CN116639685B - Recycling method of waste lithium-carbide graphite cathode - Google Patents
Recycling method of waste lithium-carbide graphite cathode Download PDFInfo
- Publication number
- CN116639685B CN116639685B CN202310725568.9A CN202310725568A CN116639685B CN 116639685 B CN116639685 B CN 116639685B CN 202310725568 A CN202310725568 A CN 202310725568A CN 116639685 B CN116639685 B CN 116639685B
- Authority
- CN
- China
- Prior art keywords
- waste lithium
- recycling
- waste
- black powder
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 68
- 239000010439 graphite Substances 0.000 title claims abstract description 68
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 238000004064 recycling Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical compound [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 title description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 7
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- -1 iron ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 238000009818 secondary granulation Methods 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 claims description 2
- 230000008022 sublimation Effects 0.000 claims description 2
- 239000011269 tar Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000010405 anode material Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 241001025261 Neoraja caerulea Species 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 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
- 230000007847 structural defect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010926 waste battery 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
- C01B32/196—Purification
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- H01M4/58—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
-
- 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
- H01M2004/027—Negative 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
Abstract
The invention provides a recycling method of a waste lithium graphite cathode, which takes waste lithium ion battery black powder as a raw material, obtains a graphite cathode material with stable performance through proper chemical acid washing, purification and impurity removal and physical and chemical modification, realizes recycling and high-value utilization of the waste lithium battery cathode, has a green recycling process of the waste lithium graphite cathode, and has the advantages of simple steps, low cost and wide prospect for realizing the recycling of the lithium graphite cathode on a large scale.
Description
Technical Field
The invention relates to the field of lithium battery negative electrode materials, in particular to a recycling method of a low-cost waste lithium carbide ink negative electrode.
Background
Along with the development of new energy industry, when a large number of lithium ion batteries are scrapped, the scrapped batteries of a plurality of electric automobiles enter a recycling factory, however, in order to facilitate disassembly, positive and negative electrode materials are not treated separately, but are mixed to form black powder. Because of the characteristics of lithium resources, nickel resources and cobalt resources, many waste battery recycling enterprises only recycle valuable metal ions, and the metal ions are recycled, and 40% of the weight of the waste graphite is remained, however, the waste graphite cannot be reused because the extraction of the metal ions or the impurity removal of black powder is not thorough. Only stacking or low-valued processing is possible, resulting in waste of graphite resources. On the one hand, the cost of graphite cathode increases year by year, and on the other hand, secondary graphite is not well utilized.
The artificial graphite is a main raw material of the lithium battery cathode, and is prepared from petroleum coke, needle coke and other raw materials through a series of carbonization, granulation, graphitization, cladding and other processes, and has the advantages of high energy consumption, heavy pollution and high cost in the processing process. Therefore, the recycling rate of the waste lithium ion battery anode material is improved, and the method is an effective supplement for the productivity of the graphite anode material.
The main carbon structure of the lithium ion battery cathode material is not destroyed in the using process, but structural defects at the edge of graphite are increased, and metal ions are doped, so that the recycling of the waste lithium ion battery graphite cathode can be realized completely through hydrometallurgy and pyrometallurgy. Researches show that the recycling of the waste negative electrode is realized by utilizing simple acid washing and ultra-high temperature thermal shock, however, along with the diversification process of the battery positive electrode material and the negative electrode material, the simple acid washing process is difficult to wash various metal ions to below 10ppm (particularly iron cobalt nickel metal ions); the ultra-high temperature thermal shock is uncontrollable in terms of industrialization and cost, so that the advantages of wet purification and high-temperature purification are considered from multiple angles, the defects are mutually compensated, and the low-cost recycling technology of the waste graphite negative electrode is developed.
