CN105800615B - A kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral - Google Patents
A kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral Download PDFInfo
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- CN105800615B CN105800615B CN201610098278.6A CN201610098278A CN105800615B CN 105800615 B CN105800615 B CN 105800615B CN 201610098278 A CN201610098278 A CN 201610098278A CN 105800615 B CN105800615 B CN 105800615B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000011863 silicon-based powder Substances 0.000 title claims abstract description 27
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 22
- 239000011707 mineral Substances 0.000 title claims abstract description 22
- 150000003839 salts Chemical class 0.000 title claims abstract description 21
- 239000004411 aluminium Substances 0.000 title claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 13
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 13
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001649 dickite Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052900 illite Inorganic materials 0.000 claims description 10
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052627 muscovite Inorganic materials 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052661 anorthite Inorganic materials 0.000 claims description 4
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 4
- 229940057995 liquid paraffin Drugs 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011435 rock Substances 0.000 claims description 4
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000013528 metallic particle Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052851 sillimanite Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011031 topaz Substances 0.000 claims description 3
- 229910052853 topaz Inorganic materials 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 239000011777 magnesium Substances 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 6
- 229910021426 porous silicon Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052850 kyanite Inorganic materials 0.000 description 2
- 239000010443 kyanite Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910001569 aluminium mineral Inorganic materials 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
Abstract
The invention discloses a kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral, comprise the following steps：Natural aluminosilicate acid salt ore is fully crushed, is soaked in dilute hydrochloric acid solution and goes the removal of impurity, acquisition main component is SiO2And Al2O3Powder.Powder and metallic reducing agent powder are sufficiently mixed, are placed in atmosphere tube type stove, completely cuts off air or is calcined under inert gas shielding and reacted.Product after the completion of reaction produces porous elemental silicon powder after washing repeatedly, filter, dry.The present invention can largely reduce reaction temperature, and will react silicon source material used from SiO2Matter raw material is expanded to natural silicon aluminium acid salt mineral, effectively improves the diversity of its products therefrom microstructure, while the reducing metal in this method is also not limited to magnesium, and metallic sodium is equally applicable.
Description
Technical field
It is specifically a kind of using natural silicon aluminium acid salt mineral as original the present invention relates to a kind of preparation method of elemental silicon powder
Material, the method that porous elemental silicon powder is prepared using metallothermic reduction.
Background technology
Simple substance silicon materials are with its unique spongiform pore passage structure, special electric conductivity, larger specific surface area, compared with
High piezoresistance coefficient, special luminescence generated by light phenomenon so that it is being sensed, microelectronics, micro-optics, fuel cell and photoelectricity material
Material application aspect has the one seat of oneself.Porous silica material possesses good biological degradability and bio-compatible simultaneously
Property so that it is as the contribution for also having uniqueness in terms of the medicinal materials such as medicament slow release agent carrier and biology sensor.These advantages
Elemental silicon is set to become the object that numerous researchers competitively study.It is rotten for electrochemistry that elemental silicon main method is prepared all the time
Erosion method, but due to its preparation technology is cumbersome, involve great expense, the environmental pollution of accessory substance is serious the problems such as, while obtained product
Exist in the form of a film more and pore structure uniformity is poor, therefore develop new, easy, easily operated porous silicon powder and prepare
Method turns into one of urgent problem to be solved.
Metallothermic processes using magnesiothermy as representative is a kind of new side for preparing porous silica material occurred in recent years
Method, cheap because its technological process is simple, accessory substance is easy to handle, obtained porous silica material homogeneity preferably etc. it is excellent
Point, thus get the attention.Magnesiothermy prepares porous silicon and uses SiO more2The natural minerals of matter, such as diatomite and albumen
Stone etc., or artificial synthesized SiO2Molecular sieve is template.Silicate mineral is extremely wide in distributed in nature, it is known that silicate mine
Thing has more than 600 to plant, and constitutes about the 85% of crustal rock circle gross weight.Wherein aluminosilicate natural crystal is in silicate mineral
An important part, its main component are SiO2And Al2O3, contain the metal cations such as a small amount of sodium ion, iron ion and sulfide
Deng impurity.Natural silicon aluminium acid salt is rich in minerals, and species is various, it is common include dickite, illite, kaolinite, anorthite,
Muscovite, potassium feldspar etc..The inner molecular structure of different types of aluminosilicate mineral is different, therefore can be with as raw material using it
Obtain the porous elemental silicon powder of a variety of different pore passage structures.In addition, from different, the silicon for preparing elemental silicon using silica as raw material
SiO is removed to obtain in aluminium mineral material2Also contain a large amount of Al2O3, and these Al during elemental silicon is prepared2O3Also can remove therewith
Go, so as to create the elemental silicon powder with bigger serface and more loose structure.
