CN108808147A - A kind of method that manganese is recycled in waste and old lithium ion battery - Google Patents
A kind of method that manganese is recycled in waste and old lithium ion battery Download PDFInfo
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- CN108808147A CN108808147A CN201810490074.6A CN201810490074A CN108808147A CN 108808147 A CN108808147 A CN 108808147A CN 201810490074 A CN201810490074 A CN 201810490074A CN 108808147 A CN108808147 A CN 108808147A
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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
- C22B47/00—Obtaining manganese
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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
- 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
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Abstract
The invention discloses a kind of methods that manganese is recycled in waste and old lithium ion battery, and to solve prior art tedious process, abstraction impurity removal causes the reduction of metallic element yield, generates a large amount of organic waste environmental pollution by water, and the problem of unsuitable large-scale production.Belong to old and useless battery recovery technology field, method includes pretreatment, oxidation acid leaching, redox, precipitation filtration washing, precipitates redox, evaporative crystallization.The present invention reduces the introducing of other impurities element using the method for potassium permanganate oxidation demanganization, shorten the technological process of waste lithium cell recycling, only two steps of need just can reach the purpose for recycling promoter manganese and yield is higher, product is manganese dioxide or manganese sulfate crystal, and purity is higher, our company's production system can be directly entered or sold outside, to realize the recycling of promoter manganese, it is simple for process, equipment requirement is low, it is easy to operate, there is environment-friendly advantage, there is good economic benefit and social benefit.
Description
Technical field
The invention belongs to old and useless battery recovery technology fields, and in particular to the side of manganese is recycled in a kind of waste and old lithium ion battery
Method.
Background technology
In recent years, the industries such as mobile communication, laptop, portable dam, electric bicycle, electric vehicle is swift and violent
Development, has driven the rapid development of lithium electricity industry.Extensive use necessarily will produce a large amount of waste and old lithium ion batteries, such as dispose not
When, environment will be polluted, in addition, containing a large amount of valuable metal nickels, cobalt, copper, iron, aluminium, lithium etc. in lithium battery, great recycling valence
Value.Therefore, the Resource recovery for carrying out to waste and old lithium ion battery and its generating waste material, will produce good economic benefit, society
It can benefit and environmental benefit.
Currently, waste lithium cell recovery method mainly use hydrometallurgic recovery, mostly use extraction, electrodeposition process, complexing from
Sub- exchange process etc..As described a kind of recovery method of waste and old lithium ion battery in CN200810198972, this method is mainly
Lithium ion battery is disassembled, is sorted, sieve pretreatment after obtain active positive electrode material, clean etc. by oxidation acid leaching, P204 net
Chemical industry sequence, obtains the mixed solutions such as pure nickel cobalt manganese lithium, which can be re-used to produce nickle cobalt lithium manganate battery material.On
Although the method for stating can recycle Metal Values From Spent Lithium-ion Batteries, process is relatively complicated, especially with extraction
The yield that the method for removal of impurities does not only result in metallic element reduces, and brings and largely contain organic wastewater, is not suitable for large-scale production.
Invention content
The object of the present invention is to provide a kind of methods that manganese is recycled in waste and old lithium ion battery, to solve prior art process
Cumbersome, abstraction impurity removal causes the reduction of metallic element yield, generates a large amount of organic waste environmental pollution by water, and be not suitable for large-scale production
The problem of.
In order to achieve the above object, the technical solution adopted by the present invention is:
A kind of method that manganese is recycled in waste and old lithium ion battery, includes the following steps:
Step 1: by waste and old lithium ion battery monomer through discharging, being crushed, selection by winnowing, the pretreatment process such as stripping, obtain positive and negative anodes object
Material;
Step 2: acid and oxidant progress oxidation acid leaching are added in the positive and negative anodes material that step 1 obtains, mixed solution is obtained;
Step 3: the mixed solution that step 2 is obtained heating water bath at 50-80 DEG C, is added KMnO4Solution, oxidationreduction
0.5-5h is reacted, MnO is obtained2Precipitation, which is filtered, washed;
Step 4: the MnO that step 3 obtains2Reducing agent redox reaction 0.5-5h, reaction end pH3-6 is added in precipitation,
Obtain MnSO4Solution;
Step 5: the MnSO obtained to step 44Solution evaporative crystallization obtains MnSO4Crystal.
