CN112803024A - Regeneration method and application of waste lithium ion battery negative electrode graphite material - Google Patents
Regeneration method and application of waste lithium ion battery negative electrode graphite material Download PDFInfo
- Publication number
- CN112803024A CN112803024A CN202110063019.0A CN202110063019A CN112803024A CN 112803024 A CN112803024 A CN 112803024A CN 202110063019 A CN202110063019 A CN 202110063019A CN 112803024 A CN112803024 A CN 112803024A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- graphite
- graphite material
- lithium ion
- ion battery
- 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.)
- Withdrawn
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention provides a regeneration method and application of a waste lithium ion battery negative electrode graphite material, which comprises the following steps: (1) screening the waste lithium ion battery negative electrode graphite material to obtain graphite powder with the particle size not greater than 50 mu m; (2) dispersing graphene oxide in water to obtain a graphene oxide solution; (3) mixing and stirring graphite powder and a graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1: 0.01-0.1, and then filtering to obtain a graphene oxide coated graphite material; (4) and calcining the graphene oxide coated graphite material in an oxygen-free environment to obtain the graphene coated graphite material. By coating the waste graphite material with the graphene, the graphene can fill up the defects on the surface of the waste graphite material, and the electrical properties such as the first coulombic efficiency, the cycle performance and the like of the regenerated graphite as the negative electrode material of the lithium ion battery are improved.
Description
Technical Field
The invention belongs to the field of battery recovery, and particularly relates to a regeneration method of a graphite material of a negative electrode of a waste lithium ion battery, and a preparation method and application thereof.
Background
The lithium ion battery is used as a green and environment-friendly secondary power supply, and has the advantages of high capacity, high specific energy, high working voltage, small self-discharge, good cycle performance, long service life, no memory effect and the like, so the development is rapid in recent years. The lithium ion battery is composed of a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell. Graphite is widely used in the negative electrode material of lithium ion batteries due to its characteristics of good conductivity, ordered layered crystal structure, high reversible lithium storage capacity, low charge-discharge potential, long and stable platform, and the like. While the lithium ion battery industry is rapidly developing, the graphite industry is also developing in a high-yield mode, which will produce a large amount of waste graphite. If not properly treated, it will inevitably have a great impact on the living environment and health of human beings. Therefore, the recycling and the reutilization of the graphite in the cathode of the waste lithium ion battery can relieve the shortage of carbon resources and avoid the environmental pollution.
The recovery and regeneration of the waste lithium ion battery negative electrode graphite material have problems, the surface structure of the graphite negative electrode is damaged in the circulation process to form surface defects, and meanwhile, the graphite negative electrode and electrolyte are irreversibly hardened to cause irreversible capacity loss, so that the cycle performance is seriously degraded, and the problems are still the major problems faced by the recovery and regeneration of the waste lithium ion battery negative electrode graphite material.
Disclosure of Invention
The invention aims to solve the problems and provides a regeneration method and application of a graphite material of a negative electrode of a waste lithium ion battery.
According to one aspect of the application, a method for regenerating a graphite material of a negative electrode of a waste lithium ion battery is provided, and the method comprises the following steps:
(1) screening the waste lithium ion battery negative electrode graphite material to obtain graphite powder with the particle size not greater than 50 mu m;
(2) dispersing graphene oxide in water to obtain a graphene oxide solution;
(3) mixing and stirring graphite powder and a graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1: 0.01-0.1, and then filtering to obtain a graphene oxide coated graphite material;
(4) and calcining the graphene oxide coated graphite material in an oxygen-free environment to obtain the graphene coated graphite material.
Further, in the step (3), the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution is 1: 0.02-0.08; preferably, in the step (3), the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution is 1: 0.05-0.06.
Further, in the step (3), the stirring speed is 10-2000 r/min, and the stirring time is 1-20 h; and/or
The filtration is at least one selected from centrifugal filtration, suction filtration and plate-and-frame filter pressing;
preferably, in the step (3), the stirring speed is 100-1000 r/min, and the stirring time is 5-10 h.
