CN118040132B - Method for recycling waste battery anode material - Google Patents
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- CN118040132B CN118040132B CN202410434158.3A CN202410434158A CN118040132B CN 118040132 B CN118040132 B CN 118040132B CN 202410434158 A CN202410434158 A CN 202410434158A CN 118040132 B CN118040132 B CN 118040132B
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000010926 waste battery Substances 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 49
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 38
- 238000002791 soaking Methods 0.000 claims abstract description 32
- 239000002699 waste material Substances 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000003929 acidic solution Substances 0.000 claims abstract description 23
- 239000011149 active material Substances 0.000 claims abstract description 23
- 238000011084 recovery Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011888 foil Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims 3
- 239000007774 positive electrode material Substances 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000012779 reinforcing material Substances 0.000 abstract description 3
- 230000001502 supplementing effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000011282 treatment Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910004493 Li(Ni1/3Co1/3Mn1/3)O2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling a waste battery anode material, which belongs to the technical field of battery materials and comprises the following steps: firstly, roasting the waste positive plate at one time to obtain aluminum foil and positive active waste; washing the positive electrode active waste material with water, drying, and then performing secondary roasting to obtain an active recovery material; secondly, adding the active recovery material into an acidic solution for soaking, and carrying out solid-liquid separation to obtain a leaching solution; thirdly, adding metal ions into the leaching solution, regulating the system to be neutral, heating and stirring to form a gel, and drying in vacuum to obtain xerogel; after primary calcination, grinding and secondary calcination, an active material is obtained, the active material, carboxyl-terminated hyperbranched polyester and MXene are mixed, and the mixture is treated in a reducing atmosphere to obtain the regenerated anode material. The method comprises the operations of disassembly and separation, roasting, acid leaching, reinforcing material supplementing, calcination and the like, so that the regenerated positive electrode material is prepared, the preparation process is simple to operate, and the regenerated positive electrode material with better performance is prepared.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a method for recycling a waste battery anode material.
Background
The positive electrode material is used as a key raw material of the battery, the safety and development of the battery are directly determined, meanwhile, the highest proportion of the material cost of the lithium ion battery is occupied, the service life of the lithium ion battery is limited, a large number of waste lithium ion batteries are generated after scrapping, and if the waste lithium ion batteries are not treated and are abandoned at will, heavy metals contained in the waste lithium ion batteries can seriously harm soil and underground water bands, so that the waste lithium ion batteries become a serious problem puzzling the sustainable development of society.
The recovery treatment of the waste batteries mainly extracts valuable metals in the lithium ion batteries, such as lithium, nickel, cobalt and the like, and the valuable metals are recycled, particularly Li resources in the valuable metals can generate huge economic and social values. Therefore, the green recovery of the lithium ion battery not only can generate certain economic benefit, but also can receive good social and environmental protection benefits. Patent application document patent CN115627346a discloses a method for recovering lithium in a waste lithium battery positive electrode material, and a method for industrially recovering metal lithium in the waste lithium battery positive electrode material through a simple pre-oxidation roasting-leaching process is realized, and does not disclose how to further treat third sediments containing Ni, co and Mn. The patent application document CN113782857A is characterized in that a carbon source and a lithium source are added into the powder of the positive electrode material of the waste lithium iron phosphate battery, the powder is processed into slurry through ultrasonic and magnetic stirring or ball milling mixing, and the slurry is dried and then subjected to one-step high-temperature calcination treatment, so that the electrochemical performance of the regenerated lithium iron phosphate positive electrode material is unstable.
Along with the addition of the lithium iron phosphate battery and the ternary waste battery, the whole recovery system is more complex, the process flow is prolonged, the technical difficulty is increased, and the recovery cost is increased by realizing the separate recovery of different elements one by one, so that the research angle is changed to the coprecipitation technology, valuable metals Ni, co and Mn are coprecipitated to form a precursor for preparing the battery material again, the process of purifying the metal mixed solution is complex, and the large-scale production is difficult.
Disclosure of Invention
The invention aims to provide a recovery method of a waste battery anode material, which aims to solve the problems that the process of purifying a metal mixed solution is complex and the electrochemical performance of a regenerated anode material is unstable in the battery recovery process.
