CN114956131A - Method for recovering metal lithium and cobalt from waste lithium cobalt oxide battery positive electrode material - Google Patents
Method for recovering metal lithium and cobalt from waste lithium cobalt oxide battery positive electrode material Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 29
- 239000010941 cobalt Substances 0.000 title claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 13
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title claims description 11
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000002386 leaching Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 23
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 23
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229960003178 choline chloride Drugs 0.000 claims abstract description 23
- 230000005496 eutectics Effects 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000010405 anode material Substances 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 3
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 206010011878 Deafness Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 231100000895 deafness Toxicity 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- OASOQJKCZXXDMI-UHFFFAOYSA-N ethane-1,2-diol;hydrochloride Chemical compound Cl.OCCO OASOQJKCZXXDMI-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 208000016354 hearing loss disease Diseases 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000028774 intestinal disease Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 208000031225 myocardial ischemia Diseases 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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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
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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 provides a method for recovering metal lithium and cobalt from a waste lithium cobaltate battery positive electrode material, which comprises the following steps: mixing choline chloride and ethylene glycol to obtain a eutectic solvent, mixing the obtained eutectic solvent with a positive electrode material of a waste lithium cobaltate battery, roasting at a high temperature, and controlling the roasting time to obtain a roasted product; leaching the roasted product with water, and performing solid-liquid separation to obtain a lithium-containing leaching solution and leaching residues; evaporating and crystallizing lithium-containing leachateTo obtain Li 2 CO 3 A solid; calcining the water-immersed slag in an oxygen-containing atmosphere to obtain Co 3 O 4 And (3) powder. The method has simple process flow, can recover lithium and cobalt at lower temperature, has high metal recovery rate, and is environment-friendly.
Description
Technical Field
The invention relates to the field of battery material recovery, in particular to a method for recovering metal lithium and cobalt from a waste lithium cobalt oxide battery positive electrode material.
Background
Since lithium cobaltate is used as a positive electrode material of a lithium ion rechargeable battery, lithium cobaltate is widely applied to portable electronic equipment such as mobile phones, digital cameras, notebook computers and the like. In recent years, the rise of electric vehicles and energy storage devices has further promoted the rapid development of the lithium ion battery industry. However, the average service life of the lithium ion battery is 3-5 years, and the lithium ion battery can be scrapped after being used up. Because the lithium cobaltate battery contains harmful substances such as heavy metals, organic matters and the like, if the waste lithium cobaltate battery is not treated properly, environmental pollution and resource waste are caused, and even the health of human beings is harmed, for example, the cobalt element can cause symptoms such as intestinal disorder, deafness, myocardial ischemia and the like. Therefore, the method is very important for reasonably recycling and utilizing the waste lithium cobalt oxide battery, is beneficial to the sustainable utilization of valuable metal resources, and has great significance for the environmental protection and the sustainable development of social economy.
At present, the recovery method of the anode material of the waste lithium cobaltate battery mainly comprises a pyrogenic process, a wet process and a biological process. In the traditional pyrogenic process, the treated lithium is mainly enriched to two phases of slag and smoke dust and exists in the form of aluminosilicate, so that the lithium resource is not easy to be effectively recycled. The wet recovery technology mainly comprises pretreatment, leaching, element separation and material regeneration, and the traditional wet method usually uses corrosive strong acid (such as hydrochloric acid, nitric acid and sulfuric acid) for treatment, so that great potential safety hazards exist to workers and the environment, and the treatment process is long. For example, the invention patent application with publication number CN111074075A entitled method for recovering waste lithium cobalt oxide battery cathode material by using eutectic solvent discloses that the method dissolves lithium cobalt oxide powder in eutectic solvent for heating leaching, belongs to wet recovery, and has the disadvantages of small solid-to-liquid ratio in the leaching process and long treatment time. The biological method has small treatment capacity and long period, and is not suitable for industrial recovery of waste lithium ion batteries at present.
Based on the problems in the prior art, the method for recovering lithium and cobalt from waste lithium cobalt oxide batteries is yet to be further improved.
Disclosure of Invention
To address the deficiencies of the prior art, it is an object of the present invention to address one or more of the problems of the prior art as set forth above. For example, an object of the present invention is to provide a method for recovering metallic lithium and cobalt at a relatively low temperature with a simple process.
