CN110814360A - Method for recovering copper powder from waste lithium battery - Google Patents
Method for recovering copper powder from waste lithium battery Download PDFInfo
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- CN110814360A CN110814360A CN201911132255.2A CN201911132255A CN110814360A CN 110814360 A CN110814360 A CN 110814360A CN 201911132255 A CN201911132255 A CN 201911132255A CN 110814360 A CN110814360 A CN 110814360A
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- Prior art keywords
- copper
- powder
- copper foil
- waste lithium
- electrode material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F2009/001—Making metallic powder or suspensions thereof from scrap particles
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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
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for recovering copper powder from waste lithium batteries, and belongs to the technical field of electrode material recovery. Which comprises the following steps: soaking a negative electrode material of a waste lithium battery in water, removing carbon powder on the surface of a copper foil on the negative electrode material, filtering, and cleaning the copper foil to obtain a clean copper foil; putting the copper foil into a stainless steel disc and compacting, introducing oxidizing gas into the stainless steel disc filled with the copper foil for oxidation treatment, and turning to obtain copper oxide fragments; grinding and crushing the copper oxide fragments to obtain copper oxide powder; and introducing reducing gas into the copper oxide powder to carry out reduction treatment to obtain the copper powder. The recovery method disclosed by the invention is green and environment-friendly, the recovery rate of the copper powder is high, and the recovered copper powder is high in purity and good in quality. And the whole recovery method has the advantages of simple required equipment, high production capacity, low production cost and no environmental pollution.
Description
Technical Field
The invention relates to the technical field of electrode material recovery, in particular to a method for recovering copper powder from waste lithium batteries.
Background
The lithium battery mainly comprises a shell, a positive electrode, a negative electrode, electrolyte and a diaphragm. The negative electrode structure is formed by bonding carbon powder on two sides of a copper foil current collector by virtue of a bonding effect. If the discarded lithium battery is not properly treated, lithium hexafluorophosphate, carbonate organic matters, cobalt, copper and other heavy metals contained in the discarded lithium battery inevitably pose potential pollution threats to the environment. Cobalt, lithium, copper, plastics and the like in the waste lithium batteries are precious resources and have extremely high recovery value. It is estimated that the production of waste lithium ion batteries in China is 10 ten thousand tons in 2015, and more than 50 ten thousand tons in 2020. Lithium ion batteries are rich in precious metals, even higher than in natural ores. The copper content in the cathode of the waste lithium battery reaches about 35 percent, the cathode is an important widely used production raw material, and the carbon powder adhered to the cathode can be used as additives such as plastics, rubber and the like. The reasonable recovery of the waste lithium ion battery not only plays an important role in environmental protection, but also has high economic value.
At present, in the recovery method of the negative electrode material of the lithium battery, some methods directly crush the negative electrode material into fragments to realize the separation of carbon powder and copper foil, and recover the carbon powder and the copper foil; and some are crushed into powder and recovered to obtain copper powder and carbon powder. In the prior patent, waste lithium battery negative electrode sheets are firstly crushed and then sent into a high-temperature furnace with a vibration screening function to react, graphite powder is obtained under a screen, fine fragments are obtained on the screen, the fine fragments are put into a stirrer with deionized water, the mechanical stirring is carried out for 0.5 to 1 hour, then the fine fragments are screened, copper foil sheets with small amount of residual graphite on the surface are obtained on the screen, and wet graphite is obtained under the screen; and (3) putting the copper foil on the sieve into deionized water, performing ultrasonic treatment for 0.5-1 h, and sieving to obtain copper foil with higher purity on the sieve and obtain a small amount of wet graphite below the sieve. Or in the prior patent, the waste lithium battery negative pole piece is crushed and sieved to obtain negative pole powder and copper powder, and in the recovery technology, the lithium battery negative pole material is crushed under the dry condition, and is subjected to hammer vibration impact and/or pressing to obtain copper foil or copper powder. On one hand, the recovery technology causes large broken dust and pollutes the environment because of being in a dry condition; on the other hand, because copper has good ductility and excellent strength and toughness, the copper foil can be subjected to bending group winding and tends to be enriched in a coarse grain size range in the crushing process; and the bonded carbon powder on the surface of the copper foil falls off by hammering vibration and can be coated in the broken copper sheets, so that the carbon powder is difficult to remove and impurities are easy to bring in the copper powder, and the prepared copper powder has the problems of irregular appearance, uneven surface, poor conductivity, incomplete copper recovery and the like.