Further, in the step (2), the sheet diameter of the graphene oxide is 1-50 μm, and the resistivity is 5-20 Ω · cm; the concentration of graphene oxide in the graphene oxide solution is 1-10 g/L;
preferably, the sheet diameter of the graphene oxide is 10-25 μm, and the resistivity is 10-15 Ω & cm; the concentration of the graphene oxide in the graphene oxide solution is 2-5 g/L.
Further, in the step (2), dispersing graphene oxide in water, adding a surface tension regulator, and performing ultrasonic dispersion to obtain a graphene oxide solution;
preferably, the concentration of the surface tension regulator in the graphene oxide solution is 0.01-0.5 g/L.
Preferably, the surface tension modifier is selected from at least one of ethanol, isopropanol, acetone, ethylene glycol, methanol, N-N dimethylformamide, dimethyl sulfoxide, glycerol, N-butanol, 1-methyl-pyrrolidone, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide and polyvinylpyrrolidone;
more preferably, the surface tension modifier is isopropanol.
Further, in the step (2), the graphene oxide is prepared by subjecting graphite to a liquid-phase oxidation reaction under the action of a strong acid and an oxidant, and washing the generated graphite oxide;
preferably, the graphite is selected from flake graphite;
the mass ratio of the graphite to the oxidant is 1: 2-5;
the liquid-phase oxidation reaction comprises the steps of adding graphite, strong acid and an oxidant into stirring at 0-2 ℃, and stirring for 5-20 min at 10-15 ℃;
and secondly, continuously stirring for 25-40 min at the temperature of 30-55 ℃.
Further, before the step (1), a step of stripping the graphite material from the negative electrode current collector of the waste lithium ion battery is also included;
preferably, the peeling method is at least one selected from the group consisting of pulverization, water immersion, and burning;
preferably, the stripping method is water immersion, and the specific steps are as follows: and (3) putting the waste lithium ion battery negative current collector into water, and soaking for 20-40 min to separate the graphite material on the current collector from the metal foil.
Further, in the step (4), the calcining temperature is 600-1000 ℃, and the time is 1-10 hours;
preferably, the calcining temperature is 800-950 ℃, and the time is 2-4 h
According to another aspect of the application, the graphene-coated graphite material obtained by the method is also provided.
According to another aspect of the application, the application of the graphene-coated graphite material as a lithium ion battery negative electrode material is also provided.
The beneficial effects of the invention include but are not limited to:
(1) according to the regeneration method of the waste lithium ion battery cathode graphite material, the waste graphite is coated by the graphene oxide, the defects on the surface of the waste graphite can be repaired, and the graphene oxide is reduced by a high-temperature firing process to obtain the graphite material uniformly coated with the graphene; the graphene can fill the defects of the surface of the waste graphite material, and the first coulombic efficiency, the cycle performance and the energy density of the regenerated graphite as the lithium ion battery cathode material are improved.
(2) According to the regeneration method of the waste lithium ion battery cathode graphite material, the particle size of the obtained coated and regenerated graphite is moderate by optimizing parameters such as the particle size of graphite powder and the sheet size of graphene oxide, the electrical property of the regenerated graphite as the lithium ion battery cathode material is improved, and the coated and regenerated graphite material completely meets the use requirement.
(3) The regeneration method of the waste lithium ion battery cathode graphite material provided by the invention has the advantages of mild conditions, easily-controlled process parameters, low energy consumption, environmental friendliness and contribution to industrial large-scale production.
Drawings
Fig. 1 is a raman spectrum of graphite material 1# obtained in example 1 of the present invention.
Detailed Description
In order to more clearly explain the overall concept of the present application, the following detailed description is given by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present application. It will be apparent, however, to one skilled in the art, that the present application may be practiced without one or more of these specific details. In other instances, well-known features of the art have not been described in order to avoid obscuring the present application.