With the application and the service life expiration of new energy lithium batteries, a large number of lithium ion batteries are retired. The problems of recycling and treating graphite anode materials and recycling resources in the production of approximately 20-40 ten thousand tons of waste graphite anodes per year in China are to be solved. Recycling of the negative graphite material for reuse in the negative electrode of a lithium ion battery provides a source of graphite. Greatly reduces the new production process of the artificial graphite. Because the decommissioning amount of the power battery is not very large at present, the scale effect is not formed in the power battery recovery, and no effective cooperation is established among an automobile manufacturing enterprise, a battery manufacturing enterprise, a recovery enterprise and a recycling enterprise in the battery recovery chain at present, so that the realization of large-scale recovery and utilization is difficult. Because no relevant standard exists at present, although the recycled negative electrodes can reach the standard of lithium-graphite negative electrodes in certain aspects, no manufacturer is willing to use the recycled graphite negative electrodes to produce batteries, however, the recycled graphite negative electrodes can be degraded or converted into middle-low end battery users according to different application scenes of the batteries, so that the high-value utilization of the recycled graphite negative electrodes can be realized.
Disclosure of Invention
The invention provides a recycling method of a waste lithium graphite anode, which aims at the dilemma of recycling the current waste lithium battery anode, and is a recycling process of the waste lithium graphite anode with low cost.
The technical scheme for realizing the technical purpose of the invention is as follows: a method for recycling waste lithium graphite negative electrode uses waste lithium black powder as raw material, and the granularity is 15 microns; the method comprises the following steps:
step 1, pickling and purifying; in the step, the aqua regia is utilized to remove metal ions, including iron ions, cobalt ions and nickel ions, in the waste lithium electric black powder;
step 2, dehydrating and modifying; in the step, calcium ions and magnesium ions are removed by modification;
step 3, coating treatment; realizing secondary granulation and recoating;
step 4, high-temperature carbonization; the modifier is removed in this step and the metal ions are removed by sublimation.
Further, in the above method for recycling the waste lithium graphite anode: in the step 1, the solid-liquid mass ratio of the aqua regia to the waste lithium electric black powder is 1:1-1:20, and the pickling time is 2-10 h.
Further, in the above method for recycling the waste lithium graphite anode: the modifying reagent comprises NH 4 Cl，NH 4 HCO 3 Or (NH) 4 ) 2 CO 3 The dosage of the mixture is 0.5-1% of the weight of the waste lithium electric black powder.
Further, in the above method for recycling the waste lithium graphite anode: the coating agent is tar, asphalt, glucose, coking coal or phenolic resin, and the addition amount is 8-12% of the weight of the waste lithium electric black powder.
Further, in the above method for recycling the waste lithium graphite anode: high-temperature carbonization temperature is 700-1400 ℃, and high-temperature carbonization time is 2-8 hours.
Further, in the above method for recycling the waste lithium graphite anode: the method also comprises a physical dispersion step and a demagnetizing step.
The invention takes the waste lithium ion battery black powder as the raw material, obtains the graphite anode material with stable performance through proper chemical acid washing, purification and impurity removal and physical and chemical modification, realizes the recycling and high-value utilization of the waste lithium ion battery anode, has green process, simple steps and low cost, and has wide prospect for realizing the recycling of the lithium graphite anode in large scale.
The invention will be described in more detail below with reference to the drawings and examples.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a scanning electron microscope image of a waste graphite anode used in an embodiment of the present invention;
FIG. 3 is a graph showing the stability of blue-ray test cycles of the waste graphite anode before and after regeneration used in the examples of the present invention.
Detailed Description
Example 1
In the embodiment, waste lithium battery black powder with the granularity of 15 microns is used as a raw material for recycling.
Black powder: aqua regia=1:5, washed for 3 hours, obtaining a waste graphite negative electrode with a purity of 99.9%. Uniformly mixing a certain mass of waste graphite negative electrode and 1% ammonium chloride by an agate mortar, putting the mixture into a corundum magnetic boat, heating to 1000 ℃ at a speed of 5 ℃/min by a muffle furnace, preserving heat for 1h at 1000 ℃ and then naturally cooling to obtain a regenerated graphite negative electrode material, assembling the regenerated graphite negative electrode material into a semi-button battery for charge and discharge performance test, wherein when the current density is 0.2A/g, the initial effect of the waste graphite negative electrode is 80.7%, and the initial specific charge capacity is 260.7mAh/g. The initial effect of the modified anode material is 80.9%, and the initial specific charge capacity is 361.8mAh/g. The modified cathode material has higher cycle stability.
In this embodiment, the high temperature carbonization process is performed under an inert atmosphere or under an air-insulated condition, and thus, is not oxidized.
