CN115224380B - Method for recycling positive electrode material of lithium cobaltate battery - Google Patents
Method for recycling positive electrode material of lithium cobaltate battery Download PDFInfo
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- CN115224380B CN115224380B CN202210987113.XA CN202210987113A CN115224380B CN 115224380 B CN115224380 B CN 115224380B CN 202210987113 A CN202210987113 A CN 202210987113A CN 115224380 B CN115224380 B CN 115224380B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 150
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 147
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000010941 cobalt Substances 0.000 claims abstract description 93
- 239000000243 solution Substances 0.000 claims abstract description 68
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 55
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 50
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 37
- 239000008247 solid mixture Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 34
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 62
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 44
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 34
- 238000001704 evaporation Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 23
- 125000001979 organolithium group Chemical group 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 22
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- QEFDHAUPZVFWDR-UHFFFAOYSA-N diphenylmethanone;lithium Chemical compound [Li].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 QEFDHAUPZVFWDR-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract description 23
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002245 particle Substances 0.000 abstract description 20
- 239000002253 acid Substances 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 6
- 238000009853 pyrometallurgy Methods 0.000 abstract description 6
- 238000009854 hydrometallurgy Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 14
- GBVSONMCEKNESD-UHFFFAOYSA-N 1,1'-biphenyl;lithium Chemical compound [Li].C1=CC=CC=C1C1=CC=CC=C1 GBVSONMCEKNESD-UHFFFAOYSA-N 0.000 description 9
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- SYHYMQPZTOVLRI-UHFFFAOYSA-N CC1=CC=C(C=C1)C1=CC=C(C=C1)C.[Li] Chemical compound CC1=CC=C(C=C1)C1=CC=C(C=C1)C.[Li] SYHYMQPZTOVLRI-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910011763 Li2 O Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 dimethyl biphenyl lithium tetrahydrofuran Chemical compound 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet 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
- 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for recycling a positive electrode material of a lithium cobalt oxide battery, which comprises the following steps: mixing: mixing and stirring a positive electrode material of a lithium cobaltate battery with an organic lithium solution to react, and then performing solid-liquid separation to obtain a solid mixture of elemental cobalt and lithium oxide; recovering cobalt: mixing the solid mixture of the simple substance cobalt and lithium oxide with water, and then carrying out solid-liquid separation to obtain an aqueous solution of simple substance cobalt particles and lithium hydroxide. Compared with pyrometallurgy and hydrometallurgy, the recovery method is easy to operate, and does not need high-temperature treatment and inorganic strong acid, so that the recovery method has low requirements on high temperature resistance and acid resistance of equipment, low energy consumption, no generation of polluting gas and reduced environmental pollution.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to a method for recovering a positive electrode material of a lithium cobalt oxide battery.
Background
The lithium cobalt oxide battery taking the lithium cobalt oxide material as the positive electrode has the advantages of high working voltage, long service life, no self-discharge, no memory effect, environmental friendliness and the like, is widely applied to the fields of portable electronic products and the like, and the demands of lithium ion batteries are increasing. However, as active metal (e.g., lithium, cobalt, etc.) resources required for the positive electrode material of the lithium battery are continuously consumed, the manufacturing cost of the lithium battery is increased, and thus, development of a recycling technology of the lithium cobaltate positive electrode material is urgently required.
In the related art, the recovery of active metals in lithium batteries mainly adopts pyrometallurgy or hydrometallurgy. The pyrometallurgy needs high-temperature heat treatment, has strict requirements on equipment and high energy consumption, and the generated gas causes certain pollution to the environment. The wet metallurgy mainly adopts inorganic strong acid such as hydrochloric acid, sulfuric acid, nitric acid and the like to dissolve and leach active metal ions, then the metal salt is recovered through precipitation reaction, sulfur dioxide and harmful gas containing nitrogen and carbon are released in the process, and the environment is polluted.
Disclosure of Invention
The embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobaltate battery, which has low energy consumption and can reduce environmental pollution.
In order to achieve the above object, the embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobalt oxide battery, comprising the following steps:
Mixing: mixing and stirring a positive electrode material of a lithium cobaltate battery with an organic lithium solution to react, and then performing solid-liquid separation to obtain a solid mixture of elemental cobalt and lithium oxide;
Recovering cobalt: and mixing the solid mixture of the simple substance cobalt and lithium oxide with water, and then carrying out solid-liquid separation to obtain an aqueous solution of the simple substance cobalt and lithium hydroxide.
