CN101724898B - Method for preparing solar grade polycrystalline silicon material - Google Patents
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- CN101724898B CN101724898B CN2008101678172A CN200810167817A CN101724898B CN 101724898 B CN101724898 B CN 101724898B CN 2008101678172 A CN2008101678172 A CN 2008101678172A CN 200810167817 A CN200810167817 A CN 200810167817A CN 101724898 B CN101724898 B CN 101724898B
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Abstract
The invention discloses a method for preparing a solar grade polycrystalline silicon material. The method comprises the step of electrolyzing a silicon-containing material in fused salt, wherein the polycrystalline silicon material of which the purity is more than or equal to 99.999 percent is used as a cathode, and an inert material is used as an anode; the silicon-containing material is a material containing silicon and metal, wherein the silicon is easier to lose electrons and be oxidized into positive ions at the anode compared with the metal, and the melting point of the silicon-containing material is not higher than the electrolyzing temperature; and the electrolyzing temperature is between 700 and 1,200 DEG C. The purity of the solar grade polycrystalline silicon material prepared by the method of the invention is higher.
Description
Technical field
The present invention relates to a kind of preparation method of polycrystalline silicon, relate more specifically to a kind of preparation method of solar-grade polysilicon.
Background technology
Sun power has received extensive concern as the novel energy of a kind of cleaning, Sustainable development.High purity polycrystalline silicon is the starting material of solar cell.At present, the technology of production polysilicon is siemens process and silane thermal decomposition process technology.Siemens process is complicated, and service temperature is high, and energy consumption is high, and facility investment is big, and the production of polysilicon cost is high.Silane thermal decomposition process is inflammable and explosive, and is dangerous big.Simultaneously, owing to the high speed development of sun power industry, cause the critical shortage of polycrystalline silicon material, 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.
Fused salt electrolysis process is a kind of method for preparing polysilicon.The method for preparing solar-grade polysilicon with fused salt electrolysis has: (1) is negative electrode with the high-purity silicon dioxide, through 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) as disclosing a kind of method of utilizing fused salt electrolysis process to prepare the solar level silicon materials among the CN101070598A; This method comprises; With silicon-dioxide or other silicon-containing compound A is raw material, and metal M 1 is a negative electrode, and 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; Said silicon-containing compound A is Li
2SiF
6, Na
2SiF
6, K
2SiF
6, Li
2SiO
3, Na
2SiO
3, K
2SiO
3, CaSiO
3, MgSiO
3, BaSiO
3, Mg
2SiO
4Or Be
2SiO
4Said metal M 1 is Ag, Bi, Cd, Ce, Cu, Co, Cr, Fe, In, Mo, Ni, Pb, at least a among Sn or the Zn; Said metal M 2 is Al, Mg, Ca, Li, Na, K, Be, Sr, Ba, at least a among Sc or the Rb; Said fluoride molten salt consists of Me
3AlF
6-Me '
2SiF
6-Me " F
x, each constituent mass percentage composition is: 1-100%Me
3AlF
6, 0-99%Me '
2SiF
6, 0-40%Me " F
xWherein Me is at least a among Na, K or the Li; Me ' is at least a among Na, K or the Li; Me " be at least a among Al, Mg, Ca, Ba, Na, K or the Li.The polysilicon purity that this method makes is not high.
Summary of the invention
The objective of the invention is to overcome the not high defective of polysilicon purity that prior art makes, a kind of preparation method that can access the solar grade polycrystalline silicon material of higher degree is provided.
CN101070598A adopts and prepares earlier the silicon alloy method of vacuum distilling again; Adopt other metal as negative electrode during the preparation silicon alloy; Will introduce other impurity inevitably, and can not the metal in the alloy that make be removed fully, and the purity of the polycrystalline silicon material that causes making is not high; And in the process of vacuum distilling, caused the loss of silicon materials inevitably, and increased cost.
