CN108083282A - A kind of preparation method of three-dimensional porous silicon materials - Google Patents
A kind of preparation method of three-dimensional porous silicon materials Download PDFInfo
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- CN108083282A CN108083282A CN201711443464.XA CN201711443464A CN108083282A CN 108083282 A CN108083282 A CN 108083282A CN 201711443464 A CN201711443464 A CN 201711443464A CN 108083282 A CN108083282 A CN 108083282A
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- porous silicon
- dimensional porous
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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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/30—Particle morphology extending in three dimensions
Abstract
A kind of preparation method of three-dimensional porous silicon materials is carried out frit reaction or solid-state diffusion reaction to obtain alloy by pore creating material and silicon source of low boiling point metal, the pore creating material in alloy is then deviate from physical method, that is, obtains three-dimensional porous silicon materials.The present invention using low boiling point metal as pore creating material together with silicon source reaction bonded after, recycle physical method removing low boiling point metal, obtain three-dimensional porous silicon materials, it is compared to chemical corrosion method, not only any chemicals, silicon materials is not utilized not to lose yet, it is and at low cost, environmentally friendly, it is also convenient for large-scale batch production, it is a kind of environmentally protective production technology, non-pollution discharge problem, and Posterior circle uses the pore creating material used through processing, considerably reduces production cost.
Description
Technical field
The present invention relates to vacuum metallurgy and field of porous materials, specifically a kind of preparations of three-dimensional porous silicon materials
Method.
Background technology
Silicon as lithium ion battery negative material there is high power capacity to store up lithium characteristic, but there are volume expansions during lithium ion insertion
It is excessive, cause rupture and dusting in charge and discharge process, the cyclical stability of battery is poor.It is to solve by silicon materials three-dimensional porousization
The important channel that silicon materials are applied in lithium ion battery.
Silicon materials have excellent chemical stability and biological safety.The silicon materials of three-dimensional porous structure are carried in drug
There is particular application value in terms of body, catalytic carrier, particular filter.
Three-dimensional porous silicon can be prepared on silicon chip using electrochemical corrosion or dyeing chemistry caustic solution, but corrode
Depth is limited, typically not greater than some tens of pm.Silica flour is handled using dyeing chemistry caustic solution, three-dimensional porous silicon can be obtained
Powder, such as Application No. CN2015101481713, CN2016103727089, CN2016111851143, CN2016111614218
The disclosure of that such as patent document.But porous material is obtained using etch, to consume substantial amounts of hydrofluoric acid, nitric acid
Harmful chemicals are waited, silicon materials also will largely lose in itself, of high cost, not environmentally, be not easy scale of mass production.
The patent of invention of Application No. CN2014102764132 discloses a kind of preparation side of porous silicon-carbon composite
Method, it is mentioned that the preparation method of porous silicon, first prepares silicon-active metal alloy, then again with the alloy and liquid phase pore-creating
Agent is reacted, and porous silicon nano material is obtained to remove active metal, then with the porous silicon nano material of hydrofluoric acid clean to go
Silicon；Liquid phase pore creating material is to be reacted with active metal without the solution with simple substance pasc reaction wherein；That is, from
Basically, which actually obtains porous silicon also with the method for chemical attack, so inevitably
There are it is above-mentioned the defects of；
The patent of invention of Application No. CN2015109222810 proposes a kind of removal alloying method, is first total to silica flour and magnesium powder
Alloy powder is fired into, then alloy powder melts to resistant alloy element magnesium together with metal chloride fused salt, then by product
Chloride is removed with salt acid soak, nano-structure porous silicon is obtained after washing drying.This method is substantially also to go to close by corrosion
Aurification, there are it is similary the shortcomings that；
The patent of invention of Application No. 2016105470638 discloses a kind of method that former Smelting magnesium prepares porous silicon simultaneously,
In disclose and redox reaction occurs at high temperature using magnesium vapor and purified silicious earth obtain porous silicon, but actually by
Entire chapter file is read, preparing that porous silicon must also wash in an acidic solution just can be with, and this washing process is actually also
The process of demagging is gone in chemical attack；
The patent of invention of Application No. 2016110399407 discloses a kind of Porous Silicon Electrode material, wherein describing magnesium powder
It is obtained with carrying out magnesium thermit after the mixture compression moulding of mesoporous silicon oxide；Just not saying its mesoporous silicon oxide utilized with
General silica is different, it is internal itself have it is substantial amounts of mesoporous, and after magnesium thermit has been carried out, specification the
It also refers to wash away magnesia in 0008 section, obtains the porous silica material of macropore, that is to say, that prepared using magnesium thermit more
Hole silicon materials, it is also desirable to carry out chemical attack to remove magnesia therein；
The patent of invention of Application No. 2016104453917 discloses a kind of cellular three-dimensional porous silicon materials, first prepares nanometer
The monodisperse spherical silicon dioxide granule of scale, reduction obtains crude product at high temperature after then it is mixed with magnesium powder, then will
Product is obtained by the reaction in crude product in dilute hydrochloric acid；Its essence is then rotten with chemistry also with magnesium powder high temperature reduction silica
The method of erosion obtains porous silica material, and equally there is also the defects of chemical attack；
The patent of invention of Application No. CN2017102423470 discloses a kind of method of nanoporous silicon materials, first by aluminium, copper
Uniform alloy melt is fused by electromagnetic induction with silicon raw material, the alloy that quenching is then obtained by quick solidification equipment is thin
Band, then remove aluminium and copper with salpeter solution selective corrosion, obtain nanoporous silicon materials.This method is also to go to close by corrosion
Aurification method obtains porous silicon, equally exists disadvantages mentioned above.