According to the method for recycling the anode material of the old lithium cobalt oxide battery, the anode material of the lithium cobalt oxide battery and an organic lithium solution are mixed and stirred, so that organic lithium and lithium cobalt oxide react to generate elemental cobalt and lithium oxide, then a solid mixture of the elemental cobalt and the lithium oxide is mixed with water, so that the lithium oxide reacts with the water to generate lithium hydroxide, and thus the elemental cobalt and the lithium hydroxide can be separated through solid-liquid separation, and the precursor of the anode material of the lithium cobalt oxide battery, namely the elemental cobalt, is recycled. Compared with pyrometallurgy and hydrometallurgy, the method disclosed by the application does not need high-temperature treatment and inorganic strong acid, so that the method has low requirements on high temperature resistance and acid resistance of equipment, low energy consumption, no generation of polluting gas and reduced environmental pollution. In addition, the recovery method does not need to calcine the positive electrode material of the lithium cobaltate battery and then carry out recovery treatment, thereby being beneficial to reducing energy consumption and reducing environmental pollution.
As an alternative embodiment, in an embodiment of the present invention, before the step of mixing, the recycling method includes:
And grinding the positive electrode material of the lithium cobaltate battery into powder. The contact area between the lithium cobaltate and the organic lithium solvent can be increased by grinding the positive electrode material of the lithium cobaltate battery into powder so as to improve the reaction rate, and in addition, the sufficiency of the reaction of the lithium cobaltate material can be improved so as to improve the recycling rate of the lithium cobaltate material.
As an alternative embodiment, in an embodiment of the present invention, the organolithium in the organolithium solution includes a lithium complex containing a condensed ring aromatic hydrocarbon; the solvent in the organolithium solution includes: one or more of tetrahydrofuran, ethylene glycol dimethyl ether and n-hexane. The lithium complex containing condensed ring aromatic hydrocarbon is used as organic lithium, so that the lithium complex has high stability and high reactivity. Tetrahydrofuran, ethylene glycol dimethyl ether, n-hexane and the like are used as solvents, so that the organic lithium can be fully dissolved, and the organic lithium solution has higher concentration, thereby being beneficial to improving the reaction rate. It is understood that the organic solvent in the product of the reaction of the lithium cobalt oxide with the lithium complex containing the polycyclic aromatic hydrocarbon is a polycyclic aromatic hydrocarbon, which can be recycled, for example, can react with lithium to form an organolithium solution, thereby reducing the waste liquid discharge.
As an alternative embodiment, in an embodiment of the present invention, the organolithium includes one or more of butyllithium, naphthyllithium, biphenyllithium, benzophenone lithium, and dimethylbiphenylalithium. When the organolithium is butyl lithium, naphthalene lithium, biphenyl lithium, benzophenone lithium, dimethyl biphenyl lithium, the reaction activity of the organolithium is higher to increase the reaction rate. Especially tetrahydrofuran solution or ethylene glycol dimethyl ether solution of biphenyl lithium and naphthalene lithium has higher reactivity and faster reaction rate with lithium carbonate.
As an alternative embodiment, in the examples of the present invention, the concentration of the organolithium solution is 0.1mol/L to 2mol/L. Illustratively, the concentration of the organolithium solution is 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, etc. Through reasonable concentration that sets up organic lithium solution, on the one hand can guarantee that organic lithium solution has sufficient concentration in order to realize with the quick reaction of lithium cobaltate, on the other hand can also guarantee that the viscosity of organic lithium solution is in reasonable within range to be convenient for stir, make organic lithium solution can fully react and have faster reaction rate with lithium cobaltate. When the concentration of the organic lithium solution is less than 0.1mol/L, the reaction rate of the organic lithium solution and lithium cobaltate is slower, and the reaction time is longer. When the concentration of the organic lithium solution is more than 2mol/L, the viscosity of the organic lithium solution is larger, the stirring is not facilitated, the reaction rate is lower, and the reaction is insufficient.
In an alternative embodiment, in the step of mixing, the reaction temperature of the positive electrode material of the lithium cobaltate battery and the organic lithium solution is 20-60 ℃ and the reaction time is 0.5-24 h. Illustratively, the reaction temperature is 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, etc., and the reaction time is 0.5h, 5h, 10h, 15h, 20h, 24h, etc. The reaction rate can be controlled within a reasonable range by setting a reasonable reaction temperature, and the sufficiency of the reaction can be improved to improve the recovery rate. When the reaction temperature is lower than 20 ℃, the reaction rate is slow, the reaction time is long, and it is difficult to complete the reaction. When the reaction temperature is higher than 60 ℃, the solvent volatilization speed is higher, so that the concentration of the organic lithium solution is changed, and the reaction process is not easy to control. By controlling the reaction time within a reasonable range, the sufficiency of the reaction can be improved, and the recovery rate can be improved. When the reaction time is less than 0.5h, there may be insufficient reaction, resulting in problems of waste of raw materials and low recovery rate. When the reaction time is longer than 24 hours, the reaction time is too long, and the production efficiency is lower.
