CN105040020A - Method for preparing high-purity silicon thin film by electrolyzing SiO2 at low temperature through ionic liquid - Google Patents
Method for preparing high-purity silicon thin film by electrolyzing SiO2 at low temperature through ionic liquid Download PDFInfo
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Abstract
The invention provides a method for preparing a high-purity silicon thin film by electrolyzing SiO2 at a low temperature through ionic liquid. The method includes the following steps that (1) the raw materials, namely, the fluorinated imidazole ionic liquid, cryolite, a hydrofluoric acid solution and silicon dioxide, of an electrolyte are prepared; (2) the electrolyte is prepared in an electrolytic cell, and silicon dioxide is electrolyzed under the inert gas circulation and stirring condition; (3) silicon dioxide is supplemented in the electrolysis process; (4) working electrodes are replaced every 1-2 h; and (5) a silicon film is peeled off, washed and dried. According to the method, silicon electro-deposition can be conducted at a low temperature, and obtained silicon is high in purity; the technical reserve is provided for environment-friendly preparation of low-cost and low-pollution solar-grade silicon thin films.
Description
Technical field
The invention belongs to field of material technology, particularly one utilizes ionic liquid low-temperature electrolytic SiO
2the method of high purity silicon film.
Background technology
The fast development of industry, consumes a large amount of fossil oil, discharges a large amount of greenhouse gases, and under the dual-pressure of the energy and environment, the exploitation of renewable energy source becomes current hotspot and emphasis; Solar energy power generating is one of renewable energy technologies of giving priority to of countries in the world, has most vast potential for future development.
China's solar energy resources is very abundant, and theoretical reserves reach annual 1.7 trillion tons of standard coals; Plan at present according to China, to the year two thousand fifty, the accumulative installation of China's photovoltaic generation will reach 600GWp; According to the prediction of China Power academy of sciences, to the year two thousand fifty, the electric power installation of Chinese renewable energy source will account for 25% of national electric power installation, and wherein photovoltaic generation installation will account for 5%.Solar energy power generating will occupy an important position in the power supply in China's future.
Crystalline silicon material (comprising polysilicon and silicon single crystal) is current topmost solar energy photovoltaic material, share of market about 80 ~ 90%; The purity requirement of solar cell raw materials silicon chip reaches more than 6N, and silicon chip price accounts for about 40% of finished silicon solar cell cost; Therefore the production cost of starting material silicon chip is reduced, to reducing photovoltaic generation cost, promoting that the development of photovoltaic industry plays key effect.
The current industrial method preparing HIGH-PURITY SILICON carries out carbothermic reduction quartz sand with electric arc furnace at 2000 DEG C, obtains the metallurgical grade silicon that purity is 2N, then adopts improved Siemens to be purified to the HIGH-PURITY SILICON of 6 ~ 11N; This method produces the CO of polysilicon per ton generation more than 1.6 tons
2with the SiCl of 8 tons
4byproduct, and the waste liquid such as trichlorosilane, chlorine waste gas, processing cost is higher, and this flow process current consumption is large; At present as state-of-the-art improved Siemens technique, the comprehensive energy consumption of overseas enterprise is about 150kWh/ (kgofSi), domestic, is 250 ~ 300kWh/ (kgofSi), and what have even reaches 400kWh/ (kgofSi).
Have many research to put forth effort on the low cost new preparation technology of exploitation solar-grade high-purity silicon in recent years, be divided into following a few class: (1) with fluoride system (as LiF-KF, NaF-CaF
2, LiF-KF-NaF etc.) or chloride system (as CaCl
2, NaCl-CaCl
2-CaO etc.) for supporting ionogen, with silicate or silicon-dioxide for solute electrodepositing silicon; This process energy consumption is high, produces discontinuous, and the use of carbon annode, the impurity such as a certain amount of boron, phosphorus can be brought into and enter in product silicon, for subsequent physical or chemical purification silicon add difficulty; (2) with high-purity Si O
2make negative electrode, at CaCl
2direct electrodeoxidation in fused salt, by solid-state SiO
2be reduced to silicon; Due to SiO
2poorly conductive, cause the inside rate of reduction that do not contact with negative electrode conductive filament slow, reduce thoroughly, product S i and starting material SiO
2and deposit, efficiency is too low; (3) with SiCl
4for solute, galvanic deposit Si in ionic liquid (as 1-ethyl-3-methylimidazole, 1-butyl-2-crassitude double imide, 3-methyl-n-hexyl ammonium double imide etc.); Due to silicon source SiCl used
4by the chlorination of Si direct heating or SiO
2prepared by carburizing chlorination, the reactant Cl of these two kinds of chlorination processes
2with product S iCl
4be toxic substance, need extra process, technical process length, production cost raise; (4) in organic solvent (as propylene carbonate, ethylene glycol, the mixed solution etc. of acetonitrile and tetrahydrofuran (THF)), with SiCl
4/ SiHCl
3for solute electrodepositing silicon.Containing impurity such as C, O, N and Cl in silicon prepared by the method, do not reach the purity requirement of Solar Silicon, and there is the problems such as organic solvent conductive capability is weak, sedimentation rate is lower, ionogen is volatile.
