CN107910612B - Method for recovering cobalt and nickel from waste lithium batteries - Google Patents
Method for recovering cobalt and nickel from waste lithium batteries Download PDFInfo
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- CN107910612B CN107910612B CN201711275527.5A CN201711275527A CN107910612B CN 107910612 B CN107910612 B CN 107910612B CN 201711275527 A CN201711275527 A CN 201711275527A CN 107910612 B CN107910612 B CN 107910612B
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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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- 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 belongs to the field of lithium battery recycling, and particularly relates to a method for recycling cobalt and nickel from waste lithium batteries, which comprises the following steps: (1) crushing the lithium battery positive plate into powder particles; (2) adding the crushed particles into an excessive first strong alkali solution, stirring until no bubbles are generated, and filtering; (3) adding sulfuric acid and hydrogen peroxide into the filter cake, and filtering after the reaction is finished; (4) heating the filtrate in a nitrogen environment, adding a first strong base solution, and performing suction filtration after the reaction is finished; (5) and washing and drying the filter cake, and then detecting. Compared with the extraction-back extraction process, the method has the advantages of simple process flow, lower requirement on equipment and strong operability, and the obtained composite hydroxide is washed to realize the separation of the precious metal cobalt nickel and the low-price metal manganese, wherein the cobalt nickel content is more than 50 percent and the manganese content is less than 2 percent.
Description
Technical Field
The invention belongs to the field of lithium battery recycling, and particularly relates to a method for recycling cobalt and nickel from waste lithium batteries.
Background
Lithium ion batteries are widely used in the fields of portable electronic devices, electric vehicles, aerospace, and the like, due to their advantages of high energy density, light weight, long service life, and no memory performance. With the popularization of lithium ion battery application, a large amount of waste lithium ion batteries are generated, and because the waste lithium ion batteries contain harmful metals such as cobalt, nickel, manganese and the like, the waste lithium ion batteries cause great harm to the environment. The recycling of the valuable metal cobalt nickel manganese lithium in the waste lithium battery is realized, so that not only can economic benefits be brought, but also the problem of increasingly serious environmental pollution can be relieved. The current recovery process for recovering waste lithium batteries mainly comprises the steps of discharging, disassembling, crushing, sorting out plastic and iron shells for recovery, and performing alkali leaching, acid leaching, impurity removal, extraction, back extraction, crystallization and the like on electrode materials. The solution of cobalt, nickel and manganese is separated by extraction, cobalt salt, nickel salt, manganese salt and the like are obtained by crystallization and concentration, and then the solution is prepared according to the proportion as required to synthesize the ternary precursor. Although the extraction-back extraction process can separate cobalt, nickel and manganese, the process is complicated and the cost is high. In addition, the method of oxalate, phosphate, sulfide and carbonate can be used for separating nickel, lithium, cobalt and manganese, but the process is complex, the metal recovery rate is not high, and the method for separating the valuable metals of cobalt, nickel, manganese and lithium from the waste lithium battery materials needs to be further optimized.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for recovering cobalt and nickel from waste lithium batteries.
Specifically, the method for recovering cobalt and nickel from waste lithium batteries comprises the following steps:
(1) crushing the lithium battery positive plate into powder particles;
(2) adding the crushed particles into an excessive first strong alkali solution, stirring until no bubbles are generated, and filtering;
(3) adding sulfuric acid and hydrogen peroxide into the filter cake, and filtering after the reaction is finished;
(4) heating the filtrate in a nitrogen environment, adding a first strong base solution, and performing suction filtration after the reaction is finished;
(5) and washing and drying the filter cake, and then detecting.
In the method for recovering cobalt and nickel from waste lithium batteries, the first strong alkali solution is one or more of NaOH, KOH and LiOH solutions.
Before the step (3), the method for recovering cobalt and nickel from waste lithium batteries further comprises the steps of pulping and washing the filter cake with a second strong alkali solution, and filtering to obtain the filter cake.
In the method for recovering cobalt and nickel from waste lithium batteries, the concentration of the second strong alkali solution is 0.05-0.15 mol/L.
In the method for recovering cobalt and nickel from waste lithium batteries, the solid-to-liquid ratio of the second strong alkali solution to the filter cake is 1:3-1: 5.