As an alternative embodiment, in the step of recovering cobalt according to the embodiment of the present invention, the mass ratio of the solid mixture of elemental cobalt and lithium oxide to the water is 1:2 to 1:50. Illustratively, the mass ratio of the solid mixture of elemental cobalt and lithium oxide to water is 1:2, 1:10, 1:20, 1:30, 1:40, 1:50, etc. By reasonably setting the mass ratio of the solid mixture of the simple substance cobalt and the lithium oxide to the water, on one hand, the lithium oxide and the water can be completely reacted to ensure that the solid after solid-liquid separation is simple substance cobalt particles, and on the other hand, the concentration of the product lithium hydroxide can be ensured to facilitate the subsequent utilization of the lithium hydroxide, for example, a lithium hydroxide solution is used as a reaction reagent or is evaporated to dryness to obtain lithium hydroxide powder. When the mass ratio of the solid mixture of the simple substance cobalt and lithium oxide to water is less than 1:2, the water is excessively small, and partial lithium oxide possibly does not react with water, and the solid particles after solid-liquid separation also contain a small amount of lithium oxide, so that the cobalt content is impure.
As an alternative embodiment, in an embodiment of the present invention, after the step of recovering elemental cobalt, the recovery method further includes:
recovering lithium: evaporating the aqueous solution of lithium hydroxide to dryness to obtain lithium hydroxide.
By evaporating the aqueous solution of lithium hydroxide to dryness, lithium hydroxide is obtained, and it is understood that lithium hydroxide is also a precursor of a lithium carbonate positive electrode material, so that the recovery rate of the lithium cobaltate battery positive electrode material is improved.
As an alternative embodiment, in an embodiment of the present invention, after the step of recovering elemental cobalt, the recovery method further includes:
Recovering lithium: and introducing carbon dioxide into the aqueous solution of lithium hydroxide to obtain an aqueous solution of lithium carbonate, and evaporating the aqueous solution of lithium carbonate to dryness to obtain lithium carbonate.
Carbon dioxide is introduced into the aqueous solution of lithium hydroxide to obtain the aqueous solution of lithium carbonate, and then the aqueous solution of lithium carbonate is evaporated to dryness to obtain lithium carbonate, and it can be understood that the lithium carbonate is a precursor of the positive electrode material of a lithium cobaltate battery, so that the recovery rate of the positive electrode material of the lithium cobaltate battery can be improved, and in addition, the melting point of the lithium carbonate is higher than that of the lithium hydroxide, so that the lithium carbonate is more favorable for being used as the positive electrode material of the lithium cobaltate battery.
In an alternative embodiment, in the step of recovering lithium, the aqueous solution of lithium carbonate is evaporated to dryness at a temperature of 50 to 400 ℃. Illustratively, the evaporating temperature is 50 ℃, 100 ℃, 200 ℃, 300 ℃, 400 ℃, etc. Through setting up reasonable evaporating temperature, can make evaporating time in reasonable within range, the heat-resisting ability requirement to equipment is lower moreover to be favorable to reduction in production cost. When the evaporating temperature is less than 50 ℃, the temperature is too low, the evaporating time is too long, and the production efficiency is low. When the evaporating temperature is higher than 400 ℃, the temperature is too high, so that the requirement on the heat resistance of equipment is high, the production cost is high, and the lithium carbonate can be decomposed and cannot be obtained.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
According to the recovery method of the positive electrode material of the lithium cobaltate battery, provided by the embodiment, the positive electrode material of the lithium cobaltate battery and the organic lithium solution are mixed and stirred, so that the organic lithium and the lithium cobaltate react to generate elemental cobalt and lithium oxide, then the solid mixture of the elemental cobalt and the lithium oxide is mixed with water, so that the lithium oxide reacts with the water to generate lithium hydroxide, and thus the elemental cobalt and the lithium hydroxide can be separated through solid-liquid separation, so that the precursor of the positive electrode material of the lithium cobaltate battery, namely the elemental cobalt, is recovered. Compared with pyrometallurgy and hydrometallurgy, the method disclosed by the application does not need high-temperature treatment and inorganic strong acid, so that the method has low requirements on high temperature resistance and acid resistance of equipment, low energy consumption, no generation of polluting gas and reduced environmental pollution.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of waste lithium cobaltate powder and recovered elemental cobalt powder in the first example;
FIG. 2 is an absorption spectrum of lithium carbonate recovered in the first example;
FIG. 3 is an X-ray diffraction chart of elemental cobalt recovered in the second example;
FIG. 4 is a scanning electron microscope picture and an X-ray diffraction pattern of the elemental cobalt recovered in the third embodiment;
FIG. 5 is a scanning electron microscope picture of the elemental cobalt recovered in the fourth example;
fig. 6 is an X-ray diffraction pattern of the lithium carbonate powder recovered in the fifth example.