Acid described in step 2 is sulfuric acid or hydrochloric acid.
Oxidant described in step 2 is hydrogen peroxide or sodium chlorate.
KMnO described in step 34The addition of solution is 0.9-1.3 times of theoretical amount.Wherein addition is more than theoretical amount
The rate of deposition that manganese can be improved then increases the rate of recovery, but addition can excessively cause nickel, the co-precipitation of cobalt metal, cause nickel, cobalt etc.
Metal loss.
Reducing agent described in step 4 is Na2SO3Or H2O2Solution.
Na in step 42SO3The addition of solution is 0.9-1.3 times of theoretical amount.Addition can be improved two more than theoretical amount
The leaching rate of manganese oxide then increases the rate of recovery, and Na2SO3Consumption acid is conducive to the raising for leaching endpoint pH.
The present invention having the beneficial effect that compared to the prior art:
The present invention reduces the introducing of other impurities element using the method for potassium permanganate oxidation demanganization, shortens waste lithium cell
The technological process of recycling, two steps of need just can reach the purpose of recycling promoter manganese and yield is higher, and product is manganese dioxide
Or manganese sulfate crystal, and purity is higher, can be directly entered our company's production system or sell outside, to realize the recycling of promoter manganese
It recycles, simple for process, equipment requirement is low, easy to operate, has environment-friendly advantage, has good economic benefit and society
It can benefit.
Specific implementation mode
The present invention will be further described With reference to embodiment.
A kind of method that manganese is recycled in waste and old lithium ion battery, includes the following steps:
A kind of method that manganese is recycled in waste and old lithium ion battery, includes the following steps:
Step 1: by waste and old lithium ion battery monomer through discharging, being crushed, selection by winnowing, the pretreatment process such as stripping, obtain positive and negative anodes object
Material;
Step 2: sulfuric acid or hydrochloric acid and hydrogen peroxide or sodium chlorate progress oxidizing acid are added in the positive and negative anodes material that step 1 obtains
Leaching, obtains mixed solution;
Step 3: the mixed solution that step 2 is obtained heating water bath at 50-80 DEG C, is added KMnO4Solution, KMnO4Solution
Addition be 0.9-1.3 times of theoretical amount, oxidation-reduction reaction 0.5-5h obtains MnO2Precipitation by precipitation filtering, is washed
It washs;
Step 4: the MnO that step 3 obtains2Na is added in precipitation2SO3Or H2O2Solution oxide reduction reaction 0.5-5h, Na2SO3It is molten
The addition of liquid is 0.9-1.3 times of theoretical amount, and reaction end pH3-6 obtains MnSO4Solution;
Step 5: the MnSO obtained to step 44Solution evaporative crystallization obtains MnSO4Crystal.
Embodiment 1
By waste and old lithium ion battery monomer through discharging, being crushed, selection by winnowing, the pretreatment process such as stripping, obtain positive and negative anodes material;It will just
Cathode material carries out sulfuric acid+hydrogen peroxide and leaches, and obtains the mixed solution containing valuable metals such as nickel, cobalt, manganese, lithiums;Its leachate
Main component is as shown in table 1.It measures leachate 1L to be placed in beaker, heating water bath, bath temperature is 80 DEG C, weighs 15gKMnO4
(It is 1.2 times of theoretical amount), it is dissolved in hot pure water, by KMnO4Solution instills in leachate, stirring while adding, terminates after 2h anti-
It answers, obtained precipitation is filtered, washed.What is obtained is precipitated as 23.22g, and 200mL pure water pulps are added, and the 26mL concentrated sulfuric acids are added
With Na2SO3Solution(Solute is 30g, is 1.2 times of theoretical amount), start to react, reaction time 1h, terminal pH is 3.22, institute
Obtain MnSO4Main component in solution is as shown in table 2.By MnSO4Evaporation, crystallization obtain MnSO4Crystal.The rate of recovery of manganese in overall process
It is 98%.
