CN116495787A - Manganese-based compound prepared based on waste lithium battery, preparation method of manganese-based compound and battery - Google Patents
Manganese-based compound prepared based on waste lithium battery, preparation method of manganese-based compound and battery Download PDFInfo
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- CN116495787A CN116495787A CN202310282865.0A CN202310282865A CN116495787A CN 116495787 A CN116495787 A CN 116495787A CN 202310282865 A CN202310282865 A CN 202310282865A CN 116495787 A CN116495787 A CN 116495787A
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- positive electrode
- lithium battery
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- 239000011572 manganese Substances 0.000 title claims abstract description 53
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 claims abstract description 32
- 238000002791 soaking Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000010406 cathode material Substances 0.000 claims abstract description 23
- 239000007770 graphite material Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 11
- 239000010935 stainless steel Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 238000011010 flushing procedure Methods 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 56
- 238000004064 recycling Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000010926 waste battery Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- -1 1, 4-butanediol sodium dodecyl benzene sulfonate Chemical compound 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940099352 cholate Drugs 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- 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
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- C01P2006/40—Electric properties
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application provides a manganese-based compound prepared based on waste lithium batteries, a preparation method thereof and batteries, wherein the method comprises the following steps: soaking the anode material and the cathode material; heating the positive electrode material to obtain a positive electrode active material; soaking and washing the negative electrode material by deionized water to obtain a negative electrode soaking solution, and filtering to obtain a graphite material; acid leaching is carried out on the positive electrode active material to obtain a positive electrode solution; adding the dried graphite material into a surfactant solution to obtain a graphene solution; adding a graphene solution and a potassium permanganate solution into a positive electrode solution, stirring and/or performing ultrasonic treatment on the mixed solution, transferring the treated solution into a stainless steel autoclave, and heating; after the reaction was cooled, the obtained precipitate was filtered and dried to obtain a manganese-based composite. The cost for preparing manganese dioxide particles can be greatly reduced, and the recycling and reutilization of the anode and cathode materials of the waste batteries are realized.
Description
Technical Field
The application relates to the field of lithium battery recovery, in particular to a manganese-based compound prepared based on waste lithium batteries, a preparation method thereof and batteries.
Background
The lithium ion battery has the advantages of high energy density, high working voltage, high safety performance and the like, and is widely applied to the fields of electric automobiles, power grid energy storage and the like. When the new energy automobile is kept in an increasing amount year by year, but is limited by the service life of the lithium ion battery, the new energy automobile enters a large-scale retired stage.
Retired lithium ion batteries have many potential safety hazards, and if the lithium ion batteries are not effectively treated, environmental pollution and waste of noble metals can be caused. And the recycling of the battery can protect the ecological environment, improve the comprehensive utilization of resources and effectively relieve the external dependence of lithium, cobalt and other resources.
At present, the recovery of the lithium ion battery is mainly the recovery of the active substances of the positive electrode, including the recovery of elements such as lithium, nickel, cobalt and the like, and the lack of a graphite recovery and utilization means for the negative electrode causes the waste of graphite resources. Therefore, how to recycle graphite in waste lithium batteries is a continuing concern for those skilled in the art.
Disclosure of Invention
One of the purposes of the application is to provide a preparation method of a manganese-based compound based on waste lithium batteries, so as to solve the technical problems.
The second object of the present application is to provide a manganese-based composite obtained by the above-mentioned method for preparing a manganese-based composite based on waste lithium batteries.
It is still another object of the present application to provide a battery having a positive electrode including the manganese-based composite prepared by the above-mentioned method for preparing a manganese-based composite based on a waste lithium battery.
The application can be realized as follows:
in a first aspect, an embodiment of the present application provides a method for preparing a manganese-based composite based on a waste lithium battery, including the steps of:
(1) Soaking the anode material and the cathode material of the waste lithium battery by using an organic solution; heating the soaked positive electrode material to obtain a positive electrode active material; soaking and flushing the soaked negative electrode material again by adopting deionized water to obtain negative electrode soaking liquid, filtering the negative electrode soaking liquid to obtain a graphite material, and drying the graphite material;
(2) Acid leaching is carried out on the positive electrode active material subjected to heat treatment by adopting an acid solution and hydrogen peroxide according to a preset first solid-to-liquid ratio so as to obtain a positive electrode solution; adding the dried graphite material into a surfactant solution according to a preset second solid-to-liquid ratio, and performing ultrasonic treatment to obtain a graphene solution;
(3) Adding the graphene solution and the potassium permanganate solution into the positive electrode solution obtained in the step (2) according to a preset third proportion, stirring and/or carrying out ultrasonic treatment on the mixed solution, transferring the treated solution into a stainless steel autoclave, and heating;
(4) After the reaction cooling in step (3), the obtained precipitate is filtered and dried to obtain a manganese-based composite.