The aim of the invention can be achieved by the following technical scheme:
A method for recycling waste battery anode materials comprises the following steps:
Firstly, disassembling and separating waste batteries to obtain waste positive plates; roasting the waste positive plate at one time to obtain aluminum foil and positive active waste; the aluminum foil can be reused after conventional water washing, drying and other treatments; washing and drying the positive electrode active waste material, and then performing secondary roasting to obtain an active recovery material; the primary roasting can remove the carbonized binder, and the secondary roasting can remove impurities such as conductive carbon black in the waste;
Secondly, adding the active recovery material into an acidic solution for soaking, and carrying out solid-liquid separation to obtain a leaching solution; the acidic solution contains 0.2-0.3mol/L phosphoric acid and 0.2-0.3mol/L citric acid, and 100mL hydrogen peroxide and 3-5g carboxyl-terminated hyperbranched polyester are added into each liter of the acidic solution;
Thirdly, adding metal ions into the leaching solution, adding ammonia water to adjust the system to be neutral, heating and stirring to form gel, and drying in vacuum to obtain xerogel; after primary calcination, grinding and secondary calcination, an active material is obtained, the active material, carboxyl-terminated hyperbranched polyester and MXene are mixed, dispersed by ultrasound, stirred, separated and dried, and treated in a reducing atmosphere, so that the regenerated anode material is obtained. MXene (metal carbon/nitride) is used as a two-dimensional material, has conductivity comparable with that of graphene, and is prepared by adopting a method of directly etching with HF acid as a Ti 3C2Tx sample of MXene.
Further, the temperature of the primary roasting is 200-350 ℃, and the primary roasting time is 2-3 hours; the temperature of the secondary roasting is 550-600 ℃, and the secondary roasting time is 4-5h.
Further, the solid-to-liquid ratio of the soaking is 18-20:1, the soaking time is more than or equal to 50min, and the soaking temperature is 40-50 ℃.
Further, the soaking time was 60min and the soaking temperature was 40 ℃.
Further, the dosage mass ratio of the active material to the carboxyl-terminated hyperbranched polyester to the MXene is 100:3-5:4.
Further, the reducing atmosphere was 400℃and 15% H 2/85% Ar.
Further, the carboxyl-terminated hyperbranched polyester is prepared by the steps of:
Mixing 2, 2-dimethylolpropionic acid and trimethylolpropane under the protection of nitrogen, adding a catalyst p-toluenesulfonic acid, reacting for 6 hours at 140 ℃, stopping introducing nitrogen, cooling to room temperature when no water is distilled, adding acetone for dissolution, carrying out suction filtration, and drying to obtain hydroxyl-terminated hyperbranched polyester; under the protection of nitrogen, adding maleic anhydride and triethylamine into the hydroxyl-terminated hyperbranched polyester, and heating and stirring at 100 ℃ for reaction for 4 hours to obtain the carboxyl-terminated hyperbranched polyester; wherein, the dosage mole ratio of the 2, 2-dimethylolpropionic acid, the trimethylolpropane and the maleic anhydride is 3:1:9.
Further, the temperature of the primary calcination is 400-450 ℃, and the primary calcination time is 6-7h; the temperature of the secondary calcination is 900-950 ℃, and the secondary calcination time is 10-12h.
Further, the solid-liquid separation is suction filtration, pressure filtration or centrifugation.
Further, the metal ions include one or more of Li, co, ni, mn mixed in any ratio.
The invention has the beneficial effects that:
The invention provides a recovery method of a waste battery anode material, which comprises the operations of disassembly and separation, roasting, acid leaching, reinforcing material (MXene) supplementing, calcining and the like, so that a regenerated anode material is prepared, the preparation process is simple to operate, and the regenerated anode material with better performance can be prepared by means of ICP-OES and other instruments.
