CN115259081B - Silicon-based composite material for controllable hydrolysis hydrogen production and preparation method and application thereof - Google Patents

Silicon-based composite material for controllable hydrolysis hydrogen production and preparation method and application thereof Download PDF

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CN115259081B
CN115259081B CN202211007488.1A CN202211007488A CN115259081B CN 115259081 B CN115259081 B CN 115259081B CN 202211007488 A CN202211007488 A CN 202211007488A CN 115259081 B CN115259081 B CN 115259081B
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CN115259081A (en
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欧阳柳章
刘米粒
刘江文
钟浩
王辉
朱敏
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South China University of Technology SCUT
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    • 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
    • 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
    • C01B3/08—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 with metals
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    • C—CHEMISTRY; METALLURGY
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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    • 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
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Abstract

The invention belongs to the technical field of hydrolysis hydrogen production, and discloses a silicon-based composite material for controllable hydrolysis hydrogen production, and a preparation method and application thereof. The invention mixes metal silicon powder and alkali metal as precursors, and ball-milling is carried out after the precursors and grinding aid are mixed, thus obtaining the silicon-based composite material. The invention adopts cheap industrial metal silicon as raw material, realizes the combination of silicon and a very small amount of alkali metal additive by using mechanical ball milling, and obtains the silicon-based composite material with low price and excellent hydrogen production performance by hydrolysis. The silicon-based composite material can release a large amount of hydrogen after reacting with neutral or near-neutral solution, has high hydrogen yield up to 1445mL/g, has good air stability, is suitable for on-site hydrogen supply under multiple working conditions and complex environments, and has good safety.

Description

Silicon-based composite material for controllable hydrolysis hydrogen production and preparation method and application thereof
Technical Field
The invention relates to the technical field of hydrogen production by hydrolysis, in particular to a silicon-based composite material for controllable hydrogen production by hydrolysis, and a preparation method and application thereof.
Background
Compared with the traditional energy, the hydrogen has the advantages of high heat value, regeneration, zero emission and the like, and is regarded as an optimal clean energy carrier. However, because of the poor compressibility of hydrogen, safe and efficient storage and transportation remain an important problem for the wide-range marketable application of hydrogen. In the traditional hydrogen storage technology, the high-pressure gaseous hydrogen storage safety coefficient is low, the low-temperature liquid hydrogen storage energy consumption is large, the hydrogen storage operation conditions and the hydrogen storage density of the organic liquid and solid materials are not matched, the hydrogen can be rapidly supplied under mild conditions by the hydrolysis hydrogen production based on spontaneous reaction, and the irreversible hydrogen storage technology has the advantages of simplicity in operation, high safety, low energy consumption and the like, and has recently attracted wide attention of domestic and foreign energy students.
Silicon has high storage in crust, low cost and reaction of silicon with water as high as 1750mL/gH 2 Is a hydrolysis hydrogen production material with great application value. However, silicon readily reacts with air to form a dense surface oxide layer that reacts in hydrolysis to produce hydrogenAnd a silicon dioxide inert layer can be generated, so that the silicon is blocked from being effectively contacted with water, and the reactivity of the silicon is obviously reduced.
For modification of silicon, most of the current researches adopt hydrofluoric acid or high-concentration strong alkali to destroy an inert layer on the surface of the silicon, so that the hydrolysis reaction kinetics and the hydrogen production of the silicon are improved. For example, ning et al prepared a silicon nanowire array by etching with hydrofluoric acid under electrochemical action, but the array released only 121mL/gH in pure water 2 . Mussabek et al prepared porous nano-silicon powder by hydrofluoric acid etching under electrochemical conditions in combination with mechanical grinding, but the powder only released 820mL/gH in a water/ethanol mixture 2 And hydrofluoric acid has extremely high harm to human bodies and natural environments. To solve the toxicity problem of hydrofluoric acid, erogbogbo et al utilized SiH 4 The superfine silicon nano powder is prepared by laser pyrolysis, and in 14mol/LKOH solution, the reaction hydrogen production rate is high, the hydrogen production is high, but the high-concentration KOH solution also requires a reaction container to have higher corrosion resistance, and the use cost is increased. In addition, the raw materials of the method are high-purity nano silicon with high price, and the method is not suitable for large-scale application. Based on this, patent 202011401535.1 proposes to use waste silicon wafer to hydrolyze and prepare hydrogen, which is prepared by coating waste silicon wafer with mixed slurry of reduced metal/salt and the like, pressing with metal sheet lamination and performing high-temperature heat treatment, but the material can only release hydrogen at 50 ℃, and the preparation process needs to perform long-time high-energy heat treatment at 300-800 ℃ to prepare a large amount of reduced metal powder, low-melting salt and metal sheet, thus obviously increasing the preparation cost of the material.
