CN114597534A - Method for in-situ repairing of waste ternary lithium battery cathode material through supercritical water - Google Patents
Method for in-situ repairing of waste ternary lithium battery cathode material through supercritical water Download PDFInfo
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- CN114597534A CN114597534A CN202210315399.7A CN202210315399A CN114597534A CN 114597534 A CN114597534 A CN 114597534A CN 202210315399 A CN202210315399 A CN 202210315399A CN 114597534 A CN114597534 A CN 114597534A
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- lithium battery
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 105
- 239000002699 waste material Substances 0.000 title claims abstract description 90
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000010406 cathode material Substances 0.000 title claims description 59
- 239000010405 anode material Substances 0.000 claims abstract description 72
- 238000001035 drying Methods 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 32
- 238000005188 flotation Methods 0.000 claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- 239000007772 electrode material Substances 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 230000001502 supplementing effect Effects 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 33
- 239000011572 manganese Substances 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 17
- 239000006258 conductive agent Substances 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000005539 carbonized material Substances 0.000 claims description 12
- 238000005067 remediation Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 7
- 229940044175 cobalt sulfate Drugs 0.000 claims description 7
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 239000011656 manganese carbonate Substances 0.000 claims description 7
- 235000006748 manganese carbonate Nutrition 0.000 claims description 7
- 229940093474 manganese carbonate Drugs 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 7
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 7
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052743 krypton Inorganic materials 0.000 claims description 6
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052754 neon Inorganic materials 0.000 claims description 6
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 22
- 230000002950 deficient Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 238000004080 punching Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- -1 Li)2CO3 Chemical class 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 241000219991 Lythraceae Species 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 235000014360 Punica granatum Nutrition 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 4
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 241000931705 Cicada Species 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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Abstract
The invention discloses a method for in-situ repairing a waste ternary lithium battery anode material by supercritical water, which aims at solving the problems of relatively complex recovery treatment, high energy consumption and a series of environmental pollution of the waste ternary lithium battery anode material, firstly sorting the waste anode material from electrode materials of the waste ternary lithium battery after being disassembled and crushed, placing the waste anode material in a supercritical water system, measuring the contents of Ni, Co, Mn and Li in the system, adding elements with insufficient contents compared with standard finished product anode materials into the system for supplementing, so that the Ni, Co and Mn elements in the system reach a set molar ratio, performing in-situ repairing on the waste anode material in the supercritical water system after supplementing, finally performing flotation, filtration and drying to obtain the finished product ternary lithium battery anode material, realizing in-situ repairing and regeneration of the waste ternary lithium battery anode material, thereby reducing the recovery cost of the waste ternary lithium battery anode material, the recovery efficiency of the battery is improved.
Description
Technical Field
The invention relates to the technical field of waste battery repair, in particular to a method for repairing a waste ternary lithium battery anode material in situ by supercritical water.
Background
As a new energy structure, the lithium battery has the advantages of high specific energy, long service life, good cycle performance, environmental friendliness and the like, and is widely applied to the fields of electronics, communication, new energy automobiles and the like. The lithium battery has been developed for more than 40 years in China, the annual output of the lithium battery in China is 157.22 hundred million according to statistics, the lithium battery industry has been the first in the world in cicada for many years, the annual output is continuously increased, but the defects exist in the initial industry standard, so that the lithium battery production of batches is uneven, and the peak time of battery scrapping is reached in recent years.
The content of noble metal contained in the positive electrode of the lithium battery is far higher than that of natural metal mineral reserves, and the recovery value is extremely high. The anode material can be divided into lithium iron phosphate and ternary material (nickel cobalt manganese lithium). In the existing recycling process, the waste lithium batteries are further subjected to positive and negative electrode separation after being disassembled, and a series of complex processes are often performed. Taking a ternary battery as an example, in the battery, nickel element mainly plays a role in improving the volume energy density of the battery, cobalt element plays a role in improving the stability and prolonging the service life of the battery (determining the charge-discharge speed and rate performance of the battery), and manganese element mainly plays a role in improving the safety and stability of the battery. In the anode material of the ternary lithium battery, one of the three metal elements is not necessary. In the traditional recovery process of the waste ternary lithium battery, metals (Ni, Co, Mn and Li) in the anode powder are often extracted and converted into corresponding soluble salts (such as Li)2CO3、CoSO4、 MnSO4And NiSO4) And then the regeneration of the ternary lithium battery anode material is realized through subsequent physical and chemical steps (such as replacement, precipitation, roasting and the like). But because the subsequent steps are relatively complicated and can bring a series of environmental pollution problems, the method greatly improvesThe recovery cost is reduced.
