CN116581412A - Recovery and repair method of lithium ion battery and battery - Google Patents
Recovery and repair method of lithium ion battery and battery Download PDFInfo
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- CN116581412A CN116581412A CN202310247787.0A CN202310247787A CN116581412A CN 116581412 A CN116581412 A CN 116581412A CN 202310247787 A CN202310247787 A CN 202310247787A CN 116581412 A CN116581412 A CN 116581412A
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- lithium ion
- negative electrode
- ion battery
- positive
- electrode plate
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 90
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000008439 repair process Effects 0.000 title claims abstract description 45
- 238000011084 recovery Methods 0.000 title claims abstract description 24
- 238000002791 soaking Methods 0.000 claims abstract description 41
- 238000004140 cleaning Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 11
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001826 dimethylphthalate Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 150000002366 halogen compounds Chemical class 0.000 claims description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 23
- 239000011149 active material Substances 0.000 abstract description 22
- 229910052744 lithium Inorganic materials 0.000 abstract description 20
- 239000007774 positive electrode material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 238000006479 redox reaction Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 10
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000010926 waste battery Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a recovery and repair method of a lithium ion battery and the battery, wherein the method comprises the following steps: s1, disassembling and cleaning: disassembling the waste lithium ion batteries after the waste lithium ion batteries are completely discharged, sorting positive and negative electrode pieces, and cleaning and drying the positive and negative electrode pieces; s2, soaking and repairing: putting the cleaned positive and negative pole pieces into a solution for soaking and repairing; s3, cleaning and drying: putting the soaked and repaired positive and negative pole pieces into a solvent, soaking, cleaning and drying; s4, reassembling: and reassembling the repaired positive and negative pole pieces to the lithium ion battery. According to the method, dead lithium on the surface of the negative electrode is activated by utilizing oxidation-reduction reaction, and the positive electrode material is relived, so that the simultaneous repair and regeneration of the positive electrode plate and the negative electrode plate are realized, the steps of separating active materials and removing impurities are not needed, the process flow is simplified, the loss of the active materials is reduced, the defects of complicated direct recovery steps and high purity requirements on waste active materials are avoided, and the direct recovery process is effectively improved.
Description
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a recovery and repair method of a lithium ion battery and the battery.
Background
Lithium ion batteries have been widely used in the fields of power, energy storage, portable electronic devices, and the like. The rapid rise in battery production results in unavoidable problems with the safety of the battery supply chain and disposal of spent batteries. The potential for battery supply is mainly in the shortage of metal resources, such as: batteries produce a large number of precious metal elements such as lithium cobalt. The problem of waste batteries is derived from various heavy metals and electrolytes contained therein.
At present, main recovery techniques of active materials of lithium ion batteries comprise pyrometallurgy, hydrometallurgy and direct recovery. Among them, pyrometallurgical recovery can obtain alloys of noble metals through high temperatures, but this energy intensive approach is relatively inefficient because of the high energy consumption and the loss of part of the lithium to slag. Hydrometallurgical techniques can obtain more metal elements by obtaining high purity salts by means of chemical precipitation, leaching, filtration, etc., but this approach consumes large amounts of chemical reagents and results in higher losses and environmental pollution. The method can retain the added value of the anode and cathode active materials to the greatest extent, and can directly reuse the degraded energy storage materials for the recovery technology of battery manufacturing in an economic and environment sustainable manner, so the method has the most prospect in the aspects of economy and sustainable development at present.
However, the applicant found that: at present, the method for directly obtaining the electroactive material with good performance by re-supplementing lithium and reconstructing the crystal structure can only recycle the positive electrode material, but can not recycle the positive electrode and the negative electrode at the same time. Such as the process disclosed in the following two patent documents.
