CN117230459A - In-situ preparation method and device of silicon-based nano-micron material - Google Patents
In-situ preparation method and device of silicon-based nano-micron material Download PDFInfo
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- CN117230459A CN117230459A CN202311500134.5A CN202311500134A CN117230459A CN 117230459 A CN117230459 A CN 117230459A CN 202311500134 A CN202311500134 A CN 202311500134A CN 117230459 A CN117230459 A CN 117230459A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 110
- 239000010703 silicon Substances 0.000 title claims abstract description 110
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 80
- 238000003756 stirring Methods 0.000 claims abstract description 62
- 230000009467 reduction Effects 0.000 claims abstract description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims description 73
- 238000005406 washing Methods 0.000 claims description 69
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 53
- 229910052749 magnesium Inorganic materials 0.000 claims description 46
- 239000011777 magnesium Substances 0.000 claims description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 43
- 239000000460 chlorine Substances 0.000 claims description 37
- 229910052801 chlorine Inorganic materials 0.000 claims description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 35
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 33
- 230000007704 transition Effects 0.000 claims description 32
- 238000005554 pickling Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000001569 carbon dioxide Substances 0.000 claims description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 19
- 230000007246 mechanism Effects 0.000 claims description 18
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 claims description 17
- 229910021338 magnesium silicide Inorganic materials 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 229910021487 silica fume Inorganic materials 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 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 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000005192 partition Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 36
- 239000002184 metal Substances 0.000 abstract description 36
- 238000004519 manufacturing process Methods 0.000 abstract description 24
- 239000000843 powder Substances 0.000 abstract description 20
- 239000002360 explosive Substances 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 description 63
- 239000007788 liquid Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- -1 at this time Inorganic materials 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Classifications
-
- 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 provides an in-situ preparation method and device of a silicon-based nano-micron material, and relates to the field of silicon-based nano-micron materials. The in-situ preparation method comprises the steps of uniformly mixing metal chloride and a silicon-containing precursor, placing the mixture in an electrolytic tank, heating the mixture until the metal chloride forms molten salt, and then electrifying to start electrolysis to generate liquid metal, wherein the liquid metal is positioned on the surface of the molten salt; and mixing the liquid metal on the surface of the molten salt with the silicon-containing precursor through stirring, and performing in-situ thermal reduction to obtain a reduction product. The method can solve the problems of complicated steps and the use of inflammable and explosive metal powder in the production process of the existing silicon-based nano-micro material, so as to realize the efficient, low-cost and large-scale safe preparation of the silicon-based nano-micro material.
Description
Technical Field
The invention relates to the field of silicon-based nano-micron materials, in particular to an in-situ preparation method and device of a silicon-based nano-micron material.
Background
The silicon-based nano-micron material mainly comprises nano-micron scale simple substance silicon, silicon oxide, silicon carbide, metal silicide and the like, and various composites thereof. The materials have excellent performances such as good lithium storage, wave absorption, thermal stability and/or acid and alkali corrosion resistance, and thus have great application in the fields of new energy, powder metallurgy, wave absorption coating electronic elements, photovoltaics and the like, and have important economic values.
Various methods for preparing the silicon-based nano-micron material are available, such as a mechanical ball milling method, a chemical vapor deposition method, a plasma evaporation condensation method and the like. One common synthesis method is a metallothermic reduction method, namely, metal powder with strong reducibility such as magnesium, aluminum and the like is utilized to react with silicon-containing precursors (such as silicon dioxide, clay minerals and the like) of fine particles under the high-temperature condition, so that the silicon dioxide is reduced into elemental silicon or the reaction is converted into other substances. However, because the metal fine powder is inflammable and explosive and has high price, the production safety requirement of the silicon-based nano material is extremely high, a special fireproof and explosion-proof production factory is needed, and the production cost is further increased.
In order to reduce the production cost and improve the production safety, the preparation process of the reduced metal powder can be properly modified, and then the reduced metal powder is coupled with the subsequent thermal reduction reaction process of the silicon-containing precursor in situ, so that flammable and explosive metal powder is not required to be used as a precursor of the reaction. The whole production process can realize high-efficiency, closed-loop, clean and safe production, and finally realize low-cost and large-scale safe preparation of the silicon-based nano material.
Disclosure of Invention
The invention aims at providing an in-situ preparation method and an in-situ preparation device for a silicon-based nano-micron material, which can solve the problems of complicated steps and the use of inflammable and explosive metal powder in the existing silicon-based nano-micron material production process, so as to realize the efficient, low-cost and large-scale safe preparation of the silicon-based nano-micron material.
Embodiments of the invention may be implemented as follows:
in a first aspect, the present invention provides a method for in situ preparation of a silicon-based nano-micro material, comprising:
uniformly mixing metal chloride and a silicon-containing precursor, placing the mixture in an electrolytic tank, heating the mixture until the metal chloride forms molten salt, and then electrifying to start liquid metal generated by electrolysis, wherein the liquid metal is positioned on the surface of the molten salt; mixing the liquid metal on the surface of the molten salt with a silicon-containing precursor by stirring and performing in-situ thermal reduction to obtain a reduction product;
the silicon-containing precursor is selected from one or more of activated clay, silica micropowder, silica fume, montmorillonite, kaolinite, halloysite, palygorskite, white talc, black talc and white mica.
In an alternative embodiment, the metal chloride comprises a melt for forming a molten salt electrolyte and an electrolyte for electrolytically generating liquid metal, the melt is selected from one or more of lithium chloride, potassium chloride, calcium chloride, sodium chloride and barium chloride, the electrolyte is selected from one or more of aluminum chloride and magnesium chloride, the molar ratio of the melt, the electrolyte and the silicon-containing precursor is 10:5:1-20:5:1, the electrolysis is performed in an inert atmosphere, the electrolysis and the in-situ thermal reduction are performed simultaneously, and the temperature is 600-1300 ℃.
In an alternative embodiment, the electrolytic cell is provided with a liquid metal outlet, the liquid metal generated by molten salt electrolysis is discharged from the liquid metal outlet and enters a receiving bin on one side of the electrolytic cell, and the liquid metal is returned to the bottom of the electrolytic cell through a circulating pump communicated to the receiving bin and the bottom of the electrolytic cell.
