CN116177551A - Preparation method of high-reactivity silicon nano-particles with mesoporous structure - Google Patents

Preparation method of high-reactivity silicon nano-particles with mesoporous structure Download PDF

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CN116177551A
CN116177551A CN202310229696.4A CN202310229696A CN116177551A CN 116177551 A CN116177551 A CN 116177551A CN 202310229696 A CN202310229696 A CN 202310229696A CN 116177551 A CN116177551 A CN 116177551A
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mesoporous
particles
silicon nano
closed crucible
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周翔
马新文
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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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
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of high-reactivity silicon nano particles with mesoporous structures, which comprises the following steps: fully mixing mesoporous silica particles, magnesium powder and NaCl in a certain weight ratio at room temperature through ball milling, and drying to obtain a uniform mixture; placing the mixture into a closed crucible, placing the closed crucible into a tube furnace, and heating the closed crucible to a certain temperature under the protection of argon to perform a magnesia reduction reaction; and finally, pickling the reaction product to remove byproducts, centrifuging and drying to obtain the high-reactivity silicon nano particles with mesoporous structures. The preparation process of the invention is easy to control, has good repeatability, avoids the use of a large amount of toxic chemicals compared with the prior corrosion preparation process, and the prepared mesoporous structure silicon nano particles keep the original template structure, are regular and orderly, and greatly advance the oxidation weight increase reaction starting temperature of silicon.

Description

Preparation method of high-reactivity silicon nano-particles with mesoporous structure
Technical Field
The invention relates to the technical field of nano composite energetic materials, in particular to a preparation method of high-reactivity silicon nano particles with mesoporous structures.
Background
The nano concept is introduced into the design of the energetic material, so that a novel high-activity composite energetic material is formed: metastable intermolecular complexes. The composition of the reactive components at the level of nanometer level to atomic level ensures that the interface contact between the components is more compact and the mass transfer rate is obviously accelerated, thereby the energetic material shows higher energy release rate and combustion efficiency. The nano aluminum powder becomes the most popular fuel choice due to good reactivity and high heat release, however, the high reactivity of the nano aluminum powder leads the nano aluminum powder to have higher sensitivity to static electricity, friction and impact, and potential safety hazard is easy to generate; and an alumina layer (2-6 nm) is easily formed on the surface of the aluminum oxide layer, so that the content of active aluminum is reduced. Nano silicon powder is an attractive candidate fuel, and the calorific value (33.9 kJ/g) of the nano silicon powder is equivalent to that of aluminum (30.8 kJ/g); in addition, the oxide layer of the nano silicon powder is thinner (1-3 nm), so that the nano silicon powder has higher activity content.
Reducing the particle size to the nano-scale naturally brings about a certain small-size effect, but also inevitably causes a serious agglomeration phenomenon, which brings about a great challenge for practical application. Researchers have found that the porosification of nanoparticles allows for both structural design and dimensional effects, and that large internal specific surface areas can provide richer reaction sites, with unique interface characteristics and limitations that reduce mass diffusion. Thus, porous silicon nanoparticles are considered as an effective way to increase the reactivity (particularly the onset temperature of the oxidative weighting reaction).
At present, the preparation of porous silicon mainly depends on an etching method, and although the nano porous silicon prepared by an electrochemical etching method has small pore diameter and uniform distribution, the silicon chip is limited to be widely applied in the field of energetic materials due to the special physical form of the silicon chip. The chemical corrosion technology has low cost and simple operation, but a large amount of HF and concentrated HNO are used in the experimental process 3 Toxic volatile gases are generated and the repeatability is poor. Therefore, it is of great importance to find a new and reliable method for preparing porous silicon nanoparticles.
Disclosure of Invention
The invention aims to adopt a new idea, firstly, a monodisperse mesoporous silica nanoparticle is constructed, and the mesoporous silica nanoparticle is used as a template, and the mesoporous silicon nanoparticle is prepared by a magnesia-thermal reduction method, so that the silicon reactivity is improved, and meanwhile, the use of a large amount of toxic chemicals is avoided.