1 waste and old lithium ion battery leachate main component of table
2 MnSO of table4Main component in solution
Embodiment 2
By waste and old lithium ion battery monomer through discharging, being crushed, selection by winnowing, the pretreatment process such as stripping, obtain positive and negative anodes material;It will just
Cathode material carries out hydrochloric acid+sodium chlorate and leaches, and obtains the mixed solution containing valuable metals such as nickel, cobalt, manganese, lithiums;Its leachate
Main component is as shown in table 1.It measures leachate 480mL to be placed in beaker, heating water bath, bath temperature is 50 DEG C, is weighed
5.4gKMnO4(Dosage is 0.9 times of theoretical amount), it is dissolved in hot pure water, by KMnO4Solution instills in leachate, stirring while adding,
Reaction was completed after 1h, and obtained precipitation is filtered, washed.What is obtained is precipitated as 45.99g(Wet slag), 200mL pure water slurry is added
Change, the 10mL concentrated sulfuric acids and H is added2O2Solution(Solute is 30g), start to react, reaction was completed after 2h, and terminal pH is 5, gained
MnSO4Main component in solution is as shown in table 2.By MnSO4Evaporation, crystallization obtain MnSO4Crystal.The yield of overall process manganese is 90.5%
Embodiment 3
By waste and old lithium ion battery monomer through discharging, being crushed, selection by winnowing, the pretreatment process such as stripping, obtain positive and negative anodes material;It will just
Cathode material carries out sulfuric acid+hydrogen peroxide and leaches, and obtains the mixed solution containing valuable metals such as nickel, cobalt, manganese, lithiums;Its leachate
Main component is as shown in table 1.It measures leachate 1L to be placed in beaker, heating water bath, bath temperature is 70 DEG C, weighs 18gKMnO4
(It is 1.3 times of theoretical amount), it is dissolved in hot pure water, by KMnO4Solution instills in leachate, stirring while adding, terminates after 0.5h
Reaction, obtained precipitation is filtered, washed.What is obtained is precipitated as 23.22g, and 200mL pure water pulps are added, and the dense sulphur of 26mL is added
Acid and Na2SO3Solution(Solute is 30g, is 1.2 times of theoretical amount), start to react, reaction time 0.5h, terminal pH is 3, institute
Obtain MnSO4Main component in solution is as shown in table 2.By MnSO4Evaporation, crystallization obtain MnSO4Crystal.The rate of recovery of manganese in overall process
It is 96%.
Embodiment 4
By waste and old lithium ion battery monomer through discharging, being crushed, selection by winnowing, the pretreatment process such as stripping, obtain positive and negative anodes material;It will just
Cathode material carries out hydrochloric acid+sodium chlorate and leaches, and obtains the mixed solution containing valuable metals such as nickel, cobalt, manganese, lithiums;Its leachate
Main component is as shown in table 1.It measures leachate 480mL to be placed in beaker, heating water bath, bath temperature is 60 DEG C, is weighed
5.4gKMnO4(Dosage is 0.9 times of theoretical amount), it is dissolved in hot pure water, by KMnO4Solution instills in leachate, stirring while adding,
Reaction was completed after 5h, and obtained precipitation is filtered, washed.What is obtained is precipitated as 45.99g(Wet slag), 200mL pure water slurry is added
Change, the 10mL concentrated sulfuric acids and H is added2O2Solution(Solute is 30g), start to react, reaction was completed after 5h, and terminal pH is 6, gained
MnSO4Main component in solution is as shown in table 2.By MnSO4Evaporation, crystallization obtain MnSO4Crystal.The yield of overall process manganese is 93%.