Unless otherwise specified, the starting materials and reagents in the following examples are all commercially available.
Example 1
A method for regenerating a graphite material of a negative electrode of a waste lithium ion battery comprises the following steps:
(1) soaking the current collector with graphite and copper foil in water for 30min to separate the graphite and the copper foil on the current collector, and taking out the copper foil; filtering and drying graphite to obtain a graphite raw material;
(2) crushing a graphite raw material by using a universal crusher, and sieving the crushed graphite raw material by using a 300-mesh sieve to obtain graphite powder with the particle size of less than or equal to 50 mu m;
(3) the method for preparing the graphene oxide by using the Hummers method comprises the following specific steps: firstly, adding flake graphite into concentrated sulfuric acid, adding potassium permanganate under the stirring condition at 0 ℃, and stirring for 10min at 15 ℃ to primarily oxidize graphite by the concentrated sulfuric acid and the potassium permanganate graphite;
secondly, continuously stirring for 30min at the temperature of 40 ℃ to further oxidize graphite by potassium permanganate;
continuing stirring at the temperature of 100 ℃ for 20min to dissociate sulfur-containing groups on the graphite oxide to obtain graphene oxide; the sheet diameter of the obtained graphene oxide is 20 micrometers, and the resistivity is 10 omega cm;
washing graphene oxide, and dispersing the graphene oxide in water to obtain a graphene oxide solution; the concentration of graphene oxide in the graphene oxide solution is 2 g/L;
(4) adding graphite powder into the graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1:0.05, stirring while adding, wherein the stirring speed is 500r/min, and the stirring time is 6 h. Filtering to obtain a filter cake to obtain a graphite material coated by graphene oxide;
(5) and (3) putting the graphene oxide coated graphite material into a tubular furnace, calcining for 2h at 950 ℃ under the protection of nitrogen to obtain a graphene coated graphite material No. 1, wherein the Raman spectrum of the graphene oxide coated graphite material is shown in figure 1, and the graphene oxide is uniformly coated on the surface of graphite particles.
Example 2
A method for regenerating a graphite material of a negative electrode of a waste lithium ion battery comprises the following steps:
(1) soaking the current collector with graphite and copper foil in water for 40min to separate the graphite and the copper foil on the current collector, and taking out the copper foil; filtering and drying graphite to obtain a graphite raw material;
(2) crushing a graphite raw material by using a universal crusher, and sieving the crushed graphite raw material by using a 300-mesh sieve to obtain graphite powder with the particle size of less than or equal to 50 mu m;
(3) the method for preparing the graphene oxide by using the Hummers method comprises the following specific steps: firstly, adding flake graphite into concentrated sulfuric acid, adding potassium permanganate under the stirring condition at 0 ℃, and stirring for 20min at 10 ℃ to primarily oxidize graphite by the concentrated sulfuric acid and the potassium permanganate graphite;
secondly, continuously stirring for 25min at the temperature of 55 ℃ to further oxidize graphite by potassium permanganate;
continuing stirring at the temperature of 95 ℃ for 30min to dissociate sulfur-containing groups on the graphite oxide to obtain graphene oxide; the sheet diameter of the obtained graphene oxide is 10 micrometers, and the resistivity is 15 omega cm;
washing graphene oxide, adding the washed graphene oxide into water, adding ethanol, and performing ultrasonic dispersion to obtain a graphene oxide solution; the concentration of graphene oxide in the graphene oxide solution is 5g/L, and the concentration of ethanol is 0.25 g/L;
(4) adding graphite powder into the graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1:0.1, stirring while adding, wherein the stirring speed is 100r/min, and the stirring time is 10 hours. Filtering to obtain a filter cake to obtain a graphite material coated by graphene oxide;
(5) and putting the graphene oxide coated graphite material into a tubular furnace, and calcining for 10 hours at 600 ℃ under the protection of nitrogen to obtain the graphene coated graphite material No. 2.
