CN104577248A - Lithium battery positive electrode material recovery method - Google Patents
Lithium battery positive electrode material recovery method Download PDFInfo
- Publication number
- CN104577248A CN104577248A CN201510009225.8A CN201510009225A CN104577248A CN 104577248 A CN104577248 A CN 104577248A CN 201510009225 A CN201510009225 A CN 201510009225A CN 104577248 A CN104577248 A CN 104577248A
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- CN
- China
- Prior art keywords
- lithium
- lithium battery
- solution
- cobalt oxide
- recovery method
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
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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
- C22B7/008—Wet processes by an alkaline or ammoniacal 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- 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
Abstract
The invention discloses a lithium battery positive electrode material recovery method. The method comprises the following steps: soaking in an alkaline solution, namely soaking a positive electrode plate of a waste lithium battery positive electrode material in a container filled with the alkaline solution; hydrolyzing, namely placing mixed liquid of an aluminum hydroxide solution obtained in former step and lithium cobalt oxide powder in pure water, hydrolyzing and then performing water screening and washing; carrying out hydrogen treatment, namely placing the lithium cobalt oxide powder treated through step a and b in an atmosphere furnace, then inflating the hydrogen in the furnace, heating at high temperature; hydrolyzing to remove lithium, namely placing the hydrogenated lithium cobalt oxide in the pure water to hydrolyze; carrying out solid-liquid separation, namely performing solid-liquid separation on the hydrogenated lithium cobalt oxide, and washing the separated solid for three times, drying, grinding to obtain cobalt oxide. The cobalt oxide as the positive electrode material is recovered by using the method of soaking in the alkaline solution, hydrolyzing, hydrogen treating, hydrolysis for lithium removal and solid-liquid separation; the recovery cost is low, the recovered cobalt oxide has few impurities, and is high in purity and good in effect.
Description
Technical field
The present invention relates to lithium cell technology field, specifically a kind of recovery method of anode material of lithium battery.
Background technology
Lithium ion battery is since commercialization, and because its energy density is high, operating voltage is high, memory-less effect, has extended cycle life and is widely used as the power supply of various mobile equipment.
The structure of lithium ion battery is made up of the major portion such as positive pole and negative pole, and positive pole is generally positive active material, acetylene black, binding agent Homogeneous phase mixing are coated in aluminum foil current collector.In lithium-ion battery system, the cost of positive electrode material accounts for 30 ~ 40% of battery total cost, if therefore need to be recycled by anode material of lithium battery, with cost-saving and protection of the environment.
At present, study the recovery of more mainly waste PAN yarn, the technical process that its recovery method is more traditional, dissolve by cobalt acid lithium, purification, then extracts cobalt salt or cobalt metal by extraction process, chemical precipitation method, electrolytic process etc. from solution.But the cost recovery of present this recovery method salvage material is high, and purity is not high enough, and recovering effect is poor, therefore have a kind of cost to be developed lower, recovering effect is good, the recovery method of the anode material of lithium battery that cobalt purity is high.
Summary of the invention
The object of the invention is the defect overcoming above-mentioned prior art, provide a kind of cost recovery low, effective, reclaim the recovery method of the high anode material of lithium battery of purity.
Technical scheme of the present invention is achieved in that a kind of anode material of lithium battery recovery method, comprises the following steps:
A. aqueous slkali soaking: be placed in the container filling basic solution by discarded anode material of lithium battery positive plate and soak, obtains aluminium hydroxide and cobalt acid lithium powder;
B. be hydrolyzed: being then placed in pure water by the mixing liquid of aluminum hydroxide solution obtained in the previous step and cobalt acid lithium powder is hydrolyzed carries out after water sieve washes, obtaining cobalt acid lithium powder;
C. hydrogen treatment: the cobalt obtained after step a and b process acid lithium powder is put into atmosphere furnace, is then filled with hydrogen through heat in stove, obtains the acid of the cobalt after hydrogenation lithium;
D. hydrolysis is except lithium: the cobalt acid lithium after hydrogenation is put into pure water and is hydrolyzed, obtain the solution after being hydrolyzed;
E. solid-liquid separation: the cobalt acid lithium after hydrogenation is carried out solid-liquid separation by tripping device by tripping device, and by the solids wash three times after being separated, then drying, pulverizes that finally obtain can as the cobalt oxide of anode material of lithium battery.