Example 2
Black powder: aqua regia=1:5, washed for 3 hours, obtaining 99.9% of waste graphite negative electrode. Adding 10% coal tar pitch into a waste graphite negative electrode with a certain mass, uniformly mixing the waste graphite negative electrode with an agate mortar, heating the mixture to 700 ℃ at a speed of 5 ℃/min under an argon atmosphere by using a tube furnace, carbonizing the mixture for 2 hours to obtain a regenerated graphite negative electrode material, assembling the regenerated graphite negative electrode material into a half-button battery, carrying out a charge and discharge performance test, wherein when the current density is 0.2A/g, the initial effect of the waste graphite negative electrode is 80.7%, and the initial specific charge capacity is 260.7mAh/g. The initial effect of the modified anode material is 79.2%, and the initial specific charge capacity is 360.9mAh/g. The modified cathode material has higher cycle stability.
Example 3
Black powder: aqua regia=1:5, washed for 3 hours, obtaining 99.9% of waste graphite negative electrode. Mixing a certain mass of waste graphite cathode with 1% ammonium chloride uniformly by an agate mortar, putting the mixture into a corundum magnetic boat, heating to 1000 ℃ at a speed of 5 ℃/min by a muffle furnace, preserving heat for 1h at 1000 ℃ and then naturally cooling to obtain a product 1, adding 10% coal tar into a certain amount of the product 1, mixing the mixture uniformly by the agate mortar, heating to 700 ℃ at a speed of 5 ℃/min by a tubular furnace under argon atmosphere and carbonizing for 2h to obtain a regenerated graphite cathode material, assembling the regenerated graphite cathode material into a semi-button battery, and testing charge and discharge performance, wherein when the current density is 0.2A/g, the initial effect of the waste graphite cathode is 80.7%, and the initial charge specific capacity is 260.7mAh/g. The initial effect of the modified anode material is 79.8%, and the initial specific charge capacity is 390.2mAh/g. The modified cathode material has higher cycle stability.
Example 4
Black powder: aqua regia=1:5, washed for 3 hours, obtaining 99.9% of waste graphite negative electrode. Mixing a certain mass of waste graphite cathode with 1% ammonium chloride uniformly by an agate mortar, putting the mixture into a corundum magnetic boat, heating to 1000 ℃ at a speed of 5 ℃/min by a muffle furnace, preserving heat for 1h at 1000 ℃ and then naturally cooling to obtain a product 1, adding 10% coal tar into a certain amount of the product 1, then mixing the mixture uniformly by the agate mortar, heating to 900 ℃ at a speed of 5 ℃/min by a tubular furnace under argon atmosphere and carbonizing for 2h to obtain a regenerated graphite cathode material, assembling the regenerated graphite cathode material into a semi-button battery, and testing charge and discharge performance, wherein when the current density is 0.2A/g, the initial effect of the waste graphite cathode is 80.7%, and the initial charge specific capacity is 260.7mAh/g. The initial effect of the modified anode material is 83.7%, and the initial specific charge capacity is 487mAh/g. The modified cathode material has higher cycle stability.
Example 5
Black powder: aqua regia=1:5, washed for 3 hours, obtaining 99.9% of waste graphite negative electrode. The waste graphite cathode with certain mass is processed1%NH 4 HCO 3 Mixing uniformly by an agate mortar, placing into a corundum magnetic boat, heating to 1000 ℃ at a speed of 5 ℃/min by using a muffle furnace, preserving heat at 1000 ℃ for 1h, naturally cooling to obtain a product 1, adding 10% coal pitch into a certain amount of product 1, mixing uniformly by using the agate mortar, heating to 700 ℃ at a speed of 5 ℃/min by using a tubular furnace, carbonizing for 2h to obtain a regenerated graphite negative electrode material, assembling the regenerated graphite negative electrode material into a half-button battery, performing charge and discharge performance test, and when the current density is 0.2A/g, the initial effect of the waste graphite negative electrode is 80.7%, and the initial charge specific capacity is 260.7mAh/g. The initial effect of the modified anode material is 82%, and the initial specific charge capacity is 435.8mAh/g. The modified cathode material has higher cycle stability.
