CN114890414B - Method for recycling graphite material in waste batteries - Google Patents
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- CN114890414B CN114890414B CN202210738986.7A CN202210738986A CN114890414B CN 114890414 B CN114890414 B CN 114890414B CN 202210738986 A CN202210738986 A CN 202210738986A CN 114890414 B CN114890414 B CN 114890414B
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- 239000007770 graphite material Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000010926 waste battery Substances 0.000 title claims abstract description 24
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000005554 pickling Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001690 polydopamine Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 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
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Processing Of Solid Wastes (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a recycling method of graphite materials in waste batteries, and relates to the technical field of battery recycling. The recycling method provided by the invention comprises the following steps: (1) Carrying out acid leaching on graphite materials in the waste batteries, and then washing and drying; (2) immersing in a metal salt solution and drying; (3) immersing in an alkali solution, filtering and drying; (4) Placing the graphite material into an organic carbon source solution for hydrothermal reaction to form a double-layer coated graphite material A; (5) Sintering the materials to form a double-layer coated graphite material B; (6) And (3) pickling the double-layer coated graphite material B to obtain the porous C coated graphite material. According to the invention, the graphite material in the battery is recycled by the method, the process of the method is simple, and the obtained recycled product can be directly applied to the production of the battery.
Description
Technical Field
The invention relates to the technical field of battery recovery, in particular to a method for recycling graphite materials in waste batteries.
Background
In recent years, the development speed of new energy automobiles is continuously accelerated, and the decommissioning of power batteries is carried out, so how to efficiently utilize the decommissioning power batteries is a hot spot in current research.
For the regeneration and utilization of retired power batteries, the foreign countries mainly use fire recovery, the raw materials in the power batteries mainly use recovered metal materials, other electrolyte, a diaphragm and graphite are all used as energy sources to provide heat for the fire recovery, secondary pollution is easy to generate in the fire recovery, harmful substances need to be prevented and treated, and the treatment cost is high. The wet recycling technology mainly recycles metal materials in battery materials, and graphite is treated as solid waste, so that resource waste is caused.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for recycling graphite materials in waste batteries, which has simple process and can be directly used for producing batteries.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a recycling method of graphite materials in waste batteries comprises the following steps:
(1) Acid leaching is carried out on graphite materials in the waste batteries, and then washing and drying are carried out;
(2) Immersing the dried graphite material into a metal salt solution, and then taking out and drying;
(3) Immersing the graphite material dried in the step (2) into an alkali solution, and taking out and drying to obtain a graphite material coated with metal hydroxide;
(4) Adding a graphite material coated by metal hydroxide into an organic carbon source solution for hydrothermal reaction to form a double-layer coated graphite material A;
(5) Sintering the material obtained in the step (4) in a protective atmosphere to form a double-layer coated graphite material B;
(6) And (3) pickling the double-layer coated graphite material B to obtain the C-coated graphite material.
The preparation method comprises the steps of firstly removing metal simple substances in a graphite material by acid leaching, then respectively soaking by a metal salt solution and an alkali solution, forming a metal hydroxide coating layer on the surface of the graphite material, then carrying out hydrothermal reaction with an organic carbon source to obtain a double-layer coated graphite material A, then sintering to obtain a double-layer coated graphite material B, and then cleaning by strong acid to obtain the porous C-coated graphite material with a core-shell structure. The method has the advantages that the used treatment materials are fewer, the process is simple, and the prepared C-coated graphite material can be directly used for preparing batteries, so that a new thought is provided for recycling graphite materials in waste batteries.
Preferably, in the step (1), at least one of hydrochloric acid, sulfuric acid and nitric acid is used for acid leaching, the acid leaching time is 1-6 h, and the acid concentration is 0.2-2 mol/L. When the acid leaching conditions meet the requirements, the metal simple substance entering the graphite material in the electrochemical reaction process can be removed completely.
Preferably, in the step (2), the metal salt is at least one of ferric sulfate, zinc sulfate and zinc chloride, and the concentration of the metal salt in the metal salt solution is 0.5-2 mol/L; in the step (3), the alkali solution is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide solution, and the concentration of alkali in the alkali solution is 0.1-1 mol/L.
