CN101724852A - Method for preparing solar grade polycrystalline silicon material - Google Patents
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- CN101724852A CN101724852A CN200810167996A CN200810167996A CN101724852A CN 101724852 A CN101724852 A CN 101724852A CN 200810167996 A CN200810167996 A CN 200810167996A CN 200810167996 A CN200810167996 A CN 200810167996A CN 101724852 A CN101724852 A CN 101724852A
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Abstract
The invention relates to a method for preparing a solar grade polycrystalline silicon material. The method comprises the step of connecting a cathode and an anode positioned in electrolyte in a molten state and a direct-current power supply, wherein industrial silicon is used as the anode and an inert conductive material is used as the cathode. The method of the invention creatively adopts the industrial silicon as the anode to prepare the polycrystalline silicon material which meets the quality requirement of solar grade polycrystalline silicon at the cathode.
Description
Technical field
The present invention relates to a kind of preparation method of solar grade polycrystalline silicon material.
Background technology
Sun power has been subjected to extensive concern as the novel energy of a kind of cleaning, Sustainable development.High purity polycrystalline silicon is the starting material of solar cell.The polysilicon purity of using in the solar cell generally is generally 99.999-99.9999% in its purity, is known as solar-grade polysilicon again.And industrial silicon (another name Pure Silicon Metal) purity that exists in the market is generally 95-99.5%, because purity is lower, foreign matter content more (major impurity is iron, aluminium, calcium, boron, phosphorus etc.) can't reach the requirement of solar-grade silicon material.
At present, the technology of production polysilicon is Siemens process and silane thermal decomposition process technology.Though the polysilicon purity height that Siemens process makes, complex process, the service temperature height, the energy consumption height, facility investment is big, production of polysilicon cost height.Silane thermal decomposition process is inflammable and explosive, and is dangerous big.Owing to the high speed development of sun power industry, cause the critical shortage of polycrystalline silicon material simultaneously, supply falls short of demand.The shortage and the expensive serious development that limits the sun power industry of silicon materials, thereby, be necessary very much to develop the novel process of production of polysilicon.Therefore, various countries are preparing Siemens Method the improved while of HIGH-PURITY SILICON material technology, are all carrying out the low-cost new preparation technology of solar-grade silicon material energetically.
Fused salt electrolysis process is a kind of method for preparing polysilicon.Fused salt electrolysis process is to utilize the electric energy heating and be converted to chemical energy, carries out electrolysis with the salt fusion of some metal and as ionogen, with the metallurgical process of extracting and purifying metals.The method for preparing solar-grade polysilicon with fused salt electrolysis has: (1) is negative electrode with the high-purity silicon dioxide, by fused salt electrolysis, realizes removing of negative electrode oxygen element, thus the preparation polysilicon; But in the method, deoxidation process does not possess the function of removal of impurities, is difficult to guarantee the purity of silicon materials, and the electroconductibility extreme difference of silicon-dioxide, and cause the current density of electrolytic process low, problem such as electrolytic efficiency is low; (2) utilize fused salt electrolysis process to prepare the method for solar level silicon materials, comprise that with silicon-dioxide or other silicon-containing compound A be raw material, metal M 1 is a negative electrode, high purity graphite or other carbon material are anode, fluoride molten salt is an ionogen, and electrolytic preparation goes out silicon-containing alloy Si-M1 under 600-1400 ℃ of temperature; Be anode again with Si-M1, high pure metal M2 is a negative electrode, and fluoride molten salt is an ionogen, carries out three layers of liquid electrorefining at 600-1400 ℃, prepares silicon-containing alloy Si-M2; With silicon-containing alloy Si-M2 is raw material, adopts vacuum distillation technique, in vacuum tightness 10
-2Pa to 10
-6The Pa state under temperature 600-1800 ℃ the condition, distilled 0.5-24 hour, obtained solar grade material.But, the preparation silicon alloy vacuum distilling more earlier of this method, adopt other metal as negative electrode during the preparation silicon alloy, to introduce other impurity inevitably, and the metal in the alloy that makes can not be removed, and cause the purity of the polycrystalline silicon material that makes not high, and in the process of vacuum distilling, caused the loss of silicon materials inevitably, and increased cost.