Summary of the invention
For the problems referred to above that existing solar-grade high-purity silicon technology of preparing exists, the invention provides one and utilize ionic liquid low-temperature electrolytic SiO
2the method of high purity silicon film, with high-purity Si O
2(>=99.995%) is raw material, is dissolved in the Short flow method that solar level silicon film is prepared in galvanic deposit in ionic liquid; While efficiently preparing solar level silicon film, reduce production cost.
Method of the present invention is carried out according to the following steps:
1, electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 94.5 ~ 99% of ionogen total mass, sodium aluminum fluoride accounts for 0.5 ~ 1.5% of ionogen total mass, silicon-dioxide accounts for 0.5 ~ 2% of ionogen total mass, and hydrofluoric acid solution accounts for 0 ~ 2% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1,3-dimethyl fluorinated glyoxaline, 1-ethyl-3-methyl fluorinated glyoxaline, 1-propyl group-3-methyl fluorinated glyoxaline or 1-butyl-3-methyl fluorinated glyoxaline; The mass concentration of described hydrofluoric acid solution is 50%; Described sodium aluminum fluoride is Na
3alF
6;
2, pass into rare gas element to electrolyzer and discharge air wherein and water vapour, then fluorinated glyoxaline ionic liquid is joined in electrolyzer, add sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide again, ionogen is mixed to form in electrolyzer, under rare gas element circulation and agitation condition, control electrolyte temperature at 20 ~ 100 DEG C, apply current electroanalysis silicon-dioxide to the working electrode in electrolyzer with to electrode, the current density controlling working electrode is 20 ~ 100mA/cm
2;
3, in electrolytic process, every 5 ~ 15min adds silicon-dioxide in electrolyzer, controls silicon-dioxide in electrolyzer and accounts for 0.5 ~ 2% of ionogen total mass;
4, along with the carrying out of electrolysis, siliceous deposits forms silicon fiml at working electrode surface, changes working electrode every 1 ~ 2h;
5, the silicon fiml of the working electrode surface changed is peeled off, with organic solvent cleaning, dry after removing organic solvent and obtain HIGH-PURITY SILICON film.
In aforesaid method, working electrode and be 10 ~ 30mm to the interpole gap between electrode.
In above-mentioned step 3, the unit time add-on of silicon-dioxide is calculated as follows:
（1）
In formula, m is the quality adding silicon-dioxide p.s., and unit is g; M
ofor the molar mass of silicon-dioxide, get 60g/mol; S is the area of working electrode, and unit is cm
2; I is the current density of working electrode, and unit is mA/cm
2; N is metastatic electron number, and the electron transfer number of this reaction is 4; F is Faraday's number, gets 96485C/mol.
Rare gas element in aforesaid method selects high-purity argon gas, purity >=99.99%.
Working electrode in aforesaid method and all select noble electrode to electrode, material is platinum.
Purity >=99.995% of the HIGH-PURITY SILICON film that aforesaid method obtains, thickness is at 40 ~ 160 μm.
In aforesaid method, the rate of recovery of silicon is 95.5 ~ 99.0%.
Above-mentioned organic solvent is ethanol and acetone.
Compared with the existing method preparing solar-grade high-purity silicon, present method has the following advantages:
1, technical process is shortened, and significantly reduces production energy consumption, also can eliminate CO
2, SiCl
4, SiHCl
3and Cl
2deng the emission pollution problem of waste liquid waste gas;
2, adopt the galvanic deposit of ionic liquid low-temperature electrolytes, can reduce and eliminate the shortcoming that when adopting high temperature fused salt electrolysis matter, energy consumption is large, temperature is high, equipment corrosion is serious;
3, galvanic deposit prepares metal and alloy firm is a kind of more ripe method for manufacturing thin film, and this method can prepare the silicon film of grain-size and morphology controllable; In addition, adopt electrodip process one step to prepare solar level silicon film, current silicon slicing process can be saved, it also avoid the silicon loss of slicing processes, and greatly reduce silicon wafer thickness, significantly reduce the preparation cost of silicon solar cell.