Therefore, the development of the modification method of the low-cost silicon-based hydrolysis hydrogen production material with low cost and simple process has very important research significance and practical value.
Disclosure of Invention
The invention aims to provide a silicon-based composite material for controllable hydrolysis hydrogen production, a preparation method and application thereof, and solves the problems of the silicon-based hydrogen production material provided by the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a silicon-based composite material for controllable hydrolysis hydrogen production, which comprises the following steps:
and mixing metal silicon powder and alkali metal as precursors, and ball milling the mixed precursors and grinding aid to obtain the silicon-based composite material.
Preferably, in the preparation method of the silicon-based composite material for the controllable hydrolysis hydrogen production, the mass ratio of the alkali metal to the metal silicon powder is 1:23 to 49.
Preferably, in the preparation method of the silicon-based composite material for controllable hydrolysis hydrogen production, the grinding aid is a solid grinding aid or a liquid grinding aid; the solid grinding aid is NaCl, na 2 SO 4 KCl or NiCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The liquid grinding aid is n-heptane or tetrahydrofuran;
when the grinding aid is a solid grinding aid, the mass of the solid grinding aid is 2-5 wt% of the precursor;
when the grinding aid is a liquid grinding aid, the volume mass ratio of the liquid grinding aid to the precursor is 1mL:1g.
Preferably, in the preparation method of the silicon-based composite material for controllable hydrolysis hydrogen production, the ball milling adopts a planetary ball mill at room temperature and normal pressure; ball milling is carried out under inert atmosphere; the rotation speed of ball milling is 300-500 rpm; the ball milling time is 3-7 h; ball-milling ball material ratio is 50-100: 1, a step of; the ball milling medium is 3:2 stainless steel balls with the particle size of 10mm and stainless steel balls with the particle size of 6 mm.
Preferably, in the preparation method of the silicon-based composite material for controllable hydrolysis hydrogen production, the metal silicon powder is one or more of 553 metal silicon powder, 441 metal silicon powder and 421 metal silicon powder; si is more than or equal to 98.7%, fe is less than or equal to 0.50%, al is less than or equal to 0.50% and Ca is less than or equal to 0.30% in 553 metal silicon powder; si in 441 metal silicon powder is more than or equal to 99.1%, fe is less than or equal to 0.40%, al is less than or equal to 0.40%, and Ca is less than or equal to 0.10%; si is more than or equal to 99.3%, fe is less than or equal to 0.40%, al is less than or equal to 0.20%, and Ca is less than or equal to 0.10% in the 421 metal silicon powder.
Preferably, in the preparation method of the silicon-based composite material for the controllable hydrolysis hydrogen production, the alkali metal is one or more of lithium, potassium and sodium.
The invention also provides the silicon-based composite material prepared by the preparation method.
The invention also provides an application of the silicon-based composite material in controllable hydrolysis hydrogen production, which comprises the following steps:
and mixing the silicon-based composite material with an aqueous solution, and performing hydrolysis reaction to obtain hydrogen.
Preferably, in the above application, the aqueous solution is an aqueous solution of salt, deionized water, tap water or seawater.
Preferably, in the above application, the temperature of the hydrolysis reaction does not exceed 90 ℃.
In the invention, a small amount of alkali metal is added to react with the natural surface oxide of the silicon particles to generate soluble Li 2 SiO 3 At the same time, a small amount of lithium remains attached to the silicon surface, this part of lithium metal and Li 2 SiO 3 The interfacial layer structure is attached to the surface of the silicon particles, and when the silicon compound after ball milling reacts with water, the interfacial layer can be rapidly dissolved and expose the fresh silicon surface, and meanwhile, a slightly alkaline environment is created, so that a large amount of hydrolysis and hydrogen release of silicon are promoted.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts cheap industrial metal silicon as raw material, realizes the combination of silicon and a very small amount of alkali metal additive (< 4.5 wt%) by using mechanical ball milling, and obtains the silicon-based composite material with low price and excellent hydrogen production performance by hydrolysis.