In conclusion the porous silicon prepared in the prior art, no matter using magnesium-reduced or magnesium thermit or other sides
Method has finally all used chemical corrosion method and has removed metallic element therein, so as to obtain porous silica material, and once used
Chemical attack then certainly exists and consumes a large amount of harmful chemicals, and silicon materials also will largely lose in itself, of high cost, not environmentally, no
The problem of easy scale of mass production.
The content of the invention
To solve to remove present in metallic element therein using chemical corrosion method when the prior art produces porous silicon
It is of high cost, not environmentally, be not easy the problem of scale of mass production, the present invention provides a kind of preparation method of three-dimensional porous silicon materials,
Its use low boiling point metal as pore creating material together with silicon source reaction bonded after, recycle physical method removing low boiling point gold
Belong to get to three-dimensional porous silicon materials, chemical corrosion method is compared to, not only without utilizing any chemicals, silicon materials
Do not lose, and it is at low cost, environmentally friendly, it is also convenient for large-scale batch production.
The used to solve above-mentioned technical problem technical solution of the present invention is：A kind of preparation side of three-dimensional porous silicon materials
Method carries out frit reaction or solid-state diffusion reaction to obtain alloy, then with physics by pore creating material and silicon source of low boiling point metal
Pore creating material in method abjection alloy, that is, obtain three-dimensional porous silicon materials.
In the present invention, the low boiling point metal is less than the easy evaporated metal of elemental silicon fusing point for boiling point.
In the present invention, the low boiling point metal for magnesium, lithium, or both mixture.
In the present invention, the silicon source is simple substance silica flour, certainly, in order to keep the purity of porous silicon and quality, the silicon of selection
The content of silicon is not lower than 90% in source.
In the present invention, the pore creating material carries out frit reaction with silicon source or solid-state diffusion reaction is referred to obtaining alloy, will
Frit reaction or solid-state diffusion reaction are carried out after the two mixing at 500-800 DEG C, so that the two combines to form alloy.
In the present invention, the physical method is deviate from pore creating material therein and is referred to, will be made with the temperature for being less than elemental silicon fusing point
Hole agent evaporation, so as to form three-dimensional porous silicon materials.
In the present invention, the physical method deviates from pore creating material therein and refers to vacuum distillation abjection pore creating material.
The mechanism of the present invention is that low boiling point metal is selected to be blended in accordance with the appropriate ratio with silicon source very as pore creating material
Frit reaction or solid-state diffusion reaction obtain uniform alloy under appropriate high temperature in empty stove, then raise temperature and evaporate low boiling point
Metal pore creating material, remaining is three-dimensional porous silicon or three-dimensional porous silicon alloy；Its concrete operations is：
1）Silicon source and pore creating material powder are mixed according to a certain percentage, is put into vacuum or protective atmosphere, is heated to 500-
It 800 DEG C, keeps the temperature until forming uniform alloy.；
2）The uniform alloy of acquisition is heated to 800-1100 DEG C of heat preservation under vacuum, until pore creating material metal steam distributes
Finish, what is left is three-dimensional porous silicon materials.
3）The three-dimensional porous silicon materials obtained are to form block-like, and three-dimensional porous silica powder can be obtained by crushing.