In a second aspect, an embodiment of the present application provides a manganese-based composite prepared based on a waste lithium battery, where the manganese-based composite is obtained by the above method for preparing a manganese-based composite based on a waste lithium battery.
In a third aspect, embodiments of the present application provide a battery comprising the manganese-based composite described above.
Compared with the prior art, the manganese-based composite prepared based on the waste lithium battery, the preparation method thereof and the battery, wherein the method comprises the following steps: (1) Soaking the anode material and the cathode material of the waste lithium battery by using an organic solution; heating the soaked positive electrode material to obtain a positive electrode active material; soaking and flushing the soaked negative electrode material again by adopting deionized water to obtain negative electrode soaking liquid, filtering the negative electrode soaking liquid to obtain a graphite material, and drying the graphite material; (2) Acid leaching is carried out on the positive electrode active material subjected to heat treatment by adopting an acid solution and hydrogen peroxide according to a preset first solid-to-liquid ratio so as to obtain a positive electrode solution; adding the dried graphite material into a surfactant solution according to a preset second solid-to-liquid ratio, and performing ultrasonic treatment to obtain a graphene solution; (3) Adding the graphene solution and the potassium permanganate solution into the positive electrode solution obtained in the step (2) according to a preset third proportion, stirring and/or carrying out ultrasonic treatment on the mixed solution, transferring the treated solution into a stainless steel autoclave, and heating; (4) After the reaction cooling in step (3), the obtained precipitate is filtered and dried to obtain a manganese-based composite. The manganese dioxide/graphene composite material can be effectively and simply recycled by adopting the retired lithium battery, the cost for preparing manganese dioxide particles can be greatly reduced, and the recycling and reutilization of the anode and cathode materials of the waste battery can be realized.
In order to make the above objects, features and advantages of the present application more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting in scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a manganese dioxide/graphene composite;
FIG. 2 is an SEM image of a manganese dioxide/graphene composite;
fig. 3 is a charge-discharge curve of an aqueous zinc ion battery assembled using a manganese dioxide/graphene composite.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
As described above, the prior art lacks means for recycling graphite for the negative electrode, resulting in waste of graphite resources. The manganese-based composite preparation method based on the waste lithium battery can effectively and simply recycle and prepare the manganese dioxide/graphene composite material by adopting the retired lithium battery, can greatly reduce the cost for preparing manganese dioxide particles, and can realize the recycling and reutilization of the anode and cathode materials of the waste battery. Specifically, in the process of recycling the anode material and the cathode material of the waste lithium battery, graphene is prepared by recycling the anode material, and manganese dioxide is prepared by recycling the cathode material, so that a manganese dioxide/graphene composite material is prepared, and sustainable development of battery recycling is realized. For specific implementation steps, please refer to the following.
The application provides a preparation method of a manganese-based compound based on a waste lithium battery, which comprises the following steps:
(1) Soaking the anode material and the cathode material of the waste lithium battery by using an organic solution; heating the soaked positive electrode material to obtain a positive electrode active material; soaking and flushing the soaked negative electrode material again by adopting deionized water to obtain negative electrode soaking liquid, filtering the negative electrode soaking liquid to obtain a graphite material, and drying the graphite material;
(2) Acid leaching is carried out on the positive electrode active material subjected to heat treatment by adopting an acid solution and hydrogen peroxide according to a preset first solid-to-liquid ratio so as to obtain a positive electrode solution; adding the dried graphite material into a surfactant solution according to a preset second solid-to-liquid ratio, and performing ultrasonic treatment to obtain a graphene solution;
(3) Adding the graphene solution and the potassium permanganate solution into the positive electrode solution obtained in the step (2) according to a preset third proportion, stirring and/or carrying out ultrasonic treatment on the mixed solution, transferring the treated solution into a stainless steel autoclave, and heating;
(4) After the reaction cooling in step (3), the obtained precipitate is filtered and dried to obtain a manganese-based composite.
(5) Adding sodium carbonate to the filtrate in the step (4) to obtain a lithium carbonate precipitate.