Disclosure of Invention
Aiming at the problems of relatively complex recovery treatment, high energy consumption and a series of environmental pollution of the anode material of the waste ternary lithium battery, the invention provides the method for in-situ repairing the anode material of the waste ternary lithium battery by using the supercritical water, and the in-situ repairing regeneration of the anode material of the waste ternary lithium battery can be realized, so that the recovery cost of the anode material of the waste ternary lithium battery is reduced, and the recovery efficiency of the battery is improved.
In order to achieve the above purpose, the technical scheme adopted by the invention comprises the following steps:
1) sorting the waste positive electrode materials of the disassembled and crushed waste ternary lithium battery;
2) placing the waste anode material in a supercritical water system, and measuring the contents of Ni, Co, Mn and Li in the system;
3) adding elements with insufficient content compared with standard finished cathode materials into the system for supplementing materials so as to enable the Ni, Co and Mn elements in the system to reach a set molar ratio;
4) after the material is supplemented, the waste anode material is subjected to in-situ remediation in a supercritical water system, and the supercritical water system has the following conditions: the water temperature is more than 374 ℃, the pressure is more than 22.1MPa, and the in-situ repair time is 40-60 min;
5) after in-situ repair, carrying out flotation to remove the conductive agent and residual carbonized materials;
6) and filtering after flotation, and drying the filter material to obtain the finished ternary lithium battery cathode material.
Further, foam sorting is adopted in the step 1).
Further, in the step 2), the contents of Ni, Co, Mn and Li in the system are determined by ICP detection.
Further, the elements with insufficient content in the step 3) are fed according to a set molar ratio under alkaline conditions.
Further, when the material is supplemented in the step 3), the Ni element adopts one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide and nickel carbonyl.
Further, when supplementing materials in the step 3), the Co element is one or more of cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt chloride.
Further, when the Mn element is supplemented in the step 3), one or more of manganese sulfate, manganese carbonate and manganese chloride is adopted.
Further, the drying in the step 6) is performed under vacuum or protective gas.
Further, the protective gas comprises one or more of nitrogen, carbon dioxide, helium, argon, neon, krypton and xenon.
Further, the drying temperature in the step 6) is 40-70 ℃, and the drying time is 10-60 min.
Compared with the prior art, the method disclosed by the invention has the advantages that the waste and old ternary lithium battery anode material is relatively complex in recycling treatment, high in energy consumption and capable of causing a series of environmental pollution problems, firstly, the electrode material of the waste and old ternary lithium battery after being disassembled and crushed is sorted out, the waste and old ternary lithium battery anode material is placed in a supercritical water system, the content of Ni, Co, Mn and Li elements in the system is measured, elements with insufficient content compared with standard finished product anode materials are added into the system for supplementing, so that the Ni, Co and Mn elements in the system reach a set molar ratio, the waste and old anode material is subjected to in-situ remediation in the supercritical water system after being supplemented, finally, the finished product ternary lithium battery anode material is obtained through flotation, filtration and drying, and the in-situ remediation of the waste and old ternary lithium battery anode material is realized by utilizing the supercritical water. Supercritical water is water in which the density of water expanded by high temperature and the density of water vapor compressed by high pressure are exactly the same when the pressure and temperature of the water reach a certain value. Under the condition of supercritical water, substances can generate a super-dynamic reaction, and the reaction rate can be increased by more than 100 times, so that the recycled anode material of the waste ternary lithium battery can be repaired in situ under a supercritical water system. In addition, the element content in the system can be measured by an ICP (inductively coupled plasma) testing technology before the repairing operation, the elements with insufficient content are added to meet the required molar ratio, and the in-situ regeneration of the anode material of the waste ternary lithium battery in the reaction system can be realized. Compared with the traditional roasting process, the supercritical water system has the advantages of safety, no toxicity, nonflammability, low price and environmental friendliness, reduces the recovery cost of the anode material of the waste ternary lithium battery, and improves the recovery efficiency of the battery.
Drawings
FIG. 1 is a flow chart of the method of the present invention;
FIG. 2 is an XRD spectrum of the in-situ repaired ternary lithium battery positive electrode material of the invention;
FIG. 3 is an SEM image of an in-situ repaired ternary lithium battery positive electrode material of the invention;
FIG. 4 is a first charge-discharge curve diagram of a button cell prepared from the in-situ repaired ternary lithium battery cathode material of the present invention at 0.2C;
fig. 5 is a cycle performance diagram of a button cell prepared from the in-situ repaired ternary lithium battery cathode material of the invention after 180 cycles at 1C.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a method for in-situ repairing of a waste ternary lithium battery cathode material by supercritical water, and particularly relates to a method shown in figure 1, which comprises the following steps:
step one, sorting. Sorting the electrode materials of the disassembled and crushed waste ternary lithium battery, and dividing the electrode materials into waste ternary positive electrode materials and waste negative electrode materials according to different physical and chemical properties by adopting foam sorting;
the anode material of the disassembled and crushed ternary waste lithium battery is left at the bottom, and the waste cathode material floats upwards.