Detailed Description
In the present invention, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal" and the like indicate an azimuth or a positional relationship based on that shown in the drawings. These terms are only used to better describe the present invention and its embodiments and are not intended to limit the scope of the indicated devices, elements or components to the particular orientations or to configure and operate in the particular orientations.
Also, some of the terms described above may be used to indicate other meanings in addition to orientation or positional relationships, for example, the term "upper" may also be used to indicate some sort of attachment or connection in some cases. The specific meaning of these terms in the present invention will be understood by those of ordinary skill in the art according to the specific circumstances.
Furthermore, the terms "mounted," "configured," "provided," "connected," and "connected" are to be construed broadly. For example, it may be a fixed connection, a removable connection, or a unitary construction; may be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements, or components. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
Furthermore, the terms "first," "second," and the like, are used primarily to distinguish between different devices, elements, or components (the particular species and configurations may be the same or different), and are not used to indicate or imply the relative importance and number of devices, elements, or components indicated. Unless otherwise indicated, the meaning of "a plurality" is two or more.
The application discloses a method for recycling a positive electrode material of a lithium cobalt oxide battery, which comprises the following steps:
Mixing: mixing and stirring a positive electrode material of a lithium cobaltate battery with an organic lithium solution to react, and then performing solid-liquid separation to obtain a solid mixture of elemental cobalt and lithium oxide;
recovering cobalt: mixing the solid mixture of the simple substance cobalt and lithium oxide with water, and then carrying out solid-liquid separation to obtain an aqueous solution of the simple substance cobalt and lithium hydroxide.
According to the recovery method of the positive electrode material of the lithium cobaltate battery, disclosed by the application, the positive electrode material of the lithium cobaltate battery and an organic lithium solution are mixed and stirred, so that organic lithium and lithium cobaltate react to generate elemental cobalt and lithium oxide, then, a solid mixture of elemental cobalt and lithium oxide is mixed with water, so that lithium oxide reacts with water to generate lithium hydroxide, and thus, the elemental cobalt and lithium hydroxide can be separated through solid-liquid separation, so that a precursor of the positive electrode material of the lithium cobaltate battery, namely elemental cobalt, is recovered. Compared with pyrometallurgy and hydrometallurgy, the method disclosed by the application does not need high-temperature treatment and inorganic strong acid, so that the method has low requirements on high temperature resistance and acid resistance of equipment, low energy consumption, no generation of polluting gas and reduced environmental pollution.
In the step of mixing, the positive electrode material of the lithium cobaltate battery is a lithium cobaltate material. The positive electrode material of the lithium cobaltate battery can be a positive electrode material of a waste lithium cobaltate battery, and can also be a waste positive electrode material generated in the production process, for example, in the coating process of the positive electrode material, particles, scratches, bubbles and the like appear on the surface of the positive electrode plate due to the existence of the particles and the bubbles in the slurry, so that the waste positive electrode material is formed, or the non-satisfactory positive electrode plate caused by the reasons of debugging a machine, substrate replacement and the like in the coating process can be called as the waste positive electrode material.
In the mixing step, the positive electrode material of the lithium cobaltate battery and the organic lithium solvent have the following reaction formula:
LiCoO 2+Li-A→Co+Li2 O+A, wherein A is a functional group coordinated with lithium in the organolithium.
It is understood that the product of the reaction of lithium cobaltate and the organic lithium solution comprises an organic solvent besides the simple substance of cobalt and lithium oxide, and the organic solvent can be used for recycling, so that the recycling method of the application can not produce pollutants such as waste liquid and the like, and reduce the pollution to the environment.
In order to increase the reaction rate, optionally, the step of mixing specifically includes:
grinding the positive electrode material of the lithium cobaltate battery into powder;
the powder is mixed and stirred with the organic lithium solution to react, and then solid-liquid separation is carried out to obtain a solid mixture of elemental cobalt and lithium oxide.
The contact area with the organic lithium solvent can be increased by grinding the positive electrode material of the lithium cobaltate battery into powder so as to improve the reaction rate, and in addition, the sufficiency of the reaction of the positive electrode material of the lithium cobaltate battery can be improved so as to improve the recycling rate of the positive electrode material of the lithium cobaltate battery.
Alternatively, the organolithium in the organolithium solution comprises a lithium complex comprising a fused ring aromatic hydrocarbon; the solvent in the organolithium solution includes: one or more of tetrahydrofuran, ethylene glycol dimethyl ether and n-hexane. The lithium complex containing condensed ring aromatic hydrocarbon is used as organic lithium, so that the lithium complex has high stability and high reactivity. Tetrahydrofuran, ethylene glycol dimethyl ether, n-hexane and the like are used as solvents, so that the organic lithium can be fully dissolved, and the organic lithium solution has higher concentration, thereby being beneficial to improving the reaction rate. It is understood that the organic solvent in the product of the reaction of the lithium cobalt oxide with the lithium complex containing the polycyclic aromatic hydrocarbon is a polycyclic aromatic hydrocarbon, which can be recycled, for example, can react with lithium to form an organolithium solution, thereby reducing the waste liquid discharge.
