CN108808155A - A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate - Google Patents
A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate Download PDFInfo
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- CN108808155A CN108808155A CN201810941024.5A CN201810941024A CN108808155A CN 108808155 A CN108808155 A CN 108808155A CN 201810941024 A CN201810941024 A CN 201810941024A CN 108808155 A CN108808155 A CN 108808155A
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- lithium
- anode material
- ion cell
- cell anode
- lithium carbonate
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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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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate, include the following steps：Step 1: waste lithium ion cell anode material powder is heated to 800 ~ 1100 DEG C in a hydrogen atmosphere and reacts 0.5 ~ 1h；Go out Step 2: water logging is added for 1-6 according to solid-to-liquid ratio in step 1 products therefrom, lithium hydroxide solution and the filter residue containing nickel, cobalt, manganese is then obtained by filtration；Step 3: being passed through carbon dioxide to lithium hydroxide solution, precipitation is begun with to generate, continue to be passed through carbon dioxide, stop being passed through carbon dioxide after precipitation is completely dissolved, solution is filtered again, gained filtrate is heated to 90 ~ 100 DEG C under agitation so that the lithium bicarbonate in filtrate decomposes completely precipitates into lithium carbonate；Step 4: up to battery-level lithium carbonate after filtrate is dried.Through the invention battery-level lithium carbonate can directly be prepared, the leaching rate of elemental lithium is very high, can reach 94% or more, can not only obtain good economic benefit, but also protect environment.
Description
Technical field
The present invention relates to old and useless battery recovery technology fields, are related specifically to one kind by waste lithium ion cell anode material
The method for preparing battery-level lithium carbonate.
Background technology
Lithium ion battery is because of remarkable advantages such as high with voltage, specific capacity is big, long lifespan and memory-less effects, from its business
Just the power source market of walkie electronic apparatus equipment has quickly been captured since change, and yield increases year by year.Lithium ion battery is
Electronics consumables, service life about 3 years, the lithium ion battery after scrapping will generate destruction, therefore, as can to waste and old to environment
Lithium ion battery carries out scientific and effective recycling disposal, can not only obtain good economic benefit, but also protect environment.
Invention content
The technical problem to be solved in the present invention is one kind by waste lithium ion cell anode material preparation LITHIUM BATTERY carbonic acid
The rate of recovery of the method for lithium, this method is higher, and battery-level lithium carbonate can directly be prepared.
To solve the above-mentioned problems, using following technical scheme：One kind is by waste lithium ion cell anode material preparation electricity
The method of pond level lithium carbonate, includes the following steps：
Step 1: positive electrode powder is heated to 800 ~ 1100 DEG C of 0.5 ~ 1h of reaction in a hydrogen atmosphere；
Go out Step 2: water logging is added for 1-6 according to solid-to-liquid ratio in step 1 products therefrom, lithium hydroxide solution is then obtained by filtration
With the filter residue containing nickel, cobalt, manganese；
Step 3: being passed through carbon dioxide to lithium hydroxide solution obtained by step 2, begins with precipitation and generate, continue to be passed through titanium dioxide
Carbon stops being passed through carbon dioxide after precipitation is completely dissolved, solution is filtered again, gained filtrate is heated under agitation
To 90 ~ 100 DEG C so that the lithium bicarbonate in filtrate decomposes completely precipitates into lithium carbonate；
Step 4: up to battery-level lithium carbonate after filtrate is dried.
Wherein, the waste lithium ion cell anode material is cobalt acid lithium, LiMn2O4 or LiFePO4.
Preferably, the solid-to-liquid ratio in step 2 is 3.
Preferably, the heating temperature of filtrate under agitation is 95 DEG C in step 3.
Wherein, drying temperature is 120 DEG C in step 4, drying time 5h.
Compared to the prior art, the invention has the advantages that：The carbonic acid that method through the invention is prepared
The purity of lithium can reach 99.8% or more, meet the purity requirement of battery-level lithium carbonate, and the leaching rate of elemental lithium is very high, reachable
To 94% or more, it can not only obtain good economic benefit, but also effective protection environment.
