CN114597326B - Negative electrode active material, negative electrode plate containing same and battery - Google Patents
Negative electrode active material, negative electrode plate containing same and battery Download PDFInfo
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- CN114597326B CN114597326B CN202210288041.XA CN202210288041A CN114597326B CN 114597326 B CN114597326 B CN 114597326B CN 202210288041 A CN202210288041 A CN 202210288041A CN 114597326 B CN114597326 B CN 114597326B
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- 239000006183 anode active material Substances 0.000 claims abstract description 32
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
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Classifications
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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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a negative electrode active material, a negative electrode sheet containing the negative electrode active material and a battery. The inventors have unexpectedly found that by constructing a negative electrode active material having a good sphericity, which is formed by binding a plurality of particles, the negative electrode active material satisfies the following relationship: d 1≤30μm,0.5μm≤D2≤6μm;D1≥5D2 is less than or equal to 10 mu m; p is more than or equal to 0.5 and less than or equal to 1. On one hand, isotropy of the active material is increased, rapid embedding and extraction can be ensured, and on the other hand, a migration path of the particulate material in the spherical particles can be shortened, and extraction efficiency is improved, so that the anode active material with the characteristics has better rate capability, and has high-power discharge and super rapid charging capability.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a negative electrode active material, a negative electrode plate containing the negative electrode active material and a battery.
Background
The birth of batteries creates a lot of convenience for human society, and with the gradual advancement of digitization and artificial intelligence, more stringent requirements are put on the performance of batteries. Super fast charge, super high power discharge, super long endurance and life, low temperature performance, safety performance and the like, which are all hot problems in the current battery research.
The appearance of the agricultural unmanned aerial vehicle brings great convenience to the agricultural development, but the battery is challenged due to the capability of high-power discharge and super fast charge.
Disclosure of Invention
The invention provides a solution for improving the high-rate charge and discharge performance of the current battery. Through constructing a negative electrode active material which is formed by bonding a plurality of particles and has good sphericity, the isotropy of the negative electrode active material is increased by the structural arrangement, the lithium ions can be rapidly inserted and extracted, the particles in the negative electrode active material with good sphericity can shorten the migration path of the lithium ions, and the extraction efficiency of the lithium ions is improved, so that the negative electrode active material with the characteristics has good multiplying power performance, and has high power discharge and super rapid charge capacity (the capacity retention rate of a battery is more than 90% after 1000 weeks of 10C charge-discharge cycle at 25 ℃).
The invention aims at realizing the following technical scheme:
A negative electrode active material, which is formed by bonding a plurality of particles and takes the shape of particles; the particle size distribution Dv50 of the negative electrode active material has a value D 1, the particle size distribution Dv50 of the fine particles has a value D 2, and the particle sphericity of the negative electrode active material has a value P, D 1、D2 and P satisfying the following relationship: d 1≤30μm,0.5μm≤D2≤6μm;D1≥5D2 is less than or equal to 10 mu m; p is more than or equal to 0.5 and less than or equal to 1.
According to an embodiment of the present invention, D 1 is 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 22 μm, 24 μm, 25 μm, 26 μm, 28 μm, 30 μm or any point value in the range of the two end points.
According to an embodiment of the present invention, D 2 is 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.5 μm, 1.8 μm, 2 μm, 2.5 μm, 2.8 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 6 μm or any point value in the range of the two end points. When the particle diameter distribution Dv50 of the fine particles has a value D 2 satisfying 0.5 μm or less and D 2. Ltoreq.6 μm, the fine particles have a smaller particle diameter, a lower tap density, a larger specific surface, and the fine particles are liable to adhere, if not in this range, and if the particle diameter of the fine particles is too small (e.g., smaller than 0.5 μm), the specific surface of the fine particles is large, defects in the microstructure thereof are large, resulting in a lower discharge capacity of the material.
In the present invention, the term Dv50 means a particle size in which particles are cumulatively distributed to 50%, i.e., a particle volume content of less than this particle size is 50% of the total particles. Also called median diameter or median particle diameter, which is a typical value representing the size of the particle size, which accurately divides the population into equal parts, that is to say 50% of the particles have a particle size exceeding this value and 50% of the particles have a particle size below this value. If dv50=5 μm for a sample, it means that of all the particles constituting the sample, particles larger than 5 μm account for 50% and particles smaller than 5 μm account for 50%.
According to an embodiment of the present invention, P is 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1 or any point value in the range consisting of both ends.
According to an embodiment of the invention 20D 2≥D1≥5D2, preferably 10D 2≥D1≥5D2.