In order to achieve the above object, the present invention provides a method for recovering metallic lithium and cobalt from a cathode material of a waste lithium cobalt oxide battery, wherein the method comprises the following steps:
1) mixing choline chloride and ethylene glycol to obtain a eutectic solvent;
2) mixing the obtained eutectic solvent with the anode material of the waste lithium cobaltate battery, roasting at a high temperature and controlling the roasting time to obtain a roasted product;
3) leaching the roasted product with water, and performing solid-liquid separation to obtain a lithium-containing leaching solution and leaching residues;
4) evaporating and crystallizing the lithium-containing leaching solution to obtain Li 2 CO 3 A solid;
5) calcining the water leaching residue in an oxygen-containing atmosphere to obtain Co 3 O 4 And (3) powder.
Compared with the prior art, the method for recovering the metal lithium and the metal cobalt from the anode material of the waste lithium cobalt oxide battery has the following beneficial effects that:
(1) according to the invention, the choline chloride-ethylene glycol eutectic solvent is added in the roasting process of the positive electrode material of the lithium cobaltate battery, so that the cobalt in the positive electrode material can be reduced into elemental cobalt at a lower temperature, and the lithium is transformed into a water-soluble lithium salt; the cobalt is left in the slag phase while the lithium is leached, so that the lithium and the cobalt are separately recovered, the recovery rate of the cobalt and the lithium in the lithium cobaltate battery is improved, the energy consumption is reduced, and the cost is reduced.
(2) According to the invention, through optimizing the roasting process, lithium cobaltate almost completely reacts, and the purity of a lithium carbonate product obtained after evaporation and crystallization of the lithium-containing leachate after water leaching reaches over 99%, so that the requirement of battery-grade lithium carbonate is met; and the lithium-containing residual liquid after evaporation and crystallization does not contain other impurity ions, can be recycled in a water immersion treatment stage after condensation and recovery, reduces the discharge of waste water and the loss of lithium, realizes the aim of a clean process, and is environment-friendly.
(3) The lithium carbonate and the cobaltosic oxide obtained by recovery can be used for manufacturing commercial lithium cobaltate batteries, and the recovery and utilization of all components in the anode materials of the waste lithium cobaltate batteries are realized.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of a calcined product in an example of the present invention.
Detailed Description
In the following, the technical solution in the embodiment of the present invention will be clearly and completely described with reference to the embodiment and the accompanying drawings, as shown in fig. 1, the method may include the following steps:
1) mixing choline chloride and ethylene glycol to obtain a eutectic solvent;
2) mixing the obtained eutectic solvent with the anode material of the waste lithium cobaltate battery, roasting at a high temperature and controlling the roasting time to obtain a roasted product;
3) soaking the roasted product in water, and performing solid-liquid separation to obtain lithium-containing leachate and water leaching residues;
4) evaporating and crystallizing the lithium-containing leaching solution to obtain Li 2 CO 3 A solid;
5) calcining the water leaching residue in an oxygen-containing atmosphere to obtain Co 3 O 4 And (3) powder.
In this example, the kind of the roasted product is closely related to the molar ratio of choline chloride to ethylene glycol and the roasting time, and the molar ratio of choline chloride to ethylene glycol and the roasting time are in a mutual matching relationship, which affects the kind of the roasted product. Specifically, if the ratio of ethylene glycol in the eutectic solvent is too large and the calcination time is too long, lithium carbonate is not generated in the calcination product. Therefore, when the mol ratio of the choline chloride to the ethylene glycol is 1 (0.8-1.2), the roasting time can be set to be 110-130 min. When the mol ratio of the choline chloride to the ethylene glycol is 1 (1.8-2.2), the roasting time can be set to be 50-70 min. Preferentially, the mol ratio of the choline chloride to the ethylene glycol is 1:1, and the roasting time is 120min, so that the lithium cobaltate in the positive electrode material can be completely reacted, the treatment efficiency of the lithium cobaltate can be further improved, and the reaction effect is better.
In the embodiment, the eutectic solvent is obtained by mixing choline chloride and ethylene glycol and then stirring at a speed of 250-350 r/min at a temperature of 70-120 ℃. Under the condition, the eutectic solvent can be synthesized quickly, and the time is saved.
In this embodiment, the mass ratio of the eutectic solvent to the lithium cobaltate positive electrode material is (0.5-5): 1 may be, for example, 0.5:1, 1:1, 1.5:1 or 2:1, and in this range, the residual lithium cobaltate in the product after firing is small.
In this embodiment, the high-temperature baking temperature is 350 ℃ to 600 ℃, and more preferably 400 ℃ to 550 ℃, for example, the high-temperature baking temperature may be 400 ℃, 450 ℃, 500 ℃, 550 ℃. The roasting temperature and the roasting time are in a matching relation, if the roasting temperature is too low and the roasting time is too short, LiCoO 2 Is not completely converted, Li is generated 2 CO 3 Less, the recovery of Li and Co is not high. Preferably, the molar ratio of choline chloride to ethylene glycol is 1:1, the calcination temperature is set at 500 ℃ when the calcination time is 120min, and LiCoO is used at this time 2 The conversion is complete, and a large amount of lithium carbonate and cobalt simple substance are generated.
