CN116315216A - Regeneration method of waste ternary material - Google Patents
Regeneration method of waste ternary material Download PDFInfo
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- CN116315216A CN116315216A CN202310089691.6A CN202310089691A CN116315216A CN 116315216 A CN116315216 A CN 116315216A CN 202310089691 A CN202310089691 A CN 202310089691A CN 116315216 A CN116315216 A CN 116315216A
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- waste ternary
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- 239000002699 waste material Substances 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000011069 regeneration method Methods 0.000 title claims abstract description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 60
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 44
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- 230000001502 supplementing effect Effects 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000011888 foil Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 238000012216 screening Methods 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 27
- 230000001172 regenerating effect Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 22
- 239000012298 atmosphere Substances 0.000 description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002203 pretreatment Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000007885 magnetic separation Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 239000010416 ion conductor Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- -1 silicate ester Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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 discloses a regeneration method of waste ternary materials, belonging to the technical field of lithium ion batteries; the method comprises the following steps: s1, disassembling a waste ternary lithium ion battery, and collecting an anode of the waste ternary lithium ion battery; s2, performing high-temperature treatment on the waste ternary lithium ion battery anode, cooling, and screening to obtain a waste anode material and an aluminum foil; s3, magnetically separating and roasting the waste anode material to obtain waste anode powder; s4, mixing and calcining the waste anode powder and lithium hydroxide to prepare a lithium supplementing precursor; s5, adding a lithium supplementing precursor and an aluminum source into the silicate solution to prepare silicon modified anode powder; s6, pre-treating the silicon modified anode powder and sintering to obtain the regenerated ternary material. The waste ternary material regenerated by the method has high capacity and good cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for regenerating waste ternary materials.
Background
Lithium ion batteries are favored by people in terms of safety, environmental protection, long cycle life, high specific energy and the like, and along with the rapid development of lithium ion batteries, more and more scrapped lithium ion batteries are faced with various problems of recovery treatment. The structure, morphology and the like of the positive electrode material in the lithium battery can be destroyed after undergoing certain charge and discharge cycle times, so that the capacity of the battery is reduced and the battery is scrapped.
The related art discloses a method for recycling a lithium battery anode material, which comprises the following steps: 1) Soaking the positive electrode waste sheet in water, wherein the mass ratio of the positive electrode waste sheet to the water is 1:3-4; 2) Then stirring to enable the anode material to fall off from the pole piece; 3) Dispersing the fallen positive electrode material to obtain positive electrode material slurry, and separating the positive electrode material slurry from the aluminum foil; 4) Evaporating water in the positive electrode material slurry to obtain the positive electrode material; the average charge quantity of the anode material prepared by the method is 96% -98%; the capacity recovery rate is 97-98.5%; full capacity recovery is not achieved.
Disclosure of Invention
The invention aims to provide a method for regenerating waste ternary materials, which aims to solve at least one aspect of the problems and the defects in the background art.
The invention provides a regeneration method of waste ternary materials, which comprises the following steps:
s1, disassembling a waste ternary lithium ion battery, and collecting an anode of the waste ternary lithium ion battery;
s2, carrying out high-temperature treatment on the waste ternary lithium ion battery anode, cooling, and screening to obtain a waste anode material and an aluminum foil;
s3, magnetically separating and roasting the waste anode material to obtain waste anode powder;
s4, mixing the waste anode powder with lithium hydroxide and calcining to prepare a lithium supplementing precursor;
s5, adding the lithium supplementing precursor and an aluminum source into silicate solution, and mixing to obtain silicon modified anode powder;
s6, pre-treating the silicon modified anode powder, and sintering to obtain a regenerated ternary material;
the mass ratio of the lithium supplementing precursor to the aluminum foil is 100:3-5;
the mass volume ratio of the lithium supplementing precursor to the silicate solution is 100g:20 mL-30 mL;
the aluminum source is selected from aluminum foils in the step S2;
the temperature of the high-temperature treatment is 400-500 ℃.