In order to achieve the above object, the technical solution of the present invention is as follows:
the preparation method of the high-reactivity silicon nano-particles with the mesoporous structure comprises the following steps: firstly, constructing mesoporous silica particles by using an organic-inorganic self-assembly method as an initial template; fully mixing mesoporous silica particles, magnesium powder and NaCl in a certain weight ratio at room temperature through ball milling, and drying to obtain a uniform mixture; placing the mixture into a closed crucible, placing the closed crucible into a tube furnace, and heating the closed crucible to a certain temperature under the protection of argon to perform a magnesia reduction reaction; and finally, pickling the reaction product to remove byproducts, centrifuging and drying to obtain the high-reactivity silicon nano particles with mesoporous structures.
Further, the mesoporous silica particles of 100-200 nm are constructed by using an organic-inorganic self-assembly method.
Further, the magnesium powder has a specification of 100-200 meshes.
Further, mesoporous silica particles, magnesium powder and NaCl with the mass ratio of 1:0.9:10 are fully mixed by ball milling at room temperature.
Further, zirconia balls with different sizes of 0.8mm and 3mm are adopted in ball milling, the grade ratio is 1:1-1:2, and the ball-material ratio is 10:1-50:1.
Further, heating to a certain temperature under the protection of argon to perform a magnesia reduction reaction, wherein the heating rate is 5-10 ℃/min, the heating temperature is 660-700 ℃, and the temperature is kept for 5 hours.
Compared with the prior art, the preparation method of the high-reactivity silicon nano-particles with the mesoporous structure provided by the invention has at least the following advantages:
the preparation process is easy to control, has good repeatability, and avoids the use of a large amount of toxic chemicals compared with the prior corrosion preparation process.
The prepared mesoporous structure silicon nano-particles retain the original template structure, are regular and orderly, and greatly advance the initial temperature of the oxidation weight increasing reaction.
The foregoing description is only an overview of the present invention and is presented below in detail with respect to preferred embodiments of the present invention.
Drawings
Fig. 1 is a schematic view of a process for preparing highly reactive silicon nanoparticles having a mesoporous structure.
Fig. 2 is an XRD pattern of mesoporous silica nanoparticles described in example 1 of the present invention.
FIG. 3 is an SEM image of mesoporous silica nanoparticles (a: 500nm, b:200 nm) according to example 1 of the present invention.
Fig. 4 is a nitrogen adsorption/desorption isotherm of the mesoporous silica nanoparticle described in example 1 of the present invention.
Fig. 5 is a pore size distribution curve of the mesoporous silica nanoparticle described in example 1 of the present invention.
Fig. 6 is an XRD pattern of the highly reactive silicon nanoparticle having a mesoporous structure described in example 1 of the present invention.
A and b in FIG. 7 are SEM images (a: 500nm, b:200 nm) of highly reactive silicon nanoparticles having a mesoporous structure obtained after rinsing with HCl in example 1 of the present invention; c and d in FIG. 7 are SEM pictures (c: 500nm, d:200 nm) of highly reactive silicon nanoparticles having a mesoporous structure obtained after sequentially rinsing with HCl and HF in example 1 of the present invention.
Fig. 8 is a nitrogen adsorption/desorption isotherm of the highly reactive silicon nanoparticle having a mesoporous structure described in example 1 of the present invention.
Fig. 9 is a pore size distribution curve of the highly reactive silicon nanoparticle having a mesoporous structure described in example 1 of the present invention.
Fig. 10 is a TG-DSC curve under argon of the highly reactive silicon nanoparticles having a mesoporous structure described in example 1 of the present invention.
FIG. 11 is a TG-DSC curve of 30nm silicon nanoparticles commercially available from Michael company under argon.