Example 3
A method for regenerating a graphite material of a negative electrode of a waste lithium ion battery comprises the following steps:
(1) soaking the current collector with graphite and aluminum foil in water for 20min to separate the graphite on the current collector from the aluminum foil, and taking out the aluminum foil; filtering and drying graphite to obtain a graphite raw material;
(2) crushing a graphite raw material by using a universal crusher, and sieving the crushed graphite raw material by using a 300-mesh sieve to obtain graphite powder with the particle size of less than or equal to 50 mu m;
(3) the method for preparing the graphene oxide by using the Hummers method comprises the following specific steps: firstly, adding flake graphite into concentrated sulfuric acid, adding potassium permanganate under stirring at the temperature of 2 ℃, and stirring for 5min at the temperature of 10 ℃ to primarily oxidize graphite by the concentrated sulfuric acid and the potassium permanganate graphite;
secondly, continuously stirring for 40min at the temperature of 30 ℃ to further oxidize graphite by potassium permanganate;
continuing stirring at the temperature of 95 ℃ for 30min to dissociate sulfur-containing groups on the graphite oxide to obtain graphene oxide; the sheet diameter of the obtained graphene oxide is 25 micrometers, and the resistivity is 10 omega cm;
washing graphene oxide, adding the washed graphene oxide into water, adding polyvinylpyrrolidone, and performing ultrasonic dispersion to obtain a graphene oxide solution; the concentration of graphene oxide in the graphene oxide solution is 10g/L, and the concentration of polyvinylpyrrolidone is 0.01 g/L;
(4) adding graphite powder into the graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1:0.02, stirring while adding, wherein the stirring speed is 2000r/min, and the stirring time is 1 h. Filtering to obtain a filter cake to obtain a graphite material coated by graphene oxide;
(5) and putting the graphene oxide coated graphite material into a tubular furnace, and calcining for 2 hours at 1000 ℃ under the protection of nitrogen to obtain the graphene coated graphite material No. 3.
Example 4
A method for regenerating a graphite material of a negative electrode of a waste lithium ion battery comprises the following steps:
(1) soaking the current collector with graphite and aluminum foil in water for 30min to separate the graphite from the aluminum foil on the current collector, and taking out the aluminum foil; filtering and drying graphite to obtain a graphite raw material;
(2) crushing a graphite raw material by using a universal crusher, and sieving the crushed graphite raw material by using a 300-mesh sieve to obtain graphite powder with the particle size of less than or equal to 50 mu m;
(3) the method for preparing the graphene oxide by using the Hummers method comprises the following specific steps: firstly, adding flake graphite into concentrated sulfuric acid, adding potassium permanganate under the stirring condition at 0 ℃, and stirring for 20min at 15 ℃ to primarily oxidize graphite by the concentrated sulfuric acid and the potassium permanganate graphite;
secondly, continuously stirring for 40min at the temperature of 30 ℃ to further oxidize graphite by potassium permanganate;
continuing stirring at the temperature of 100 ℃ for 20min to dissociate sulfur-containing groups on the graphite oxide to obtain graphene oxide; the sheet diameter of the obtained graphene oxide is 5 micrometers, and the resistivity is 20 omega cm;
washing graphene oxide, adding the washed graphene oxide into water, adding isopropanol, and performing ultrasonic dispersion to obtain a graphene oxide solution; the concentration of graphene oxide in the graphene oxide solution is 1g/L, and the concentration of isopropanol ketone is 0.5 g/L;
(4) adding graphite powder into the graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1:0.01, stirring while adding, wherein the stirring speed is 1000r/min, and the stirring time is 5 h. Filtering to obtain a filter cake to obtain a graphite material coated by graphene oxide;
(5) and putting the graphene oxide coated graphite material into a tubular furnace, and calcining for 4 hours at 800 ℃ under the protection of nitrogen to obtain the graphene coated graphite material No. 4.
