CN113782709A - Graphite negative electrode material, preparation method, negative electrode plate and lithium ion battery - Google Patents
Graphite negative electrode material, preparation method, negative electrode plate and lithium ion battery Download PDFInfo
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- CN113782709A CN113782709A CN202111003002.2A CN202111003002A CN113782709A CN 113782709 A CN113782709 A CN 113782709A CN 202111003002 A CN202111003002 A CN 202111003002A CN 113782709 A CN113782709 A CN 113782709A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 69
- 239000010439 graphite Substances 0.000 title claims abstract description 66
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 239000010426 asphalt Substances 0.000 claims abstract description 29
- 239000000084 colloidal system Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims abstract description 4
- 238000005087 graphitization Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 239000011230 binding agent Substances 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 238000010902 jet-milling Methods 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- 238000007600 charging Methods 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 description 25
- 238000003756 stirring Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910021382 natural graphite Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010277 constant-current charging Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- 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
Abstract
The invention provides a graphite negative electrode material, a preparation method thereof, a negative electrode plate and a lithium ion battery. The preparation method of the graphite negative electrode material comprises the following steps: (1) mixing asphalt and pore-forming agent, and fusing at high temperature to form a colloid mixture; (2) crushing the colloid mixture to obtain colloid powder; (3) mixing the colloidal powder with graphite, and then carrying out spheroidization treatment to obtain spherical composite powder; (4) and carrying out carbonization treatment and graphitization treatment on the composite powder to obtain the graphite cathode material. The graphite negative electrode material, the negative electrode plate with the graphite negative electrode material and the lithium battery provided by the invention can show excellent double charging performance even in a low-temperature environment.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a graphite negative electrode material, a preparation method of the graphite negative electrode material, a negative electrode plate and a lithium ion battery.
Background
In the 21 st century, lithium batteries are widely used in various fields such as mobile phones, computers, wearable devices, electric automobiles, two-wheel bicycles, electric tools, street lamps and the like.
In recent years, with the wider application of lithium batteries in various fields, the requirements on the performance and the application environment of the batteries are higher and higher, such as high-power discharge, ultralow-temperature discharge below-30 ℃, 10000 times of ultra-long cycle life and the like. Particularly, in the low temperature field, the demand is becoming more and more vigorous, and accordingly, many researches are being made on this, such as ultra-low temperature electrolyte, nanocrystallization of positive electrode material, small granulation of negative electrode material, and the like. The method has obvious progress in the aspect of ultralow temperature electrolyte and positive electrode material nanocrystallization, however, normal charging and discharging of the battery still cannot be guaranteed in the direction of small granulation of the negative electrode material, particularly, under the condition of low-temperature charging, the constant current rush-in ratio of the battery is very low, namely, the battery cannot be charged, lithium precipitation easily occurs in the negative electrode after low-temperature charging, and the battery after lithium precipitation easily spontaneously ignites or explodes to cause safety accidents.
Disclosure of Invention
The invention aims to provide a graphite negative electrode material, a preparation method, a negative electrode plate and a lithium ion battery.
Specifically, the invention provides the following technical scheme: .
A preparation method of a graphite negative electrode material comprises the following steps:
(1) mixing asphalt and pore-forming agent, and fusing at high temperature to form a colloid mixture;
(2) crushing the colloid mixture to obtain colloid powder;
(3) mixing the colloidal powder with graphite, and then carrying out spheroidization treatment to obtain spherical composite powder;
(4) and carrying out carbonization treatment and graphitization treatment on the composite powder to obtain the graphite cathode material.
As a known technology, the liquid absorption property and the rate capability can be improved by carrying out nano-porous treatment on a graphite negative electrode material, and the invention discovers that the carbonized material asphalt and a specific pore-forming agent are fused at high temperature to form a colloid mixture, and then the colloid mixture is used for carrying out porous modification on graphite, so that the obtained graphite negative electrode material has excellent low-temperature charge and discharge. Further, the pore-forming agent is selected from CaO, Ca (OH)2、CaCO3、BaO、Ba(OH)2、BaCO3More preferably, the pore-forming agent has a D50 particle size of 1 to 100 nm.