According to one of the technical schemes of the regeneration method, the regeneration method at least has the following beneficial effects:
in the invention, the positive plate is treated at high temperature, and the adhesive is removed by pyrolysis; the pole piece is cooled after high-temperature treatment, and the waste positive pole material is stripped from the aluminum foil by utilizing inconsistent contractility and ductility of the material at different temperatures, so that the waste positive pole material and the aluminum foil are separated;
removing metal scraps after magnetic separation of the waste anode materials, and removing residual carbon powder after roasting; preparing waste anode powder;
mixing and sintering the waste anode powder and lithium hydroxide to promote lithium ions to initially enter the waste anode powder, and wrapping a layer of lithium hydroxide on the surface of the waste anode material to realize lithium supplementing regeneration of the waste anode powder;
mixing the lithium supplementing precursor, an aluminum source and silicate solution; and silicate ester is arranged on the surface of the lithium supplementing precursor; meanwhile, the full mixing of an aluminum source and a lithium supplementing precursor is realized; finally, sintering the mixture, and coating the surface of the lithium supplementing precursor, thereby improving the cycle performance of the final regenerated ternary material; meanwhile, lithium metaaluminate can be generated by utilizing the reaction of the rest lithium hydroxide and an aluminum source, and a fast ion conductor is formed on the surface, so that the electrochemical performance of the regenerated material is improved.
According to the invention, various metal elements in the positive electrode of the waste ternary lithium battery are fully utilized, and the high-value quick ion conductor coated aluminum-doped nickel-cobalt-manganese ternary material is developed. The proper amount of aluminum ion doping can reduce the cation mixing degree in the lattice of the ternary material and enhance the structural stability of the ternary material, thereby improving the electrochemical performance and the cycling stability of the ternary material.
According to some embodiments of the invention, the waste ternary material is a waste nickel cobalt manganese ternary material.
According to some embodiments of the invention, the temperature of the cooling in step S2 is-200 ℃ to 20 ℃.
According to some embodiments of the invention, the cooled medium comprises liquid nitrogen.
According to some embodiments of the invention, the cooling time is 3min to 10min.
According to some embodiments of the invention, the screening is performed in a vibrating screen.
According to some embodiments of the invention, the screen mesh of the vibrating screen is 0.25mm to 1mm.
According to some embodiments of the invention, the high temperature treatment is for a period of time ranging from 3 hours to 4 hours.
According to some embodiments of the invention, the temperature of the firing in step S3 is 700 ℃ to 800 ℃.
According to some embodiments of the invention, the firing time in step S3 is 4h to 5h.
According to some embodiments of the invention, the atmosphere of calcination in step S3 is oxygen.
According to some embodiments of the present invention, in the step S4, the molar ratio of the lithium hydroxide to the waste positive electrode powder is 1.1 to 1.3:1.
the addition amount of the lithium hydroxide is in an excessive state, so that the full lithium supplement of the waste anode powder is facilitated, and meanwhile, a lithium hydroxide layer can be formed on the surface of the waste anode powder, so that the subsequent coating treatment of silicon element and aluminum element is facilitated.
The amount of the materials of the waste anode powder is calculated by the amount of the total materials of ternary metal elements (Ni element, co element and Mn element); the metal element is measured by a component measuring apparatus.
According to some embodiments of the invention, the temperature of the calcination in step S4 is 400 ℃ to 500 ℃.
According to some embodiments of the invention, the calcination in step S4 takes 3 to 4 hours.
According to some embodiments of the invention, the silicate solution consists of the following preparation raw materials:
silicate, solvent and polyvinyl alcohol.
The polyvinyl alcohol is wrapped on the surface of the lithium supplementing precursor, so that the distribution uniformity of the silicon element and the aluminum element is further improved.
According to some embodiments of the invention, the silicate is ethyl orthosilicate.
According to some embodiments of the invention, the polyvinyl alcohol is PVA1788.
According to some embodiments of the invention, the silicate has a mass concentration of 0.5g/L to 2g/L.