In the embodiment, the roasted product is subjected to water leaching in deionized water, the solid-to-liquid ratio of the roasted product to the deionized water is 15 g/L-50 g/L, and more preferably 25g/L, when the solid-to-liquid ratio is less than 15g/L, the waste of water resources is large, and the energy consumption during evaporation is increased; when the solid-to-liquid ratio is more than 50g/L, part of Li is generated 2 CO 3 Insolubilization, resulting in incomplete Li and Co separation. The water immersion temperature is 20-30 ℃, and the preferable temperature is 25 ℃; the leaching time is 40-80 min, more preferably 60min, if the leaching time is too short, part of Li is generated 2 CO 3 Not dissolved. Evaporation crystallization of lithium-containing leaching liquidThe residual liquid can be condensed and recycled, and is returned to the water leaching treatment stage to be used as the leachate for recycling, and the water leaching slag is mainly a mixture of Co and CoO.
In the embodiment, the water-immersed slag is calcined in an oxygen-containing atmosphere, wherein the calcination temperature is 700-800 ℃, and more preferably 750 ℃; the calcination time is 15min to 75min, and more preferably 45 min. The simple substance cobalt can not be completely converted when the calcination temperature is too low or the calcination time is too short, and the simple substance cobalt or the cobalt oxide can be completely converted into Co when the calcination temperature is 750 ℃ for 45min 3 O 4 And the recovery of the lithium battery cathode material is better realized.
In order that the above-described embodiments of the invention may be better understood, further description thereof may be had with reference to specific examples.
Example 1:
(1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:2, mixing at the temperature of 70 ℃ and the rotating speed of 300r/min to obtain a eutectic solvent;
(2) mixing 1mL of the eutectic solvent obtained in the step (1) with 0.5g of the waste lithium cobaltate battery positive electrode material, and roasting at 500 ℃ for 60min to obtain a roasted product, wherein XRD of the roasted product is shown as a curve (A) in figure 2, and the product is Co, CoO or Co 3 O 4 、Li 2 CO 3 And a small amount of residual LiCoO 2 ；
(3) Leaching the roasted product and deionized water according to a solid-to-liquid ratio of 25g/L for 1h at the temperature of 25 ℃, and filtering to obtain lithium-containing leachate and water leaching residues;
(4) evaporating and crystallizing the lithium-containing leaching solution to obtain Li 2 CO 3 A solid;
(5) placing the water leaching slag into a muffle furnace, calcining for 45min at 750 ℃ in an oxygen-containing atmosphere to obtain Co 3 O 4 。
Example 2:
(1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:2, mixing at the temperature of 70 ℃ and the rotating speed of 300r/min to obtain a eutectic solvent;
(2) mixing 1mL of the eutectic solvent obtained in the step (1) with 0.5g of waste lithium cobaltateMixing the anode materials of the battery, and roasting at 500 ℃ for 120min to obtain a roasted product, wherein XRD of the roasted product is shown as a curve (B) in figure 2, and the product is CoO and Co 3 O 4 And a small amount of residual LiCoO 2 ；
(3) Leaching the roasted product and deionized water at a solid-to-liquid ratio of 25g/L for 1h at 25 ℃, and filtering to obtain a lithium-containing leaching solution and water leaching residues;
(4) evaporating and crystallizing the lithium-containing leaching solution to obtain Li 2 CO 3 A solid;
(5) placing the water leaching slag into a muffle furnace, calcining for 45min at 750 ℃ in an oxygen-containing atmosphere to obtain Co 3 O 4 。
Example 3:
(1) mixing choline chloride and ethylene glycol according to a molar ratio of 1:1, mixing at the temperature of 130 ℃ and the rotating speed of 300r/min to obtain a eutectic solvent;
(2) mixing 1mL of the eutectic solvent obtained in the step (1) with 0.5g of the waste lithium cobaltate battery positive electrode material, and roasting at 500 ℃ for 120min to obtain a roasted product, wherein XRD of the roasted product is shown as a curve (C) in figure 2, and the product is Co, CoO and Li 2 CO 3 ；
(3) Leaching the roasted product and deionized water at a solid-to-liquid ratio of 25g/L for 1h at 25 ℃, and filtering to obtain a lithium-containing leaching solution and water leaching residues;
(4) evaporating and crystallizing the lithium-containing leaching solution to obtain Li 2 CO 3 A solid;
(5) placing the water leaching slag into a muffle furnace, calcining for 45min at 750 ℃ in an oxygen-containing atmosphere to obtain Co 3 O 4 。
Comparative example 1:
compared with example 3, the difference is that the waste lithium cobalt oxide battery cathode material is mixed with choline chloride, ethylene glycol is not added, and XRD of the calcination product is shown as curve (D) in fig. 2.