Further, the organic lithium comprises one or more of butyl lithium, naphthalene lithium, biphenyl lithium, benzophenone lithium and dimethylbiphenyl lithium. When the organolithium is butyl lithium, naphthalene lithium, biphenyl lithium, benzophenone lithium, dimethyl biphenyl lithium, the reaction activity of the organolithium is higher to increase the reaction rate. Especially tetrahydrofuran solution or ethylene glycol dimethyl ether solution of biphenyl lithium and naphthalene lithium has higher reactivity and faster reaction rate with lithium carbonate.
It should be noted that, the chemical formula of the biphenyl lithium is C 12H9 Li, and illustratively, the structural formula of the biphenyl lithium may be:
The chemical formula of dimethylbiphenyl lithium is C 14H13 Li, and illustratively, the structural formula of dimethylbiphenyl lithium may be:
Alternatively, the concentration of the organolithium solution is 0.1mol/L to 2mol/L. Illustratively, the concentration of the organolithium solution is 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, etc. Through reasonable concentration that sets up organic lithium solution, on the one hand can guarantee that organic lithium solution has sufficient concentration in order to realize with the quick reaction of lithium cobaltate, on the other hand can also guarantee that the viscosity of organic lithium solution is in reasonable within range to be convenient for stir, make organic lithium solution can fully react and have faster reaction rate with lithium cobaltate. When the concentration of the organic lithium solution is less than 0.1mol/L, the reaction rate of the organic lithium solution and lithium cobaltate is slower, and the reaction time is longer. When the concentration of the organic lithium solution is more than 2mol/L, the viscosity of the organic lithium solution is larger, the stirring is not facilitated, the reaction rate is lower, and the reaction is insufficient.
In some embodiments, in the step of mixing, the reaction temperature of the positive electrode material of the lithium cobaltate battery and the organic lithium solution is 20-60 ℃ and the reaction time is 0.5-24 h. Illustratively, the reaction temperature is 20 ℃,30 ℃, 40 ℃,50 ℃,60 ℃, etc., and the reaction time is 0.5h, 5h, 10h, 15h, 20h, 24h, etc. The reaction rate can be controlled within a reasonable range by setting a reasonable reaction temperature, and the sufficiency of the reaction can be improved to improve the recovery rate. When the reaction temperature is lower than 20 ℃, the reaction rate is slow, the reaction time is long, and it is difficult to complete the reaction. When the reaction temperature is higher than 60 ℃, the solvent volatilization speed is higher, so that the concentration of the organic lithium solution is changed, and the reaction process is not easy to control. By controlling the reaction time within a reasonable range, the sufficiency of the reaction can be improved, and the recovery rate can be improved. When the reaction time is less than 0.5h, there may be insufficient reaction, resulting in problems of waste of raw materials and low recovery rate. When the reaction time is longer than 24 hours, the reaction time is too long, and the production efficiency is lower.
In some embodiments, in the step of recovering cobalt, the mass ratio of the solid mixture of elemental cobalt and lithium oxide to water is from 1:2 to 1:50. Illustratively, the mass ratio of the solid mixture of elemental cobalt and lithium oxide to water is 1:2, 1:10, 1:20, 1:30, 1:40, 1:50, etc. Through reasonable setting of the mass ratio of the solid mixture of the simple substance cobalt and the lithium oxide to the water, on one hand, the lithium oxide and the water can be completely reacted to ensure that the solid after solid-liquid separation is simple substance cobalt, and on the other hand, the concentration of the product lithium hydroxide can be ensured to facilitate the subsequent utilization of the lithium hydroxide, for example, a lithium hydroxide solution is used as a reaction reagent or the lithium hydroxide solution is evaporated to dryness to obtain lithium hydroxide powder. When the mass ratio of the solid mixture of the simple substance cobalt and lithium oxide to water is less than 1:2, the water is excessively small, and partial lithium oxide possibly does not react with water, and the solid particles after solid-liquid separation also contain a small amount of lithium oxide, so that the cobalt content is impure.
In some embodiments, after the step of recovering elemental cobalt, the recovery method further comprises:
Recovering lithium: and evaporating the aqueous solution of lithium hydroxide to dryness to obtain lithium hydroxide.