In an alternative embodiment, after the in situ thermal reduction is completed, further comprising discharging the reduction product into a transition bin for cooling; when the metal chloride is magnesium chloride, the reduction product contains magnesium silicide as a byproduct, and the method further comprises vacuumizing the transition bin and then preserving heat at 650-900 ℃ to decompose the magnesium silicide to form magnesium simple substance, wherein the magnesium simple substance is melted and evaporated to form magnesium vapor before the reduction product is cooled;
or alternatively;
and before cooling the reduction product, introducing carbon dioxide into the transition bin, and then preserving heat at 700-900 ℃ to decompose the byproduct magnesium silicide into magnesium simple substance and silicon, wherein the magnesium simple substance reacts with the carbon dioxide to generate magnesium oxide and carbon, and the carbon is coated on the surface of the silicon in an amorphous state.
In an alternative embodiment, after said cooling, further comprising washing said reduced product with water and acid; the acid for pickling is at least one selected from hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid.
In an alternative embodiment, the chlorine generated by electrolysis enters a multistage acid making bin through an air duct to prepare hydrochloric acid, the prepared hydrochloric acid is used for pickling, and a heating device and an ultraviolet lamp are arranged in the multistage acid making bin.
In a second aspect, the present invention provides an in-situ preparation apparatus for implementing the in-situ preparation method for a silicon-based nano-micron material according to any one of the preceding embodiments, which comprises an electrolytic cell, wherein a temperature control mechanism, an inert gas mechanism, a stirring assembly, a cathode chamber, an anode chamber and a separator for separating the cathode chamber and the anode chamber are arranged in the electrolytic cell; the stirring assembly comprises a stirring rod body, stirring paddles, a transmission device and a motor, wherein the stirring paddles are arranged on the stirring rod body and positioned in the electrolytic tank, the motor is connected with the transmission device, and the transmission device is connected with the stirring rod body.
In an alternative embodiment, the in-situ preparation device of the silicon-based nano-micro material further comprises a receiving bin, a transition bin, a washing bin and a pickling bin, wherein a liquid metal outlet and a chlorine outlet are formed in the side wall of the electrolytic tank, a liquid metal inlet and a reduction product outlet are formed in the bottom of the electrolytic tank, a circulating pump is arranged outside the receiving bin, an inlet of the circulating pump is communicated with the receiving bin, an outlet of the circulating pump is communicated with the liquid metal inlet, a reduction product outlet is communicated with the transition bin, the transition bin is communicated with the washing bin, and the washing bin is communicated with the pickling bin.
In an alternative embodiment, the in-situ preparation device of the silicon-based nano-micro material further comprises a multi-stage acid making bin, wherein a chlorine pipeline, a heating device, an ultraviolet lamp and a vacuum pump are arranged in the multi-stage acid making bin, the chlorine pipeline is communicated with the chlorine outlet and is inserted into the multi-stage acid making bin, the vacuum pump is arranged on the chlorine pipeline, the ultraviolet lamp is arranged at the top of the multi-stage acid making bin, the heating device is arranged in the multi-stage acid making bin, and a discharge hole of the multi-stage acid making bin is communicated with the acid washing bin.
The beneficial effects of the embodiment of the application include, for example:
according to the in-situ preparation method of the silicon-based nano-micro material, the metal chloride is utilized to melt and electrolyze to generate the liquid metal, the liquid metal and the silicon-containing precursor are directly mixed in the electrolytic tank and subjected to thermal reduction reaction, in-situ thermal reduction of the silicon-containing precursor can be realized in the process, as the molten salt system is larger, different molten salts have different viscosities in melting, wherein the magnesium chloride and the calcium chloride have larger viscosities in melting, and the liquid metal magnesium and the silicon nano-particles are not easy to gather in moving in fluid with larger viscosities. The raw materials of the application are metal chloride and silicon-containing precursor substances, so that the nano-micron metal powder required by the traditional metal thermal reduction reaction is avoided, and the whole process is protected by inert gas, thus greatly improving the safety and economy of the whole production process. The matched device has simple structure and is easy to realize.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural diagram of an in-situ preparation device for silicon-based nano-micron materials provided by the application;
FIG. 2 is a front view of an electrolytic cell in an in situ preparation device of a silicon-based nano-micro material provided by the application;
fig. 3 is a side cross-sectional view of an electrolytic cell in an in-situ preparation device of a silicon-based nano-micro material provided by the application.
Icon: an in-situ preparation device of the 100-silicon-based nano-micron material; 110-an electrolytic cell; a 111-cathode chamber; 1111-cathode; 112-an anode chamber; 1121-an anode; 113-a separator; 114-liquid metal outlet; 115-chlorine outlet; 116-liquid metal inlet; 117-reduction product outlet; 118-a stirring assembly; 119-a movable discharge plate; 120-a material receiving bin; 121-a circulation pump; 130-a transition bin; 140-washing the bin; 141-a water filling port; 142-a water wash outlet; 150-pickling the bin; 151-acid injection port; 152-pickling solution outlet; 160-a multistage acid making bin; 161-chlorine line; 162-ultraviolet lamp; 163-vacuum pump; 170-a stirring mechanism; 180-inert atmosphere mechanism.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. 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.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the present invention, it should be noted that, if the terms "upper", "lower", "inner", "outer", and the like indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, or the azimuth or the positional relationship in which the inventive product is conventionally put in use, it is merely for convenience of describing the present invention and simplifying the description, and it is not indicated or implied that the apparatus or element referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus it should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, if any, are used merely for distinguishing between descriptions and not for indicating or implying a relative importance.
It should be noted that the features of the embodiments of the present invention may be combined with each other without conflict.
The invention provides an in-situ preparation method of a silicon-based nano-micron material, which comprises the following steps:
s1, electrolyzing to form liquid metal and chlorine.
And uniformly mixing the metal chloride and the silicon-containing precursor, placing the mixture in an electrolytic tank 110, heating the mixture to 600-1300 ℃ in an inert atmosphere (argon or helium), melting the metal chloride to form molten salt, and then electrifying (the tank voltage is 2.0-5.4V) to start electrolysis for 0.5-24 h, wherein liquid metal is generated in the electrolysis process, and the liquid metal is positioned on the surface of the molten salt.