(2) The preparation method only adopts simple planetary ball milling at room temperature and normal pressure, does not need complicated steps such as high pressure, high temperature, rapid cooling or other retreatment, and has safe and controllable process, mild condition and easy large-scale amplification. Therefore, the silicon-based composite material prepared by the invention and the preparation method thereof have commercial application value.
(3) The silicon-based composite material can release a large amount of hydrogen by reacting with neutral or near-neutral solution, and the hydrogen yield is up to 1445mL/g.
(4) The hydrolysate of the silicon-based composite material is nontoxic and harmless, has low corrosiveness and has low requirements on a reaction container.
(5) The silicon-based composite material has good air stability, is suitable for on-site hydrogen supply under multiple working conditions and in complex environments, and has good safety.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an XRD pattern for a silicon-based composite of example 1;
FIG. 2 is a TEM image of the silicon-based composite of example 1;
FIG. 3 is an XPS diagram of a silicon-based composite material of example 1;
wherein (a) is XPS diagram of silicon element; (b) XPS diagram of lithium element;
FIG. 4 is a kinetic profile of hydrogen production by hydrolysis of the silicon-based composites of example 1 and comparative example 1;
FIG. 5 is a kinetic profile of hydrogen production by hydrolysis of the silicon-based composite of example 2;
FIG. 6 is a kinetic profile of hydrogen production by hydrolysis of the silicon-based composites of examples 9-12;
FIG. 7 is a kinetic profile of hydrogen production by hydrolysis of the silicon-based composites of examples 13-15.
Detailed Description
The invention provides a preparation method of a silicon-based composite material for controllable hydrolysis hydrogen production, which comprises the following steps:
and mixing metal silicon powder and alkali metal as precursors, and ball milling the mixed precursors and grinding aid to obtain the silicon-based composite material.
In the invention, the mass ratio of the alkali metal to the metal silicon powder is preferably 1:23 to 49, more preferably 1:27 to 45, more preferably 1:36.
in the present invention, the grinding aid is preferably a solid grinding aid or a liquidA bulk grinding aid; the solid grinding aid is preferably NaCl or Na 2 SO 4 KCl or NiCl 2 Further preferably NaCl, KCl or NiCl 2 More preferably NaCl; the liquid grinding aid is preferably n-heptane or tetrahydrofuran, more preferably n-heptane;
when the grinding aid is a solid grinding aid, the mass of the solid grinding aid is preferably 2 to 5wt%, more preferably 2.7 to 4.5wt%, and even more preferably 3.7wt% of the mass of the precursor;
when the grinding aid is a liquid grinding aid, the volume to mass ratio of the liquid grinding aid to the precursor is preferably 1mL:1g.
In the invention, the ball milling adopts a planetary ball mill with room temperature and normal pressure; the ball milling is preferably carried out under an inert atmosphere, more preferably an argon atmosphere; the rotation speed of the ball mill is preferably 300 to 500rpm, more preferably 360 to 430rpm, and still more preferably 380rpm; the ball milling time is preferably 3 to 7 hours, more preferably 4 to 6 hours, and still more preferably 5.5 hours; the ball-to-material ratio of ball milling is preferably 50-100: 1, more preferably 60 to 90:1, more preferably 85:1, a step of; the ball milling medium is preferably a material with a mass ratio of 3:2 stainless steel balls with the particle size of 10mm and stainless steel balls with the particle size of 6 mm.
In the present invention, the metal silicon powder is preferably one or more of 553 metal silicon powder, 441 metal silicon powder and 421 metal silicon powder, more preferably 553 metal silicon powder or 441 metal silicon powder, and still more preferably 553 metal silicon powder.
In the invention, si is more than or equal to 98.7%, fe is less than or equal to 0.50%, al is less than or equal to 0.50% and Ca is less than or equal to 0.30% in the 553 metal silicon powder; si is more than or equal to 99.1%, fe is less than or equal to 0.40%, al is less than or equal to 0.40%, and Ca is less than or equal to 0.10% in the 441 metal silicon powder; si is more than or equal to 99.3%, fe is less than or equal to 0.40%, al is less than or equal to 0.20%, and Ca is less than or equal to 0.10% in the 421 metal silicon powder.
