CN109088119A - A method of recycling lithium in waste and old graphite series lithium ion battery negative electrode tab - Google Patents
A method of recycling lithium in waste and old graphite series lithium ion battery negative electrode tab Download PDFInfo
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- CN109088119A CN109088119A CN201810942393.6A CN201810942393A CN109088119A CN 109088119 A CN109088119 A CN 109088119A CN 201810942393 A CN201810942393 A CN 201810942393A CN 109088119 A CN109088119 A CN 109088119A
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
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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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- Manufacture And Refinement Of Metals (AREA)
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Abstract
A method of recycling lithium in waste and old graphite series lithium ion battery negative electrode tab, comprising the following steps: Step 1: waste and old graphite series lithium ion battery is fully charged；Step 2: battery fully charged obtained by step 1 is disassembled, negative electrode tab, positive plate, diaphragm and battery case are obtained；Step 3: being heat-treated at a temperature of negative electrode tab obtained by step 2 is placed in 150-550 DEG C；Step 4: water is added according to the solid-to-liquid ratio of 1:10-1:3 to the negative electrode tab after step 3 heat treatment, solidliquid mixture is obtained after stirring 0.5-4h；Step 5: being filtered with the reciprocating sieve of 20-80 mesh to solidliquid mixture obtained by step 4, the aqueous solution of metallic copper, graphitiferous powder is obtained；Step 6: then the pH value that sulfuric acid or hydrochloric acid conditioning solution are added into the aqueous solution of the resulting graphitiferous powder of step 5 is filtered to 0.5-2.0 up to the solution of graphite powder, lithium-containing compound.This method can isolate the lithium of 17g or more from the negative electrode tab of the waste and old graphite series lithium ion battery of 1kg, have extremely wide application prospect.
Description
Technical field
The present invention relates to lithium recycling field, it is related specifically to lithium in a kind of waste and old graphite series lithium ion battery negative electrode tab of recycling
Method.
Background technique
Graphite system lithium cell is anti-during charging and discharging using the lithium ion and electronics that are stored in positive electrode
To mobile to realize normal work, positive electrode generally uses lithium alloy metals oxide, such as cobalt acid lithium, mangaic acid
Lithium, lithium manganese phosphate etc., negative electrode material use graphite.It is not timely that graphite series lithium ion battery is easy to happen lithium in use
Deviate from the phenomenon that being deposited in negative electrode tab, utilizes the applying waste lithium ionic electricity of the remaining insufficient half of rear capacity especially for echelon
Pond.In addition, deposition of the lithium in negative electrode tab is also very tight after abusing under high/low temperature, super-charge super-discharge or other special operation conditions
Weight.By dismantling it can be found that there is a large amount of yellow metal lithium simple substance on negative electrode tab surface, and oxygen occurs rapidly in air
Change.If the waste to lithium resource cannot be not only, it is also possible to cause using the lithium deposited in reasonable method recycling negative electrode tab
The pollution of environment.
The Chinese patent of Publication No. CN107394298A discloses lithium resource in a kind of waste and old lithium ion battery negative electrode tab
Recovery method comprising following steps: fine powder is made in the blocky powder on negative electrode tab surface first, and is reacted with dilute hydrochloric acid
It is aided with ultrasonic agitation in the process, to realize the leaching of lithium resource.This method although higher lithium carbonate powder of available purity
End, but leaching rate is not high, it is relatively low so as to cause the rate of recovery of lithium.
In conclusion also finding no in the prior art a kind of it is possible to prevente effectively from the waste and old graphite of recycling that lithium resource wastes
The method of lithium in series lithium ion battery negative electrode tab.
Summary of the invention
The technical problem to be solved in the present invention is that providing lithium in a kind of waste and old graphite series lithium ion battery negative electrode tab of recycling
Method, the waste it is possible to prevente effectively from lithium resource is recycled to waste and old graphite series lithium ion battery using this method.
To solve the above-mentioned problems, using following technical scheme: a kind of waste and old graphite series lithium ion battery negative electrode tab of recycling
The method of middle lithium, comprising the following steps:
Step 1: waste and old graphite series lithium ion battery is fully charged；
Step 2: battery fully charged obtained by step 1 is disassembled, negative electrode tab, positive plate, diaphragm and battery case are obtained；
Step 3: being heat-treated at a temperature of negative electrode tab obtained by step 2 is placed in 150-550 DEG C；
Step 4: water is added according to the solid-to-liquid ratio of 1:10-1:3 to the negative electrode tab after step 3 heat treatment, obtained after stirring 0.5-4h
To solidliquid mixture；
Step 5: being filtered with the reciprocating sieve of 20-80 mesh to solidliquid mixture obtained by step 4, metallic copper, graphitiferous powder are obtained
Aqueous solution；
Step 6: the pH value of sulfuric acid or hydrochloric acid conditioning solution is added into the aqueous solution of the resulting graphitiferous powder of step 5 to 0.5-
2.0, the solution up to graphite powder and lithium-containing compound is then filtered, the lithium compound is lithium sulfate or lithium chloride.