The present invention satisfies the following conditions by constructing a negative electrode active material having a spherical structure with a particle sphericity P of 0.5 to 1, and controlling the value D2 of the particle size distribution Dv50 of the fine particles constituting the spherical structure to the value D1 of the particle size distribution Dv50 of the finally formed negative electrode active material: d 1≤30μm,0.5μm≤D2≤6μm;D1≥5D2 (specifically, 5D 2≤D1≤20D2) with a thickness of 10 μm or less, the material of the negative electrode active material formed is excellent in performance. If the particle diameter of the fine particles is too large, the negative electrode active material having a spherical structure of the sphericity cannot be formed, and if the particle diameter of the fine particles is too small, the discharge capacity performance of the negative electrode active material is seriously lost.
According to an embodiment of the invention, the particle size distribution is tested by a laser particle size method using an instrument model Mastersizer 3000.
According to the embodiment of the invention, the sphericity of the particles is tested by using a Michael S3500SI laser particle size and shape analyzer.
According to an embodiment of the present invention, the anode active material is formed by binding a plurality of fine particles through a coating layer.
According to an embodiment of the present invention, the surfaces of the plurality of fine particles are coated with a coating layer.
According to the embodiment of the invention, the particles and the substance forming the coating layer are mixed, the substance forming the coating layer preferentially diffuses on the surfaces of the particles, the surfaces of the particles are infiltrated, so that the coating layer is formed, and when all the particles are fully infiltrated, the rest of the substance forming the coating layer can bond each particle together and form the anode active material with higher sphericity.
According to an embodiment of the invention, the mass ratio of the particles to the coating layer is 100 (15-40), for example 100:15, 100:20, 100:25, 100:30, 100:35 or 100:40.
According to an embodiment of the present invention, the component of the microparticles includes a carbon material selected from one or more of natural graphite, artificial graphite, soft carbon, hard carbon, and the like.
According to an embodiment of the invention, the particles have a tap density of 0.7g/cm 3 or less.
According to an embodiment of the invention, the specific surface area of the particles is 20m 2/g or less.
According to an embodiment of the present invention, the material forming the coating layer is selected from one or more of hard carbon, soft carbon, graphene, conductive carbon black, and the like.
According to an embodiment of the invention, the coating layer is prepared by one or more of the following raw materials:
Asphalt (liquid petroleum asphalt), epoxy resin, petroleum heavy oil, phenolic resin, graphene dispersion, carbon nanotube dispersion, polyvinyl alcohol, polyvinylpyrrolidone, and sodium carboxymethyl cellulose.
Preferably, the coating layer is prepared by spray drying, heat treatment and carbonization of the raw materials; or the coating layer is prepared by spray drying, heat treatment and graphitization of the raw materials.
Illustratively, the components of the particles include a carbon material, and when the carbon material is selected from one or more of artificial graphite, soft carbon, hard carbon, and the like, the coating layer is prepared by spray-drying, heat-treating, and carbonizing the above raw materials.
Illustratively, the composition of the microparticles comprises a carbon material, and when the carbon material is selected from natural graphite, the coating is prepared by spray drying, heat treatment and graphitization of the above-described raw materials.
According to an embodiment of the present invention, the spray drying is performed in a spray drying apparatus, the spray drying being performed at a temperature of 80 to 200 ℃ and the spray drying being performed for a time of 5to 10 hours.
According to an embodiment of the present invention, the heat treatment is performed in a reaction kettle, the temperature of the heat treatment is 450-650 ℃, and the time of the heat treatment is 5-15 hours.
According to an embodiment of the invention, the carbonization is performed in a reaction kettle, the temperature of the carbonization is 800-1500 ℃, and the time of the carbonization is 12-24 hours.
According to an embodiment of the present invention, the graphitization is performed in a reaction vessel, the graphitization is performed at a temperature of 2800 ℃ or higher, and the graphitization is performed for 1 to 24 hours.
According to an embodiment of the present invention, the coating layer-forming substance may be prepared before mixing with the microparticles, or the raw material for preparing the coating layer may be prepared in situ after mixing with the microparticles.
In the invention, the spray drying process can uniformly mix the substances forming the coating layer with the particles or the raw materials for preparing the coating layer with the particles, and bond the particles together, so that the coating layer is distributed more uniformly and the coating is more complete; the heat treatment process can discharge superfluous volatile matters in the coating layer so that spherical secondary particles cannot be bonded with each other during carbonization; the carbonization process can lead the evenly mixed substances to be carbonized to obtain one or more of hard carbon, soft carbon, graphene, conductive carbon black and the like; the graphitization process can graphitize the uniformly mixed substance to obtain soft carbon containing a graphite structure, and the capacity and the compaction density of the natural graphite are improved.