The ferric sulfate, ferric chloride, zinc sulfate and zinc chloride can react with alkali to generate metal hydroxide precipitate which is attached to the surface of the graphite material. The reason why the concentration of the metal salt is selected is that if the concentration of the metal salt is too high, the thickness of the prepared coating layer is too large, the pore structure in the finally formed porous C-coated graphite material is also increased, and the performance of the battery prepared with the C-coated graphite material is adversely affected; if the concentration of the metal salt is too low, the subsequent coating effect is not ideal, the coating on the surface of the graphite material is uneven, and the comprehensive performance of the C-coated graphite material is also affected. The concentration of the base in the alkaline solution will also have the same effect.
Preferably, in the step (4), the organic carbon source is at least one of glucose, sucrose and polydopamine; the concentration of the organic carbon source in the organic carbon source solution is 0.2-1 mol/L.
The concentration of the organic carbon source is limited to control the thickness of the C layer, the concentration is too high, the thickness of the carbon layer is large, the metal oxide layer in the middle is difficult to remove in the subsequent acid etching process, the electrical property of the graphite material coated by the C can be greatly influenced, the concentration is too low, the coating of the carbon layer is uneven, the full coating cannot be completed, and the stability is poor after the metal oxide is etched by the subsequent acid.
Preferably, in the step (4), the hydrothermal reaction temperature is 150-200 ℃ and the time is 2-12 h. Under the above conditions, the organic carbon source can fully react with the metal hydroxide/graphite material to form a double-layer coated graphite material A.
Preferably, in the step (5), the sintering temperature is 400-1000 ℃ and the time is 1-6 h, and the protective atmosphere is at least one of nitrogen and rare gas. Further preferably, in the step (5), the sintering temperature is 700 to 900 ℃.
The amorphous carbon coating layer is formed when the temperature is lower than 700 ℃, and the battery prepared from the graphite material coated by the C has poor charge and discharge performance and relatively short service life; when the temperature is higher than 900 ℃, the mechanical property of the C-coated graphite material is poor, and the comprehensive performance of the battery can be influenced.
Preferably, in the step (6), the acid is at least one of hydrochloric acid, sulfuric acid and nitric acid; the concentration of the acid is 0.5-2 mol/L. The metal oxide in the double-layer coated graphite material B can be sufficiently removed by acid etching with the acid to form a C-coated graphite material.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, by means of the adsorptivity of the graphite material, metal hydroxide precipitate is formed on the surface of the graphite material, then carbon coating and sintering are carried out, then acid is utilized to remove metal oxide, so that the pore structure between the graphite and the carbon coating layer is increased, a more sufficient expansion space is provided for the graphite, a buffer effect is achieved in the charging and discharging process of the graphite, and the service life of the graphite material is prolonged.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
The invention relates to an embodiment of a method for recycling graphite materials in waste batteries, which comprises the following steps:
(1) Immersing graphite materials in the waste batteries in hydrochloric acid with the HCl concentration of 1mol/L, removing metal impurities, washing the graphite materials subjected to impurity removal until the graphite materials are neutral and drying;
(2) Immersing the dried graphite material into an aqueous solution of ferric chloride with the concentration of 0.5mol/L, immersing for 5 hours, and drying;
(3) Immersing the dried graphite material in NH 3 ·H 2 Soaking in 0.5mol/L ammonia water for 10min, and drying to obtain surface-coated Fe (OH) 3 Is a graphite material of (a) a graphite material;
(4) Coating the surface with Fe (OH) 3 Adding the graphite material into a glucose aqueous solution with the glucose concentration of 1mol/L, carrying out hydrothermal reaction for 3 hours at 180 ℃, taking out and drying to obtain a double-layer coated graphite material A;
(5) Calcining the double-layer coated graphite material A in argon at 700 ℃ for 2 hours to obtain a double-layer coated graphite material B;
(6) Washing the double-layer coated graphite material B with hydrochloric acid with HCl concentration of 1mol/L to remove Fe 2 O 3 And obtaining the porous C-coated graphite material.
Example 2
The invention relates to an embodiment of a method for recycling graphite materials in waste batteries, which comprises the following steps:
(1) Immersing graphite materials in the waste batteries in hydrochloric acid with the HCl concentration of 1mol/L, removing metal impurities, washing the graphite materials subjected to impurity removal until the graphite materials are neutral and drying;
(2) Immersing the dried graphite material into ferric chloride aqueous solution with the ferric chloride concentration of 2mol/L, and drying after immersing for 1 h;
(3) Immersing the dried graphite material in a sodium hydroxide aqueous solution with the concentration of sodium hydroxide of 2mol/L, immersing for 10min, taking out and drying to form surface-coated Fe (OH) 3 Is a graphite material of (a) a graphite material;
(4) Will beSurface coating Fe (OH) 3 Adding the graphite material into polydopamine aqueous solution with polydopamine concentration of 1mol/L, carrying out hydrothermal reaction for 3 hours at 180 ℃, taking out and drying to obtain double-layer coated graphite material A;
(5) Calcining the double-layer coated graphite material A in argon at 900 ℃ for 2 hours to obtain a double-layer coated graphite material B;
(6) Washing the double-layer coated graphite material B with hydrochloric acid with HCl concentration of 1mol/L to remove Fe 2 O 3 And obtaining the porous C-coated graphite material.