CN 115149139A patent literature discloses a method of recovering active materials. The method comprises the steps of separating active substances after pyrolyzing positive and negative plates of waste batteries, mixing and ball milling the active substances with a lithium source, a ferric iron compound and an organic carbon source, and roasting the mixture in a protective atmosphere. The method not only needs to ensure the integrity and high purity of the waste active materials during pretreatment when separating the active materials, but also needs to add a large amount of mixture and calculate the proportion during repair, and needs to be roasted for a long time at high temperature during repair. The whole process is complex, high in energy consumption and more in waste, is only suitable for recycling lithium batteries in a small scale, and is difficult to realize in large-scale industrial production.
CN 112271349A patent literature discloses a method for recycling lithium ion positive electrode materials, which disassembles a lithium ion battery in a discharge state to obtain a positive electrode plate or separates active substances on the positive electrode plate after disassembly, sprays a lithiation reagent on the positive electrode plate or soaks the positive electrode plate or the active substances with the above solution to supplement lithium. However, this solution requires stripping the active material and adjusting the concentration of the lithiation reagent according to the amount of attenuation of the positive electrode sheet, and is difficult to adapt to positive electrode materials with different attenuation conditions in a large scale.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a recovery and repair method of a lithium ion battery and the battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for recovering and repairing a lithium ion battery, including.
S1, disassembling and cleaning: disassembling the waste lithium ion batteries after the waste lithium ion batteries are completely discharged, sorting out positive pole pieces and negative pole pieces, and cleaning and drying;
s2, soaking and repairing: putting the cleaned positive pole piece and the cleaned negative pole piece into a solution for soaking and repairing;
s3, cleaning and drying: soaking and cleaning the soaked and repaired positive electrode plate and the soaked and repaired negative electrode plate in a solvent, and drying to obtain the repaired positive electrode plate and the repaired negative electrode plate;
s4, reassembling: and reassembling the repaired positive pole piece and the repaired negative pole piece to the lithium ion battery.
According to the recovery and repair method, on one hand, the capacity of the attenuated active materials on the positive pole piece and the negative pole piece of the waste lithium ion battery can be directly recovered, the process of refining the element re-synthesized materials is omitted, and the value in the manufacturing process of the lithium ion battery can be additionally reserved; the two aspects can be applicable to different kinds of active materials, directly act on the active materials which are not stripped from a current collector, have strong adaptability and simple pretreatment mode, and can repair the active materials of the positive electrode plate and the negative electrode plate with different sources and attenuation conditions; the three aspects do not need to recycle common steps at present to perform prelithiation and high-temperature recrystallization, and the anode and cathode electrodes with good performance can be obtained through simple soaking treatment, thereby providing possibility for large-scale industrialized direct recycling of active materials.
Further, in S2, the solvent of the solution is at least one of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, tetrahydrofuran, 1, 2-dimethoxyethane, dipropylene glycol dimethyl ether, and dimethyl phthalate, and the solute of the solution is at least one of halogen or a halogen compound, and the concentration is 0.01-0.1 MOL/L.
Further, the solvent in S3 is the same as the solvent of the solution in S2.
Further, in S2, the soaking time of the positive electrode plate and the negative electrode plate is 5-24 hours, and the temperature of the solution is 20-100 ℃.
Further, in S3, the soaking time of the positive electrode sheet and the negative electrode sheet is 30min.
Further, in S2, the positive electrode tab and the negative electrode tab are placed in the same container while being immersed.
Further, the positive electrode plate is one of lithium iron phosphate, ternary nickel cobalt manganese, lithium cobalt oxide, lithium manganese phosphate and lithium vanadium phosphate, and the negative electrode plate is one of graphite, a silicon negative electrode and a silicon carbon negative electrode.
Further, when the repaired positive and negative electrode sheets are reassembled to the lithium ion battery in S4, the electrolyte and separator use the formulation of the original battery.
In a second aspect, the invention also provides a lithium ion battery, and the lithium ion battery is repaired by adopting the recovery and repair method of the lithium ion battery.
The technical effects that may be achieved by the second aspect and the respective aspects of the second aspect are referred to above for the technical effects that may be achieved by the first aspect or the respective possible aspects of the first aspect, and the description is not repeated here.