Method of the present invention compares the preparation method of other solar-grade high-purity silicon materials, can electrodepositing silicon at low temperatures, and the silicon purity obtained is high, and efficiency is high; For low cost, oligosaprobic solar level silicon film Green synthesis provide tachnical storage.
Accompanying drawing explanation
Fig. 1 utilizes ionic liquid low-temperature electrolytic SiO in the embodiment of the present invention
2the structural representation of high purity silicon film device;
In figure, 1, silicon-dioxide, 2, feeder, 3, inert gas import, 4, electro bath-lid, 5, thermopair, 6, working electrode, 7, electric heating cover, 8, ionogen, 9, magnetic stirring, 10, electrolyzer, 11, to electrode, 12, reference electrode, 13, inert gas outlet, 14, rubber plug.
Embodiment
Adopt in the embodiment of the present invention 1,3-dimethyl fluorinated glyoxaline, 1-ethyl-3-methyl fluorinated glyoxaline, 1-propyl group-3-methyl fluorinated glyoxaline and 1-butyl-3-methyl fluorinated glyoxaline adopt publication number two synthetic methods replacing fluorinated glyoxaline class ionic liquid disclosed in the patent application of CN103613547A to synthesize.
The general structure of the fluorinated glyoxaline ionic liquid adopted in the embodiment of the present invention is:
Be abbreviated as: [RMIm] F;
Wherein R is methyl CH
3 -, ethyl CH
3cH
2 -, propyl group CH
3cH
2cH
2 -or butyl CH
3cH
2cH
2cH
2 -.
Sodium aluminum fluoride purity >=99.995% adopted in the embodiment of the present invention, granularity is 300 ~ 400 orders.
The hydrofluoric acid solution adopted in the embodiment of the present invention is commercial products, and Solute mass fraction is 50%, and purity is that top grade is pure, and specification is with reference to GB/T620-1993.
Silica purity >=99.995% adopted in the embodiment of the present invention; Granularity is 300 ~ 400 orders.
The working electrode adopted in the embodiment of the present invention, be high-purity platinum filament of purity 99.9999% to the material of electrode and reference electrode.
Adopt the PGSTAT30 electrochemical workstation of Wan Tong company of Switzerland as electrode supply in the embodiment of the present invention.
In the embodiment of the present invention, theoretical yield is calculated as follows:
（2）
In formula, m
lfor theoretical yield, unit is g; M
sifor the molar mass of silicon, 28g/mol; T is electrodeposition time, and unit is s; S is working electrode area, and unit is cm
2; I is the current density of working electrode, and unit is mA/cm
2; N is metastatic electron number, is 4; F is Faraday's number, gets 96485C/mol.
The rate of recovery=the m of electrodepositing silicon in the embodiment of the present invention
s/ m
l, wherein m
sfor the silicon film quality that working electrode in embodiment deposits, unit is g.
In the embodiment of the present invention is silicon fiml is put into successively ethanol and acetone to soak and clean with organic solvent cleaning.
The rare gas element adopted in the embodiment of the present invention is the high-purity argon gas of purity >=99.99%.