The metal chloride comprises a melt for forming molten salt electrolyte and an electrolyte for generating liquid metal through electrolysis, wherein the mole ratio of the melt to the electrolyte to the silicon-containing precursor is 10:5:1-20:5:1; the melt is selected from one or more of lithium chloride, potassium chloride, calcium chloride, sodium chloride and barium chloride, and the electrolyte is selected from one or more of aluminum chloride and magnesium chloride.
The siliceous precursor includes, but is not limited to, one or more of activated clay, silica fume, montmorillonite, kaolinite, halloysite, palygorskite, talc, black talc, and muscovite. Wherein the silicon micropowder is quartz powder; the silica fume is industrial smelting fume, is silica, and has the same chemical formula, different structure and source and finer silica fume. If the montmorillonite is a montmorillonite adsorbed with crystal violet, the montmorillonite needs to be carbonized for 2-4 hours at 500-700 ℃ in advance.
Because the melting point of the silicon-containing precursor (about 800-1750 ℃) is higher than that of the metal chloride, when the temperature is raised to 600-1300 ℃ in an inert atmosphere, the metal chloride is melted to form molten salt, and the silicon-containing precursor is not melted and still is in a powder shape or a particle shape. In the reaction system, the density of the common mixed molten salt electrolyte is 1.6-1.8 g/cm 3 The density of the silicon-containing precursor is 2.5-2.8 g/cm 3 While the density of the liquid magnesium is 1.58g/cm 3 . At this time, a silicon-containing precursor having a high specific gravity may be located at the bottom of the electrolytic cell 110. And the molten salt is electrolyzed to form liquid metal simple substance and chlorine, and the liquid metal simple substance is positioned on the upper surface of the molten salt.
In the application, the electrolysis of magnesium chloride can be realized by controlling the electrolysis temperature and the bath voltage, liquid magnesium metal is generated, when the electrolysis temperature and the bath voltage exceed the scope of the application, the electrolysis temperature is too high, the current efficiency is reduced, the evaporation loss of the melt is increased, the heat loss is increased, and the operation condition is deteriorated. The cell voltage is a plurality of components and is greatly different from the decomposition voltage, and generally the cell voltage is higher than the decomposition voltage, but since the decomposition voltage of magnesium chloride is lower than the decomposition voltage of other electrolytes, the voltage is generally controlled to be the decomposition voltage of magnesium chloride. The actual decomposition voltage can be calculated according to the actual situation.
S2, preparing acid by using chlorine.
Chlorine generated by electrolysis enters a multi-stage acid making bin 160 filled with water through an air duct, and a heating device and an ultraviolet lamp 162 are arranged in the multi-stage acid making bin 160; the heating device is used for heating a solution in the multistage acid making bin 160, the ultraviolet lamp 162 is used for providing illumination for the multistage acid making bin 160, the multistage acid making bin 160 is a plurality of mutually independent bin bodies, water is filled in each bin body, the heating device and the ultraviolet lamp 162 are arranged in each bin body, hydrochloric acid and hypochlorous acid can be generated by the reaction of chlorine and water, part of hypochlorous acid can be decomposed into hydrochloric acid and oxygen by heating and illumination, gas generated in the reaction process of the chlorine and the water is sequentially introduced into the bin bodies at the rear, and the efficiency of preparing the hydrochloric acid by the chlorine can be effectively improved by the multistage acid making and the heating and illumination.
Wherein the ultraviolet lamp 162 adopts a wavelength of 180-360 nm and a radiation intensity of 1.00-100 mW/cm in an irradiation distance of 10-120 cm 2 The irradiation time is 10-50 min, and the solution is heated to 35-70 ℃ by a heating device.
The hydrochloric acid produced in the present application can be used in the pickling in the subsequent step S5.
S3, in-situ thermal reduction.
Because the liquid metal at the top cannot be contacted with the silicon-containing precursor at the bottom, the stirring method can realize that the liquid metal at the top cannot be mixed with the silicon-containing precursor at the bottom, and the stirring method comprises the modes of stirring blades, an aeration device, ultrasonic vibration and the like. The liquid metal and the silicon-containing precursor are subjected to in-situ thermal reduction at the bottom of the electrolytic cell 110 to obtain a reduced product.
In-situ thermal reduction and electrolysis are carried out simultaneously, and the application is only for facilitating understanding, and the in-situ thermal reduction and electrolysis are divided into two steps, but are actually carried out simultaneously, namely, the generated liquid metal is subjected to in-situ thermal reduction after being mixed and contacted with a silicon-containing precursor in the process of raising the temperature to 600-1300 ℃ and carrying out electrolysis for 0.5-24 h.
S4, decomposing and cooling the reduction product.
After the in-situ thermal reduction is finished, introducing the reduction product into the transition bin 130, and if the metal chloride is magnesium chloride, the reduction product contains a byproduct magnesium silicide, and at the moment, vacuumizing the transition bin 130 for thermal decomposition or introducing carbon dioxide to remove the byproduct. The decomposition or conversion of metal silicide (e.g., magnesium silicide) to silicon and magnesium vapor may be promoted by evacuation or introduction of carbon dioxide to increase yield.
Specifically, if a continuous vacuumizing mode is adopted, heat is preserved for 1-5 hours at 650-900 ℃, at this time, magnesium silicide is decomposed into magnesium simple substance at a high temperature in vacuum, the magnesium simple substance is melted at a high temperature (more than 650 ℃), and evaporation is started to form magnesium steam, in the application, a transition bin 130 is communicated with a material receiving bin 120 to recover the magnesium steam; preferably, the temperature for decomposing magnesium silicide by vacuumizing is 700-750 ℃, and the reaction time is 2-3 hours.
If a proper amount of carbon dioxide is introduced into the bin, and the temperature is kept at 700-900 ℃ for 1-3 hours, at this time, magnesium silicide is decomposed into magnesium simple substance and silicon, and then the magnesium simple substance reacts with the carbon dioxide to generate magnesium oxide and carbon, wherein the carbon is coated on the surface of the silicon in an amorphous state. Preferably, the reaction temperature of carbon dioxide and magnesium silicide is 720-780 ℃ and the reaction time is 1.5-2.5 h.
In order to avoid carbon monoxide generation, carbon dioxide and inert gas are simultaneously introduced when carbon dioxide is introduced, and the mass ratio of the inert gas to the carbon dioxide is controlled to be 3-5:1, so that the reaction speed of the carbon dioxide and the magnesium silicide is controlled, and excessive carbon generated in a certain time is avoided, and the carbon dioxide and the carbon react to generate the carbon monoxide. And after the decomposition is finished, cooling the reduction product to 20-60 ℃ by adopting air cooling or water cooling.
