CN115084477A - Preparation method of graphite cathode material, graphite cathode and application of graphite cathode material - Google Patents
Preparation method of graphite cathode material, graphite cathode and application of graphite cathode material Download PDFInfo
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- CN115084477A CN115084477A CN202210807691.0A CN202210807691A CN115084477A CN 115084477 A CN115084477 A CN 115084477A CN 202210807691 A CN202210807691 A CN 202210807691A CN 115084477 A CN115084477 A CN 115084477A
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- 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
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- 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
- C01B32/205—Preparation
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- 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
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- 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
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- 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
Abstract
The invention discloses a preparation method of a graphite cathode material, a graphite cathode and application thereof, wherein the preparation method comprises the following steps: (1) preparing a coke aggregate, and respectively carrying out coarse crushing, grinding and grading treatment on a plurality of cokes to obtain a plurality of corresponding coke aggregates; (2) preparing modified coke, respectively adding an acidic solution into a plurality of coke aggregates, stirring to prepare slurry, and washing, filtering, dehydrating and drying the slurry to obtain a plurality of corresponding first materials; (3) preparing a second material, and mixing at least two first materials to obtain the second material, or mixing at least one coke aggregate and at least one first material to obtain the second material; (4) and (4) coating and graphitizing, namely mixing the second material with a coating agent, and then granulating and graphitizing. According to the invention, the graphite negative electrode material which has high dynamics and high granulation performance and improves the cycle performance of the secondary battery can be obtained by firstly carrying out acidic solution modification treatment on the coke aggregate subjected to the preliminary treatment.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a preparation method of a graphite cathode material, a graphite cathode and application of the graphite cathode material.
Background
The secondary battery has the characteristics of higher energy density, excellent dynamic performance, long cycle life, cleanness, environmental protection and the like, and is widely applied to the fields of power and consumer new energy. The graphite negative electrode is still the mainstream of the current negative electrode material market demand, but along with the increasingly strict requirements of consumers on the high specific capacity and the high dynamic performance of the secondary battery, the graphite negative electrode only having the single high specific capacity or the high dynamic performance is increasingly difficult to meet the requirements of the consumers.
At present, a conventional scheme of a graphite cathode with high specific capacity and high dynamic performance is to simply mix a graphite material with high specific capacity and a graphite material with high dynamic performance in a certain proportion so as to seek the consideration of the advantages and the performances of the two. Then, in the practical battery application process, the simple graphitized product is easy to be mixed with charge and discharge non-uniformly, so that the risk of obvious lithium dendritic crystal precipitation is easily caused, and even the safety accident of the battery is caused.
On the other hand, the combination of the raw material with high specific capacity and the raw material with high dynamic characteristics, and the formation of the composite secondary particle structure by mixing and granulating become a research direction with considerable prospect. However, the existing single or mixed granulation technology for the raw material with high specific capacity and the raw material with high dynamic characteristics often faces a series of problems of low granulation degree, low bonding strength, uneven granulation and the like in the actual production process, and can further influence the performances of the graphite negative electrode such as cyclic expansion, cyclic service life and the like in the battery cycle process.
In order to solve the problems of low bonding strength and poor stability of the secondary particles after the single or mixed raw material granulation, insufficient dynamic performance of the battery, high risk of cycle expansion and cycle life deterioration, and the like, the development of a graphite negative electrode material with high dynamic, low expansion and long service life is urgently needed.
Disclosure of Invention
Based on the problems, the invention can obtain the graphite cathode material with high dynamic performance and granulation performance by modifying the raw material coke, and can greatly improve the cycle performance of the secondary battery.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a graphite anode material, comprising the steps of:
(1) preparation of Coke aggregate
Respectively carrying out coarse crushing, grinding and grading treatment on a plurality of cokes to obtain a plurality of corresponding coke aggregates;
(2) preparation of modified Coke
Respectively adding an acidic solution into the plurality of types of coke aggregates, stirring to prepare a slurry, and washing, filtering, dehydrating and drying the slurry to obtain a plurality of corresponding first materials;
(3) preparation of the second Material
Mixing at least two first materials to obtain a second material, or mixing at least one coke aggregate and at least one first material to obtain a second material;
(4) coating and graphitization
And mixing the second material with a coating agent, and then granulating and graphitizing.
