CN114890429A - Purification method for removing resin impurities from solar silicon wafer cutting waste residues - Google Patents
Purification method for removing resin impurities from solar silicon wafer cutting waste residues Download PDFInfo
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- CN114890429A CN114890429A CN202210552085.9A CN202210552085A CN114890429A CN 114890429 A CN114890429 A CN 114890429A CN 202210552085 A CN202210552085 A CN 202210552085A CN 114890429 A CN114890429 A CN 114890429A
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention discloses a purification method for removing resin impurities from solar silicon wafer cutting waste residues, which is characterized in that the solar silicon wafer cutting waste residues are uniformly dispersed in an acidic aqueous solution, and silicon materials are naturally settled or centrifugally separated, so that resin particles with lighter specific gravity and water-soluble impurities are left in a water phase; filter pressing or centrifugal separation is carried out on the sediment, and cleaning is carried out; repeating the steps for multiple times until the impurity removal rate reaches the standard. The method can reduce or remove impurities such as resin particles in the silicon cutting waste material, and provides a high-quality silicon material for preparing the lithium ion battery cathode material nano silicon.
Description
Technical Field
The invention relates to a purification method for removing resin impurities from solar silicon wafer cutting waste residues, and belongs to the technical field of lithium ion battery cathode materials and solar-grade silicon cutting waste recovery.
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 lithium ion battery is about 372mAh/g, so that the requirements of people in the fields of mobile phones, new energy automobiles and the like cannot be met. Because the silicon material has good lithium storage performance, the theoretical lithium intercalation capacity of the silicon material as a negative electrode material can reach 4200mAh/g, but the silicon material is easy to expand and crush in the lithium intercalation and lithium deintercalation processes, so that the performance of the battery is rapidly reduced.
One of the existing methods for solving the problem is to prepare a silicon material into a nano-scale so as to reduce the expansion amount of silicon, one of the raw material sources for preparing the nano-silicon is to purify the silicon material from silicon cutting waste, when a high-purity silicon ingot is cut, a plastic plate or a resin plate for fixing the silicon ingot is cut by a diamond wire when the cutting is nearly completed, a certain amount of high-molecular fine particles are generated, the resin particles are abbreviated as resin particles in the text, the particle diameter range is 10-5000nm, and the existence of the resin particles can influence the subsequent treatment and preparation cost of the silicon material, even influence the electrochemical performance of the silicon material. Therefore, the reduction or removal of impurities such as resin particles in the silicon cutting waste is very important for preparing high-purity nano silicon of the lithium ion battery cathode material.
Early (2017 ago) solar silicon wafer cutting is performed by matching a metal wire saw with a silicon carbide abrasive, the cutting line is thick, and high-purity silicon is seriously wasted. The main components and contents (mass fraction) of the silicon cutting waste mortar are 40-50% of polyethylene glycol; 23% -33% of silicon carbide; silicon (Si), 20-24%; 2.5 to 3.0 percent of scrap iron (Fe). The main objects of purification and recovery are polyethylene glycol and silicon carbide, and the difficulty of purifying silicon is higher and the value of the purification is lower than that of the polyethylene glycol and the silicon carbide. The main obstacle to purifying silicon is how the polyethylene glycol and silicon carbide, which are present in large amounts, separate from the silicon. For example, a method for cutting a silicon wafer and recovering a cutting waste are disclosed in the following publication: CN 102626954A; the method for recovering silicon powder from crystalline silicon cutting waste materials has the following publication number: CN 107758672 a and other patents are about the recovery and purification of cutting waste residue of wire saw matched with silicon carbide abrasive. After 2016, the technology of domestic solar silicon cutting enterprises develops rapidly and cutting equipment is replaced rapidly, the cutting technology of a metal wire saw matched with silicon carbide abrasive is improved to be a diamond wire cutting technology, the diameter of a cutting wire is reduced from hundreds of micrometers to dozens of micrometers, and the quantity of cutting waste residues is greatly reduced. The silicon content in the waste residue is greatly increased. At present, the water content of silicon waste slag generated by solar silicon cutting enterprises is about 45%, and more than 97% of the rest solid slag is high-purity metal silicon. At present, the main removing parts of the cutting silicon slag are as follows:
1. reducing agents for metallurgy and the preparation of silicon alloys, such as: method CN110273075A for preparing high-silicon aluminum silicon alloy by using metal aluminum recovered crystalline silicon cutting waste;
2. further melting and purifying the silicon metal at high temperature, such as a method for preparing high-purity silicon by using silicon cutting waste CN 112456499A, but the method has high energy consumption and higher recovery cost;
3. after purification, nano silicon is prepared and used as a cathode material of a lithium ion battery, and the method and the device for preparing the high-purity micro-nano silicon powder by utilizing the silicon waste in the photovoltaic industry are CN 111086991A.