And step two, measuring. Waste anode materials are placed in a supercritical water system, and the content of Ni, Co, Mn and Li in the supercritical water system is measured by an ICP (inductively coupled plasma) technology.
And step three, feeding materials. Supplementing elements lacking in the waste ternary material according to the molar ratio of the elements.
The material supplement is based on the fact that elements with insufficient content in the waste ternary cathode material are supplemented according to the molar ratio of the required elements by ICP (inductively coupled plasma) technology measurement compared with a standard finished cathode material. The Ni element is supplemented by one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide and nickel carbonyl; the Co element is supplemented by one or more of cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt chloride; mn element is supplemented by one or more of manganese sulfate, manganese carbonate and manganese chloride.
And step four, repairing. Repairing the supplemented waste ternary cathode material in a supercritical water system, and simultaneously removing residual electrolyte, adhesive (PVDF) and other substances;
wherein, the condition of the supercritical water system is as follows: the temperature (T) of water is more than 374 ℃, the pressure (P) is more than 22.1MPa, and the time is 40-60 min, and the SEI film on the surface of the anode material of the waste ternary lithium battery can be cleaned under the condition, so that the aim of in-situ repairing the ternary anode material is fulfilled.
And step five, floating. The conductive agent (super P) and residual carbonized material were removed by flotation.
The conductive agent (super P) and the residual carbonized material are placed on the upper layer of the solution system in the flotation process through the flotation process, and the repaired ternary positive electrode material is placed at the bottom of the system.
And step six, filtering. The filter material is an electrode material of the repaired ternary lithium battery.
And filtering the repaired electrode material of the ternary lithium battery from a supercritical water system to form a filter cake through filtering operation.
And step seven, drying. And drying the obtained electrode material filter cake of the repaired ternary lithium battery under the condition of vacuum or protective atmosphere to obtain the dried anode material of the finished ternary lithium battery.
The present invention will be described in detail with reference to specific examples.
Example 1
The process for in-situ repairing the anode material (namely, the molar ratio of nickel, cobalt and manganese elements in the anode material is 1:1:1) of the waste ternary 111 lithium battery by using supercritical water, provided by the embodiment, comprises the following steps:
step one, sorting. Sorting the electrode materials of the disassembled and crushed waste ternary (111) lithium batteries, and classifying the electrode materials into waste ternary positive electrode materials and waste negative electrode materials according to different physical and chemical properties by adopting foam sorting;
and the anode material of the disassembled and crushed ternary waste lithium battery is left at the bottom, and the cathode material floats upwards.
And step two, measuring. And (3) measuring the contents of Ni, Co, Mn and Li in the supercritical water system by using an ICP (inductively coupled plasma) technology.
And step three, feeding materials. Supplementing elements lacking in the waste ternary material according to the molar ratio of nickel, cobalt and manganese elements of 1:1: 1.
The feeding is carried out on the elements with insufficient content in the waste lithium iron phosphate positive electrode material according to the molar ratio of Ni to Co to Mn of 1 to 1 under the alkaline condition based on ICP (inductively coupled plasma) technology measurement.
Further, the deficient Ni element can be supplemented by one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide and nickel carbonyl.
Further, the deficient Co element can be supplemented by one or more of cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt chloride.
Further, the deficient Mn element can be supplemented by one or more of manganese sulfate, manganese carbonate and manganese chloride.
And step four, repairing. Repairing the supplemented waste ternary cathode material in a supercritical water system, and simultaneously removing residual electrolyte, a binder (PVDF) and other substances;
wherein, the condition of the supercritical water system is as follows: the temperature (T) of water is more than 374 ℃, the pressure (P) is more than 22.1MPa, and the time is 40-60 min, and the SEI film on the surface of the anode material of the waste ternary lithium battery can be cleaned under the condition, so that the aim of in-situ repairing the ternary anode material is fulfilled.
And step five, performing flotation. The conductive agent (super P) and residual carbonized material were removed by flotation.
The conductive agent (super P) and the residual carbonized material are placed on the upper layer of the solution system in the flotation process through the flotation process, and the repaired ternary positive electrode material is placed at the bottom of the system.
And step six, filtering. The filter material is the anode material of the repaired ternary lithium battery.