Disclosure of Invention
The invention aims to provide a method for recovering copper powder from waste lithium batteries, which aims to solve the problems that the existing waste lithium batteries are large in dust, easy to cause environmental pollution and low in quality of obtained copper powder.
The technical scheme for solving the technical problems is as follows:
a method for recovering copper powder from waste lithium batteries comprises the following steps:
(1) soaking a negative electrode material of a waste lithium battery in water, removing carbon powder on the surface of a copper foil on the negative electrode material, filtering, and cleaning the copper foil to obtain a clean copper foil;
(2) putting the copper foil into a stainless steel disc and compacting, introducing oxidizing gas into the stainless steel disc filled with the copper foil for oxidation treatment, and turning to obtain copper oxide fragments;
(3) grinding and crushing the copper oxide fragments to obtain copper oxide powder;
(4) and introducing reducing gas into the copper oxide powder to carry out reduction treatment to obtain the copper powder.
The invention firstly soaks the cathode material into water to separate the copper foil and the carbon powder, thus facilitating the separation of the copper foil and the carbon powder, and simultaneously avoiding the generation of dust and the pollution to the environment when the cathode material is soaked in water. And then cleaning the copper foil, and oxidizing the cleaned copper foil to convert the copper foil into copper oxide fragments. The generated copper oxide fragments are easier to be crushed into powder than copper foil, and the copper oxide powder obtained after crushing is subjected to reduction treatment to obtain copper powder with a flat, smooth and flawless surface. The recovery method disclosed by the invention is green and environment-friendly, the recovery rate of the copper powder is high, and the recovered copper powder is high in purity and good in quality. The whole recovery method of the invention has the advantages of simple required equipment, large production capacity, low production cost and no environmental pollution.
Further, in a preferred embodiment of the present invention, the thickness of the copper foil on the negative electrode material in the step (1) is 10 to 30 μm.
Further, in a preferred embodiment of the present invention, the oxidizing gas introduced in the step (2) is oxygen.
Further, in a preferred embodiment of the present invention, the oxidation treatment conditions in the step (2) are as follows: the oxidation temperature is 500-900 ℃, and the heat preservation time is 30-120 min.
Under the oxidation temperature and the heat preservation time, the copper foil can be fully oxidized, the generated copper oxide fragments can be prevented from being adhered, and the crystal grains of the copper oxide are uniform, so that the subsequent crushing of the copper oxide fragments is facilitated. If the temperature is too low or the heat preservation time is not enough, the slow oxidation reaction of the copper foil is easy to be insufficient; if the temperature is too high or the heat preservation time is too long, the generated copper oxide fragments are adhered and have thick grains, and unnecessary waste is also caused.
Further, in a preferred embodiment of the present invention, the reducing gas introduced in the step (4) is hydrogen.
Further, in a preferred embodiment of the present invention, the reduction treatment conditions in the step (4) are as follows: the reduction temperature is 300-800 ℃, and the heat preservation time is 30-120 min.
Under the reduction temperature and the heat preservation time, the generated copper powder grains are uniform, and the copper powder with flat, smooth and flawless surface is ensured to be obtained.
The invention has the following beneficial effects:
the copper foil and the carbon powder in the negative electrode material are separated, then the cleaned copper foil is subjected to oxidation treatment, the copper foil is converted into copper oxide fragments, the generated copper oxide fragments are easy to break into powder, and the broken copper oxide powder is subjected to reduction treatment to obtain the copper powder with a flat, smooth and flawless surface. The recovery method disclosed by the invention is green and environment-friendly, the recovery rate of the copper powder is high, and the recovered copper powder is high in purity and good in quality. And the whole recovery method has the advantages of simple required equipment, high production capacity, low production cost and no environmental pollution.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
the method for recovering copper powder from waste lithium batteries comprises the following steps:
(1) soaking a negative electrode material of a waste lithium battery in water, adopting a mechanical vibration method to drop carbon powder on the surface of a copper foil on the negative electrode material and filter the carbon powder, and then adopting clear water to clean the copper foil to obtain a clean copper foil; wherein the copper foil has a thickness of 10 μm.
