CN104928704A - Method for preparing monatomic silicon with electrolytic deposition in ionic liquid - Google Patents
Method for preparing monatomic silicon with electrolytic deposition in ionic liquid Download PDFInfo
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- CN104928704A CN104928704A CN201510346035.5A CN201510346035A CN104928704A CN 104928704 A CN104928704 A CN 104928704A CN 201510346035 A CN201510346035 A CN 201510346035A CN 104928704 A CN104928704 A CN 104928704A
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Abstract
The invention discloses a method for preparing monatomic silicon with electrolytic deposition in ionic liquid with an aim to achieve the purpose to have silicon deposited electrically at one step with substances of SiCl4 and the like under the action of direct current by taking the ionic liquid as media. The method is characterized in that one or two mixed systems in the ionic liquid of imidazoles, pyridines, piperidines, quaternary ammoniums and quaternary phosphoniums are taken as the media, the SiCl4 or metal silicate are dissolved in the ionic liquid systems, electrodeposition temperature ranges from 50DEG C to 200DEG C, and the monatomic silicon is deposited on a solid metal cathode. The method has the advantages that the operation temperature is low, the ionic liquid systems are stable and the process sequence is simple and easy to operate; control through constant current and constant voltage is achieved, continuous production is easy to realize, current efficiency is high, and silicon production energy consumption and cost can be remarkably reduced. The method has quite good application prospect in preparation of semiconducting materials.
Description
Technical field
The invention belongs to electrolysis field, relate to novel method prepared by a kind of elemental silicon.
Background technology
The comprehensive advantages such as relative to other semi-conductors, elemental silicon has that fusing point is high, Heat stability is good, energy gap are large, stable performance and environmental friendliness, have very important application in material, information and energy field.Along with its demand of development of solar photovoltaic industry constantly expands, elemental silicon as solar cell exploitation, produce and application material of main part, its preparation process also receives extensive concern.
No matter be manufacture order crystal silicon, polysilicon or non-crystalline silicon at present, its step is all first quartzite or silica (SiO
2) carry out carbothermic reduction and obtain industrial silicon product, the method is seriously polluted, energy consumption is high, product foreign matter content is high.Different according to purposes, adopt Du Pont process, Bel's method or Siemens Method etc. to be purified by industrial silicon more respectively and obtain silicon single crystal, polysilicon etc., comprising industrial silicon being carried out to the preparation of silicon-containing compound, purification, the various step such as reduction or decomposition of silicon-containing compound and the process of complexity, these processes mainly contain that energy consumption is high, poor stability, purity are difficult to the problems such as control.Therefore, electrolytic process one step is adopted to prepare the direction that high purity elemental silicon is metallargist's effort always.
The report of the fused salt galvanic deposit about silicon is just had as far back as 1865, under temperature 600 ~ 900 DEG C of conditions, K
2siF
6the galvanic deposit of silicon is carried out in/KF fused salt.Gopalakrishna M.Rao afterwards, cohen, Li Yungang, Zhang Mingjie etc. are studied electrodepositing silicon in different molten salt systems.Aluminium wire is wrapped in high purity quartz sand glass and makes negative electrode, at the CaCl of 850 DEG C by Kouji Yasuda etc.
2in fused salt, electrolytic reduction has obtained silicon.Wuhan University Xianbo Jin etc. adopts the CaCl used the same method at 850 DEG C
2in fused salt, under 2.8V voltage, electrolysis 4h obtains the thick silicon ingot of 0.5mm.But because the technology such as electrolysis temperature is high, anticorrosion are difficult to the reasons such as solution, fused salt electrolysis process is in the laboratory study stage always.In order to reduce electrolysis temperature, organic solvent electrolysis system is also attempted, the system of JunsiGu silicon electrolyzation is organic solution system, at 80 DEG C ~ 200 DEG C, electrolysis obtains elemental silicon, YusakuNishimuraa obtains the amorphous silicon of 50 μm of thickness by organic solvent electrolysis, and this shortcoming preparing silicon by organic solvent shows that needs are in high pressure vacuum state, to avoid the volatilization of electrolyte system, meanwhile, also there is the shortcomings such as electrochemical window is narrow as electrolytic solution in organic solvent.