Wherein, the electrode material of the repaired ternary lithium battery is filtered out from the supercritical water system through filtering operation to form a filter cake.
And step seven, drying. And drying the obtained electrode material filter cake of the repaired ternary lithium battery under the condition of vacuum or protective atmosphere to obtain the dried anode material of the finished ternary lithium battery.
Wherein the protective gas is one or any combination of nitrogen, carbon dioxide, helium, argon, neon, krypton and xenon. The drying time is 10-60 min, and the drying temperature is 40-70 ℃.
The in-situ repaired ternary cathode material is prepared by adopting the method. Adopting a 6100 polycrystalline target-rotating X-ray diffractometer of SHIMADZ and a Ni filter, wherein the tube current is 20mA, the tube voltage is 20kV, the scanning angle 2 theta is 10-80 degrees, and the scanning speed is 8 DEG min-1The regenerated ternary cathode material of this example was subjected to X-ray diffraction, and the XRD spectrum obtained is shown in fig. 2. Scanning electron microscope analysis was performed on the repaired ternary cathode material of this example using a Gemini 500 scanning electron microscope, and the results of the Scanning Electron Microscope (SEM) obtained are shown in fig. 3.
As can be seen from FIG. 2, the main diffraction peaks of the repaired ternary cathode material of the embodiment can be indexed by alpha-NaFeO2The peaks of the hexagonal type layered structure (space group R-3m (166)) 006 and 012 are clearly split, indicating that the synthesized material is a ternary cathode material, and the repaired ternary cathode material of the present example has a good layered structure. From FIG. 3, it can be seen that the repaired ternary cathode material of the present embodimentThe appearance is irregular block or pomegranate seed.
The electrochemical performance of the synthesized material is characterized by using a CR2032 button cell.
Firstly, mixing an active material, a conductive agent acetylene black and a binder (10 mass percent of PVDF) according to a mass ratio of 8:1:1, then adding a proper amount of N-methylpyrrolidone as a solvent, and fully and uniformly stirring. And coating the obtained slurry on an aluminum foil, drying for 10h at 120 ℃ under a vacuum condition, then punching a wafer with the diameter of 14mm by using a punching machine, and compacting under the condition of 20Mpa to obtain the button cell positive plate. In a glove box filled with argon, lithium metal is taken as a negative electrode, and LiPF is 1mol/L6Dissolving the mixture in EC-DMC (volume ratio of 1:1) as electrolyte, and Celgard 2400 microporous polypropylene membrane as separator to obtain the button cell. In the embodiment, a BTS test system of Shenzhen Neware company is adopted to carry out constant current charging and discharging test at room temperature of 2.5-4.3V, wherein 1C is 190mAh · g-1。
Fig. 4 is a graph of the first charge and discharge of the button cell battery 0.2C, and fig. 5 is a graph of the cycle performance of the button cell battery 1C after 180 cycles. From fig. 4 and fig. 5, it can be seen that the first charge and discharge curve of the regenerated ternary cathode material of the present embodiment is a typical ternary cathode material, and the first discharge specific capacity at 0.2C is 180mAh · g-1Capacity of about 189mAh g in 1C circulation-1Attenuation to 180mAh g-1The capacity retention rate was 95.2%.
Example 2
The process for in-situ repairing the anode material (i.e., the molar ratio of nickel, cobalt and manganese elements in the anode material is 6:2:2) of the waste ternary 622 lithium battery by using supercritical water, provided by the embodiment, comprises the following steps:
step one, sorting. Sorting the electrode materials of the disassembled and crushed waste ternary (622) lithium battery, and dividing the electrode materials into waste ternary positive electrode materials and waste negative electrode materials according to different physical and chemical properties by adopting foam sorting;
and the anode material of the disassembled and crushed ternary waste lithium battery is left at the bottom, and the cathode material floats upwards.
And step two, measuring. And (3) measuring the contents of Ni, Co, Mn and Li in the supercritical water system by using an ICP (inductively coupled plasma) technology.
And step three, feeding materials. Supplementing elements lacking in the waste ternary material according to the molar ratio of the nickel, cobalt and manganese elements of 6:2: 2.
The feeding is carried out on the elements with insufficient content in the waste lithium iron phosphate anode material according to the molar ratio of Ni to Co to Mn of 6 to 2 under the alkaline condition based on ICP (inductively coupled plasma) technology measurement.
Further, the deficient Ni element can be supplemented by one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide and nickel carbonyl.
Further, the deficient Co element can be supplemented by one or more of cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt chloride.