Summary of the invention
The objective of the invention is to overcome the not high defective of polysilicon purity that makes when the available technology adopting fused salt electrolysis process prepares solar grade polycrystalline silicon material, a kind of preparation method that can access the solar grade polycrystalline silicon material of higher degree is provided.
The invention provides a kind of preparation method of solar grade polycrystalline silicon material, this method comprises that the negative electrode that will be arranged in the ionogen of molten state is connected with direct supply with anode, it is characterized in that, and be anode with the industrial silicon, with the inactive, conductive material negative electrode.
The present invention is directed to the not high problem of purity that adopts the solar grade polycrystalline silicon material that fused salt electrolysis process makes, a kind of new method for preparing the solar power silicon material is provided, creatively adopt industrial silicon as anode, making purity at negative electrode is polycrystalline silicon material more than 99.999%.Compare with silane thermal decomposition process with Siemens process, method of the present invention has high-level efficiency, less energy-consumption, low cost, oligosaprobic advantage, has realized the continuous production of solar grade polycrystalline silicon material.
Embodiment
According to the preparation method of solar grade polycrystalline silicon material provided by the invention, comprise that the negative electrode that will be arranged in the ionogen of molten state is connected with direct supply with anode, it is characterized in that, be anode with the industrial silicon, with the inactive, conductive material negative electrode.
Described industrial silicon is meant that purity is the silicon of 95%-99.5%, adopts the method for carbon reduction quartz sand to prepare industrial silicon usually in electric furnace.Described industrial silicon can be commercially available, and also can prepare according to the method for well known to a person skilled in the art, for example, employing method of reduction with carbon quartz sand in electric furnace prepares industrial silicon.As a kind of embodiment, can use the commercial industrial silicon of buying, as 441 model industrial silicons of the rich silicon materials of perseverance Industrial Co., Ltd. production.Usually, be benchmark with the gross weight, the elementary silicon content in the industrial silicon is 95%-99.5%, the impurity that contains mainly comprises one or more in iron, aluminium, calcium, boron and the phosphorus, also contains a small amount of other impurity that comprise copper, nickel, manganese etc. in the industrial silicon.
Under the preferable case, described anode is a porous flake, and preferred thickness is the 0.01-5 millimeter, more preferably the 0.1-2 millimeter.Flaky porosity can be 10%-30%.Flaky electrode can increase silicon and electrolytical contact area, improves electrolytic efficiency, reduces the influence of silicon poorly conductive to electrolytic efficiency, improves the preparation efficiency of silicon materials.According to the present invention, can adopt conventional method that industrial silicon is made sheet, for example prepare by " die cast-sintering " technology.Silica flour is dropped into mould, afterwards mould is put into universal hydraulic machine (magnificent forge press machines Manufacturing Co., Ltd, YJH32-315 four-column hydraulic press are built in Nantong) die cast, pressure is between the 0.5Mpa-5Mpa.Afterwards the sheet silicon that presses is put into vacuum sintering furnace (Shanghai Chen Hua Electric Furnace Corp Ltd.; the ZT-40-20B type) in; vacuum sintering furnace is evacuated to 5Pa, charges into purity and be 99.9% argon gas and protect sinter molding to 0.05MPa, sintering temperature is 1200 ℃.The porosity of the laminar silicon of gained adopts mercury injection apparatus (Micromeritics Instrument Corp. U.S.A, the full-automatic mercury injection apparatus of AutoPoreIV9500) test to obtain.
Described inactive, conductive material as negative electrode can be for well known to a person skilled in the art various inert materials, as graphite, platinum, rhodium and platinum rhodium etc.