In the preparation of the graphite cathode material, the coke aggregate treated in the early stage is firstly modified by the acid solution. The acidic solution modification treatment of the coke aggregate can enhance the isotropy of the coke aggregate, particularly the coke aggregate with higher orientation degree, the acid solution modification treatment can reduce the orientation degree of the surface layer and improve the isotropy, and meanwhile, the lithium ion embedding end faces can be increased on the coke aggregate so as to improve the dynamic performance of the obtained graphite cathode material. In addition, after the coke aggregate is modified by the acid solution, the surface of the coke aggregate has a reduced group structure such as-CHn (n is 1,2 and 3), the oxygen-containing functional group carbonyl (-C is O) and the like is increased, so that the active site on the surface of the coke aggregate can be enhanced, the coating agent can form a filling and pinning effect on the surface of the coke aggregate, the granulation degree is further improved, the granulation uniformity and the like are improved, the bonding strength between particles can be enhanced, in other words, the structural strength of secondary particles formed by granulation can be improved, and when the coke aggregate is used as a negative electrode active material, low cycle expansion and excellent long cycle performance can be realized in the cycle process of a secondary battery. In a word, the graphite negative electrode material which has high dynamics and granulation performance and improves the cycle performance of the secondary battery can be obtained by firstly carrying out acid solution modification treatment on the coke aggregate treated in the earlier stage.
The second aspect of the invention provides a graphite negative electrode material, the particle size D50 is 15-21 μm, and the graphite negative electrode material has good high dynamics and high granulation performance.
The third aspect of the present invention provides a use of a graphite negative electrode material in a negative electrode active material for a secondary battery, which enables the secondary battery to exhibit low cycle expansion and excellent long cycle performance, i.e., the secondary battery has better cycle performance.
Detailed Description
The preparation method of the graphite cathode material comprises the following steps:
(1) preparation of Coke aggregate
Respectively carrying out coarse crushing, grinding and grading treatment on a plurality of cokes to obtain a plurality of corresponding coke aggregates;
(2) preparation of modified Coke
Respectively adding an acidic solution into a plurality of coke aggregates, stirring to prepare a slurry, and washing, filtering, dehydrating and drying the slurry to obtain a plurality of corresponding first materials;
(3) preparation of the second Material
Mixing at least two first materials to obtain a second material, or mixing at least one coke aggregate and at least one first material to obtain a second material;
(4) coating and graphitization
And mixing the second material with the coating agent, and then granulating and graphitizing.
Wherein, the coke in the step (1) is at least one of needle coke, common coke and pitch coke, and the corresponding one or more coke aggregates can be prepared by adopting one or more single cokes. The volatile component content of the coke is 0.2-15.0 wt%, and the coke can be green coke or cooked coke. Generally, the raw coke has high volatile component (more than 1.5 percent), high dynamic performance and low boiled coke volatile component (less than 1 percent), and has high specific capacity, at least one raw coke and at least one boiled coke are preferably adopted to prepare corresponding coke aggregate, and the graphite negative electrode material prepared by mixing the raw coke and the boiled coke can simultaneously give consideration to high specific capacity and high dynamic performance. The particle diameter D50 of the coke aggregate obtained after the coke is subjected to rough crushing, grinding and classification treatment is 5-15 μm, and the particle diameter is preferably 8 μm.
In the step (2), the acidic solution is at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, carbonic acid, acetic acid and oxalic acid, preferably nitric acid, and has the advantages of high production safety, easily obtained materials, and convenience in transportation and storage. The concentration of the acidic solution is 0.2-2.5 mol/L, preferably 1.5 mol/L. Each acidic solution accounts for 40-120% of the mass of the corresponding coke aggregate, and preferably accounts for 60%. By selecting the acid solution with specific concentration and quality, the increase degree of lithium ion intercalation end face and surface active sites can be increased, thereby improving the surface modification effect of the coke aggregate. The increase of the lithium ion insertion end face can promote the dynamic performance of the battery to be improved, and the increase of the surface active sites can improve the granulation effect, thereby being beneficial to the improvement of the cycle performance. The rotating speed of stirring is 50-200 r/min, preferably 100r/min, and the stirring time is 1.5-6 h, preferably 3 h.