Further, the deficient Mn element can be supplemented by one or more of manganese sulfate, manganese carbonate and manganese chloride. And step four, repairing. Repairing the supplemented waste ternary cathode material in a supercritical water system, and simultaneously removing residual electrolyte, binder (PVDF) and other substances;
wherein, the condition of the supercritical water system is as follows: the temperature (T) of water is more than 374 ℃, the pressure (P) is more than 22.1MPa, and the time is 40-60 min, and the SEI film on the surface of the anode material of the waste ternary lithium battery can be cleaned under the condition, so that the aim of in-situ repairing the ternary anode material is fulfilled.
And step five, performing flotation. The conductive agent (super P) and residual carbonized material were removed by flotation.
The conductive agent (super P) and the residual carbonized material are placed on the upper layer of the solution system in the flotation process through the flotation process, and the repaired ternary positive electrode material is placed at the bottom of the system.
And step six, filtering. The filter material is the anode material of the repaired ternary lithium battery.
Wherein, the electrode material of the repaired ternary lithium battery is filtered out from the supercritical water system through filtering operation to form a filter cake.
And step seven, drying. And drying the obtained electrode material filter cake of the repaired ternary lithium battery under the condition of vacuum or protective atmosphere to obtain the dried anode material of the finished ternary lithium battery.
Wherein the protective gas is one or any combination of nitrogen, carbon dioxide, helium, argon, neon, krypton and xenon. The drying time is 10-60 min, and the drying temperature is 40-70 ℃.
The in-situ repaired ternary cathode material is prepared by adopting the method. Adopting a 6100 polycrystalline target-rotating X-ray diffractometer of SHIMADZ and a Ni filter, wherein the tube current is 20mA, the tube voltage is 20kV, the scanning angle 2 theta is 10-80 degrees, and the scanning speed is 8 DEG min-1The regenerated ternary cathode material of the present example was subjected to X-ray diffraction, and the XRD spectrum obtained is shown in fig. 2. Scanning electron microscope analysis was performed on the repaired ternary cathode material of this example using a Gemini 500 scanning electron microscope, and the results of the Scanning Electron Microscope (SEM) obtained are shown in fig. 3.
As can be seen from FIG. 2, the main diffraction peaks of the repaired ternary cathode material of the embodiment can be indexed as alpha-NaFeO2The peaks of the hexagonal type layered structure (space group R-3m (166)) 006 and 012 are clearly split, indicating that the synthesized material is a ternary cathode material, and the repaired ternary cathode material of the present example has a good layered structure. It can be seen from fig. 3 that the morphology of the repaired ternary cathode material of the present embodiment is irregular block or pomegranate seed.
The electrochemical performance of the synthesized material is characterized by using a CR2032 button cell.
Firstly, mixing an active material, a conductive agent acetylene black and a binder (10 mass percent of PVDF) according to a mass ratio of 8:1:1, then adding a proper amount of N-methylpyrrolidone as a solvent, and fully and uniformly stirring. And coating the obtained slurry on an aluminum foil, drying for 10h at 120 ℃ under a vacuum condition, then punching a wafer with the diameter of 14mm by using a punching machine, and compacting under the condition of 20Mpa to obtain the button cell positive plate. In a glove box filled with argon, lithium metal is taken as a negative electrode, and LiPF is 1mol/L6Dissolving in mixed solution of EC-DMC (volume ratio of 1:1) as electrolyte, using Celgard 2400 microporous polypropylene membrane as diaphragm, and adopting button type electric weldingThe order of cell assembly produced button cells. In this embodiment, a BTS test system of shenzhen software corporation is adopted to perform constant current charge and discharge test at room temperature of 2.5-4.3V, where 1C is 190mAh · g-1。
Fig. 4 is a graph of the first charge and discharge of the button cell battery 0.2C, and fig. 5 is a graph of the cycle performance of the button cell battery 1C after 180 cycles. It can be seen from fig. 4 and 5 that the first charge-discharge curve of the regenerated ternary cathode material of the present embodiment is a typical ternary cathode material, and the first discharge specific capacity at 0.2C is 180 mAh-g-1Capacity of about 189mAh g in 1C circulation-1Attenuation to 180mAh g-1The capacity retention rate was 95.2%.
Example 3
The process for in-situ repairing the anode material (namely, the molar ratio of nickel, cobalt and manganese elements in the anode material is 8:1:1) of the waste ternary 811 lithium battery by using the supercritical water comprises the following steps:
step one, sorting. Sorting the electrode materials of the disassembled and crushed waste ternary (811) lithium battery, and dividing the electrode materials into waste ternary positive electrode materials and waste negative electrode materials according to different physical and chemical properties by adopting foam sorting;
and the anode material of the disassembled and crushed ternary waste lithium battery is left at the bottom, and the cathode material floats upwards.