Example 5
A method for regenerating a graphite material of a negative electrode of a waste lithium ion battery comprises the following steps:
(1) soaking the current collector with graphite and copper foil in water for 50min to separate the graphite and the copper foil on the current collector, and taking out the copper foil; filtering and drying graphite to obtain a graphite raw material;
(2) crushing a graphite raw material by using a universal crusher, and sieving the crushed graphite raw material by using a 300-mesh sieve to obtain graphite powder with the particle size of less than or equal to 50 mu m;
(3) the method for preparing the graphene oxide by using the Hummers method comprises the following specific steps: firstly, adding flake graphite into concentrated sulfuric acid, adding potassium permanganate under the stirring condition at 0 ℃, and stirring for 20min at 10 ℃ to primarily oxidize graphite by the concentrated sulfuric acid and the potassium permanganate graphite;
secondly, continuously stirring for 25min at the temperature of 55 ℃ to further oxidize graphite by potassium permanganate;
continuing stirring at the temperature of 100 ℃ for 20min to dissociate sulfur-containing groups on the graphite oxide to obtain graphene oxide; the sheet diameter of the obtained graphene oxide is 40m, and the resistivity is 5 omega cm;
washing graphene oxide, adding the washed graphene oxide into water, adding dimethyl sulfoxide, and performing ultrasonic dispersion to obtain a graphene oxide solution; the concentration of graphene oxide in the graphene oxide solution is 4g/L, and the concentration of dimethyl sulfoxide is 0.05 g/L;
(4) adding graphite powder into the graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1:0.06, stirring while adding, wherein the stirring speed is 2000r/min, and the stirring time is 2 hours. Filtering to obtain a filter cake to obtain a graphite material coated by graphene oxide;
(5) and putting the graphene oxide coated graphite material into a tubular furnace, and calcining for 1h at 1000 ℃ under the protection of nitrogen to obtain the graphene coated graphite material No. 5.
Comparative example 1
The comparative example 1 differs from example 1 in that: (4) adding graphite powder into the graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1:0.02, stirring while adding, wherein the stirring speed is 500r/min, and the stirring time is 6 h. Filtering to obtain a filter cake to obtain a graphite material coated by graphene oxide; the rest of the procedure was the same as in example 1, to obtain graphite material D1 #.
Comparative example 2
The comparative example 2 differs from example 1 in that: (2) crushing a graphite raw material by using a universal crusher, and sieving the crushed graphite raw material by using a 100-mesh sieve to obtain graphite powder with the particle size of less than or equal to 100 mu m; the rest of the procedure was the same as in example 1, to obtain graphite material D1 #. The rest of the procedure was the same as in example 1 to obtain graphite material D2#
Comparative example 3
The comparative example 3 differs from example 1 in that: (3) preparing graphene oxide by using a Hummers method, wherein the sheet diameter of the obtained graphene oxide is 5 microns, and the resistivity of the graphene oxide is 10 omega cm; washing graphene oxide, and dispersing the graphene oxide in water to obtain a graphene oxide solution; the concentration of the graphene oxide in the graphene oxide solution is 2 g/L. The rest of the procedure was the same as in example 1, to obtain graphite material D3 #.
The graphite material No. 1-5 obtained in the embodiment of the application, the graphite material D1-D3 obtained in the comparative example and the graphite powder before regeneration of graphite (prepared according to the steps (1) and (2) in the embodiment 1 of the application) are used as a graphite material D4#, and after ball milling is carried out for 2 hours at a low speed (300 revolutions per minute), the graphite material is mixed with sodium carboxymethylcellulose and ultrafine carbon powder according to the mass ratio of 8:1:1 to prepare slurry and then coated, a metal lithium sheet is selected as a negative electrode, an electrolyte is LiPF 6/ethylene carbonate + diethyl carbonate (1:1) with the electrolyte of 1mol/L, a diaphragm is a polypropylene microporous film, and a button cell is prepared and evaluated for the physical and chemical properties of the button cell as a negative electrode material of a lithium battery.