S5, water washing and acid washing.
The water washing is used for washing and recovering the metal inorganic salt, and the water washing liquid can be recycled through treatment such as evaporation and the like. The solid is processed by acid washing and the like to obtain the target silicon-based nano-micron material, and the acid washing liquid can be recycled after being processed by evaporation, crystallization and the like.
In the application, the acid washing comprises the step of washing for 0.1-10 h by adopting acid with the volume concentration of 1-20%. Wherein, the acid washing is divided into two steps, the acid washing is carried out for 3 to 5 hours by adopting first acid with volume concentration of 1 to 10 percent, and then the acid washing is carried out for 0.2 to 1 h by adopting second acid with volume concentration of 1 to 1.6 percent; the first acid and the second acid are different and are respectively and independently selected from at least one of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid.
The method sequentially performs acid washing by using two different acids with different concentrations, wherein the first acid (such as hydrochloric acid) is used for removing metal oxides (such as MgO) in the reduction product, and the second acid (such as hydrofluoric acid) is used for removing oxide layers on the surfaces of silicon particles.
The hydrochloric acid prepared in the step S2 can be used for pickling, and oxides generated by the thermal reduction reaction of the metal can be removed when the hydrochloric acid is used for pickling, so that metal chloride is obtained, and the obtained metal chloride can be further electrolyzed to generate metal reducing powder and chlorine, so that circulation is formed.
According to the application, the metal reducing agent and chlorine are prepared by electrolyzing metal chloride, the prepared metal reducing agent reacts with a silicon-containing precursor in situ, so that a silicon-based nano-micron material is prepared, the chlorine is used for preparing hydrochloric acid, the prepared hydrochloric acid is used for removing oxides generated by metal thermal reduction reaction, vacuum pumping or carbon dioxide charging of a transition bin 130 can be realized to decompose metal silicide generated by in-situ thermal reduction into silicon and magnesium steam, the transition bin 130 is communicated with a pipeline of a circulating pump 121 to recycle magnesium steam, the magnesium steam is recycled, salt-containing wastewater obtained by washing a metal reduction reaction product can be further evaporated and concentrated for recycling, and metal chloride obtained by acid washing can be further electrolyzed to generate metal reducing powder and chlorine. The production process can realize efficient, green, safe and closed-loop production of the silicon-based nano-material, obviously reduces the production cost of the silicon-based nano-micron material, and has wide industrialized prospect. The raw materials of the application are metal chloride and a silicon-containing precursor, so that the nano-micron metal powder required by the traditional metal thermal reduction reaction is avoided, and the whole process is protected by inert gas, thus greatly improving the safety and economy of the whole production process.
In addition, referring to fig. 1, 2 and 3, the present application further provides an in-situ preparation apparatus 100 for silicon-based nano-micron materials, which is used for implementing the in-situ preparation method of silicon-based nano-micron materials, and comprises an electrolytic tank 110, a material receiving bin 120, a transition bin 130, a water washing bin 140, an acid washing bin 150 and a multi-stage acid making bin 160.
A cathode chamber 111, an anode chamber 112 and a separator 113 for separating the cathode chamber 111 and the anode chamber 112 are arranged in the electrolytic tank 110, a liquid metal outlet 114 and a chlorine outlet 115 are arranged on the side wall of the electrolytic tank 110, and a liquid metal inlet 116 and a reduction product outlet 117 are arranged on the bottom of the electrolytic tank 110.
The height of the separator 113 can be adjusted to effectively distinguish between the cathode and the anode while preventing the metal droplets from moving from the cathode to the anode.
The electrolytic bath 110 is internally provided with a stirring assembly 118 for stirring materials in the electrolytic bath 110, the stirring assembly 118 comprises a stirring rod body, stirring paddles, a transmission device and a motor, the stirring paddles are arranged on the stirring rod body and are positioned in the electrolytic bath 110, the motor is connected with the transmission device, and the transmission device is connected with the stirring rod body. In the application, the stirring assembly 118 can be used for mixing the liquid metal circulated from the material receiving bin 120 to the bottom of the electrolytic tank 110 with the precursor at the bottom, so as to realize the purpose of in-situ reaction.
The upper end of the electrolytic cell 110 is provided with an inert atmosphere mechanism 180, and the inert atmosphere mechanism 180 is used for providing inert gas into the electrolytic cell 110 so that electrolysis is performed under inert atmosphere. In the application, a movable discharging plate 119 and a molten salt liquid level monitoring probe (not shown) are also arranged in the electrolytic tank 110, the movable discharging plate 119 can move up and down relative to the electrolytic tank 110, a gap between the movable discharging plate 119 and the top of the electrolytic tank 110 encloses a liquid metal outlet 114, the molten salt liquid level monitoring probe is connected with the movable discharging plate 119, the molten salt liquid level monitoring probe can detect the liquid level of molten salt, and the movable discharging plate 119 is controlled to move up and down, so that the position of the liquid metal outlet 114 is adjusted, and the liquid metal obtained by electrolyzing the electrolytic metal chloride in the electrolytic tank 110 can be conveniently discharged from the liquid metal outlet 114.
The recycling pump 121 is arranged outside the receiving bin 120, an inlet of the recycling pump 121 is communicated with the liquid metal outlet 114, and an outlet of the recycling pump 121 is communicated with the liquid metal inlet 116. Specifically, in this embodiment, the liquid metal enters the receiving bin 120, then flows back to the bottom of the electrolytic tank 110 through the circulating pump 121, and contacts and reacts with a part of the silicon-containing precursor at the bottom of the electrolytic tank 110, but the density of magnesium droplets is smaller, the magnesium droplets continue to float up to reach the liquid level again, then enter the receiving bin 120 and enter the bottom of the electrolytic tank 110 through the circulating pump 121 again, and the repeated process realizes the reduction reaction. The stirring assembly 118 of the present application is configured to mix as much of the liquid metal recycled to the bottom as possible with the silicon-containing precursor. The stirring blades of the stirring assembly 118 are elongated, and extend from the middle of the bottom of the electrolytic tank 110 to a position close to the liquid metal inlet 116, and the liquid metal circularly discharged from the liquid metal inlet 116 is driven to rotate by the stirring blades in time after entering the electrolytic tank 110, so that better mixing is realized.
