CN105384175A - Purification method of industrial waste silicon - Google Patents
Purification method of industrial waste silicon Download PDFInfo
- Publication number
- CN105384175A CN105384175A CN201510990499.XA CN201510990499A CN105384175A CN 105384175 A CN105384175 A CN 105384175A CN 201510990499 A CN201510990499 A CN 201510990499A CN 105384175 A CN105384175 A CN 105384175A
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- China
- Prior art keywords
- silicon
- powder
- industry waste
- waste silicon
- sheet material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
Abstract
Provided is a purification method of industrial waste silicon. High-purity silicon powder waste materials with good electrochemical reaction activity can be generated in the silicon wafer cutting process of photovoltaic industry. According to the purification method of the industrial waste silicon, organic compound impurities attached to the surface of the industrial waste silicon are removed by adopting an electrochemical oxidation method, and then other oxides on the surface are removed through an electrochemical reduction method, so that purified high-purity silicon powder is obtained. The obtained silicon powder which is small in particle size, large in specific surface and high in purity can be used as the anode material of a lithium ion battery, and therefore the use ratio of the waste silicon and the specific energy of the battery are increased.
Description
Technical field
The present invention is a kind of purification process of silicon, relates to new energy materials and electrochemistry.
Background technology
Along with the development of science and technology, be that the mechanism of new electrochemical power sources of representative is widely used in the field of portable electronic apparatus such as mobile phone, notebook computer with lithium ion battery.Nowadays, become power truck especially, the research emphasis of the power system that electromobile is used and focus.The theoretical capacity of business-like graphite cathode only has 372mAh/g, seeks the lithium ion battery negative material that security is high, specific energy is high and also becomes the key solving battery technology Problems Existing.
In the waste material that the cutting of photovoltaic industry silicon produces, the silicon materials of this part, up to 30%-40%, reclaim and can greatly save industry cost by the content of HIGH-PURITY SILICON.In addition, the purity of such silica flour own is high, and specific surface is large, and particle diameter is little of micron order, also has good chemical reactivity, the more important thing is, silicon and lithium can form Li
12si
7, Li
13si
4, Li
7si
3, Li
15si
4, Li
22si
5deng alloy, specific storage can up to 4200mAh/g, and be 11.29 times of commercialization graphite, removal lithium embedded voltage is low (lower than 0.5VvsLi/Li
+), low with electrolytic solution reactive behavior, be a kind of very rising lithium ion battery negative material.Being widely used of lithium ion battery, the demand of anticathode material also can increase, and thus needs a large amount of silicon materials, except exploiting silicon materials, also will become reduce costs the recycling of silicon, improves one of important channel of raw material availability.But, domesticly there is no the research useless silicon in solar photovoltaic industry being applied to lithium ion battery at present.
Summary of the invention
The object of the invention is to overcome the defect existed in prior art, provide a kind of purification process of Industry Waste silicon, purified silicon can be applicable to lithium ion battery negative, the specific energy of lithium ion battery can be improved, be conducive to the production cost simultaneously reducing solar photovoltaic industry and lithium ion battery simultaneously.
For achieving the above object, technical scheme of the present invention comprises the following steps:
A purification process for Industry Waste silicon, comprises the steps:
1) adopt electrochemical oxidation process, remove the organic chemistry material of Industry Waste silicon face attachment, be mainly polyoxyethylene glycol and poly-propyl alcohol etc.; In electrochemical oxidation process, using graphite rod or platinized platinum as anode, using stereotype as negative electrode, using water as ionogen, Industry Waste Si powder is added to the water, utilizes hydroxyl radical free radical (OH) that organic group is decomposed into CO
2and H
2o, simultaneously anode surface and near generation water decomposition reaction: 2H
2o-4e
-→ 4H
++ O
2↑; Reaction times is 0.5h ~ 5h.