The second material in step (3) may be two different first materials mixed. It is also possible to mix at least one coke aggregate with at least one first material to obtain a second material, preferably a second material in which the coke aggregate is different from the coke aggregate used in the first material. The mass fraction ratio of the coke aggregate to the first material can be 0-100: 100-0, and the mass fraction ratio of the coke aggregate to the first material is not 0, and the mass fraction ratio of the coke aggregate to the first material can be, but is not limited to 30:70, 50:50 and 70: 30.
The coating agent in the step (4) comprises asphaltene with the softening point of 100-280 ℃, and the preferred temperature is 150 ℃. The particle size of the asphaltene is 3.0 to 8.0 μm, preferably 7.0 μm. The coating agent accounts for 5-20 wt% of the sum of the second material and the coating agent, and is preferably 14%. The equipment used for granulation is a carbon substance granulation reaction kettle, and specifically, but not limited to, a vertical reaction kettle, a horizontal reaction kettle, a drum-type reaction kettle or a continuous granulation kettle, preferably a horizontal reaction kettle. The equipment used for graphitization is an Acheson graphitization furnace, a box type graphitization furnace, an inner series type graphitization furnace or a continuous graphitization furnace, preferably the Acheson graphitization furnace, and the graphitization temperature is 2400-3200 ℃.
The particle diameter D50 of the graphite cathode material prepared by the preparation method of the graphite cathode material is 15-21 mu m. The graphite negative electrode material of the present invention can be used as a negative electrode active material for a secondary battery. The secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolyte.
The positive electrode is obtained by coating positive electrode slurry containing a positive electrode active material, a binder and a conductive agent on a positive electrode current collector, drying and cold pressing. The positive active material may be selected from lithium cobaltate-based positive electrode materials, lithium iron phosphate-based positive electrode materials, lithium manganate-based positive electrode materials, lithium nickel cobalt manganese oxide-based positive electrode materials, and aluminum nickel cobalt manganese oxide-based positive electrode materials. The binder is used to improve the adhesion between the positive active material particles and the aluminum foil current collector. At least one selected from the group consisting of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber and epoxy resin, preferably the binder is polyvinylidene fluoride. The conductive agent is used for improving the conductivity of the positive electrode and can be selected from carbon-containing materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber and the like, or metal powder or metal fiber materials such as copper, nickel, aluminum, silver and the like, or conductive polymers such as polyphenylene derivatives, or mixtures thereof. The solvent of the positive electrode slurry may be N-methylpyrrolidone. The positive current collector may be an aluminum foil.
The negative electrode is obtained by coating a negative electrode slurry containing a negative electrode active material and a binder on a negative electrode current collector, drying, and cold-pressing. The negative electrode active material may be the graphite negative electrode material described above in the present invention, or may be a mixed material of the graphite negative electrode material described above and another material (silicon/carbon composite negative electrode material or silicon oxide negative electrode material). The binder is used to improve the adhesion between the negative active material particles and between the positive active material particles and the aluminum foil current collector. At least one selected from the group consisting of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, and epoxy resin, preferably the binder is carboxymethyl cellulose and styrene-butadiene rubber. The graphite negative electrode material of the invention has conductivity, so that a conductive agent can be selectively added or not added. The solvent of the negative electrode slurry may be N-methylpyrrolidone. The negative current collector may be selected from copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, polymer substrate coated with conductive metal, and the like.
The electrolyte includes a nonaqueous organic solvent and a lithium salt. The non-aqueous organic solvent acts as a medium for transporting ions that participate in the electrochemical reaction of the cell. The non-aqueous organic solvent may include a carbonate solvent, an ester solvent, an ether solvent, a ketone solvent or an alcohol solvent. The carbonate-based solvent may be a linear carbonate and/or a branched carbonate, and specifically may include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), methyl ethyl carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), and the like. The ester solvent may include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, gamma-butyrolactone, delta-decalactone, gamma-valerolactone, gamma-caprolactone, and the like. The ether solvent may include dibutyl ether, tetraglyme, 1, 2-dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc., and the ketone solvent may include cyclohexanone, etc. The alcoholic solvent may include ethanol, isopropanol, and the like. The lithium salt may be LiPF 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiC 4 F 9 SO 3 、 LiClO 4 、LiAlO 2 、LiAlCl 4 、LiN(C x F 2x+1 SO 2 )(C y F 2y+ 1 SO 2 ) (wherein x and y are natural numbers) and LiB (C) 2 O 4 ) 2 At least one ofAnd (4) seed preparation. The concentration of lithium salt is 0.1-2.0M. Additives may be added to the electrolyte to improve the battery performance, and may be, but not limited to, at least one of ethylene sulfite, fluoroethylene carbonate, vinylene carbonate, vinyl ethylene carbonate, 1, 3-propane sultone, and ethylene sulfate.
