CN108110359A - The circulation utilization method of positive electrode - Google Patents
The circulation utilization method of positive electrode Download PDFInfo
- Publication number
- CN108110359A CN108110359A CN201711355282.7A CN201711355282A CN108110359A CN 108110359 A CN108110359 A CN 108110359A CN 201711355282 A CN201711355282 A CN 201711355282A CN 108110359 A CN108110359 A CN 108110359A
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- China
- Prior art keywords
- positive electrode
- lithium
- positive
- lye
- circulation utilization
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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
-
- 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 present invention relates to a kind of valuable metal circulation utilization methods, and in particular to a kind of circulation utilization method of positive electrode.The chemical composition for discarding lithium-ion-power cell is analyzed, according to chemical composition handles discarded lithium-ion-power cell classification；Waste and old lithium ion battery is disassembled; positive/negative plate separates; positive plate is placed in lye after separation and is impregnated; positive electrode is made to be peeled off from positive plate; aluminium foil is made to be dissolved in lye, positive electrode is obtained by filtration, is washed with deionized; positive electrode after washing roasts under protective atmosphere, organics removal.The present invention studies positive electrode utilization process in waste and old lithium ion battery by the methods of fractionation, positive and negative anodes separation, dipping by lye, roasting, and positive electrode active materials need not separate, and so as to fulfill comprehensive utilization of resources, short route, low consumption, cleaning, pollution is less.
Description
Technical field
The present invention relates to a kind of valuable metal circulation utilization methods, and in particular to a kind of side of recycling of positive electrode
Method.
Background technology
Since 21 century, as energy crisis and environmental pollution are increasingly sharpened, increasingly surging, the new energy of energy-saving and emission-reduction appealing
Source automobile is fast-developing, and electric vehicle may be scrapped using 3 to five years, and by 2018, accumulative learies will be more than 170,000
Ton, after Vehicular dynamic battery is retired, if without necessary recycling and processing, not only results in the wasting of resources, also can be to ring
Border pollutes.Thus contradiction will be protruded increasingly between the new energy vehicle industry development brought and environment, resource.
In power battery, lithium-ion-power cell just slowly change LiFePO4 dominance situation, 2017 with
Come, ferric phosphate lithium cell is quickly caught up with and surpassed in the installation of ternary battery.Therefore the recovery technology of ternary battery is particularly important.
Patent " recovery method 201510967179.2 of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium ion battery) "
Disclose a kind of recovery method of the positive electrode of waste and old nickel-cobalt-manganese ternary lithium ion battery., positive electrode adds alkali by this method
Dissolving, separation obtain lysate I and insoluble matter；By insoluble matter acidolysis, lysate II is obtained, adjusts pH value to alkalescence, it is heavy to be formed
It forms sediment, obtains filtrate I and sediment I；By sediment I acidolysis, lysate III is obtained, ammonium hydroxide is added in thereto and is complexed, adjusted
After pH value to alkalescence, soluble carbonate salt is added, is filtered, obtains filtrate II and sediment II；It is added in into filtrate II solvable
Acid carbonate, heating, obtains sediment III；Again after acidolysis, pH value is adjusted to 3.0~3.5, hypochlorite is added and adjusts pH
For value to 2.0~3.0, filtering obtains filtrate II I and sediment IV.The patent uses Wet-process metallurgy method, recycles ternary electricity step by step
Metal in pond.
Patent " a kind of waste lithium ion cell anode material full constituent resource recycle method (201210230857.3) "
Disclose a kind of waste lithium ion cell anode material full constituent resource recycle method.It mainly includes the following steps that：1) use
Active material and aluminium foil in fluorine-containing aqueous solutions of organic acids separating waste, worn anode material for lithium-ion batteries, Gu it is liquid-solid-isolated
Leachate, active material containing lithium and aluminium foil；2) active material containing lithium carries out high-temperature roasting, lye removal of impurities processing respectively；3) leach
Liquid carries out acid adding and is distilled to recover fluorine-containing organic acid, alkaline chemical precipitation foreign ion, ammonium carbonate co-precipitation preparation nickel cobalt manganese carbonic acid respectively
Salt ternary precursor；4) will treated active material and the regulation and control of nickel cobalt manganese carbonate ternary precursor component of mixture, supplying
High temperature solid-phase sintering prepares nickle cobalt lithium manganate ternary composite cathode material again after a certain proportion of lithium carbonate.This method be use by
Grade recycling metal, then it is prepared into ternary precursor.