In the method for recovering cobalt and nickel from waste lithium batteries, the concentration of the first strong alkali solution is 4.5-5.5 mol/L.
In the method for recovering cobalt and nickel from waste lithium batteries, in the step (3), the concentration of the sulfuric acid is 1-2 mol/L.
In the method for recovering cobalt and nickel from waste lithium batteries, in the step (3), the concentration of the hydrogen peroxide is 25-30%.
In the method for recovering cobalt and nickel from waste lithium batteries, in the step (4), the first strong alkali solution is slowly added into the filtrate in a dropwise manner.
In the method for recovering cobalt and nickel from waste lithium batteries, in the step (4), the reaction is carried out at 50-60 ℃ for 2-6 hours.
In the method for recovering cobalt and nickel from waste lithium batteries, in the step (5), the filter cake is pulped and washed for 3 times by using water with the weight being 3-5 times that of the filter cake.
In the method for recovering cobalt and nickel from waste lithium batteries, in the step (5), the washing is performed under the protection of nitrogen and under the water bath condition of 50-60 ℃.
Compared with the extraction-back extraction process, the method has the advantages of simple process flow, lower requirement on equipment and strong operability, and the obtained composite hydroxide is washed to realize the separation of the precious metal cobalt nickel and the low-price metal manganese, wherein the cobalt nickel content is more than 50 percent and the manganese content is less than 2 percent.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The process of the present invention employs conventional methods or apparatus in the art, except as described below. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
According to the method, the sodium hydroxide solution is added into the ternary composite sulfate solution by utilizing the difference of the solubility products of the hydroxides of cobalt, nickel and manganese, and because the solubility products of cobalt hydroxide and nickel hydroxide are smaller than that of manganese hydroxide, cobalt and nickel are firstly precipitated, most of manganese is remained in the solution, and the separation of cobalt, nickel and manganese is realized.
The technical scheme of the invention is as follows: the method comprises the steps of taking waste lithium battery positive plates as raw materials, crushing, removing aluminum through alkaline leaching, dissolving powder with dilute sulfuric acid and hydrogen peroxide, and filtering to obtain a ternary composite sulfate solution. Adding a certain amount of sodium hydroxide solution into the ternary composite sulfate solution to generate the composite hydroxide, and washing the solid after solid-liquid separation for three times to obtain the high-cobalt-nickel low-manganese composite hydroxide, wherein the content of cobalt and nickel is more than 50 percent, and the content of manganese is less than 2 percent.
Specifically, the method for recovering cobalt and nickel from waste lithium batteries comprises the following steps:
(1) weighing and crushing the lithium battery positive plate;
and randomly weighing a certain mass of the waste lithium battery positive plate, and crushing by using a small crusher.
The invention has no special requirement on the particle size of the crushed particles, and the purpose of crushing the positive plate is mainly to accelerate the reaction.
(2) Adding excessive strong base solution, stirring until no bubbles are generated, and filtering;
slowly adding the positive plate particles into the excessive first strong base solution, stirring until no gas is generated, filtering, removing filtrate, and pulping and washing the filter cake for 2 times by adopting the second strong base solution.
Wherein the concentration of the first strong alkali solution is 4.5-5.5mol/L, preferably 5 mol/L; the concentration of the second alkali solution is 0.05-0.15mol/L, preferably 0.1 mol/L.
Since aluminum and its oxide can react with hydroxide ions in the positive electrode sheet particles, aluminum and its oxide can be removed without loss of chromium and nickel. The ion reaction equation of this step is as follows:
2Al+2OH-+2H2O＝2AlO- 2+3H2↑
Al2O3+2OH-＝2AlO- 2+H2O
the strong base in the invention is NaOH, KOH, LiOH and other strong bases which do not influence the subsequent reaction.
(3) Adding sulfuric acid and hydrogen peroxide into the filter cake, and filtering after the reaction is finished;
slowly adding the washed powder into 1-2mol/L sulfuric acid solution, slowly adding hydrogen peroxide with the mass fraction of 25-30% while stirring, reacting for 2 hours, and filtering to obtain the NiSO-containing powder4、CoSO4、MnSO4The filtrate of (2) is the ternary complex sulfate solution. The reaction equation is as follows:
2LiMO2+3H2SO4+H2O2＝Li2SO4+2MSO4+4H2O+O2↑
wherein M represents a mixture of Ni, Co and Mn with an indefinite proportion.