Disclosure of Invention
The invention aims to provide a simple, convenient and practical purification method for removing resin impurities from solar silicon wafer cutting waste residues aiming at the defects in the prior art, and the purified silicon material is mainly used for preparing high-purity nano silicon.
In order to achieve the aim, the invention provides a purification method for removing resin impurities from solar silicon wafer cutting waste residues, which comprises the following steps: s1, uniformly dispersing the solar silicon wafer cutting waste residue in an acidic aqueous solution, and keeping for a certain time; s2, after being diluted properly, the mixture is naturally settled (or centrifugally separated), so that the resin particles with lighter specific gravity and water-soluble impurities are left in the water phase; s3, performing filter pressing or centrifugal separation on the sediment, and cleaning; s4, repeating the steps for multiple times until the impurity removal rate reaches the standard.
Furthermore, the resin particles in the scheme are derived from a resin plate or a plastic plate for fixing a silicon ingot when the silicon wafer is cut, and the particle diameter range is 10-5000 nm.
Further, the uniform dispersion in the above scheme means that the silicon material is uniformly dispersed into the acidic solution by a pulverizer, a stirrer, a dispersing machine, an emulsifying machine or a wall breaking machine.
Further, the acidic aqueous solution in the above scheme is one or any combination of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, oxalic acid and phosphoric acid, and the concentration of the acidic aqueous solution is 0.01-5 mol.L -1 . The keeping time is 5min-168 h.
Further, the term "appropriately diluted" in the above-mentioned embodiment means that the acid is diluted with water so that the concentration of the acid is 0.001 to 3 mol.L -1 . The silicon material and the acidic aqueous solution have a solid-liquid weight ratio of 1:5-1: 50. Furthermore, the natural sedimentation in the scheme is to allow the uniformly stirred silicon slurry to stand for a period of time, so that the heavier silicon slurry sinks, and the lighter resin particles and water-soluble impurities stay on the upper layer. The natural settling time is 0.5-150 hours, and the natural settling temperature is room temperature or-5-120 ℃. Further, the centrifugal separation in the above scheme is solid-liquid separation by using a centrifuge, and the centrifuge is one of a flat centrifuge, a three-leg centrifuge, a tubular centrifuge and a horizontal screw centrifuge. The filter pressing refers to the solid-liquid separation by using a filter press.
Furthermore, in the above scheme, while removing impurities in the resin particles, impurities such as nickel ions, cobalt ions, iron ions, aluminum ions, calcium ions, magnesium ions, silicon oxide, and cutting fluid (or cutting fluid, the main components of which include phosphate, organic acid, ether, alcohol, surfactant, etc.) can be removed.
Further, in the above scheme, the resin impurity removal rate is 20% to 99.999%, and the impurity removal rate (the removal amount of impurities after purification/the amount of impurities before purification) x 100%.
Further, in the above scheme, the purified silicon material is mainly used for preparing nano silicon in the lithium ion battery cathode material.