By evaporating the aqueous solution of lithium hydroxide to dryness, a lithium hydroxide powder is obtained, and it is understood that the lithium hydroxide powder is also a precursor of a lithium carbonate positive electrode material, and thus the recovery rate of the lithium cobaltate battery positive electrode material is improved.
In other embodiments, after the step of recovering elemental cobalt, the recovery method further comprises:
Recovering lithium: introducing carbon dioxide into the aqueous solution of lithium hydroxide to obtain an aqueous solution of lithium carbonate, and evaporating the aqueous solution of lithium carbonate to dryness to obtain lithium carbonate.
Carbon dioxide is introduced into the aqueous solution of lithium hydroxide to obtain the aqueous solution of lithium carbonate, and then the aqueous solution of lithium hydroxide is evaporated to dryness to obtain lithium carbonate powder, and it is understood that the lithium carbonate powder is a precursor of the positive electrode material of a lithium cobaltate battery, so that the recovery rate of the positive electrode material of the lithium cobaltate battery can be improved, and in addition, the melting point of the lithium carbonate is higher than that of the lithium hydroxide, so that the lithium carbonate is more favorable for being used as the positive electrode material of the lithium cobaltate battery.
Optionally, in the step of recovering lithium, the aqueous solution of lithium carbonate is evaporated to dryness at a temperature of 50 to 400 ℃. Illustratively, the evaporating temperature is 50 ℃, 100 ℃,200 ℃, 300 ℃, 400 ℃, etc. Through setting up reasonable evaporating temperature, can make evaporating time in reasonable within range, the heat-resisting ability requirement to equipment is lower moreover to be favorable to reduction in production cost. When the evaporating temperature is less than 50 ℃, the temperature is too low, the evaporating time is too long, and the production efficiency is low. When the evaporating temperature is higher than 400 ℃, the temperature is too high, so that the requirement on the heat resistance of equipment is high, the production cost is high, and the lithium carbonate can be decomposed and cannot be obtained.
Further, the evaporating temperature of the aqueous solution of lithium carbonate is 100-200 ℃. Illustratively, the evaporating temperature is 100deg.C, 120deg.C, 150deg.C, 180deg.C, 200deg.C, etc. Through further setting up reasonable evaporating temperature, can make evaporating time in reasonable within range, the heat resistance requirement to equipment is lower moreover to be favorable to reduction in production cost.
According to the recovery method of the positive electrode material of the lithium cobaltate battery, disclosed by the application, the acid solution is not generated in the reaction process, the organic solution used in the whole recovery process can be recovered and reused, the post-treatment procedure of waste liquid is not generated, the manufacturing cost is reduced, and the environment is not polluted. In addition, the chemical reaction process of the recovery method is high in controllability, the recovery efficiency of waste lithium cobalt oxide can be greatly improved, the purity of the recovered and converted elemental cobalt and lithium carbonate is high, the recovered and converted elemental cobalt and lithium carbonate can be directly used as reaction raw materials for preparing electrode materials, the secondary purification treatment is not needed, and the material preparation cost is greatly reduced.
The technical scheme of the invention will be further described with reference to the examples and the accompanying drawings.
Example 1
The embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobaltate battery, which comprises the following steps:
Mixing: 100g of lithium cobalt oxide powder obtained by grinding the anode material of the disassembled waste lithium cobalt oxide battery is mixed and stirred with 6L of tetrahydrofuran solution of naphthalene lithium with the concentration of 0.5mol/L for 6h at the temperature of 30 ℃, and then solid-liquid separation is carried out to obtain a solid mixture of simple substance cobalt and lithium oxide and a recyclable organic solution. The solid mixture of elemental cobalt and lithium oxide was then centrifugally washed three times with solvent and dried.
Recovering cobalt: mixing the obtained solid mixture of the simple substance cobalt and lithium oxide with deionized water according to the mass ratio of 1:10, fully reacting, and carrying out solid-liquid separation to obtain an aqueous solution of simple substance cobalt particles and lithium hydroxide.
Recovering lithium: and (3) introducing CO 2 into the aqueous solution of lithium hydroxide, evaporating and drying at 200 ℃ to obtain lithium carbonate powder.
As shown in fig. 1, fig. 1 is a scanning electron microscope image of the waste lithium cobaltate powder and the recovered elemental cobalt powder in the first embodiment, wherein fig. 1a is a scanning electron microscope image of the waste lithium cobaltate powder, and fig. b is a scanning electron microscope image of the recovered elemental cobalt powder, and as can be seen from fig. 1, the particle size of the waste lithium cobaltate powder is about 20 μm, and the particle size of the recovered elemental cobalt is about 5 μm, because the volume expansion and cracking occur when the lithium cobaltate powder reacts with the organic lithium solution, so that the particle size of the recovered elemental cobalt is reduced. As shown in fig. 2, fig. 2 shows the absorption spectrum of the recovered lithium carbonate in the first embodiment, and as can be seen from fig. 2, the recovered lithium carbonate does not contain other impurities, and has high purity.