In the present invention, the alkali metal is preferably one or more of lithium, potassium and sodium, more preferably one or both of lithium and sodium, and still more preferably sodium.
The invention also provides the silicon-based composite material prepared by the preparation method.
The invention also provides an application of the silicon-based composite material in controllable hydrolysis hydrogen production, which comprises the following steps:
and mixing the silicon-based composite material with an aqueous solution, and performing hydrolysis reaction to obtain hydrogen.
In the present invention, the aqueous solution is preferably an aqueous solution of salt, deionized water, tap water or seawater, more preferably deionized water or seawater, and still more preferably seawater.
In the present invention, the temperature of the hydrolysis reaction is preferably not more than 90 ℃, more preferably 20 to 50 ℃, still more preferably 25 ℃.
In the invention, the mass volume ratio of the silicon-based composite material to the aqueous solution is preferably 0.1-0.3 g:5 to 10mL, more preferably 0.15 to 0.27g:6 to 9mL, more preferably 0.23g:8mL.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 49:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding NaCl with 3wt% of the mass of the precursors as a grinding aid, and mixing according to a ball-to-material ratio of 50: and 1, adding a ball milling medium, placing the ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 400rpm, and ball milling for 6 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of the silicon-based composite material is added into 5mL of deionized water at 30 ℃, the hydrolysis hydrogen production reaction is mild, and 1213mL/g of hydrogen can be released within 180 min.
Example 2
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 49:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding NaCl with 3wt% of the mass of the precursors as a grinding aid, and mixing according to a ball-to-material ratio of 50: and 1, adding a ball milling medium, placing a ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 400rpm, and ball milling for 3 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of the silicon-based composite material is added into 5mL of deionized water at 30 ℃, the hydrolysis hydrogen production reaction is mild, and 995mL/g of hydrogen can be released within 180 min.
Example 3
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 49:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding NaCl with 3wt% of the mass of the precursors as a grinding aid, and mixing according to a ball-to-material ratio of 50: and 1, adding a ball milling medium, placing a ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 400rpm, and ball milling for 4 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of the silicon-based composite material is added into 5mL of deionized water at 30 ℃, the hydrolysis hydrogen production reaction is mild, and 1051mL/g of hydrogen can be released within 180 min.
Example 4
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 49:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding NaCl with 3wt% of the mass of the precursors as a grinding aid, and mixing according to a ball-to-material ratio of 50: and 1, adding a ball milling medium, placing a ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 400rpm, and ball milling for 7 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of the silicon-based composite material is added into 5mL of deionized water at 30 ℃, the hydrolysis hydrogen production reaction is mild, and 1026mL/g of hydrogen can be released within 180 min.
Example 5
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 49:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding 1mL of n-heptane (the volume mass ratio of the n-heptane to the precursors is 1mL to 1 g) as a grinding aid, and according to the ball-to-material ratio of 75: and 1, adding a ball milling medium, placing the ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 450rpm, and ball milling for 5 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of the silicon-based composite material is added into 5mL of deionized water at 30 ℃, the hydrolysis hydrogen production reaction is mild, and 1129mL/g of hydrogen can be released within 180 min.
Example 6
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 23:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding 1mL of n-heptane (the volume mass ratio of the n-heptane to the precursors is 1mL to 1 g) as a grinding aid, and taking the mixture as a ball material ratio of 100: and 1, adding a ball milling medium, placing a ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 300rpm, and ball milling for 6 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of silicon-based composite material is added into 5mL of deionized water at 30 ℃, the hydrolysis hydrogen production reaction is mild, and 1170mL/g of hydrogen can be released within 180 min.
Example 7
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 31:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding 1mL of n-heptane (the volume mass ratio of the n-heptane to the precursors is 1mL to 1 g) as a grinding aid, and mixing according to a ball-to-material ratio of 50: and 1, adding a ball milling medium, placing the ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 450rpm, and ball milling for 6 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of the silicon-based composite material is added into 5mL of deionized water at 30 ℃, the hydrolysis hydrogen production reaction is mild, and 1169mL/g of hydrogen can be released within 180 min.