The invention has the beneficial effects that: the purification method for removing resin impurities from the solar silicon wafer cutting waste residue is simple, convenient, quick and low in cost, can reduce or remove impurities such as resin particles in silicon cutting waste materials, and provides a high-quality silicon material for preparing the lithium ion battery cathode material nano silicon.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
Example 1
Dispersing silicon cutting waste in 1 mol. L with a stirrer rotating at 2000rpm -1 Sulfuric acid and 1 mol. L -1 And standing in a hydrochloric acid mixed solution for 6 hours. After being diluted by water, the solid-liquid mass ratio is controlled to be 1:30, and the acid concentration is 0.2 mol.L -1 Sulfuric acid and 0.2 mol. L -1 Hydrochloric acid, stirring uniformly, then using a plate centrifuge with the frequency set as 50Hz, carrying out centrifugal separation for 15min, removing filtrate, and reserving a crude solid silicon material; re-dispersing the crude solid silicon material in an acid solution, wherein the concentration of the acid is 0.2 mol.L -1 Sulfuric acid and 0.2 mol. L -1 And (4) carrying out centrifugal separation again by using hydrochloric acid, circulating for at least three times, and finally carrying out vacuum drying on the obtained finished silicon material and finally carrying out vacuum packaging for later use. The method has the advantages that the removal rate of resin particles reaches 99%, the removal rate of nickel and iron reaches more than 90%, and the recovery rate of silicon reaches more than 94%. The contents of the elements after purification are shown in table 1:
| element(s) | Silicon | Oxygen gas | Iron | Nickel (II) | Aluminium | Cobalt | Carbon (C) |
| Content (%) | 97.86 | 2.1 | 0.0040 | 0.0032 | 0.0066 | 0.0011 | 0.018 |
TABLE 1
Example 2
Dispersing silicon cutting waste by using an emulsifying machine, wherein the rotating speed of the emulsifying machine is 2500rpm, so that the concentration of hydrochloric acid in the slurry is 0.5 mol.L -1 The solid-liquid mass ratio is controlled to be 1:50, the mixture is stirred evenly and then kept stand for 6 hours, the upper layer is removed, the upper layer solution is filtered and adsorbed, can be recycled and reused, the settled lower layer is subjected to filter pressing by a filter press and is filtered by 0.2 mol.L -1 Washing with hydrochloric acid for 3 times. The method has the advantages that the removal rate of resin particles is more than 98%, the removal rate of nickel and iron is more than 85%, and the recovery rate of silicon is more than 95%. The contents of the elements after purification are shown in table 2:
| element(s) | Silicon | Oxygen gas | Iron | Nickel (II) | Aluminium | Cobalt | Carbon (C) |
| Content (%) | 96.53 | 3.4 | 0.0045 | 0.0036 | 0.0063 | 0.0010 | 0.020 |
TABLE 2
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
The above-described embodiments are not intended to limit the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A purification method for removing resin impurities from solar silicon wafer cutting waste residues is characterized by comprising the following steps: the method comprises the following steps:
s1, uniformly dispersing solar silicon wafer cutting waste residues (hereinafter referred to as silicon materials) in an acidic aqueous solution;
s2, naturally settling or centrifugally separating the resin particles to make the resin particles with light specific gravity and water-soluble impurities remain in the water phase;
s3, performing filter pressing or centrifugal separation on the heavy sediment, and cleaning;
s4, repeating the steps for multiple times until the impurity removal rate reaches the standard.
2. The purification method for removing resin impurities from solar silicon wafer cutting waste residues as claimed in claim 1, wherein the purification method comprises the following steps: the resin particles in step S2 are generated when the silicon wafer is cut, and the resin plate or the plastic plate to which the silicon ingot is fixed is cut, and the particle diameter range thereof is 10 to 5000 nm.
3. The purification method for removing resin impurities from solar silicon wafer cutting waste residue according to claim 1, wherein the purification method comprises the following steps: the uniform dispersion in step S1 is to uniformly disperse the silicon material into the acidic solution by a pulverizer or a stirrer or a disperser or an emulsifying machine or a wall breaking machine.