Example two
The second embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobaltate battery, which comprises the following steps:
Mixing: mixing and stirring 100g of lithium cobalt oxide powder obtained by grinding a positive electrode material of a disassembled waste lithium cobalt oxide battery with 3L of ethylene glycol dimethyl ether solution of biphenyl lithium with the concentration of 1mol/L at 30 ℃ for 12 hours, and then carrying out solid-liquid separation to obtain a solid mixture of simple substance cobalt and lithium oxide and a recyclable organic solution. The solid mixture of elemental cobalt and lithium oxide was then centrifugally washed three times with solvent and dried.
Recovering cobalt: mixing the obtained solid mixture of the simple substance cobalt and lithium oxide with deionized water according to the mass ratio of 1:20, fully reacting, and carrying out solid-liquid separation to obtain an aqueous solution of simple substance cobalt particles and lithium hydroxide.
Recovering lithium: and (3) introducing CO 2 into the aqueous solution of lithium hydroxide, evaporating and drying at 250 ℃ to obtain lithium carbonate powder.
As shown in fig. 3, fig. 3 is an X-ray diffraction chart of the elemental cobalt recovered in the second embodiment, and as can be seen from fig. 3, the obtained powder is pure phase elemental cobalt particles.
Example III
The third embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobaltate battery, which comprises the following steps:
Mixing: and (3) mixing and stirring 100g of lithium cobalt oxide powder obtained by grinding the positive electrode material of the disassembled waste lithium cobalt oxide battery with 2L of ethylene glycol dimethyl ether solution of benzophenone lithium with the concentration of 2mol/L for 0.5h at the temperature of 60 ℃, and then carrying out solid-liquid separation to obtain a solid mixture of elemental cobalt and lithium oxide and a reusable organic solution. And centrifugally cleaning the solid mixture particles of the simple substance cobalt and the lithium oxide by using a solvent for three times and drying.
Recovering cobalt: mixing the obtained solid mixture of the simple substance cobalt and lithium oxide with deionized water according to the mass ratio of 1:50, fully reacting, and carrying out solid-liquid separation to obtain an aqueous solution of simple substance cobalt particles and lithium hydroxide.
Recovering lithium: and (3) introducing CO 2 into the aqueous solution of lithium hydroxide, evaporating and drying at 100 ℃ to obtain lithium carbonate powder.
As shown in fig. 4, fig. 4a and fig. b are respectively a scanning electron microscope picture and an X-ray diffraction diagram of the elemental cobalt recovered in the third embodiment, and as can be seen from fig. 4, the size of the elemental cobalt particles generated by ball milling of the waste lithium cobaltate and then by the recovery method is smaller than 200nm, which is favorable for reducing the temperature and the reaction time required by the recovery reaction, improving the recovery efficiency and reducing the recovery cost. Since the obtained cobalt particles were of nano-scale in size, no diffraction peak of cobalt was observed by X-ray diffraction, and the side surface also confirmed that the obtained cobalt particles had a very small size.
Example IV
The fourth embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobaltate battery, which comprises the following steps:
Mixing: and (3) mixing 100g of lithium cobalt oxide powder obtained by grinding the positive electrode material of the disassembled waste lithium cobalt oxide battery with 3L of dimethyl biphenyl lithium tetrahydrofuran solution with the concentration of 0.1mol/L at 20 ℃ and stirring for 24 hours, and then carrying out solid-liquid separation to obtain a solid mixture of simple substance cobalt and lithium oxide and a reusable organic solution. The solid mixture of elemental cobalt and lithium oxide was then centrifugally washed three times with solvent and dried.
Recovering cobalt: mixing the obtained solid mixture of simple substance cobalt and lithium oxide with deionized water according to the mass ratio of 1:2, mixing and fully reacting, and carrying out solid-liquid separation to obtain the aqueous solution of the simple substance cobalt particles and lithium hydroxide.
Recovering lithium: and (3) introducing CO 2 into the aqueous solution of lithium hydroxide, evaporating and drying at 300 ℃ to obtain lithium carbonate powder.
As shown in fig. 5, fig. 5 is a scanning electron microscope picture of the elemental cobalt recovered in the fourth embodiment, and it can be seen from the picture that the size of the elemental cobalt particles generated after ball milling, recovery and conversion of the waste lithium cobaltate is less than 200nm.
