CN114853023A - Anti-oxidation method for solar silicon wafer cutting waste generation and purification stage - Google Patents
Anti-oxidation method for solar silicon wafer cutting waste generation and purification stage Download PDFInfo
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- CN114853023A CN114853023A CN202210552083.XA CN202210552083A CN114853023A CN 114853023 A CN114853023 A CN 114853023A CN 202210552083 A CN202210552083 A CN 202210552083A CN 114853023 A CN114853023 A CN 114853023A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to the technical field of oxidation resistance, and discloses an oxidation resistance method in a solar silicon wafer cutting waste generation and purification stage, which comprises the following steps: s1: the cutting of the silicon wafer is carried out in a low humidity environment or vacuum or low temperature or oxygen-free protective gas or in an acidic cutting fluid or cutting fluid containing an antioxidant, or any combination of the six. S2: the silicon material is in vacuum or oxygen-free protective gas or acid or low temperature or antioxidant or any combination of the five in the transportation, storage and purification of the silicon cutting waste material; s3: drying the purified silicon material by adopting oven drying or vacuum drying or heating and drying by oxygen-free protective gas; s4: the dried silicon material is packaged in a sealing package or a vacuum package or a bag filled with oxygen-free protective gas, and the antioxidation technology provides a raw material of high-quality silicon for preparing the nano-scale silicon of the cathode material of the lithium ion battery.
Description
Technical Field
The solar silicon wafer cutting waste material is recycled, and the lithium ion battery cathode material and the micron and nano silicon are used as antioxidant technologies.
Background
The lithium ion battery is widely applied due to small volume, good cycle stability, large energy density, small self-discharge, safety and reliability, but with the continuous improvement of technological level and economic level, people have higher and higher requirements on the performance of the lithium ion battery, and higher capacity and endurance are needed.
At present, the negative electrode of the lithium ion battery used in the market is mainly made of graphite materials, and the theoretical specific capacity of the negative electrode is about 372mAh/g, so that the negative electrode cannot meet the higher requirements of people. The silicon material has good lithium storage performance, and the theoretical lithium intercalation capacity of the silicon material as a negative electrode material can reach 4200 mAh/g. However, silicon materials are easily expanded and crushed during charging and discharging processes, resulting in rapid degradation of battery performance. One of the methods to solve this problem is to make the silicon material into a nano-scale to reduce the amount of silicon expansion.
The nanometer silicon particles have high activity and are easy to be oxidized, which obviously reduces the performance of the battery, the oxidation degree of the nanometer silicon is generally required to be below 8 percent, which puts higher requirements on the raw material for preparing the nanometer silicon, namely the micron silicon particles, particularly the silicon recovered from silicon cutting waste is easy to be subjected to O in the air 2 How to prevent and reduce the oxidation of silicon in the purification process of silicon cutting wastes by oxidizing or reacting with water in a neutral (or alkaline) solution to generate silicon oxide and release hydrogen, and therefore, an anti-oxidation method for the generation and purification stages of solar silicon wafer cutting wastes is provided.
Disclosure of Invention
The invention aims to provide an anti-oxidation method for the generation and purification stages of solar silicon wafer cutting waste materials, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: an anti-oxidation method for the generation and purification stage of solar silicon wafer cutting waste comprises the following steps:
s1: the cutting of the silicon wafer is carried out in a low humidity environment or vacuum or in an oxygen-free protective gas or a low temperature or acidic cutting fluid or an antioxidant-containing cutting fluid, or any combination of the six. The cutting process and the resulting silicon waste minimize oxidation of the silicon.
S2: the silicon material is subjected to vacuum or oxygen-free protective gas or acidic or cryogenic or antioxidant, or any combination of the five, in the transportation, storage and purification of the silicon cut waste.
S3: drying the purified silicon material by adopting oven drying or vacuum drying or heating and drying by oxygen-free protective gas.
S4: and (3) packaging the dried silicon material in a sealed package or a vacuum package or in a bag filled with oxygen-free protective gas.
Wherein, the oxygen-free protective gas in S1, S2, S3 and S4 comprises: nitrogen, argon, helium, oxygen free air, carbon dioxide, and the like, or any combination thereof.
Wherein the low temperature in S1 and S2 refers to the ambient temperature, the temperature of the cutting waste liquid and the waste material, and the numerical value is below 5 ℃ or room temperature and below room temperature.
In the interim, the low humidity in S1 means that the relative humidity is 20-70%.
Wherein, the acid cutting fluid in the S1 is prepared by adding acid with the weight percentage concentration of 0.01-10% into the cutting fluid.