The content of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of circulation utilization method of positive electrode, to whole
The unified recycling of positive electrode is realized in the centralized processing of a positive electrode, and flow is short, and used energy consumption and consumptive material are few, clearly
Clean, pollution is few.
The circulation utilization method of positive electrode of the present invention, comprises the following steps：
(1) chemical composition for discarding lithium-ion-power cell is analyzed, according to chemical composition by discarded lithium ion power
Battery classification is handled；
(2) waste and old lithium ion battery to be disassembled, positive plate after separation is placed in lye and impregnates by positive/negative plate separation,
Positive electrode is made to be peeled off from positive plate, aluminium foil is made to be dissolved in lye, positive electrode is obtained by filtration, is washed with deionized, is washed
Positive electrode after washing roasts under protective atmosphere, organics removal.
Wherein：
The means that step (1) chemical composition is analyzed are fluorescence analysis.
It is by discarded lithium-ion-power cell classification processing according to chemical composition：By the lithium ion power electricity of identical chemical composition
Pond is classified as one kind and handles together, and classification is divided into cobalt acid lithium, LiMn2O4, lithium phosphate or ternary lithium battery.
Lye is NaOH solution, KOH solution or Ca (OH)2Solution, the concentration of lye is 5w%-20w%.
The condition of immersion is：Temperature is 20-100 DEG C, time 10-30min, mixing speed 200-400r/min.
Being impregnated in lye makes positive electrode be separated with aluminum foil current collector.
It is washed with deionized 3-5 times.
Calcination temperature is 250-400 DEG C.
Organics removal is roasted, organic matter is binding agent or remaining membrane.
Compared with prior art, the present invention has the following advantages：
(1) present invention is studied by the methods of fractionation, positive and negative anodes separation, dipping by lye, roasting in waste and old lithium ion battery
Positive electrode utilization process, positive electrode active materials need not separate, so as to fulfill comprehensive utilization of resources.
(2) present invention be it is a kind of realize resources circulation, the technical process of economical and efficient, short route, low consumed cleaning life
Production mode finally recycles discarded li-ion electrode materials realization, achievees the purpose that environmental protection.
(3) recycled one by one using metal mostly compared with the prior art, the present invention is using the concentration to entire positive electrode
The unified recycling of positive electrode is realized in processing, and flow is short, and used energy consumption and consumptive material are few, cleaning, and pollution is few.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of positive electrode circulation utilization method, step are：
1st, the chemical composition for discarding lithium-ion-power cell is analyzed, according to chemical composition by discarded lithium ion power electricity
Pond classification processing；
2nd, lithium ion battery is disassembled, positive plate after separation is placed in lye and impregnates by positive/negative plate separation, the lye
For NaOH solution, concentration is 20% (w%), and time 30min, temperature is 100 DEG C, mixing speed 400r/min；
3rd, positive electrode is washed with deionized 3 times after filtering；
4th, the positive electrode after washing roasts for 400 DEG C under protective atmosphere, organics removal.
Embodiment 2：
A kind of positive electrode circulation utilization method, step are：
1st, the chemical composition for discarding lithium-ion-power cell is analyzed, according to chemical composition by discarded lithium ion power electricity
Pond classification processing；
2nd, lithium ion battery is disassembled, positive plate after separation is placed in lye and impregnates by positive/negative plate separation, the lye
For KOH solution, concentration is 10% (w%), and time 20min, temperature is 60 DEG C, mixing speed 300r/min；
3rd, positive electrode is washed with deionized 5 times after filtering；
4th, the positive electrode after washing roasts for 300 DEG C under protective atmosphere, organics removal.
Embodiment 3：
A kind of positive electrode circulation utilization method, step are：
1st, the chemical composition for discarding lithium-ion-power cell is analyzed, according to chemical composition by discarded lithium ion power electricity
Pond classification processing；
2nd, lithium ion battery is disassembled, positive plate after separation is placed in lye and impregnates by positive/negative plate separation, the lye
For Ca (OH)2Solution, concentration are 15% (w%), and time 30min, temperature is 450 DEG C, mixing speed 200r/min；
3rd, positive electrode is washed with deionized 5 times after filtering；
4th, the positive electrode after washing roasts for 250 DEG C under protective atmosphere, organics removal.