Embodiment 1
Utilize ionic liquid low-temperature electrolytic SiO
2high purity silicon film apparatus structure as shown in Figure 1, comprises the electrolyzer 10 of electric heating cover 7 and inside thereof; Be provided with thermopair 5 in electric heating cover 7, the electro bath-lid 4 at electrolyzer 10 top is provided with inert gas import 3 and inert gas outlet 13; The inside of electrolyzer 10 is provided with working electrode 6, to electrode 11 and reference electrode 12, working electrode 6, insert in the rubber plug 14 had openning hole respectively to the guide rod of electrode 11 and reference electrode 12, fill on electro bath-lid 4, form a whole, insert electrolyzer 10 inner; Also be provided with feeder 2 above electrolyzer 10, feeder 2 splendid attire silica 1, be the filling tube of band valve bottom feeder 2, this filling tube is communicated with electrolyzer 10 inside; Magnetic stirring 9 is provided with in electrolyzer 10;
Adopt said apparatus, method is carried out according to the following steps:
Prepare electrolytical raw material, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 94.5% of ionogen total mass, sodium aluminum fluoride accounts for 1.5% of ionogen total mass, silicon-dioxide accounts for 2% of ionogen total mass, and hydrofluoric acid solution accounts for 2% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1,3-dimethyl fluorinated glyoxaline; The mass concentration of described hydrofluoric acid solution is 50%; Described sodium aluminum fluoride is Na
3alF
6;
Pass into rare gas element to electrolyzer and discharge air wherein and water vapour, then fluorinated glyoxaline ionic liquid is joined in electrolyzer, add sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide again, ionogen is mixed to form in electrolyzer, under rare gas element circulation and agitation condition, control electrolyte temperature at 100 DEG C, apply current electroanalysis silicon-dioxide to the working electrode in electrolyzer with to electrode, control current density is 100mA/cm
2;
Working electrode and be 10mm to the interpole gap between electrode; The useful area S of working electrode is 100cm
2;
In electrolytic process, every 5min adds silicon-dioxide in electrolyzer, and the add-on per second of silicon-dioxide presses m=60 × 100 × 100/(1000 × 4 × 96485), calculate every 5min and add silicon-dioxide 0.47g;
Along with the carrying out of electrolysis, siliceous deposits forms silicon fiml at working electrode surface, changes working electrode every 1h;
The silicon fiml of the working electrode surface changed is peeled off, with organic solvent cleaning, dries after removing organic solvent and obtain HIGH-PURITY SILICON film, purity 99.998%, thickness 110 μm; Calculate the rate of recovery 99.0% of silicon.
Embodiment 2
Apparatus structure is with embodiment 1, and method is with embodiment 1, and difference is:
(1) electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 96% of ionogen total mass, sodium aluminum fluoride accounts for 1% of ionogen total mass, silicon-dioxide accounts for 1.5% of ionogen total mass, and hydrofluoric acid solution accounts for 1.5% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1-ethyl-3-methyl fluorinated glyoxaline;
(2) control electrolyte temperature at 20 DEG C, control current density is 20mA/cm
2; Working electrode and be 25mm to the interpole gap between electrode; The useful area S of working electrode is 200cm
2;
(3) in electrolytic process, every 10min adds silicon-dioxide in electrolyzer, and the add-on calculating the every 10min of silicon-dioxide by formula (1) is 0.37g;
(4) working electrode is changed every 2h;
(5) purity 99.995% of HIGH-PURITY SILICON film, thickness 44 μm; The rate of recovery 95.5% of silicon.
Embodiment 3
Apparatus structure is with embodiment 1, and method is with embodiment 1, and difference is:
(1) electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 97% of ionogen total mass, sodium aluminum fluoride accounts for 0.5% of ionogen total mass, silicon-dioxide accounts for 1% of ionogen total mass, and hydrofluoric acid solution accounts for 1.5% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1-propyl group-3-methyl fluorinated glyoxaline;
(2) control electrolyte temperature at 85 DEG C, control current density is 80mA/cm
2; Working electrode and be 15mm to the interpole gap between electrode; The useful area S of working electrode is 200cm
2;
(3) in electrolytic process, every 15min adds silicon-dioxide in electrolyzer, and the add-on calculating the every 15min of silicon-dioxide by formula (1) is 2.25g;
(4) purity 99.997% of HIGH-PURITY SILICON film, thickness 88 μm; The rate of recovery 97.7% of silicon.
Embodiment 4
Apparatus structure is with embodiment 1, and method is with embodiment 1, and difference is:
(1) electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 99% of ionogen total mass, and sodium aluminum fluoride accounts for 0.5% of ionogen total mass, and silicon-dioxide accounts for 0.5% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1-butyl-3-methyl fluorinated glyoxaline;
(2) control electrolyte temperature at 60 DEG C, control current density is 90mA/cm
2; Working electrode and be 30mm to the interpole gap between electrode; The useful area S of working electrode is 150cm
2;
(3) in electrolytic process, every 5min adds silicon-dioxide in electrolyzer, and the add-on calculating the every 5min of silicon-dioxide by formula (1) is 0.63g;
(4) purity 99.995% of HIGH-PURITY SILICON film, thickness 98 μm; The rate of recovery 98.0% of silicon.