The transition bin 130 is used for cooling the reduction product, a temperature control mechanism is arranged in the transition bin 130, and the reduction product outlet 117 is communicated with the transition bin 130.
The washing bin 140 is used for washing the cooled reduction product, the washing bin 140 is provided with a stirring mechanism 170, an inert atmosphere mechanism 180 and a washing liquid outlet 142, the transition bin 130 is communicated with the washing bin 140, the washing bin 140 is also provided with a water filling port 141, and the washing liquid discharged from the washing liquid outlet 142 can be evaporated, concentrated and recycled to recover inorganic salt.
The pickling bin 150 is used for further pickling the washed solids, the washing bin 140 is communicated with the pickling bin 150, the pickling bin 150 is provided with a stirring mechanism 170, an inert atmosphere mechanism 180, an acid injection port 151 and a pickling solution outlet 152, and metal chlorides in the pickling solution discharged from the pickling solution can be further electrolyzed to generate metal reducing powder and chlorine.
The multistage acid making bin 160 is internally provided with a chlorine pipeline 161, a heating device, an ultraviolet lamp 162 and a vacuum pump 163, wherein the chlorine pipeline 161 is communicated with the chlorine outlet 115 and is inserted into the multistage acid making bin 160, the vacuum pump 163 is arranged on the chlorine pipeline 161, the ultraviolet lamp 162 is arranged at the top of the multistage acid making bin 160, and the heating device is arranged in the multistage acid making bin 160. The outlet of the multistage acid making bin 160 is communicated with the acid injection port 151 of the acid washing bin 150, and is used for providing hydrochloric acid for the acid washing bin 150.
It should be understood that the stirring device, the heating device and the inert atmosphere mechanism 180 are all existing mechanisms, for example, the stirring device may be configured by a stirring shaft, a stirring blade and a stirring motor, and the inert atmosphere mechanism 180 is implemented by introducing an inert atmosphere into the bin. The inert atmosphere mechanisms 180 of the present application may be connected to each other via a pipeline to provide an inert atmosphere in a circulating manner. The stirring device, the heating device, the inert atmosphere mechanism 180 and other structures in the present application are all existing structures, and various optional structures can be provided as long as the above functions can be achieved.
The application designs matched equipment for in-situ preparation of a silicon-based nano-micron material, which comprises an electrolytic tank 110, a transition bin 130, a washing bin 140, a multistage acid making bin 160 and a pickling bin 150. The set of equipment can effectively realize in-situ, green and closed-loop production of the silicon-based nano-micron material. Wherein, for the electrolytic tank 110, the partition 113 is adopted to separate the anode 1121 area from the cathode 1111 area, so that the problem of low reaction efficiency caused by the re-reaction of the generated metal and chlorine is avoided; the bottom of the electrolytic bath 110 is provided with stirring paddles, so that the generated liquid metal and the silicon-containing precursor can be fully and uniformly mixed and reacted; in addition, part of the liquid metal floats to the molten salt liquid level because the density is less than that of the molten salt, and part of the liquid metal sublimates in the electrolysis process, and the part of the liquid metal is discharged from the liquid metal outlet 114 into the receiving bin 120, so that the liquid metal can be directly injected into the bottom of the electrolytic tank 110 by the circulating pump 121, and further, the full reaction of the liquid metal and the silicon-containing precursor is ensured. After the reaction is finished, the obtained mixture is sent to a transition bin 130, on one hand, metal silicide generated in the reaction process is decomposed into silicon and magnesium steam by vacuumizing or introducing a proper amount of carbon dioxide gas and the like, the yield is improved, and meanwhile, the magnesium steam is collected and sent to a metal receiving bin 120 of an electrolytic tank 110 for recycling; on the one hand, the mixture is cooled down and then sent to a water washing bin 140 to remove inorganic salt, and the inorganic salt is recovered through evaporation concentration and recycled. The product after water washing is sent to a pickling bin 150 for pickling under inert atmosphere, then solid-liquid separation is carried out, liquid is collected, and metal chloride in the liquid is further crystallized and collected for electrolysis raw materials; and collecting the solid, namely the target silicon-based nano-micron material. For the multistage acid making bin 160, a temperature control device and an ultraviolet lamp 162 are designed in the bin wall and the bin, and the efficiency of preparing hydrochloric acid by chlorine gas is improved by controlling the temperature and the illumination intensity in the bin and assisting in multistage reaction.
The technical scheme of the application will be further described in the following with reference to examples.
Example 1
(1) And taking 35% of sodium chloride and 65% of lithium chloride by mass as a melt for forming electrolyte molten salt, taking anhydrous magnesium chloride as an electrolyte to be electrolyzed, drying and dehydrating sodium chloride and lithium chloride until the weight content of water is less than 0.1%, mixing the dried and dehydrated sodium chloride, the dried and dehydrated lithium chloride, the anhydrous magnesium chloride and the dried and dehydrated silica fume, wherein the mass ratio of the anhydrous magnesium chloride to the silica fume is 5:2, the granularity is above 100 meshes, and putting the mixture into an electrolytic tank 110 to be heated to 710 ℃ after uniform mixing, and at the moment, the sodium chloride, the lithium chloride and the anhydrous magnesium chloride all form the molten salt.
(2) Graphite is adopted as the anode 1121 material, stainless steel is adopted as the cathode 1111 material, the bath pressure is controlled to be 3.8V to carry out molten salt anhydrous magnesium chloride electrolysis 3 h, and the stirring component 118 provides stirring action in the bath while magnesium is produced by electrolysis, and as the stirring component 118 is spiral, magnesium liquid drops can be contacted with silica fume to carry out metallothermic reduction reaction, and a reduction product is obtained. The liquid metal generated during the electrolysis is discharged from the liquid metal outlet 114 and enters the receiving bin 120 at one side of the electrolysis cell 110, and the liquid metal is returned to the bottom of the electrolysis cell 110 by the circulation pump 121.
(3) After the reaction is finished, the reduction product is discharged into a transition bin 130, the mixed gas of argon and carbon dioxide (the volume ratio is 5:1) is introduced into the transition bin 130, the temperature is kept at 710 ℃ for 2 h, the carbon dioxide reacts with silicon carbide on the surface of the reduction product to produce magnesium oxide, silicon, carbon and magnesium steam, the magnesium steam returns into a material receiving bin 120, and returns into an electrolytic tank 110 through a circulating pump 121 to continue the reaction. After the decomposition reaction is finished, the material body is cooled to 40 ℃ by adopting a water cooling mode.