(2) Putting the clean copper foil into a stainless steel disc and compacting, introducing oxygen into the stainless steel disc filled with the copper foil in a heating furnace for oxidation treatment, and turning over for 2-3 times to obtain copper oxide fragments; wherein the oxidation treatment conditions are as follows: the oxidation temperature is 500 ℃, and the heat preservation time is 120 min.
(3) And grinding and crushing the copper oxide fragments to obtain copper oxide powder.
(4) And introducing hydrogen into the copper oxide powder to carry out reduction treatment to obtain the copper powder. Wherein, the reduction treatment conditions are as follows: the reduction temperature is 300 ℃, and the heat preservation time is 120 min.
The recovery rate of copper in the example reaches 95.8%.
Example 2:
the method for recovering copper powder from waste lithium batteries comprises the following steps:
(1) soaking a negative electrode material of a waste lithium battery in water, adopting a mechanical vibration method to drop carbon powder on the surface of a copper foil on the negative electrode material and filter the carbon powder, and then adopting clear water to clean the copper foil to obtain a clean copper foil; wherein the copper foil has a thickness of 20 μm.
(2) Putting the clean copper foil into a stainless steel disc and compacting, introducing oxygen into the stainless steel disc filled with the copper foil in a heating furnace for oxidation treatment, and turning over for 3 times to obtain copper oxide fragments; wherein the oxidation treatment conditions are as follows: the oxidation temperature is 750 ℃ and the heat preservation time is 60 min.
(3) And grinding and crushing the copper oxide fragments to obtain copper oxide powder.
(4) And introducing hydrogen into the copper oxide powder to carry out reduction treatment to obtain the copper powder. Wherein, the reduction treatment conditions are as follows: the reduction temperature is 500 ℃, and the heat preservation time is 60 min.
The recovery rate of copper in the example reaches 95.5%.
Example 3:
the method for recovering copper powder from waste lithium batteries comprises the following steps:
(1) soaking a negative electrode material of a waste lithium battery in water, adopting a mechanical vibration method to drop carbon powder on the surface of a copper foil on the negative electrode material and filter the carbon powder, and then adopting clear water to clean the copper foil to obtain a clean copper foil; wherein the copper foil has a thickness of 30 μm.
(2) Putting the clean copper foil into a stainless steel disc and compacting, introducing oxygen into the stainless steel disc filled with the copper foil in a heating furnace for oxidation treatment, and turning for 2 times to obtain copper oxide fragments; wherein the oxidation treatment conditions are as follows: the oxidation temperature is 900 deg.C, and the holding time is 30 min.
(3) And grinding and crushing the copper oxide fragments to obtain copper oxide powder.
(4) And introducing hydrogen into the copper oxide powder to carry out reduction treatment to obtain the copper powder. Wherein, the reduction treatment conditions are as follows: the reduction temperature is 800 ℃, and the heat preservation time is 30 min.
The recovery rate of copper in the embodiment reaches 96.2 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A method for recovering copper powder from waste lithium batteries is characterized by comprising the following steps:
(1) soaking a negative electrode material of a waste lithium battery in water, removing carbon powder on the surface of a copper foil on the negative electrode material, filtering, and cleaning the copper foil to obtain a clean copper foil;
(2) putting the copper foil into a stainless steel disc and compacting, introducing oxidizing gas into the stainless steel disc filled with the copper foil for oxidation treatment, and turning to obtain copper oxide fragments;
(3) grinding and crushing the copper oxide fragments to obtain copper oxide powder;
(4) and introducing reducing gas into the copper oxide powder to carry out reduction treatment to obtain the copper powder.