Embodiment 5
Apparatus structure is with embodiment 1, and method is with embodiment 1, and difference is:
(1) electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 98% of ionogen total mass, sodium aluminum fluoride accounts for 0.5% of ionogen total mass, silicon-dioxide accounts for 1% of ionogen total mass, and hydrofluoric acid solution accounts for 0.5% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1,3-dimethyl fluorinated glyoxaline;
(2) control electrolyte temperature at 45 DEG C, control current density is 20mA/cm
2; Working electrode and be 20mm to the interpole gap between electrode; The useful area S of working electrode is 200cm
2;
(3) in electrolytic process, every 10min adds silicon-dioxide in electrolyzer, and the add-on calculating the every 10min of silicon-dioxide by formula (1) is 0.56g;
(4) working electrode is changed every 2h;
(5) purity 99.995% of HIGH-PURITY SILICON film, thickness 43 μm; The rate of recovery 96.9% of silicon.
Embodiment 6
Apparatus structure is with embodiment 1, and method is with embodiment 1, and difference is:
(1) electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 95% of ionogen total mass, sodium aluminum fluoride accounts for 1% of ionogen total mass, silicon-dioxide accounts for 2% of ionogen total mass, and hydrofluoric acid solution accounts for 22% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1-ethyl-3-methyl fluorinated glyoxaline;
(2) control electrolyte temperature at 30 DEG C, control current density is 60mA/cm
2; Working electrode and be 15mm to the interpole gap between electrode; The useful area S of working electrode is 200cm
2;
(3) in electrolytic process, every 15min adds silicon-dioxide in electrolyzer, and the add-on calculating the every 15min of silicon-dioxide by formula (1) is 1.71g;
(4) working electrode is changed every 1.5h;
(5) purity 99.997% of HIGH-PURITY SILICON film, thickness 97 μm; The rate of recovery 97.1% of silicon.
Embodiment 7
Apparatus structure is with embodiment 1, and method is with embodiment 1, and difference is:
(1) electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 96% of ionogen total mass, sodium aluminum fluoride accounts for 0.5% of ionogen total mass, silicon-dioxide accounts for 2% of ionogen total mass, and hydrofluoric acid solution accounts for 1.5% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1-propyl group-3-methyl fluorinated glyoxaline;
(2) control electrolyte temperature at 90 DEG C, control current density is 25mA/cm
2; Working electrode and be 20mm to the interpole gap between electrode; The useful area S of working electrode is 300cm
2;
(3) in electrolytic process, every 10min adds silicon-dioxide in electrolyzer, and the add-on calculating the every 10min of silicon-dioxide by formula (1) is 0.69g;
(4) working electrode is changed every 1.5h;
(5) purity 99.998% of HIGH-PURITY SILICON film, thickness 40 μm; The rate of recovery 97.0% of silicon.
Embodiment 8
Apparatus structure is with embodiment 1, and method is with embodiment 1, and difference is:
(1) electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 97% of ionogen total mass, sodium aluminum fluoride accounts for 1% of ionogen total mass, silicon-dioxide accounts for 1.5% of ionogen total mass, and hydrofluoric acid solution accounts for 0.5% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1-butyl-3-methyl fluorinated glyoxaline;
(2) control electrolyte temperature at 40 DEG C, control current density is 75mA/cm
2; Working electrode and be 15mm to the interpole gap between electrode; The useful area S of working electrode is 100cm
2;
(3) in electrolytic process, every 10min adds silicon-dioxide in electrolyzer, and the add-on calculating the every 10min of silicon-dioxide by formula (1) is 0.69g;
(4) working electrode is changed every 2h;
(5) purity 99.997% of HIGH-PURITY SILICON film, thickness 160 μm; The rate of recovery 95.9% of silicon.