Example 8
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 40:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding 1mL of n-heptane (the volume mass ratio of the n-heptane to the precursors is 1mL to 1 g) as a grinding aid, and mixing according to a ball-to-material ratio of 50: and 1, adding a ball milling medium, placing a ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 500rpm, and ball milling for 6 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of silicon-based composite material is added into 5mL of deionized water at 30 ℃, the hydrolysis hydrogen production reaction is mild, and 1210mL/g of hydrogen can be released within 180 min.
Example 9
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and the preparation method comprises the following steps:
in a 0.1MPa argon glove box, the mass ratio is 49:1, weighing 553 metal silicon powder and lithium foil as precursors, mixing, adding the mixture into a ball milling tank, adding NaCl with 3wt% of the mass of the precursors as a grinding aid, and mixing according to a ball-to-material ratio of 50: and 1, adding a ball milling medium, placing the ball milling tank on a planetary ball mill, adjusting the ball milling rotating speed to 400rpm, and ball milling for 6 hours in an argon atmosphere to obtain the silicon-based composite material.
The application of the silicon-based composite material for hydrogen production by hydrolysis is as follows: 0.1g of the silicon-based composite material is added into 5mL of deionized water at 25 ℃, the hydrolysis hydrogen production reaction is mild, 705mL/g of hydrogen can be released within 30min, and 1097mL/g of hydrogen can be released within 180 min.
Example 10
The present example provides a silicon-based composite material for controlled hydrolysis hydrogen production, with specific reference to example 9, except that in the application of hydrolysis hydrogen production, the deionized water temperature is 35 ℃, the material can release 926mL/g hydrogen in 30min, and 1407mL/g hydrogen in 180 min.
Example 11
The present example provides a silicon-based composite material for controlled hydrolysis hydrogen production, with specific reference to example 9, except that in the application of hydrolysis hydrogen production, the deionized water temperature is 45 ℃, the material can release 1132mL/g hydrogen in 30min, and 1423mL/g hydrogen in 180 min.
Example 12
The present example provides a silicon-based composite material for controlled hydrolysis hydrogen production, with particular reference to example 9, except that in the application of hydrolysis hydrogen production, the deionized water temperature is 55deg.C, the material can release 1311mL/g hydrogen in 30min, and 1445mL/g hydrogen in 180 min.
Example 13
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and particularly relates to embodiment 9, wherein the difference is that deionized water at 25 ℃ is replaced by tap water at 30 ℃ in the application of hydrolysis hydrogen production, and the material can release 722mL/g of hydrogen within 30min and 1178mL/g of hydrogen within 180 min.
Example 14
This example provides a silicon-based composite for controlled hydrolysis hydrogen production, with specific reference to example 9, except that 25 ℃ deionized water was replaced with 30 ℃ Na at 0.62mol/L in the application of hydrolysis hydrogen production 2 SO 4 In water, 887mL/g of hydrogen can be released from the material within 30min, and 1224mL/g of hydrogen can be released within 180 min.
Example 15
The embodiment provides a silicon-based composite material for controllable hydrolysis hydrogen production, and particularly relates to embodiment 9, which is different in that deionized water at 25 ℃ is replaced by seawater at 30 ℃ in the application of hydrolysis hydrogen production, 857mL/g of hydrogen can be released within 30min, and 1181mL/g of hydrogen can be released within 180 min.
Comparative example 1
This comparative example provides a silicon-based composite, see in particular example 1, except that no lithium foil is added to the precursor, and in the application of hydrogen production by hydrolysis, 0.1g of the silicon-based composite is mixed with lithium foil of the corresponding mass to example 1 and then added to 5mL of 25 ℃ deionized water, and the material can release only 623mL/g of hydrogen within 180 minutes.