The method for testing the first charge-discharge coulombic efficiency refers to the national standard GB/T243334-2009 graphite cathode material for lithium ion batteries; the cycle performance test method is as follows: the battery is charged at a constant current of 0.5C at 23 DEG CThe power is charged to the upper limit voltage, then constant voltage charging is carried out, and the current is cut off by 0.05C; standing for 10min, discharging to 2.7V at constant current of 0.5C, and measuring to obtain initial discharge capacity C of the battery0(ii) a After standing for 10min, repeating the above steps for 100 weeks, and performing continuous charge-discharge test to obtain the capacity C of the battery after 100 cycles1. The capacity remaining rate of the battery after 100 cycles was calculated according to the following formula: capacity remaining rate ═ C1/C0X 100%. The battery energy density measurement method is as follows: charging the current to the upper limit voltage at 23 ℃ with a constant current of 0.5C, then converting to constant voltage charging, and cutting off the current by 0.05C; standing for 10min, discharging to 2.7V at constant current of 0.5C, and measuring the discharge capacity of the battery; after standing for 10min, the above steps were repeated 3 times, and the average value of the 3 discharge capacities was calculated. The different types of batteries were weighed using an electronic balance. The 23 ℃ cell energy density was calculated as follows: battery energy density is the average capacity of discharge x median voltage/weight of the battery.
TABLE 1 Battery Performance test results
As can be seen from table 1, the coated and regenerated graphite material obtained by the preparation method of the embodiment of the present application has excellent first charge-discharge efficiency and cycle performance, and has high energy density; particularly, the capacity retention rate of the battery after 100-week circulation can reach 96 percent at most. The regeneration method of the waste lithium ion battery cathode graphite material can effectively improve the electrical property of the coated regenerated graphite.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A regeneration method of a graphite material of a negative electrode of a waste lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
(1) screening the waste lithium ion battery negative electrode graphite material to obtain graphite powder with the particle size not greater than 50 mu m;
(2) dispersing graphene oxide in water to obtain a graphene oxide solution;
(3) mixing and stirring graphite powder and a graphene oxide solution according to the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution of 1: 0.01-0.1, and then filtering to obtain a graphene oxide coated graphite material;
(4) and calcining the graphene oxide coated graphite material in an oxygen-free environment to obtain the graphene coated graphite material.
2. The method for regenerating the graphite material of the negative electrode of the waste lithium ion battery as claimed in claim 1, wherein the method comprises the following steps: step (3), the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution is 1: 0.02-0.08;
preferably, in the step (3), the mass ratio of the graphite powder to the graphene oxide in the graphene oxide solution is 1: 0.05-0.06.
3. The method for regenerating the graphite material of the negative electrode of the waste lithium ion battery as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the stirring speed is 10-2000 r/min, and the stirring time is 1-20 h; and/or
The filtration is at least one selected from centrifugal filtration, suction filtration and plate-and-frame filter pressing;
preferably, in the step (3), the stirring speed is 100-1000 r/min, and the stirring time is 5-10 h.
4. The method for regenerating the graphite material of the negative electrode of the waste lithium ion battery as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the sheet diameter of the graphene oxide is 1-50 μm, and the resistivity is 5-20 Ω & cm; the concentration of graphene oxide in the graphene oxide solution is 1-10 g/L;
preferably, the sheet diameter of the graphene oxide is 10-25 μm, and the resistivity is 10-15 Ω & cm; the concentration of the graphene oxide in the graphene oxide solution is 2-5 g/L.
5. The method for regenerating the graphite material of the negative electrode of the waste lithium ion battery as claimed in claim 1, wherein the method comprises the following steps: in the step (2), dispersing graphene oxide in water, adding a surface tension regulator, and performing ultrasonic dispersion to obtain a graphene oxide solution;
preferably, the concentration of the surface tension regulator in the graphene oxide solution is 0.01-0.5 g/L.