Further, the basic solution in described steps A is sodium hydroxide solution.
Particularly, in described step C, high-temperature temperature is 580 degree of-780 degree.
Further, liquid after solid-liquid separation in described step e is reclaimed and the liquid after recovery is put in the hydrating solution after being hydrolyzed in step D and mix, when the concentration of lithium reaches 30g/L in the solution after the hydrolysis of D step, carry out lithium recycling again.
Further, described lithium recycling step comprises: the lithium solution obtained after described step D hydrolysis adds soda ash, obtains Quilonum Retard, is returned by remaining solution in the solution after joining step D hydrolysis again, repeatedly reclaim after being reclaimed by Quilonum Retard.
Particularly, the tripping device in described step e is whizzer, pumping and filtering device or belt separating device.
Compared with prior art, the method that the present invention adopts aqueous slkali soaking-hydrolysis-hydrogen treatment-hydrolysis to remove lithium-solid-liquid separation is incorporated as the cobalt oxide into positive electrode material back and forth, and cost recovery is low, and the cobalt oxide impurity of recovery is few, and purity is high, has certain marketable value.
Embodiment
Below specific embodiment of the invention case is illustrated:
A kind of anode material of lithium battery recovery method, comprises the following steps:
A. aqueous slkali soaking: be placed in the container filling basic solution by discarded anode material of lithium battery positive plate and soak, adopts in the present embodiment and obtains aluminium hydroxide and cobalt acid lithium powder;
B. be hydrolyzed: being then placed in pure water by the mixing liquid of aluminum hydroxide solution obtained in the previous step and cobalt acid lithium powder is hydrolyzed carries out after water sieve washes, and obtain cobalt acid lithium powder, wherein water sieve is washed and adopted water screening and washing plant conventional on market;
C. hydrogen treatment: the cobalt obtained after step a and b process acid lithium powder is put into atmosphere furnace, is then filled with hydrogen through heat in stove, obtains the acid of the cobalt after hydrogenation lithium, and the temperature of high temperature is 580 degree of-780 degree here;
D. hydrolysis is except lithium: the cobalt acid lithium after hydrogenation is put into pure water and is hydrolyzed, obtain the solid-liquid mixing solutions after being hydrolyzed;
E. solid-liquid separation: after hydrogenation being hydrolyzed by tripping device cobalt acid lithium solid-liquid solution carry out solid-liquid separation by equipment for separating liquid from solid, obtain solid and liquid after separation, described tripping device adopts whizzer, pumping and filtering device or belt separating device.Wherein, by the solids wash three times after being separated, then dry, pulverize, finally obtaining can as the cobalt oxide of anode material of lithium battery, and whole removal process completes.Particularly, liquid in described step e after solid-liquid separation reclaims and is put in the hydrating solution after being hydrolyzed in step D by the liquid after reclaiming and mixes, and concentrates again and carry out lithium recycling when the concentration of lithium reaches 30g/L in the solution after the hydrolysis of D step.And described lithium recycling step comprises: the lithium solution obtained after described step D hydrolysis adds soda ash, obtain Quilonum Retard, after Quilonum Retard is reclaimed, remaining solution is returned again in the solution after joining step D hydrolysis, repeatedly reclaim Quilonum Retard, and Quilonum Retard is also one of starting material manufacturing anode material of lithium battery.
The method that the present invention adopts aqueous slkali soaking-hydrolysis-hydrogen treatment-hydrolysis to remove lithium-solid-liquid separation is incorporated as the cobalt oxide into positive electrode material back and forth, and its technical process is simple, and cost recovery is low, and the cobalt oxide impurity of recovery is few, and purity is high, has certain marketable value.
As described above, be only preferred embodiment of the present invention, when not limiting scope of the invention process with this, the simple equivalence namely generally done according to the present patent application the scope of the claims and invention description content changes and modifies, and all still remains within the scope of the patent.