Specific implementation mode
Embodiment is given below so that the present invention to be specifically described, it is necessary to which indicated herein is following embodiment
It is used to further illustrate the present invention, should not be understood as limiting the scope of the invention, the ordinary skill in the field
Personnel still fall within protection scope of the present invention to the nonessential improvement of some made of the invention or adjustment according to this embodiment.
The positive electrode of used waste and old lithium ion battery is cobalt acid lithium, those skilled in the art in following embodiment
Member is in carrying out the present invention it should be understood that in addition to cobalt acid lithium, and the one kind provided in the present invention is by waste lithium ion cell anode
The method of material preparation battery-level lithium carbonate can be equally used for the positive material of the lithium ion batteries such as processing LiMn2O4, LiFePO4
Material, and obtain identical advantageous effect.
Embodiment 1
A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate, include the following steps：
Step 1: 1kg waste lithium ion cell anodes material powder is heated to 950 DEG C in a hydrogen atmosphere and reacts 1h, it will
Product after reaction is as in container；
Step 2: being filtered after step 1 products therefrom is sufficiently stirred 1h according to solid-to-liquid ratio for 3 addition deionized waters, hydrogen-oxygen is obtained
Change lithium solution and the filter residue containing nickel, cobalt, manganese；
Step 3: being passed through carbon dioxide to lithium hydroxide solution obtained by step 2, begins with precipitation and generate, continue to be passed through titanium dioxide
Carbon stops being passed through carbon dioxide after precipitation is completely dissolved, solution is filtered again, gained filtrate is heated under agitation
To 95 DEG C so that the lithium bicarbonate in filtrate decomposes completely precipitates into lithium carbonate；
Step 4: filtrate to be dried at 120 DEG C to 5h up to product lithium carbonate 292g, GB ∕ T11064.16- according to national standards
It is 99.93% that 2013 tests, which obtain product purity, meets the purity requirement of battery-level lithium carbonate.
It is prepared into according to the content of lithium in lithium metal battery in flame atomic absorption method respectively testing procedure one and finally
To battery-level lithium carbonate in lithium content, calculate known to lithium leaching rate be 94.8%.
Embodiment 2
A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate, include the following steps：
Step 1: 1kg waste lithium ion cell anodes material powder is heated to 800 DEG C in a hydrogen atmosphere and reacts 1h, it will
Product after reaction is as in container；
Step 2: being filtered after step 1 products therefrom is sufficiently stirred 1h according to solid-to-liquid ratio for 1 addition deionized water, hydrogen-oxygen is obtained
Change lithium solution and the filter residue containing nickel, cobalt, manganese；
Step 3: being passed through carbon dioxide to lithium hydroxide solution obtained by step 2, begins with precipitation and generate, continue to be passed through titanium dioxide
Carbon stops being passed through carbon dioxide after precipitation is completely dissolved, solution is filtered again, gained filtrate is heated under agitation
To 90 DEG C so that the lithium bicarbonate in filtrate decomposes completely precipitates into lithium carbonate；
Step 4: filtrate to be dried at 120 DEG C to 5h up to product lithium carbonate 288g, GB ∕ T11064.16- according to national standards
It is 99.82% that 2013 tests, which obtain product purity, meets the purity requirement of battery-level lithium carbonate.
It is prepared into according to the content of lithium in lithium metal battery in flame atomic absorption method respectively testing procedure one and finally
To battery-level lithium carbonate in lithium content, calculate known to lithium leaching rate be 94.4%.
Embodiment 3
A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate, include the following steps：
Step 1: 1kg waste lithium ion cell anodes material powder is heated to 1100 DEG C in a hydrogen atmosphere and reacts 1h, it will
Product after reaction is as in container；
Step 2: being filtered after step 1 products therefrom is sufficiently stirred 1h according to solid-to-liquid ratio for 6 addition deionized waters, hydrogen-oxygen is obtained
Change lithium solution and the filter residue containing nickel, cobalt, manganese；
Step 3: being passed through carbon dioxide to lithium hydroxide solution obtained by step 2, begins with precipitation and generate, continue to be passed through titanium dioxide
Carbon stops being passed through carbon dioxide after precipitation is completely dissolved, solution is filtered again, gained filtrate is heated under agitation
To 100 DEG C so that the lithium bicarbonate in filtrate decomposes completely precipitates into lithium carbonate；
Step 4: filtrate to be dried at 120 DEG C to 5h up to product lithium carbonate 280g, GB ∕ T11064.16- according to national standards
It is 99.80% that 2013 tests, which obtain product purity, meets the purity requirement of battery-level lithium carbonate.