Ionic liquid is a kind of novel green solvent, refers to the complete material be made up of ion be in a liquid state under room temperature or near room temperature temperature.Ionic liquid has many merits, such as: non-combustible, electroconductibility is strong, viscosity at room temperature is large, thermal capacitance is large, vapour pressure is little, stable in properties, there is good solubility to many inorganic salt and organism, be widely used in fields such as electrochemistry, organic synthesis, catalysis, separation.Glyoxaline ion liquid and organic solvent mixed electrolytic solution system ([Bmim] OTf+PC) electrolysis at 40 DEG C are obtained thickness 3 μm of unformed elemental silicons, S.Zein El Abedin ionic liquid [BMP] Tf by the Li Yaqiong of Northeastern University
2n at room temperature electrolysis obtains the elemental silicon film that thickness is 100nm, the people such as J.Mallet utilize ionic liquid BMPy-TFSA to adopt template at room temperature to prepare silicon nanowires, and A.M.Martineza obtains the amorphous silicon of film under ionic liquid BMPy-TFSA room temperature in electrolytic experiment.Current result of study shows, no matter be in the mixed system of organic electrolyte or organic liquor and ionic liquid, the silicon product obtained also rests on micron order film, and product volume is little, is difficult to industrialization.
In sum, how to overcome the high temperature existed in aforesaid method, high pressure, complex process, environment is unfriendly, and product volume is little, is difficult to the shortcomings such as industrialization, exploring a kind of method of carrying out galvanic deposit elemental silicon steady in a long-term at lower temperature and normal pressure, is those skilled in the art's problem demanding prompt solutions.
Summary of the invention
This patent provides a kind of ionic liquid adopting Heat stability is good, and electrolysis goes out the method for grade thickness elemental silicon at a lower temperature.It is low that this has electrolysis temperature, and without the need to high pressure, technique is simple to operation, advantages of environment protection.Technical scheme is as follows:
A kind of method of galvanic deposit elemental silicon in ionic liquid, first soluble silicon source is dissolved in ion liquid system, with copper, iron (stainless steel), titanium solid metal sheet for negative electrode, noble electrode is anode, carry out constant voltage or Constant Electric Current deposition at 50 DEG C ~ 200 DEG C, galvanic deposit product obtains elemental silicon after ionic liquid is isolated in organism cleaning.Add silicon-containing material continuously in electrolytic process, electrolysate is continuously removed by bottom of electrolytic tank, carries out the continuous seepage of silicon.
The present invention prepares the method for elemental silicon, and described silicon source is SiCl
4, SiBr
4, SiHC1
3, Si
2h
6, Si
3h
8, Si
4h
10, Li
2siO
3and K
2siO
3in one.
The present invention prepares the method for elemental silicon, described ionic liquid cation is imidazole type, pyridine type, quaternary ammonium type, quaternary phosphine type, Bi Kaxing, piperidines type, morpholine type and sulfonium salt type, and valence state is+1, and its structure is as follows, R1, R2, R3, R4, R5, R6, R7 represent alkyl, alkoxyl group, fluorine or hydrogen; Negatively charged ion is F
-, Cl
-, Br
-, I
-, SCN
-, CN
-, [N (CF
3sO
2)
2]
-[N (CN)
2]
-
The present invention prepares the method for elemental silicon, and in described ionic liquid, in electrodepositing silicon system, the concentration of silicon tetrachloride is 0.1M ~ 1M.
The present invention prepares the method for elemental silicon, and the current density in described deposition method during galvanostatic deposition is 0.01 ~ 0.3A/dm
2, constant voltage deposition time slot pressure scope is-2.0V ~-2.7V.
The present invention prepares the method for elemental silicon, and described galvanic deposit product cleaning solution is organic solvent-acetone, ethanol, one or more mixed solvents in methylene dichloride and acetonitrile.
The present invention prepares the method for elemental silicon, its preferred condition be 50 DEG C containing 0.2M SiCl
4quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage-2.4V, product carries out washing and obtains elemental silicon.
The present invention prepares the method for elemental silicon, another preferred condition be 110 DEG C containing 0.2M SiCl
4quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage-2.4V, product carries out washing and obtains elemental silicon.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of product;
Fig. 2 is the transmission electron microscope picture of product.
Embodiment
Embodiment 1
By SiCl
4be dissolved in N4441 (the two fluoroform sulfimide of tributyl-methyl phosphonium ammonium) ionic liquid, active material concentration is 0.1M, and working electrode is copper sheet, and supporting electrode is glass-carbon electrode, and reference electrode is Ag/ (AgNO
3acetonitrile).Constant voltage galvanic deposit, operating voltage is-2.4V, and temperature is 50 DEG C, obtains product silicon through 4h galvanic deposit at working electrode, after being taken out by working electrode, first repeatedly guarantees that ionic liquid is cleaned through washed with dichloromethane.The product finally obtained is placed on vacuum drying oven 60 DEG C, 12h, and the deposition layer thickness obtained is about 0.01mm.