In a preferred embodiment of the present invention, in the step (1), the asphalt is a high-temperature asphalt with a softening point of 200 to 250 ℃, preferably a high-temperature asphalt with a softening point of 210 to 230 ℃;
and/or the temperature of the high-temperature fusion is 250-300 ℃.
In a preferred embodiment of the invention, the mass ratio of the asphalt to the pore-forming agent is 1-4: 1.
In a preferred embodiment of the present invention, in the step (2), the pulverization treatment is specifically to perform jet milling on the pulverized colloidal mixture to obtain colloidal powder with a D50 particle size in a range of 30 to 100 nm.
In a preferred embodiment of the present invention, in the step (3), the graphite is spherical graphite having a D50 particle size in the range of 1 to 2 μm.
In a preferred embodiment of the present invention, in the step (3), the spheroidizing treatment is specifically to mix colloidal powder and graphite and then spheroidize the mixture to obtain spherical composite powder with a D50 particle size in a range of 5 to 15 μm.
In a preferred embodiment of the present invention, in the step (3), the mass ratio of the colloidal powder to the graphite is 1-2: 3-4.
In a preferred embodiment of the invention, in the step (4), the carbonization treatment is specifically carried out for 2-4 hours at 1200-1400 ℃;
and/or graphitizing for 24-48 h at 2500-3300 ℃.
The present invention also provides a graphite negative electrode material prepared by the above-described preparation method, wherein the graphite negative electrode material preferably has a D50 particle size within a range of 3 to 10 μm.
The invention also provides a negative pole piece, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises a conductive agent, a thickening agent, a binder and the graphite negative pole material or the graphite negative pole material prepared by the preparation method; preferably, the first and second liquid crystal materials are,
the current collector is a copper foil with the thickness of 6-12 mu m;
and/or the areal density of the coating material is 4-20mg/cm2；
And/or in the coating material, the using amount of the conductive agent is 0-2 wt%, the using amount of the thickening agent is 1-1.5%, the using amount of the binder is 1-2%, and the balance is the graphite negative electrode material;
and/or the conductive agent is selected from one or more of carbon black, acetylene black, conductive graphite, carbon nano tubes, conductive carbon fibers and graphene;
and/or the binder is selected from one or more of styrene-butadiene rubber emulsion, styrene-acrylic emulsion, polyacrylic acid and polyacrylonitrile multipolymer emulsion.
The invention also provides a lithium ion battery which comprises the negative pole piece, the diaphragm, the electrolyte and the positive pole piece, wherein the negative pole excess is 1.06-1.20.
The beneficial effects obtained by the invention are as follows:
the graphite negative electrode material provided by the invention effectively improves the wettability of the negative electrode plate and electrolyte, improves the liquid retention capacity of the negative electrode plate, reduces the interface reaction impedance of lithium ions, and effectively improves the lithium intercalation dynamic characteristic of the graphite material; because the interface reaction impedance of lithium ions is reduced, the low-temperature performance and the rate performance of the battery core are correspondingly optimized, and particularly in the aspect of low-temperature charging and discharging, the constant current charging ratio of the battery is higher than 84% at minus 30 ℃, which is far larger than that of the common graphite cathode material.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the following examples, the equipment and the like used are not shown to manufacturers, and are all conventional products available from regular vendors. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
Example 1
1. Embodiment 1 provides a graphite negative electrode material, which is prepared by the following steps:
(1) selecting commercially available natural spherical graphite (MSG-1 of Dongdao graphite Co., Ltd.), wherein the particle size D50 of the graphite is 1.56 μm;
(2) selecting commercial high-temperature asphalt (HK 009 from Kyobei culvert Kai energy science and technology development Co., Ltd.), wherein the softening point of the high-temperature asphalt is 220-;
(3) selecting pore-forming agent CaCO3The particle size D50 of the pore-forming agent is 15 nm;
(4) carrying out fusion stirring on the high-temperature asphalt in the step (2) and the pore-forming agent in the step (3) in a three-slurry stirrer according to the mass percentage of 80:20, wherein the stirring speed is 40r/min, the stirring temperature is 260 ℃, and the stirring time is 200 min; discharging the colloid after the graphite and the high-temperature asphalt are fused from the three-slurry stirrer, and cooling to room temperature;
(5) coarsely crushing the colloid obtained in the step (4) → jaw crushing → airflow crushing to obtain colloid powder with the particle size D50 of 295 nm;
(6) mixing the natural graphite in the step (1) with the colloid powder in the step (5) in a mass ratio of 7:3, and then spheroidizing in a spheroidizing machine to obtain a secondary ball mixture with the particle size D50 of 14.8 mu m;
(7) mixing the secondary balls in (6) in N2Calcining at 1400 ℃ for 4h under the protection of gas to obtain porous carbon spheres;
(8) and (4) acid-washing the porous carbon spheres obtained in the step (7) in 1mol/L diluted hydrochloric acid solution to eliminate metal impurities, washing the porous carbon spheres with distilled water to pH7.0, and drying the porous carbon spheres.