It is prepared into according to the content of lithium in lithium metal battery in flame atomic absorption method respectively testing procedure one and finally
To battery-level lithium carbonate in lithium content, calculate known to lithium leaching rate be 94.4%.
Claims (5)
1. a kind of method by waste lithium ion cell anode material preparation battery-level lithium carbonate, which is characterized in that including following
Step：
Step 1: by waste lithium ion cell anode material powder be heated in a hydrogen atmosphere 800 ~ 1100 DEG C and react 0.5 ~
1h；
Go out Step 2: water logging is added for 1-6 according to solid-to-liquid ratio in step 1 products therefrom, lithium hydroxide solution is then obtained by filtration
With the filter residue containing nickel, cobalt, manganese；
Step 3: being passed through carbon dioxide to lithium hydroxide solution obtained by step 2, begins with precipitation and generate, continue to be passed through titanium dioxide
Carbon stops being passed through carbon dioxide after precipitation is completely dissolved, solution is filtered again, gained filtrate is heated under agitation
To 90 ~ 100 DEG C so that the lithium bicarbonate in filtrate decomposes completely precipitates into lithium carbonate；
Step 4: up to battery-level lithium carbonate after filtrate is dried.
2. the method according to claim 1 by waste lithium ion cell anode material preparation battery-level lithium carbonate, special
Sign is that the waste lithium ion cell anode material is cobalt acid lithium, LiMn2O4 or LiFePO4.
3. the method according to claim 1 by waste lithium ion cell anode material preparation battery-level lithium carbonate, special
Sign is that the solid-to-liquid ratio in step 2 is 3.
4. the method according to claim 1 by waste lithium ion cell anode material preparation battery-level lithium carbonate, special
Sign is that the heating temperature of filtrate under agitation is 95 DEG C in step 3.
5. the method according to claim 1 by waste lithium ion cell anode material preparation battery-level lithium carbonate, special
Sign is that drying temperature is 120 DEG C in step 4, drying time 5h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106362A (en) * | 2019-05-27 | 2019-08-09 | 昆明理工大学 | A method of recycling lithium carbonate, cobalt oxide from waste and old cobalt acid lithium battery positive electrode |
| CN110190351A (en) * | 2019-05-20 | 2019-08-30 | 秦晋娜 | A kind of regeneration method of useless cobalt acid lithium electrode material |
| CN112680598A (en) * | 2020-12-15 | 2021-04-20 | 中南大学 | Method for low-cost clean treatment of waste lithium ion battery anode material |
| CN113314778A (en) * | 2021-05-28 | 2021-08-27 | 中国科学院宁波材料技术与工程研究所 | Recycling method of retired lithium ion battery positive electrode material |
| CN114006067A (en) * | 2021-09-30 | 2022-02-01 | 钢研晟华科技股份有限公司 | Method and system for recycling anode and cathode mixed powder of waste ternary lithium ion battery |
| US20220194806A1 (en) * | 2020-12-22 | 2022-06-23 | Pukyong National University Industry-University Cooperation Foundation | Lithium oxide recovery method from lithium manganese oxide (lmo) |
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| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190351A (en) * | 2019-05-20 | 2019-08-30 | 秦晋娜 | A kind of regeneration method of useless cobalt acid lithium electrode material |
| CN110106362A (en) * | 2019-05-27 | 2019-08-09 | 昆明理工大学 | A method of recycling lithium carbonate, cobalt oxide from waste and old cobalt acid lithium battery positive electrode |
| CN112680598A (en) * | 2020-12-15 | 2021-04-20 | 中南大学 | Method for low-cost clean treatment of waste lithium ion battery anode material |
| US20220194806A1 (en) * | 2020-12-22 | 2022-06-23 | Pukyong National University Industry-University Cooperation Foundation | Lithium oxide recovery method from lithium manganese oxide (lmo) |
| CN113314778A (en) * | 2021-05-28 | 2021-08-27 | 中国科学院宁波材料技术与工程研究所 | Recycling method of retired lithium ion battery positive electrode material |
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Application publication date: 20181113 |