Preferably, the surface tension modifier is selected from at least one of ethanol, isopropanol, acetone, ethylene glycol, methanol, N-N dimethylformamide, dimethyl sulfoxide, glycerol, N-butanol, 1-methyl-pyrrolidone, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide and polyvinylpyrrolidone;
more preferably, the surface tension modifier is isopropanol.
6. The method for regenerating the graphite material of the negative electrode of the waste lithium ion battery as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the graphene oxide is prepared by carrying out liquid-phase oxidation reaction on graphite under the action of strong acid and an oxidant and washing the generated graphite oxide;
preferably, the graphite is selected from flake graphite;
the mass ratio of the graphite to the oxidant is 1: 2-5;
the liquid-phase oxidation reaction comprises the steps of adding graphite, strong acid and an oxidant into stirring at 0-2 ℃, and stirring for 5-20 min at 10-15 ℃;
and secondly, continuously stirring for 25-40 min at the temperature of 30-55 ℃.
7. The method for regenerating the graphite material of the negative electrode of the waste lithium ion battery as claimed in claim 1, wherein the method comprises the following steps: before the step (1), a step of stripping the graphite material from the negative current collector of the waste lithium ion battery is also included;
preferably, the peeling method is at least one selected from the group consisting of pulverization, water immersion, and burning;
preferably, the stripping method is water immersion, and the specific steps are as follows: and (3) putting the waste lithium ion battery negative current collector into water, and soaking for 20-40 min to separate the graphite material on the current collector from the metal foil.
8. The method for regenerating the graphite material of the negative electrode of the waste lithium ion battery as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the calcining temperature is 600-1000 ℃, and the time is 1-10 h;
preferably, the calcining temperature is 800-950 ℃, and the time is 2-4 h.
9. A graphene-coated graphite material obtained by the method according to any one of claims 1 to 8.
10. Use of the graphene-coated graphite material of claim 9 as a negative electrode material for a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110063019.0A CN112803024A (en) | 2021-01-18 | 2021-01-18 | Regeneration method and application of waste lithium ion battery negative electrode graphite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110063019.0A CN112803024A (en) | 2021-01-18 | 2021-01-18 | Regeneration method and application of waste lithium ion battery negative electrode graphite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112803024A true CN112803024A (en) | 2021-05-14 |
Family
ID=75810136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110063019.0A Withdrawn CN112803024A (en) | 2021-01-18 | 2021-01-18 | Regeneration method and application of waste lithium ion battery negative electrode graphite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112803024A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955747A (en) * | 2021-10-20 | 2022-01-21 | 北京化工大学常州先进材料研究院 | Preparation method of graphene-coated natural graphite negative electrode material |
| CN114551830A (en) * | 2022-02-21 | 2022-05-27 | 海城申合科技有限公司 | Preparation method of graphene oxide coated artificial graphite lithium ion negative electrode material |
| CN115286952A (en) * | 2022-08-30 | 2022-11-04 | 广东一纳科技有限公司 | Graphene composite powder applied to electrophoretic paint, preparation method of graphene composite powder and electrophoretic paint |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744928A (en) * | 2015-11-18 | 2017-05-31 | 青岛智信生物科技有限公司 | The preparation technology of graphene oxide |
| CN108281634A (en) * | 2015-04-21 | 2018-07-13 | 常州第六元素材料科技股份有限公司 | A kind of method and its application of graphene coated graphite negative material of lithium ion battery |
| CN108376807A (en) * | 2018-04-09 | 2018-08-07 | 湖南省正源储能材料与器件研究所 | A kind of waste and old lithium ion battery graphite cathode material restorative procedure |
| CN110137469A (en) * | 2019-05-16 | 2019-08-16 | 湖南鸿捷新材料有限公司 | A kind of waste and old lithium ion battery graphite cathode material regeneration method |
-
2021