(4) And (3) discharging the decomposed and cooled reduction product into a washing bin 140, washing with water, drying and recovering the discharged washing liquid to obtain a mixture of sodium chloride and lithium chloride, stirring and washing with hydrochloric acid with the volume concentration of 7% for 3 h, drying the discharged washing liquid in HCl airflow to obtain anhydrous magnesium chloride, washing the solid with 1% hydrofluoric acid for 15 min, washing with water to be neutral, and drying to obtain the nano silicon material. The hydrofluoric acid pickling solution is added into lime for neutralization, so that calcium fluoride can be obtained as a byproduct.
(5) Introducing chlorine generated by electrolysis into a multistage acid making bin 160, controlling the temperature of the acid solution to be 45 ℃, controlling the irradiation distance of an ultraviolet lamp 162 at 100 cm, controlling the wavelength to be 320 nm and the irradiation intensity to be 40 mW/cm 2 The irradiation time was 30 minutes, and the produced hydrochloric acid was returned to step (4) for pickling.
Example 2
(1) Anhydrous magnesium chloride, sodium chloride, potassium chloride and calcium chloride (the mole fraction is 10 percent: 50 percent: 20 percent) are added into an electrolytic tank 110 to be heated to 720 ℃, and argon is introduced into the tank for protection, wherein the mass ratio of the anhydrous magnesium chloride to the activated clay is 5:2.
(2) The electrolytic tank 110 adopts graphite as an anode 1121 material, stainless steel as a cathode 1111 material, the tank pressure is controlled to be 4.0V to carry out molten salt anhydrous magnesium chloride electrolysis 3 h, and the stirring assembly 118 provides stirring action in the tank when magnesium is produced by electrolysis, and as the stirring assembly 118 is spiral, molten magnesium and activated clay can be subjected to in-situ metallothermic reduction reaction in the electrolytic tank 110, and the temperature is kept for 3 h, so that a reduction product is obtained. The liquid metal generated during the electrolysis is discharged from the liquid metal outlet 114 and enters the receiving bin 120 at one side of the electrolysis cell 110, and the liquid metal is returned to the bottom of the electrolysis cell 110 by the circulation pump 121.
(3) After the reaction is finished, the reduction product is discharged into the transition bin 130, a vacuum pump 163 at the top of the starting device continuously vacuumizes and heats to 800 ℃ and keeps the temperature at 1 h, magnesium silicide generated in the thermal reduction process is decomposed into silicon and magnesium steam, the magnesium steam returns to the receiving bin 120, and returns to the electrolytic tank 110 through a circulating pump 121 to continue the reaction. After the decomposition reaction is finished, the material body is cooled to 40 ℃ by adopting a water cooling mode.
(4) And (3) discharging the decomposed and cooled reduction product into a washing bin 140, washing with water, drying and recovering the discharged washing liquid to obtain a mixture of sodium chloride, potassium chloride and calcium chloride, stirring and washing with 5.2% hydrochloric acid to obtain 3h, drying the discharged washing liquid in HCl gas flow to obtain anhydrous magnesium chloride, washing the solid with 2% hydrofluoric acid for 10 min, washing with water to be neutral, and drying to obtain the nano silicon material. The hydrofluoric acid pickling solution is added into lime for neutralization, so that calcium fluoride can be obtained as a byproduct.
(5) Introducing chlorine generated by electrolysis into a multistage acid making bin 160, controlling the temperature of the acid solution to be 50 ℃, controlling the irradiation distance of an ultraviolet lamp 162 at 60 cm, controlling the wavelength to be 280 nm and the irradiation intensity to be 20 mW/cm 2 The irradiation time was 45 minutes and the hydrochloric acid produced was returned to step (4) for pickling.
Example 3
(1) Firstly, drying and dehydrating electrolyte molten salt until the weight content of water is less than 0.1%, uniformly mixing the electrolyte molten salt, anhydrous magnesium chloride and montmorillonite which adsorbs crystal violet and is carbonized for 3 hours at 600 ℃ (the mass ratio of the anhydrous magnesium chloride to the montmorillonite which adsorbs crystal violet is 6:1), and then putting the mixture into an electrolytic tank 110, wherein the electrolyte molten salt is lithium chloride and calcium chloride, and the mass percentages of the electrolyte molten salt and the calcium chloride are respectively 22% and 78%.
(2) Graphite is adopted as an anode 1121 material, stainless steel is adopted as a cathode 1111 material, the temperature is raised to 720 ℃, the bath pressure is controlled to be 3.6V for molten salt electrolysis 3 h, and the stirring component 118 provides stirring action in the bath while magnesium is produced by electrolysis, and as the stirring component 118 is spiral, the stirring component 118 can perform metal thermal reduction reaction on magnesium drops and montmorillonite in situ, and the temperature is kept for 2 h, so that a reduction product is obtained. The liquid metal generated during the electrolysis is discharged from the liquid metal outlet 114 and enters the receiving bin 120 at one side of the electrolysis cell 110, and the liquid metal is returned to the bottom of the electrolysis cell 110 by the circulation pump 121.
(3) After the reaction is finished, the reduction product is discharged into a transition bin 130, the mixed gas of argon and carbon dioxide (the volume ratio is 3:1) is introduced into the transition bin 130, the temperature is kept at 700 ℃ for 2 h, the carbon dioxide reacts with silicon carbide on the surface of the reduction product to produce magnesium oxide, silicon, carbon and magnesium steam, the magnesium steam returns into a material receiving bin 120, and returns into an electrolytic tank 110 through a circulating pump 121 to continue the reaction. After the decomposition reaction is finished, the material body is cooled to 40 ℃ by adopting a water cooling mode.
(4) And (3) discharging the decomposed and cooled reduction product into a washing bin 140, washing with water, drying and recovering the discharged washing liquid to obtain a mixture of lithium chloride and calcium chloride, stirring and washing with hydrochloric acid with the volume concentration of 4% for 3 h, drying the discharged washing liquid in HCl airflow to obtain anhydrous magnesium chloride, washing the solid with 1% hydrofluoric acid for 15 min, washing with water to be neutral and drying, washing the solid with water to be neutral and drying to obtain the carbon-coated silicon/silicon carbide micro-nano material. The hydrofluoric acid pickling solution is added into lime for neutralization, so that calcium fluoride can be obtained as a byproduct.
