CN103594754A - Method and device for recycling treatment of waste lithium ion battery with oxalic acid as extracting solution - Google Patents
Method and device for recycling treatment of waste lithium ion battery with oxalic acid as extracting solution Download PDFInfo
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- CN103594754A CN103594754A CN201310541240.8A CN201310541240A CN103594754A CN 103594754 A CN103594754 A CN 103594754A CN 201310541240 A CN201310541240 A CN 201310541240A CN 103594754 A CN103594754 A CN 103594754A
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
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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
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Abstract
A method for recycling treatment of a waste lithium ion battery with oxalic acid as an extracting solution comprises the steps: carrying out electric discharge treatment of the waste lithium ion battery, mechanically crushing by a shear-type crusher, screening out a material having the particle size smaller than 1.43 mm, placing a beaker on a constant-temperature stirrer to form a leaching device, carrying out a reaction of the screened material and oxalic acid with the concentration of 0.5-1 mol/L according to the solid-liquid ratio of 15-25 g/L in the beaker for 40-90 min, carrying out filtering separation of a mixture obtained after the oxalic acid leaching reaction, and thus obtaining a solid precipitate containing cobalt oxalate and a leached solution containing lithium oxalate. The invention also provides a device for realizing the method. The method can effectively recycle cobalt oxalate and lithium oxalate in a positive electrode material of the waste lithium ion battery; and by adopting environment-friendly oxalic acid as the leaching solution, the recycling rate of cobalt oxalate and lithium oxalate is more than 99%.
Description
Technical field
The invention belongs to electronic waste resource treatment technique field, particularly a kind ofly take used Li ion cell recovery and treatment method and the device that oxalic acid is extract.
Background technology
Used Li ion cell is high with its energy density, operating voltage is large, memory-less effect and the advantage such as have extended cycle life, be widely used in being widely used in daily life, in various consumer electronics such as video camera, mobile phone, notebook computer and Portable Measurement Instrument, it is also the light high-energy power power supply of electric automobile first-selection.And these lithium ion batteries are after scrapping, conventionally can bring certain risk to environmental and human health impacts.Meanwhile, the metallic cobalt containing in used Li ion cell (Co) is the strategic resources that a kind of value is very high, therefore no matter from environmental protection or economic angle, considers, all should carry out resource recovery to used Li ion cell.
After measured, in used Li ion cell, the content of cobalt, lithium, copper, aluminium, iron etc. is respectively 23.18%, 3.39%, 2.90%, 0.94%, 0.32%.The cobalt resource of China relatively lacks, and the source of cobalt is mainly leaned on the recovery of nickel, copper, zinc smelting system and produced and using a large amount of cobaltiferous waste materials that produce to refine.Although the lithium resource of China is abundanter, producing capacity imperfection, carries lithium cost and does not possess competitiveness.The resource of used Li ion cell not only has Significance for Environment, and industry development is had more to long-range strategic value.
The recycling treatment process of used Li ion cell mainly comprises physical-chemical process, chemical method and bioanalysis three major types.Pyrogenic process, wet method, bioanalysis.Wherein wet method leaches the metal ions such as the cobalt in lithium battery anode, lithium with chemical reagent such as NaOH, sulfuric acid, nitric acid, hydrogen peroxide conventionally, then by follow-up process for purification such as precipitating, extract, saltout purify, separated, purify, the metallic elements such as cobalt, lithium.The method mainly adopts strong acid, easily causes secondary pollution; Meanwhile, the product of lixiviate is as CoCl
2, CoSO
4deng often just obtaining the industrial raw material (Co using as battery through more complicated technique
2o
3), and cobalt oxalate is very easy to obtain Co through calcining
2o
3.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of used Li ion cell recovery and treatment method and device that oxalic acid is extract of take, there is reaction condition gentleness, technological process is simple, and leaching efficiency is high, eco-friendly feature.