Claims (5)
1. one kind utilizes ionic liquid low-temperature electrolytic SiO
2the method of high purity silicon film, is characterized in that carrying out according to the following steps:
(1) electrolytical raw material is prepared, electrolytical raw material is fluorinated glyoxaline ionic liquid, sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide, wherein fluorinated glyoxaline ionic liquid accounts for 94.5 ~ 99% of ionogen total mass, sodium aluminum fluoride accounts for 0.5 ~ 1.5% of ionogen total mass, silicon-dioxide accounts for 0.5 ~ 2% of ionogen total mass, and hydrofluoric acid solution accounts for 0 ~ 2% of ionogen total mass; Described fluorinated glyoxaline ionic liquid is 1,3-dimethyl fluorinated glyoxaline, 1-ethyl-3-methyl fluorinated glyoxaline, 1-propyl group-3-methyl fluorinated glyoxaline or 1-butyl-3-methyl fluorinated glyoxaline; The mass concentration of described hydrofluoric acid solution is 50%; Described sodium aluminum fluoride is Na
3alF
6;
(2) pass into rare gas element to electrolyzer and discharge air wherein and water vapour, then fluorinated glyoxaline ionic liquid is joined in electrolyzer, add sodium aluminum fluoride, hydrofluoric acid solution and silicon-dioxide again, ionogen is mixed to form in electrolyzer, under rare gas element circulation and agitation condition, control electrolyte temperature at 20 ~ 100 DEG C, apply current electroanalysis silicon-dioxide to the working electrode in electrolyzer with to electrode, the current density controlling working electrode is 20 ~ 100mA/cm
2;
(3) in electrolytic process, every 5 ~ 15min adds silicon-dioxide in electrolyzer, controls silicon-dioxide in electrolyzer and accounts for 0.5 ~ 2% of ionogen total mass;
(4) along with the carrying out of electrolysis, siliceous deposits forms silicon fiml at working electrode surface, changes working electrode every 1 ~ 2h;
(5) silicon fiml of the working electrode surface changed is peeled off, with organic solvent cleaning, dry after removing organic solvent and obtain HIGH-PURITY SILICON film.
2. according to claim 1ly utilize ionic liquid low-temperature electrolytic SiO
2the method of high purity silicon film, is characterized in that, in step (3), the unit time add-on of silicon-dioxide is calculated as follows:
（1）
In formula, m is the quality adding silicon-dioxide p.s., and unit is g; M
ofor the molar mass of silicon-dioxide, get 60g/mol; S is the area of working electrode, and unit is cm
2; I is the current density of working electrode, and unit is mA/cm
2; N is metastatic electron number, and the electron transfer number of this reaction is 4; F is Faraday's number, gets 96485C/mol.
3. according to claim 1ly utilize ionic liquid low-temperature electrolytic SiO
2the method of high purity silicon film, it is characterized in that purity>=99.995% of the HIGH-PURITY SILICON film obtained, thickness is at 40 ~ 160 μm.
4. according to claim 1ly utilize ionic liquid low-temperature electrolytic SiO
2the method of high purity silicon film, is characterized in that the rate of recovery of silicon is 95.5 ~ 99.0%.
5. according to claim 1ly utilize ionic liquid low-temperature electrolytic SiO
2the method of high purity silicon film, is characterized in that described sodium aluminum fluoride purity>=99.995%, and granularity is 300 ~ 400 orders; Described silica purity>=99.995%; Granularity is 300 ~ 400 orders.
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Cited By (1)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100059118A1 (en) * | 2006-05-26 | 2010-03-11 | Kunio Saegusa | Method for producing silicon |
| CN102864473A (en) * | 2012-10-22 | 2013-01-09 | 哈尔滨工业大学 | Preparation method of three-dimensional ordered macroporous silicon or germanium film |
| CN103992275A (en) * | 2014-05-22 | 2014-08-20 | 东北大学 | Synthesis method of fluoride salt ionic liquid |
| CN104746130A (en) * | 2015-04-17 | 2015-07-01 | 中国科学院过程工程研究所 | Method for preparing crystalline silicon by direct electrolysis in ionic liquid at low temperature |
-
2015
- 2015-08-10 CN CN201510484983.5A patent/CN105040020B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100059118A1 (en) * | 2006-05-26 | 2010-03-11 | Kunio Saegusa | Method for producing silicon |
| CN102864473A (en) * | 2012-10-22 | 2013-01-09 | 哈尔滨工业大学 | Preparation method of three-dimensional ordered macroporous silicon or germanium film |
| CN103992275A (en) * | 2014-05-22 | 2014-08-20 | 东北大学 | Synthesis method of fluoride salt ionic liquid |
| CN104746130A (en) * | 2015-04-17 | 2015-07-01 | 中国科学院过程工程研究所 | Method for preparing crystalline silicon by direct electrolysis in ionic liquid at low temperature |
Non-Patent Citations (1)
| Title |
|---|
| 孟祥东等: ""离子液体中电沉积半导体材料的研究"", 《化学进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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