It is understood that lithium recovery can be achieved by obtaining lithium carbonate precipitates, further improving the utilization rate of waste resources.
It is understood that the heat treatment in step (2) is followed by heating the positive electrode material in step (1).
Optionally, the second solid to liquid ratio is selected to be 1g/L to 20g/L.
The positive electrode of the waste lithium battery is any one of lithium manganate, lithium nickel manganate, lithium cobalt manganate and lithium nickel cobalt manganate, and the negative electrode is a graphite negative electrode.
Before the step (1) is executed, the completely discharged waste lithium battery can be disassembled, and the plastic shell of the lithium battery is removed to obtain the anode material and the cathode material of the waste lithium battery respectively. Alternatively, the lithium battery may be discharged by a discharge circuit so that its voltage is less than a preset safety threshold. The waste lithium battery can be soaked in the sodium chloride solution, so that the discharging effect is achieved.
In a preferred embodiment, the organic solution in step (1) may be a dimethyl carbonate solution. The anode material and the cathode material of the waste lithium battery are soaked by the organic solution, and electrolyte in the anode material and the cathode material can be removed based on the principle of similar compatibility.
In a preferred embodiment, the positive electrode material immersed in the organic solution in step (1) may be heated in a muffle furnace or other container at a temperature ranging from 400 ℃ to 900 ℃ for 4 to 10 hours, preferably at a temperature ranging from 500 ℃ to 800 ℃ for 4 to 6 hours. The binder and the conductive agent (such as acetylene black) in the cathode material can be removed by heating, and the impurity part in the cathode material is fully combusted on the premise of not causing energy waste by limiting the temperature range and the heating time.
When the soaked positive electrode material is heated in the step (1), not only a positive electrode active material but also an aluminum foil can be obtained, so that the aluminum foil can be recycled.
In the step (1), the soaked negative electrode material is soaked and rinsed again with deionized water to remove the binder in the negative electrode material. In the process, the copper foil can be recovered by filtering and drying, so that the recycling is realized.
In a preferred embodiment, the graphite material in step (1) is baked in a vacuum environment, the graphite material comprising graphitic carbon.
It should be appreciated that the graphite material may be dried in a vacuum oven which may be brought to a higher drying rate at a lower temperature, with sufficient heat utilization, and is suitable for drying heat sensitive materials and materials containing a compatibilizer and solvents to be recovered.
Optionally, the graphite material obtained after filtration is placed in a vacuum oven, the oven is heated to 80 ℃ to 150 ℃ and the drying time is 24 hours. It should be noted that when the drying temperature of the oven is 80 ℃, the drying effect can be ensured, and the waste of energy sources can be avoided.
Alternatively, the acidic solution in step (2) may be an organic acid or an inorganic acid. In one possible scenario, the acidic solution uses an inorganic acid, which is cheaper and safer.
In a preferred embodiment, in the step (2), the first solid-to-liquid ratio is 50-200g/L, the acidic solution is 1-5mol/L sulfuric acid solution, the volume ratio of the hydrogen peroxide to the sulfuric acid solution is 2-10%, and the acid leaching is performed for 30-300 min. Preferably, the acid solution is sulfuric acid solution with the volume ratio of 2mol/L, the hydrogen peroxide solution to the sulfuric acid solution is 4%, and the acid leaching is carried out for 30-60 min. Hydrogen peroxide is used as a reducing agent.
The acidic solution may be hydrochloric acid solution, and the reducing agent may be sodium sulfite. The mass ratio of the acid to the positive electrode material is 5:1-20 (L/g).
It should be noted that, if the first solid-to-liquid ratio is too small, for example, less than 50g/L, the positive electrode active material may be not completely dissolved, and if the first solid-to-liquid ratio is too large, for example, more than 200g/L, the PH value and the manganese ion concentration of the solution may be too low, which is unfavorable for the subsequent synthesis of manganese dioxide. Through reasonable setting of the first solid-to-liquid ratio in the application, the positive electrode active material can be completely dissolved, the PH value and manganese ions in the solution are guaranteed, and the subsequent synthesis of manganese dioxide is facilitated.
In the present application, the first solid-to-liquid ratio may be selected to be 100g/L, at which the reaction speed is faster, and the conversion can be sufficiently completed.
In a preferred embodiment, the concentration of the surfactant solution is 0.01mol/L and the second solid to liquid ratio is 20g/L. The surfactant solution can be sodium cholate solution, deoxysodium cholate solution, 1, 4-butanediol sodium dodecyl benzene sulfonate and other surfactants, and the ultrasonic time is 1-4 h.