When the particles are natural graphite and the coating layer is prepared in situ, more raw materials for preparing the coating layer are needed to be added to enable the natural graphite to be bonded into spherical secondary particles, so that after volatile matters are discharged through heat treatment, the amorphous carbon content is high, the amorphous carbon can be converted into a graphite structure after graphitization treatment, the capacity and the compaction density of the natural graphite are improved, and the influence on the primary discharge efficiency and the compaction density of the anode active material is avoided. In addition, the natural graphite has high ash content, and can be purified after graphitization without purification treatment.
According to an embodiment of the present invention, the lithium ion diffusion coefficient of the anode active material is 10 -14～10-12cm2/S.
According to an embodiment of the present invention, the ratio of the intensity D 004 of the crystal face 004 to the intensity D 110 of the crystal face 110 of the anode active material (defined as the OI value of the anode active material) is 1 to 5, indicating that the anode active material is isotropic.
The invention also provides a preparation method of the anode active material, which comprises the following steps:
(1) Preparing fine particles having a particle size distribution Dv50 of D 2;
(2) Mixing the particles in the step (1) with a raw material for preparing a coating layer, and performing spray drying, heat treatment, carbonization, shaping, classification, screening and demagnetizing to prepare the negative electrode active material with the particle sphericity P of which the particle size distribution Dv50 is D 1;
or mixing the particles in the step (1) with the raw materials for preparing the coating layer, and performing spray drying, heat treatment, graphitization, shaping, classification, screening and demagnetizing to prepare the negative electrode active material with the particle sphericity P of which the particle size distribution Dv50 is D 1;
Or mixing the particles in the step (1) with a substance forming a coating layer, shaping, grading, screening and demagnetizing to prepare the negative electrode active material with the particle sphericity P and the particle size distribution Dv50 of D 1;
wherein, D 1、D2 and P simultaneously satisfy the following relation:
10μm≤D1≤30μm,0.5μm≤D2≤6μm;D1≥5D2；0.5≤P≤1。
According to an embodiment of the invention, the particles are defined as described above.
According to an embodiment of the present invention, the raw materials for preparing the coating layer are defined as above.
According to an embodiment of the invention, the mass ratio of the microparticles to the raw material for preparing the coating layer is 100 (15-40), for example 100:15, 100:20, 100:25, 100:30, 100:35 or 100:40.
According to an embodiment of the invention, the mass ratio of the particles to the coating layer is 100 (15-40), for example 100:15, 100:20, 100:25, 100:30, 100:35 or 100:40.
According to an embodiment of the present invention, the spray drying is performed in a spray drying apparatus, the spray drying being performed at a temperature of 80 to 200 ℃ and the spray drying being performed for a time of 5to 10 hours.
According to an embodiment of the present invention, the heat treatment is performed in a reaction kettle, the temperature of the heat treatment is 450-650 ℃, and the time of the heat treatment is 5-15 hours.
According to an embodiment of the invention, the carbonization is performed in a reaction kettle, the temperature of the carbonization is 800-1500 ℃, and the time of the carbonization is 12-24 hours.
The invention also provides a negative electrode sheet, which comprises the negative electrode active material.
According to an embodiment of the present invention, the negative electrode sheet includes a current collector and an active material layer on at least one side surface of the current collector, the active material layer including the above-described negative electrode active material therein.
According to an embodiment of the present invention, the current collector is selected from at least one of copper foil, chromium foil, nickel foil or titanium foil.
According to an embodiment of the invention, the negative electrode sheet has a compacted density of 1.5 to 1.8g/cm 3.
Preferably, the compacted density is obtained by rolling under a pressure of 17 MPa.
According to an embodiment of the present invention, the active material layer further includes a conductive agent and a binder.
According to an embodiment of the present invention, the binder is at least one selected from the group consisting of polyacrylic acid, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyvinyl alcohol, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyimide, polyamideimide, styrene-butadiene rubber, and polyvinylidene fluoride. Illustratively, the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber.
According to an embodiment of the present invention, the conductive agent is selected from at least one of acetylene black, conductive carbon black, single-walled carbon nanotubes, multi-walled carbon nanotubes or graphene.
The invention also provides a battery, which comprises the negative electrode active material or the negative electrode plate.