Drawings
FIG. 1 is a schematic flow chart of a method for recovering and repairing a lithium ion battery according to the present invention;
FIG. 2 is a process flow diagram of recovery repair of a recovery dead lithium ion battery according to example 1 of the present invention;
FIG. 3 is an SEM comparative view of graphite negative electrode sheets before and after repair in example 1 of the present invention;
FIG. 4 is a graph showing the charge-discharge curves of lithium iron phosphate lithium ion batteries before and after repair in example 1 of the present invention;
FIG. 5 is a graph showing the cycle performance of lithium iron phosphate lithium ion batteries before and after repair in example 1 of the present invention;
FIG. 6 is a graph showing the cycle performance of the lithium iron phosphate positive electrode before and after repair in example 1 of the present invention;
FIG. 7 is a graph showing the comparison of charge and discharge curves of the lithium iron phosphate lithium ion battery before and after repair in example 2 of the present invention;
fig. 8 is a graph showing the cycle performance of the lithium iron phosphate lithium ion battery before and after repair in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 1, the recovery and repair method of the lithium ion battery provided by the invention comprises the following steps:
s1, disassembling and cleaning: disassembling the waste lithium ion batteries after the waste lithium ion batteries are completely discharged, sorting out positive pole pieces and negative pole pieces, and cleaning and drying; the positive pole piece and the negative pole piece do not need to separate active materials from a current collector; the washing is to wash away the remaining electrolyte, and is usually performed using an organic solvent used in the electrolyte, such as: dimethyl carbonate (DMC), ethylmethyl carbonate (EMC).
S2, soaking and repairing: putting the cleaned positive pole piece and the cleaned negative pole piece into a solution for soaking and repairing; wherein the soaking time of the positive pole piece and the negative pole piece is 5-24 h, and the temperature of the solution is 20-100 ℃.
The solvent of the solution is at least one of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, tetrahydrofuran, 1, 2-dimethoxyethane, dipropylene glycol dimethyl ether and dimethyl phthalate, and the solute of the solution is at least one of halogen or halogen compound, and the concentration is 0.01-0.1 MOL/L.
And when the solvent of the solution is two of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, tetrahydrofuran, 1, 2-dimethoxyethane, dipropylene glycol dimethyl ether and dimethyl phthalate, the mass ratio of the two solvents is 1:1.
s3, cleaning and drying: soaking and cleaning the soaked and repaired positive electrode plate and the soaked and repaired negative electrode plate in a solvent, and drying to obtain the repaired positive electrode plate and the repaired negative electrode plate; wherein the soaking time of the positive electrode plate and the negative electrode plate is 30min.
S4, reassembling: reassembling the repaired positive pole piece and the repaired negative pole piece to the lithium ion battery; and the electrolyte and separator preferably use the original cell formulation.
The recovery and repair method of the lithium ion battery can directly recover the capacities of the attenuated active materials on the positive pole piece and the negative pole piece of the waste lithium ion battery, realize the simultaneous repair of the positive pole piece and the negative pole piece, omit the process of refining element re-synthesized materials, and additionally reserve the value in the manufacturing process of the lithium ion battery; moreover, the method is suitable for different kinds of active materials, can directly act on the active materials which are not stripped from the current collector, has strong adaptability and simple pretreatment mode, and can repair the active materials of the positive electrode plate and the negative electrode plate with different sources and attenuation conditions; in addition, the invention does not need to recycle common steps to perform prelithiation and high-temperature recrystallization at present, and can obtain the anode and cathode electrodes with good performance through simple soaking treatment, thereby providing possibility for directly recycling active materials in large-scale industrialization.
Although the scheme of repairing by lithium supplementing and thermal annealing of the waste lithium ion battery active material is disclosed, according to the result of repeated experiments, the sectional repairing mode is complicated and has higher energy consumption, which leads to the reduction of direct recovery income and difficulty in scale-up.