In a preferred embodiment, graphene is added to a positive electrode solution containing 0.001mol of manganese ions in an amount of 5 to 15wt% based on the mass of manganese dioxide formed, and then Mn is added 2+ :MnO- 4 - 0.1mol/L potassium permanganate solution with the mol ratio of 1:1-1:6.
The addition of a proper amount of graphene can ensure sufficient compounding, and excessive graphene can cause agglomeration, so that the performance of the battery is poor.
Optionally, the mass ratio of the potassium permanganate solution to the positive electrode solution is 5:1-10:1.
Optionally, in the step (3), the mixed solution is stirred for 1 to 2 hours, and then subjected to ultrasonic treatment for 20 to 60 minutes, so that the mixed solution is more uniformly dispersed. The autoclave may be a polytetrafluoroethylene lined stainless steel autoclave. In the step (3), the polytetrafluoroethylene lining stainless steel autoclave is controlled to react for 6-24 hours at the temperature of 100-150 ℃. And the crystal form of the manganese dioxide is adjusted to obtain alpha manganese dioxide.
It should be noted that different hydrothermalsThe temperature and the hydrothermal time can influence the crystal morphology of the generated product, the electrochemical properties of manganese dioxide with different crystal forms are different, and the longer the hydrothermal time is, the easier the alpha-MnO is formed 2 。
In a preferred embodiment, after the reaction is cooled to room temperature in step (3), the obtained precipitate is washed, filtered and dried for a period of 6 to 18 hours to obtain the manganese-based composite. The manganese-based composite may be a manganese dioxide-graphene composite.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
(1) Disassembling the completely discharged retired lithium manganate battery, removing the plastic shell, and then soaking the anode and cathode materials in dimethyl carbonate (DMC) to remove electrolyte. The positive electrode material is placed in a muffle furnace and heated to 600 ℃, kept for 5 hours, binder and acetylene black are removed, aluminum foil and positive electrode active substances are separated, and the aluminum foil is recovered. The negative electrode material is soaked and washed by deionized water, the binder is removed, and the copper foil is recovered. The graphite soaking solution of the negative electrode is filtered and then placed in a vacuum oven to be dried for 24 hours at 80 ℃.
(2) And (3) carrying out acid leaching on the positive electrode active material subjected to heat treatment by adopting 2mol/L sulfuric acid and 4% (vol/vol) hydrogen peroxide for 60min according to the solid-liquid ratio of 100 g/L. And adding negative graphite into sodium cholate solution for ultrasonic treatment to prepare graphene solution.
(3) Adding graphene into a positive electrode solution containing 0.001mol of manganese ions according to 5wt% of the mass of manganese dioxide, then adding a potassium permanganate solution containing 0.1mol/L of MnO 4-mol ratio of 3:2, stirring for 1h, uniformly dispersing by ultrasonic for 30min, transferring into a polytetrafluoroethylene lining stainless steel autoclave, and reacting at 120 ℃ for 12h.
(4) And after the reaction is cooled to room temperature, washing, drying, filtering and drying the obtained precipitate for 12 hours to obtain the high-performance graphene composite manganese dioxide cathode material. Adding sodium carbonate into the filtrate to obtain lithium carbonate precipitate, and realizing lithium recovery.
Example 2
(1) Disassembling the completely discharged retired cobalt lithium manganate battery, removing the plastic shell, and then soaking the anode and cathode materials in dimethyl carbonate (DMC) to remove electrolyte. The positive electrode material is placed in a muffle furnace and heated to 600 ℃, kept for 5 hours, binder and acetylene black are removed, aluminum foil and positive electrode active substances are separated, and the aluminum foil is recovered. The negative electrode material is soaked and washed by deionized water, the binder is removed, and the copper foil is recovered. The graphite soaking solution of the negative electrode is filtered and then placed in a vacuum oven to be dried for 24 hours at 80 ℃.
(2) And (3) carrying out acid leaching on the positive electrode active material subjected to heat treatment by adopting 2mol/L sulfuric acid and 4% (vol/vol) hydrogen peroxide for 60min according to the solid-liquid ratio of 100 g/L. And adding negative graphite into sodium cholate solution for ultrasonic treatment to prepare graphene solution.