2) the siliceous powder after oxide treatment is leached, mix with binding agent, make diameter 2 ~ 50mm at 5 ~ 20MPa pressure, the electrode slice of thick about 0.2 ~ 2mm, then sinter 2 ~ 6h at 300 ~ 800 DEG C, make sheet material;
3) adopt the oxide compound in electrochemical reducing removal sheet material, be mainly SiO
2and other metal oxides that may exist, as ferric oxide etc.; In electrochemical reducing, using carbon-point as anode, using iron staff or molybdenum filament as negative electrode, with molten state CaCl
2as ionogen, because reduction method is carried out in molten state, be difficult to pulverous material to be collected after having reacted, therefore need material to make sheet, can react after the sheet material boring after sintering after molybdenum filament or iron staff make contacts electrode; At 600 ~ 1000 DEG C, at molten state CaCl under-1.0 ~-1.25V condition
2middle electrolysis 0.5 ~ 5h, then takes out silicon chip, grinds from electrolyzer, and gained powder is the Si powder after purifying.
More specifically, the silicon of aforesaid method purifying is adopted to be mainly used in lithium ion battery negative.
Advantage of the present invention and beneficial effect are:
1) the useless silicon materials in solar photovoltaic industry are carried out purification recycling, be conducive to the production cost reducing photovoltaic industry and lithium ion battery industry;
2) present method step is simple, easy to operate, and purifying velocity is fast, effectively can recycle useless silicon materials, reach the object of energy-conserving and environment-protective.
Accompanying drawing explanation
Fig. 1 adopts purification process in the present invention to Industry Waste Si powder XRD figure before and after treatment;
Fig. 2 is the surface sweeping Electronic Speculum figure after Industry Waste Si powder purifying.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is further described.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
The technical scheme that the present invention specifically implements is:
A purification process for Industry Waste silicon, comprises the steps:
1) adopt electrochemical oxidation process, remove the polyoxyethylene glycol of Industry Waste silicon face and poly-propyl alcohol; In electrochemical oxidation process, using graphite rod as anode, using stereotype as negative electrode, using water as ionogen, be added to the water Industry Waste Si powder reaction 3h, and polyoxyethylene glycol can be completely broken down as CO
2and H
2o;
2) the siliceous powder after oxide treatment is leached, mix with binding agent all with, make diameter 10mm at 10MPa pressure, the electrode slice of thick about 2mm, then sinter 4h at 700 DEG C, make sheet material;
3) SiO in electrochemical reducing removal sheet material is adopted
2; In electrochemical reducing, using carbon-point as anode, using molybdenum filament as negative electrode, with molten state CaCl
2as ionogen, will be inserted in ionogen through molybdenum filament being made contacts electrode after the sheet material boring after sintering; At 900 DEG C, electrolysis 3h under-1.20V condition, the SiO in material
2namely be reduced to silicon, then from electrolyzer, take out silicon chip, grind, gained powder is the Si powder after purifying.
As shown in Figure 1, be the XRD comparison diagram by the silicon after above method purifying and the useless silicon before purifying; Fig. 2 is the electron-microscope scanning figure of the Si powder after purifying.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (3)
1. a purification process for Industry Waste silicon, is characterized in that, comprises the steps:
1) adopt electrochemical oxidation process, remove the attachment of Industry Waste silicon face organic chemistry material, in described electrochemical oxidation process, using graphite rod or platinized platinum as anode, using stereotype as negative electrode, using water as electrolytic solution, described Industry Waste Si powder is joined in described water and reacts 0.5h ~ 5h;
2) the siliceous powder after oxide treatment is leached, mix with binding agent, make diameter 2 ~ 50mm at 5 ~ 20MPa pressure, the electrode slice of thick about 0.2 ~ 2mm, then sinter 2 ~ 6h at 300 ~ 800 DEG C, make sheet material;
3) adopt electrochemical reducing remove described in sheet material in oxide compound, in described electrochemical reducing, using carbon-point as anode, using iron staff or molybdenum filament as negative electrode, with molten state CaCl
2as ionogen, after being holed by described sheet material, make contacts electrode through on described iron staff or molybdenum filament, at 600 ~ 1000 DEG C, at described molten state CaCl under-1.0 ~-1.25V condition
2after middle electrolysis 0.5 ~ 5h, take out silicon chip, grind, gained powder is the Si powder after purifying.
2. according to the purification process of the Industry Waste silicon described in claim 1, it is characterized in that, described organic compound is polyoxyethylene glycol and poly-propyl alcohol, and described oxide compound is the SiO of silicon face
2and metal oxide.