(5) Introducing chlorine generated by electrolysis into a multistage acid making bin 160, controlling the temperature of the acid solution to be 60 ℃, controlling the irradiation distance of an ultraviolet lamp 162 at 70 cm, controlling the wavelength to be 300 nm and the irradiation intensity to be 35 mW/cm 2 The irradiation time was 40 minutes, and the produced hydrochloric acid was returned to step (4) for pickling.
Comparative example 1
In the comparative example, magnesium powder is directly contacted with silica fume to carry out metallothermic reduction reaction, the reaction temperature is 710 ℃, the reaction time is 3 hours, and then the reaction product is washed with water and acid according to the step (4) in the example 1 to obtain the silicon-based nano-micro material.
Because magnesium powder is directly adopted as a reducing agent, the reduced metal powder is inflammable and explosive and has high price, so that the production safety requirement of the silicon-based nano-micro material is extremely high, a special fireproof and explosion-proof production factory is required, the safety and environmental protection requirements are extremely high, and the production cost and the safety risk are greatly increased.
Comparative example 2
This comparative example is substantially the same as example 1 except that the temperature at the time of electrolysis and the cell voltage are different from example 1, and in this comparative example, the temperature at the time of electrolysis is 1600℃and the cell voltage is 8V. The electrolysis temperature is too high, the load of the electrolytic tank is too large, and the electrolyte is evaporated, so that the production cannot be realized.
Comparative example 3
This comparative example is substantially the same as example 1 except that the stirring manner at the time of electrolysis and thermal reduction in this comparative example is a conventional horizontal stirring shaft. Because the conventional stirring shaft is only used for stirring through stirring blades horizontally distributed at one end of the shaft, the uniform mixing of melt and other materials in the vertical direction cannot be well realized, the silicon-containing precursor is difficult to contact with liquid metal, the reaction efficiency is low, and the reaction is incomplete.
Comparative example 4
This comparative example is substantially the same as example 1 except that the step of introducing carbon dioxide into the transition bin 130 in example 1 is omitted and the reduction product is cooled immediately after being discharged into the transition bin 130. When the reduction product is led into an acid washing bin for acid washing, magnesium silicide reacts with acid to generate a large amount of silane gas and strongly releases heat, so that the safety problem is easily caused, the temperature in the bin is rapidly increased, the silicon particles are secondarily agglomerated, and the performance of the silicon particles is influenced.
Experimental example
The particle size, specific surface area and yield of the silicon-based nano-micro materials obtained in examples 1 to 3 and comparative examples 1 to 4 were examined.
The detection method comprises the following steps:
(1) The particle size is calculated from the XRD pattern by the Shelle formula.
Instrument model: rigaku D/Max-2000 diffractometer
Test conditions: cu ka target (λ=0.154 nm), tube current 10 mA, tube voltage 40 kV, scan speed 10 °/min -1 Scanning range is 3-80 degrees (2 theta).
The testing method comprises the following steps: filling the powder sample into the groove of the sample rack, and flattening to be measured. The data obtained by the experiment are processed by MDI Jade 6.5 analysis software, and the diffraction pattern is sequentially subjected to smoothing, back buckling, peak searching and phase searching. The grain size is calculated by the scherrer formula.
(2) The specific surface area is calculated by BET method
Instrument model: ASAP2020 specific surface area and pore size analyzer (Micromeritics Instrument Corporation, usa).
The testing method comprises the following steps: the sample was placed in the instrument at 200℃for vacuum degassing for 12h and then transferred to the test station at 200℃for in situ degassing 4 h. The specific surface area was calculated by the multipoint Brunauer-Emmett-Teller (BET) method, and the total pore volume was estimated as the nitrogen adsorption amount at a relative pressure of 0.97.
The test results are shown in Table 1.
TABLE 1 statistical tables of performance test results for silicon-based nano-micro materials obtained in different examples
It can be seen from the above table that, since magnesium chloride is electrolyzed to produce liquid magnesium metal by melting and then electrolyzing the metal chloride in the application, and other metal chlorides take on the role of electrolyte molten salt, the system of the molten salt is larger, and different molten salts have different viscosities when melted, and the liquid magnesium metal is not easy to gather when moving in fluid with larger viscosity, that is, the nano-size of crystal grains is smaller than that of the magnesium thermal reduction mode in comparative example 1 by carrying out in-situ thermal reduction on the liquid magnesium metal and silicon-containing precursor. In addition, since the liquid metal outlet 114 is provided in the application, the sublimated magnesium in the electrolytic tank 110 can be collected and returned to the bottom of the electrolytic tank 110 through the circulating pump 121, the utilization of the liquid metal magnesium can be fully realized, meanwhile, the liquid metal entering the bottom of the electrolytic tank 110 can react with the silicon-containing precursor at the bottom of the electrolytic tank 110 after entering the electrolytic tank 110, and meanwhile, part of the liquid metal can move upwards, so that the mixing effect of molten salt, the liquid metal magnesium and the silicon-containing precursor in the electrolytic tank 110 is enhanced, and the reaction of the liquid metal magnesium and the silicon-containing precursor is more facilitated.
As can be seen from the data of comparative example 1, the grain size of the product is larger and the yield is lower because the magnesium powder is in direct contact with the silica fume, the reaction is too severe, the heat release causes particle agglomeration, the local magnesium excess causes the generation of magnesium silicide, and the yield is reduced.
As can be seen from the data of comparative example 2, the reaction cannot proceed under this parameter.
As can be seen from the data of comparative example 3, the reduction of the silicon-containing precursor species was incomplete due to insufficient agitation.
As can be seen from the data of comparative example 4, the large amount of heat released from the acid washing increases the particle size, and after the magnesium silicide is formed, it is not converted into a simple substance of silicon or the like by carbon dioxide, and the yield is still further improved.