The silicon-based composite material prepared in example 1 was subjected to XRD, TEM, XPS characterization, and the results are shown in fig. 1 to 3. As can be seen from fig. 1, the characteristic diffraction peak intensity of silicon in the silicon-based composite material prepared after ball milling is significantly reduced, the half-width is widened, but the peak position is not changed, which indicates that particle refinement occurs during ball milling, and lithium mainly reacts with the surface layer of silicon and does not alloy with the silicon phase, compared with 553 metal silicon powder. As can be seen from fig. 2, an amorphous film structure having a thickness of about 5nm is formed on the silicon substrate surface. As can be seen from fig. 3, after ball milling and compounding with lithium, the silicon dioxide on the silicon surface is successfully converted into lithium silicate, accompanied by part of unreacted lithium metal, which indicates that the ball milling process effectively damages the compact oxide layer on the silicon surface and improves the reactivity of silicon.
The hydrolysis hydrogen production kinetics curves of the silicon-based composites of example 1 and comparative example 1 were measured, and the results are shown in fig. 4 (curve (a) is the hydrolysis hydrogen production kinetics curve of the silicon-based composite of example 1, and curve (b) is the hydrolysis hydrogen production kinetics curve of the silicon-based composite of comparative example 1). As can be seen from fig. 4, the hydrogen production activity by hydrolysis of metallic silicon is greatly improved after the surface modification is realized by mechanical ball milling.
The hydrolysis hydrogen production kinetics curves for the silicon-based composites of example 2 were determined and the results are shown in fig. 5. As can be seen from fig. 5, the ball milling time affects the performance of hydrogen production by hydrolysis, and the hydrogen production performance by hydrolysis of metallic silicon can be improved better even by ball milling modification for a short time as compared with comparative example 1 (curve (b) of fig. 4).
The hydrolysis hydrogen production kinetics curves of the silicon-based composites of examples 9 to 12 were measured and the results are shown in FIG. 6. As can be seen from fig. 6, the kinetics of hydrogen production by hydrolysis of the silicon-based composite material is excellent, and the hydrogen production performance can be further improved with the increase of temperature.
The hydrolysis hydrogen production kinetics curves of the silicon-based composites of examples 13 to 15 were measured and the results are shown in FIG. 7. As can be seen from fig. 7, the kinetics of hydrogen production by hydrolysis of the silicon-based composite material is excellent, and the total hydrogen production amount is little affected by different solutions.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (4)

1. The preparation method of the silicon-based composite material for the controllable hydrolysis hydrogen production is characterized by comprising the following steps of:
mixing metal silicon powder and alkali metal as precursors, and ball milling the mixed precursors and grinding aid to obtain a silicon-based composite material;
wherein, the mass ratio of the alkali metal to the metal silicon powder is 1: 23-49; the alkali metal is one or more of lithium, potassium and sodium;
the grinding aid is a liquid grinding aid; the liquid grinding aid is n-heptane or tetrahydrofuran; the volume mass ratio of the liquid grinding aid to the precursor is 1mL:1g;
the rotation speed of the ball milling is 300-500 rpm; the ball milling time is 3-7 hours; ball-milling ball material ratio is 50-100: 1, a step of; the ball milling medium is 3:2 stainless steel balls with the particle size of 10mm and stainless steel balls with the particle size of 6 mm;
the metal silicon powder is one or more of 553 metal silicon powder, 441 metal silicon powder and 421 metal silicon powder; si is more than or equal to 98.7%, fe is less than or equal to 0.50%, al is less than or equal to 0.50% and Ca is less than or equal to 0.30% in 553 metal silicon powder; si in 441 metal silicon powder is more than or equal to 99.1%, fe is less than or equal to 0.40%, al is less than or equal to 0.40%, and Ca is less than or equal to 0.10%; si is more than or equal to 99.3%, fe is less than or equal to 0.40%, al is less than or equal to 0.20%, and Ca is less than or equal to 0.10% in the 421 metal silicon powder.
2. The method for preparing a silicon-based composite material for controllable hydrolysis hydrogen production according to claim 1, wherein the ball milling adopts a planetary ball mill at room temperature and normal pressure; ball milling is carried out under an inert atmosphere.
3. Use of the preparation method according to claim 1 or 2 for the controlled hydrolysis hydrogen production, characterized by comprising the steps of:
mixing the silicon-based composite material prepared by the preparation method of claim 1 or 2 with an aqueous solution, and performing hydrolysis reaction to obtain hydrogen;
the temperature of the hydrolysis reaction is 20-45 ℃.
4. Use according to claim 3, wherein the aqueous solution is an aqueous solution of a salt, deionized water, tap water or seawater.
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