The invention provides a kind of preparation method of solar grade polycrystalline silicon material, this method is included in electrolysis material in the fused salt, wherein, is negative electrode with purity more than or equal to 99.9999% polycrystalline silicon material, is anode with the inactive, conductive material; Said material is siliceous and material metal, and wherein, silicon loses electronics at anode more easily than metal and is oxidized to positively charged ion, and the fusing point of material is not more than electrolysis temperature; Electrolysis temperature is 700-1200 ℃.
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; Provide a kind of new fused salt electrolysis to prepare the method for solar level silicon materials; Creationary employing pure silicon is as negative electrode; Make silicon in the material that silicon purity is lower in electrolytic process constantly separate out and attached on the negative electrode, making negative electrode constantly grow up and make purity is the polycrystalline silicon material more than 99.9999%.Adopt the purity of the solar grade polycrystalline silicon material that method of the present invention makes higher, and method of the present invention also has high-level efficiency, less energy-consumption, low cost, oligosaprobic advantage, realized the continuous production of solar grade polycrystalline silicon material.
Embodiment
Method provided by the invention is included in electrolysis material in the fused salt, wherein, is negative electrode with purity more than or equal to 99.9999% polycrystalline silicon material, is anode with the inactive, conductive material; Said material is siliceous and material metal; Wherein, Silicon loses electronics at anode more easily than metal and is oxidized to positively charged ion, and the metal of said material is preferably one or more in copper, silver, zinc, gold, molybdenum and the nickel, and the fusing point of material is not more than electrolysis temperature; Electrolytic temperature is 700-1200 ℃, is preferably 750-1000 ℃.
Different according to the weight ratio of the different or silicon of metallic element contained in the material and metal; The fusing point of material is also different; According to the present invention, the selectable range broad of metal in the material, also broad of the variable range of the weight ratio of silicon and metal in addition; As long as guarantee under electrolysis temperature, said material fusion fully gets final product.Is about 1420 ℃ as the purity of negative electrode more than or equal to the fusing point of 99.9999% polycrystalline silicon material, be higher than electrolysis temperature far away, thereby negative electrode fusion can not take place under electrolysis temperature.In addition, under electrolysis temperature, the activity of metal is weaker than the activity of silicon in the said material; That is, silicon loses electronics at anode more easily than metal and is oxidized to positively charged ion, therefore; In electrolytic process; Silicon in the material loses the positively charged ion that electronics is oxidized to silicon at anode more easily than metal, is reduced into silicon and on attached to negative electrode, makes the polycrystalline silicon material of negative electrode constantly grow up at negative electrode then.
Said material can be commercially available, and also can prepare according to the method for well known to a person skilled in the art, for example, adopts arc-melting furnace to come the melting material; In the method for the invention; The content of silicon can be adjusted in the scope of broad in the said material; In order to take into account high production efficiency and low cost; And the fusing point that guarantees material is not higher than electrolysis temperature, is benchmark with the weight of material, and the content of said silicon can be 5-50 weight %; The content of metal can be 50-95 weight %.The range of choice broad of metal in the said material, the kind of said metal is not higher than electrolysis temperature as long as guarantee the fusing point of material, and in some cases, said metal is selected from one or more in copper, silver, zinc, gold, molybdenum and the nickel.
Said purity as negative electrode can be commercially available more than or equal to 99.9999% polycrystalline silicon material, and for example, the purity that Wa Ke company produces is 99.9999999% polycrystalline silicon material, also can prepare according to the method for prior art.Said can be as the anodic inactive, conductive material for well known to a person skilled in the art various inactive, conductive material, like graphite, platinum, rhodium or platinum rhodium etc.
Wherein, Said fused salt can be the formed fused salt of mixture fusion with alkali-metal silicate and/or alkali-metal silicofluoride and alkali-metal fluorochemical; The weight ratio of said alkali-metal silicate and/or alkali-metal silicofluoride and alkali-metal fluorochemical can be 1-6:1, is preferably 2-4:1.
