, and the increase of the number of hydroxide ions improves the reactivity of silicon; and the reaction kinetics are accelerated by the temperature rise of the system caused by the heat released at the beginning of the reaction. Meanwhile, as a local high-concentration alkaline environment is formed around the fine silicon particles, high-concentration hydroxide ions and silicon react quickly to generate a large amount of hydrogen, so that the concentration of the hydroxide ions in the final solution is low, and the concentration of the hydroxide ions in the whole solution can be kept at a reasonable level.
The mol ratio of silicon in the composite material is 0.3-0.5, more preferably 0.45-0.5, namely the addition mol ratio of hydride in the invention exceeds 50%, the invention can improve the hydrogen release rate, change the hydrogen release path and increase the hydrogen yield by regulating and controlling the proportion, and the product can be CaSiO only when the mol content of Si in the composite material is less than 0.5 in the case of calcium hydride 3 Salts of the group (I) according to the reaction principle of formula (1):
Si+CaH 2 +3H 2 O→CaSiO 3 +4H 2 ↑ (1)
Si+4H 2 O→Si(OH) 4 +2H 2 ↑ (2)
if the content of Si is increased, the product becomes silicon hydroxide, and as shown in formula (2), one silicon hydroxide molecule contains four hydrogen atoms, which can obviously reduce the hydrogen release amount of Si. When the Si content is further reduced to less than 0.3, the proportion of calcium hydride increases to 0.7 or more, and the hydrogen release amount of calcium hydride itself is not as high as that of Si, which in turn reduces the hydrogen release amount of the entire reaction system.
The preparation method of the silicon/metal hydride solid composite material comprises the following steps:
(1) Weighing a certain amount of silicon powder and metal hydride powder according to a proportion, placing the silicon powder and the metal hydride powder in a ball milling tank, decompressing and exhausting to a vacuum state, and then filling hydrogen with a certain pressure as protective gas;
(2) And carrying out planetary ball milling under the protection of hydrogen atmosphere to obtain the silicon/metal hydride composite material.
In the step (1), a stainless steel ball is adopted in the ball milling tank, and the mass ratio of the stainless steel ball to the total amount of the sample is 100.
In the step (2), the pressure of the protective gas hydrogen is 10-20 bar, so that air is prevented from entering the oxidation raw material, and the metal hydride is also prevented from decomposing in the ball milling process.
In the step (2), the specific parameters of the mechanical ball milling process are as follows: the rotating speed is 500rpm; the stop ratio is 5:1 (15 min/3 min), and the raw material components are prevented from being damaged due to the increase of the high-speed ball milling temperature for a long time; the ball milling time is 2-40 h, and the two raw materials are fully and uniformly mixed.
In the step (2), the silicon and the metal hydride are both brittle materials, and the two materials are mutually impacted and crushed in the ball milling process, so that a smaller size can be obtained, the specific surface area is increased, and the hydrogen production by hydrolysis is facilitated. And the ball milling mixing energy is higher, so that calcium hydride and silicon can be mixed more uniformly, a local high-concentration alkaline environment can be formed in the hydrolysis process, and the hydrogen production quantity and the hydrogen production rate are improved.
The invention designs a silicon/metal hydride solid composite material for hydrogen production by hydrolysis. The mechanical ball milling method can not only reduce the particle size of raw materials and increase the specific surface area, but also fully and uniformly mix silicon and metal hydride, thereby forming local high-concentration alkaline environment in the hydrolysis process, and simultaneously, the solution temperature is increased due to the exothermic reaction, and the hydrolysis reaction activity of the silicon is obviously improved. Compared with the prior art, the silicon/metal hydride composite material has the following advantages:
(1) The preparation method is simple, high in safety and good in repeatability;
(2) The hydroxide generated by the reaction of the metal hydride and water forms a local high-concentration alkaline environment around the fine silicon particles, so that the reaction activity of silicon can be improved without adding a strong alkaline solution in the hydrolysis process, and the hydrogen production by silicon hydrolysis in the real sense is realized;
(3) The method has mild conditions and no corrosion, and reduces the cost of hydrogen production equipment;
(4) The hydrolysis process of the composite material has high initial reaction rate, the maximum hydrogen capacity is 10.25wt%, and the final reaction conversion rate can reach more than 95%, so that the composite material has a good application prospect in the field of portable hydrogen production.
Drawings
FIG. 1 is a graph of hydrogen production by hydrolysis of a silicon/calcium hydride composite prepared in example 1;
FIG. 2 is a graph showing the rate change of hydrolysis process of the silicon/calcium hydride composite prepared in example 1;
FIG. 3 is a graph showing the change in the concentration of hydroxide ions during the hydrolysis of the silicon/calcium hydride composite prepared in example 1.
Detailed Description
For further explanation and illustration of the present invention, the following examples are set forth in the detailed description and are presented in conjunction with the following drawings:
example 1
(1) Weighing 0.24g of silicon powder and 0.36g of calcium hydride powder, and placing the silicon powder and the calcium hydride powder in a 100ml ball milling tank; wherein, the purity of the used silicon and calcium hydride raw materials is more than 99 percent, and the mass of the stainless steel ball is 60g;
(2) Fixing the cover of the ball milling tank, taking the ball milling tank out of the glove box, evacuating and exhausting for 3-5min, and completely pumping out argon in the ball milling tank so as to achieve a vacuum state;
(3) Adding 10bar hydrogen into the ball milling tank by using a hydrogenation tester;
(4) And (3) carrying out planetary ball milling under the protection of hydrogen atmosphere, wherein the ball milling rotating speed is 500rpm, the stop ratio is 5:1 (15 min/3 min), and the time duration is 40h.