Wherein, described ionogen contains alkali-metal silicate and/or alkali-metal silicofluoride, described ionogen also contains alkali-metal fluorochemical, and the weight ratio of described alkali-metal silicate and/or alkali-metal silicofluoride and alkali-metal fluorochemical can be 1-6: 1, be preferably 2-4: 1.
Described alkali-metal silicate can be in lithium silicate, water glass and the potassium silicate one or more; Described alkali-metal silicofluoride can be in lithium fluosilicate, Sodium Silicofluoride and the potassium silicofluoride one or more; Described alkali-metal fluorochemical can be in lithium fluoride, Sodium Fluoride and the Potassium monofluoride one or more.In order to make described ionogen keep molten state, temperature should be higher than electrolytical fusing point, is generally 700-1200 ℃, is preferably 750-1000 ℃.
The described condition that is connected with direct supply can comprise that anodic current density is a 0.01-1.1 peace/square centimeter, is preferably 0.1-0.5 peace/square centimeter.The time that connects with direct supply is relevant with the weight of anodic silicon chip, and silicon chip is heavy more, and the time is long more.Under the usual conditions, the time that is connected with direct supply is 0.5-80 hour, is preferably 5-15 hour.In the process of reaction, anode originally reduces gradually until disappearance, and solar grade polycrystalline silicon material forms on negative electrode.
According to method provided by the invention, in order to remove the fused salt of the polysilicon surface that obtains, improving its purity, this method can also be included in electrolysis finish the back with resistivity more than or equal to 18M Ω cm, or near the water washing anode of 18.3M Ω cm ultimate value.
Described resistivity is more than or equal to 18M Ω cm, or generally need pass through pre-treatment, reverse osmosis, ultrapureization processing and back level near the water of 18.3M Ω cm ultimate value and handle four big steps, and cascade filtration, high-performance ion-exchange unit, ultra filtration filter, ultraviolet lamp, except that obtaining after the multiple processing such as TOC device.
According to the present invention, described electrolysis is carried out in inert gas atmosphere, and described rare gas element is preferably in the zero group gas one or more for do not participate in the gas that reacts under condition of the present invention.
To be described in more detail the present invention by specific embodiment below.
Embodiment 1
Present embodiment is used to illustrate the preparation of solar grade polycrystalline silicon material of the present invention.
(1) anodic preparation
With 10 gram silica flours (the 441 model industrial silicons that permanent rich silicon materials Industrial Co., Ltd. produces, the purity of silicon is 98.5%) the input mould, (magnificent forge press machines Manufacturing Co., Ltd is built in Nantong afterwards mould to be put into universal hydraulic machine, the YJH32-315 four-column hydraulic press) die cast, pressure are 0.5Mpa.Afterwards the sheet silicon that presses is put into vacuum sintering furnace (Shanghai Chen Hua Electric Furnace Corp Ltd.; the ZT-40-20B type) in; vacuum sintering furnace is evacuated to 5Pa, charges into purity and be 99.9% argon gas and protect sinter molding to 0.05MPa, sintering temperature is 1200 ℃.Vacuum sintering furnace is reduced to room temperature with 20K/S speed obtain 140 millimeters * 100 millimeters * 0.3 millimeter laminar silicon.It is 29.6% that the laminar silicon of gained is adopted mercury injection apparatus (Micromeritics Instrument Corp. U.S.A, the full-automatic mercury injection apparatus of AutoPoreIV9500) test porosity.
(2) exsiccant 700 gram potassium silicates, 400 gram potassium silicofluorides and 400 gram Potassium monofluorides are mixed,, put into electrolyzer, in reactor, feed Ar gas, under 850 ℃, negative electrode is connected with direct supply with anode.Negative electrode is a graphite, and anode is the anode that above-mentioned steps (1) obtains, and the anodic current density is 0.1A/cm
2, the time that is connected with direct supply is 6 hours.
The polysilicon that fused salt electrolysis is obtained at the negative electrode place is with the water flushing of 18 megaohms 50-80 minute, and removing the fused salt on surface, and at the vacuum drying oven inner drying of nitrogen protection, drying temperature is 40 ℃, obtains polycrystalline silicon material A1.