According to an embodiment of the invention, the battery has a relatively high energy density, such as 500-600 Wh/L.
The invention has the beneficial effects that:
The invention provides a negative electrode active material, a negative electrode sheet containing the negative electrode active material and a battery. The inventors have unexpectedly found that by constructing a negative electrode active material having a good sphericity, which is formed by binding a plurality of particles, the negative electrode active material satisfies the following relationship: d 1≤30μm,0.5μm≤D2≤6μm;D1≥5D2 is less than or equal to 10 mu m; p is more than or equal to 0.5 and less than or equal to 1. On one hand, isotropy of the active material is increased, rapid embedding and extraction can be ensured, and on the other hand, a migration path of the particulate material in the spherical particles can be shortened, and extraction efficiency is improved, so that the anode active material with the characteristics has better rate capability, and has high-power discharge and super rapid charging capability.
Drawings
Fig. 1 is a schematic structural view of a negative electrode active material according to a preferred embodiment of the present invention.
FIG. 2 is a graph showing the relationship between the capacity retention rate of the battery of example 1 at 25℃and 1000 charge/discharge cycles of 10C/10C.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Related tests referred to in the following examples and comparative examples:
particle size test the sphericity of the particles was measured by a laser method from Mastersize 3000,3000 (malvern 3000) and tested using a macke S3500SI laser particle size shape analyzer.
Example 1
Preparation of a negative electrode active material: and (3) crushing and shaping the petroleum coke to obtain the artificial graphite raw material. And (3) loading the artificial graphite raw material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and cooling the material to obtain the artificial graphite material. Shaping and grading the obtained artificial graphite material to obtain artificial graphite particles with the particle size distribution Dv50 of 2.3 mu m. Mixing the artificial graphite particles with petroleum heavy oil (the mass ratio is 100:18), spray drying at 150 ℃ for 5h, heat treatment at 550 ℃ for 10h, carbonization at 1200 ℃ for 12h, screening and demagnetizing to obtain the artificial graphite negative electrode active material.
The particle size distribution Dv50 of the obtained artificial graphite anode active material was 14.9 μm, and the sphericity was 0.88.
The button cell assembly process is as follows: mixing the prepared anode active material with CMC, conductive carbon black and SBR according to 92 percent at 25 ℃:1.5%:1.5%: mixing 5% (mass ratio) in pure water uniformly to prepare slurry; the slurry was uniformly coated on a copper foil having a thickness of 8 μm and a coating surface density of about 8mg/cm 2, and then the copper foil was dried at 80℃for 12 hours in a vacuum drying oven. Cutting the dried pole piece into a wafer with the diameter of 20mm, and manufacturing the negative pole piece.
And under the condition of 25 ℃, taking a metal lithium sheet as a counter electrode, taking the obtained negative electrode sheet as a working electrode, taking a polyethylene diaphragm as a battery diaphragm, taking a 1mol/L LiPF 6/EC:DEC (volume ratio is 1:1) solution as electrolyte, and assembling the CR2430 button battery in a glove box under an Ar environment. The compacted density of the negative electrode plate is 1.50g/cm 3, and the single-sided density of the negative electrode plate is 8mg/cm 2.
The assembled button cell was allowed to stand at room temperature for 24 hours and then electrochemical testing was initiated on a cell tester of model ArbinBT, U.S. Pat. No. 2000.
Capacity and first effect test: discharging 0.05C to 5mV, standing for 10min, discharging 0.05mA to 5mV to obtain the first lithium intercalation capacity of the anode active material, and charging to 2.0V at 0.1C after standing for 10min to complete the first circulation to obtain the first lithium deintercalation capacity of the anode active material. The first lithium removal capacity is divided by the mass of the anode active material to obtain the first discharge specific capacity of the anode active material, and the first lithium removal capacity/first lithium intercalation capacity is the first efficiency of the anode active material.
The soft package battery is assembled as follows: the mass ratio of the full-cell anode active material to the conductive carbon black to the CMC to the SBR is 95 percent: 2%:1.2%:1.8% of the negative electrode slurry is prepared, the slurry is uniformly coated on copper foil with the thickness of 8 mu m, the single-sided density of the negative electrode is 5mg/cm 3, and the compacted density of the pole piece is 1.5g/cm 3. The positive electrode of the full cell is NCM111, and the slurry formula is NCM111: SP: pvdf=96.5%: 2.0%:1.5% (mass ratio), full cell electrolyte 1mol/L LiPF 6 solvent EC/DMC/EMC volume ratio 1.5:2.5:6, wherein the used diaphragm is a polyethylene diaphragm, the design capacity of the positive electrode is 145mAh/g, the design capacity of the negative electrode is designed according to the half-cell capacity test result, and the CB value is 1.15. After the soft package full battery is assembled, a ArbinBT-2000 battery tester is used for battery charge and discharge test, and a charge and discharge interval is set to be 4.2-2.75V.