The separator may be a single layer or a combination of multiple layers of polyethylene, polypropylene, polyvinylidene fluoride, such as a polyethylene/polypropylene two-layer separator, a polyethylene/polypropylene/polyethylene three-layer separator, or a polypropylene/polyethylene/polypropylene three-layer separator. The separator may be provided with a ceramic layer to prevent short-circuiting of the secondary battery when thermal shrinkage occurs.
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
Example 1
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile component of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, coarsely crushing, grinding and classifying common coke with the volatile component of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding nitric acid with the concentration of 0.2mol/L into the coke aggregate A, wherein the mass of the nitric acid is 60 percent of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding nitric acid with the concentration of 0.2mol/L into the coke aggregate B, wherein the mass of the nitric acid is 60% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, and performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material B;
(3) preparation of the second Material
Mixing a coke aggregate A and a first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitizing furnace at 3000 ℃ to obtain the graphite cathode material.
Example 2
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding nitric acid with the concentration of 1.0mol/L into the coke aggregate A, wherein the mass of the nitric acid is 60 percent of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding nitric acid with the concentration of 1.0mol/L into the coke aggregate B, wherein the mass of the nitric acid is 60% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, and performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material B;
(3) preparation of the second Material
Mixing the coke aggregate A and the first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
Example 3
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding nitric acid with the concentration of 1.5mol/L into the coke aggregate A, wherein the mass of the nitric acid is 60 percent of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding nitric acid with the concentration of 1.5mol/L into the coke aggregate B, wherein the mass of the nitric acid is 60% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2%, so as to obtain a first material B;
(3) preparation of the second Material
Mixing the coke aggregate A and the first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
Example 4
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified coke
Adding nitric acid with the concentration of 2.0mol/L into the coke aggregate A, wherein the mass of the nitric acid is 60 percent of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding nitric acid with the concentration of 2.0mol/L into the coke aggregate B, wherein the mass of the nitric acid is 60% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, and performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material B;
(3) preparation of the second Material
Mixing a coke aggregate A and a first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
Example 5
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding nitric acid with the concentration of 2.5mol/L into the coke aggregate A, wherein the mass of the nitric acid is 60 percent of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding nitric acid with the concentration of 2.5mol/L into the coke aggregate B, wherein the mass of the nitric acid is 60% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, and performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material B;
(3) preparation of the second Material
Mixing a coke aggregate A and a first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
Example 6
A preparation method of a graphite negative electrode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding 1.5mol/L nitric acid into the coke aggregate A, wherein the mass of the nitric acid is 40% of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3h to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material A,
adding nitric acid with the concentration of 1.5mol/L into the coke aggregate B, wherein the mass of the nitric acid is 40% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, and performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material B;
(3) preparation of the second Material
Mixing a coke aggregate A and a first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitizing furnace at 3000 ℃ to obtain the graphite cathode material.