Wherein, solid-to-liquid ratio described in step 4 is 1:3.7.
Wherein, the mass fraction of sulfuric acid described in step 6 or hydrochloric acid is 98%.When sulfuric acid is added, what is ultimately generated contains
Major solute in the solution of lithium compound is lithium sulfate；When hydrochloric acid is added, in the solution of the lithium-containing compound ultimately generated
Major solute be lithium chloride.
Preferably, after step 6 obtains the solution of lithium-containing compound, the pH that sodium hydrate regulator solution is added is 10, then
The filtrate being obtained by filtration sufficiently is reacted with sodium carbonate and is concentrated by evaporation up to lithium carbonate by filtering.
Compared to the prior art, the invention has the following advantages: technique of the invention is relatively simple, first to negative electrode tab
It is heat-treated, water is then added and obtains solidliquid mixture and filters, be eventually adding hydrochloric acid or sulfuric acid and adjust the pH value of solution
To a lower range, the solution (lithium sulfate or lithium chloride) of graphite powder, lithium-containing compound can be obtained after filtering, and contain lithium
The solution of compound can be used for producing all kinds of lithium-containing compounds, such as lithium carbonate.This method can be from the waste and old graphite based lithium-ion of 1kg
The lithium of 17g or more is isolated in the negative electrode tab of battery, the rate of recovery is higher, and the waste of lithium resource is avoided, ecological environment is protected,
With extremely wide application prospect.
Specific embodiment
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 some nonessential improvement of the invention made or adjustment according to this embodiment.
Embodiment 1
A method of recycling lithium in waste and old graphite series lithium ion battery negative electrode tab, comprising the following steps:
Step 1: taking positive electrode is cobalt acid lithium, negative electrode material is the chargeable waste and old lithium ion battery 1kg of graphite, with charging
Device is fully charged by battery；
Step 2: battery fully charged obtained by step 1 is disassembled, negative electrode tab, positive plate, diaphragm and battery case are obtained；
30min is heat-treated Step 3: negative electrode tab is placed at a temperature of 550 DEG C；
Step 4: the 270g negative electrode tab after heat treated is placed in container, 1000mL water is added, obtains solid-liquid mixing after stirring 1h
Object；
Step 5: being filtered with the reciprocating sieve of 80 mesh to solidliquid mixture obtained by step 4, the water of metallic copper, graphitiferous powder is obtained
Solution；
Step 6: 98% sulfuric acid is added into the aqueous solution of the resulting graphitiferous powder of step 5 and is stirred continuously, solution is adjusted
Then pH value is filtered to 1.0 up to graphite powder and 930mL lithium sulfate solution.
The concentration of lithium in gained lithium sulfate solution, test result 18.8g/ are tested using flame atomic absorption spectrometry
L, i.e., finally recycling obtained lithium is 17.5g.
Embodiment 2
A method of recycling lithium in waste and old graphite series lithium ion battery negative electrode tab, comprising the following steps:
Step 1: taking positive electrode is LiMn2O4, negative electrode material is the chargeable waste and old lithium ion battery 1kg of graphite, with charging
Device is fully charged by battery；
Step 2: battery fully charged obtained by step 1 is disassembled, negative electrode tab, positive plate, diaphragm and battery case are obtained；
2h is heat-treated Step 3: negative electrode tab is placed at a temperature of 200 DEG C；
Step 4: the 270g negative electrode tab after heat treated is placed in container, 870mL water is added, obtains solid-liquid mixing after stirring 1h
Object；
Step 5: being filtered with the reciprocating sieve of 80 mesh to solidliquid mixture obtained by step 4, the water of metallic copper, graphitiferous powder is obtained
Solution；
Step 6: 98% hydrochloric acid is added into the aqueous solution of the resulting graphitiferous powder of step 5 and is stirred continuously, solution is adjusted
Then pH value is filtered to 0.5 up to graphite powder and 830mL lithium chloride solution.
The concentration of lithium in gained lithium chloride solution, test result 20.7g/ are tested using flame atomic absorption spectrometry
L, i.e., finally recycling obtained lithium is 17.2g.