Claims (7)
1. a kind of circulation utilization method of positive electrode, it is characterised in that：Comprise the following steps：
(1) chemical composition for discarding lithium-ion-power cell is analyzed, according to chemical composition by discarded lithium-ion-power cell
Classification is handled；
(2) waste and old lithium ion battery is disassembled, positive plate after separation is placed in lye and impregnates, makes just by positive/negative plate separation
Pole material is peeled off from positive plate, and aluminium foil is made to be dissolved in lye, and positive electrode is obtained by filtration, and is washed with deionized, after washing
Positive electrode roasted under protective atmosphere, organics removal.
2. the circulation utilization method of positive electrode according to claim 1, it is characterised in that：What chemical composition was analyzed
Means are fluorescence analysis.
3. the circulation utilization method of positive electrode according to claim 1, it is characterised in that：According to chemical composition by discarded lithium
Ion battery classification is handled：The lithium-ion-power cell of identical chemical composition is classified as one kind to handle together, classification point
For cobalt acid lithium, LiMn2O4, lithium phosphate or ternary lithium battery.
4. the circulation utilization method of positive electrode according to claim 1, it is characterised in that：Lye is NaOH solution, KOH
Solution or Ca (OH)2Solution, the concentration of lye is 5w%-20w%.
5. the circulation utilization method of positive electrode according to claim 1, it is characterised in that：The condition of immersion is：Temperature
For 20-100 DEG C, time 10-30min, mixing speed 200-400r/min.
6. the circulation utilization method of positive electrode according to claim 1, it is characterised in that：3-5 is washed with deionized
Time.
7. the circulation utilization method of positive electrode according to claim 1, it is characterised in that：Calcination temperature is 250-400
℃。
Priority Applications (1)
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| CN201711355282.7A CN108110359A (en) | 2017-12-16 | 2017-12-16 | The circulation utilization method of positive electrode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108923094A (en) * | 2018-08-03 | 2018-11-30 | 泉州市锂灿新材料科技有限公司 | A kind of regeneration method of LiMn2O4 refuse battery positive plate |
| CN114430081A (en) * | 2018-12-14 | 2022-05-03 | 有研资源环境技术研究院(北京)有限公司 | Method for separating positive active material and current collector of waste lithium 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 |
| JP2005042189A (en) * | 2003-07-25 | 2005-02-17 | Ise Chemicals Corp | Recovery method of cobalt |
| CN101183740A (en) * | 2007-12-24 | 2008-05-21 | 深圳市格林美高新技术股份有限公司 | Method of controlling fragmentation and recovery of waste battery and system thereof |
| CN104810566A (en) * | 2014-07-01 | 2015-07-29 | 万向A一二三系统有限公司 | Environmentally friendly recovery and treatment method of waste and old lithium iron phosphate power cells |
| CN105375078A (en) * | 2015-10-23 | 2016-03-02 | 赣州市芯隆新能源材料有限公司 | Method for circularly preparing spherical lithium nickel cobalt manganese oxide by lithium-ion battery positive plate |
| CN106505273A (en) * | 2017-01-11 | 2017-03-15 | 湘潭大学 | The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled |
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2017
- 2017-12-16 CN CN201711355282.7A patent/CN108110359A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11185834A (en) * | 1997-12-25 | 1999-07-09 | Matsushita Electric Ind Co Ltd | Positive electrode active material recovering method of lithium ion secondary battery |
| JP2005042189A (en) * | 2003-07-25 | 2005-02-17 | Ise Chemicals Corp | Recovery method of cobalt |
| CN101183740A (en) * | 2007-12-24 | 2008-05-21 | 深圳市格林美高新技术股份有限公司 | Method of controlling fragmentation and recovery of waste battery and system thereof |
| CN104810566A (en) * | 2014-07-01 | 2015-07-29 | 万向A一二三系统有限公司 | Environmentally friendly recovery and treatment method of waste and old lithium iron phosphate power cells |
| CN105375078A (en) * | 2015-10-23 | 2016-03-02 | 赣州市芯隆新能源材料有限公司 | Method for circularly preparing spherical lithium nickel cobalt manganese oxide by lithium-ion battery positive plate |
| CN106505273A (en) * | 2017-01-11 | 2017-03-15 | 湘潭大学 | The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108923094A (en) * | 2018-08-03 | 2018-11-30 | 泉州市锂灿新材料科技有限公司 | A kind of regeneration method of LiMn2O4 refuse battery positive plate |
| CN114430081A (en) * | 2018-12-14 | 2022-05-03 | 有研资源环境技术研究院(北京)有限公司 | Method for separating positive active material and current collector of waste lithium battery |
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Application publication date: 20180601 |
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