The content of the invention
To overcome the shortcomings of the prior art, the present invention provides one kind and prepares porous list using natural silicon aluminium acid salt mineral
The method of matter Si powder, cost can be reduced, effectively improve its products therefrom microstructure, and silicon source material used will be reacted
From SiO2Matter raw material is expanded to natural silicon aluminium acid salt mineral, while the reducing metal in this method is also not limited to magnesium, gold
It is equally applicable to belong to sodium.
The purpose of the present invention is realized by following scheme：
A kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral is provided, comprised the following steps：
1) alumino-silicate ore is fully crushed, is soaked in 0.1~1mol/L dilute hydrochloric acid solution and go the removal of impurity, obtained
Main component is SiO2And Al2O3Powder；
2) by your ratio is 1 with metallic reducing agent massage after the product drying of step 1)：1~1：10 co-grounds make it
Be sufficiently mixed, be put into atmosphere tube type stove, completely cut off air or under inert gas shielding at 300~800 DEG C calcination 0.5~
12h, taken out after cooling；
3) product after the completion of step 2) is reacted soaks 1 in 0.1~1mol/L dilute hydrochloric acid solution or ethanol solution
~24h simultaneously carries out 5~60min of ultrasonic cleaning；Black solid after ultrasonic cleaning is immersed into distilled water, dilute HCl solution, HF successively
Pickling repeatedly, filtering are carried out in solution, porous elemental silicon is produced after drying.Purpose using distillation water washing is anti-in order to remove
The accessory substances such as sodium metasilicate, sodium aluminate in answering；The purpose of pickling is to remove MgO and Mg in reaction2The accessory substances such as Si.
A kind of described method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral, use in step 1)
Alumino-silicate ore is the siliceous rock of natural output, and its main component is SiO2And Al2O3。
A kind of described method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral, alumino-silicate ore are
One kind in dickite, illite, kaolinite, anorthite, muscovite, potassium feldspar, topaz, kyanite or sillimanite.
A kind of described method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral, use in step 2)
Metallic reducing agent is simple substance magnesium powder or surface liquid paraffin is wiped into sodium metallic particles net and with certain diameter size.
A kind of described method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral, use in step 2)
Inert gas is high pure nitrogen or high-purity argon gas.
A kind of described method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral, the ultrasound in step 3)
Cleaning refers to clean in the ultrasonic wave more than 20000 hertz.
The method that elemental silicon powder is prepared using natural aluminosilicate hydrochlorate proposed by the invention, the cost of raw material is cheap, comes
Source is extremely wide, and preparation method is simple.Because alumino-silicate ore structures are loose, impurities are easily removed, and are advantageous to directly
Using or be processed further handling.The global demand amount of elemental silicon is very big, and application is extremely wide, therefore the present invention is with extremely strong
Economic value and application prospect.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram of the porous silicon powder of embodiment 1；
Fig. 2 is the desorption curve spectrogram of nitrogen adsorption one of the porous silicon powder of embodiment 1；
Fig. 3 is the ESEM spectrogram of the porous silicon powder of embodiment 1；
Fig. 4 is the infrared vibrational spectra figure of the porous silicon powder of embodiment 1；
Embodiment
The step of preparing the preparation method of porous elemental silicon using alumino-silicate natural crystal is as follows：
1) impurity in alumino-silicate ore, such as MgO, CaO are removed：Alumino-silicate ore is fully crushed to 1000~
10000 mesh, 1~24h is soaked in 0.1~1mol/L dilute hydrochloric acid solution.Alumino-silicate ore is because its is loosely organized, in more
Poroid, oxide impurity therein is simultaneously introduced into inside mineral lattice and is easily removed.Therefore, by ore in watery hydrochloric acid fully
Immersion can remove oxide impurity therein, and acquisition main component is SiO2And Al2O3Powder.