(4) Heating the filtrate in a nitrogen environment, adding a strong base solution, and performing suction filtration after the reaction is finished;
in 50-60 deg.C water bath and N2And under protection, dropwise adding the first strong alkali solution into the three-neck flask of the ternary composite sulfate solution, and continuing to react for 2 hours after dropwise adding is completed for about 2 hours. After the reaction, suction filtration was carried out.
Wherein the amount of the substance added with the strong base cannot exceed 90% of the theoretical molar amount of completely precipitated cobalt and nickel.
The purpose of adding strong base in the invention is to generate hydroxide precipitate, and the chemical reaction equation is as follows:
MSO4+2NaOH＝M(OH)2↓+Na2SO4
wherein M represents a mixture of Ni, Co and Mn with an indefinite proportion.
(5) And washing and drying the filter cake, and then detecting.
Putting the filter cake obtained in the step (4) in N2Under protection and water bath at 50-60 ℃, pulping and washing with water 3-5 times the weight of the filter cake for 4h, washing for 3 times under the same condition, and drying to detect the content of each component.
The purpose of the nitrogen protection is to prevent M (OH) in the washing process2Wherein M represents a mixture of Ni, Co and Mn.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were carried out according to conventional methods and conditions. The starting materials used in the following examples are all conventionally commercially available.
Example 1
200g of waste lithium battery positive plates are randomly weighed, crushed by a small crusher, slowly added into 1L5.0mol/L NaOH solution, and stirred until no gas is generated. After filtration, the filter cake is pulped and washed twice by 0.1mol/L NaOH solution according to the solid-to-liquid ratio of 1: 4. Slowly adding the washed powder into 1.3L of 1.5mol/L sulfuric acid solution, slowly adding 200mL of 30% hydrogen peroxide while stirring, reacting for 2h, and filtering to obtain about 1.5L of filtrate, wherein NiSO4：63.80g/L，CoSO4：78.65g/L，MnSO4: 41.60 g/L. In N2Under protection and water bath at 55 ℃, 160mL of NaOH solution with the concentration of 5.05mol/L (30 percent of cobalt-nickel precipitation) is dripped into a three-neck flask containing ternary compound sulfate solution, the reaction is continued for 2h after about 2h of dripping, and the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath condition of 55 ℃, pulping and washing for 4 hours by using water with 4 times of the weight of the filter cake, washing for 3 times under the same condition, and drying. The obtained solid was examined, wherein the content of Ni was 32.46%, the content of Co was 21.05%, and the content of Mn was 0.64% in terms of weight%.
Example 2
200g of waste lithium battery positive plates are randomly weighed, crushed by a small crusher, slowly added into 1L4.5mol/L NaOH solution, and stirred until no gas is generated. After filtration, the filter cake is pulped and washed twice by 0.05mol/L NaOH solution according to the solid-to-liquid ratio of 1: 3. Slowly adding the washed powder into 1.6mol/L sulfuric acid solution, slowly adding 200mL of 25% hydrogen peroxide while stirring, reacting for 2h, and filtering to obtain about 1.5L of filtrate, wherein NiSO4：64.00g/L，CoSO4：76.55g/L，MnSO4: 42.59 g/L. In N2Under protection and water bath at 55 ℃, 160mL of NaOH solution with the concentration of 5.05mol/L (30 percent of cobalt-nickel precipitation) is dripped into a three-neck flask containing ternary compound sulfate solution, the reaction is continued for 2h after about 2h of dripping, and the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath condition of 55 ℃, pulping and washing for 4 hours by using water with 4 times of the weight of the filter cake, washing for 3 times under the same condition, and drying. Detecting the obtained solid, wherein the content of Ni is 31.26 in percentage by weightPercent, Co content 20.99 percent and Mn content 0.75 percent.