(3) Adding graphene into a positive electrode solution containing 0.001mol of manganese ions according to 10wt% of the mass of manganese dioxide, then adding a potassium permanganate solution containing 0.1mol/L of MnO 4-mol ratio of 3:2, stirring for 1 hour, uniformly dispersing by ultrasonic for 30 minutes, transferring into a polytetrafluoroethylene lining stainless steel autoclave, and reacting for 12 hours at 120 ℃.
(4) And after the reaction is cooled to room temperature, washing, drying, filtering and drying the obtained precipitate for 12 hours to obtain the high-performance graphene composite manganese dioxide cathode material. Adding sodium carbonate into the filtrate to obtain lithium carbonate precipitate, and realizing lithium recovery.
Example 3
(1) Disassembling the completely discharged retired nickel cobalt lithium manganate battery, removing the plastic shell, and then soaking the anode and cathode materials in dimethyl carbonate (DMC) to remove electrolyte. The positive electrode material is placed in a muffle furnace and heated to 600 ℃, kept for 5 hours, binder and acetylene black are removed, aluminum foil and positive electrode active substances are separated, and the aluminum foil is recovered. The negative electrode material is soaked and washed by deionized water, the binder is removed, and the copper foil is recovered. The graphite soaking solution of the negative electrode is filtered and then placed in a vacuum oven to be dried for 24 hours at 80 ℃.
(2) And (3) carrying out acid leaching on the positive electrode active material subjected to heat treatment by adopting 2mol/L sulfuric acid and 4% hydrogen peroxide for 60min according to the solid-liquid ratio of 100 g/L. And adding negative graphite into sodium cholate solution for ultrasonic treatment to prepare graphene solution.
(3) Adding graphene into a positive electrode solution containing 0.001mol of manganese ions according to 15wt% of the mass of manganese dioxide, then adding a potassium permanganate solution containing 0.1mol/L of MnO 4-mol ratio of 3:2, stirring for 1 hour, uniformly dispersing by ultrasonic for 30 minutes, transferring into a polytetrafluoroethylene lining stainless steel autoclave, and reacting for 12 hours at 120 ℃.
(4) And after the reaction is cooled to room temperature, washing, drying, filtering and drying the obtained precipitate for 12 hours to obtain the high-performance graphene composite manganese dioxide cathode material. Adding sodium carbonate into the filtrate to obtain lithium carbonate precipitate, and realizing lithium recovery.
In a preferred embodiment, the prepared manganese-based composite (for example, manganese dioxide-graphene composite) can be used as an anode active material, the manganese dioxide-graphene composite, acetylene black and polyvinylidene fluoride are prepared into slurry according to the ratio of 7:2:1, the slurry is uniformly coated on a steel mesh, the steel mesh is used as an anode, a zinc sheet is used as a cathode, and after the cathode is assembled into a button cell in air, a constant current charge-discharge test is performed, wherein the voltage interval is 0.8-1.8V.
Referring to fig. 1-3, fig. 1 is an XRD pattern of a manganese dioxide/graphene composite material; FIG. 2 is an SEM image of a manganese dioxide/graphene composite; fig. 3 is a charge-discharge curve of an aqueous zinc ion battery assembled using a manganese dioxide/graphene composite.
Wherein XRD refers to X-ray diffraction, diffraction peaks of the synthesized product are obvious, and all diffraction peaks can be matched with alpha-MnO 2 Standard cards are in one-to-one correspondence, and the synthesized manganese dioxide is indicated to be alpha-MnO 2 The method comprises the steps of carrying out a first treatment on the surface of the SEM refers to a scanning electron microscope image, the morphology of the synthesized product is nanowire, and the synthesized product is partially agglomerated; and a charge-discharge curve graph, wherein when the manganese-based compound is an anode active material, the first-circle discharge capacity reaches 250mAh/g, and the charge capacity is 275mAh/g. Correspondingly, the application also provides a manganese-based compound obtained by the preparation method of the manganese-based compound based on the waste lithium battery, which can be a manganese dioxide-graphene compound.
In addition, the application also provides a battery, the anode of which is prepared by the manganese-based composite obtained by the preparation method of the manganese-based composite based on the waste lithium battery, and the manganese-based composite, acetylene black and polyvinylidene fluoride are prepared into slurry according to the ratio of 7:2:1, and the slurry is uniformly coated on a steel mesh to serve as the anode.
Optionally, the zinc sheet is used as a negative electrode, and after the button cell is assembled in the air, constant-current charge and discharge tests are carried out, wherein the voltage interval is 0.8-1.8V.