Embodiment 2
Present embodiment is used to illustrate the preparation of solar grade polycrystalline silicon material of the present invention.
(1) anodic preparation
With 16 gram silica flours (the 441 model industrial silicons that permanent rich silicon materials Industrial Co., Ltd. produces, the purity of silicon is 98.5%) the input mould, (magnificent forge press machines Manufacturing Co., Ltd is built in Nantong afterwards mould to be put into universal hydraulic machine, the YJH32-315 four-column hydraulic press) die cast, pressure are 0.8Mpa.Afterwards the sheet silicon that presses is put into vacuum sintering furnace (Shanghai Chen Hua Electric Furnace Corp Ltd.; the ZT-40-20B type) in; vacuum sintering furnace is evacuated to 5Pa, charges into purity and be 99.9% argon gas and protect sinter molding to 0.05MPa, sintering temperature is 1200 ℃.Vacuum sintering furnace is reduced to room temperature with 20K/S speed obtain 140 millimeters * 100 millimeters * 0.5 millimeter laminar silicon.It is 24.5% that the laminar silicon of gained is adopted mercury injection apparatus (Micromeritics Instrument Corp. U.S.A, the full-automatic mercury injection apparatus of AutoPoreIV9500) test porosity.
(2) exsiccant 1000 gram potassium silicates and 500 gram Potassium monofluorides are mixed, put into electrolyzer, in reactor, feed Ar gas, under 1000 ℃, negative electrode is connected with direct supply with anode.Negative electrode is a graphite, and anode is the anode that above-mentioned steps (1) obtains, and the anodic current density is 0.2A/cm
2, the electrolysis time that is connected with direct supply is 8 hours.
The polysilicon that fused salt electrolysis is obtained at the negative electrode place is with the water flushing of 18 megaohms 50-80 minute, and removing the fused salt on surface, and at the vacuum drying oven inner drying of nitrogen protection, drying temperature is 40 ℃, obtains polycrystalline silicon material A2.
Embodiment 3
Present embodiment is used to illustrate the preparation of solar grade polycrystalline silicon material of the present invention.
(1) anodic preparation
With 22.5 gram silica flours (the 441 model industrial silicons that permanent rich silicon materials Industrial Co., Ltd. produces, the purity of silicon is 98.5%) the input mould, (magnificent forge press machines Manufacturing Co., Ltd is built in Nantong afterwards mould to be put into universal hydraulic machine, the YJH32-315 four-column hydraulic press) die cast, pressure are 1.2Mpa.Afterwards the sheet silicon that presses is put into vacuum sintering furnace (Shanghai Chen Hua Electric Furnace Corp Ltd.; the ZT-40-20B type) in; vacuum sintering furnace is evacuated to 5Pa, charges into purity and be 99.9% argon gas and protect sinter molding to 0.05MPa, sintering temperature is 1200 ℃.Vacuum sintering furnace is reduced to room temperature with 20K/S speed obtain 140 millimeters * 100 millimeters * 0.7 millimeter laminar silicon.It is 20.6% that the laminar silicon of gained is adopted mercury injection apparatus (Micromeritics Instrument Corp. U.S.A, AutoPore IV 9500 full-automatic mercury injection apparatuses) test porosity.
(2) exsiccant 1100 gram water glass and 400 gram Potassium monofluorides are mixed, put into electrolyzer, in reactor, feed Ar gas, under 1100 ℃, negative electrode is connected with direct supply with anode.Negative electrode is a graphite, and anode is the anode that above-mentioned steps (1) obtains, and the anodic current density is 0.4A/cm
2, the time that is connected with direct supply is 5 hours.
The polysilicon that fused salt electrolysis is obtained at the negative electrode place is with the water flushing of 18 megaohms 50-80 minute, and removing the fused salt on surface, and at the vacuum drying oven inner drying of nitrogen protection, drying temperature is 40 ℃, obtains polycrystalline silicon material A3.