FIG. 12 is an SEM image of highly reactive silicon nanoparticles having a mesoporous structure (a: 500nm, b:200 nm) of example 2 of the present invention.
Fig. 13 is an XRD pattern of the highly reactive silicon nanoparticle having a mesoporous structure described in example 3 of the present invention.
Fig. 14 is an XRD pattern of the highly reactive silicon nanoparticle having a mesoporous structure described in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings.
Referring to fig. 1, the invention discloses a preparation method of high-reactivity silicon nanoparticles with mesoporous structures. The preparation method comprises the following steps: firstly, constructing mesoporous silica nano particles with the diameter of 180nm by using an organic-inorganic self-assembly method as an initial template; fully mixing mesoporous silica particles, magnesium powder and NaCl in a certain weight ratio at room temperature through a planetary ball mill, and drying in vacuum to obtain a uniform mixture; placing the mixture into a closed crucible, placing the closed crucible into a tube furnace, heating to a certain temperature under the protection of argon, and preserving heat to perform a magnesian reduction reaction; and finally, sequentially soaking and washing the reaction product by HCl and HF, centrifuging and drying to obtain the high-reactivity silicon nano particles with mesoporous structures. The method comprises the following specific steps:
step 1: the mesoporous silica nano-particles are constructed by adopting an organic-inorganic self-assembly method and serve as an initial template. The organic-inorganic self-assembly method comprises the following steps: 50mL of deionized water, 963mg of cetyltrimethyl ammonium p-toluenesulfonate (CTATos) and 141mg of Tris (hydroxymethyl) aminomethane (Tris base) are stirred for 1h at 80 ℃, 7.75mL of tetraethyl orthosilicate (TEOS) is rapidly added into the solution, the reaction is vigorously stirred for 2h, the product is centrifugally collected and washed by deionized water and ethanol, and finally the product is calcined in air at 600 ℃ for 6h to remove the residual template, so that mesoporous silica particles with the thickness of 180nm are obtained;
step 2: fully mixing mesoporous silica particles, magnesium powder and NaCl according to the mass ratio of 1:0.9:10 by a planetary ball mill, and vacuum drying to obtain a uniform mixture;
step 3: placing the uniform mixture in a closed crucible, placing the closed crucible into a tube furnace, heating to 660-700 ℃ under the protection of argon, and preserving heat for 5 hours to perform a magnesian reduction reaction;
step 4: and sequentially carrying out pickling on the reaction product by 1M HCl and 5wt% HF, removing byproducts, sequentially centrifuging and drying to obtain the high-reactivity silicon nano particles with the mesoporous structure.
Example 1
Step 1: constructing 180n by adopting organic-inorganic self-assembly methodm mesoporous silica nanoparticles as initial templates. The organic-inorganic self-assembly method comprises the following steps: 50mL of deionized water was stirred with 963mg of cetyltrimethyl-p-toluenesulfonic acid ammonium salt (CTATos) and 141mg of Tris (hydroxymethyl) aminomethane (Tris base) at 80℃for 1 hour, 7.75mL of tetraethyl orthosilicate (TEOS) was rapidly added to the above solution, the reaction was vigorously stirred for 2 hours, the product was collected by centrifugation, washed with deionized water and ethanol, and finally the product was calcined in air at 600℃for 6 hours to remove the remaining template, to obtain pure mesoporous silica nanoparticles. The phase composition information of the product was characterized by XRD, as shown in fig. 2, showing amorphous swell peaks of silica around 23 °; the morphology structure of the mesoporous silica particles is characterized by SEM, as shown in figure 3, the mesoporous silica particles have a porous spherical structure, uniform size and a particle size of about 180nm, and have good dispersibility; in order to further understand the pore structure characteristics, the specific surface area and the pore size distribution are tested by a full-automatic specific surface area and a porosity analyzer, the results are respectively shown in fig. 4 and 5, the existence of isothermal hysteresis loops and the pore size distribution of 2-20 nm are observed, the existence of mesopores is proved, and the measured BET surface area is 371.7m 2 The average pore diameter calculated by BJH method was 7nm.