Said alkali-metal silicate can be in lithium silicate, water glass and the potassium silicate one or more; Said alkali-metal silicofluoride can be in lithium fluosilicate, Sodium Silicofluoride 98min and the potassium silicofluoride one or more; Said alkali-metal fluorochemical can be in lithium fluoride, Sodium Fluoride and the Potassium monofluoride one or more.Under electrolysis temperature, said fused salt can be in molten state; Generally, the melt temperature of fused salt can be 700-1200 ℃, is preferably 750-1000 ℃.
Said fused salt mainly plays electric action, and silicon materials and fused salt are an equilibrium system when electrolysis, and in electrolytic process, fused salt can not be consumed.Therefore, according to the present invention, the adjustable extent broad of the amount of said fused salt; As long as the amount of fused salt guarantees to play electric action, according to the present invention, generally speaking; In order to guarantee electrolytic efficiency, avoid the wasting of resources again, the weight ratio of said fused salt and material can be 5-50:1.
According to a kind of preferred implementation of the present invention, under electrolysis temperature, in above-mentioned fused salt,, generate silicon at the negative electrode place with the material electrolysis, through continuous rotary lifting negative electrode, silicon is constantly generated at the negative electrode place, thereby realized serialization production.The speed of said lifting can for the 0.05-60 millimeter/hour, be preferably the 0.5-5 millimeter/hour; The speed of rotation can be the 1-50 mm/min; Be preferably the 4-10 mm/min; Said negative electrode is a rotary lifting, and the speed of lifting refers to the vertical range (being the displacement of negative electrode) that the unit time inner cathode promotes, and SR refers to the distance that the unit time inner cathode moves along helical trajectory.
The method that promotes can adopt and well known to a person skilled in the art the whole bag of tricks; For example; Before electrolysis, negative electrode is fixed on wire or the metal bar, constantly rotary lifting wire or metal bar and negative electrode is constantly promoted in electrolytic process, said wire or metal bar can be selected from conduction; And the not various metals of fused, for example copper or stainless steel under the electrolysis temperature.
Wherein, electrolytic condition comprises that cathode current density is a 0.01-1.2 peace/square centimeter, is preferably 0.05-0.5 peace/square centimeter; The electroconductibility of material that plays electric action as antianode (inert material) is better, and therefore, the current density of antianode is not special to be limited, and generally reaches 0.1-1 peace/square centimeter and gets final product.Not special qualification of electrolytic time, the amount that can generate silicon is as required confirmed.
According to method provided by the invention; In order to remove the fused salt of the polysilicon surface that obtains; To improve its purity; This method can also be included in electrolysis and finish the polysilicon that the back makes with the ultrapure water washing, said ultrapure water refer in the water conducting medium, dissociative colloidalmaterial, gas and organism all are not removed to the very water of low degree.We can say that also said ultrapure water is that resistivity is more than or equal to 18M Ω cm, or near the water of 18.3M Ω cm ultimate value.
Ultrapure water generally need pass through pre-treatment, r-o-, ultrapureization processing and back level and handle; Comprise cascade filtration, high-performance ion-exchange unit, ultra filtration filter, ultra violet lamp, remove TOC multiple processing such as (total organic carbons), obtain the ultrapure water of resistivity more than or equal to 18M Ω cm.Above-mentioned PREPARATION OF ULTRA-PURE WATER method is conventionally known to one of skill in the art, according to the present invention, can prepare ultrapure water according to above-mentioned known method, also can be commercially available.
According to the method for the invention; In order to remove the metallic impurity of negative electrode polycrystalline silicon material surface adhesion; Like iron, aluminium, calcium etc., before this method also is included in electrolysis, use concentration to be detected up to non-metallic ion as the aqueous hydrochloric acid cleaning negative electrode of 1-5 weight %; Water cleans then, is detected up to no cl ions.
According to the present invention, said electrolysis is carried out under inert atmosphere, and said inert atmosphere can be selected from one or more in the zero group gas.
To be described in more detail the present invention through specific embodiment below.
Embodiment 1
Present embodiment is used to explain the preparation of solar grade polycrystalline silicon material of the present invention.