According to some embodiments of the invention, the polyvinyl alcohol has a mass concentration of 1g/L to 3g/L.
According to some embodiments of the invention, the solvent is an aqueous ethanol solution.
According to some embodiments of the invention, the volume fraction of the aqueous ethanol solution is 20% to 30%.
According to some embodiments of the invention, the temperature of the mixing in step S5 is between 90 ℃ and 100 ℃.
According to some embodiments of the invention, the mixing time in step S5 is between 10min and 30min.
According to some embodiments of the invention, the temperature of the pretreatment in step S6 is 700 ℃ to 800 ℃.
According to some embodiments of the invention, the pretreatment in step S6 takes 2-3 hours.
According to some embodiments of the invention, the pre-treated atmosphere in step S6 is a noble gas.
During the pretreatment, the aluminum source melts to form a liquid phase; thereby fully contacting with ternary materials, lithium hydroxide and silicon element, reducing cation mixing and discharging, and improving the stability and safety of the final regenerated ternary materials; meanwhile, the liquid phase doping process can fully ensure that aluminum is uniformly doped into the regenerated ternary material, and fully plays a role.
In the process, aluminum element is in solid solution and enters the waste anode material, and lithium hydroxide and aluminum are reacted at high temperature to generate lithium metaaluminate, so that a fast ion conductor is formed on the surface, and the electrochemical performance of the regenerated ternary material is improved.
According to some embodiments of the invention, the sintering temperature in step S6 is 800 ℃ to 1000 ℃.
According to some embodiments of the invention, the sintering time in step S6 is 8h to 12h.
According to some embodiments of the invention, the atmosphere for sintering in step S6 is oxygen.
According to some embodiments of the invention, the sintering in step S6 has a temperature rise rate of 2 ℃/min to 3 ℃/min.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment is a regeneration method of waste ternary materials, which comprises the following preparation steps:
s1, discharging a waste ternary lithium ion battery (a waste NCM523 battery), removing a shell, cutting an end head in a closed protective atmosphere, extracting a pole piece and a diaphragm, cleaning electrolyte and electrolyte in a cleaning tank, and sorting, cutting and classifying the air-dried pole piece to obtain a waste ternary lithium ion battery anode;
s2, performing high-temperature treatment (3 hours at 450 ℃) on the positive electrode of the waste ternary lithium ion battery, cooling (the cooling temperature is-196 ℃ (liquid nitrogen), the cooling time is 10 minutes), and screening (screening is performed in a vibrating screen, and the screen holes of the vibrating screen are 0.25 mm) after cooling to obtain a waste positive electrode material and an aluminum foil;
s3, drying the waste anode material (the drying temperature is 80 ℃, the drying time is 30 min), roasting (the heating speed is 5 ℃/min, the roasting temperature is 750 ℃, the roasting atmosphere is oxygen, and the roasting time is 4 h) after magnetic separation, so as to obtain waste anode powder;
s4, mixing and calcining the waste anode powder and lithium hydroxide (the molar ratio of the waste anode powder to the lithium hydroxide is 1.3:1, the calcining temperature is 450 ℃, and the calcining time is 4 hours) to prepare a lithium supplementing precursor;
s5, adding a lithium supplementing precursor and an aluminum source (the mass ratio of the aluminum source to the lithium supplementing precursor is 3:100; the aluminum foil is recovered and prepared in the step S2, and the aluminum foil is crushed and added) into a silicate solution for mixing (the mass volume ratio of the lithium supplementing precursor to the silicate solution is 100g:20mL; the mixing temperature is 95 ℃ and the mixing time is 30 min) to prepare silicon modified anode powder;
the silicate solution in the step consists of tetraethoxysilane, polyvinyl alcohol (PVA 1788) and a solvent (ethanol water solution with the volume fraction of 20 percent);
the mass concentration of the tetraethoxysilane in the silicate solution is 1g/L;
the mass concentration of the polyvinyl alcohol in the silicate solution is 2g/L;
s6, pre-treating the silicon modified anode powder (the pre-treatment temperature is 700 ℃, the pre-treatment time is 2 hours, the pre-treatment atmosphere is nitrogen, the heating rate is 5 ℃/min), and then sintering (the sintering temperature is 800 ℃, the sintering time is 10 hours, the heating rate is 2 ℃/min, and the sintering atmosphere is oxygen) to obtain the regenerated ternary material.