Comparing example 1 and example 2, it can be seen that, at a molar ratio of choline chloride to ethylene glycol of 1:2, the calcined product was free from the formation of lithium carbonate at a reaction time of 120min, indicating that the calcination time cannot be too long when the ethylene glycol content is relatively large.
Comparing example 2 with example 3, it can be seen that, under the same roasting temperature and roasting time, the addition amount of the ethylene glycol cannot be too high, and after the ratio of the choline chloride to the ethylene glycol exceeds 1:2, lithium cobaltate appears in the roasted product, the reaction of the lithium cobaltate is incomplete, and no lithium carbonate or elemental cobalt is generated. Under the conditions that the molar ratio of choline chloride to ethylene glycol is 1:1, the roasting time is 120min, and the roasting temperature is 500 ℃, lithium cobaltate is completely absent in the roasted product, which indicates that the lithium cobaltate is completely reacted at the temperature, and a large amount of lithium carbonate and simple substance cobalt appear in the roasted product at the moment.
Comparing examples 2 to 3 with comparative example 1, only choline chloride was used without ethylene glycol, lithium carbonate did not appear in the calcined product, and the reaction of lithium cobaltate was incomplete, indicating that the addition of ethylene glycol can promote the reaction of lithium cobaltate and the generation of lithium carbonate.
It is to be understood that the above-described embodiments are only some of the presently preferred embodiments of the invention, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any inventive work belong to the scope of the present invention.
Claims (9)
1. A method for recovering metal lithium and cobalt from a waste lithium cobalt oxide battery cathode material is characterized by comprising the following steps:
mixing choline chloride and ethylene glycol to obtain a eutectic solvent;
mixing the obtained eutectic solvent with the anode material of the waste lithium cobaltate battery, roasting at a high temperature and controlling the roasting time to obtain a roasted product;
soaking the roasted product in water, and carrying out solid-liquid separation to obtain a lithium-containing leaching solution and water leaching slag;
evaporating and crystallizing the lithium-containing leaching solution to obtain Li 2 CO 3 A solid;
calcining the water leaching residue in an oxygen-containing atmosphere to obtain Co 3 O 4 。
2. The method for recovering the metallic lithium and the metallic cobalt from the anode material of the waste lithium cobaltate battery as claimed in claim 1, wherein the molar ratio of the choline chloride to the glycol is 1 (0.8-1.2), and the roasting time is 110 min-130 min.
3. The method for recovering the metallic lithium and the metallic cobalt from the anode material of the waste lithium cobaltate batteries according to claim 1 or 2, wherein the molar ratio of the choline chloride to the glycol is 1:1, and the roasting time is 120 min.
4. The method for recovering the metal lithium and the metal cobalt from the anode material of the waste lithium cobaltate battery as claimed in claim 1, wherein the molar ratio of the choline chloride to the glycol is 1 (1.8-2.2), and the roasting time is 50-70 min.
5. The method for recovering the metal lithium and the metal cobalt from the waste lithium cobaltate battery cathode material as claimed in claim 1, 2 or 4, wherein the obtaining of the eutectic solvent comprises mixing choline chloride and ethylene glycol and then applying a stirring speed of 250 r/min to 350 r/min at a temperature of 70 ℃ to 120 ℃.
6. The method for recovering the metallic lithium and the metallic cobalt from the anode material of the waste lithium cobaltate battery as claimed in claim 1, 2 or 4, wherein the mass ratio of the eutectic solvent to the lithium cobaltate anode material is (0.5-5): 1.
7. The method for recovering the metallic lithium and the metallic cobalt from the anode material of the waste lithium cobaltate battery as claimed in claim 1, 2 or 4, wherein the high-temperature roasting temperature is 350 ℃ to 600 ℃, and the high-temperature roasting time is 20min to 180 min.
8. The method for recovering the metal lithium and the metal cobalt from the waste lithium cobaltate battery cathode material as claimed in claim 1, 2 or 4, wherein the solid-liquid ratio of water leaching is 15-50 g/L, the water leaching temperature is 20-30 ℃, and the leaching time is 40-80 min.
9. The method for recovering the metallic lithium and the metallic cobalt from the positive electrode material of the waste lithium cobaltate battery as claimed in claim 1, 2 or 4, wherein the calcining temperature is 700-800 ℃, and the calcining time is 15-75 min.
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