(9) Graphitizing the porous carbon spheres obtained in the step (8) at 3300 ℃ for 24h to obtain a graphite negative electrode material, wherein the D50 particle size is 9.6 mu m.
2. The embodiment also provides a negative electrode plate, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 2% of conductive agent acetylene black, 1% of thickener sodium carboxymethyl cellulose, 1.5% of binder styrene butadiene rubber, and the balance of the graphite negative electrode material;
the current collector is a copper foil with the thickness of 10 mu m;
the coating material has a coating areal density of 18.00mg/cm2；
3. The embodiment provides a lithium ion secondary battery, which consists of a positive pole piece, the negative pole piece, a diaphragm and electrolyte;
the positive pole piece comprises a 15-micron thick aluminum foil current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 3% of acetylene black, 3% of binder PVDF, 94% of German nanometer technology Limited lithium iron phosphate DY-3, and the coating surface density of the positive pole material is 34.20mg/cm2；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF618 wt%, 40 wt% of dimethyl carbonate, 20 wt% of ethylene carbonate and 20 wt% of methyl ethyl carbonate as organic solvent, and 1 wt% of ethylene sulfate and 1 wt% of vinylene carbonate as additives;
wherein the negative pole piece is in excess of 1.08;
the lithium ion secondary battery has an outer diameter of 26mm and a height of 65 mm.
Example 2
1. Embodiment 2 provides a graphite negative electrode material, which is prepared by the following steps:
(1) selecting commercially available natural spherical graphite (MSG-1 of Dongdao graphite Co., Ltd.), wherein the particle size D50 of the graphite is 1.56 μm;
(2) selecting commercial high-temperature asphalt (HK 009 from Kyobei culvert Kai energy science and technology development Co., Ltd.), wherein the softening point of the high-temperature asphalt is 220-;
(3) selecting pore-forming agent Ca (OH)2And CaCO3(mass ratio is 1: 1), the particle size D50 of the pore-forming agent is 10 nm;
(4) carrying out fusion stirring on the high-temperature asphalt in the step (2) and the pore-forming agent in the step (3) in a three-slurry stirrer according to the mass percentage of 60:40, wherein the stirring speed is 30r/min, the stirring temperature is 270 ℃, and the stirring time is 300 min; discharging the colloid after the graphite and the high-temperature asphalt are fused from the three-slurry stirrer, and cooling to room temperature;
(5) coarsely crushing the colloid obtained in the step (4) → jaw crushing → airflow crushing to obtain colloid powder with the particle size D50 of 95 nm;
(6) mixing the natural graphite in the step (1) with the colloid powder in the step (5) in a mass ratio of 8:2, and then spheroidizing in a spheroidizing machine to obtain a secondary ball mixture with the particle size D50 of 6.35 mu m;
(7) mixing the secondary balls in (6) in N2Calcining at 1350 ℃ for 4h under the protection of gas to obtain porous carbon spheres;
(8) and (4) acid-washing the porous carbon spheres obtained in the step (7) in 1mol/L diluted hydrochloric acid solution to eliminate metal impurities, washing the porous carbon spheres with distilled water to pH7.0, and drying the porous carbon spheres.