Example 7
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding nitric acid with the concentration of 1.5mol/L into the coke aggregate A, wherein the mass of the nitric acid is 80 percent of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding nitric acid with the concentration of 1.5mol/L into the coke aggregate B, wherein the mass of the nitric acid is 80% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, and performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material B;
(3) preparation of the second Material
Mixing a coke aggregate A and a first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
Example 8
A preparation method of a graphite negative electrode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding nitric acid with the concentration of 1.5mol/L into the coke aggregate A, wherein the mass of the nitric acid is 100 percent of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding nitric acid with the concentration of 1.5mol/L into the coke aggregate B, wherein the mass of the nitric acid is 100% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, and performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material B;
(3) preparation of the second Material
Mixing a coke aggregate A and a first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
Example 9
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding nitric acid with the concentration of 1.5mol/L into the coke aggregate A, wherein the mass of the nitric acid is 120 percent of that of the coke aggregate A, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding nitric acid with the concentration of 1.5mol/L into the coke aggregate B, wherein the mass of the nitric acid is 120% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3h to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2%, so as to obtain a first material B;
(3) preparation of the second Material
Mixing a coke aggregate A and a first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
Example 10
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying asphalt coke with 5.0 wt% of volatile component to obtain coke aggregate A with particle size D50 of 10.0 μm, and coarsely crushing, grinding and classifying common coke with 2.5 wt% of volatile component to obtain coke aggregate B with particle size D50 of 8.0 μm;
(2) preparation of modified coke
Adding oxalic acid with the concentration of 0.2mol/L into the coke aggregate A, stirring the mixture for 2 hours at the rotating speed of 150r/min to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the moisture content is lower than 0.2 percent by mass to obtain a first material A,
adding nitric acid with the concentration of 0.2mol/L into the coke aggregate B, wherein the mass of the nitric acid is 60% of that of the coke aggregate B, stirring at the rotating speed of 100r/min for 3 hours to obtain slurry, washing the slurry to be neutral, and performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2% to obtain a first material B;
(3) preparation of the second Material
Mixing a first material A and a first material B according to the mass fraction ratio of 40: 60 mixing uniformly to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
Example 11
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile component of 6.5 wt% to obtain coke aggregate with the particle size D50 of 8.0 mu m;
(2) preparation of modified Coke
Adding nitric acid with the concentration of 0.2mol/L into the coke aggregate, wherein the mass of the nitric acid is 60 percent of that of the coke aggregate, stirring and soaking for 2 hours at the rotating speed of 180r/min to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the moisture mass content is lower than 0.2 percent to obtain a first material;
(3) preparation of the second Material
Mixing the coke aggregate and the first material according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 200 ℃ and the granularity of 5.5 mu m into the second material, wherein the asphaltene accounts for 20 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in a chamber-type graphitization furnace at 3200 ℃ to obtain the graphite cathode material.
Comparative example 1
A preparation method of a graphite anode material comprises the following steps:
(1) preparation of Coke aggregate
Coarsely crushing, grinding and classifying needle coke with the volatile content of 5.0 wt% to obtain coke aggregate A with the particle size D50 of 8.0 mu m, and coarsely crushing, grinding and classifying common coke with the volatile content of 0.5 wt% to obtain coke aggregate B with the particle size D50 of 8.0 mu m;
(2) preparation of Coke slurries
Adding distilled water into the coke aggregate A, wherein the mass of the distilled water is 60 percent of that of the coke aggregate A, stirring for 3 hours at the rotating speed of 100r/min to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the mass content of water is lower than 0.2 percent to obtain a first material A,
adding distilled water into the coke aggregate B, stirring for 3 hours at a rotating speed of 100r/min to obtain slurry, washing the slurry to be neutral, performing suction filtration, dehydration and drying until the moisture mass content is lower than 0.2%, so as to obtain a first material B, wherein the mass of the distilled water is 60% of that of the coke aggregate B;
(3) preparation of the second Material
Mixing a coke aggregate A and a first material B according to the mass fraction ratio of 50:50, uniformly mixing to obtain a second material;
(4) coating and graphitization
Adding the asphaltene with the softening point of 150 ℃ and the granularity of 7.0 mu m into the second material, wherein the asphaltene accounts for 14 percent of the sum of the weight of the asphaltene and the weight of the second material, uniformly mixing, granulating by using a horizontal reaction kettle, putting the granulated material into a graphite crucible, and carrying out heat treatment in an Acheson graphitization furnace at 3000 ℃ to obtain the graphite cathode material.
The average particle size D50 of the graphite negative electrode materials in examples 1 to 11 and comparative example 1 was tested, and the graphite negative electrode materials were respectively combined into a standard button cell to test the first specific discharge capacity and the first coulombic efficiency, and the results are shown in table 1.