Wherein, the antioxidants in S1 and S2 can effectively prevent the oxidation of the silicon material, and comprise organic compounds of ascorbic acid, phenols, hydrazines and the like, wherein the weight percentage concentration of the antioxidants in S1 is 0.01-10%, and the amount of the antioxidants added in S2 is 0.01-10% of the weight of the silicon material.
The silicon materials in S2, S3 and S4 are silicon waste materials recovered in silicon cutting, and the silicon materials include polycrystalline silicon and monocrystalline silicon. The silicon material can be obtained from S1, and can also be obtained from waste materials of silicon wafer cutting factories or waste residues after filter pressing.
In S1, the silicon wafer was sliced from a high purity silicon ingot.
In S2, acidic means containing sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, oxalic acid or phosphoric acid, or any combination thereof, and having a concentration of 0.001-5 mol.L -1 。
In S2, the purification is performed by removing one or more or all of the following impurities, including metal ions, diamond, a main component of a cutting fluid (or a cutting fluid) for cutting, and polymer material microparticles.
Compared with the prior art, the invention has the beneficial effects that:
the method effectively prevents and reduces the oxidation of silicon in the cutting process and the waste storage, transportation and purification processes, and provides a raw material of high-quality silicon for the preparation of the nano-scale silicon of the cathode material of the lithium ion battery.
Meanwhile, the method has the advantages of low cost of raw materials, simple and convenient operation steps, capability of providing a silicon raw material with high cost performance for the preparation of the lithium ion battery cathode material nano silicon, and convenience in popularization and use.
Drawings
FIG. 1 is a schematic view of the process of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In the silicon cutting process, a cutting cavity of the cutting machine is protected by nitrogen, the concentration of citric acid in cutting liquid is 0.2mol L-1, the relative humidity of a cutting environment is 35%, and the room temperature is 20 ℃. After the silicon wafer is cut, taking a certain amount of silicon slag, and uniformly dispersing silicon materials in 1.0mol L by using a stirrer on site -1 Sulfuric acid and 1.0mol L -1 And (4) in the hydrochloric acid mixed solution, conveying the slurry to a purification site. Dispersing a silicon material in acid-containing purified water, wherein the silicon material: water (weight ratio) 1: 40, the concentration of sulfuric acid and hydrochloric acid in the slurry was 0.2mol L each -1 And after fully stirring, separating the solid silicon material by using a plate centrifuge at 50Hz for 15 min. And repeating the steps twice to remove impurities such as metal ions, cutting fluid components, resin and the like. The silicon material enters an oven, is dried for 48 hours at 120 ℃ under the protection of nitrogen, and then,and (5) vacuum packaging the silicon material. The oxidation degree of the final product silicon material is measured to be 3% by an element analyzer.
Example 2
In the silicon cutting process, the concentration of ascorbic acid in the cutting fluid is 2%, the relative humidity of the cutting environment is 40%, and the room temperature is 25 ℃. After the silicon chip is cut, the cutting waste liquid is filter-pressed, a certain amount of silicon slag is taken, and the silicon slag is crushed by a stirrer on site and uniformly dispersed in 2.0mol L -1 The slurry was transported back to the production site in ascorbic acid at 0.2% by weight of hydrochloric acid and silicon stock. The silicon slurry was diluted with water to give a hydrochloric acid concentration of 0.2mol L -1 Mixing with ascorbic acid with concentration of 0.2% of the weight of silicon material, stirring, press filtering with filter press, discarding water solution, and filtering with 0.2mol L -1 And (3) washing with hydrochloric acid and ascorbic acid accounting for 0.2 percent of the weight of the silicon material, carrying out filter pressing again, washing for three times, and carrying out filter pressing for three times. The silicon material is put into a vacuum drying oven for drying for 48 hours, the vacuum degree is 20kPa, and the temperature is 100 ℃. And finally, vacuum packaging the silicon material. The oxidation degree of the final product silicon material was measured to be 3.7% by an elemental analyzer.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. An anti-oxidation method for the generation and purification stages of solar silicon wafer cutting waste is characterized by comprising the following steps:
s1: the cutting of the silicon wafer is carried out in a low humidity environment or vacuum or in an oxygen-free protective gas or a low temperature or acid cutting fluid (or cutting fluid) or an antioxidant-containing cutting fluid or any combination of the six;
s2: the silicon material is in vacuum or oxygen-free protective gas or acid or low temperature or antioxidant or any combination of the five in the transportation, storage and purification of the silicon cutting waste material;
s3: drying the purified silicon material by adopting oven drying or vacuum drying or heating and drying by oxygen-free protective gas;
s4: and (3) packaging the dried silicon material in a sealed package or a vacuum package or in a bag filled with oxygen-free protective gas.
2. The oxidation resistance method for the generation and purification stage of the solar silicon wafer cutting waste material as claimed in claim 1, wherein: wherein the oxygen-free shielding gas in S1, S2, S3 and S4 comprises: nitrogen, argon, helium, oxygen free air, carbon dioxide, and the like, or any combination thereof.