- 2021-01-18 CN CN202110063019.0A patent/CN112803024A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108281634A (en) * | 2015-04-21 | 2018-07-13 | 常州第六元素材料科技股份有限公司 | A kind of method and its application of graphene coated graphite negative material of lithium ion battery |
| CN106744928A (en) * | 2015-11-18 | 2017-05-31 | 青岛智信生物科技有限公司 | The preparation technology of graphene oxide |
| CN108376807A (en) * | 2018-04-09 | 2018-08-07 | 湖南省正源储能材料与器件研究所 | A kind of waste and old lithium ion battery graphite cathode material restorative procedure |
| CN110137469A (en) * | 2019-05-16 | 2019-08-16 | 湖南鸿捷新材料有限公司 | A kind of waste and old lithium ion battery graphite cathode material regeneration method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955747A (en) * | 2021-10-20 | 2022-01-21 | 北京化工大学常州先进材料研究院 | Preparation method of graphene-coated natural graphite negative electrode material |
| CN114551830A (en) * | 2022-02-21 | 2022-05-27 | 海城申合科技有限公司 | Preparation method of graphene oxide coated artificial graphite lithium ion negative electrode material |
| CN115286952A (en) * | 2022-08-30 | 2022-11-04 | 广东一纳科技有限公司 | Graphene composite powder applied to electrophoretic paint, preparation method of graphene composite powder and electrophoretic paint |
| CN115286952B (en) * | 2022-08-30 | 2023-10-03 | 广东一纳科技有限公司 | Graphene composite powder applied to electrophoretic paint, preparation method of graphene composite powder and electrophoretic paint |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112803024A (en) | Regeneration method and application of waste lithium ion battery negative electrode graphite material | |
| CN109626352B (en) | Hard carbon-like graphite negative electrode material for high-rate lithium ion battery and preparation method thereof | |
| CN106505273A (en) | The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled | |
| CN102664294A (en) | Method for recycling waste lithium iron phosphate batteries | |
| CN103187556B (en) | Lithium ion battery and its negative material, preparation method | |
| CN107026262A (en) | The spherical hard charcoal negative material of high power capacity of surface graphene coated | |
| CN111916735B (en) | Amorphous carbon material, preparation method thereof and lithium ion battery | |
| CN111252757A (en) | Method for preparing graphene by using waste lithium ion power battery | |
| CN115566255B (en) | Secondary battery and electric equipment | |
| CN109742476A (en) | A kind of recoverying and utilizing method of waste lithium ion cell anode material | |
| CN114229816A (en) | Method for recycling and preparing anode material from waste lithium iron phosphate battery | |
| CN111977646A (en) | Method for preparing expanded graphite/silicon carbon material from graphite cathode of waste battery | |
| CN113725408A (en) | Negative electrode material, preparation method thereof, negative electrode sheet and battery | |
| WO2023061115A1 (en) | Method for recovering lithium iron phosphate material | |
| CN110707290A (en) | Preparation method of flexible lithium ion battery negative electrode with sandwich-like structure | |
| CN109879279A (en) | A method of improving artificial graphite high rate performance | |
| CN115051062A (en) | Method for directly regenerating waste graphite by using eutectic solvent | |
| CN115249799A (en) | Rosin-based nitrogen-doped coated hard carbon negative electrode material of sodium ion battery and preparation method of rosin-based nitrogen-doped coated hard carbon negative electrode material | |
| CN114784271A (en) | Regenerated lithium iron phosphate positive electrode material, preparation method and application | |
| CN112599878B (en) | Treatment method and application of electrode waste | |
| CN115000408A (en) | Composite binder, preparation method and preparation method of negative plate | |
| CN114824542A (en) | Method for recovering negative graphite in waste lithium ion battery and application | |
| CN109119607B (en) | Polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material and preparation method thereof | |
| CN113526488A (en) | Method for recovering and modifying positive electrode material in waste lithium/carbon fluoride battery | |
| CN113437295A (en) | Hard carbon negative electrode material and preparation method thereof |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210514 |