Therefore, the recovery and repair method of the lithium ion battery has the following advantages:
1. the method does not need to strip the active materials of the positive pole piece and the negative pole piece from the current collector, and solves the problems of complicated steps, difficult active material stripping and high actual cost in the pretreatment stage;
2. the method does not need high-temperature treatment in the generation process, so that the energy consumption and potential safety hazard in the repair process are reduced;
3. the method only needs to carry out one-step soaking treatment in the process of production, simplifies the production process and provides possibility for large-scale production;
4. the method can recover the positive electrode and the negative electrode simultaneously, and has higher benefit.
In one possible implementation, the solvent in S3 is the same as the solvent of the solution in S2, that is, the solvent is at least one of ethylene carbonate, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, tetrahydrofuran, 1, 2-dimethoxyethane, dipropylene glycol dimethyl ether, and dimethyl phthalate, and when the two solvents are the same, the mass ratio is 1:1.
Therefore, the halogen such as iodine and the like remained on the positive electrode plate and the negative electrode plate can be washed away by adopting the same solvent as the S2 solution, the problem of reducing the cleaning effect due to the mutual solubility difference between the cleaning solvent used in S3 and the solvent of S2 is avoided, and the aluminum and copper current collectors of the positive electrode plate and the negative electrode plate cannot be damaged by adopting the solvents, so that the repairing quality is ensured.
In addition, in the existing method for repairing the positive and negative electrode plates of the waste battery, the positive electrode plate and the negative electrode plate are respectively placed in different containers for independent repair, wherein the positive electrode is re-lithiated by adding an additional lithium source, no effect is achieved even if the positive electrode plate and the negative electrode plate are placed in the same container, and a repair system and an operation procedure are complex.
In S2, the positive electrode plate is one of lithium iron phosphate, ternary nickel cobalt manganese, lithium cobalt oxide, lithium manganese phosphate and lithium vanadium phosphate, and the negative electrode plate is one of graphite, a silicon negative electrode and a silicon carbon negative electrode, and the positive electrode plate and the negative electrode plate are placed in the same container to be soaked simultaneously; the soaking time is 5-24 h, and the temperature is 20-30 ℃.
Therefore, the negative electrode plate can be cleaned and the positive electrode plate can be religion simultaneously through a chemical restoration mode (particularly, dead lithium of the negative electrode plate is used as a lithium source, the positive electrode plate can be religion simultaneously after the dead lithium is activated), the simultaneous restoration of positive and negative electrode active materials in the waste battery is realized, a restoration system and an operation program are simplified, chemical restoration is not required to be completed in a high-temperature environment, and the energy consumption is lower.
The recovery and repair method of the lithium ion battery and the lithium ion battery are further described below through the embodiments.
Example 1
As shown in fig. 2, the recovery and repair method of the lithium ion battery of the present embodiment 1 includes the following steps:
1) And after the waste lithium iron phosphate lithium ion battery is completely discharged, disassembling and sorting out the positive pole piece and the negative pole piece, and cleaning and drying the positive pole piece and the negative pole piece.
2) Immersing the positive electrode plate and the negative electrode plate sorted in the step 1) into a solution, wherein the solvent is ethylene carbonate: diethyl carbonate=1: 1, the solute is iodine simple substance of 0.1MOL/L. The soaking time was 12 hours and the temperature was 30 degrees.
The positive pole piece and the negative pole piece are placed in iodine-containing solution for soaking treatment, and dead lithium on the surface of the graphite negative pole is activated by oxidation-reduction reaction and the positive pole material is reliithiated. In solution I 3 - 、IO 3 - Will be in contact with Li 2 O、Li 0 The following reactions occur:
3Li 2 O+3I 3 - ＝6Li + +IO 3 - +8I - ；
6Li 0 +IO 3 - ＝I - +3Li 2 O；2Li+I 3 - ＝2Li + +3I - ；
2Li + +3I - +2FePO 4 ＝2LiFePO 4 +I 3 - 。
3) And (2) using ethylene carbonate for the positive electrode plate and the negative electrode plate after the soaking treatment in the step (2): diethyl carbonate=1: 1 for 30min and cleaning and drying.