Embodiment 2
By SiBr
4be dissolved in [EMIM] TFSI (the two fluoroform sulfimide of 1-ethyl-3-methylimidazole) ionic liquid, active material concentration is 0.2M, and working electrode is stainless steel substrates, and supporting electrode is glass-carbon electrode, and reference electrode is Ag/ (AgNO
3acetonitrile).Constant Electric Current deposits, and working current density is 0.1A/dm
2, temperature is 50 DEG C, obtains product silicon through 8h galvanic deposit at working electrode, after being taken out by working electrode, first repeatedly guarantees that ionic liquid is cleaned through ethanol+washing with acetone.The product finally obtained is placed on vacuum drying oven 60 DEG C, 12h, and the deposition layer thickness obtained is about 0.02mm.
Embodiment 3
By SiHCl
3be dissolved in N4441 (the two fluoroform sulfimide of tributyl-methyl phosphonium ammonium) ionic liquid, active material concentration is 0.3M, and working electrode is titanium sheet, and supporting electrode is glass-carbon electrode, and reference electrode is Ag/ (AgNO
3acetonitrile).Constant voltage galvanic deposit, operating voltage is-2.6V, and temperature is 50 DEG C, obtains product silicon through 4h galvanic deposit at working electrode, after being taken out by working electrode, first repeatedly guarantees that ionic liquid is cleaned through washing with acetone.The product finally obtained is placed on vacuum drying oven 60 DEG C of 12h, and the deposition layer thickness obtained is about 0.02mm.
Embodiment 4
By SiCl
4be dissolved in PP13 (the two fluoroform sulfimide of N-Methyl-N-propyl piperidines) ionic liquid, active material concentration is 0.5M, and working electrode is copper sheet, and supporting electrode is glass-carbon electrode, and reference electrode is Ag/ (AgNO
3acetonitrile).Constant Electric Current deposits, and current density is 0.2A/dm
2, temperature is 50 DEG C, obtains product silicon through 8h galvanic deposit at working electrode, after being taken out by working electrode, first repeatedly guarantees that ionic liquid is cleaned through acetonitrile wash.The product finally obtained is placed on vacuum drying oven 60 DEG C, 8h, and the deposition layer thickness obtained is about 0.02mm.
Embodiment 5
By Si
2h
6be dissolved in N4441 (the two fluoroform sulfimide of tributyl-methyl phosphonium ammonium) ionic liquid, active material concentration is 0.7M, and working electrode is copper sheet, and supporting electrode is metal foil electrodes, and reference electrode is Ag/ (AgNO
3acetonitrile).Constant voltage galvanic deposit, operating voltage is-2.4V, and temperature is 100 DEG C, obtains product silicon through 4h galvanic deposit at working electrode, after being taken out by working electrode, first repeatedly guarantees that ionic liquid is cleaned through washed with dichloromethane.The product finally obtained is placed on vacuum drying oven 60 DEG C, 10h, and the deposition layer thickness obtained is about 0.015mm.
Embodiment 6
By Li
2siO
3be dissolved in PP13 (the two fluoroform sulfimide of N-Methyl-N-propyl piperidines) ionic liquid, active material concentration is 0.9M, and working electrode is stainless steel substrates, and supporting electrode is metal foil electrodes, and reference electrode is Ag/ (AgNO
3acetonitrile).Constant voltage galvanic deposit, operating voltage is-2.4V, and temperature is 130 DEG C, obtains product silicon through 4h galvanic deposit at working electrode, after being taken out by working electrode, first repeatedly guarantees that ionic liquid is cleaned through washing with acetone.The product finally obtained is placed on vacuum drying oven 60 DEG C, 4h, and the deposition layer thickness obtained is about 0.01mm.
Embodiment 7
By SiCl
4be dissolved in [EMIM] TFSI (the two fluoroform sulfimide of 1-ethyl-3-methylimidazole) ionic liquid, active material concentration is 1.0M, and working electrode is copper sheet, and supporting electrode is metal foil electrodes, and reference electrode is Ag/ (AgNO
3acetonitrile).Constant Electric Current deposits, and current density is 0.2A/dm
2, temperature is 100 DEG C, obtains product silicon through 4h galvanic deposit at working electrode, after being taken out by working electrode, first repeatedly guarantees that ionic liquid is cleaned through ethanol+washing with acetone.The product finally obtained is placed on vacuum drying oven 60 DEG C, 12h, and the deposition layer thickness obtained is about 0.03mm.