To achieve these goals, the technical solution used in the present invention is:
The used Li ion cell recovery and treatment method that oxalic acid is extract, comprises the steps:
Step 1: used Li ion cell is carried out to discharge process;
Step 2: the used Li ion cell after electric discharge is carried out to Mechanical Crushing, sieve out the material that particle diameter is less than 1.43mm, take cobalt acid lithium in material as main;
Step 3: beaker is placed in and forms leaching device on thermostatic mixer, the oxalic acid that is 0.5-1mol/L with concentration by the material after described screening reacts 40-90min according to solid-to-liquid ratio 15-25g/L in beaker, the temperature of thermostatic mixer is set at 75-95 ℃ in process, rotor speed is 300-400rpm;
Step 4: Separation of Solid and Liquid, by step 3 after oxalic acid Leaching reaction mixture carry out isolated by filtration, obtain containing the solid sediment of cobalt oxalate with containing the leachate of lithium oxalate.
Described Mechanical Crushing equipment therefor is shear crusher.
Described thermostatic mixer is comprised of temperature automatically controlled water-bath and the insertion adjustable electric mixer of rotating speed wherein.
The present invention also provides a kind of described device of take the used Li ion cell recovery and treatment method that oxalic acid is extract of realizing, and comprising:
By the discharging device of used Li ion cell electric discharge;
Used Li ion cell after electric discharge is carried out to the shear crusher of Mechanical Crushing;
By beaker, be placed in the leaching device forming on thermostatic mixer;
And the filtering separation device that carries out Separation of Solid and Liquid.
Compared with prior art, the present invention's method of the present invention can effectively reclaim cobalt oxalate and the lithium oxalate in used Li ion cell positive electrode, and the present invention adopts eco-friendly oxalic acid as infusion solution, and the rate of recovery of cobalt oxalate and lithium oxalate surpasses 99%.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.
Embodiment
Below in conjunction with drawings and Examples, describe embodiments of the present invention in detail.
Embodiment mono-
As shown in Figure 1, a kind ofly take the used Li ion cell recovery and treatment method that oxalic acid is extract, comprise the steps:
Step 1: used Li ion cell is carried out to discharge process.
Step 2: the used Li ion cell by after electric discharge, utilize shear crusher to carry out Mechanical Crushing, sieve out the material (cobalt acid lithium is main) that is less than 1.43mm.
Step 3: beaker is placed on thermostatic mixer and forms leaching device, and thermostatic mixer is comprised of temperature automatically controlled water-bath and the insertion adjustable electric mixer of rotating speed wherein.Used Li ion cell positive electrode crushing and screening is less than to the material of 1.43mm, the oxalic acid that is 0.5mol/L with concentration reacts 40min according to solid-to-liquid ratio 15g/L in beaker.The temperature of thermostatic mixer is set at 75 ℃ in process, rotor speed is 300rpm.
Step 4: Separation of Solid and Liquid, by step 3 after oxalic acid Leaching reaction mixture carry out isolated by filtration, obtain containing the solid sediment of cobalt oxalate with containing the leachate of lithium oxalate.
Embodiment bis-
As shown in Figure 1, a kind ofly take the used Li ion cell recovery and treatment method that oxalic acid is extract, comprise the steps:
Step 1: used Li ion cell is carried out to discharge process.
Step 2: the used Li ion cell by after electric discharge, utilize shear crusher to carry out Mechanical Crushing, sieve out the material (cobalt acid lithium is main) that is less than 1.43mm.
Step 3: beaker is placed in and forms leaching device on thermostatic mixer.Used Li ion cell positive electrode crushing and screening is less than to the material of 1.43mm, the oxalic acid that is 1mol/L with concentration reacts 90min according to solid-to-liquid ratio 25g/L in beaker.The temperature of thermostatic mixer is set at 95 ℃ in process, rotor speed is 400rpm.
Step 4: Separation of Solid and Liquid, by step 3 after oxalic acid Leaching reaction mixture carry out isolated by filtration, obtain containing the solid sediment of cobalt oxalate with containing the leachate of lithium oxalate.
Embodiment tri-
As shown in Figure 1, a kind ofly take the used Li ion cell recovery and treatment method that oxalic acid is extract, comprise the steps:
Step 1: used Li ion cell is carried out to discharge process.