The invention adopts the form of combining organic acid and inorganic acid in the acid leaching process, and adds oxidant and carboxyl-terminated hyperbranched polyester, thereby improving the composite leaching rate in the acid leaching process, improving the recovery efficiency, improving the dispersion effect of active ingredients by the carboxyl-terminated hyperbranched polyester, having good chelating effect with valuable metals, reducing leaching difficulty by combining the oxidation effect of the oxidant, and improving the leaching recovery effect of the valuable metals.
The invention is added with a reinforcing material of MXene (metal carbon/nitride) which belongs to a two-dimensional material, is widely applied to the fields of supercapacitors, batteries, catalysis, electromagnetic shielding and the like, has conductivity comparable with graphene, and simultaneously has rich functional groups, good water dispersibility and richer active edges. The addition of the carboxyl-terminated hyperbranched polyester improves the dispersibility of the material, and the structure after calcination is more complete, so that the material has stronger cycle stability.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The main elements in the positive electrode material of the waste lithium battery used in the embodiment are as follows: ni24.12%; 23.36% of Co23%; mn22.54%; li3.111wt%; the balance of unavoidable ions such as copper, aluminum and the like.
Example 1
Preparing carboxyl-terminated hyperbranched polyester:
3mol of 2, 2-dimethylolpropionic acid and 1mol of trimethylolpropane (the mass ratio of the substances is 3:1) are mixed under the protection of nitrogen, p-toluenesulfonic acid serving as a catalyst is added to react for 6 hours at 140 ℃, nitrogen is stopped from being introduced, the mixture is cooled to room temperature when no water is distilled, acetone is added to dissolve, and the mixture is filtered by suction and dried to obtain hydroxyl-terminated hyperbranched polyester;
Under the protection of nitrogen, adding 9mol of maleic anhydride and 5g of triethylamine into the hydroxyl-terminated hyperbranched polyester, and heating and stirring at 100 ℃ for reaction for 4 hours to obtain the carboxyl-terminated hyperbranched polyester.
Example 2
The embodiment provides a method for recycling a waste battery anode material, which comprises the following steps:
Firstly, disassembling and separating waste batteries to obtain waste positive plates; roasting the waste positive plate at 200 ℃ for 3 hours to obtain aluminum foil and positive active waste; the aluminum foil can be reused after conventional water washing, drying and other treatments; washing and drying the positive electrode active waste, and then performing secondary roasting at 900 ℃ for 5 hours to obtain an active recovery material; the primary roasting can remove the carbonized binder, and the secondary roasting can remove impurities such as conductive carbon black in the waste;
Secondly, adding the active recovery material into an acidic solution for soaking, and carrying out suction filtration to obtain a leaching solution; the acidic solution contains 0.2mol/L phosphoric acid and 0.2mol/L citric acid, and 100mL hydrogen peroxide and 3g carboxyl-terminated hyperbranched polyester prepared in the example 1 are added into each liter of the acidic solution; the solid-to-liquid ratio of the soaking is 18:1, soaking time is 50min, and soaking temperature is 50 ℃; the composite leaching rate is 97.4%.
Calculating the composite leaching rate；
Wherein: η is the composite leaching rate/%; m 0 is mass/g of ternary positive electrode active material added into the waste lithium battery; m 1 is the mass/g of filter residue; eta 1 is the mass retention rate/% of the filter residue after calcination at 400 ℃ for 3 hours.
Thirdly, adding metal ions into the leaching solution, and adjusting Li: co: ni: mn molar ratio of 3.05:1:1:1 (measuring ion concentration by ICP-OES), adding ammonia water to adjust the system to neutrality, heating and stirring at 70-80deg.C to form gel, and vacuum drying at 110-120deg.C to xerogel; after primary calcination, grinding and secondary calcination, an active material is obtained, the active material, carboxyl-terminated hyperbranched polyester and MXene are mixed, and the dosage and mass ratio of the active material, the carboxyl-terminated hyperbranched polyester and the MXene is 100:3:4, a step of; adding ethanol, performing ultrasonic dispersion, stirring at 35 ℃ for 6 hours, separating and drying, and treating in a reducing atmosphere (15% H 2/85% Ar) at 400 ℃ for 2 hours to obtain the regenerated positive electrode material. The primary calcination temperature is 400 ℃, and the primary calcination time is 6 hours; the temperature of the secondary calcination is 900 ℃, and the secondary calcination time is 12 hours.