Example 3
The invention relates to an embodiment of a method for recycling graphite materials in waste batteries, which comprises the following steps:
(1) Immersing graphite materials in the waste batteries in hydrochloric acid with the HCl concentration of 1mol/L, removing metal impurities, washing the graphite materials subjected to impurity removal until the graphite materials are neutral and drying;
(2) Immersing the dried graphite material in a zinc sulfate aqueous solution with zinc sulfate concentration of 1mol/L, immersing for 5 hours, and drying;
(3) Immersing the dried graphite material in NH 3 ·H 2 Soaking in ammonia water with O concentration of 1mol/L for 10min, taking out, and drying to form surface coated Zn (OH) 2 Is a graphite material of (a) a graphite material;
(4) Coating Zn (OH) on the surface 2 Adding the graphite material into a sucrose aqueous solution with the sucrose concentration of 1mol/L, carrying out hydrothermal reaction for 3 hours at 180 ℃, taking out and drying to obtain a double-layer coated graphite material A;
(5) Calcining the double-layer coated graphite material A in argon at 800 ℃ for 2 hours to obtain a double-layer coated graphite material B;
(6) And (3) cleaning the double-layer coated graphite material B by hydrochloric acid with the HCl concentration of 1mol/L to remove ZnO, thereby obtaining the porous C-coated graphite material.
Example 4
In one embodiment of the method for recycling graphite materials in waste batteries of the present invention, the method in this embodiment is different from that in embodiment 1 only in that in the step (5), the sintering temperature is 600 ℃.
Example 5
In one embodiment of the method for recycling graphite materials in waste batteries of the present invention, the method in this embodiment is different from that in embodiment 1 only in that in the step (5), the sintering temperature is 1000 ℃.
Example 6
The method of the present invention differs from the method of the present invention in that in the step (2), the concentration of ferric chloride in the ferric chloride aqueous solution is 0.3mol/L, and in the step (3), the graphite material is immersed in NH 3 ·H 2 The solution was added to aqueous ammonia having an O concentration of 0.3 mol/L.
Example 7
In one embodiment of the method for recycling graphite materials in waste batteries, the method in this embodiment is different from that in embodiment 2 only in that in step (2), the concentration of ferric chloride in the ferric chloride aqueous solution is 3mol/L, and in step (3), the graphite materials are immersed in the sodium hydroxide aqueous solution with the concentration of sodium hydroxide being 3 mol/L.
Comparative example 1
A recycling method of graphite materials in waste batteries comprises the following steps:
(1) Immersing graphite materials in the waste batteries in hydrochloric acid with the HCl concentration of 1mol/L, removing metal impurities, washing the graphite materials subjected to impurity removal until the graphite materials are neutral and drying;
(2) Adding the dried graphite material into a glucose aqueous solution with the glucose concentration of 1mol/L, carrying out hydrothermal reaction for 3 hours at 180 ℃, and taking out and drying;
(3) Calcining the product of the step (2) for 2 hours at 700 ℃ in argon, cleaning the product with hydrochloric acid with the HCl concentration of 1mol/L, and drying to obtain a recovered product.
Comparative example 2
A recycling method of graphite materials in waste batteries comprises the following steps:
(1) Immersing graphite materials in the waste batteries in hydrochloric acid with the HCl concentration of 1mol/L, removing metal impurities, washing the graphite materials subjected to impurity removal until the graphite materials are neutral and drying;
(2) Immersing the dried graphite material in NH 3 ·H 2 Soaking in ammonia water with O concentration of 1mol/L for 10min, and taking out and drying;
(3) Adding the treated product of the step (2) into a glucose aqueous solution with the glucose concentration of 1mol/L, carrying out hydrothermal reaction for 3 hours at 180 ℃, taking out and drying;
(4) Calcining the product dried in the step (3) for 2 hours at 700 ℃ in argon, cleaning the product with hydrochloric acid with the HCl concentration of 1mol/L, and drying to obtain a recovered product.