(9) Graphitizing the porous carbon spheres obtained in the step (8) at 3000 ℃ for 36h to obtain a graphite negative electrode material, wherein the D50 particle size is 3.6 mu m.
2. The embodiment also provides a negative electrode plate, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 2% of conductive agent acetylene black, 1% of thickener sodium carboxymethyl cellulose, 1.5% of binder styrene butadiene rubber, and the balance of the graphite negative electrode material;
the current collector is a copper foil with the thickness of 10 mu m;
the coating material has a coating areal density of 18.00mg/cm2；
3. The embodiment provides a lithium ion secondary battery, which consists of a positive pole piece, the negative pole piece, a diaphragm and electrolyte;
the positive pole piece comprises a 15-micron thick aluminum foil current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 3% of acetylene black, 3% of binder PVDF, 94% of German nanometer technology Limited lithium iron phosphate DY-3, and the coating surface density of the positive pole material is 35.98mg/cm2；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF618 wt%, 40 wt% of dimethyl carbonate, 20 wt% of ethylene carbonate and 20 wt% of methyl ethyl carbonate as organic solvent, and 1 wt% of ethylene sulfate and 1 wt% of vinylene carbonate as additives;
wherein the negative pole piece is in excess of 1.20;
the lithium ion secondary battery has an outer diameter of 26mm and a height of 65 mm.
Example 3
1. Embodiment 3 provides a graphite anode material, which is prepared by the following steps:
(1) selecting commercially available natural spherical graphite (MSG-1 of Dongdao graphite Co., Ltd.), wherein the particle size D50 of the graphite is 1.56 μm;
(2) selecting commercial high-temperature asphalt (HK 009 from Kyobei culvert Kai energy science and technology development Co., Ltd.), wherein the softening point of the high-temperature asphalt is 220-;
(3) selecting pore-forming agent Ca (OH)2And CaCO3(mass ratio is 4: 6), and the particle size D50 of the pore-forming agent is 10 nm;
(4) carrying out fusion stirring on the high-temperature asphalt in the step (2) and the pore-forming agent in the step (3) in a three-slurry stirrer according to the mass percentage of 50:50, wherein the stirring speed is 30r/min, the stirring temperature is 270 ℃, and the stirring time is 300 min; discharging the colloid after the graphite and the high-temperature asphalt are fused from the three-slurry stirrer, and cooling to room temperature;
(5) coarsely crushing the colloid obtained in the step (4) → jaw crushing → airflow crushing to obtain colloid powder with the particle size D50 of 35 nm;
(6) mixing the natural graphite in the step (1) with the colloid powder in the step (5) in a mass ratio of 6:4, and then spheroidizing in a spheroidizing machine to obtain a secondary ball mixture with the particle size D50 of 6.8 mu m;
(7) mixing the secondary balls in (6) in N2Calcining at 1350 ℃ for 4h under the protection of gas to obtain porous carbon spheres;
(8) and (4) acid-washing the porous carbon spheres obtained in the step (7) in 1mol/L diluted hydrochloric acid solution to eliminate metal impurities, washing the porous carbon spheres with distilled water to pH7.0, and drying the porous carbon spheres.
(9) Graphitizing the porous carbon spheres obtained in the step (8) at 3000 ℃ for 40h to obtain a graphite negative electrode material, wherein the D50 particle size is 3.9 mu m.