4) And (3) reassembling the positive electrode piece and the negative electrode piece which are cleaned and dried in the step (3) to the lithium ion battery.
As shown in fig. 3, fig. 3 is an SEM image of the graphite negative electrode sheet before and after repair of example 1. In the figure, a new graphite negative electrode piece (figure 3 a), a waste and invalid graphite negative electrode piece (figure 3 b) and a repaired and regenerated graphite negative electrode piece (figure 3 c) are sequentially arranged from left to right, and as can be seen from the figure, dead lithium on the surface of the graphite negative electrode piece in figure 3c is activated and eliminated after the repairing method is used for repairing, and the graphite surface becomes as smooth and uniform as the new graphite negative electrode piece in figure 3 a.
The lithium ion battery of example 1 after repair and reassembly was subjected to charge and discharge measurement, and the measured charge and discharge curves are shown in fig. 4. In the figure, a 'Fresh' curve is a charge-discharge curve of a newly manufactured lithium ion battery, a 'Spent' curve is a charge-discharge curve of the lithium ion battery after the abandoned failure, and a 'Regenerate' curve is a charge-discharge curve of the lithium ion battery after the repair and reassembly. As can be seen from the figure, the capacity of the reconditioned lithium ion battery is close to that of the fresh lithium ion battery, and most of the capacity has been restored.
The cycle performance of the lithium ion battery of example 1 after repair and reassembly was measured, and the measured cycle performance is shown in fig. 5. In the figure, the 'Fresh' curve is the cycle performance curve of a newly manufactured lithium ion battery, the 'Spent' curve is the cycle performance curve of the lithium ion battery after the abandoned failure, and the 'Regenerate' curve is the cycle performance curve of the lithium ion battery after the repair and reassembly. From the graph, the cycle performance of the repaired and reassembled lithium ion battery is close to that of the newly manufactured lithium ion battery, and compared with the cycle performance of the lithium ion battery after the abandoned and failed lithium ion battery, the cycle performance of the repaired and reassembled lithium ion battery is greatly improved.
XRD testing was performed on the repaired lithium iron phosphate anode of example 1, and the measured cycle performance chart is shown in fig. 6. In the figure, "Fresh" is the XRD peak curve of Fresh lithium iron phosphate, the "Spent" curve is the XRD curve of Spent lithium iron phosphate, and the "Regenerate" curve is the XRD curve of repaired lithium iron phosphate. As can be seen from the figure, the lithium deficiency of the waste lithium iron phosphate forms iron phosphate, and iron oxide. And the peak value of the repaired lithium iron phosphate is consistent with the peak value of the newly prepared lithium iron phosphate, and no additional miscellaneous peak exists.
Example 2
1) And after the waste lithium iron phosphate lithium ion battery is completely discharged, disassembling and sorting out the positive pole piece and the negative pole piece, and cleaning and drying the positive pole piece and the negative pole piece.
2) Immersing the positive electrode plate and the negative electrode plate sorted in the step 1) into a solution, wherein the solvent is ethylene carbonate: diethyl carbonate=1: 1, and the solute is bromine simple substance of 0.1MOL/L. The soaking time was 12 hours and the temperature was 30 degrees. The step utilizes oxidation-reduction reaction to activate dead lithium on the surface of a graphite negative electrode and re-lithiate chemical repair reaction of a positive electrode material, and the specific reaction is as follows:
3Li 2 O+3Br 3 - ＝6Li + +IO 3 - +8I - ；
6Li 0 +Br O 3 - ＝Br - +3Li 2 O；
2Li 0 +Br 3 - ＝2Li + +3Br - ；
2Li + +3Br - +2FePO 4 ＝2LiFePO 4 +Br 3 - 。
3) And (2) using ethylene carbonate for the positive electrode plate and the negative electrode plate after the soaking treatment in the step (2): diethyl carbonate=1: 1 for 30min and cleaning and drying.