The prepared silicon/calcium hydride composite material is the silicon/metal hydride solid composite material, and the change of the hydrogen hydrolysis capacity and the hydrogen hydrolysis rate of the silicon/calcium hydride composite material are respectively shown in figures 1 and 2.
Example 2
(1) Weighing 0.31g of silicon powder and 0.29g of magnesium hydride powder, and placing the silicon powder and the magnesium hydride powder in a 100ml ball milling tank, wherein the purity of the used silicon and magnesium hydride raw materials is more than 99 percent, and the mass of the stainless steel ball is 60g;
(2) Fixing the cover of the ball milling tank, taking the ball milling tank out of the glove box, evacuating and exhausting for 3-5min, and completely pumping out argon in the ball milling tank so as to achieve a vacuum state;
(3) Adding 10bar hydrogen into the ball milling tank by using a hydrogenation tester;
(4) And (3) carrying out planetary ball milling under the protection of hydrogen atmosphere, wherein the ball milling rotation speed is 500rpm, the stop ratio is 5:1 (15 min/3 min), and the time duration is 40h.
The prepared silicon/magnesium hydride composite material is the silicon/metal hydride solid composite material.
Example 3
(1) Weighing 0.22g of silicon powder and 0.38g of sodium hydride powder, and placing the silicon powder and the sodium hydride powder in a 100ml ball milling tank, wherein the purity of the used silicon and sodium hydride raw materials is more than 99%, and the mass of the stainless steel ball is 60g;
(2) Fixing the cover of the ball milling tank, taking the ball milling tank out of the glove box, evacuating and exhausting for 3-5min, and completely pumping out argon in the ball milling tank so as to achieve a vacuum state;
(3) Adding 10bar hydrogen into the ball milling tank by using a hydrogenation tester;
(4) And (3) carrying out planetary ball milling under the protection of hydrogen atmosphere, wherein the ball milling rotation speed is 500rpm, the stop ratio is 5:1 (15 min/3 min), and the time duration is 40h.
The prepared silicon/sodium hydride composite material is the silicon/metal hydride solid composite material.
The foregoing detailed description is exemplary and is intended to provide those skilled in the art with a better understanding of the invention; any changes or modifications made on the basis of the above-mentioned technical scheme are within the scope of the invention as defined by the appended claims.
Claims (6)
1. A silicon/metal hydride composite material for rapid hydrolysis hydrogen production, characterized in that: the composite material is the composition of silicon and metal hydride, wherein the molar ratio of the silicon is 0.3-0.5.
2. A silicon/metal hydride composite according to claim 1, wherein the mole ratio of silicon in the composite is 0.45 to 0.5.
3. The silicon/metal hydride composite of claim 1, wherein the metal hydride is one or more of calcium hydride, magnesium hydride, and sodium hydride.
4. A method of preparing a silicon/metal hydride composite as claimed in claim 1, comprising:
(1) Weighing silicon powder and metal hydride powder according to a ratio, placing the silicon powder and the metal hydride powder in a ball milling tank, decompressing and exhausting to a vacuum state, and then filling hydrogen with certain pressure as protective gas;
(2) And carrying out ball milling under the protection of hydrogen atmosphere to obtain the silicon/metal hydride composite material.
5. The method of claim 4, wherein: the pressure of the protective gas hydrogen is 10-20 bar.
6. The method of claim 4, wherein: in the step (2), the specific parameters of the ball milling process are as follows: the rotating speed is 500rpm; a dwell ratio of 5:1; the ball material ratio is 100; the ball milling time is 2-40 h.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102769125A (en) * | 2012-07-10 | 2012-11-07 | 浙江大学 | Alkaline-earth metal silicide preparation method |
| CN107324279A (en) * | 2017-09-06 | 2017-11-07 | 四川大学 | It is a kind of to improve the method that silicon alkaline process prepares hydrogen |
| CN108862192A (en) * | 2018-09-06 | 2018-11-23 | 四川大学 | A method of hydrogen is prepared for the composite hydrogen manufacturing agent of hydrolytic hydrogen production and using it |
| US20200223691A1 (en) * | 2019-01-10 | 2020-07-16 | Ge Solartech, LLC | Hydrogen Storage and Delivery System using a Synergistic Hydrolysis Technology |
| CN111481425A (en) * | 2019-01-25 | 2020-08-04 | 曹荣华 | Microenvironment hydrogen supply breathable layer and external application bag |
| CN111634884A (en) * | 2020-07-04 | 2020-09-08 | 上海镁源动力科技有限公司 | Controllable hydrogen release material, preparation method thereof and hydrolysis hydrogen production method |
-
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- 2022-09-30 CN CN202211215363.8A patent/CN115417375A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102769125A (en) * | 2012-07-10 | 2012-11-07 | 浙江大学 | Alkaline-earth metal silicide preparation method |
| CN107324279A (en) * | 2017-09-06 | 2017-11-07 | 四川大学 | It is a kind of to improve the method that silicon alkaline process prepares hydrogen |
| CN108862192A (en) * | 2018-09-06 | 2018-11-23 | 四川大学 | A method of hydrogen is prepared for the composite hydrogen manufacturing agent of hydrolytic hydrogen production and using it |
| US20200223691A1 (en) * | 2019-01-10 | 2020-07-16 | Ge Solartech, LLC | Hydrogen Storage and Delivery System using a Synergistic Hydrolysis Technology |
| CN111481425A (en) * | 2019-01-25 | 2020-08-04 | 曹荣华 | Microenvironment hydrogen supply breathable layer and external application bag |
| CN111634884A (en) * | 2020-07-04 | 2020-09-08 | 上海镁源动力科技有限公司 | Controllable hydrogen release material, preparation method thereof and hydrolysis hydrogen production method |
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