In the present invention, the granularity of silicon source used is no more than 80 mesh, and preferred size is no more than 150 mesh；
When silicon source is simple substance silica flour, and pore creating material is magnesium, lithium or both mixture, the 25-90% of both pore creating material accounts for gross mass,
Remaining is simple substance silica flour, and the temperature for forming alloy is preferably 500-800 DEG C, further preferably 550-700 DEG C, further excellent
Elect 600-650 DEG C as, when evaporating pore creating material, vacuum degree 10-4It is preferably 10 between Pa-100Pa-3Pa-10-1Pa；
Further, in the present invention, when simple substance silica flour is selected to do silicon source, during by the use of magnesium as pore creating material, the granularity of magnesium powder grain is not
More than 80 mesh, further preferred granularity is no more than 150 mesh；
Preferred simple substance silica flour weight ratio is 10-40%, and the weight ratio of magnesium powder is 60-90%；Further preferred simple substance silica flour weight
Amount is than being 65-70% for the weight ratio of 30-35%, magnesium powder；
Temperature when forming alloy is preferably 550-700 DEG C, is still more preferably 600-650 DEG C；
Further, in the present invention, when simple substance silica flour is selected to do silicon source, during by the use of lithium as pore creating material, lithium is preferably using particle
Shape recommends grain size 1-10mm, preferable particle size 2-5mm；
It is preferred that the weight ratio of simple substance silica flour is 40-75%, the weight ratio of lithium is 25-60%；Further preferred simple substance silica flour weight
Than being 30-40% for the weight ratio of 60-70%, lithium；
Temperature when forming alloy is preferably 550-700 DEG C, is still more preferably 600-650 DEG C.
When evaporating pore creating material, vacuum degree 10-4It is preferably 10 between Pa-100Pa-3Pa-10-1Pa；
Advantageous effect：The present invention using low boiling point metal as pore creating material together with silicon source reaction bonded after, recycling physics
Method removes low boiling point metal to get to three-dimensional porous silicon materials, chemical corrosion method is compared to, not only not using any
Chemicals, silicon materials also do not lose, and at low cost, environmentally friendly, are also convenient for large-scale batch production, are a kind of environmentally protective
Posterior circle uses through processing for production technology, non-pollution discharge problem, and the pore creating material used, considerably reduces production
Cost.
Description of the drawings
Fig. 1 is the stereoscan photograph of the three-dimensional porous silicon of present invention gained.
Specific embodiment
Technical scheme is clearly and completely described below in conjunction with specific embodiment, it is clear that described
Embodiment be only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ability
Domain those of ordinary skill all other embodiments obtained without making creative work, belong to guarantor of the present invention
The scope of shield.
A kind of preparation method of three-dimensional porous silicon materials, using low boiling point metal as pore creating material and silicon source carry out frit reaction or
Solid-state diffusion is reacted to obtain alloy, and the pore creating material in alloy is then deviate from physical method, that is, obtains three-dimensional porous silicon materials；
Low boiling point metal described above is less than the metal of elemental silicon fusing point for boiling point, is preferably two kinds of metals of magnesium, lithium or more
Arbitrary proportion mixture；
Silicon source described above is simple substance silica flour, and certainly, in order to keep the purity of porous silicon and quality, silicon contains in the silicon source of selection
Amount not lower than 90%；
Pore creating material described above carries out frit reaction with silicon source or solid-state diffusion reaction is referred to obtaining alloy, after the two is mixed
Frit reaction or solid-state diffusion reaction are carried out at 500-800 DEG C, so that the two combines to form alloy；
Physical method described above is deviate from pore creating material therein and is referred to, is evaporated pore creating material with the temperature for being less than elemental silicon fusing point,
So as to form three-dimensional porous silicon materials, the preferential mode for selecting vacuum distillation deviates from pore creating material.
Specific examples below is carried out using magnesium, lithium and simple substance silica flour as raw material below, technical scheme is done
It is further elucidated above.
Embodiment 1
A kind of preparation method of three-dimensional porous silicon materials, concrete operations are as follows：
1）The simple substance silica flour 30g that grain size is less than 150 mesh is weighed, grain size is less than the magnesium powder 70g of 120 mesh, two kinds of powder is mixed equal
It is even, it is fitted into aluminium oxide porcelain boat；
2）By the porcelain boat equipped with mixed-powder be put into vacuum tube furnace heating district center, seal boiler tube, be evacuated to 1Pa with
Under, argon gas is then charged with to 0.1MPa；
3）Electrified regulation is heated to 600 DEG C, when heat preservation 6 is small with 10 degrees/min of firing rate, forms the two fully fusion
Alloy；
4）It is evacuated to vacuum degree and reaches below 1Pa, be heated to 1000 DEG C with 10 degrees/min of speed, when heat preservation 6 is small, make it
In magnesium evaporating completely；
5）Stop heating, be cooled to room temperature, take out porcelain boat, what the inside obtained is exactly three-dimensional porous silicon.