Performance testing
The porous C-coated graphite materials obtained in examples 1 to 7 and comparative examples 1 to 2 were mixed with acetylene black and a binder PVDF in a mass ratio of 8:1:1 to prepare a button half cell positive electrode, and a metal lithium sheet was used as a negative electrode to prepare a button half cell, and electrochemical performance tests were performed, with the test results shown in Table 1.
TABLE 1
As shown in Table 1, the recovered products of examples 1 to 7 have good electrical properties, the specific capacity for the first discharge is higher than 335mAh/g, the efficiency for the first charge and discharge is higher than 92%, and the cycle life of 1C is more than 2200 times, thus having good service performance.
The test results of comparative example 1 and examples 4 and 5 revealed that the sintering temperature had a great influence on the properties of the recovered product, and that the properties of the battery prepared from the recovered product were significantly superior when the sintering temperature was 700 to 900 ℃.
The test results of comparative example 1 and example 6 show that when the concentration of ferric chloride is too low, the porous C-coated graphite material formed has smaller pores, and the 1C cycle life of the battery is greatly reduced.
The test results of comparative example 2 and example 7 revealed that when the concentration of ferric chloride was too high, the pores of the formed C/graphite material were too large, and the electrical properties of the battery were relatively poor.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. The method for recycling the graphite material in the waste battery is characterized by comprising the following steps of:
(1) Acid leaching is carried out on graphite materials in the waste batteries, and then washing and drying are carried out;
(2) Immersing the dried graphite material into a metal salt solution, and then taking out and drying;
(3) Immersing the graphite material dried in the step (2) into an alkali solution, and taking out and drying to obtain a graphite material coated with metal hydroxide;
(4) Adding a graphite material coated by metal hydroxide into an organic carbon source solution for hydrothermal reaction to form a double-layer coated graphite material A;
(5) Sintering the double-layer coated graphite material A obtained in the step (4) in a protective atmosphere to form a double-layer coated graphite material B;
(6) Pickling the double-layer coated graphite material B to obtain a porous C coated graphite material;
in the step (2), the metal salt is at least one of ferric sulfate, ferric chloride, zinc sulfate and zinc chloride, and the concentration of the metal salt in the metal salt solution is 0.5-2 mol/L;
in the step (3), the alkali solution is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide solution, and the concentration of the alkali in the alkali solution is 0.1-1 mol/L;
in the step (5), the sintering temperature is 700-900 ℃;
in the step (4), the organic carbon source is at least one of glucose, sucrose and polydopamine; the concentration of the organic carbon source in the organic carbon source solution is 0.2-1 mol/L.
2. The method according to claim 1, wherein in the step (1), acid leaching is performed using at least one of hydrochloric acid, sulfuric acid, and nitric acid for 1 to 6 hours, and the concentration of the acid is 0.2 to 2mol/L.
3. The method of claim 1, wherein in the step (4), the hydrothermal reaction temperature is 150 to 200 ℃ and the time is 2 to 12 hours.
4. The method of claim 1, wherein in the step (5), the protective atmosphere is at least one of nitrogen and rare gas.
5. The method of claim 1, wherein in step (6), the acid is at least one of hydrochloric acid, sulfuric acid, and nitric acid; the concentration of the acid is 0.5-2 mol/L.
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| CN202210738986.7A CN114890414B (en) | 2022-06-27 | 2022-06-27 | Method for recycling graphite material in waste batteries |
| PCT/CN2022/122271 WO2024000886A1 (en) | 2022-06-27 | 2022-09-28 | Method for recycling graphite material from waste battery |
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| CN116375022A (en) * | 2023-04-06 | 2023-07-04 | 骆驼集团资源循环襄阳有限公司 | Method for recycling graphite powder from waste lithium batteries |
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| CN108134063A (en) * | 2017-12-21 | 2018-06-08 | 哈尔滨工业大学深圳研究生院 | Silicon-carbon composite material, preparation method and application thereof |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
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| KR20170032656A (en) * | 2015-09-15 | 2017-03-23 | 일진다이아몬드(주) | A method for manufacturing graphene using abandoned graphite |
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| CN113594420B (en) * | 2021-09-30 | 2022-02-01 | 中南大学 | Regeneration method of lithium ion battery graphite cathode and regenerated graphite cathode thereof |
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| CN108134063A (en) * | 2017-12-21 | 2018-06-08 | 哈尔滨工业大学深圳研究生院 | Silicon-carbon composite material, preparation method and application thereof |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
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