Example 2
The embodiment is a regeneration method of waste ternary materials, which comprises the following preparation steps:
s1, discharging a waste ternary lithium ion battery (a waste NCM523 battery), removing a shell, cutting an end head in a closed protective atmosphere, extracting a pole piece and a diaphragm, cleaning electrolyte and electrolyte in a cleaning tank, and sorting, cutting and classifying the air-dried pole piece to obtain a waste ternary lithium ion battery anode;
s2, performing high-temperature treatment (3 hours at 450 ℃) on the positive electrode of the waste ternary lithium ion battery, cooling (the cooling temperature is-196 ℃ (liquid nitrogen), the cooling time is 10 minutes), and screening (screening is performed in a vibrating screen, and the screen holes of the vibrating screen are 0.25 mm) after cooling to obtain a waste positive electrode material and an aluminum foil;
s3, drying the waste anode material (the drying temperature is 80 ℃, the drying time is 30 min), roasting (the heating speed is 5 ℃/min, the roasting temperature is 800 ℃, the roasting atmosphere is oxygen, and the roasting time is 4 h) after magnetic separation, so as to obtain waste anode powder;
s4, mixing and calcining the waste anode powder and lithium hydroxide (the molar ratio of the waste anode powder to the lithium hydroxide is 1.1:1, the calcining temperature is 400 ℃, and the calcining time is 4 hours) to prepare a lithium supplementing precursor;
s5, adding a lithium supplementing precursor and an aluminum source (the mass ratio of the aluminum source to the lithium supplementing precursor is 4:100; the aluminum foil is recovered and prepared in the step S2, and the aluminum foil is crushed and added) into a silicate solution for mixing (the mass volume ratio of the lithium supplementing precursor to the silicate solution is 100g:30mL; the mixing temperature is 90 ℃ and the mixing time is 30 min) to prepare silicon modified anode powder;
the silicate solution in the step consists of tetraethoxysilane, polyvinyl alcohol (PVA 1788) and a solvent (ethanol water solution with the volume fraction of 20 percent);
the mass concentration of the tetraethoxysilane in the silicate solution is 1.5g/L;
the mass concentration of the polyvinyl alcohol in the silicate solution is 1g/L;
s6, pre-treating the silicon modified anode powder (the pre-treatment temperature is 700 ℃, the pre-treatment time is 2 hours, the pre-treatment atmosphere is nitrogen, the heating rate is 5 ℃/min), and then sintering (the sintering temperature is 800 ℃, the sintering time is 10 hours, the heating rate is 2 ℃/min, and the sintering atmosphere is oxygen) to obtain the regenerated ternary material.