Embodiment 2
A kind of preparation method of three-dimensional porous silicon materials, concrete operations are as follows：
1）The simple substance silica flour 60g that grain size is less than 80 mesh is weighed, grain size is the lithium grain 40g of 3mm, and two kinds of materials are uniformly mixed, and is filled
Enter in aluminium oxide porcelain boat；
2）By the porcelain boat equipped with mixed-powder be put into vacuum tube furnace heating district center, seal boiler tube, be evacuated to 1Pa with
Under, argon gas is then charged with to 0.1MPa；
3）Electrified regulation is heated to 700 DEG C, when heat preservation 4 is small with 10 degrees/min of firing rate, forms the two fully fusion
Alloy；
4）It is evacuated to vacuum degree and reaches below 1Pa, be heated to 1050 DEG C with 10 degrees/min of speed, when heat preservation 6 is small, make it
In magnesium evaporating completely；
5）Stop heating, be cooled to room temperature, take out porcelain boat, what the inside obtained is exactly three-dimensional porous silicon.
Embodiment 3
A kind of preparation method of three-dimensional porous silicon materials, concrete operations are as follows：
1）Grain size is weighed less than 150 mesh simple substance silica flour 45g, grain size is less than magnesium powder 50g, the lithium grain 10g of grain size 1mm of 120 mesh, will
Three kinds of materials are uniformly mixed, and are fitted into aluminium oxide porcelain boat；
2）By the porcelain boat equipped with mixed-powder be put into vacuum tube furnace heating district center, seal boiler tube, be evacuated to 1Pa with
Under, argon gas is then charged with to 0.1MPa；
3）Electrified regulation is heated to 650 DEG C, when heat preservation 5 is small with 10 degrees/min of firing rate, forms the two fully fusion
Alloy；
4）It is evacuated to vacuum degree and reaches below 1Pa, be heated to 1050 DEG C with 10 degrees/min of speed, when heat preservation 6 is small, make it
In magnesium evaporating completely；
5）Stop heating, be cooled to room temperature, take out porcelain boat, what the inside obtained is exactly three-dimensional porous silicon.
Product made from embodiment 3 is observed into its structure as shown in Figure 1 under scanning electron microscope.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requirement rather than above description limit, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.Any reference numeral in claim should not be considered as to the involved claim of limitation.
Moreover, it will be appreciated that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
Using specification as an entirety, the technical solutions in each embodiment can also be properly combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (7)
1. a kind of preparation method of three-dimensional porous silicon materials, it is characterised in that：It is carried out by pore creating material and silicon source of low boiling point metal
Frit reaction or solid-state diffusion reaction are then deviate from the pore creating material in alloy with physical method, that is, obtained three-dimensional to obtain alloy
Porous silica material.
2. a kind of preparation method of three-dimensional porous silicon materials according to claim 1, it is characterised in that：The low boiling point gold
Belong to the easy evaporated metal for being less than elemental silicon fusing point for boiling point.
3. a kind of preparation method of three-dimensional porous silicon materials according to claim 1 or 2, it is characterised in that：The low boiling
Point metal is the mixture of magnesium, lithium or both.
4. a kind of preparation method of three-dimensional porous silicon materials according to claim 1, it is characterised in that：The silicon source is single
Matter silica flour.
5. a kind of preparation method of three-dimensional porous silicon materials according to claim 1, it is characterised in that：The pore creating material with
Silicon source carries out frit reaction or solid-state diffusion reaction is referred to obtaining alloy, is melted after the two is mixed at 500-800 DEG C
Reaction or solid-state diffusion reaction, so that the two combines to form alloy.
6. a kind of preparation method of three-dimensional porous silicon materials according to claim 1, it is characterised in that：The physical method
Deviate from pore creating material therein to refer to, evaporated pore creating material with the temperature for being less than elemental silicon fusing point, so as to form three-dimensional porous silicon material
Material.
7. a kind of preparation method of three-dimensional porous silicon materials according to claim 1 or 6, it is characterised in that：The physics
Method deviates from pore creating material therein and refers to vacuum distillation abjection pore creating material.
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