Example 3
200g of waste lithium battery positive plates are randomly weighed, crushed by a small crusher, slowly added into 1L5.5mol/L NaOH solution, and stirred until no gas is generated. After filtration, the filter cake is pulped and washed twice by 0.15mol/L NaOH solution according to the solid-to-liquid ratio of 1: 5. Slowly adding the washed powder into 1.3L of 2mol/L sulfuric acid solution, slowly adding 200mL of 30% hydrogen peroxide while stirring, reacting for 2h, and filtering to obtain about 1.5L of filtrate, wherein the NiSO4：65.02g/L，CoSO4：80.05g/L，MnSO4: 43.58 g/L. In N2Under protection and a water bath at 55 ℃, 170mL of NaOH solution with the concentration of 5.0mol/L (30 percent of cobalt-nickel precipitation) is dripped into a three-neck flask containing the ternary composite sulfate solution, the reaction is continued for 2 hours after the dripping is finished for about 2 hours, and the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath condition of 55 ℃, pulping and washing for 4 hours by using water with 4 times of the weight of the filter cake, washing for 3 times under the same condition, and drying. The obtained solid was examined, wherein the content of Ni was 32.83 wt%, the content of Co was 21.57 wt%, and the content of Mn was 0.81 wt%.
Example 4
Preparing 1.5L of ternary compound sulfate solution according to the preparation method of the embodiment 1-3, wherein the NiSO4：45.87g/L，CoSO4：61.21g/L，MnSO4: 37.08 g/L. In N2200mL of 4.96mol/L NaOH solution (50% of cobalt and nickel precipitation) is dripped into a three-neck flask containing ternary complex sulfate solution under protection and 50 ℃ water bath, the reaction is continued for 2.5h after about 2.5h dripping, and then the filtration is carried out. The obtained filter cake is added in N2Under protection and 50 ℃ water bath condition, pulping and washing for 2h by using water with 4 times of the weight of the filter cake, washing for 3 times under the same condition and drying. The obtained solid was examined, wherein the content of Ni was 30.97%, the content of Co was 22.53%, and the content of Mn was 0.84% by weight.
Example 5
Instead, 1.5L of ternary composite sulfate solution is prepared according to the preparation method of embodiment 1-3Medium, NiSO4：38.52g/L，CoSO4：56.35g/L，MnSO4: 30.64 g/L. In N2Under protection and 60 ℃ water bath, 320mL of 5.16mol/L NaOH solution (90% of cobalt nickel precipitation) is dripped into a three-neck flask containing ternary complex sulfate solution, the reaction is continued for 3h after about 3h of dripping, and then the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath at 60 ℃, pulping and washing for 3 hours by using water with 3 times of the weight of the filter cake, washing for 3 times under the same condition and drying. The obtained solid was examined, wherein the content of Ni was 19.93%, the content of Co was 32.20%, and the content of Mn was 1.88% by weight.
Example 6
Preparing 1.0L of ternary compound sulfate solution according to the preparation method of the embodiment 1-3, wherein the NiSO4：67.48g/L，CoSO4：67.96g/L，MnSO4: 54.28 g/L. In N2Under protection and water bath at 57 ℃, 260mL of NaOH solution with the concentration of 4.75mol/L (70 percent of cobalt-nickel precipitation) is dropwise added into a three-neck flask containing ternary complex sulfate solution, the reaction is continued for 3 hours after the dropwise addition is finished for about 3 hours, and then the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath at 57 ℃, pulping and washing for 4h by using water with the weight 5 times of that of the filter cake, washing for 3 times under the same condition and drying. The obtained solid was examined, wherein the content of Ni was 31.83%, the content of Co was 22.28%, and the content of Mn was 0.99% by weight.
Example 7
Preparing 1.0L of ternary compound sulfate solution according to the preparation method of the embodiment 1-3, wherein the NiSO4：48.68g/L，CoSO4：69.01g/L，MnSO4: 50.46 g/L. In N2Under protection and water bath at 53 ℃, 60mL of NaOH solution with the concentration of 5.02mol/L (20 percent of cobalt nickel precipitation) is dripped into a three-neck flask containing ternary complex sulfate solution, the reaction is continued for 1.5h after about 1.5h of dripping, and then the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath at 53 ℃, pulping and washing for 3 hours by using water with 3 times of the weight of the filter cake, washing for 3 times under the same condition, and drying. The obtained solid was examined for Ni content of 29.56%, Co content of 23.08%, and Mn content by weightThe amount was 0.73%.