4) And (3) reassembling the positive electrode piece and the negative electrode piece which are cleaned and dried in the step (3) to the lithium ion battery.
The lithium ion battery of example 2 after repair and reassembly was subjected to charge and discharge measurement, and the measured charge and discharge curves are shown in fig. 7. In the figure, a 'Fresh' curve is a charge-discharge curve of a newly manufactured lithium ion battery, a 'Spent' curve is a charge-discharge curve of the lithium ion battery after the abandoned failure, and a 'Regenerate' curve is a charge-discharge curve of the lithium ion battery after the repair and reassembly. As can be seen from the figure, the capacity of the reconditioned lithium ion battery is close to that of the fresh lithium ion battery, and most of the capacity has been restored.
The cycle performance of the lithium ion battery of example 2 after repair and reassembly was measured, and the measured cycle performance is shown in fig. 8. In the figure, the 'Fresh' curve is the cycle performance curve of a newly manufactured lithium ion battery, the 'Spent' curve is the cycle performance curve of the lithium ion battery after the abandoned failure, and the 'Regenerate' curve is the cycle performance curve of the lithium ion battery after the repair and reassembly. From the graph, the cycle performance of the repaired and reassembled lithium ion battery is close to that of the newly manufactured lithium ion battery, and compared with the cycle performance of the lithium ion battery after the abandoned and failed lithium ion battery, the cycle performance of the repaired and reassembled lithium ion battery is greatly improved.
Example 3
1) And after the waste lithium iron phosphate lithium ion battery is completely discharged, disassembling and sorting out the positive pole piece and the negative pole piece, and cleaning and drying the positive pole piece and the negative pole piece.
2) Immersing the positive electrode plate and the negative electrode plate sorted in the step 1) into a solution, wherein the solvent is ethylene carbonate: diethyl carbonate=1: 1, and the solute is 0.01MOL/L of elemental iodine. The soaking time was 12 hours and the temperature was 60 degrees. The principle of the chemical repair reaction of activating dead lithium on the surface of the graphite negative electrode and re-lithiating the positive electrode material by using the oxidation-reduction reaction in this step is the same as that of example 1, and the detailed description is not repeated here.
3) And (2) using ethylene carbonate for the positive electrode plate and the negative electrode plate after the soaking treatment in the step (2): diethyl carbonate=1: 1 for 30min and cleaning and drying.
4) And (3) reassembling the positive electrode piece and the negative electrode piece which are cleaned and dried in the step (3) to the lithium ion battery.
Example 4
1) And after the waste lithium iron phosphate lithium ion battery is completely discharged, disassembling and sorting out the positive pole piece and the negative pole piece, and cleaning and drying the positive pole piece and the negative pole piece.
2) Immersing the positive electrode plate and the negative electrode plate separated in the step 1) into a solution for soaking, wherein the solvent is 1, 2-dimethoxyethane, and the solute is iodine simple substance of 0.1MOL/L. The soaking time was 12 hours and the temperature was 30 degrees. The principle of the chemical repair reaction of activating dead lithium on the surface of the graphite negative electrode and re-lithiating the positive electrode material by using the oxidation-reduction reaction in this step is the same as that of example 1, and the detailed description is not repeated here.
3) Soaking the positive electrode plate and the negative electrode plate which are subjected to the soaking treatment in the step 2) in a 1, 2-dimethoxyethane solvent for 30min, and cleaning and drying.
4) And (3) reassembling the positive electrode piece and the negative electrode piece which are cleaned and dried in the step (3) to the lithium ion battery.
Example 5
1) And after the waste ternary nickel-cobalt-manganese lithium ion battery is completely discharged, disassembling and sorting out the positive pole piece and the negative pole piece, and cleaning and drying the positive pole piece and the negative pole piece.