(1) preparation of material
The silica flour that with purity is copper powder and the oven dry of 99 weight % drops in the arc-melting furnace (Shenyang scientific instrument factory) according to the weight ratio of 75:25; Arc-melting furnace is evacuated to 0.1Pa; Charging into purity and be 99.9% argon gas protects to 0.05MPa; 1500 ℃ of following meltings 6 minutes, make the abundant fusion of raw material, melt is cast in the copper mold with 10
2The speed of cooling of K/s is carried out water-cooled, obtains to be of a size of 95 millimeters * 10 millimeters * 3 millimeters material.
(2) electrolysis
It is in 2% the aqueous hydrochloric acid 30 minutes that purity is immersed in concentration more than or equal to 99.9999% polysilicon (Wa Ke company buys), and non-metallic ion is detected, and water cleans then, and no cl ions is detected.
The material (200 gram) that step (1) is obtained places electrolyzer; Then exsiccant 600 gram potassium silicates, 500 gram potassium silicofluorides and 400 gram Potassium monofluorides are mixed, put into electrolyzer, in electrolyzer, feed argon gas; Under 900 ℃, carry out constant-current electrolysis.Anode is a graphite, and negative electrode is a purity more than or equal to 99.9999% polysilicon (weight is 50 grams), cathode current density be 0.1 peace/centimetre
2, anodic current density be 0.3 the peace/centimetre
2Electrolysis time is 12 hours., begin negative electrode is constantly rotated up lifting after 10 minutes from the beginning electrolysis, promoting speed is 1.2 millimeters/hour, and SR is 5 mm/min.
The polycrystalline silicon rod that fused salt electrolysis is obtained is with the ultrapure 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 (weight is 70 grams).
Scrape from the above-mentioned polycrystalline silicon material surface that obtains and to get the 1-2 gram, take by weighing 0.2 gram and adopt icp ms (ICP-MS) to detect, the purity that records polysilicon is 99.99993%; Iron level 0.032ppm wherein; Aluminium content 0.057ppm, calcium contents 0.063ppm, boron content 0.26ppm; Phosphorus 0.22ppm, other 0.067ppm.
Embodiment 2
Present embodiment is used to explain the preparation of solar grade polycrystalline silicon material of the present invention.
(1) preparation of material
The silica flour that with purity is silver powder and the oven dry of 99 weight % drops in the arc-melting furnace (Shenyang scientific instrument factory) according to the weight ratio of 90:10; Arc-melting furnace is evacuated to 0.1Pa; Charging into purity and be 99.9% argon gas protects to 0.05MPa; 1500 ℃ of following meltings 6 minutes, make the abundant fusion of raw material, melt is cast in the copper mold with 10
2The speed of cooling of K/s is carried out water-cooled, obtains to be of a size of 95 millimeters * 10 millimeters * 3 millimeters material.
(2) electrolysis
It is in 2% the aqueous hydrochloric acid 30 minutes that purity is immersed in concentration more than or equal to 99.9999% polysilicon (Wa Ke company buys), and non-metallic ion is detected, and water cleans then, and no cl ions is detected.
The material (200 gram) that step (1) is obtained places electrolyzer; Then exsiccant 700 gram potassium silicates, 400 gram potassium silicofluorides and 400 gram Potassium monofluorides are mixed, put into electrolyzer, in electrolyzer, feed argon gas; Under 900 ℃, carry out constant-current electrolysis.Anode is a graphite, and negative electrode is a purity more than or equal to 99.9999% polysilicon (weight is 50 grams), cathode current density be 0.2 peace/centimetre
2, anodic current density be 0.4 the peace/centimetre
2Electrolysis time is 6 hours., begin negative electrode is constantly rotated up lifting after 10 minutes from the beginning electrolysis, promoting speed is 2.4 millimeters/hour, and SR is 5 mm/min.
The polycrystalline silicon rod that fused salt electrolysis is obtained is with the ultrapure 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 (weight is 66 grams).