Embodiment 4
Present embodiment is used to illustrate the preparation of solar grade polycrystalline silicon material of the present invention.
(1) anodic preparation
With 32 gram silica flours (the 441 model industrial silicons that permanent rich silicon materials Industrial Co., Ltd. produces, the purity of silicon is 98.5%) the input mould, (magnificent forge press machines Manufacturing Co., Ltd is built in Nantong afterwards mould to be put into universal hydraulic machine, the YJH32-315 four-column hydraulic press) die cast, pressure are 1.5Mpa.Afterwards the sheet silicon that presses is put into vacuum sintering furnace (Shanghai Chen Hua Electric Furnace Corp Ltd.; the ZT-40-20B type) in; vacuum sintering furnace is evacuated to 5Pa, charges into purity and be 99.9% argon gas and protect sinter molding to 0.05MPa, sintering temperature is 1200 ℃.Vacuum sintering furnace is reduced to room temperature with 20K/S speed obtain 140 millimeters * 100 millimeters * 1.0 millimeters laminar silicon.It is 16.9% that the laminar silicon of gained is adopted mercury injection apparatus (Micromeritics Instrument Corp. U.S.A, the full-automatic mercury injection apparatus of AutoPoreIV9500) test porosity.
(2) exsiccant 600 gram water glass, 500 gram Sodium Silicofluorides and 400 gram lithium fluoride are mixed, put into electrolyzer, in reactor, feed Ar gas, under 1200 ℃, negative electrode is connected with direct supply with anode.Negative electrode is a graphite, and anode is the anode that above-mentioned steps (1) obtains, and the anodic current density is 0.3A/cm
2, the electrolysis time that is connected with direct supply is 6 hours.
The polysilicon that fused salt electrolysis is obtained at the negative electrode place is with the water flushing of 18 megaohms 50-80 minute, and removing the fused salt on surface, and at the vacuum drying oven inner drying of nitrogen protection, drying temperature is 40 ℃, obtains polycrystalline silicon material A4.
Embodiment 5
Present embodiment is used to illustrate the preparation of solar grade polycrystalline silicon material of the present invention.
(1) anodic preparation
With silica flour (the 441 model industrial silicons that permanent rich silicon materials Industrial Co., Ltd. produces, the purity of silicon is 98.5%) the input mould, afterwards mould is put into universal hydraulic machine (magnificent forge press machines Manufacturing Co., Ltd, YJH32-315 four-column hydraulic press are built in Nantong) die cast, pressure is 1.8Mpa.Afterwards the sheet silicon that presses is put into vacuum sintering furnace (Shanghai Chen Hua Electric Furnace Corp Ltd.; the ZT-40-20B type) in; vacuum sintering furnace is evacuated to 5Pa, charges into purity and be 99.9% argon gas and protect sinter molding to 0.05MPa, sintering temperature is 1200 ℃.Vacuum sintering furnace is reduced to room temperature with 20K/S speed obtain 140 millimeters * 100 millimeters * 0.2 millimeter laminar silicon.It is 14.1% that the laminar silicon of gained is adopted mercury injection apparatus (Micromeritics Instrument Corp. U.S.A, the full-automatic mercury injection apparatus of AutoPoreIV9500) test porosity.
(2) exsiccant 700 gram potassium silicates, 400 gram potassium silicofluorides and 400 gram Potassium monofluorides are mixed,, put into electrolyzer, in reactor, feed Ar gas, under 850 ℃, negative electrode is connected with direct supply with anode.Negative electrode is a graphite, and anode is the anode that above-mentioned steps (1) obtains, and the anodic current density is 0.1A/cm
2, the time that is connected with direct supply is 5 hours.
The polysilicon that fused salt electrolysis is obtained at the negative electrode place is with the water flushing of 18 megaohms 50-80 minute, and removing the fused salt on surface, and at the vacuum drying oven inner drying of nitrogen protection, drying temperature is 40 ℃, obtains polycrystalline silicon material A5.