And step two, measuring. And (4) measuring the contents of Ni, Co, Mn and Li in the supercritical water system by using an ICP (inductively coupled plasma) technology.
And step three, feeding materials. Supplementing elements lacking in the waste ternary material according to the molar ratio of nickel, cobalt and manganese elements of 8:1: 1.
The feeding is carried out on the elements with insufficient content in the waste lithium iron phosphate anode material according to the molar ratio of Ni to Co to Mn to 8 to 1 under the alkaline condition based on ICP technology determination.
Further, the deficient Ni element can be supplemented by one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide and nickel carbonyl.
Further, the deficient Co element can be supplemented by one or more of cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt chloride.
Further, the deficient Mn element can be supplemented by one or more of manganese sulfate, manganese carbonate and manganese chloride. And step four, repairing. Repairing the supplemented waste ternary cathode material in a supercritical water system, and simultaneously removing residual electrolyte, a binder (PVDF) and other substances;
wherein, the condition of the supercritical water system is as follows: the temperature (T) of water is more than 374 ℃, the pressure (P) is more than 22.1MPa, and the time is 40-60 min, and the SEI film on the surface of the anode material of the waste ternary lithium battery can be cleaned under the condition, so that the aim of in-situ repairing the ternary anode material is fulfilled.
And step five, performing flotation. The conductive agent (super P) and residual carbonized material were removed by flotation.
The conductive agent (super P) and the residual carbonized material are placed on the upper layer of the solution system in the flotation process through the flotation process, and the repaired ternary positive electrode material is placed at the bottom of the system.
And step six, filtering. The filter material is the anode material of the repaired ternary lithium battery.
Wherein, the electrode material of the repaired ternary lithium battery is filtered out from the supercritical water system through filtering operation to form a filter cake.
And step seven, drying. And drying the obtained electrode material filter cake of the repaired ternary lithium battery under the condition of vacuum or protective atmosphere to obtain the dried anode material of the finished ternary lithium battery.
Wherein the protective gas is one or any combination of nitrogen, carbon dioxide, helium, argon, neon, krypton and xenon. The drying time is 10-60 min, and the drying temperature is 40-70 ℃.
An in-situ repaired ternary cathode material is prepared by adopting the method. Adopting a 6100 polycrystalline target-rotating X-ray diffractometer of SHIMADZ and a Ni filter, wherein the tube current is 20mA, the tube voltage is 20kV, the scanning angle 2 theta is 10-80 degrees, and the scanning speed is 8 DEG min-1The regenerated ternary cathode material of this example was subjected to X-ray diffraction, and the XRD spectrum obtained is shown in fig. 2. By usingScanning electron microscope analysis of the repaired ternary cathode material of this example was performed by a Gemini 500 scanning electron microscope, and the results of the Scanning Electron Microscope (SEM) obtained are shown in fig. 3.
As can be seen from FIG. 2, the main diffraction peaks of the repaired ternary cathode material of the embodiment can be indexed by alpha-NaFeO2The peaks of the hexagonal type layered structure (space group R-3m (166)) 006 and 012 split clearly, indicating that the synthesized material is a ternary cathode material, and the repaired ternary cathode material of the present example has a good layered structure. It can be seen from fig. 3 that the morphology of the repaired ternary cathode material of the present embodiment is irregular block or pomegranate seed.
The electrochemical performance of the synthesized material is characterized by using a CR2032 button cell.
Firstly, mixing an active material, a conductive agent acetylene black and a binder (10 mass percent of PVDF) according to a mass ratio of 8:1:1, then adding a proper amount of N-methylpyrrolidone as a solvent, and fully and uniformly stirring. And coating the obtained slurry on an aluminum foil, drying for 10h at 120 ℃ under a vacuum condition, then punching a wafer with the diameter of 14mm by using a punching machine, and compacting under the condition of 20Mpa to obtain the button cell positive plate. In a glove box filled with argon, lithium metal is taken as a negative electrode, and LiPF is 1mol/L6Dissolving the mixture in EC-DMC (volume ratio of 1:1) as electrolyte, and Celgard 2400 microporous polypropylene membrane as separator to obtain the button cell. In this embodiment, a BTS test system of shenzhen software corporation is adopted to perform constant current charge and discharge test at room temperature of 2.5-4.3V, where 1C is 190mAh · g-1。
Fig. 4 is a graph of the first charge and discharge of the button cell battery 0.2C, and fig. 5 is a graph of the cycle performance of the button cell battery 1C after 180 cycles. It can be seen from fig. 4 and 5 that the first charge-discharge curve of the regenerated ternary cathode material of the present embodiment is a typical ternary cathode material, and the first discharge specific capacity at 0.2C is 180 mAh-g-1Capacity of about 189mAh g in 1C circulation-1Attenuation to 180mAh g-1The capacity retention rate was 95.2%.