Step 2: fully mixing mesoporous silica particles, magnesium powder and NaCl according to a mass ratio of 1:0.9:10 by a planetary ball mill, adopting two zirconia balls of 0.8mm and 3mm, wherein the grading ratio is 1:2, the ball material ratio is 10:1, the ball milling rotating speed is 150r/min, the effective ball milling time is 1h, and drying to obtain a uniform mixture;
step 3: placing the uniform mixture into a closed crucible, placing the closed crucible into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon, and preserving the temperature for 5 hours to perform a magnesian reduction reaction;
step 4: and sequentially carrying out 1M HCl and 5wt% HF on the reaction product, centrifuging and drying to obtain the high-reactivity silicon nano particles with mesoporous structures. Characterization of the phase composition of the acid-washed product after magnesium reduction by XRD, the results are shown in FIG. 6 for SiO at around 23 DEG 2 The bulge peak becomes gentle, which indicates that the purity of the obtained mesoporous silicon nano-particles is good after 1M HCl and 5wt% HF are soaked;characterization of the morphology of the product by SEM, a and b in fig. 7 show the morphology of the magnesium reduction product by 1M HCl pickling, c and d in fig. 7 show the morphology of the magnesium reduction product by 1M HCl, 5wt% HF pickling in sequence, showing that the mesoporous silicon nanoparticles can well maintain their structure even after the magnesium reduction treatment at 700 ℃, and in addition, the small size of the nanoparticles is kept below 200 nm; the specific surface area and pore size distribution were measured by a full-automatic specific surface area and porosity analyzer, and the BET specific surface area was 93.0m as shown in FIGS. 8 and 9, respectively 2 /g, and the pore size distribution is concentrated within 50 nm; the exothermic properties and weight changes of the product in the oxidation weight gain reaction under air atmosphere were analyzed by a differential scanning calorimeter and a simultaneous thermogravimetry, and the results are shown in fig. 10 and 11, respectively, and DSC curves indicate that exothermic peaks, which are not possessed by commercially available nonporous silicon nanoparticles, appear near 300 ℃, due to the special surface characteristics of the porous structure. More importantly, the TG curve shows that the initial oxidation weight increase temperature of the mesoporous structure high-reactivity silicon nanoparticle is 468 ℃, and compared with the commercially available nonporous silicon nanoparticle, the initial oxidation weight increase temperature is 304 ℃, so that the reactivity of the mesoporous structure high-reactivity silicon nanoparticle is improved.
Example 2
Step 1 otherwise identical to example 1;
step 2: fully mixing mesoporous silica particles and magnesium powder according to a mass ratio of 1:0.9 by a planetary ball mill, adopting two zirconia balls of 0.8mm and 3mm, grading the balls in a ratio of 1:2, ball-milling the balls in a material ratio of 10:1 at a ball-milling rotating speed of 150r/min for 1h, and drying to obtain a uniform mixture;
step 3: placing the uniform mixture into a closed crucible, placing the closed crucible into a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under the protection of argon, and preserving the temperature for 5 hours to perform a magnesian reduction reaction;
step 4: the reaction product is sequentially soaked and washed by 1M HCl and 5wt percent HF, and is dried after centrifugation to obtain the high-reactivity silicon nano-particles with mesoporous structures. The morphology was characterized by SEM, as shown in FIG. 12, indicating that after reduction, siO 2 The spherical mesoporous structure of (C) is destroyed because of Mg and SiO 2 Is highly exothermic, without the introduction of an endothermic agent,the temperature generated may even be higher than the melting point of silicon, resulting in a substantial fusion of the reduction products.