4. The purification method for removing resin impurities from solar silicon wafer cutting waste residues as claimed in claim 1, wherein the purification method comprises the following steps: the acidic aqueous solution is one or any combination of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, oxalic acid and phosphoric acid, and the concentration of the acidic aqueous solution is 0.001-5 mol.L -1 The solid-liquid weight ratio of the silicon material to the acidic aqueous solution is1:5-1:50。
5. The purification method for removing resin impurities from solar silicon wafer cutting waste residues as claimed in claim 1, wherein the purification method comprises the following steps: and the natural sedimentation in the step S2 is to allow the uniformly stirred silicon slurry to stand for a period of time to allow the heavy-phase silicon slurry to sink, the light-phase resin particles and the water-soluble impurities to stay on the upper layer, the natural sedimentation time is 0.5 to 150 hours, and the natural sedimentation temperature is room temperature or-5 to 120 ℃.
6. The purification method for removing resin impurities from solar silicon wafer cutting waste residues as claimed in claim 1, wherein the purification method comprises the following steps: the centrifugal separation in the steps S2 and S3 is solid-liquid separation by a centrifuge, the centrifuge is one of a plate centrifuge, a three-leg centrifuge, a tube centrifuge, and a horizontal screw centrifuge, and the pressure filtration in the steps S2 and S3 is solid-liquid separation by a filter press.
7. The purification method for removing resin impurities from solar silicon wafer cutting waste residues as claimed in claim 1, wherein the purification method comprises the following steps: the water-soluble impurities in step S2 refer to nickel ions, cobalt ions, iron ions, aluminum ions, calcium ions, magnesium ions, silicon oxide, and cutting fluid (or cutting fluid, the main components of which include phosphate, organic acid, ethers, alcohols, surfactants, etc.).
8. The purification method for removing resin impurities from solar silicon wafer cutting waste residues as claimed in claim 1, wherein the purification method comprises the following steps: the impurity removal rate of step S4 is 20% to 99.999%, and the impurity removal rate (the amount of removed impurities after purification/the amount of impurities before purification) x 100%.
9. The purification method for removing resin impurities from solar silicon wafer cutting waste residues as claimed in claim 1, wherein the purification method comprises the following steps: and the silicon material obtained after the removal rate of the step S4 reaches the standard is mainly used for preparing nano silicon in the lithium ion battery cathode material.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011121852A (en) * | 2009-12-14 | 2011-06-23 | Toyokazu Nakasone | Method for producing high purity silicon |
| CN106115714A (en) * | 2016-06-24 | 2016-11-16 | 河南易成新能源股份有限公司 | A kind of preparation method of metallic silicon |
| CN109112638A (en) * | 2018-10-10 | 2019-01-01 | 镇江环太硅科技有限公司 | A kind of method of sheet stock recycling and reusing fine crushing |
| CN211920881U (en) * | 2019-12-30 | 2020-11-13 | 江苏载驰科技股份有限公司 | Device for preparing high-purity micro-nano silicon powder by utilizing photovoltaic industry silicon waste |
| WO2021182341A1 (en) * | 2020-03-12 | 2021-09-16 | グローバルウェーハズ・ジャパン株式会社 | Device for cleaning silicon raw material |
| CN113582184A (en) * | 2021-08-06 | 2021-11-02 | 河南盛达光伏科技有限公司 | Purification method of silicon scrap impurities |
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- 2022-05-18 CN CN202210552085.9A patent/CN114890429A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011121852A (en) * | 2009-12-14 | 2011-06-23 | Toyokazu Nakasone | Method for producing high purity silicon |
| CN106115714A (en) * | 2016-06-24 | 2016-11-16 | 河南易成新能源股份有限公司 | A kind of preparation method of metallic silicon |
| CN109112638A (en) * | 2018-10-10 | 2019-01-01 | 镇江环太硅科技有限公司 | A kind of method of sheet stock recycling and reusing fine crushing |
| CN211920881U (en) * | 2019-12-30 | 2020-11-13 | 江苏载驰科技股份有限公司 | Device for preparing high-purity micro-nano silicon powder by utilizing photovoltaic industry silicon waste |
| WO2021182341A1 (en) * | 2020-03-12 | 2021-09-16 | グローバルウェーハズ・ジャパン株式会社 | Device for cleaning silicon raw material |
| CN113582184A (en) * | 2021-08-06 | 2021-11-02 | 河南盛达光伏科技有限公司 | Purification method of silicon scrap impurities |
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