Example 4
The process for in-situ repairing the anode material (i.e., the molar ratio of nickel, cobalt and manganese elements in the anode material is 5:2:3) of the waste ternary 523 lithium battery by using the supercritical water provided by the embodiment comprises the following steps:
step one, sorting. Sorting the electrode materials of the disassembled and crushed waste ternary (523) lithium batteries into waste ternary positive electrode materials and waste negative electrode materials according to different physical and chemical properties by adopting foam sorting;
and the anode material of the disassembled and crushed ternary waste lithium battery is left at the bottom, and the cathode material floats upwards.
And step two, measuring. And (3) measuring the contents of Ni, Co, Mn and Li in the supercritical water system by using an ICP (inductively coupled plasma) technology.
And step three, feeding materials. Supplementing elements lacking in the waste ternary material according to the molar ratio of nickel, cobalt and manganese elements of 5:2: 3.
The feeding is carried out on the elements with insufficient content in the waste lithium iron phosphate anode material according to the molar ratio of Ni to Co to Mn of 5 to 2 to 3 under the alkaline condition based on ICP (inductively coupled plasma) technology measurement.
Further, the deficient Ni element can be supplemented by one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide and nickel carbonyl.
Further, the deficient Co element can be supplemented by one or more of cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt chloride.
Further, the deficient Mn element can be supplemented by one or more of manganese sulfate, manganese carbonate and manganese chloride. And step four, repairing. Repairing the supplemented waste ternary cathode material in a supercritical water system, and simultaneously removing residual electrolyte, a binder (PVDF) and other substances;
wherein, the condition of the supercritical water system is as follows: the temperature (T) of water is more than 374 ℃, the pressure (P) is more than 22.1MPa, and the time is 40-60 min, and the SEI film on the surface of the anode material of the waste ternary lithium battery can be cleaned under the condition, so that the aim of in-situ repairing the ternary anode material is fulfilled.
And step five, performing flotation. The conductive agent (super P) and residual carbonized material were removed by flotation.
The conductive agent (super P) and the residual carbonized material are placed on the upper layer of the solution system in the flotation process through the flotation process, and the repaired ternary positive electrode material is placed at the bottom of the system.
And step six, filtering. The filter material is the anode material of the repaired ternary lithium battery.
Wherein, the electrode material of the repaired ternary lithium battery is filtered out from the supercritical water system through filtering operation to form a filter cake.
And step seven, drying. And drying the obtained electrode material filter cake of the repaired ternary lithium battery under the condition of vacuum or protective atmosphere to obtain the dry anode material of the finished ternary lithium battery.
Wherein the protective gas is one or any combination of nitrogen, carbon dioxide, helium, argon, neon, krypton and xenon. The drying time is 10-60 min, and the drying temperature is 40-70 ℃.
The in-situ repaired ternary cathode material is prepared by adopting the method. Adopting a 6100 polycrystalline target-rotating X-ray diffractometer of SHIMADZ and a Ni filter, wherein the tube current is 20mA, the tube voltage is 20kV, the scanning angle 2 theta is 10-80 degrees, and the scanning speed is 8 DEG min-1The regenerated ternary cathode material of the present example was subjected to X-ray diffraction, and the XRD spectrum obtained is shown in fig. 2. Scanning electron microscope analysis was performed on the repaired ternary cathode material of this example using a Gemini 500 scanning electron microscope, and the results of the Scanning Electron Microscope (SEM) obtained are shown in fig. 3.
As can be seen from FIG. 2, the main diffraction peaks of the repaired ternary cathode material of the embodiment can be indexed by alpha-NaFeO2The peaks of the hexagonal type layered structure (space group R-3m (166)) 006 and 012 are clearly split, indicating that the synthesized material is a ternary cathode material, and the repaired ternary cathode material of the present example has a good layered structure. It can be seen from fig. 3 that the morphology of the repaired ternary cathode material of the present embodiment is irregular block or pomegranate seed.
And characterizing the electrochemical performance of the synthetic material by using a CR2032 button cell.
