WO2002099166A1 - Electrolyte and method for manufacturing and/or refining of silicon - Google Patents
Electrolyte and method for manufacturing and/or refining of silicon Download PDFInfo
- Publication number
- WO2002099166A1 WO2002099166A1 PCT/NO2002/000195 NO0200195W WO02099166A1 WO 2002099166 A1 WO2002099166 A1 WO 2002099166A1 NO 0200195 W NO0200195 W NO 0200195W WO 02099166 A1 WO02099166 A1 WO 02099166A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silicon
- melt
- cao
- electrolyte
- cathode
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/33—Silicon
Definitions
- Electrolyte and method for manufacturing and/or refining of silicon are Electrolyte and method for manufacturing and/or refining of silicon.
- the present invention relates to an electrolyte.
- the invention further relates to a method for the manufacture of or refining of silicon, by which the electrolyte is utilized.
- Silicon may in terms of quality be divided into three categories, silicon for metallurgical purposes, high-grade silicon for solar cell production (SoG-Si) and extremely high- grade silicon for electronic purposes.
- the cryolite melt has the advantageous property that it dissolves silicon dioxide well and that it is inexpensive. It is thus convenient for the manufacture of metallurgic grade silicon with a typical purity of 99.5 - 99.7%, provided there is no requirement for absence of particular kinds of impurities. This method has, however, severe drawbacks when it comes to the manufacture of high grade silicon.
- the cryolite melt is extremely corrosive, particularly at high temperatures, as a consequence of its fluoride content. Therefore the range of allowable electrode materials in such a melt is very limited. In practice only carbon electrodes have been able to be utilized for this purpose.
- Carbon electrodes are encumbered with certain disadvantages related to manufacture of very pure silicon as they tend to contaminate the melt, and thus the silicon produced therefrom, with traces of boron and phosphorous. These elements, which are found as trace elements in carbon, are not removable from the product by any known purification method, which renders silicon manufactured this way very difficult to use for the purposes of solar cells.
- cryolite melt deposits with the product, and this contamination is also very difficult to remove from the silicon by any l ⁇ iown refining or purification method.
- SoG-Si solar cell quality silicon
- the invention thus concerns an electrolyte as defined by claim 1.
- the invention also concerns a method for the manufacture of silicon as defined by claim 4.
- phase diagrams a melt of CaCl 2 will be able to dissolve SiO 2 in an amount sufficient for the salt to serve as an electrolyte in a process of the kind mentioned above, and more precisely in the magnitude of 5%. It was, however, discovered during the work leading to the present invention, that said phase diagrams are incorrect. Pure CaCl 2 dissolves SiO, only to a very limited degree, namely in the magnitude of 0.1 %. CaCl 2 is highly hygroscopic, and a possible source of error for the known phase diagram(s) may be that the measurements have been conducted with a not completely pure CaCl 2 , which means that oxygen in the form of water may have been included in the melt.
- a possible disadvantage of chloride based melts for electrolysis of dissolved oxides is that significant amounts of chlorine gas develop at the anode.
- Thermodynamically oxygen should form before chloride, but kinetical relations will in practice decide the relative amounts of these gases. Therefore it is convenient to use an anode material that promotes the development of oxygen and inhibits the development of chloride gas.
- Carbon is an example of an anode material that is well suited for this purpose, but as mentioned above it has the disadvantage that it (usually) contains phosphorous and boron that easily transfer to the product.
- Some carbon sources may, however, be well suited as anode material for the method according to the invention.
- modified nickel ferrite, doped tin oxide or an oxidation resistant metal alloy chosen among the metals, tungsten, silver, gold, platinum and palladium may be used as anode material.
- inert i.e. non-consumable, anodes.
- cathode material e.g. silicon or alloys containing silicon are well suited. Silicon alone has, however, an inconveniently low electrical conductivity , which is why some amount of metal, e.g. calcium, is preferably added. The amount of calcium in such an alloy may vary typically from a few per cent to e.g. 30%.
- Other materials that by experience may be included in such alloys are tungsten, nickel and iron. Iron or tungsten have proved to be particularly advantageous, as well as alloys including silicon and said metals, as these metals/ alloys do not react with metals that deposit in the process, particularly calcium.
- the process may - with less purification - be competitive also with production processes of silicon of a lower quality than the solar cell quality.
- the invention may be utilized for refining silicon of an arbitrary degree of purity.
- an alloy of the "impure" silicon together with another metal is used as anode in an electrolyte of said type.
- Particularly preferred is an alloy of copper and silicon.
- test la and lb indicates a certain content of phosphorous, which mainly origins from the raw materials. Typically the CaO would contain some phosphorous. With respect to boron, the very low levels found in the test runs la and lb indicate that the method works according to the expectations with platinum anode and CaSi cathode.