Example five
The fifth embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobaltate battery, which comprises the following steps:
Mixing: 100g of lithium cobalt oxide powder obtained by grinding the positive electrode material of the disassembled waste lithium cobalt oxide battery is mixed and stirred with 2L of n-hexane solution of naphthalene lithium with the concentration of 1.5mol/L for 8 hours at the temperature of 40 ℃, and then solid-liquid separation is carried out to obtain a solid mixture of simple substance cobalt and lithium oxide and a recyclable organic solution. The solid mixture of elemental cobalt and lithium oxide was then centrifugally washed three times with solvent and dried.
Recovering cobalt: mixing the obtained solid mixture of the simple substance cobalt and lithium oxide with deionized water according to the mass ratio of 1:20, fully reacting, and carrying out solid-liquid separation to obtain an aqueous solution of simple substance cobalt particles and lithium hydroxide.
Recovering lithium: and (3) introducing CO 2 into the aqueous solution of lithium hydroxide, evaporating and drying at 150 ℃ to obtain lithium carbonate powder.
As shown in fig. 6, fig. 6 is an X-ray diffraction chart of the lithium carbonate powder recovered in the fifth embodiment, and as can be seen from fig. 6, the lithium carbonate powder does not contain other impurities, is pure-phase lithium carbonate, and can be directly used as a raw material for preparing other lithium battery electrode materials.
Example six
The sixth embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobaltate battery, which is different from the first embodiment in that: the organic lithium is benzophenone lithium, and the reaction time of stirring and mixing the lithium cobaltate powder and tetrahydrofuran solution of the benzophenone lithium is 24 hours.
According to the embodiment, the organic lithium has higher reactivity when the naphthalene lithium is adopted, the reaction rate is faster, the reaction time is shorter, and the production efficiency is improved.
Example seven
The seventh embodiment of the invention discloses a method for recycling a positive electrode material of a lithium cobaltate battery, which is different from the second embodiment in that: the organic lithium is benzophenone lithium, and the reaction time of stirring and mixing the lithium cobaltate powder and the glycol dimethyl ether solution of the benzophenone lithium is 24 hours.
According to the embodiment, the organic lithium has higher reactivity when the biphenyl lithium is adopted, the reaction rate is faster, the reaction time is shorter, and the production efficiency is improved.
The above describes the method for recovering the positive electrode material of the lithium cobaltate battery disclosed in the embodiment of the present invention in detail, and specific examples are applied to the description of the principle and the implementation mode of the present invention, and the description of the above examples is only used for helping to understand the method for recovering the positive electrode material of the lithium cobaltate battery and the core idea thereof; meanwhile, as those skilled in the art will vary in the specific embodiments and application scope according to the idea of the present invention, the present disclosure should not be construed as limiting the present invention in summary.
Claims (7)
1. A method for recovering a positive electrode material of a lithium cobaltate battery, the method comprising the steps of:
Mixing: mixing and stirring a positive electrode material of a lithium cobaltate battery and an organic lithium solution to react, wherein the concentration of the organic lithium solution is 0.1-2 mol/L, the reaction temperature of the positive electrode material of the lithium cobaltate battery and the organic lithium solution is 20-60 ℃, and the reaction time is 0.5-24 h; then carrying out solid-liquid separation to obtain a solid mixture of simple substance cobalt and lithium oxide;
recovering cobalt: mixing the solid mixture of the simple substance cobalt and the lithium oxide with water, wherein the mass ratio of the solid mixture of the simple substance cobalt and the lithium oxide to the water is 1:2-1:50, and then carrying out solid-liquid separation to obtain an aqueous solution of the simple substance cobalt and the lithium hydroxide.
2. The recycling method according to claim 1, characterized in that, before the step of mixing, the recycling method further comprises:
and grinding the positive electrode material of the lithium cobaltate battery into powder.
3. The recovery method according to claim 1, wherein the organolithium in the organolithium solution comprises a lithium complex containing a condensed ring aromatic hydrocarbon; the solvent in the organolithium solution includes: one or more of tetrahydrofuran, ethylene glycol dimethyl ether and n-hexane.
4. The recovery method of claim 3, wherein the organolithium comprises one or more of butyllithium, naphthalyllithium, biphenyllithium, benzophenone lithium, dimethylbiphenyyllithium.
5. The recovery method of any one of claims 1-4, wherein after the step of recovering elemental cobalt, the recovery method further comprises:
recovering lithium: evaporating the aqueous solution of lithium hydroxide to dryness to obtain lithium hydroxide.
6. The recovery method of any one of claims 1-4, wherein after the step of recovering elemental cobalt, the recovery method further comprises:
Recovering lithium: and introducing carbon dioxide into the aqueous solution of lithium hydroxide to obtain an aqueous solution of lithium carbonate, and evaporating the aqueous solution of lithium carbonate to dryness to obtain lithium carbonate.
7. The method according to claim 6, wherein in the step of recovering lithium, the aqueous solution of lithium carbonate is evaporated to dryness at a temperature of 50 to 400 ℃.
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