3. The oxidation resistance method for the generation and purification stage of the solar silicon wafer cutting waste material as claimed in claim 1, wherein: wherein the low temperature in S1 and S2 refers to the ambient temperature, the temperature of the cutting waste liquid and the waste material, and the numerical value is below 5 ℃ or room temperature and below room temperature.
4. The oxidation resistance method in the generation and purification stages of solar silicon wafer cutting waste according to claim 1, wherein: wherein, the acid cutting fluid in the S1 is prepared by adding acid with the weight percentage concentration of 0.01-10% into the cutting fluid.
5. The oxidation resistance method for the generation and purification stage of the solar silicon wafer cutting waste material as claimed in claim 1, wherein: the antioxidant in S1 and S2 can effectively prevent the oxidation of the silicon material, and comprises organic compounds of ascorbic acid, phenols and hydrazines, wherein the weight percentage concentration of the antioxidant in S1 is 0.01-10%, and the amount of the antioxidant added in S2 is 0.01-10% of the weight of the silicon material.
6. The oxidation resistance method for the generation and purification stage of the solar silicon wafer cutting waste material as claimed in claim 1, wherein: the silicon materials in S2, S3 and S4 are silicon waste materials recovered in silicon cutting, and the silicon materials comprise polycrystalline silicon and monocrystalline silicon; the silicon material is obtained from S1, or from waste material of silicon wafer cutting factories or waste residue after filter pressing;
in S1, the silicon wafer was sliced from a high purity silicon ingot.
7. The oxidation resistance method for the generation and purification stage of the solar silicon wafer cutting waste material as claimed in claim 1, wherein: in S2, acidic means containing sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, oxalic acid or phosphoric acid, or any combination thereof, and having a concentration of 0.001-5 mol.L -1 。
8. The oxidation resistance method for the generation and purification stage of the solar silicon wafer cutting waste material as claimed in claim 1, wherein: in S2, the purification is performed to remove one or more or all of the following impurities including metal ions, diamond, a main component of a cutting fluid (or cutting fluid) for cutting, and polymer material particles such as resin particles.
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| CN202210552083.XA CN114853023A (en) | 2022-05-18 | 2022-05-18 | Anti-oxidation method for solar silicon wafer cutting waste generation and purification stage |
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| CN202210552083.XA CN114853023A (en) | 2022-05-18 | 2022-05-18 | Anti-oxidation method for solar silicon wafer cutting waste generation and purification stage |
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Citations (6)
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| CN101513752A (en) * | 2009-04-10 | 2009-08-26 | 江西省新华仁科技有限公司 | Antioxidant cutting method and device |
| US20100032630A1 (en) * | 2008-08-04 | 2010-02-11 | Hariharan Alleppey V | Recovery of silicon from kerf silicon waste |
| CN101823712A (en) * | 2010-04-02 | 2010-09-08 | 河南新大新材料股份有限公司 | Recovery processing method of silicon slice cut waste mortar |
| CN101935576A (en) * | 2010-10-09 | 2011-01-05 | 辽宁奥克化学股份有限公司 | Cutting fluid with anti-oxidation performance, preparation method and application thereof |
| CN106753734A (en) * | 2017-01-23 | 2017-05-31 | 杭州传化精细化工有限公司 | A kind of silicon chip cutting fluid |
| CN113023732A (en) * | 2021-03-05 | 2021-06-25 | 昆明理工大学 | Method for preparing high-purity silicon by recovering silicon wafer cutting waste |
-
2022
- 2022-05-18 CN CN202210552083.XA patent/CN114853023A/en active Pending
Patent Citations (6)
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| US20100032630A1 (en) * | 2008-08-04 | 2010-02-11 | Hariharan Alleppey V | Recovery of silicon from kerf silicon waste |
| CN101513752A (en) * | 2009-04-10 | 2009-08-26 | 江西省新华仁科技有限公司 | Antioxidant cutting method and device |
| CN101823712A (en) * | 2010-04-02 | 2010-09-08 | 河南新大新材料股份有限公司 | Recovery processing method of silicon slice cut waste mortar |
| CN101935576A (en) * | 2010-10-09 | 2011-01-05 | 辽宁奥克化学股份有限公司 | Cutting fluid with anti-oxidation performance, preparation method and application thereof |
| CN106753734A (en) * | 2017-01-23 | 2017-05-31 | 杭州传化精细化工有限公司 | A kind of silicon chip cutting fluid |
| CN113023732A (en) * | 2021-03-05 | 2021-06-25 | 昆明理工大学 | Method for preparing high-purity silicon by recovering silicon wafer cutting waste |
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