Step 2: the used Li ion cell by after electric discharge, utilize shear crusher to carry out Mechanical Crushing, sieve out the material (cobalt acid lithium is main) that is less than 1.43mm.
Step 3: beaker is placed in and forms leaching device on thermostatic mixer.Used Li ion cell positive electrode crushing and screening is less than to the material of 1.43mm, the oxalic acid that is 0.8mol/L with concentration reacts 60min according to solid-to-liquid ratio 20g/L in beaker.The temperature of thermostatic mixer is set at 85 ℃ in process, rotor speed is 340rpm.
Step 4: Separation of Solid and Liquid, by step 3 after oxalic acid Leaching reaction mixture carry out isolated by filtration, obtain containing the solid sediment of cobalt oxalate with containing the leachate of lithium oxalate.
By utilizing oxalic acid for extract, cobalt, lithium metal are carried out to lixiviate, and separated recovery, the rate of recovery of cobalt, lithium metal can surpass 99%.
Experimental technique and process are: 1. sample preparation: prepare certain density oxalic acid; Used Li ion cell is processed the cobalt acid lithium mixed material (< 1.43mm) making.2. leaching process: according to the solid-to-liquid ratio of design, take and contain cobalt acid lithium material and be placed in beaker, add 100ml oxalic acid solution (1mol/L) to react with it.Beaker is placed in and on thermostatic mixer, forms leaching device.Temperature and rotating speed are according to design setting.3. sample preparation: carry out Separation of Solid and Liquid.Solution censorship ICP, analyzes cobalt, lithium content.4. basis
calculate leaching rate.
Claims (5)
1. the used Li ion cell recovery and treatment method that the oxalic acid of take is extract, is characterized in that, comprises the steps:
Step 1: used Li ion cell is carried out to discharge process;
Step 2: the used Li ion cell after electric discharge is carried out to Mechanical Crushing, sieve out the material that particle diameter is less than 1.43mm;
Step 3: beaker is placed in and forms leaching device on thermostatic mixer, the oxalic acid that is 0.5-1mol/L with concentration by the material after described screening reacts 40-90min according to solid-to-liquid ratio 15-25g/L in beaker, the temperature of thermostatic mixer is set at 75-95 ℃ in process, rotor speed is 300-400rpm;
Step 4: Separation of Solid and Liquid, by step 3 after oxalic acid Leaching reaction mixture carry out isolated by filtration, obtain containing the solid sediment of cobalt oxalate with containing the leachate of lithium oxalate.
2. according to claim 1ly take the used Li ion cell recovery and treatment method that oxalic acid is extract, it is characterized in that, described Mechanical Crushing equipment therefor is shear crusher.
3. according to claim 1ly take the used Li ion cell recovery and treatment method that oxalic acid is extract, it is characterized in that, described thermostatic mixer is comprised of temperature automatically controlled water-bath and the adjustable electric mixer of rotating speed inserted wherein.
4. realize and take the device of the used Li ion cell recovery and treatment method that oxalic acid is extract described in claim 1, it is characterized in that, comprising:
By the discharging device of used Li ion cell electric discharge;
Used Li ion cell after electric discharge is carried out to the shear crusher of Mechanical Crushing;
By beaker, be placed in the leaching device forming on thermostatic mixer;
And the filtering separation device that carries out Separation of Solid and Liquid.
5. according to claim 4ly take the used Li ion cell recovery and treatment method that oxalic acid is extract, it is characterized in that, described thermostatic mixer is comprised of temperature automatically controlled water-bath and the adjustable electric mixer of rotating speed inserted wherein.