Example 8
Preparing 1.0L of ternary compound sulfate solution according to the preparation method of the embodiment 1-3, wherein the NiSO4：62.34g/L，CoSO4：74.24g/L，MnSO4: 31.41 g/L. In N2Under protection and water bath at 55 ℃, 300mL of NaOH solution with the concentration of 5.26mol/L (90% of cobalt-nickel precipitation) is dripped into a three-neck flask containing ternary complex sulfate solution, the reaction is continued for 3h after the dripping is finished for about 3h, and then the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath at 55 ℃, pulping and washing for 3 hours by using water with the weight 5 times of that of a filter cake, washing for 3 times under the same condition, and drying. The obtained solid was examined, wherein the content of Ni was 23.11%, the content of Co was 28.09%, and the content of Mn was 1.74% by weight.
Example 9
Preparing 1.0L of ternary compound sulfate solution according to the preparation method of the embodiment 1-3, wherein the NiSO4：62.34g/L，CoSO4：74.24g/L，MnSO4: 31.41 g/L. In N2Under protection and water bath at 55 ℃, 280mL of NaOH solution with the concentration of 5.02mol/L (80 percent of cobalt-nickel precipitation) is dripped into a three-neck flask containing ternary complex sulfate solution, the reaction is continued for 3 hours after the dripping is finished for about 3 hours, and then the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath at 55 ℃, pulping and washing for 6h by using water with the weight 5 times that of a filter cake, washing for 3 times under the same condition, and drying. The obtained solid was examined, wherein the content of Ni was 22.68%, the content of Co was 28.57%, and the content of Mn was 1.51% by weight.
Example 10
200g of waste lithium battery positive plates are randomly weighed, crushed by a small crusher and slowly added into 1L5.0mol/L KOH solution, and stirred until no gas is generated. After filtration, the filter cake is washed twice by pulping with 0.1mol/L KOH solution according to the solid-to-liquid ratio of 1: 4. Slowly adding the washed powder into 1.3L1.5mol/L sulfuric acid solution, slowly adding 200mL hydrogen peroxide with the mass fraction of 30% while stirring, reacting for 2h, and filtering to obtain about 1.5L filtrate, wherein the NiSO4：62.91g/L，CoSO4：78.63g/L，MnSO4: 42.11 g/L. In N2Under protection and water bath at 55 ℃, 110mL of KOH solution with the concentration of 5.0mol/L (30 percent of cobalt nickel precipitation) is dropwise added into a three-neck flask containing ternary compound sulfate solution, the reaction is continued for 2h after the dropwise addition is finished for about 2h, and the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath condition of 55 ℃, pulping and washing for 4 hours by using water with 4 times of the weight of the filter cake, washing for 3 times under the same condition, and drying. The obtained solid was examined, wherein the content of Ni was 31.17%, the content of Co was 22.99%, and the content of Mn was 0.71% by weight.
Example 11
200g of waste lithium battery positive plates are randomly weighed, crushed by a small crusher, slowly added into 1L4.5mol/L LiOH solution, and stirred until no gas is generated. After filtration, the filter cake is washed twice by pulping 0.1mol/L LiOH solution according to the solid-to-liquid ratio of 1: 4. Slowly adding the washed powder into 1.3L1.5mol/L sulfuric acid solution, slowly adding 200mL hydrogen peroxide with the mass fraction of 30% while stirring, reacting for 2h, and filtering to obtain about 1.5L filtrate, wherein the NiSO4：59.91g/L，CoSO4：80.44g/L，MnSO4: 39.11 g/L. In N2Under protection and a water bath at 55 ℃, 180mL of LiOH solution (30 percent of cobalt nickel precipitation) with the concentration of 4.5mol/L is dropwise added into a three-neck flask containing ternary complex sulfate solution, the reaction is continued for 2h after the dropwise addition is finished for about 2h, and the filtration is carried out. The obtained filter cake is added in N2Under protection and water bath condition of 55 ℃, pulping and washing for 4 hours by using water with 4 times of the weight of the filter cake, washing for 3 times under the same condition, and drying. The obtained solid was examined, wherein the content of Ni was 31.57%, the content of Co was 21.68%, and the content of Mn was 0.81% by weight.
The present invention has been disclosed in the foregoing in terms of preferred embodiments, but it will be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that all changes and substitutions equivalent to those of the embodiments are intended to be included within the scope of the claims of the present invention. Therefore, the protection scope of the present invention should be subject to the scope defined in the claims.