Embodiment 8
By K
2siO
3be dissolved in [EMIM] TFSI (the two fluoroform sulfimide of 1-ethyl-3-methylimidazole) ionic liquid, active material concentration is 0.2M, and working electrode is copper sheet, and supporting electrode is glass-carbon electrode, and reference electrode is Ag/ (AgNO
3acetonitrile).Operating voltage is-2.2V, and temperature is 50 DEG C, obtains product silicon through 8h galvanic deposit at working electrode, after being taken out by working electrode, first repeatedly guarantees that ionic liquid is cleaned through washed with dichloromethane, then rinses with hydrochloric acid.The product finally obtained is placed on vacuum drying oven 60 DEG C, 12h, and the deposition layer thickness obtained is about 0.01mm.
Claims (6)
1. the preparation method of an ionic liquid low-temperature electrolytic elemental silicon, it is characterized in that: soluble silicon source is dissolved in ion liquid system, with solid metal sheets such as copper, iron (stainless steel), titaniums for negative electrode, noble electrode is anode, at 50 DEG C ~ 200 DEG C temperature, carry out constant voltage or Constant Electric Current deposition, galvanic deposit product obtains elemental silicon after ionic liquid is isolated in organism cleaning.
2. method according to claim 1, is characterized in that: described silicon source is SiCl
4, SiBr
4, SiHC1
3, Si
2h
6, Si
3h
8, Si
4h
10, Li
2siO
3and K
2siO
3in one.
3. method according to claim 1, is characterized in that: ionic liquid cation is imidazole type, pyridine type, quaternary ammonium type, quaternary phosphine type, Bi Kaxing, piperidines type, morpholine type and sulfonium salt type, and valence state is+1, and its structure is as follows, R
1, R
2, R
3, R
4, R
5, R
6, R
7represent alkyl, alkoxyl group, fluorine or hydrogen; Negatively charged ion is F
-, Cl
-, Br
-, I
-, SCN
-, CN
-, [N (CF
3sO
2)
2]
-[N (CN)
2]
-.
4. method according to claim 1, is characterized in that: in described ionic liquid, in electrodepositing silicon system, the concentration of silicon tetrachloride is 0.1M ~ 1M.
5. method according to claim 1, is characterized in that: the current density in described deposition method during galvanostatic deposition is 0.01 ~ 0.3A/dm
2, during constant voltage deposition, with Ag/ (AgNO
3acetonitrile) be reference electrode, voltage range is-2.0V ~-2.7V.
6. method according to claim 1, is characterized in that: galvanic deposit product cleaning solution is organic solvent-acetone, ethanol, one or more mixed solvents in methylene dichloride and acetonitrile.
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|---|---|---|---|
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| CN2014106486403 | 2014-11-15 | ||
| CN201410648640 | 2014-11-15 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154905A (en) * | 2015-10-12 | 2015-12-16 | 上海第二工业大学 | Method for electrodeposition preparation of monatomic silicon from poly-silicon industry by-product based on ionic liquids |
| CN109860567A (en) * | 2019-02-26 | 2019-06-07 | 成都爱敏特新能源技术有限公司 | A kind of Copper substrate graphene/silicon/carbon nitrogen combination electrode and preparation method thereof |
| CN114318456A (en) * | 2022-01-17 | 2022-04-12 | 桐乡市思远环保科技有限公司 | Method for electrodepositing silicon film |
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| DE102006013871A1 (en) * | 2006-03-23 | 2007-09-27 | Justus-Liebig-Universität Giessen | Electrochemical process for the deposition of nanoscale metals, semimetals and compounds of these metals and / or semimetals at the interface between a Niedertempereturentladung and an ionic liquid |
| CN101981731A (en) * | 2008-02-26 | 2011-02-23 | 原子能与替代能源委员会 | Process for fabricating a silicon-based electrode, silicon-based electrode and lithium battery comprising such an electrode |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102006013871A1 (en) * | 2006-03-23 | 2007-09-27 | Justus-Liebig-Universität Giessen | Electrochemical process for the deposition of nanoscale metals, semimetals and compounds of these metals and / or semimetals at the interface between a Niedertempereturentladung and an ionic liquid |
| CN101981731A (en) * | 2008-02-26 | 2011-02-23 | 原子能与替代能源委员会 | Process for fabricating a silicon-based electrode, silicon-based electrode and lithium battery comprising such an electrode |
Non-Patent Citations (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154905A (en) * | 2015-10-12 | 2015-12-16 | 上海第二工业大学 | Method for electrodeposition preparation of monatomic silicon from poly-silicon industry by-product based on ionic liquids |
| CN109860567A (en) * | 2019-02-26 | 2019-06-07 | 成都爱敏特新能源技术有限公司 | A kind of Copper substrate graphene/silicon/carbon nitrogen combination electrode and preparation method thereof |
| CN114318456A (en) * | 2022-01-17 | 2022-04-12 | 桐乡市思远环保科技有限公司 | Method for electrodepositing silicon film |
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Application publication date: 20150923 |
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