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105907989A (en) * | 2016-07-08 | 2016-08-31 | 长沙理工大学 | Method for recycling cobalt and lithium from waste lithium ion battery material |
CN107083484A (en) * | 2017-04-20 | 2017-08-22 | 常州市鼎日环保科技有限公司 | A kind of method that metal is reclaimed from waste lithium cell |
CN107513618A (en) * | 2017-08-01 | 2017-12-26 | 苏州协鑫纳米科技有限公司 | The lead recovery method and device of perovskite battery |
CN108258351A (en) * | 2016-12-29 | 2018-07-06 | 中国科学院深圳先进技术研究院 | The recovery method of the positive electrode of waste and old cobalt acid lithium battery |
CN110079671A (en) * | 2019-04-23 | 2019-08-02 | 北京科技大学 | A kind of method of waste and old lithium ion battery valuable element synthetical recovery |
CN110661052A (en) * | 2018-07-01 | 2020-01-07 | 临沂春光磁业有限公司 | Production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder |
CN111646446A (en) * | 2020-06-10 | 2020-09-11 | 江苏科盈选煤技术有限公司 | Lithium battery positive electrode material recovery system and recovery method thereof |
CN113517484A (en) * | 2021-03-08 | 2021-10-19 | 清华大学 | Method for treating waste lithium cobalt oxide battery and product thereof |
CN114702084A (en) * | 2022-06-06 | 2022-07-05 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for recovering cobalt in waste lithium cobaltate positive electrode material |
CN115232755A (en) * | 2022-05-23 | 2022-10-25 | 天津科技大学 | Waste lithium ion battery metal recovery strain capable of producing oxalic acid, method and application |
CN115893453A (en) * | 2023-01-31 | 2023-04-04 | 湖南五创循环科技股份有限公司 | Recovery method and recovery system for preparing high-purity lithium hydroxide by recovering lithium from lithium-containing fluoride slag |
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CN101318712A (en) * | 2008-07-08 | 2008-12-10 | 清华大学 | Method for recycling cobalt from waste and old lithium ion battery |
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JPH11185834A (en) * | 1997-12-25 | 1999-07-09 | Matsushita Electric Ind Co Ltd | Positive electrode active material recovering method of lithium ion secondary battery |
CN1973399A (en) * | 2004-06-21 | 2007-05-30 | 丰田自动车株式会社 | Method of disposing of lithium battery |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105907989A (en) * | 2016-07-08 | 2016-08-31 | 长沙理工大学 | Method for recycling cobalt and lithium from waste lithium ion battery material |
CN105907989B (en) * | 2016-07-08 | 2017-11-10 | 长沙理工大学 | A kind of method of Call Provision and lithium in material from used Li ion cell |
CN108258351A (en) * | 2016-12-29 | 2018-07-06 | 中国科学院深圳先进技术研究院 | The recovery method of the positive electrode of waste and old cobalt acid lithium battery |
CN107083484A (en) * | 2017-04-20 | 2017-08-22 | 常州市鼎日环保科技有限公司 | A kind of method that metal is reclaimed from waste lithium cell |
CN107513618A (en) * | 2017-08-01 | 2017-12-26 | 苏州协鑫纳米科技有限公司 | The lead recovery method and device of perovskite battery |
CN110661052A (en) * | 2018-07-01 | 2020-01-07 | 临沂春光磁业有限公司 | Production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder |
CN110079671A (en) * | 2019-04-23 | 2019-08-02 | 北京科技大学 | A kind of method of waste and old lithium ion battery valuable element synthetical recovery |
CN111646446A (en) * | 2020-06-10 | 2020-09-11 | 江苏科盈选煤技术有限公司 | Lithium battery positive electrode material recovery system and recovery method thereof |
CN113517484A (en) * | 2021-03-08 | 2021-10-19 | 清华大学 | Method for treating waste lithium cobalt oxide battery and product thereof |
CN113517484B (en) * | 2021-03-08 | 2022-08-05 | 清华大学 | Method for treating waste lithium cobalt oxide battery and product thereof |
CN115232755A (en) * | 2022-05-23 | 2022-10-25 | 天津科技大学 | Waste lithium ion battery metal recovery strain capable of producing oxalic acid, method and application |
CN114702084A (en) * | 2022-06-06 | 2022-07-05 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for recovering cobalt in waste lithium cobaltate positive electrode material |
CN115893453A (en) * | 2023-01-31 | 2023-04-04 | 湖南五创循环科技股份有限公司 | Recovery method and recovery system for preparing high-purity lithium hydroxide by recovering lithium from lithium-containing fluoride slag |
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