In summary, according to the in-situ preparation method of the silicon-based nano-micro material provided by the application, the metal chloride is utilized to melt and electrolyze to generate the liquid metal, and the liquid metal and the silicon-containing precursor are directly mixed in the electrolytic tank 110 and subjected to the thermal reduction reaction, in-situ thermal reduction of the silicon-containing precursor can be realized in the process, and as the molten salt system is larger, different molten salts have different viscosities in melting, and the liquid metal magnesium is not easy to aggregate in moving in the fluid with larger viscosity. In addition, the application directly selects metal chloride as the raw material instead of conventional metal simple substance powder, thereby solving the problems of complicated steps and flammable and explosive metal powder in the production process of the existing silicon-based nano-micro material, and realizing the efficient, low-cost and large-scale safe preparation of the silicon-based nano-micro material. In addition, the chlorine generated by electrolysis in the application is used for preparing hydrochloric acid, and then is used for removing oxides generated by the metal thermal reduction reaction, and the obtained metal chloride can be further electrolyzed to generate metal reducing powder and chlorine. Wherein, the salt-containing wastewater obtained by washing the metal reduction reaction product can be further evaporated, concentrated and recycled. The production process can realize efficient, green, safe and closed-loop production of the silicon-based nano-material, obviously reduces the production cost of the silicon-based nano-micron material, and has wide industrialized prospect. The raw materials of the application are metal chloride and silicon-containing precursor substances, so that the nano-micron metal powder required by the traditional metal thermal reduction reaction is avoided, and the whole process is protected by inert gas, thus greatly improving the safety and economy of the whole production process. The matched device has simple structure and is easy to realize.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. An in-situ preparation method of a silicon-based nano-micron material is characterized by comprising the following steps: uniformly mixing metal chloride and a silicon-containing precursor, placing the mixture in an electrolytic tank, heating the mixture until the metal chloride forms molten salt, and then electrifying to start liquid metal generated by electrolysis, wherein the liquid metal is positioned on the surface of the molten salt; mixing the liquid metal on the surface of the molten salt with a silicon-containing precursor by stirring and performing in-situ thermal reduction to obtain a reduction product;
the silicon-containing precursor is selected from one or more of activated clay, silica micropowder, silica fume, montmorillonite, kaolinite, halloysite, palygorskite, white talc, black talc and white mica.
2. The in-situ preparation method of a silicon-based nano-micro material according to claim 1, wherein the metal chloride comprises a melt for forming electrolyte molten salt and an electrolyte for generating liquid metal through electrolysis, the melt is one or more selected from lithium chloride, potassium chloride, calcium chloride, sodium chloride and barium chloride, the electrolyte is one or more selected from aluminum chloride and magnesium chloride, the molar ratio of the melt, the electrolyte and the silicon-containing precursor is 10:5:1-20:5:1, the electrolysis is carried out in an inert atmosphere, the electrolysis and the in-situ thermal reduction are carried out simultaneously, and the temperature is 600-1300 ℃.
3. The in-situ preparation method of a silicon-based nano-micro material according to claim 1, wherein the electrolytic cell is provided with a liquid metal outlet, liquid metal generated by molten salt electrolysis is discharged from the liquid metal outlet and enters a receiving bin at one side of the electrolytic cell, and the liquid metal is returned to the bottom of the electrolytic cell through a circulating pump communicated to the receiving bin and the bottom of the electrolytic cell.
4. The in situ preparation method of silicon-based nano-micro material according to claim 1, further comprising discharging the reduced product into a transition bin for cooling after the in situ thermal reduction is completed; when the metal chloride is magnesium chloride, the reduction product contains magnesium silicide as a byproduct, and the method further comprises vacuumizing the transition bin and then preserving heat at 650-900 ℃ to decompose the magnesium silicide to form magnesium simple substance, wherein the magnesium simple substance is melted and evaporated to form magnesium vapor before the reduction product is cooled;
or alternatively;
and before cooling the reduction product, introducing carbon dioxide into the transition bin, and then preserving heat at 700-900 ℃ to decompose magnesium silicide into magnesium simple substance and silicon, wherein the magnesium simple substance reacts with the carbon dioxide to generate magnesium oxide and carbon, and the carbon is coated on the surface of the silicon in an amorphous state.
5. The in situ preparation method of a silicon-based nano-micro material according to claim 4, further comprising water washing and acid washing the reduction product after the cooling; the acid for pickling is at least one selected from hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid.
6. The in-situ preparation method of the silicon-based nano-micron material according to claim 1, wherein chlorine generated by electrolysis enters a multistage acid preparation bin through an air duct to prepare hydrochloric acid, the prepared hydrochloric acid is used for pickling, and a heating device and an ultraviolet lamp are arranged in the multistage acid preparation bin.
7. An in-situ preparation device for a silicon-based nano-micron material for realizing the in-situ preparation method of the silicon-based nano-micron material as claimed in any one of claims 1 to 6, which is characterized by comprising an electrolytic cell, wherein a temperature control mechanism, an inert gas mechanism, a stirring assembly, a cathode chamber, an anode chamber and a partition plate for separating the cathode chamber and the anode chamber are arranged in the electrolytic cell;
the stirring assembly comprises a stirring rod body, stirring paddles, a transmission device and a motor, wherein the stirring paddles are arranged on the stirring rod body and positioned in the electrolytic tank, the motor is connected with the transmission device, and the transmission device is connected with the stirring rod body.
8. The in-situ preparation device of the silicon-based nano-micron material according to claim 7, further comprising a receiving bin, a transition bin, a washing bin and a pickling bin, wherein a liquid metal outlet and a chlorine outlet are formed in the side wall of the electrolytic tank, a liquid metal inlet and a reduction product outlet are formed in the bottom of the electrolytic tank, a circulating pump is arranged outside the receiving bin, an inlet of the circulating pump is communicated with the receiving bin, an outlet of the circulating pump is communicated with the liquid metal inlet, a reduction product outlet is communicated with the transition bin, the transition bin is communicated with the washing bin, and the washing bin is communicated with the pickling bin.
9. The in-situ preparation device of the silicon-based nano-micron material according to claim 8, further comprising a multi-stage acid making bin, wherein a chlorine pipeline, a heating device, an ultraviolet lamp and a vacuum pump are arranged in the multi-stage acid making bin, the chlorine pipeline is communicated with the chlorine outlet and is inserted into the multi-stage acid making bin, the vacuum pump is arranged on the chlorine pipeline, the ultraviolet lamp is arranged at the top of the multi-stage acid making bin, the heating device is arranged in the multi-stage acid making bin, and a discharge port of the multi-stage acid making bin is communicated with the acid washing bin.
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