Firstly, mixing an active material, a conductive agent acetylene black and a binder (10 mass percent of PVDF) according to a mass ratio of 8:1:1, then adding a proper amount of N-methylpyrrolidone as a solvent, and fully and uniformly stirring. And coating the obtained slurry on an aluminum foil, drying for 10 hours at 120 ℃ under a vacuum condition, then punching a wafer with the diameter of 14mm by using a punching machine, and compacting under the condition of 20Mpa to obtain the positive plate of the button cell. In a glove box filled with argon, lithium metal is taken as a negative electrode, and LiPF is 1mol/L6Dissolving the mixture in EC-DMC (volume ratio of 1:1) as electrolyte, and Celgard 2400 microporous polypropylene membrane as separator to obtain the button cell. In the embodiment, a BTS test system of Shenzhen Neware company is adopted to carry out constant current charging and discharging test at room temperature of 2.5-4.3V, wherein 1C is 190mAh · g-1。
Fig. 4 is a graph of the first charge and discharge of the button cell battery 0.2C, and fig. 5 is a graph of the cycle performance of the button cell battery 1C after 180 cycles. It can be seen from fig. 4 and 5 that the first charge-discharge curve of the regenerated ternary cathode material of the present embodiment is a typical ternary cathode material, and the first discharge specific capacity at 0.2C is 180 mAh-g-1Capacity of about 189mAh g in 1C circulation-1Attenuation to 180mAh g-1The capacity retention rate was 95.2%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the scope of the embodiments of the present invention in nature.
Claims (10)
1. A method for in-situ repairing of a waste ternary lithium battery anode material by supercritical water is characterized by comprising the following steps:
1) sorting the electrode materials of the disassembled and crushed waste ternary lithium batteries to obtain waste positive electrode materials;
2) placing the waste anode material in a supercritical water system, and measuring the contents of Ni, Co, Mn and Li elements in the system;
3) adding elements with insufficient content compared with the standard finished product cathode material into the system for supplementing materials so as to enable the Ni, Co and Mn elements in the system to reach a set molar ratio;
4) after the material is supplemented, the waste anode material is subjected to in-situ remediation in a supercritical water system, and the supercritical water system has the following conditions: the water temperature is more than 374 ℃, the pressure is more than 22.1MPa, and the in-situ repair time is 40-60 min;
5) after in-situ repair, carrying out flotation to remove the conductive agent and residual carbonized materials;
6) and filtering after flotation, and drying the filter material to obtain the finished ternary lithium battery cathode material.
2. The method for in-situ remediation of waste ternary lithium battery cathode material by supercritical water as claimed in claim 1, wherein in step 1), foam sorting is adopted for sorting.
3. The method for in-situ remediation of waste ternary lithium battery cathode material by supercritical water as claimed in claim 1, wherein in step 2) ICP is used for detecting and measuring the contents of Ni, Co, Mn and Li in the system.
4. The method for in-situ remediation of the positive electrode material of the waste ternary lithium battery by using supercritical water as claimed in claim 1, wherein the elements with insufficient content in the step 3) are supplemented according to a set molar ratio under an alkaline condition.
5. The method for in-situ remediation of the anode material of the waste ternary lithium battery by supercritical water as claimed in claim 1 or 4, wherein the Ni element in the feeding in step 3) is one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide and nickel carbonyl.
6. The method for in-situ remediation of the anode material of the waste ternary lithium battery by supercritical water as claimed in claim 1 or 4, wherein the Co element during the material supplementing in step 3) is one or more of cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt chloride.
7. The method for in-situ remediation of the anode material of the waste ternary lithium battery by supercritical water as claimed in claim 1 or 4, wherein the Mn element in the step 3) is one or more of manganese sulfate, manganese carbonate and manganese chloride during feeding.
8. The method for in-situ remediation of waste ternary lithium battery cathode material by supercritical water as claimed in claim 1, wherein the drying in step 6) is performed under vacuum or protective gas conditions.
9. The method for supercritical water in-situ remediation of waste ternary lithium battery positive electrode materials as claimed in claim 8, wherein the protective gas comprises one or more of nitrogen, carbon dioxide, helium, argon, neon, krypton and xenon.
10. The method for in-situ repairing the anode material of the waste ternary lithium battery by using the supercritical water as claimed in claim 1, 8 or 9, wherein the drying temperature in the step 6) is 40-70 ℃, and the drying time is 10-60 min.
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| CN110061319A (en) * | 2018-12-31 | 2019-07-26 | 圣戈莱（北京）科技有限公司 | A kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material |
| CN110838601A (en) * | 2019-11-15 | 2020-02-25 | 武汉瑞杰特材料有限责任公司 | Dry repairing method for failed lithium ion battery positive active material and material obtained by repairing |
| CN113120971A (en) * | 2021-03-17 | 2021-07-16 | 广东邦普循环科技有限公司 | Regeneration method and application of waste ternary cathode material |
| CN113582251A (en) * | 2021-07-27 | 2021-11-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for recycling and regenerating anode material |
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