2. The method for recovering the copper powder from the waste lithium batteries as claimed in claim 1, wherein the thickness of the copper foil on the negative electrode material in the step (1) is 10-30 μm.
3. The method for recovering copper powder from waste lithium batteries as claimed in claim 1, wherein the oxidizing gas introduced in the step (2) is oxygen.
4. The method for recovering copper powder from waste lithium batteries as claimed in claim 3, wherein the oxidation treatment conditions in the step (2) are as follows: the oxidation temperature is 500-900 ℃, and the heat preservation time is 30-120 min.
5. The method for recovering the copper powder from the waste lithium batteries as claimed in claim 1, wherein the reducing gas introduced in the step (4) is hydrogen.
6. The method for recovering copper powder from waste lithium batteries as claimed in claim 5, wherein the reduction treatment conditions in the step (4) are as follows: the reduction temperature is 300-800 ℃, and the heat preservation time is 30-120 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201911132255.2A CN110814360A (en) | 2019-11-19 | 2019-11-19 | Method for recovering copper powder from waste lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911132255.2A CN110814360A (en) | 2019-11-19 | 2019-11-19 | Method for recovering copper powder from waste lithium battery |
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| CN110814360A true CN110814360A (en) | 2020-02-21 |
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| CN201911132255.2A Pending CN110814360A (en) | 2019-11-19 | 2019-11-19 | Method for recovering copper powder from waste lithium battery |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06104571A (en) * | 1992-09-22 | 1994-04-15 | Sumitomo Metal Ind Ltd | Production of low temperature fired ceramic multilayer board |
| CN1611308A (en) * | 2003-10-31 | 2005-05-04 | 登峰机械工业有限公司 | Copper foil recovery method for circuit board |
| CN102569941A (en) * | 2011-01-20 | 2012-07-11 | 常州翔宇资源再生科技有限公司 | Method for recycling negative electrode material of lithium ion battery by wet method |
| CN104588676A (en) * | 2015-02-06 | 2015-05-06 | 福建紫鑫金属材料科技有限公司 | Method for producing low-loose-specific-weight copper powder by using recycled waste copper sand material |
| CN105304967A (en) * | 2015-10-28 | 2016-02-03 | 东莞市凯金新能源科技有限公司 | Method for recycling scrapped lithium ion battery graphite cathode pieces |
| CN107887666A (en) * | 2016-09-29 | 2018-04-06 | 中国科学院过程工程研究所 | A kind of recovery method of negative electrode material of waste lithium ion battery |
| JP2019169309A (en) * | 2018-03-22 | 2019-10-03 | 三菱マテリアル株式会社 | Cobalt, copper, and aluminum separation method |
-
2019
- 2019-11-19 CN CN201911132255.2A patent/CN110814360A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06104571A (en) * | 1992-09-22 | 1994-04-15 | Sumitomo Metal Ind Ltd | Production of low temperature fired ceramic multilayer board |
| CN1611308A (en) * | 2003-10-31 | 2005-05-04 | 登峰机械工业有限公司 | Copper foil recovery method for circuit board |
| CN102569941A (en) * | 2011-01-20 | 2012-07-11 | 常州翔宇资源再生科技有限公司 | Method for recycling negative electrode material of lithium ion battery by wet method |
| CN104588676A (en) * | 2015-02-06 | 2015-05-06 | 福建紫鑫金属材料科技有限公司 | Method for producing low-loose-specific-weight copper powder by using recycled waste copper sand material |
| CN105304967A (en) * | 2015-10-28 | 2016-02-03 | 东莞市凯金新能源科技有限公司 | Method for recycling scrapped lithium ion battery graphite cathode pieces |
| CN107887666A (en) * | 2016-09-29 | 2018-04-06 | 中国科学院过程工程研究所 | A kind of recovery method of negative electrode material of waste lithium ion battery |
| JP2019169309A (en) * | 2018-03-22 | 2019-10-03 | 三菱マテリアル株式会社 | Cobalt, copper, and aluminum separation method |
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Application publication date: 20200221 |