Alumino-silicate ore is the siliceous rock of natural output, includes but are not limited to dickite, illite, kaolinite,
Anorthite, muscovite, potassium feldspar, topaz, kyanite, sillimanite etc., its main component are SiO2And Al2O3。
2) reaction of ore and metallic reducing agent：By by step 1) purification after ore drying after with a certain amount of metal
Reducing agent powder (such as metal magnesium powder, metal sodium powder) is fully ground mixing, and isolation air (refers to vacuum allowed band as 0.1
~1MPa) or be placed under inert gas (for high pure nitrogen or high-purity argon gas) protection in atmosphere tube type stove, at 300~800 DEG C
At a temperature of be calcined 0.5~12h, taken out after product is cooled down.
Wherein, metallic reducing agent is wiped only and is cut into certain for the magnesium powder of 100~300 mesh or by surface liquid paraffin
A certain kind in the sodium metallic particles of diameter dimension.
3) preparation of elemental silicon：By step 2) react after the completion of product 0.1~1mol/L dilute hydrochloric acid solution or second
5~60min of ultrasonic cleaning is carried out in 1~24h of alcohol solution for soaking and ultrasonic wave more than 20000 hertz.It will be cleaned by ultrasonic
Black solid afterwards immerses in distilled water, dilute HCl solution, HF solution successively carries out pickling repeatedly, centrifugation, filtering, will with filter paper
Centrifugation channel closure produces porous elemental silicon after 50~150 DEG C of 8~12h of scope inside holding are dried.
The watery hydrochloric acid used is that commercially available concentrated hydrochloric acid is obtained by mixing according to a certain volume with absolute ethyl alcohol.
The use of the purpose of distillation water washing is to remove the sodium metasilicate in reaction, the by-product such as sodium aluminate in preparation process
Thing；The purpose of pickling is to remove MgO and Mg in reaction2The accessory substances such as Si.
Using this method prepare porous elemental silicon can be widely applied to sensing, microelectronics, micro-optics, fuel cell and
Photoelectric material etc..
The present invention is further illustrated with reference to embodiment.
Embodiment one：Using dickite as raw material
1) take dickite to crush, 1h is soaked in 1mol/L dilute hydrochloric acid solution, acquisition main component is SiO2And Al2O3
Powder；
2) with magnesium powder according to 1 after step 1) product dickite powder is dried：6 mixed in molar ratio, it is put into 650 DEG C of atmosphere
In tube furnace, fully calcined 4h under vacuum environment, taken out after cooling.
3) step 2) gains are immersed to magnetic agitation 10h in 0.5mol/L dilute hydrochloric acid solution, outwell after supernatant from
The heart.Pour into after distilled water is cleaned by ultrasonic 10min and centrifuge, wash repeatedly.Channel closure will be centrifuged with filter paper, is placed in 100 DEG C of drying 10h
After obtain porous elemental silicon.
Embodiment two：Using dickite as raw material
1) take dickite to crush, 1h is soaked in 1mol/L dilute hydrochloric acid solution, acquisition main component is SiO2And Al2O3
Powder；
2) with magnesium powder according to 1 after step 1) product dickite powder is dried：10 mixed in molar ratio, it is put into 650 DEG C of gas
In atmosphere tube furnace, fully calcined 4h under vacuum environment, taken out after cooling.
3) step 2) gains are immersed to magnetic agitation 24h in 0.1mol/L dilute hydrochloric acid solution, outwell after supernatant from
The heart.Pour into after distilled water is cleaned by ultrasonic 5min and centrifuge, wash repeatedly.Channel closure will be centrifuged with filter paper, is placed in 100 DEG C of drying 10h
After obtain porous elemental silicon.
Embodiment three：Using illite as raw material
1) take illite to crush, gained powder is soaked into 24h in 0.1mol/L dilute hydrochloric acid solution, it is therein to remove
Impurity.
2) with magnesium powder according to 1 after step 1) product illite powder is dried：1 mixed in molar ratio, in the protection of argon gas
Under be put into calcination 0.5h in 800 DEG C of atmosphere tube type stoves, taken out after cooling.