2. The embodiment also provides a negative electrode plate, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 2% of conductive agent graphene, 1% of thickener sodium carboxymethyl cellulose, 1.5% of binder styrene-butadiene rubber emulsion, and the balance of the graphite negative electrode material;
the current collector is a copper foil with the thickness of 10 mu m;
the coating material has a coating areal density of 22.50mg/cm2；
3. The embodiment provides a lithium ion secondary battery, which consists of a positive pole piece, the negative pole piece, a diaphragm and electrolyte;
the positive pole piece comprises a 15-micron thick aluminum foil current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises 3% of acetylene black, 3% of binder PVDF, 94% of German nanometer technology Limited lithium iron phosphate DY-3, and the coating surface density of the positive pole material is 42.05mg/cm2；
The diaphragm is made of polypropylene;
the lithium salt of the electrolyte is LiPF618 wt%, 40 wt% of dimethyl carbonate, 20 wt% of ethylene carbonate and 20 wt% of methyl ethyl carbonate as organic solvent, and 1 wt% of ethylene sulfate and 1 wt% of vinylene carbonate as additives;
wherein the negative pole piece is in excess of 1.20;
the lithium ion secondary battery has an outer diameter of 26mm and a height of 65 mm.
Comparative example 1
1. Comparative example 1 provides a graphite negative electrode material, which is prepared by the following steps:
(1) selecting commercially available natural spherical graphite with the particle size D50 of 1.56 mu m;
(2) selecting commercial high-temperature asphalt, wherein the softening point of the high-temperature asphalt is 220-230 ℃;
(3) selecting pore-forming agent CaCO3The particle size D50 of the pore-forming agent is 15 nm;
(4) mixing natural graphite with high-temperature asphalt and a pore-forming agent according to the mass ratio of 12:4:1, and then spheroidizing in a spheroidizing machine to obtain a secondary sphere mixture with the particle size D50 of 14.2 mu m;
(5) mixing the secondary balls in (4) in N2Calcining at 1400 ℃ for 4h under the protection of gas to obtain porous carbon spheres;
(6) and (3) acid-washing the porous carbon spheres obtained in the step (5) in 1mol/L diluted hydrochloric acid solution to eliminate metal impurities, washing the porous carbon spheres to pH7.0 with distilled water, and drying the porous carbon spheres.
(7) Graphitizing the porous carbon spheres obtained in the step (6) at 3300 ℃ for 24 hours to obtain a graphite negative electrode material, wherein the D50 particle size is 9.3 mu m.
Comparative example 1 also provides a negative electrode tab and a lithium ion secondary battery, and the preparation methods are the same as example 1.
Comparative example 2
Comparative example 2 provides a graphite negative electrode material, which is prepared by the following steps:
(1) selecting commercially available natural spherical graphite with the particle size D50 of 1.56 mu m;
(2) selecting commercial high-temperature asphalt, wherein the softening point of the high-temperature asphalt is 220-230 ℃;
(3) selecting pore-forming agent silicon powder, wherein the particle size D50 of the pore-forming agent is 20 nm;
(4) carrying out fusion stirring on the high-temperature asphalt in the step (2) and the pore-forming agent in the step (3) in a three-slurry stirrer according to the mass percentage of 80:20, wherein the stirring speed is 40r/min, the stirring temperature is 260 ℃, and the stirring time is 200 min; discharging the colloid after the graphite and the high-temperature asphalt are fused from the three-slurry stirrer, and cooling to room temperature;
(5) coarsely crushing the colloid obtained in the step (4) → jaw crushing → airflow crushing to obtain colloid powder with the particle size D50 of 283 nm;
(6) mixing the natural graphite in the step (1) with the colloid powder in the step (5) in a mass ratio of 7:3, and then spheroidizing in a spheroidizing machine to obtain a secondary ball mixture with the particle size D50 of 13.9 mu m;
(7) mixing the secondary balls in (6) in N2Calcining at 1400 ℃ for 4h under the protection of gas to obtain porous carbon spheres;
(8) and (4) acid-washing the porous carbon spheres obtained in the step (7) in 1mol/L diluted hydrochloric acid solution to eliminate metal impurities, washing the porous carbon spheres with distilled water to pH7.0, and drying the porous carbon spheres.
(9) Graphitizing the porous carbon spheres obtained in the step (8) at 3300 ℃ for 24h to obtain a graphite negative electrode material, wherein the D50 particle size is 9.1 mu m.