In summary, the preparation method of the manganese-based composite based on the waste lithium battery provided by the embodiment of the application comprises the following steps: (1) Soaking the anode material and the cathode material of the waste lithium battery by using an organic solution; heating the soaked positive electrode material to obtain a positive electrode active material; soaking and flushing the soaked negative electrode material again by adopting deionized water to obtain negative electrode soaking liquid, filtering the negative electrode soaking liquid to obtain a graphite material, and drying the graphite material; (2) Acid leaching is carried out on the positive electrode active material subjected to heat treatment by adopting an acid solution and hydrogen peroxide according to a preset first solid-to-liquid ratio so as to obtain a positive electrode solution; adding the dried graphite material into a surfactant solution according to a preset second solid-to-liquid ratio, and performing ultrasonic treatment to obtain a graphene solution; (3) Adding the graphene solution and the potassium permanganate solution into the positive electrode solution obtained in the step (2) according to a preset third proportion, stirring and/or carrying out ultrasonic treatment on the mixed solution, transferring the treated solution into a stainless steel autoclave, and heating; (4) After the reaction cooling in step (3), the obtained precipitate is filtered and dried to obtain a manganese-based composite. The manganese dioxide/graphene composite material can be effectively and simply recycled by adopting the retired lithium battery, the cost for preparing manganese dioxide particles can be greatly reduced, and the recycling and reutilization of the anode and cathode materials of the waste battery can be realized.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the manganese-based compound based on the waste lithium battery is characterized by comprising the following steps of:
(1) Soaking the anode material and the cathode material of the waste lithium battery by using an organic solution; heating the soaked positive electrode material to obtain a positive electrode active material; soaking and flushing the soaked negative electrode material again by adopting deionized water to obtain negative electrode soaking liquid, filtering the negative electrode soaking liquid to obtain a graphite material, and drying the graphite material;
(2) Acid leaching is carried out on the positive electrode active material subjected to heat treatment by adopting an acid solution and hydrogen peroxide according to a preset first solid-to-liquid ratio so as to obtain a positive electrode solution; adding the dried graphite material into a surfactant solution according to a preset second solid-to-liquid ratio, and performing ultrasonic treatment to obtain a graphene solution;
(3) Adding the graphene solution and the potassium permanganate solution into the positive electrode solution obtained in the step (2) according to a preset third proportion, stirring and/or carrying out ultrasonic treatment on the mixed solution, transferring the treated solution into a stainless steel autoclave, and heating;
(4) After the reaction cooling in step (3), the obtained precipitate is filtered and dried to obtain a manganese-based composite.
2. The method for preparing a manganese-based composite based on a waste lithium battery according to claim 1, further comprising the step (5);
(5) Adding sodium carbonate to the filtrate in the step (4) to obtain a lithium carbonate precipitate.
3. The method for preparing the manganese-based composite based on the waste lithium battery as claimed in claim 1, wherein the soaked positive electrode material is heated in the step (1) and is further used for obtaining aluminum foil, the heating temperature is 400-900 ℃, and the heating time is 4-10 hours.
4. The method for preparing the manganese-based composite based on the waste lithium battery according to claim 1, wherein deionized water is used for soaking and flushing the soaked negative electrode material in the step (1) again, and the method is also used for obtaining copper foil.
5. The method for preparing a manganese-based composite according to claim 1, wherein the graphite material is baked in a vacuum environment in step (1), and the graphite material comprises graphite carbon.
6. The method for preparing the manganese-based composite based on the waste lithium battery as claimed in claim 1, wherein in the step (2), the first solid-to-liquid ratio is 50-200g/L, the acidic solution is sulfuric acid solution of 1-5mol/L, the volume ratio of the hydrogen peroxide to the sulfuric acid solution is 2-10%, and the acid leaching is performed for 30-300 min.
7. The method for preparing a manganese-based composite based on a waste lithium battery as claimed in claim 1, wherein the manganese-based composite is a manganese dioxide-graphene composite.
8. The method for preparing a manganese-based composite based on a waste lithium battery according to claim 1, wherein the organic solution is a dimethyl carbonate solution.
9. A manganese-based composite prepared based on a waste lithium battery, characterized by being obtained by the method for preparing a manganese-based composite based on a waste lithium battery according to any one of claims 1 to 8.
10. A battery comprising the manganese-based composite of claim 9.
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