Embodiment 6
Present embodiment is used to illustrate the preparation of solar grade polycrystalline silicon material of the present invention.
(1) anodic preparation
With silica flour (the 441 model industrial silicons that permanent rich silicon materials Industrial Co., Ltd. produces, the purity of silicon is 98.5%) the input mould, afterwards mould is put into universal hydraulic machine (magnificent forge press machines Manufacturing Co., Ltd, YJH32-315 four-column hydraulic press are built in Nantong) die cast, pressure is 2.5Mpa.Afterwards the sheet silicon that presses is put into vacuum sintering furnace (Shanghai Chen Hua Electric Furnace Corp Ltd.; the ZT-40-20B type) in; vacuum sintering furnace is evacuated to 5Pa, charges into purity and be 99.9% argon gas and protect sinter molding to 0.05MPa, sintering temperature is 1200 ℃.Vacuum sintering furnace is reduced to room temperature with 20K/S speed obtain 140 millimeters * 100 millimeters * 2.0 millimeters laminar silicon.It is 11.8% that the laminar silicon of gained is adopted mercury injection apparatus (Micromeritics Instrument Corp. U.S.A, the full-automatic mercury injection apparatus of AutoPoreIV9500) test porosity.
(2) exsiccant 700 gram potassium silicates, 400 gram potassium silicofluorides and 400 gram Potassium monofluorides are mixed,, put into electrolyzer, in reactor, feed Ar gas, under 850 ℃, negative electrode is connected with direct supply with anode.Negative electrode is a graphite, and anode is the anode that above-mentioned steps (1) obtains, and the anodic current density is 0.1A/cm
2, the time that is connected with direct supply is 10 hours.
The polysilicon that fused salt electrolysis is obtained at the negative electrode place is with the water flushing of 18 megaohms 50-80 minute, and removing the fused salt on surface, and at the vacuum drying oven inner drying of nitrogen protection, drying temperature is 40 ℃, obtains polycrystalline silicon material A6.
From A1-6, wipe 0.2 gram respectively off, with ICP-MS (jigger coupling mass spectrum, the Agilent 7500cs type ICP-MS that Japan Agilent (Agilent) company makes) measure iron, aluminium, calcium, boron and the phosphorus among the A1-6 and comprise the content of other impurity of copper, nickel, manganese etc., the result is as shown in table 1.
Table 1
| The embodiment numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Sample number into spectrum | ??A1 | ??A2 | ??A3 | ??A4 | ??A5 | ??A6 |
| Silicone content (weight %) | ??99.999915 | ??99.99990 | ??99.99989 | ??99.99988 | ??99.99991 | ??99.99977 |
| Iron level (weight) | ??0.038ppm | ??0.060ppm | ??0.025ppm | ??0.036ppm | ??0.044ppm | ??0.042ppm |
| The embodiment numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Aluminium content (weight) | ??0.051ppm | ??0.044ppm | ??0.067ppm | ??0.093ppm | ??0.061ppm | ??0.074ppm |
| Calcium contents (weight) | ??0.065ppm | ??0.083ppm | ??0.074ppm | ??0.056ppm | ??0.058ppm | ??0.081ppm |
| Boron content (weight) | ??0.21ppm | ??0.26ppm | ??0.22ppm | ??0.39ppm | ??0.24ppm | ??0.46ppm |
| Phosphorus content (weight) | ??0.24ppm | ??0.37ppm | ??0.45ppm | ??0.31ppm | ??0.27ppm | ??0.50ppm |
| Copper content (weight) | ??0.037ppm | ??0.044ppm | ??0.065ppm | ??0.045ppm | ??0.042ppm | ??0.042ppm |
| Nickel content (weight) | ??0.044ppm | ??0.051ppm | ??0.040ppm | ??0.066ppm | ??0.039ppm | ??0.047ppm |
| Manganese content (weight) | ??0.048ppm | ??0.039ppm | ??0.044ppm | ??0.053ppm | ??0.041ppm | ??0.036ppm |
| Chromium content (weight) | ??0.052ppm | ??0.058ppm | ??0.077ppm | ??0.049ppm | ??0.055ppm | ??0.051ppm |
| Other foreign matter content (weight) | ??0.063ppm | ??0.053ppm | ??0.046ppm | ??0.059ppm | ??0.072ppm | ??0.044ppm |
As can be seen from Table 1, method provided by the invention can be removed the impurity in the low-purity silicon, makes the polycrystalline silicon material of the specification of quality that meets solar-grade polysilicon at negative electrode.