- Test 2 shows an undesired high content of boron with respect to the use of the material for electronic purposes. This content mainly originates from the electrodes.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002449659A CA2449659A1 (en) | 2001-06-05 | 2002-06-03 | Electrolyte and method for manufacturing and/or refining of silicon |
EP02731017A EP1402086A1 (en) | 2001-06-05 | 2002-06-03 | Electrolyte and method for manufacturing and/or refining of silicon |
JP2003502269A JP2004532933A (en) | 2001-06-05 | 2002-06-03 | Electrolyte and method for producing and / or purifying silicon |
US10/477,747 US20040238372A1 (en) | 2001-06-05 | 2002-06-03 | Electrolyte and method for manufacturing and/or refining of silicon |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO20012749 | 2001-06-05 | ||
NO20012749A NO317073B1 (en) | 2001-06-05 | 2001-06-05 | Electrolyte and process for the manufacture or refining of silicon |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002099166A1 true WO2002099166A1 (en) | 2002-12-12 |
Family
ID=19912527
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NO2002/000195 WO2002099166A1 (en) | 2001-06-05 | 2002-06-03 | Electrolyte and method for manufacturing and/or refining of silicon |
Country Status (6)
Country | Link |
---|---|
US (1) | US20040238372A1 (en) |
EP (1) | EP1402086A1 (en) |
JP (1) | JP2004532933A (en) |
CA (1) | CA2449659A1 (en) |
NO (1) | NO317073B1 (en) |
WO (1) | WO2002099166A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005063621A1 (en) * | 2003-12-29 | 2005-07-14 | Elkem Asa | Silicon feedstock for solar cells |
NL1031734C2 (en) * | 2006-05-03 | 2007-11-06 | Girasolar B V | Process for purifying a semiconductor material using an oxidation-reduction reaction. |
JP2010530637A (en) * | 2007-06-18 | 2010-09-09 | アール・イー・シー・スキャンウェハー・アー・エス | Method to regenerate elemental silicon from cutting residue |
CN101967649A (en) * | 2010-09-09 | 2011-02-09 | 昆明理工大学 | Method for preparing silicon from composite molten salt electrolyte |
CN103173780A (en) * | 2013-03-01 | 2013-06-26 | 中南大学 | Method and device for preparing solar polycrystalline silicon material by semi-continuous molten salt electrolysis |
US10147836B2 (en) | 2012-05-31 | 2018-12-04 | Board Of Regents Of The University Of Texas System | Production of thin film solar grade silicon on metals by electrodeposition from silicon dioxide in a molten salt |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4765066B2 (en) * | 2005-05-19 | 2011-09-07 | 国立大学法人京都大学 | Method for producing silicon |
AU2007226754B2 (en) * | 2006-03-10 | 2011-01-20 | Elkem As | Method for electrolytic production and refining of metals |
JP2010523450A (en) * | 2007-04-05 | 2010-07-15 | ソルヴェイ(ソシエテ アノニム) | High purity calcium compound |
US7872676B2 (en) * | 2007-07-13 | 2011-01-18 | Micron Technology, Inc. | Methods, systems, and devices for offset compensation in CMOC imagers |
CN101736354B (en) * | 2008-11-06 | 2011-11-16 | 北京有色金属研究总院 | Method for preparing one or more of silicon nano power, silicon nanowires and silicon nanotubes by electrochemical method |
CN101979712A (en) * | 2010-12-01 | 2011-02-23 | 武汉大学 | Method for preparing elemental silicon |
US20180291513A1 (en) * | 2017-04-11 | 2018-10-11 | Wisconsin Alumni Research Foundation | Low temperature electrochemical production of silicon |
CN110629241B (en) * | 2019-09-16 | 2021-06-22 | 上海大学 | Silicon material manufacturing method |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2480796A1 (en) * | 1980-04-21 | 1981-10-23 | Extramet Sarl | High purity silicon deposit formation - by electrolytic deposition from alkali (ne earth) metal halide melt contg. dissolved silicon |
US4699704A (en) * | 1985-02-13 | 1987-10-13 | Hiroshi Ishizuka | Electrolytic cell for a molten salt |
US4738759A (en) * | 1984-10-05 | 1988-04-19 | Extramet S.A. Zone Industrielle | Method for producing calcium or calcium alloys and silicon of high purity |