Example 3
The embodiment is a regeneration method of waste ternary materials, which comprises the following preparation steps:
s1, discharging a waste ternary lithium ion battery (a waste NCM523 battery), removing a shell, cutting an end head in a closed protective atmosphere, extracting a pole piece and a diaphragm, cleaning electrolyte and electrolyte in a cleaning tank, and sorting, cutting and classifying the air-dried pole piece to obtain a waste ternary lithium ion battery anode;
s2, performing high-temperature treatment (3 hours at 450 ℃) on the positive electrode of the waste ternary lithium ion battery, cooling (the cooling temperature is-195 ℃ (liquid nitrogen), the cooling time is 10 minutes), and screening (screening is performed in a vibrating screen, and the screen holes of the vibrating screen are 0.25 mm) after cooling to obtain a waste positive electrode material and an aluminum foil;
s3, drying the waste anode material (the drying temperature is 80 ℃, the drying time is 30 min), roasting (the heating speed is 5 ℃/min, the roasting temperature is 750 ℃, the roasting atmosphere is oxygen, and the roasting time is 4 h) after magnetic separation, so as to obtain waste anode powder;
s4, mixing and calcining the waste anode powder and lithium hydroxide (the molar ratio of the waste anode powder to the lithium hydroxide is 1.1:2, the calcining temperature is 450 ℃, and the calcining time is 4 hours) to prepare a lithium supplementing precursor;
s5, adding a lithium supplementing precursor and an aluminum source (the mass ratio of the aluminum source to the lithium supplementing precursor is 5:100; the aluminum foil is recovered and prepared in the step S2, and the aluminum foil is crushed and added) into a silicate solution for mixing (the mass volume ratio of the lithium supplementing precursor to the silicate solution is 100g:25mL; the mixing temperature is 90 ℃ and the mixing time is 30 min) to prepare silicon modified anode powder;
the silicate solution in the step consists of tetraethoxysilane, polyvinyl alcohol (PVA 1788) and a solvent (ethanol water solution with the volume fraction of 20 percent);
the mass concentration of the tetraethoxysilane in the silicate solution is 0.5g/L;
the mass concentration of the polyvinyl alcohol in the silicate solution is 3g/L;
s6, pre-treating the silicon modified anode powder (the pre-treatment temperature is 700 ℃, the pre-treatment time is 2 hours, the pre-treatment atmosphere is nitrogen, the heating rate is 5 ℃/min), and then sintering (the sintering temperature is 800 ℃, the sintering time is 10 hours, the heating rate is 2 ℃/min, and the sintering atmosphere is oxygen) to obtain the regenerated ternary material.
Example 4
The embodiment is a regeneration method of waste ternary materials, and the difference from embodiment 1 is that:
the silicate solution in this example consisted of ethyl orthosilicate, polyvinyl alcohol (PVA 1788) and solvent (25% by volume of aqueous ethanol);
the mass concentration of the tetraethoxysilane in the silicate solution is 1.5g/L;
the mass concentration of polyvinyl alcohol in the silicate solution was 1.5g/L.
Example 5
The embodiment is a regeneration method of waste ternary materials, and the difference from embodiment 1 is that:
the silicate solution in this example consisted of ethyl orthosilicate, polyvinyl alcohol (PVA 1788) and solvent (30% by volume of aqueous ethanol);
the mass concentration of the tetraethoxysilane in the silicate solution is 0.5g/L;
the mass concentration of polyvinyl alcohol in the silicate solution is 2g/L.
Comparative example 1
The comparative example is a method for regenerating waste ternary materials, and the difference from example 1 is that:
the silicate solution in this comparative example consisted of ethyl orthosilicate and a solvent (20% by volume of aqueous ethanol);
the mass concentration of the tetraethoxysilane in the silicate solution is 1g/L.
Comparative example 2
The comparative example is a method for regenerating waste ternary materials, and the difference from example 1 is that:
this comparative example replaces the silicate solution with a polyvinyl alcohol solution.
The polyvinyl alcohol solution consists of polyvinyl alcohol (PVA 1788) and a solvent (ethanol water solution with the volume fraction of 20 percent);
the mass concentration of the polyvinyl alcohol in the polyvinyl alcohol solution is 2g/L.
Comparative example 3
The comparative example is a method for regenerating waste ternary materials, and the difference from example 1 is that:
in this comparative example, no aluminum source was added in step S5.
Comparative example 4
The comparative example is a method for regenerating waste ternary materials, and the difference from example 1 is that:
in this comparative example, no silicate solution was added in step S5.
Comparative example 5
This comparative example is a ternary positive electrode material (NCM 532).
Electrochemical performance test:
putting 1.6g of ternary cathode material (the regenerated ternary materials in examples 1-5 and comparative examples 1-4 and the ternary cathode material in comparative example 5) and 0.2g of PVDF and 0.2g of gSP conductive agent into a ball milling tank, adding a certain amount of N-methylpyrrolidone, and performing ball milling for 5 hours under the condition of 280r/min to prepare cathode material slurry;
the positive electrode material slurry is coated on a bright aluminum foil with the thickness of 9 mu m as a current collector, after NMP is volatilized completely, a roll is used for rolling the electrode plate, then the electrode plate with the required diameter is punched and cut into the electrode plate, and the electrode plate is dried in a vacuum oven at 105 ℃ for 12 hours and is quickly transferred into a glove box.
The metal lithium is used as a counter electrode, celgard2400 is used as a diaphragm, and the electrolyte is 1mol/L LiP containing 2% VC (vinylene carbonate)F 6 The solvent was EC/DMC/EMC (volume ratio 1:1:1), and CR2032 type button cell was assembled.
Discharge capacity test: at 25 ℃, the charging multiplying power is 0.5C, the discharging multiplying power is 0.5C, and the voltage range is 2.8V-4.25V.
And (3) cyclic test: under the condition of 25 ℃, the charging multiplying power is 0.5 ℃, the discharging multiplying power is 0.5 ℃, the voltage range is 2.8V-4.25V, and the capacity retention rate after 500 weeks of test cycle is measured; the test results are shown in Table 1.
TABLE 1 Performance test results of the corresponding cathode materials in examples 1 to 5 and comparative examples 1 to 5 of the present invention
| - | Initial discharge capacity (mAh/g) | Cycle retention (%) |
| Example 1 | 168.58 | 92.7 |
| Example 2 | 165.26 | 91.6 |
| Example 3 | 163.25 | 90.3 |
| Example 4 | 162.31 | 89.8 |
| Example 5 | 161.39 | 89.3 |
| Comparative example 1 | 158.31 | 84.2 |
| Comparative example 2 | 146.35 | 81.5 |
| Comparative example 3 | 151.23 | 83.6 |
| Comparative example 4 | 142.39 | 81.2 |
| Comparative example 5 | 156.81 | 86.3 |
In summary, the positive plate is treated at high temperature, and the adhesive is removed by pyrolysis; the pole piece is cooled after high-temperature treatment, and the waste positive pole material is stripped from the aluminum foil by utilizing inconsistent contractility and ductility of the material at different temperatures, so that the waste positive pole material and the aluminum foil are separated; removing metal scraps after magnetic separation of the waste anode materials, and removing residual carbon powder after roasting; preparing waste anode powder; mixing and sintering the waste anode powder and lithium hydroxide to promote lithium ions to initially enter the waste anode powder, and wrapping a layer of lithium hydroxide on the surface of the waste anode material to realize lithium supplementing regeneration of the waste anode powder; mixing the lithium supplementing precursor, an aluminum source and silicate solution; and silicate ester is arranged on the surface of the lithium supplementing precursor; meanwhile, the full mixing of an aluminum source and a lithium supplementing precursor is realized; finally, sintering the mixture, and coating the surface of the lithium supplementing precursor, thereby improving the cycle performance of the final regenerated ternary material; meanwhile, lithium metaaluminate is generated by utilizing the reaction of lithium hydroxide and an aluminum source, and a fast ion conductor is formed on the surface, so that the electrochemical performance of the regenerated material is improved.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (10)
1. The regeneration method of the waste ternary material is characterized by comprising the following steps of:
s1, disassembling a waste ternary lithium ion battery, and collecting an anode of the waste ternary lithium ion battery;
s2, carrying out high-temperature treatment on the waste ternary lithium ion battery anode, cooling, and screening to obtain a waste anode material and an aluminum foil;
s3, magnetically separating and roasting the waste anode material to obtain waste anode powder;
s4, mixing the waste anode powder with lithium hydroxide and calcining to prepare a lithium supplementing precursor;
s5, adding the lithium supplementing precursor and an aluminum source into silicate solution, and mixing to obtain silicon modified anode powder;
s6, pre-treating the silicon modified anode powder, and sintering to obtain a regenerated ternary material;
the mass ratio of the lithium supplementing precursor to the aluminum foil is 100:3-5;
the mass volume ratio of the lithium supplementing precursor to the silicate solution is 100g:20 mL-30 mL;
the aluminum source is selected from aluminum foils in the step S2;
the temperature of the high-temperature treatment is 400-500 ℃.
2. The method for regenerating a waste ternary material according to claim 1, wherein the cooling temperature in the step S2 is-180 ℃ to 20 ℃.
3. The method for regenerating a waste ternary material according to claim 1, wherein the roasting temperature in the step S3 is 700-800 ℃.
4. The method for regenerating a waste ternary material according to claim 1, wherein the calcining temperature in the step S4 is 400-500 ℃.
5. The method for regenerating a waste ternary material according to claim 1, wherein the silicate solution is composed of the following preparation raw materials:
silicate, solvent and polyvinyl alcohol.
6. The method for regenerating a waste ternary material according to claim 5, wherein the mass concentration of the silicate is 1g/L to 2g/L.
7. The method for regenerating a waste ternary material according to claim 5, wherein the mass concentration of the polyvinyl alcohol is 2g/L to 3g/L.
8. The method for regenerating a waste ternary material according to claim 1, wherein the temperature of the mixing in the step S5 is 90-100 ℃.
9. The method for regenerating a waste ternary material according to claim 1, wherein the temperature of the pretreatment in the step S6 is 700-800 ℃.
10. The method for regenerating a waste ternary material according to claim 1, wherein the sintering temperature in step S6 is 900 ℃ to 1000 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195863A (en) * | 2017-06-07 | 2017-09-22 | 四川科能锂电有限公司 | The preparation method of nickel-cobalt-manganternary ternary anode material |
| CN108807931A (en) * | 2018-06-26 | 2018-11-13 | 桑顿新能源科技有限公司 | A kind of high-nickel material and preparation method of surface coating alumina silicate lithium and surface layer doping fluorine |
| CN110165324A (en) * | 2019-06-24 | 2019-08-23 | 中国科学院青海盐湖研究所 | A kind of method and system recycling anode and Regeneration and Repair from waste lithium cell |
| CN110690435A (en) * | 2019-10-17 | 2020-01-14 | 中南大学 | Fast ion conductor coated high-nickel ternary positive electrode material and preparation method thereof |
| CN112490527A (en) * | 2020-12-03 | 2021-03-12 | 东莞理工学院 | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery |
| 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 |
| CN113764762A (en) * | 2021-08-16 | 2021-12-07 | 华中科技大学 | Method for synthesizing high-performance lithium ion battery anode material by using waste lithium ion battery |
-
2023
- 2023-02-09 CN CN202310089691.6A patent/CN116315216B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195863A (en) * | 2017-06-07 | 2017-09-22 | 四川科能锂电有限公司 | The preparation method of nickel-cobalt-manganternary ternary anode material |
| CN108807931A (en) * | 2018-06-26 | 2018-11-13 | 桑顿新能源科技有限公司 | A kind of high-nickel material and preparation method of surface coating alumina silicate lithium and surface layer doping fluorine |
| CN110165324A (en) * | 2019-06-24 | 2019-08-23 | 中国科学院青海盐湖研究所 | A kind of method and system recycling anode and Regeneration and Repair from waste lithium cell |
| CN110690435A (en) * | 2019-10-17 | 2020-01-14 | 中南大学 | Fast ion conductor coated high-nickel ternary positive electrode material and preparation method thereof |
| CN112490527A (en) * | 2020-12-03 | 2021-03-12 | 东莞理工学院 | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery |
| 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 |
| WO2022193781A1 (en) * | 2021-03-17 | 2022-09-22 | 广东邦普循环科技有限公司 | Regeneration method for waste ternary positive electrode material, and use thereof |
| CN113764762A (en) * | 2021-08-16 | 2021-12-07 | 华中科技大学 | Method for synthesizing high-performance lithium ion battery anode material by using waste lithium ion battery |
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