Comparative example 2 also provides a negative electrode tab and a lithium ion secondary battery, and the preparation methods are the same as example 1.
Test examples Low temperature Performance test
(1) The lithium batteries prepared in examples 1-3 and comparative examples 1-2 were charged at-20 ℃ and-30 ℃ at 0.2C or 0.5C rates, respectively, and the constant current charging ratio data during charging was recorded, with the results shown in table 1 below;
TABLE 1
As is clear from table 1, it was confirmed that the constant current charging ratio of the lithium batteries of examples 1 to 3 was more than 94% in the low-temperature environment of-20 ℃, and that the constant current charging ratio of the lithium batteries of examples 1 to 3 was still more than 84% even in the low-temperature environment of-30 ℃, and that the low-temperature double-charge performance was excellent.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the graphite negative electrode material is characterized by comprising the following steps of:
(1) mixing asphalt and pore-forming agent, and fusing at high temperature to form a colloid mixture;
(2) crushing the colloid mixture to obtain colloid powder;
(3) mixing the colloidal powder with graphite, and then carrying out spheroidization treatment to obtain spherical composite powder;
(4) and carrying out carbonization treatment and graphitization treatment on the composite powder to obtain the graphite cathode material.
2. The method according to claim 1, wherein in the step (1), the pore-forming agent is selected from CaO, Ca (OH)2、CaCO3、BaO、Ba(OH)2、BaCO3Preferably, the D50 particle size of the pore-forming agent is within the range of 1-100 nm.
3. The preparation method according to claim 1 or 2, wherein in the step (1), the asphalt is high-temperature asphalt with a softening point of 200-250 ℃, preferably 210-230 ℃;
and/or the temperature of the high-temperature fusion is 250-300 ℃.
4. The preparation method according to any one of claims 1 to 3, wherein in the step (2), the pulverization treatment is specifically that the pulverized colloidal mixture is subjected to jet milling to obtain colloidal powder with D50 particle size in the range of 30-100 nm.
5. The production method according to any one of claims 1 to 4, wherein in the step (3), the graphite is spherical graphite having a D50 particle size in the range of 1 to 2 μm.
6. The preparation method according to any one of claims 1 to 5, wherein in the step (3), the spheroidizing treatment is specifically to mix colloidal powder with graphite and then spheroidize the mixture to obtain spherical composite powder with D50 particle size in the range of 5-15 μm.
7. The preparation method according to any one of claims 1 to 6, wherein in the step (4), the carbonization treatment is specifically carried out at 1200 to 1400 ℃ for 2 to 4 hours;
and/or graphitizing for 24-48 h at 2500-3300 ℃.
8. The graphite negative electrode material is prepared by the preparation method of any one of claims 1 to 7, and preferably, the D50 particle size of the graphite negative electrode material is within a range of 3-10 μm.
9. A negative electrode plate, which is characterized by comprising a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises a conductive agent, a thickening agent, a binder and the graphite negative electrode material in the claim 8 or the graphite negative electrode material prepared by the preparation method in any one of the claims 1 to 7; preferably, the first and second liquid crystal materials are,
the current collector is a copper foil with the thickness of 6-12 mu m;
and/or the areal density of the coating material is 4-20mg/cm2；
And/or in the coating material, the using amount of the conductive agent is 0-2 wt%, the using amount of the thickening agent is 1-1.5%, the using amount of the binder is 1-2%, and the balance is the graphite negative electrode material;
and/or the conductive agent is selected from one or more of carbon black, acetylene black, conductive graphite, carbon nano tubes, conductive carbon fibers and graphene;
and/or the binder is selected from one or more of styrene-butadiene rubber emulsion, styrene-acrylic emulsion, polyacrylic acid and polyacrylonitrile multipolymer emulsion.
10. A lithium ion battery, characterized by comprising the negative electrode plate, the diaphragm, the electrolyte and the positive electrode plate of claim 9, wherein the negative electrode excess is 1.06-1.20.
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