2) Immersing the positive electrode plate and the negative electrode plate separated in the step 1) into a solution for soaking, wherein the solvent is tetrahydrofuran, and the solute is lithium chloride of 0.01 MOL/L. The soaking time was 12 hours and the temperature was 30 degrees. The principle of the chemical repair reaction of activating dead lithium on the surface of the graphite negative electrode and re-lithiating the positive electrode material by using the oxidation-reduction reaction in this step is the same as that of example 1, and the detailed description is not repeated here.
3) Soaking the positive electrode plate and the negative electrode plate which are subjected to the soaking treatment in the step 2) in a 1, 2-dimethoxyethane solvent for 30min, and cleaning and drying.
4) And (3) reassembling the positive electrode piece and the negative electrode piece which are cleaned and dried in the step (3) to the lithium ion battery.
Example 6
1) And after the waste ternary nickel-cobalt-manganese lithium ion battery is completely discharged, disassembling and sorting out the positive pole piece and the negative pole piece, and cleaning and drying the positive pole piece and the negative pole piece.
2) Immersing the positive electrode plate and the negative electrode plate separated in the step 1) into a solution for soaking, wherein the solvent is dipropylene glycol dimethyl ether, and the solute is lithium fluoride of 0.01 MOL/L. The soaking time was 12 hours and the temperature was 30 degrees. The principle of the chemical repair reaction of activating dead lithium on the surface of the graphite negative electrode and re-lithiating the positive electrode material by using the oxidation-reduction reaction in this step is the same as that of example 1, and the detailed description is not repeated here.
3) Soaking the positive electrode plate and the negative electrode plate which are subjected to the soaking treatment in the step 2) in a 1, 2-dimethoxyethane solvent for 30min, and cleaning and drying.
4) And (3) reassembling the positive electrode piece and the negative electrode piece which are cleaned and dried in the step (3) to the lithium ion battery.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (9)
1. The recovery and repair method of the lithium ion battery is characterized by comprising the following steps of:
s1, disassembling and cleaning: disassembling the waste lithium ion batteries after the waste lithium ion batteries are completely discharged, sorting out positive pole pieces and negative pole pieces, and cleaning and drying;
s2, soaking and repairing: putting the cleaned positive pole piece and the cleaned negative pole piece into a solution for soaking and repairing;
s3, cleaning and drying: soaking and cleaning the soaked and repaired positive electrode plate and the soaked and repaired negative electrode plate in a solvent, and drying to obtain the repaired positive electrode plate and the repaired negative electrode plate;
s4, reassembling: and reassembling the repaired positive pole piece and the repaired negative pole piece to the lithium ion battery.
2. The method according to claim 1, wherein in S2, the solvent of the solution is at least one of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, tetrahydrofuran, 1, 2-dimethoxyethane, dipropylene glycol dimethyl ether, and dimethyl phthalate, and the solute of the solution is at least one of halogen or a halogen compound, and the concentration is 0.01 to 0.1MOL/L.
3. The method according to claim 1 or 2, characterized in that the solvent in S3 is the same as the solvent of the solution in S2.
4. The method according to claim 1 or 2, wherein in S2, the soaking time of the positive electrode sheet and the negative electrode sheet is 5 to 24 hours, and the temperature of the solution is 20 to 100 ℃.
5. The method according to claim 1 or 2, wherein in S3, the soaking time of the positive electrode tab and the negative electrode tab is 30min.
6. The method according to claim 1 or 2, wherein in S2, the positive electrode tab and the negative electrode tab are placed in the same container and immersed simultaneously.
7. The method of claim 1 or 2, wherein the positive electrode sheet is one of lithium iron phosphate, ternary nickel cobalt manganese, lithium cobalt oxide, lithium manganese phosphate, lithium vanadium phosphate, and the negative electrode sheet is one of graphite, silicon negative electrode, silicon carbon negative electrode.
8. The method according to claim 1 or 2, wherein the electrolyte and separator are used in the original battery formulation when the repaired positive and negative electrode sheets are reassembled to the lithium ion battery in S4.
9. A lithium ion battery characterized in that the recovery and repair method of the lithium ion battery is adopted for repair.
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