The charge-discharge cycle capacity retention rate test of the soft pack battery is:
1. Discharging the fresh battery to a battery lower limit voltage of 2.75V at a current density of 0.5C in a25 ℃ environment;
2. Standing for 30min;
3. Charging to an upper limit voltage of 4.2V at a current density of 10C, then keeping constant voltage charging of 4.2V, and keeping a cut-off current of 0.5C;
4. Standing for 30min;
5. Discharging to a lower voltage of 2.75V at a current density of 10C;
6. Repeating the test in 2-5 steps to form a charge-discharge cycle until the cycle number is 1000.
The soft pack battery was cycled 1000 times capacity retention = 1000 th battery discharge capacity/first battery discharge capacity 100%.
Example 2
Preparation of a negative electrode active material: and (3) crushing and shaping the coal-based coke to obtain the artificial graphite raw material. And (3) loading the artificial graphite raw material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and cooling the material to obtain the artificial graphite material. Shaping and grading the obtained artificial graphite material to obtain artificial graphite particles with the particle size distribution Dv50 of 3.8 mu m. Mixing the artificial graphite particles with epoxy resin (the mass ratio is 100:23), spray drying at 150 ℃ for 5h, heat treatment at 550 ℃ for 10h, carbonization at 1300 ℃ for 15h, screening and demagnetizing to obtain the artificial graphite anode active material.
The particle size distribution Dv50 of the obtained artificial graphite anode active material was 21.6 μm, and the sphericity was 0.91.
Button cell and pouch cell fabrication processes and tests were consistent with example 1.
Example 3
Preparation of a negative electrode active material: and (3) crushing and shaping the natural crystalline flake graphite to obtain a natural graphite raw material. The obtained natural graphite raw material was pulverized and classified to obtain natural graphite fine particles having a particle size distribution Dv50 of 0.6 μm. Mixing graphite particles with liquid petroleum asphalt (the mass ratio is 100:16), spray drying at 180 ℃ for 5 hours, and heat treatment at 600 ℃ for 8 hours to obtain the natural graphite material. And (3) loading the natural graphite material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and sieving and demagnetizing the material after cooling to obtain the natural graphite negative electrode active material.
The obtained natural graphite anode active material had a particle size distribution Dv50 of 11.0 μm and a sphericity of 0.85.
Button cell and pouch cell fabrication processes and tests were consistent with example 1.
Comparative example 1
Preparation of a negative electrode active material: and (3) crushing and shaping the petroleum coke to obtain the artificial graphite raw material. And (3) loading the artificial graphite raw material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and cooling the material to obtain the artificial graphite material. Shaping and grading the obtained artificial graphite material to obtain artificial graphite particles with the particle size distribution Dv50 of 9.6 mu m. Mixing the artificial graphite particles with petroleum heavy oil (the mass ratio is 100:8), spray drying at 180 ℃ for 5 hours, heat treatment at 600 ℃ for 8 hours, carbonization at 1200 ℃ for 12 hours, screening and demagnetizing to obtain the artificial graphite negative electrode active material.
The particle size distribution Dv50 of the obtained artificial graphite anode active material was 10.5 μm, and the sphericity was 0.45.
Button cell and pouch cell fabrication processes and tests were consistent with example 1.
Comparative example 2
Preparation of a negative electrode active material: and (3) crushing and shaping the natural crystalline flake graphite to obtain a graphite raw material. The graphite raw material obtained was pulverized and classified to obtain graphite fine particles having a particle size distribution Dv50 of 7.8 μm. Mixing graphite particles with liquid petroleum asphalt (the mass ratio is 100:30), spray drying at 180 ℃ for 5 hours, and heat treatment at 600 ℃ for 8 hours to obtain the natural graphite material. And (3) loading the natural graphite material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and sieving and demagnetizing the material after cooling to obtain the natural graphite negative electrode active material.
The particle size distribution dv50=23.0 μm of the obtained natural graphite anode active material had a sphericity of 0.62.
The button pouch cell fabrication process and test were identical to those of example 1.