Claims (10)
1. the preparation method of a solar grade polycrystalline silicon material, this method comprises that the negative electrode that will be arranged in the ionogen of molten state is connected with direct supply with anode, it is characterized in that, be described anode with industrial silicon, be described negative electrode with inactive, conductive material.
2. method according to claim 1, wherein, described anode is a porous flake, and thickness is the 0.01-5 millimeter, and porosity is 10%-30%.
3. method according to claim 1, wherein, the anodic current density that is connected with described direct supply is a 0.01-1.1 peace/square centimeter.
4. according to claim 1 or 3 described methods, wherein, the anodic current density that is connected with described direct supply is a 0.1-0.5 peace/square centimeter.
5. method according to claim 1 wherein, is a benchmark with the gross weight of described industrial silicon, and the silicone content in the described industrial silicon is 95-99.5%.
6. method according to claim 1, wherein, described ionogen contains alkali-metal silicate and/or alkali-metal silicofluoride, described ionogen also contains alkali-metal fluorochemical, and the weight ratio of described alkali-metal silicate and/or alkali-metal silicofluoride and alkali-metal fluorochemical is 1-6: 1.
7. method according to claim 6, wherein, described alkali-metal silicate is one or more in lithium silicate, water glass and the potassium silicate; Described alkali-metal silicofluoride is one or more in lithium fluosilicate, Sodium Silicofluoride and the potassium silicofluoride; Described alkali-metal fluorochemical is one or more in lithium fluoride, Sodium Fluoride and the Potassium monofluoride.
8. method according to claim 1, wherein, making described ionogen keep the temperature of molten state is 700-1200 ℃.
9. method according to claim 1, wherein, this method also is included in described direct supply and is connected afterwards with the water washing described anode of resistivity more than or equal to 18M Ω cm.
10. method according to claim 1, wherein, the described negative electrode that will be arranged in the ionogen of described molten state in inert gas atmosphere is connected with direct supply with anode.
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| CN101979712A (en) * | 2010-12-01 | 2011-02-23 | 武汉大学 | Method for preparing elemental silicon |
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| US3983012A (en) * | 1975-10-08 | 1976-09-28 | The Board Of Trustees Of Leland Stanford Junior University | Epitaxial growth of silicon or germanium by electrodeposition from molten salts |
| US4298587A (en) * | 1980-10-28 | 1981-11-03 | Atlantic Richfield Company | Silicon purification |
| CN101012566A (en) * | 2006-12-25 | 2007-08-08 | 杨贻方 | Silicon electrolyzation |
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| CN102534716A (en) * | 2012-03-29 | 2012-07-04 | 河海大学常州校区 | Solution for preparing silicon nano-column arrays on surface of silicon slice and preparation method |
| CN102534716B (en) * | 2012-03-29 | 2015-04-01 | 河海大学常州校区 | Solution for preparing silicon nano-column arrays on surface of silicon slice and preparation method |
| RU2671206C1 (en) * | 2018-07-25 | 2018-10-30 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" (КБГУ) | Electrochemical method of producing a microcrystalline powder of silicon |
| CN110565107A (en) * | 2019-09-27 | 2019-12-13 | 东北大学 | method and device for regulating and controlling electrochemical deposition silicon preferred orientation growth in high-temperature molten salt |
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