3. according to the purification process of the Industry Waste silicon described in claim 2, it is characterized in that, the silicon of described purifying is applied to the negative pole of lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510990499.XA CN105384175A (en) | 2015-12-25 | 2015-12-25 | Purification method of industrial waste silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510990499.XA CN105384175A (en) | 2015-12-25 | 2015-12-25 | Purification method of industrial waste silicon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105384175A true CN105384175A (en) | 2016-03-09 |
Family
ID=55417017
Family Applications (1)
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|---|---|---|---|
| CN201510990499.XA Pending CN105384175A (en) | 2015-12-25 | 2015-12-25 | Purification method of industrial waste silicon |
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| CN101058888A (en) * | 2007-05-24 | 2007-10-24 | 昆明理工大学 | Method of preparing solar energy level silicon from optical fibre prefabricated bar waste material |
| CN101255598A (en) * | 2007-12-17 | 2008-09-03 | 史珺 | Method for preparing solar energy grade polycrystalline silicon |
| CN101743342A (en) * | 2007-06-18 | 2010-06-16 | Rec斯坎沃佛股份有限公司 | Method for recovering elemental silicon from cutting remains |
| CN101857232A (en) * | 2009-04-07 | 2010-10-13 | 瑞贤科技股份有限公司 | Manufacturing method of high-purity silicon material |
| CN201809445U (en) * | 2010-08-06 | 2011-04-27 | 昆明理工大学 | Fused salt electrolyzing device for reducing SiO2 into Si |
| US20110176984A1 (en) * | 2006-03-15 | 2011-07-21 | Amendola Steven C | Method for making silicon for solar cells and other applications |
| CN102206013A (en) * | 2011-04-28 | 2011-10-05 | 波鹰(厦门)科技有限公司 | Device for recycling silicon powder and waste water from waste water from silicon cutting and method thereof |
| US20110262339A1 (en) * | 2008-09-30 | 2011-10-27 | Hartwig Rauleder | Production of solar-grade silicon from silicon dioxide |
| CN102629644A (en) * | 2012-04-21 | 2012-08-08 | 湖南红太阳光电科技有限公司 | Reworking technology of finished crystalline silicon solar cell |
| 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 |
| CN103882465A (en) * | 2014-03-05 | 2014-06-25 | 江苏华富储能新技术股份有限公司 | Preparation method and application of high-purity nanometer silicon |
-
2015
- 2015-12-25 CN CN201510990499.XA patent/CN105384175A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110176984A1 (en) * | 2006-03-15 | 2011-07-21 | Amendola Steven C | Method for making silicon for solar cells and other applications |
| CN101058888A (en) * | 2007-05-24 | 2007-10-24 | 昆明理工大学 | Method of preparing solar energy level silicon from optical fibre prefabricated bar waste material |
| CN101743342A (en) * | 2007-06-18 | 2010-06-16 | Rec斯坎沃佛股份有限公司 | Method for recovering elemental silicon from cutting remains |
| CN101255598A (en) * | 2007-12-17 | 2008-09-03 | 史珺 | Method for preparing solar energy grade polycrystalline silicon |
| US20110262339A1 (en) * | 2008-09-30 | 2011-10-27 | Hartwig Rauleder | Production of solar-grade silicon from silicon dioxide |
| CN101857232A (en) * | 2009-04-07 | 2010-10-13 | 瑞贤科技股份有限公司 | Manufacturing method of high-purity silicon material |
| CN201809445U (en) * | 2010-08-06 | 2011-04-27 | 昆明理工大学 | Fused salt electrolyzing device for reducing SiO2 into Si |
| CN102206013A (en) * | 2011-04-28 | 2011-10-05 | 波鹰(厦门)科技有限公司 | Device for recycling silicon powder and waste water from waste water from silicon cutting and method thereof |
| CN102629644A (en) * | 2012-04-21 | 2012-08-08 | 湖南红太阳光电科技有限公司 | Reworking technology of finished crystalline silicon solar cell |
| 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 |
| CN103882465A (en) * | 2014-03-05 | 2014-06-25 | 江苏华富储能新技术股份有限公司 | Preparation method and application of high-purity nanometer silicon |
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Application publication date: 20160309 |
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