Comparative example 3
Preparation of a negative electrode active material: and (3) crushing and shaping the petroleum coke raw material to obtain the artificial graphite raw material. And (3) loading the artificial graphite raw material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and cooling the material to obtain the artificial graphite material. Shaping and grading the obtained artificial graphite material to obtain artificial graphite particles with the particle size distribution Dv50 of 0.3 mu m. Mixing the artificial graphite particles with liquid petroleum asphalt (the mass ratio is 100:20), spray drying at 180 ℃ for 5 hours, heat treatment at 600 ℃ for 8 hours, carbonization at 1300 ℃ for 12 hours, screening and demagnetizing to obtain the artificial graphite negative electrode active material.
The particle size distribution Dv50 of the obtained artificial graphite anode active material was 5 μm, and the sphericity was 0.86.
Button cell and pouch cell fabrication processes and tests were consistent with example 1.
Comparative example 4
And (3) crushing and shaping the petroleum coke raw material to obtain the artificial graphite raw material. And (3) loading the artificial graphite raw material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and cooling the material to obtain the artificial graphite material. Shaping and grading the obtained artificial graphite material to obtain artificial graphite particles with the particle size distribution Dv50 of 1.5 mu m. Mixing the artificial graphite particles with liquid petroleum asphalt (the mass ratio is 100:30), spray drying at 180 ℃ for 5 hours, heat treatment at 600 ℃ for 6 hours, carbonization at 1300 ℃ for 12 hours, screening and demagnetizing to obtain the artificial graphite negative electrode active material.
The particle size distribution dv50=17.3 μm of the obtained natural graphite anode active material had a sphericity of 0.45.
The button pouch cell fabrication process and test were identical to those of example 1.
The button cells and the performance test results of the cells assembled with the negative electrode active materials of the above examples and comparative examples are shown in the following table:
As can be seen from the test results of the above table, the particle size distribution Dv50 and the microparticle size distribution Dv50 of the negative electrode active materials in examples 1 to 3 satisfy D 1≥5D2, and both D 1、D2 and the sphericity P of the particles are within the range defined by the present application, and the negative electrode material having this feature has better rate capability, and the battery using it as the negative electrode sheet has better high rate charge-discharge capability than comparative examples 1 to 4. Since the anode active material is a secondary particle having a high sphericity composed of particles, the isotropy thereof is good, so that it is possible to rapidly insert and remove the particles, and the particle diameter of the particles is small, so that the migration path can be greatly shortened, and thus the battery has a capability of rapidly charging and discharging.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The negative electrode active material is characterized by being formed by bonding a plurality of particles and being granular; the particle size distribution Dv50 of the negative electrode active material has a value D 1, the particle size distribution Dv50 of the fine particles has a value D 2, and the particle sphericity of the negative electrode active material has a value P, D 1、D2 and P satisfying the following relationship: d 1≤30μm,2.3μm≤D2≤4μm;10D2≥D1≥5D2 is less than or equal to 10 mu m; p is more than or equal to 0.5 and less than or equal to 1; the tap density of the particles is less than or equal to 0.7g/cm 3; the specific surface area of the particles is less than or equal to 20m 2/g;
the ratio of the intensity D 004 of the crystal face 004 of the anode active material to the intensity D 110 of the crystal face 110 is 1-5; the lithium ion diffusion coefficient of the negative electrode active material is 10 -14~10-12cm2/S.
2. The anode active material according to claim 1, wherein the anode active material is formed by binding a plurality of fine particles through a coating layer.
3. The negative electrode active material according to claim 2, wherein the mass ratio of the fine particles to the coating layer is 100 (15 to 40).
4. The anode active material according to claim 1, wherein surfaces of the plurality of fine particles are coated with a coating layer.
5. The anode active material according to claim 1, wherein the component of the fine particles includes a carbon material selected from one or more of natural graphite, artificial graphite, soft carbon, and hard carbon.
6. The anode active material according to any one of claims 2 to 4, wherein the substance forming the coating layer is selected from one or more of hard carbon, soft carbon, graphene, conductive carbon black;
And/or the coating layer is prepared from one or more of the following raw materials:
Asphalt, epoxy resin, petroleum heavy oil, phenolic resin, graphene dispersion liquid, carbon nanotube dispersion liquid, polyvinyl alcohol, polyvinylpyrrolidone and sodium carboxymethyl cellulose.
7. A negative electrode sheet comprising the negative electrode active material according to any one of claims 1 to 6.
8. A battery comprising the negative electrode active material according to any one of claims 1 to 6 or the negative electrode sheet according to claim 7.
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