WO1997027143A1 (en) * | 1996-01-22 | 1997-07-31 | Jan Reidar Stubergh | Production of high purity silicon metal, aluminium, their alloys, silicon carbide and aluminium oxide from alkali alkaline earth alumino silicates |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB833767A (en) * | 1956-10-19 | 1960-04-27 | Timax Corp | Continuous electrolytic production of titanium |
US3003934A (en) * | 1959-01-08 | 1961-10-10 | Timax Associates | Process for the electrolytic production of metals |
NL7605625A (en) * | 1975-05-27 | 1976-11-30 | Univ Bruxelles | PROCESS FOR THE PREPARATION OF MANGANESE CHLORIDE AND PROCESS FOR THE PREPARATION OF MANGANESE BY ELECTROLYSIS IN THE MELT OF THE OBTAINED MANGANESE CHLORIDE. |
-
2001
- 2001-06-05 NO NO20012749A patent/NO317073B1/en unknown
-
2002
- 2002-06-03 EP EP02731017A patent/EP1402086A1/en not_active Withdrawn
- 2002-06-03 CA CA002449659A patent/CA2449659A1/en not_active Abandoned
- 2002-06-03 JP JP2003502269A patent/JP2004532933A/en not_active Ceased
- 2002-06-03 WO PCT/NO2002/000195 patent/WO2002099166A1/en active Application Filing
- 2002-06-03 US US10/477,747 patent/US20040238372A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2480796A1 (en) * | 1980-04-21 | 1981-10-23 | Extramet Sarl | High purity silicon deposit formation - by electrolytic deposition from alkali (ne earth) metal halide melt contg. dissolved silicon |
US4738759A (en) * | 1984-10-05 | 1988-04-19 | Extramet S.A. Zone Industrielle | Method for producing calcium or calcium alloys and silicon of high purity |
US4699704A (en) * | 1985-02-13 | 1987-10-13 | Hiroshi Ishizuka | Electrolytic cell for a molten salt |
WO1997027143A1 (en) * | 1996-01-22 | 1997-07-31 | Jan Reidar Stubergh | Production of high purity silicon metal, aluminium, their alloys, silicon carbide and aluminium oxide from alkali alkaline earth alumino silicates |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7381392B2 (en) | 2003-12-29 | 2008-06-03 | Elkem As | Silicon feedstock for solar cells |
EP2607308A1 (en) * | 2003-12-29 | 2013-06-26 | Elkem AS | Silicon feedstock for solar cells |
US7931883B2 (en) | 2003-12-29 | 2011-04-26 | Elkem As | Silicon feedstock for solar cells |
WO2005063621A1 (en) * | 2003-12-29 | 2005-07-14 | Elkem Asa | Silicon feedstock for solar cells |
EA009791B1 (en) * | 2003-12-29 | 2008-04-28 | Элкем Ас | Silicon feedstock for solar cells |
WO2007126309A3 (en) * | 2006-05-03 | 2008-04-03 | Girasolar B V | Method for the purification of a semiconductor material by application of an oxidation-reduction reaction |
WO2007126309A2 (en) * | 2006-05-03 | 2007-11-08 | Girasolar B.V. | Method for the purification of a semiconductor material by application of an oxidation-reduction reaction |
NL1031734C2 (en) * | 2006-05-03 | 2007-11-06 | Girasolar B V | Process for purifying a semiconductor material using an oxidation-reduction reaction. |
JP2010530637A (en) * | 2007-06-18 | 2010-09-09 | アール・イー・シー・スキャンウェハー・アー・エス | Method to regenerate elemental silicon from cutting residue |
DE112008001644T5 (en) | 2007-06-18 | 2010-09-09 | Rec Scan Wafer As | Process for recovering elemental silicon from cutting residues |
CN101967649A (en) * | 2010-09-09 | 2011-02-09 | 昆明理工大学 | Method for preparing silicon from composite molten salt electrolyte |
US10147836B2 (en) | 2012-05-31 | 2018-12-04 | Board Of Regents Of The University Of Texas System | Production of thin film solar grade silicon on metals by electrodeposition from silicon dioxide in a molten salt |
CN103173780A (en) * | 2013-03-01 | 2013-06-26 | 中南大学 | Method and device for preparing solar polycrystalline silicon material by semi-continuous molten salt electrolysis |
CN103173780B (en) * | 2013-03-01 | 2015-06-03 | 中南大学 | Method and device for preparing solar polycrystalline silicon material by semi-continuous molten salt electrolysis |
Also Published As
Publication number | Publication date |
---|---|
US20040238372A1 (en) | 2004-12-02 |
CA2449659A1 (en) | 2002-12-12 |
JP2004532933A (en) | 2004-10-28 |
NO20012749L (en) | 2002-12-06 |
NO20012749D0 (en) | 2001-06-05 |
EP1402086A1 (en) | 2004-03-31 |
NO317073B1 (en) | 2004-08-02 |
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