Claims (6)
1. a kind of method for recycling manganese in waste and old lithium ion battery, it is characterised in that include the following steps:
Step 1: by waste and old lithium ion battery monomer through discharging, being crushed, selection by winnowing, the pretreatment process such as stripping, obtain positive and negative anodes object
Material;
Step 2: acid and oxidant progress oxidation acid leaching are added in the positive and negative anodes material that step 1 obtains, mixed solution is obtained;
Step 3: the mixed solution that step 2 is obtained heating water bath at 50-80 DEG C, is added KMnO4Solution, oxidationreduction are anti-
0.5-5h is answered, MnO is obtained2Precipitation, which is filtered, washed;
Step 4: the MnO that step 3 obtains2Reducing agent redox reaction 0.5-5h is added in precipitation, and reaction end pH3-6 is obtained
To MnSO4Solution;
Step 5: the MnSO obtained to step 44Solution evaporative crystallization obtains MnSO4Crystal.
2. the method for recycling manganese in waste and old lithium ion battery as described in claim 1, it is characterised in that:Described in step 2
Acid is sulfuric acid or hydrochloric acid.
3. the method for recycling manganese in waste and old lithium ion battery as described in claim 1, it is characterised in that:Described in step 2
Oxidant is hydrogen peroxide or sodium chlorate.
4. the method for recycling manganese in waste and old lithium ion battery as described in claim 1, it is characterised in that:Described in step 3
KMnO4The addition of solution is 0.9-1.3 times of theoretical amount.
5. the method for recycling manganese in waste and old lithium ion battery as described in claim 1, it is characterised in that:Described in step 4
Reducing agent is Na2SO3Or H2O2Solution.
6. the method for recycling manganese in waste and old lithium ion battery as claimed in claim 5, it is characterised in that:The Na2SO3Solution
Addition be 0.9-1.3 times of theoretical amount.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109179359A (en) * | 2018-11-27 | 2019-01-11 | 成都绿锂环保科技有限公司 | A method of extracting lithium and ferric phosphate from LiFePO4 waste material |
CN112481493A (en) * | 2019-09-11 | 2021-03-12 | 荆门市格林美新材料有限公司 | Method for recovering valuable metals from ternary positive electrode materials of waste power batteries |
CN112746174A (en) * | 2020-12-30 | 2021-05-04 | 西安建筑科技大学 | Method for recovering nickel and cobalt in waste ternary lithium ion battery |
CN113584309A (en) * | 2021-07-05 | 2021-11-02 | 广东佳纳能源科技有限公司 | Method for separating manganese in ternary lithium ion battery anode leachate |
CN115028237A (en) * | 2021-03-05 | 2022-09-09 | 中国石油化工股份有限公司 | Electrode material for electrochemical desalination and preparation method thereof |
CN115612844A (en) * | 2022-09-27 | 2023-01-17 | 暨南大学 | Method for separating cobalt, manganese and nickel and lithium in waste ternary lithium battery |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109179359A (en) * | 2018-11-27 | 2019-01-11 | 成都绿锂环保科技有限公司 | A method of extracting lithium and ferric phosphate from LiFePO4 waste material |
CN112481493A (en) * | 2019-09-11 | 2021-03-12 | 荆门市格林美新材料有限公司 | Method for recovering valuable metals from ternary positive electrode materials of waste power batteries |
CN112746174A (en) * | 2020-12-30 | 2021-05-04 | 西安建筑科技大学 | Method for recovering nickel and cobalt in waste ternary lithium ion battery |
CN115028237A (en) * | 2021-03-05 | 2022-09-09 | 中国石油化工股份有限公司 | Electrode material for electrochemical desalination and preparation method thereof |
CN115028237B (en) * | 2021-03-05 | 2024-06-07 | 中国石油化工股份有限公司 | Electrode material for electrochemical desalination and preparation method thereof |
CN113584309A (en) * | 2021-07-05 | 2021-11-02 | 广东佳纳能源科技有限公司 | Method for separating manganese in ternary lithium ion battery anode leachate |
CN115612844A (en) * | 2022-09-27 | 2023-01-17 | 暨南大学 | Method for separating cobalt, manganese and nickel and lithium in waste ternary lithium battery |
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