Embodiment 3
A method of recycling lithium in waste and old graphite series lithium ion battery negative electrode tab, comprising the following steps:
Step 1: taking positive electrode is LiMn2O4, negative electrode material is the chargeable waste and old lithium ion battery 1kg of graphite, with charging
Device is fully charged by battery；
Step 2: battery fully charged obtained by step 1 is disassembled, negative electrode tab, positive plate, diaphragm and battery case are obtained；
1.5h is heat-treated Step 3: negative electrode tab is placed at a temperature of 300 DEG C；
Step 4: the 270g negative electrode tab after heat treated is placed in container, 2700mL water is added, obtains solid-liquid mixing after stirring 1h
Object；
Step 5: being filtered with the reciprocating sieve of 80 mesh to solidliquid mixture obtained by step 4, the water of metallic copper, graphitiferous powder is obtained
Solution；
Step 6: 98% hydrochloric acid is added into the aqueous solution of the resulting graphitiferous powder of step 5 and is stirred continuously, solution is adjusted
Then pH value is filtered to 2.0 up to graphite powder and 2600mL lithium chloride solution.
The concentration of lithium in gained lithium chloride solution, test result 6.62g/ are tested using flame atomic absorption spectrometry
L, i.e., finally recycling obtained lithium is 17.2g.
Claims (4)
1. a kind of method for recycling lithium in waste and old graphite series lithium ion battery negative electrode tab, which comprises the following steps:
Step 1: waste and old graphite series lithium ion battery is fully charged；
Step 2: battery fully charged obtained by step 1 is disassembled, negative electrode tab, positive plate, diaphragm and battery case are obtained；
Step 3: being heat-treated at a temperature of negative electrode tab obtained by step 2 is placed in 150-550 DEG C；
Step 4: water is added according to the solid-to-liquid ratio of 1:10-1:3 to the negative electrode tab after step 3 heat treatment, obtained after stirring 0.5-4h
To solidliquid mixture；
Step 5: being filtered with the reciprocating sieve of 20-80 mesh to solidliquid mixture obtained by step 4, metallic copper, graphitiferous powder are obtained
Aqueous solution；
Step 6: the pH value of sulfuric acid or hydrochloric acid conditioning solution is added into the aqueous solution of the resulting graphitiferous powder of step 5 to 0.5-
2.0, the solution up to graphite powder and lithium-containing compound is then filtered, the lithium compound is lithium sulfate or lithium chloride.
2. the method for lithium in the waste and old graphite series lithium ion battery negative electrode tab of recycling according to claim 1, which is characterized in that
Solid-to-liquid ratio described in step 4 is 1:3.7.
3. the method for lithium in the waste and old graphite series lithium ion battery negative electrode tab of recycling according to claim 1, which is characterized in that
The mass fraction of sulfuric acid described in step 6 or hydrochloric acid is 98%.
4. the method for lithium in the waste and old graphite series lithium ion battery negative electrode tab of recycling according to claim 1, which is characterized in that
After step 6 obtains the solution of lithium-containing compound, the pH that sodium hydrate regulator solution is added is 10, then filters, will be obtained by filtration
Filtrate sufficiently react and be concentrated by evaporation up to lithium carbonate with sodium carbonate.
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| CN201810942393.6A CN109088119B (en) | 2018-08-17 | 2018-08-17 | Method for recycling lithium in waste graphite system lithium ion battery negative electrode plate |
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| CN201810942393.6A CN109088119B (en) | 2018-08-17 | 2018-08-17 | Method for recycling lithium in waste graphite system lithium ion battery negative electrode plate |
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| CN109088119A true CN109088119A (en) | 2018-12-25 |
| CN109088119B CN109088119B (en) | 2020-09-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668473A (en) * | 2019-08-13 | 2020-01-10 | 中国科学院过程工程研究所 | Method for recovering lithium from waste lithium ion battery negative electrode material |
| CN111268703A (en) * | 2019-10-10 | 2020-06-12 | 中国科学院生态环境研究中心 | Method for recovering lithium carbonate from waste lithium iron phosphate batteries |
| CN112259821A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for recovering valuable metals from waste lithium ion batteries |
| CN114447465A (en) * | 2022-01-14 | 2022-05-06 | 清华大学深圳国际研究生院 | Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668473A (en) * | 2019-08-13 | 2020-01-10 | 中国科学院过程工程研究所 | Method for recovering lithium from waste lithium ion battery negative electrode material |
| CN111268703A (en) * | 2019-10-10 | 2020-06-12 | 中国科学院生态环境研究中心 | Method for recovering lithium carbonate from waste lithium iron phosphate batteries |
| CN112259821A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for recovering valuable metals from waste lithium ion batteries |
| CN114447465A (en) * | 2022-01-14 | 2022-05-06 | 清华大学深圳国际研究生院 | Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material |
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| CN109088119B (en) | 2020-09-29 |
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Address after: No. 421, Dongjiang Circular Industrial Park, Dongyang City, Hunan Province Patentee after: Hunan Jinkai Recycling Technology Co.,Ltd. Address before: No. 421, Dongjiang Circular Industrial Park, Dongyang City, Hunan Province Patentee before: HUNAN KEYKING CYCLE TECHNOLOGY Co.,Ltd. |
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