Claims (6)
1. an anode material of lithium battery recovery method, comprises the following steps:
A. aqueous slkali soaking: be placed in the container filling basic solution by discarded anode material of lithium battery positive plate and soak, obtains aluminium hydroxide and cobalt acid lithium powder;
B. be hydrolyzed: being then placed in pure water by the mixing liquid of aluminum hydroxide solution obtained in the previous step and cobalt acid lithium powder is hydrolyzed carries out after water sieve washes, obtaining cobalt acid lithium powder;
C. hydrogen treatment: the cobalt obtained after step a and b process acid lithium powder is put into atmosphere furnace, is then filled with hydrogen through heat in stove, obtains the acid of the cobalt after hydrogenation lithium;
D. hydrolysis is except lithium: the cobalt acid lithium after hydrogenation is put into pure water and is hydrolyzed, obtain the solution after being hydrolyzed;
E. solid-liquid separation: the cobalt acid lithium after hydrogenation is carried out solid-liquid separation by tripping device, and by the solids wash three times after being separated, then drying, pulverizes that finally obtain can as the cobalt oxide of anode material of lithium battery.
2. a kind of lithium battery material recovery method as claimed in claim 1, is characterized in that, the basic solution in described steps A is sodium hydroxide solution.
3. a kind of lithium battery material recovery method as claimed in claim 1, is characterized in that, in described step C, high-temperature temperature is 580 degree of-780 degree.
4. a kind of lithium battery material recovery method as claimed in claim 1, it is characterized in that, liquid after solid-liquid separation in described step e is reclaimed and the liquid after recovery is put in the hydrating solution after being hydrolyzed in step D and mix, when the concentration of lithium reaches 30g/L in the solution after the hydrolysis of D step, carry out lithium recycling again.
5. a kind of lithium battery material recovery method as claimed in claim 4, it is characterized in that, described lithium recycling step comprises: the lithium solution obtained after described step D hydrolysis adds soda ash, obtain Quilonum Retard, after Quilonum Retard is reclaimed, remaining solution is returned in the solution after joining step D hydrolysis again, repeatedly reclaim.
6. a kind of lithium battery material recovery method as claimed in claim 1, is characterized in that, the tripping device in described step e is whizzer, pumping and filtering device or belt separating device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510009225.8A CN104577248A (en) | 2015-01-09 | 2015-01-09 | Lithium battery positive electrode material recovery method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510009225.8A CN104577248A (en) | 2015-01-09 | 2015-01-09 | Lithium battery positive electrode material recovery method |
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| CN201510009225.8A Pending CN104577248A (en) | 2015-01-09 | 2015-01-09 | Lithium battery positive electrode material recovery method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746180A (en) * | 2017-10-11 | 2018-03-02 | 山西省玻璃陶瓷科学研究所（有限公司） | A kind of ceramic black colorant prepared using old and useless battery lithium cobaltate cathode material |
| CN108384955A (en) * | 2018-03-20 | 2018-08-10 | 中国科学院过程工程研究所 | A method of from selectively carrying lithium in waste material containing lithium battery |
| CN110304663A (en) * | 2019-07-26 | 2019-10-08 | 长沙佳纳锂业科技有限公司 | The method and ceramic grade cobalt oxide of cobalt acid lithium battery positive electrode preparation ceramic grade cobalt oxide and its application |
-
2015
- 2015-01-09 CN CN201510009225.8A patent/CN104577248A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746180A (en) * | 2017-10-11 | 2018-03-02 | 山西省玻璃陶瓷科学研究所（有限公司） | A kind of ceramic black colorant prepared using old and useless battery lithium cobaltate cathode material |
| CN108384955A (en) * | 2018-03-20 | 2018-08-10 | 中国科学院过程工程研究所 | A method of from selectively carrying lithium in waste material containing lithium battery |
| CN110304663A (en) * | 2019-07-26 | 2019-10-08 | 长沙佳纳锂业科技有限公司 | The method and ceramic grade cobalt oxide of cobalt acid lithium battery positive electrode preparation ceramic grade cobalt oxide and its application |
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Application publication date: 20150429 |