Scrape from the above-mentioned polycrystalline silicon material surface that obtains and to get the 1-2 gram, take by weighing 0.2 gram, adopt icp ms (ICP-MS) to detect; The purity that records polysilicon is 99.99992%, iron level 0.043ppm wherein, aluminium content 0.064ppm; Calcium contents 0.073ppm; Boron content 0.30ppm, phosphorus 0.27ppm, other 0.058ppm.
Embodiment 3
Present embodiment is used to explain the preparation of solar grade polycrystalline silicon material of the present invention.
(1) preparation of material
The silica flour that with purity is zinc powder and the oven dry of 99 weight % drops in the arc-melting furnace (Shenyang scientific instrument factory) according to the weight ratio of 93:7; Arc-melting furnace is evacuated to 0.1Pa; Charging into purity and be 99.9% argon gas protects to 0.05MPa; 1500 ℃ of following meltings 6 minutes, make the abundant fusion of raw material, melt is cast in the copper mold with 10
2The speed of cooling of K/s is carried out water-cooled, obtains to be of a size of 95 millimeters * 10 millimeters * 3 millimeters material.
(2) electrolysis
It is in 2% the aqueous hydrochloric acid 30 minutes that purity is immersed in concentration more than or equal to 99.9999% polysilicon (Wa Ke company buys), and non-metallic ion is detected, and water cleans then, and no cl ions is detected.
The material (200 gram) that step (1) is obtained places electrolyzer; Then exsiccant 550 gram potassium silicates, 450 gram potassium silicofluorides and 500 gram Potassium monofluorides are mixed, put into electrolyzer, in electrolyzer, feed argon gas; Under 900 ℃, carry out constant-current electrolysis.Anode is a graphite, and negative electrode is a purity more than or equal to 99.9999% polysilicon (weight is 50 grams), cathode current density be 0.05 peace/centimetre
2, anodic current density be 0.1 the peace/centimetre
2Electrolysis time is 10 hours., begin negative electrode is constantly rotated up lifting after 10 minutes from the beginning electrolysis, promoting speed is 0.6 millimeter/hour, and SR is 5 mm/min.
The polycrystalline silicon rod that fused salt electrolysis is obtained is with the ultrapure 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 (weight is 60 grams).
Scrape from the above-mentioned polycrystalline silicon material surface that obtains and to get the 1-2 gram, take by weighing 0.2 gram, adopt icp ms (ICP-MS) to detect; The purity that obtains polysilicon is 99.99993%, iron level 0.050ppm wherein, aluminium content 0.041ppm; Calcium contents 0.078ppm; Boron content 0.22ppm, phosphorus 0.21ppm, other 0.093ppm.
Embodiment 4
Present embodiment is used to explain the preparation of solar grade polycrystalline silicon material of the present invention.
(1) preparation of material
The silica flour that with purity is copper powder and the oven dry of 99 weight % drops in the arc-melting furnace (Shenyang scientific instrument factory) according to the weight ratio of 85:15; Arc-melting furnace is evacuated to 0.1Pa; Charging into purity and be 99.9% argon gas protects to 0.05MPa; 1500 ℃ of following meltings 6 minutes, make the abundant fusion of raw material, melt is cast in the copper mold with 10
2The speed of cooling of K/s is carried out water-cooled, obtains to be of a size of 95 millimeters * 10 millimeters * 3 millimeters material.
(2) electrolysis
The material (200 gram) that step (1) is obtained places electrolyzer; Then exsiccant 600 gram potassium silicates, 600 gram potassium silicofluorides and 300 gram Potassium monofluorides are mixed, put into electrolyzer, in electrolyzer, feed argon gas; Under 1000 ℃, carry out constant-current electrolysis.Anode is a graphite, and negative electrode is a purity more than or equal to 99.9999% polysilicon (Wa Ke company buys) (weight is 50 grams), cathode current density be 0.15 peace/centimetre
2, anodic current density be 0.2 the peace/centimetre
2Electrolysis time is 8 hours., begin the continuous rotary lifting of negative electrode after 10 minutes from the beginning electrolysis, promoting speed is 1.8 millimeters/hour, and SR is 5 mm/min.