The graphite negative electrode materials in examples 1-11 and comparative example 1 are respectively used as negative electrode active materials, and are prepared into negative electrode slurry with conductive agents SuperP, carboxymethyl cellulose and styrene-butadiene rubber according to the mass ratio of 97:1:1:1, the negative electrode slurry is uniformly mixed, the mixed slurry is coated on two sides of a copper foil, and then the copper foil is dried and rolled to obtain a negative electrode sheet. Uniformly mixing lithium cobaltate, PVDF (polyvinylidene fluoride) as a binder and SuperP (super P) as a conductive agent according to a mass ratio of 98:1:1 to prepare a secondary battery positive electrode slurry with a certain viscosity, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain a positive electrode sheet. Arranging a polyethylene/polypropylene double-layer isolating film between the positive plate and the negative plate, stacking and fully automatically winding to obtain a bare cell, packaging by adopting an aluminum plastic film, injecting an electrolyte, standing, forming, shaping, grading and the like, and carrying out 2C charging constant current ratio and cycle performance, wherein the test conditions are as follows, and the test results are shown in Table 1.
(1)2C constant current ratio of charging
The following charge and discharge operations (1C capacity C0) were carried out on the battery at ambient temperature (25 ℃): charging to 4.4V at constant current and constant voltage of 0.2C, and cutting off the current of 0.05C; discharging to 3.0V at constant current of 0.5C; charging to 4.4V at constant current and constant voltage of 0.2C, and cutting off current of 0.05C; discharging to 3.0V at a constant current of 0.5C; charging to 4.4V at constant current and constant voltage of 2.0C, and cutting off current of 0.05C; recording the charging capacity C1 of the constant current section in the fifth step, the total charging capacity C2 in the fifth step, and the C1/C2 is the 2C charging constant current ratio.
(2) Cycle performance
Under the condition of normal temperature (25 ℃), the battery is charged and discharged at 1.2C/1.0C once (1C capacity is C0), the upper limit voltage is 4.4V, the thickness of the battery at the middle position of a lug pole in the 50% SOC of a discharging stage is d0, then the battery is charged and discharged at 1.2C/1.0C under the condition of normal temperature for 100 weeks, 300 weeks, 500 weeks and 800 weeks, the corresponding discharge capacity of the battery is C1, and the thickness of the battery at the middle position of the lug pole in the 50% SOC of the discharging stage is d 1. Wherein the content of the first and second substances,
capacity retention rate (C1/C0) × 100%
The battery expansion rate is (d1-d0)/d0 × 100%
Table 1 testing of material properties and battery performance for each example
Note: a represents the capacity retention rate, B represents the battery expansion rate
From the results in table 1, it is understood that the particle diameter D50 of the graphite negative electrode material particles obtained by the acidic solution modification treatment in examples 1 to 11 is larger and the 2C charge constant current ratio is higher than that in comparative example 1. The isotropy of the coke aggregate can be enhanced through the modification treatment of the acidic solution, the lithium ion embedding end face can be increased on the coke aggregate, so that the dynamic performance of the obtained graphite cathode material is improved, the charging constant current ratio can be increased, in addition, the active site on the surface of the coke aggregate can be enhanced, the filling and pinning effect can be formed on the surface of the coke aggregate by the coating agent, the granulation degree is further improved, so that secondary particles are easier to form, and the particle size of the obtained secondary particles is larger.
Meanwhile, it can be seen from the results in table 1 that the cycle performance of the batteries obtained in examples 1 to 11 is better, and especially, the larger the cycle number is, the more remarkable the difference between the cycle performance of examples 1 to 11 and that of comparative example 1 is. The surface active sites of the coke aggregate can be enhanced through the modification treatment of the acidic solution, and the structural strength of the secondary particles formed by granulation is improved, so that when the secondary particles are used as a negative electrode active material, the secondary particles can show lower cycle expansion and excellent long cycle performance in the cycle process of a secondary battery.