3) taken out after step 2) product is cooled down, 1h is soaked in 1mol/L dilute hydrochloric acid solution, after being cleaned by ultrasonic 15min
Centrifugation, centrifuged 3 times with distillation water washing.Channel closure will be centrifuged with filter paper, porous elemental silicon is obtained after being placed in 80 DEG C of drying 12h.
Example IV：Using illite as raw material
1) take illite to crush, gained powder is soaked into 24h in 0.1mol/L dilute hydrochloric acid solution, it is therein to remove
Impurity.
2) with magnesium powder according to 1 after step 1) product illite powder is dried：1 mixed in molar ratio, in the protection of argon gas
Under be put into calcination 0.5h in 800 DEG C of atmosphere tube type stoves, taken out after cooling.
3) taken out after step 2) product is cooled down, 1h is soaked in 1mol/L dilute hydrochloric acid solution, after being cleaned by ultrasonic 15min
Centrifugation, centrifuged 3 times with distillation water washing.Channel closure will be centrifuged with filter paper, porous elemental silicon is obtained after being placed in 80 DEG C of drying 12h.
Embodiment five：Using muscovite as raw material
1) take muscovite to crush, gained powder is soaked into 16h in 0.1mol/L dilute hydrochloric acid solution, it is therein to remove
Impurity.
2) metallic sodium block is weighed, wipes surface liquid paraffin away, graininess of the diameter in 3mm or so is cut into scissors, will walk
It is rapid 1) and both metallic sodium particles presses 1：4 mixed in molar ratio are put into porcelain boat, and are put it into atmosphere tube type stove.Using vacuum
Pumping is taken to 0.85MPa.System is put into 300 DEG C of stoves, fully calcined 12h under vacuum environment.
3) 1h is soaked after step 2) gains are cooled down in ethanol solution, is centrifuged after being cleaned by ultrasonic 15min.Centrifugation is produced
Dilute hydrochloric acid solution of the thing in 1mol/L soaks 1h, and product is finally soaked 30min by centrifugation in HF acid after being cleaned by ultrasonic 10min,
And centrifuged after being cleaned by ultrasonic 20min, produce porous elemental silicon after being placed in 150 DEG C of drying 8h.
Claims (6)
- A kind of 1. method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral, it is characterised in that including following step Suddenly：1) alumino-silicate ore is fully crushed, is soaked in 0.1~1mol/L dilute hydrochloric acid solution and go the removal of impurity, obtained main Composition is SiO2And Al2O3Powder；2) by your ratio is 1 with metallic reducing agent massage after the product drying of step 1)：1~1：10 co-grounds make its abundant Mixing, is put into atmosphere tube type stove, completely cuts off air or is calcined 0.5~12h at 300~800 DEG C under inert gas shielding, cold But take out afterwards；3) product after the completion of step 2) is reacted soaks 1~24h in 0.1~1mol/L dilute hydrochloric acid solution or ethanol solution And carry out 5~60min of ultrasonic cleaning；Black solid after ultrasonic cleaning is immersed into distilled water, dilute HCl solution, HF solution successively Middle progress pickling, filtering repeatedly, produces porous elemental silicon after drying.
- 2. a kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral as claimed in claim 1, it is special Sign is that the alumino-silicate ore used in the step 1) is the siliceous rock of natural output, and its main component is SiO2With Al2O3。
- 3. a kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral as claimed in claim 2, it is special Sign is that the alumino-silicate ore is dickite, illite, kaolinite, anorthite, muscovite, potassium feldspar, topaz, aquamaine One kind in stone or sillimanite.
- 4. a kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral as claimed in claim 1, it is special Sign is that the metallic reducing agent used in the step 2) is simple substance magnesium powder or wipes net by surface liquid paraffin and have certain The sodium metallic particles of diameter dimension.
- 5. a kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral as claimed in claim 1, it is special Sign is that the inert gas used in the step 2) is high pure nitrogen or high-purity argon gas.
- 6. a kind of method that porous elemental silicon powder is prepared using natural silicon aluminium acid salt mineral as claimed in claim 1, it is special Sign is that the ultrasonic cleaning in the step 3) refers to clean in the ultrasonic wave more than 20000 hertz.
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