The polycrystalline silicon rod that fused salt electrolysis is obtained is with the ultrapure 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 60 ℃, obtains polycrystalline silicon material (weight is 68 grams).
Scrape from the above-mentioned polycrystalline silicon material surface that obtains and to get the 1-2 gram, take by weighing 0.2 gram, adopt icp ms (ICP-MS) to detect; The purity that obtains polysilicon is 99.99991%, iron level 0.040ppm wherein, aluminium content 0.068ppm; Calcium contents 0.066ppm; Boron content 0.32ppm, phosphorus 0.28ppm, other 0.087ppm.
Claims (9)
1. the preparation method of a solar grade polycrystalline silicon material, this method is included in electrolysis material in the fused salt, it is characterized in that, be negative electrode with purity more than or equal to 99.9999% polycrystalline silicon material, with the inactive, conductive material anode; Said material is siliceous and material metal, and wherein, silicon loses electronics at anode more easily than metal and is oxidized to positively charged ion, and the fusing point of material is not more than electrolysis temperature; Electrolysis temperature is 700-1200 ℃.
2. method according to claim 1 wherein, is a benchmark with the weight of material, and the content of silicon is 5-50 weight %, and the content of metal is 50-95 weight %.
3. method according to claim 1 and 2, wherein, said metal is selected from one or more in copper, silver, zinc, gold, molybdenum and the nickel.
4. method according to claim 1; Wherein, Said fused salt is that the weight ratio of said alkali-metal silicate and/or alkali-metal silicofluoride and alkali-metal fluorochemical is 1-6:1 with the formed fused salt of mixture fusion of alkali-metal silicate and/or alkali-metal silicofluoride and alkali-metal fluorochemical.
5. method according to claim 1, wherein, said electrolytic condition comprises that cathode current density is a 0.01-1.2 peace/square centimeter.
6. method according to claim 1, wherein, said inactive, conductive material is graphite, platinum, rhodium or platinum rhodium.
7. method according to claim 1, wherein, this method also is included in the electrolytic process, with the continuous rotary lifting of negative electrode, the speed of lifting be the 0.05-60 millimeter/hour, the speed of rotation is the 1-50 mm/min.
8. method according to claim 1, wherein, this method also is included in electrolysis and finishes the polysilicon that the back makes more than or equal to the water washing of 18M Ω cm with resistivity.
9. method according to claim 1 wherein, before this method also is included in electrolysis, uses concentration to be detected up to non-metallic ion as the aqueous hydrochloric acid cleaning negative electrode of 1-5 weight %, and water cleans then, is detected up to no cl ions.
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| CN103774216B (en) * | 2013-12-02 | 2017-03-29 | 内蒙古机电职业技术学院 | The method that molten-salt electrolysis and directional solidification combination technique produce solar-grade polysilicon |
| CN108823637A (en) * | 2018-07-30 | 2018-11-16 | 孟静 | The device of purifying polycrystalline silicon |
| CN108842183A (en) * | 2018-09-10 | 2018-11-20 | 孟静 | The preparation method of polysilicon chip |
| CN110512223B (en) * | 2019-08-07 | 2020-12-01 | 武汉大学 | Fused salt electrochemical method for preparing silicon nanotube without template |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298587A (en) * | 1980-10-28 | 1981-11-03 | Atlantic Richfield Company | Silicon purification |
| CN101070598A (en) * | 2007-03-26 | 2007-11-14 | 中南大学 | Method for preparing solar-grade silicon material by melt-salt electrolysis method |
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2008
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298587A (en) * | 1980-10-28 | 1981-11-03 | Atlantic Richfield Company | Silicon purification |
| CN101070598A (en) * | 2007-03-26 | 2007-11-14 | 中南大学 | Method for preparing solar-grade silicon material by melt-salt electrolysis method |
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