In addition, as can be seen from the results in table 1, even though the graphite negative electrode material of the present invention is subjected to the acid solution modification treatment in the preparation process, the first discharge specific capacity and the first coulombic efficiency of the material are not affected, so that the present invention can achieve both high kinetics and high granulation performance, improve the cyclicity of the secondary battery, and have better first discharge specific capacity and first coulombic efficiency by subjecting the coke aggregate to the acid solution modification treatment.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a graphite negative electrode material is characterized by comprising the following steps:
(1) preparation of Coke aggregate
Respectively carrying out coarse crushing, grinding and grading treatment on a plurality of cokes to obtain a plurality of corresponding coke aggregates;
(2) preparation of modified Coke
Respectively adding an acidic solution into the plurality of types of the coke aggregates, stirring to prepare a slurry, and washing, filtering, dehydrating and drying the slurry to obtain a plurality of corresponding first materials;
(3) preparation of the second Material
Mixing at least two first materials to obtain a second material, or mixing at least one coke aggregate and at least one first material to obtain a second material;
(4) coating and graphitization
And mixing the second material with a coating agent, and then granulating and graphitizing.
2. The method for preparing a graphite negative electrode material according to claim 1, wherein the coke is at least one of needle coke, normal coke, and pitch coke.
3. The method for preparing the graphite anode material according to claim 1, wherein the volatile content of the coke is 0.2 to 15.0 wt%, and the particle diameter D50 of the coke aggregate is 5 to 15 μm.
4. The method for preparing the graphite anode material according to claim 1, wherein the acidic solution is at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, carbonic acid, acetic acid and oxalic acid, the concentration of the acidic solution is 0.2-2.5 mol/L, and each acidic solution accounts for 40-120% of the mass of the corresponding coke aggregate.
5. The preparation method of the graphite anode material as claimed in claim 1, wherein the stirring speed is 50-200 r/min and the stirring time is 1.5-6 h.
6. The method for preparing the graphite negative electrode material of claim 1, wherein the coating agent comprises asphaltene with a softening point of 100-280 ℃, the particle size of the asphaltene is 3.0-8.0 μm, and the coating agent accounts for 5-20 wt% of the sum of the second material and the coating agent.
7. The method for preparing the graphite anode material according to claim 1, wherein the equipment used for granulation is a carbon substance granulation reaction kettle.
8. The method for preparing the graphite negative electrode material according to claim 1, wherein the graphitization equipment is an Acheson graphitization furnace, a box-type graphitization furnace, an internal-string graphitization furnace or a continuous graphitization furnace, and the graphitization temperature is 2400-3200 ℃.
9. The graphite anode material prepared by the preparation method of the graphite anode material according to any one of claims 1 to 8, characterized in that: the particle diameter D50 is 15-21 μm.
10. The graphite negative electrode material prepared by the preparation method of the graphite negative electrode material according to any one of claims 1 to 8 or the application of the graphite negative electrode material according to claim 9 in a negative electrode active material of a secondary battery.
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|---|---|---|---|---|
| US6346225B1 (en) * | 1996-12-20 | 2002-02-12 | Danionics A/S | Preparation of modified cokes and/or blacks |
| CN109449420A (en) * | 2018-11-08 | 2019-03-08 | 安徽科达洁能新材料有限公司 | A kind of surface low-level oxidation and liquid phase coating modified graphite cathode material and preparation method thereof |
| CN112573923A (en) * | 2020-12-10 | 2021-03-30 | 广东凯金新能源科技股份有限公司 | High-rate lithium ion battery artificial graphite negative electrode material and preparation method thereof |
| CN113548662A (en) * | 2021-07-12 | 2021-10-26 | 孙仲振 | Preparation method of coal-based artificial graphite negative electrode material |
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- 2022-07-08 CN CN202210807691.0A patent/CN115084477A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6346225B1 (en) * | 1996-12-20 | 2002-02-12 | Danionics A/S | Preparation of modified cokes and/or blacks |
| CN109449420A (en) * | 2018-11-08 | 2019-03-08 | 安徽科达洁能新材料有限公司 | A kind of surface low-level oxidation and liquid phase coating modified graphite cathode material and preparation method thereof |
| CN112573923A (en) * | 2020-12-10 | 2021-03-30 | 广东凯金新能源科技股份有限公司 | High-rate lithium ion battery artificial graphite negative electrode material and preparation method thereof |
| CN113548662A (en) * | 2021-07-12 | 2021-10-26 | 孙仲振 | Preparation method of coal-based artificial graphite negative electrode material |
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