Example 3
Other steps 1 and 2 as in example 1;
step 3: placing the uniform mixture into a closed crucible, placing the closed crucible into a tube furnace, heating to 660 ℃ at 5 ℃/min under the protection of argon, and preserving heat for 5 hours to perform a magnesian reduction reaction;
step 4: the reaction product is sequentially soaked and washed by 1M HCl and 5wt percent HF, and is dried after centrifugation to obtain the high-reactivity silicon nano-particles with mesoporous structures. FIG. 13 shows the XRD pattern of the acid-washed product after magnesium reduction in this example, in the vicinity of 23℃as compared with example 1 2 The bulge peaks became apparent, indicating that SiO was still retained in the magnesium reduction product 2 And due to unreacted SiO 2 The presence inside the particles results in HF not being able to etch the encapsulated core silica. Therefore, the completion of the magnesia reduction reaction can be effectively increased by increasing the reaction temperature, and SiO is reduced 2 Is a residue of (a).
Example 4
Step 1 otherwise identical to example 1;
step 2: grinding mesoporous silica particles, magnesium powder and NaCl in a mortar in a manual grinding and mixing mode according to a mass ratio of 1:0.9:10 for 40min to obtain a mixture;
step 3: placing the mixture into a closed crucible, placing the closed crucible into a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under the protection of argon, and preserving the temperature for 5 hours to perform a magnesian reduction reaction;
step 4: the reaction product is sequentially soaked and washed by 1M HCl and 5wt percent HF, and is dried after centrifugation to obtain the high-reactivity silicon nano-particles with mesoporous structures. FIG. 14 shows the characteristic diffraction peaks of the product resulting from the manual mixture, siO at around 23℃compared to example 1 2 The amorphous peaks are slightly inhomogeneous, especially around 28 °, 41 ° and 53 ° with respect to MgF 2 This may be due to insufficient reactant contact caused by non-uniformity of the manual mixing process. Such non-uniformity may lead to localized Mg overages or shortages and further to residual MgO and SiO 2 Of which some of the MgO reacts with HF to form MgF 2 . Thus, the mixing mode is also a key factor for improving the reaction integrity.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any modification made to the above embodiment according to the technical principles of the present invention falls within the scope of the technical solutions of the present invention.

Claims (6)

1. The preparation method of the high-reactivity silicon nano-particles with the mesoporous structure is characterized by comprising the following steps of: fully mixing mesoporous silica particles, magnesium powder and NaCl in a certain weight ratio at room temperature through ball milling, and drying to obtain a uniform mixture; placing the mixture into a closed crucible, placing the closed crucible into a tube furnace, and heating the closed crucible to a certain temperature under the protection of argon to perform a magnesia reduction reaction; and finally, pickling the reaction product to remove byproducts, centrifuging and drying to obtain the high-reactivity silicon nano particles with mesoporous structures.
2. The method of claim 1, wherein the mesoporous silica particles of 100-200 nm are built by organic-inorganic self-assembly.
3. The method of claim 1, wherein the magnesium powder is 100-200 mesh in size.
4. The method according to claim 1, wherein the mesoporous silica particles, the magnesium powder and the NaCl in a mass ratio of 1:0.9:10 are thoroughly mixed by ball milling at room temperature.
5. The method according to claim 1 or 4, wherein zirconia balls with different sizes of 0.8mm and 3mm are adopted in ball milling, the grade ratio is 1:1-1:2, and the ball-material ratio is 10:1-50:1.
6. The method of claim 1, wherein the magnesium reduction reaction is performed by heating to a certain temperature under the protection of argon, the heating rate is 5-10 ℃/min, the heating temperature is 660-700 ℃, and the temperature is kept for 5 hours.
CN202310229696.4A 2023-03-10 2023-03-10 Preparation method of high-reactivity silicon nano-particles with mesoporous structure Pending CN116177551A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116969464A (en) * 2023-09-22 2023-10-31 中石油深圳新能源研究院有限公司 Lithium ion battery negative electrode material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116969464A (en) * 2023-09-22 2023-10-31 中石油深圳新能源研究院有限公司 Lithium ion battery negative electrode material and preparation method thereof

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