Example 6
Black powder: aqua regia=1:5, washed for 3 hours, obtaining 99.9% of waste graphite negative electrode. Mixing a certain mass of waste graphite cathode with 1% (NH) 4 ) 2 CO 3 Mixing uniformly by an agate mortar, placing into a corundum magnetic boat, heating to 600 ℃ at a speed of 5 ℃/min by using a muffle furnace, preserving heat at 600 ℃ for 1h, naturally cooling to obtain a product 1, adding 10% coal pitch into a certain amount of product 1, mixing uniformly by using the agate mortar, heating to 700 ℃ at a speed of 5 ℃/min by using a tubular furnace, carbonizing for 2h to obtain a regenerated graphite negative electrode material, assembling the regenerated graphite negative electrode material into a half-button battery, performing charge and discharge performance test, and when the current density is 0.2A/g, the initial effect of the waste graphite negative electrode is 80.7%, and the initial charge specific capacity is 260.7mAh/g. The initial effect of the modified anode material is 81%, and the initial specific charge capacity is 430.2mAh/g. The modified cathode material has higher cycle stability.
Claims (3)
1. A method for recycling waste lithium graphite negative electrode uses waste lithium black powder as raw material, and the granularity is 15 microns; the method is characterized in that: the method comprises the following steps:
step 1, pickling and purifying; in the step, the aqua regia is utilized to remove metal ions, including iron ions, cobalt ions and nickel ions, in the waste lithium electric black powder;
step 2, dehydrating and modifying; in the step, calcium ions and magnesium ions are removed by modification; in the steps: the modifying reagent comprises NH 4 Cl，NH 4 HCO 3 Or (NH) 4 ) 2 CO 3 The dosage of the mixture is 0.5-1% of the weight of the waste lithium electric black powder;
step 3, coating treatment; realizing secondary granulation and recoating; in the steps: the coating agent is tar, asphalt, glucose, coking coal or phenolic resin, and the addition amount is 8-12% of the weight of the waste lithium electric black powder;
step 4, high-temperature carbonization; the modifier is removed in this step and the metal ions are removed by sublimation.
2. The method for recycling the waste lithium graphite anode according to claim 1, which is characterized in that: in the step 1, the solid-liquid mass ratio of the aqua regia to the waste lithium electric black powder is 1:1-1:20, and the pickling time is 2-10 h.
3. The method for recycling the waste lithium graphite anode according to claim 1, which is characterized in that: high-temperature carbonization temperature is 700-1400 ℃, and high-temperature carbonization time is 2-8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310725568.9A CN116639685B (en) | 2023-06-19 | 2023-06-19 | Recycling method of waste lithium-carbide graphite cathode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310725568.9A CN116639685B (en) | 2023-06-19 | 2023-06-19 | Recycling method of waste lithium-carbide graphite cathode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116639685A CN116639685A (en) | 2023-08-25 |
| CN116639685B true CN116639685B (en) | 2023-12-22 |
Family
ID=87643504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310725568.9A Active CN116639685B (en) | 2023-06-19 | 2023-06-19 | Recycling method of waste lithium-carbide graphite cathode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116639685B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001152048A (en) * | 1999-09-13 | 2001-06-05 | Mitsubishi Chemicals Corp | Method of producing resin-coated carbon black |
| CN1304187A (en) * | 1999-12-15 | 2001-07-18 | 北京有色金属研究总院 | Composite graphite negative electrode material for lithium cell and its preparation method |
| CN106252597A (en) * | 2016-08-09 | 2016-12-21 | 北京化工大学 | A kind of long circulation life carbon negative electrode material of lithium ion cell and preparation method thereof |
| JP2018106917A (en) * | 2016-12-26 | 2018-07-05 | 新日鐵住金株式会社 | Negative electrode active material, manufacturing method therefor, negative electrode and battery |
| CN111204754A (en) * | 2020-01-14 | 2020-05-29 | 大同新成新材料股份有限公司 | Preparation method of graphene oxide silicon-carbon composite negative electrode material |
| CN112047335A (en) * | 2020-08-31 | 2020-12-08 | 湖南宸宇富基新能源科技有限公司 | Combined treatment method for black powder of waste lithium ion battery |
| CN114212786A (en) * | 2021-10-26 | 2022-03-22 | 中南大学 | Method for preparing high-capacity high-rate graphite by taking waste lithium ion battery cathode material as raw material |