Claims (9)
1. A method for recovering cobalt and nickel from waste lithium batteries is characterized by comprising the following steps:
(1) crushing the lithium battery positive plate into powder particles;
(2) adding the crushed particles into an excessive first strong alkali solution, stirring until no bubbles are generated, and filtering;
(3) adding sulfuric acid and hydrogen peroxide into the filter cake, and filtering after the reaction is finished;
(4) heating the filtrate in a nitrogen environment, slowly dropwise adding 4.5-5.5mol/L first strong alkali solution, reacting at 50-60 ℃ for 2-6 hours, and then carrying out suction filtration;
wherein the amount of material of the first strong base is no more than 90% of the theoretical molar amount of completely precipitated cobalt nickel;
(5) and (4) washing and drying the filter cake, and detecting, wherein the content of cobalt and nickel is more than 50%.
2. The method for recovering cobalt and nickel from waste lithium batteries according to claim 1, wherein the first strong alkali solution is one or more of NaOH, KOH and LiOH solution.
3. The method for recovering cobalt and nickel from waste lithium batteries according to claim 1 or 2, characterized in that, before the step (3), the method further comprises the steps of pulping and washing the filter cake with a second strong alkaline solution, and filtering to obtain the filter cake.
4. The method for recovering cobalt and nickel from waste lithium batteries as recited in claim 3, wherein the concentration of the second alkali solution is 0.05-0.15 mol/L.
5. The method for recovering cobalt and nickel from waste lithium batteries according to claim 3, wherein the solid-to-liquid ratio of the second strong alkali solution to the filter cake is 1:3-1: 5.
6. The method for recovering cobalt and nickel from waste lithium batteries according to claim 1, wherein the concentration of the sulfuric acid in the step (3) is 1-2 mol/L.
7. The method for recovering cobalt and nickel from waste lithium batteries according to claim 1, wherein in the step (3), the mass fraction of the hydrogen peroxide is 25-30%.
8. The method for recovering cobalt and nickel from waste lithium batteries according to claim 1, wherein in the step (5), the filter cake is beaten and washed 3 times by using water with 3-5 times weight of the filter cake.
9. The method for recovering cobalt and nickel from waste lithium batteries as claimed in claim 1, wherein in the step (5), the washing is performed under the protection of nitrogen and in a water bath at 50-60 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002226923A (en) * | 2001-01-31 | 2002-08-14 | Sumitomo Metal Mining Co Ltd | Method for recovering valuable metal from nickel- hydrogen secondary battery scrap |
| CN1770513A (en) * | 2004-11-03 | 2006-05-10 | 深圳市比克电池有限公司 | Manganese-included multi-element metal oxide, lithium ion secondary battery anode material and its preparing method |
| CN101323908A (en) * | 2008-07-31 | 2008-12-17 | 广西冶金研究院 | Method for reclaiming cobalt from manganese cobalt slag |
| CN101628761A (en) * | 2009-08-18 | 2010-01-20 | 湖南邦普循环科技有限公司 | Treatment method of nickel-cobalt-manganese wastewater generated in waste and old battery treatment process |
| CN102244309A (en) * | 2011-06-03 | 2011-11-16 | 佛山市邦普循环科技有限公司 | Method for recovering lithium from lithium power battery of electric automobile |
-
2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002226923A (en) * | 2001-01-31 | 2002-08-14 | Sumitomo Metal Mining Co Ltd | Method for recovering valuable metal from nickel- hydrogen secondary battery scrap |
| CN1770513A (en) * | 2004-11-03 | 2006-05-10 | 深圳市比克电池有限公司 | Manganese-included multi-element metal oxide, lithium ion secondary battery anode material and its preparing method |
| CN101323908A (en) * | 2008-07-31 | 2008-12-17 | 广西冶金研究院 | Method for reclaiming cobalt from manganese cobalt slag |
| CN101628761A (en) * | 2009-08-18 | 2010-01-20 | 湖南邦普循环科技有限公司 | Treatment method of nickel-cobalt-manganese wastewater generated in waste and old battery treatment process |
| CN102244309A (en) * | 2011-06-03 | 2011-11-16 | 佛山市邦普循环科技有限公司 | Method for recovering lithium from lithium power battery of electric automobile |
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