Example 3
The embodiment provides a method for recycling a waste battery anode material, which comprises the following steps:
Firstly, disassembling and separating waste batteries to obtain waste positive plates; the waste positive plate is roasted for 2 hours at the temperature of 350 ℃ to obtain aluminum foil and positive active waste; the aluminum foil can be reused after conventional water washing, drying and other treatments; washing and drying the positive electrode active waste, and then performing secondary roasting at 950 ℃ for 4 hours to obtain an active recovery material; the primary roasting can remove the carbonized binder, and the secondary roasting can remove impurities such as conductive carbon black in the waste;
secondly, adding the active recovery material into an acidic solution for soaking, and carrying out suction filtration to obtain a leaching solution; the acidic solution contains 0.3mol/L phosphoric acid and 0.3mol/L citric acid, and 100mL hydrogen peroxide and 5g carboxyl-terminated hyperbranched polyester prepared in the example 1 are added into each liter of the acidic solution; the solid-to-liquid ratio of the soaking is 20:1, soaking time is 60min, and soaking temperature is 40 ℃; the composite leaching rate is 98.2 percent.
Thirdly, adding metal ions into the leaching solution, and adjusting Li: co: ni: mn molar ratio of 3.05:1:1:1 (measuring ion concentration by ICP-OES), adding ammonia water to adjust the system to neutrality, heating and stirring at 70-80deg.C to form gel, and vacuum drying at 110-120deg.C to xerogel; after primary calcination, grinding and secondary calcination, an active material is obtained, the active material, carboxyl-terminated hyperbranched polyester and MXene are mixed, and the dosage and mass ratio of the active material, the carboxyl-terminated hyperbranched polyester and the MXene is 100:5:4, a step of; adding ethanol, performing ultrasonic dispersion, stirring at 35 ℃ for 6 hours, separating and drying, and treating in a reducing atmosphere (15% H 2/85% Ar) at 400 ℃ for 2 hours to obtain the regenerated positive electrode material. The temperature of primary calcination is 450 ℃, and the primary calcination time is 6 hours; the temperature of the secondary calcination is 950 ℃, and the secondary calcination time is 10 hours.
Comparative example 1
In this comparative example, as compared to example 2, no carboxyl-terminated hyperbranched polyester was added to the acidic solution, and the remaining raw materials and preparation process remained unchanged. In a specific second step:
Adding the active recovery material into an acidic solution for soaking, and carrying out suction filtration to obtain a leaching solution; the acidic solution contains 0.2mol/L phosphoric acid and 0.2mol/L citric acid, and 100mL of hydrogen peroxide is added into each liter of the acidic solution; the solid-to-liquid ratio of the soaking is 18:1, soaking time is 50min, and soaking temperature is 50 ℃. The composite leaching rate is 90.2%.
Example 4
The embodiment provides a method for recycling a waste battery anode material, which comprises the following steps:
First step, same as in example 2;
Secondly, adding the active recovery material into an acidic solution for soaking, and carrying out suction filtration to obtain a leaching solution; the acidic solution contains 0.3mol/L phosphoric acid and 0.3mol/L citric acid, and 100mL hydrogen peroxide and 5g carboxyl-terminated hyperbranched polyester prepared in the example 1 are added into each liter of the acidic solution; the solid-to-liquid ratio of the soaking is 20:1, soaking time is 60min, and soaking temperature is 40 ℃;
Thirdly, adding metal ions into the leaching solution, and adjusting Li: co: ni: mn molar ratio of 3.05:1:1:1, adding ammonia water to adjust the system to be neutral, heating and stirring at 70-80 ℃ to form a gel, and vacuum drying at 110-120 ℃ to obtain xerogel; after primary calcination, grinding and secondary calcination, an active material is obtained, the active material, carboxyl-terminated hyperbranched polyester and MXene are mixed, and the dosage and mass ratio of the active material, the carboxyl-terminated hyperbranched polyester and the MXene is 100:4:4, a step of; adding ethanol, performing ultrasonic dispersion, stirring at 35 ℃ for 6 hours, separating and drying, and treating in a reducing atmosphere (15% H 2/85% Ar) at 400 ℃ for 2 hours to obtain the regenerated positive electrode material. The primary calcination temperature is 420 ℃, and the primary calcination time is 6 hours; the temperature of the secondary calcination is 920 ℃, and the secondary calcination time is 11h.
Example 5
The embodiment provides a method for recycling a waste battery anode material, which comprises the following steps:
First step, same as in example 2;
Secondly, adding the active recovery material into an acidic solution for soaking, and carrying out suction filtration to obtain a leaching solution; the acidic solution contains 0.3mol/L phosphoric acid and 0.3mol/L citric acid, and 100mL hydrogen peroxide and 5g carboxyl-terminated hyperbranched polyester prepared in the example 1 are added into each liter of the acidic solution; the solid-to-liquid ratio of the soaking is 20:1, soaking time is 60min, and soaking temperature is 40 ℃;
Thirdly, adding metal ions into the leaching solution, and adjusting Li: co: ni: mn molar ratio of 3.05:1:1:1, adding ammonia water to adjust the system to be neutral, heating and stirring at 70-80 ℃ to form a gel, and vacuum drying at 110-120 ℃ to obtain xerogel; after primary calcination, grinding and secondary calcination, an active material is obtained, the active material, carboxyl-terminated hyperbranched polyester and MXene are mixed, and the dosage and mass ratio of the active material, the carboxyl-terminated hyperbranched polyester and the MXene is 100:4:4, a step of; adding ethanol, performing ultrasonic dispersion, stirring at 35 ℃ for 6 hours, separating and drying, and treating in a reducing atmosphere (15% H 2/85% Ar) at 400 ℃ for 2 hours to obtain the regenerated positive electrode material. The temperature of primary calcination is 450 ℃, and the primary calcination time is 7 hours; the temperature of the secondary calcination is 950 ℃, and the secondary calcination time is 12 hours.
Comparative example 2
In this comparative example, compared with example 4, no carboxyl-terminated hyperbranched polyester was added in the third step, and the remaining raw materials and preparation process remained the same as in example 4, specifically as follows:
Thirdly, adding metal ions into the leaching solution, and adjusting Li: co: ni: mn molar ratio of 3.05:1:1:1, adding ammonia water to adjust the system to be neutral, heating and stirring at 70-80 ℃ to form a gel, and vacuum drying at 110-120 ℃ to obtain xerogel; after primary calcination, grinding and secondary calcination, an active material is obtained, the active material and MXene are mixed, and the dosage and mass ratio of the active material to the MXene are 100:4, a step of; adding ethanol, performing ultrasonic dispersion, stirring at 35 ℃ for 6 hours, separating and drying, and treating in a reducing atmosphere (15% H 2/85% Ar) at 400 ℃ for 2 hours to obtain the regenerated positive electrode material. The primary calcination temperature is 420 ℃, and the primary calcination time is 6 hours; the temperature of the secondary calcination is 920 ℃, and the secondary calcination time is 11h.
Comparative example 3
In this comparative example, as compared with example 2, no MXene was added, and the remaining raw materials and preparation process were kept the same as in comparative example 2.
Performance test:
The mass ratio is respectively 8:1:1 example 2-example 5 and comparative example 2-comparative example 3 (corresponding to Li (Ni 1/3Co1/3Mn1/3)O2), acetylene black, PVDF), were mixed in a mortar, ground to mix thoroughly, then an appropriate amount of organic solvent N-methyl-2-pyrrolidone (NMP) was added to coat, dry, slice, and finally a half cell using lithium sheets as a counter electrode was assembled in a glove box, and a constant current charge and discharge test was performed on the sample at a voltage interval of 2.8 to 4.3V at a test temperature of 25 ℃, the specific capacity of the first discharge was recorded, and the capacity after 50 cycles of charge and discharge was performed on the material, and the results are shown in table 1 below:
From the test results, the prepared samples are recovered according to the method provided by the invention, so that the advantages of the materials can be fully exerted, and the prepared battery has higher capacity and capacity retention rate. The MXene (metal carbon/nitride) added in the embodiment is taken as a two-dimensional material, has conductivity comparable with that of graphene, plays a bridging role in the regenerated positive electrode material, and is combined with the carboxyl-terminated hyperbranched polyester, so that aggregation of components is effectively inhibited, the material is fully contacted with electrolyte, and the advantages of the material are fully exerted. The addition of the carboxyl-terminated hyperbranched polyester improves the dispersibility of the material, and the structure after calcination is more complete, so that the material has stronger cycle stability.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The method for recycling the anode material of the waste battery is characterized by comprising the following steps of:
Firstly, roasting the waste positive plate at one time to obtain aluminum foil and positive active waste; washing the positive electrode active waste material with water, drying, and then performing secondary roasting to obtain an active recovery material;
Secondly, adding the active recovery material into an acidic solution for soaking, and carrying out solid-liquid separation to obtain a leaching solution; the acidic solution contains 0.2-0.3mol/L phosphoric acid and 0.2-0.3mol/L citric acid, and 100mL hydrogen peroxide and 3-5g carboxyl-terminated hyperbranched polyester are added into each liter of the acidic solution;
thirdly, adding metal ions into the leaching solution, adding ammonia water to adjust the system to be neutral, heating and stirring to form gel, and drying in vacuum to obtain xerogel; after primary calcination, grinding and secondary calcination, an active material is obtained, the active material, carboxyl-terminated hyperbranched polyester and MXene are mixed, dispersed in an ultrasonic manner, stirred, separated and dried, and treated in a reducing atmosphere to obtain a regenerated anode material;
the carboxyl-terminated hyperbranched polyester is prepared by the following steps:
Mixing 2, 2-dimethylolpropionic acid and trimethylolpropane under the protection of nitrogen, adding p-toluenesulfonic acid, reacting for 6 hours at 140 ℃, stopping introducing nitrogen, cooling to room temperature when no more water is distilled off, adding acetone for dissolution, carrying out suction filtration, and drying to obtain hydroxyl-terminated hyperbranched polyester; under the protection of nitrogen, adding maleic anhydride and triethylamine into the hydroxyl-terminated hyperbranched polyester, and heating and stirring at 100 ℃ for reaction for 4 hours to obtain the carboxyl-terminated hyperbranched polyester; wherein, the dosage mole ratio of the 2, 2-dimethylolpropionic acid, the trimethylolpropane and the maleic anhydride is 3:1:9.
2. The method for recycling the anode material of the waste battery according to claim 1, wherein the temperature of the primary roasting is 200-350 ℃, and the primary roasting time is 2-3 hours; the temperature of the secondary roasting is 550-600 ℃, and the secondary roasting time is 4-5h.
3. The method for recycling waste battery anode materials according to claim 1, wherein the soaked solid-to-liquid ratio is 18-20:1, the soaking time is more than or equal to 50min, and the soaking temperature is 40-50 ℃.
4. The method for recycling waste battery cathode materials according to claim 1, wherein the soaking time is 60min and the soaking temperature is 40 ℃.
5. The method for recycling the waste battery anode material according to claim 1, wherein the dosage mass ratio of the active material to the carboxyl-terminated hyperbranched polyester to the MXene is 100:3-5:4.
6. The method for recycling waste battery cathode materials according to claim 1, wherein the reducing atmosphere is 400 ℃ and 15% H 2/85% Ar.
7. The method for recycling the anode material of the waste battery according to claim 1, wherein the temperature of the primary calcination is 400-450 ℃, and the primary calcination time is 6-7h; the temperature of the secondary calcination is 900-950 ℃, and the secondary calcination time is 10-12h.
8. The method for recycling the anode material of the waste battery according to claim 1, wherein the solid-liquid separation is suction filtration, pressure filtration or centrifugation.
9. The method for recycling waste battery cathode materials according to claim 1, wherein the metal ions are one or more of Li, co, ni, mn.
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| WO2020018731A1 (en) * | 2018-07-18 | 2020-01-23 | Nanotek Instruments, Inc. | Fast-chargeable lithium battery electrodes |
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