| CN115806292A (en) * | 2022-11-28 | 2023-03-17 | 武汉瑞科美新能源有限责任公司 | Impurity removal method for waste graphite cathode |
-
2023
- 2023-06-19 CN CN202310725568.9A patent/CN116639685B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001152048A (en) * | 1999-09-13 | 2001-06-05 | Mitsubishi Chemicals Corp | Method of producing resin-coated carbon black |
| CN1304187A (en) * | 1999-12-15 | 2001-07-18 | 北京有色金属研究总院 | Composite graphite negative electrode material for lithium cell and its preparation method |
| CN106252597A (en) * | 2016-08-09 | 2016-12-21 | 北京化工大学 | A kind of long circulation life carbon negative electrode material of lithium ion cell and preparation method thereof |
| JP2018106917A (en) * | 2016-12-26 | 2018-07-05 | 新日鐵住金株式会社 | Negative electrode active material, manufacturing method therefor, negative electrode and battery |
| CN111204754A (en) * | 2020-01-14 | 2020-05-29 | 大同新成新材料股份有限公司 | Preparation method of graphene oxide silicon-carbon composite negative electrode material |
| CN112047335A (en) * | 2020-08-31 | 2020-12-08 | 湖南宸宇富基新能源科技有限公司 | Combined treatment method for black powder of waste lithium ion battery |
| CN114212786A (en) * | 2021-10-26 | 2022-03-22 | 中南大学 | Method for preparing high-capacity high-rate graphite by taking waste lithium ion battery cathode material as raw material |
| CN115806292A (en) * | 2022-11-28 | 2023-03-17 | 武汉瑞科美新能源有限责任公司 | Impurity removal method for waste graphite cathode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116639685A (en) | 2023-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113594420B (en) | Regeneration method of lithium ion battery graphite cathode and regenerated graphite cathode thereof | |
| CN111573662A (en) | Method for preparing high-capacity negative electrode material by utilizing recovered graphite | |
| CN105552469B (en) | A kind of recycling method of applying waste lithium ionic power battery cathode material | |
| AU2021103805A4 (en) | Method for degrading poly(vinylidene fluoride) (pvdf) in cathode of waste lithium iron phosphate battery | |
| CN112794300A (en) | Separation, recovery and regeneration method of waste lithium iron phosphate battery positive plate | |
| CN106785163A (en) | The method of reparative regeneration graphite negative material of lithium ion battery | |
| CN114583315B (en) | Method for recycling carbon cathode material from waste lithium ion battery | |
| CN116639685B (en) | Recycling method of waste lithium-carbide graphite cathode | |
| CN117393886A (en) | Method for regenerating and repairing graphite of negative electrode of waste lithium ion battery | |
| CN117003235A (en) | Method for regenerating graphite in waste battery | |
| CN116169386A (en) | Method for efficiently recycling waste ternary lithium ion battery anode material by using green solvent prepared from fruits such as pome fruits | |
| CN115498185A (en) | Regeneration method of waste graphite negative electrode material | |
| CN112320802A (en) | Recycling method of silicon-carbon negative electrode material | |
| CN116573632B (en) | Asphalt-based hard carbon, preparation method and application thereof in sodium ion battery | |
| CN113735112B (en) | Method for preparing expanded graphite from graphite cathode of waste lithium ion battery | |
| CN115939561A (en) | Negative electrode leftover material regenerated active material and preparation and application thereof | |
| CN111675251B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| CN117619859A (en) | Recycling recovery method of waste lithium ion power battery | |
| CN117865105A (en) | Demagnetizing method of lithium iron phosphate material | |
| CN117977042A (en) | Synergistic method for impurity removal and repair of graphite cathode material of waste lithium ion battery | |
| CN117658091A (en) | Repairing method of regenerated lithium iron phosphate positive electrode material, positive electrode material and application | |
| CN115377544A (en) | Method for recovering lithium iron phosphate positive electrode material and separating current collector | |
| CN117585655A (en) | Regeneration method of lithium iron phosphate positive electrode material waste and lithium ion battery | |
| CN114709506A (en) | Modification method of retired lithium ion battery negative electrode material | |
| CN113871742A (en) | Method for recycling and reusing graphite cathode in waste battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |