CN114597326A - Negative electrode active material, negative plate containing negative electrode active material and battery - Google Patents
Negative electrode active material, negative plate containing negative electrode active material and battery Download PDFInfo
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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
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 surprisingly found that by constructing a negative active material having a good sphericity formed by binding a plurality of fine particles, the negative active material satisfies the following relationship: d is less than or equal to 10 mu m1≤30μm，0.5μm≤D2≤6μm；D1≥5D2(ii) a P is more than or equal to 0.5 and less than or equal to 1. On one hand, the isotropy of the active material is increased, the active material can be rapidly embedded and removed, on the other hand, the particle material in the spherical particles can shorten the migration path, and the extraction efficiency is improved, so that the negative active material with the characteristics has better multiplying powerThe performance of the device is that the device has the capability of high-power discharge and super quick charge.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a negative electrode active material, a negative electrode sheet containing the negative electrode active material and a battery.
Background
The birth of the battery creates a great deal of convenience for the human society, and along with the gradual promotion of digitalization and artificial intelligence, people put forward more severe requirements on the performance of the battery. Super fast charge, super high power discharge, super long endurance and life, low temperature performance, safety performance and the like are all hot problems of current battery research.
The appearance of agricultural unmanned aerial vehicles brings great convenience to agricultural development, but the agricultural unmanned aerial vehicles provide great challenges for batteries due to the requirement of high-power discharge and super fast charge capacity.
Disclosure of Invention
The invention provides a solution for improving the high-rate charge-discharge performance of the conventional battery. Through constructing the negative active material which is formed by bonding a plurality of particles and has better sphericity, the structural arrangement increases the isotropy of the negative active material on one hand, ensures that lithium ions can be rapidly inserted and extracted, and on the other hand, the particles in the negative active material with better sphericity can shorten the migration path of the lithium ions and improve the extraction efficiency of the lithium ions, so that the negative active material with the characteristics has better rate capability, and has the capacity of high-power discharge and super quick charge (the capacity retention rate of the battery is up to more than 90 percent after the battery is subjected to 10C charge-discharge cycle for 1000 weeks at 25 ℃).
The purpose of the invention is realized by the following technical scheme:
a negative active material is formed by binding a plurality of particles and is in a granular shape; the particle diameter distribution Dv50 of the negative electrode active material has a value D1The particle size distribution Dv50 of the fine particles has a value D2The negative active material has a particle sphericity value of P, D1、D2And P simultaneously satisfy the following relation: d is less than or equal to 10 mu m1≤30μm，0.5μm≤D2≤6μm；D1≥5D2；0.5≤P≤1。
According to an embodiment of the present invention, D1Is 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 in the range consisting of the two endpoints.
According to an embodiment of the present invention, D2Is 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 in the range of the two endpoints. When the particle size distribution Dv50 of the particles has a value D2D is more than or equal to 0.5 mu m2When the particle size is less than or equal to 6 mu m, the particle size is small, the tap density is low, the specific surface area is large, the particles are easy to bond, if the particle size is not in the range, the particles are not easy to bond, and if the particle size is too small (if the particle size is less than 0.5 mu m), the specific surface area of the particles is large, defects in the microstructure are more, and the discharge capacity of the material is low.
In the present invention, the term Dv50 refers to a particle size having a cumulative particle distribution of 50%, i.e., the volume content of particles smaller than this particle size is 50% of the total particles. Also called median diameter or median diameter, is a typical value for the size of the particle size, which accurately divides the population into two equal parts, that is to say that 50% of the particles have a diameter above this value and 50% below this value. If Dv50 of a sample is 5 μm, it indicates that particles larger than 5 μm account for 50% and particles smaller than 5 μm account for 50% of all the particles constituting the sample.
According to an embodiment of the 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 of the above ranges of endpoints.
According to an embodiment of the present invention, 20D2≥D1≥5D2Preferably, 10D2≥D1≥5D2。
The present invention is configured by a negative electrode active material of a spherical structure having a particle sphericity P of 0.5 to 1, and satisfies the following requirements between a value D2 of a particle size distribution Dv50 of fine particles constituting the spherical structure and a value D1 of a particle size distribution Dv50 of a negative electrode active material to be finally formed: d is less than or equal to 10 mu m1≤30μm，0.5μm≤D2≤6μm；D1≥5D2(specifically, 5D)2≤D1≤20D2) The performance of the formed negative electrode active material is excellent. If the particle diameter of the fine particles is too large, the negative electrode active material having a spherical structure of the above-described 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 measured by laser granulometry, using a Mastersizer 3000.
According to an embodiment of the present invention, the particle sphericity is tested using a macchian S3500SI laser particle size particle shape analyzer.
According to an embodiment of the present invention, the negative active material is formed by binding a plurality of particles through a coating layer.
According to an embodiment of the present invention, a surface of the plurality of particles is coated with a coating layer.
According to an embodiment of the present invention, during the mixing of the fine particles and the coating-forming substance, the coating-forming substance is preferentially diffused on the surface of the fine particles, and the surface of the fine particles is wetted, thereby forming a coating layer, and when all the fine particles are fully wetted, the remaining coating-forming substance binds each fine particle together and forms a negative electrode active material having a high degree of particle sphericity.
According to an embodiment of the present invention, the mass ratio of the fine particles to the coating layer is 100 (15 to 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 composition of the particles comprises 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 present invention, the fine particles have a tap density of 0.7g/cm or less3。
According to an embodiment of the present invention, the microparticles have a specific surface area of 20m or less2/g。
According to the embodiment of the present invention, the coating layer forming substance 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 from one or more of the following raw materials:
asphalt (liquid petroleum asphalt), epoxy resin, petroleum heavy oil, phenolic resin, graphene dispersion liquid, carbon nano tube dispersion liquid, polyvinyl alcohol, polyvinylpyrrolidone and sodium carboxymethylcellulose.
Preferably, the coating layer is prepared by spray drying, heat treatment and carbonization of the raw materials; or the coating layer is prepared by carrying out spray drying, heat treatment and graphitization on the raw materials.
Illustratively, when the composition of the particles comprises a carbon material selected from one or more of artificial graphite, soft carbon, hard carbon and the like, the coating layer is prepared by spray drying, heat treatment and carbonization of the raw materials.
Illustratively, when the component of the fine particles includes a carbon material selected from natural graphite, the coating layer is prepared by spray drying, heat treatment and graphitization of the above raw materials.
According to the embodiment of the invention, the spray drying is carried out in spray drying equipment, the temperature of the spray drying is 80-200 ℃, and the time of the spray drying is 5-10 hours.
According to the embodiment of the invention, the heat treatment is carried out 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 the embodiment of the invention, the carbonization is carried out in a reaction kettle, the carbonization temperature is 800-1500 ℃, and the carbonization time is 12-24 hours.
According to the embodiment of the invention, the graphitization is carried out in a reaction kettle, the graphitization temperature is 2800 ℃ or more, and the graphitization time is 1-24 hours.
According to embodiments of the present invention, the coating layer forming material may be prepared before mixing with the fine particles, or may be prepared in situ after mixing the raw material for preparing the coating layer with the fine particles.
In the invention, the spray drying process can uniformly mix the substances forming the coating layer and the particles or the raw materials for preparing the coating layer and the particles, and bond the particles together, so that the coating layer is more uniformly distributed and the coating is more complete; the heat treatment process can discharge redundant volatile components in the coating layer, so that the spherical secondary particles can not be bonded with each other during carbonization; the carbonization process can carbonize the uniformly mixed substance to obtain one or more of hard carbon, soft carbon, graphene, conductive carbon black and the like; the graphitizing process can graphitize the uniformly mixed substance to obtain the 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 components are discharged through heat treatment, the content of amorphous carbon 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 first discharge efficiency and the compaction density of the negative active material is avoided. In addition, the natural graphite has high ash content, is not purified, and can be purified after being graphitized.
According to an embodiment of the present invention, the negative active material has a lithium ion diffusion coefficient of 10-14～10-12cm2/S。
According to the embodiments of the present inventionStrength D of crystal face 004 of the negative electrode active material004Intensity D with crystal plane 110110And (c) a ratio (defined as an OI value of the negative electrode active material) of 1 to 5, indicating that the negative electrode active material is isotropic.
The invention also provides a preparation method of the anode active material, which comprises the following steps:
(1) preparation of the value D of the particle size distribution Dv502The fine particles of (a);
(2) mixing the particles obtained in the step (1) with the raw materials for preparing the coating layer, spray drying, heat treatment, carbonization, shaping, grading, sieving and demagnetizing to obtain the material with the particle size distribution Dv50 with the value D1The negative electrode active material having a particle sphericity P;
or mixing the particles obtained in the step (1) with raw materials for preparing the coating layer, and performing spray drying, heat treatment, graphitization, shaping, classification, screening and demagnetization to obtain the particle size distribution Dv50 with the value D1The negative electrode active material having a particle sphericity P;
or mixing the particles obtained in step (1) with the coating material, shaping, classifying, sieving, and demagnetizing to obtain a mixture with a particle size distribution Dv50 with a value of D1The negative electrode active material having a particle sphericity P;
wherein D is1、D2And 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 as defined 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 present invention, the mass ratio of the fine particles 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 present invention, the mass ratio of the fine particles to the coating layer is 100 (15 to 40), for example, 100:15, 100:20, 100:25, 100:30, 100:35, or 100: 40.
According to the embodiment of the invention, the spray drying is carried out in spray drying equipment, the temperature of the spray drying is 80-200 ℃, and the time of the spray drying is 5-10 hours.
According to the embodiment of the invention, the heat treatment is carried out 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 the embodiment of the invention, the carbonization is carried out in a reaction kettle, the carbonization temperature is 800-1500 ℃, and the carbonization time is 12-24 hours.
The invention also provides a negative plate which comprises the negative 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 negative electrode active material described above therein.
According to an embodiment of the present invention, the current collector is selected from at least one of a copper foil, a chromium foil, a nickel foil, or a titanium foil.
According to the embodiment of the invention, the compacted density of the negative plate is 1.5-1.8 g/cm3。
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 selected from at least one of polyacrylic acid, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyvinyl alcohol, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyimide, polyamideimide, styrene butadiene rubber, or 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 sheet.
According to the embodiment of the invention, the battery has higher 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 surprisingly found that by constructing a negative active material having a good sphericity formed by binding a plurality of fine particles, the negative active material satisfies the following relationship: d is less than or equal to 10 mu m1≤30μm，0.5μm≤D2≤6μm；D1≥5D2(ii) a P is more than or equal to 0.5 and less than or equal to 1. On one hand, the isotropy of the active material is increased, the active material can be rapidly embedded and removed, on the other hand, the particle material in the spherical particles can shorten the migration path, and the extraction efficiency is improved, so that the negative active material with the characteristics has better rate performance, and has the capabilities of high-power discharge and super rapid charge.
Drawings
Fig. 1 is a schematic structural view of a negative 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 in example 1 after 1000 cycles of charging and discharging at 25 ℃ and 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 only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The relevant tests referred to in the following examples and comparative examples:
particle size testing the particle sphericity was measured by laser method from Mastersize 3000 (malvern 3000) using a macque S3500SI laser particle size analyser.
Example 1
Preparing a negative active material: and (4) crushing and shaping the petroleum coke to obtain the artificial graphite raw material. Putting 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. The obtained artificial graphite material was shaped and classified to obtain artificial graphite fine particles having a particle size distribution Dv50 of 2.3 μm. Mixing the artificial graphite particles with petroleum heavy oil (the mass ratio is 100:18), carrying out spray drying at 150 ℃ for 5h, carrying out heat treatment at 550 ℃ for 10h, then carrying out carbonization at 1200 ℃ for 12h, screening and demagnetizing to obtain the artificial graphite cathode active material.
The resulting artificial graphite negative electrode active material had a particle size distribution Dv50 of 14.9 μm and a sphericity of 0.88.
The button cell assembly process is as follows: mixing the prepared negative active material with CMC, conductive carbon black and SBR at the temperature of 25 ℃ according to the proportion of 92%: 1.5%: 1.5%: 5 percent (mass ratio) is evenly mixed in pure water to prepare slurry; the slurry was uniformly coated on a copper foil 8 μm thick with a coating surface density of about 8mg/cm2Then the copper foil is put into a vacuum drying oven to be dried for 12 hours at the temperature of 80 ℃. And cutting the dried pole piece into a circular piece with the diameter of 20mm to prepare the negative pole piece.
Under the condition of 25 ℃, a metal lithium sheet is taken as a counter electrode, the obtained negative electrode sheet is taken as a working electrode, a polyethylene diaphragm is taken as a battery diaphragm, and 1mol/L LiPF6DEC (volume ratio of 1:1) solution is used as electrolyte, and the CR2430 type button cell is assembled in a glove box under Ar environment. The compacted density of the negative plate is 1.50g/cm3The single-side density of the negative plate is 8mg/cm2。
The assembled button cell was allowed to stand at room temperature for 24 hours before electrochemical testing was initiated on an ArbinBT bt2000 model cell tester.
Capacity and first effect test: discharging to 5mV at 0.05C, standing for 10min, discharging to 5mV at 0.05mA to obtain the first lithium intercalation capacity of the negative electrode active material, standing for 10min, charging to 2.0V at 0.1C to complete the first circulation, and obtaining the first lithium deintercalation capacity of the negative electrode active material. The first lithium removal capacity is divided by the mass of the negative active material to obtain the first discharge specific capacity of the negative active material, and the first lithium removal capacity/first lithium insertion capacity is the first efficiency of the negative active material.
The soft package battery assembling process comprises the following steps: the mass ratio of the full-cell negative active material to the conductive carbon black, CMC and SBR is 95%: 2%: 1.2%: 1.8 percent of the mixture is prepared into negative electrode slurry, the slurry is evenly coated on copper foil with the thickness of 8 mu m, and the single-side density of the negative electrode is 5mg/cm3The compacted density of the pole piece is 1.5g/cm3. The full battery anode is NCM111, and the slurry formula is NCM 111: SP: PVDF 96.5%: 2.0%: 1.5% (mass ratio), 1mol/L LiPF for full cell electrolyte6The solvent is EC/DMC/EMC volume ratio of 1.5: 2.5: 6, the used diaphragm is a polyethylene diaphragm, the designed positive electrode capacity is 145mAh/g, the designed negative electrode capacity 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, an ArbinBT2000 type battery tester is used for carrying out battery charge and discharge tests, and a charge and discharge interval is set to be 4.2V-2.75V.
The charge-discharge cycle capacity retention rate of the soft package battery is tested as follows:
1. in an environment at 25 ℃, discharging a fresh battery to the lower limit voltage of 2.75V at the current density of 0.5C;
2. standing for 30 min;
3. charging to the upper limit voltage of 4.2V at the current density of 10C, and then keeping constant voltage charging of 4.2V, wherein the cut-off current is 0.5C;
4. standing for 30 min;
5. discharging at a current density of 10C to a lower limit voltage of 2.75V;
6. repeating the test of 2-5 steps to form a charge-discharge cycle until the cycle number is 1000.
The capacity retention rate of the soft package battery after 1000 times of cycling is 1000-time battery discharge capacity/100% of first-time battery discharge capacity.
Example 2
Preparing a negative active material: and (3) crushing and shaping the coal-based coke to obtain the artificial graphite raw material. Putting 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. The obtained artificial graphite material was shaped and classified to obtain artificial graphite fine particles having a particle size distribution Dv50 of 3.8 μm. Mixing the artificial graphite particles with epoxy resin (the mass ratio is 100:23), carrying out spray drying at 150 ℃ for 5h, carrying out heat treatment at 550 ℃ for 10h, then carrying out carbonization at 1300 ℃ for 15h, screening and demagnetizing to obtain the artificial graphite cathode active material.
The particle size distribution Dv50 of the obtained artificial graphite negative electrode active material was 21.6 μm, and the sphericity was 0.91.
Button cell and pouch cell fabrication procedures and tests were consistent with those in example 1.
Example 3
Preparing a negative active material: and (3) crushing and shaping the natural crystalline flake graphite to obtain a natural graphite raw material. The obtained natural graphite 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 (mass ratio of 100:16), spray drying at 180 deg.C for 5h, and heat treating at 600 deg.C for 8 hr to obtain natural graphite material. And (2) putting the natural graphite material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and carrying out screening and demagnetization after the material is cooled to obtain the natural graphite negative electrode active material.
The particle size distribution Dv50 of the obtained natural graphite negative electrode active material was 11.0 μm, and the sphericity was 0.85.
Button cell and pouch cell fabrication procedures and tests were consistent with those in example 1.
Comparative example 1
Preparing a negative electrode active material: and (4) crushing and shaping the petroleum coke to obtain the artificial graphite raw material. Putting the artificial graphite raw material into a graphite crucible, carrying out graphitization treatment at a graphitization temperature of more than 3000 ℃, and cooling the material to obtain the artificial graphite material. The obtained artificial graphite material was shaped and classified to obtain artificial graphite fine particles having a particle size distribution Dv50 of 9.6 μm. Mixing the artificial graphite particles with petroleum heavy oil (the mass ratio is 100:8), carrying out spray drying at 180 ℃ for 5h, carrying out heat treatment at 600 ℃ for 8 h, then carbonizing at 1200 ℃ for 12h, screening and demagnetizing to obtain the artificial graphite cathode active material.
The resulting artificial graphite negative electrode active material had a particle size distribution Dv50 of 10.5 μm and a sphericity of 0.45.
Button cell and pouch cell fabrication procedures and tests were consistent with those in example 1.
Comparative example 2
Preparing a negative active material: and (3) crushing and shaping the natural crystalline flake graphite to obtain a graphite raw material. The obtained graphite material 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 (mass ratio of 100:30), spray drying at 180 deg.C for 5h, and heat treating at 600 deg.C for 8 hr to obtain natural graphite material. And (2) putting the natural graphite material into a graphite crucible, carrying out graphitization treatment, wherein the graphitization temperature is more than 3000 ℃, and carrying out screening and demagnetization after the material is cooled to obtain the natural graphite negative electrode active material.
The particle size distribution Dv50 of the obtained natural graphite negative electrode active material was 23.0 μm, and the sphericity was 0.62.
The button pouch cell fabrication process and testing was consistent with example 1.
Comparative example 3
Preparing a negative active material: and (3) crushing and shaping the petroleum coke raw material to obtain the artificial graphite raw material. Putting 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. The obtained artificial graphite material was shaped and classified to obtain artificial graphite fine particles having a particle size distribution Dv50 of 0.3 μm. Mixing the artificial graphite particles with liquid petroleum asphalt (the mass ratio is 100:20), carrying out spray drying at 180 ℃ for 5h, carrying out heat treatment at 600 ℃ for 8 h, then carbonizing at 1300 ℃ for 12h, screening and demagnetizing to obtain the artificial graphite cathode active material.
The particle size distribution Dv50 of the obtained artificial graphite negative electrode active material was 5 μm, and the sphericity was 0.86.
Button cell and pouch cell fabrication procedures and tests were consistent with those in example 1.
Comparative example 4
And (3) crushing and shaping the petroleum coke raw material to obtain the artificial graphite raw material. Putting 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. The obtained artificial graphite material was shaped and classified to obtain artificial graphite fine particles having a particle size distribution Dv50 of 1.5 μm. Mixing the artificial graphite particles with liquid petroleum asphalt (the mass ratio is 100:30), carrying out spray drying at 180 ℃ for 5h, carrying out heat treatment at 600 ℃ for 6 h, then carbonizing at 1300 ℃ for 12h, screening and demagnetizing to obtain the artificial graphite cathode active material.
The particle size distribution Dv50 of the obtained natural graphite negative electrode active material was 17.3 μm, and the sphericity was 0.45.
The button pouch cell fabrication process and testing was consistent with example 1.
The performance test results of the button cell and the cell assembled with the negative active material of the above examples and comparative examples are shown in the following table:
as can be seen from the test results in the above table, the particle size distribution Dv50 and the particle size distribution Dv50 of the negative electrode active materials in examples 1 to 3 satisfy D1≥5D2And D is1、D2And the sphericity P of the particles are within the range defined by the application, the negative electrode material with the characteristics has better rate performance, and compared with comparative examples 1-4, the battery taking the negative electrode material as the negative electrode piece has better large-rate charge and discharge performance. The negative active material is a secondary particle with high sphericity and good isotropy, which is composed of particles, so that the negative active material can be rapidly inserted and removed, and the particles have small particle size, so that the migration path can be greatly shortenedTherefore, the battery has the capability of being rapidly charged and discharged.
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 attributes 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 embodiment. 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 negative active material is characterized in that the negative active material is formed by bonding a plurality of particles and is in a granular shape; the particle diameter distribution Dv50 of the negative electrode active material has a value D1The particle size distribution Dv50 of the fine particles has a value D2The negative active material has a particle sphericity value of P, D1、D2And P simultaneously satisfy the following relation: d is less than or equal to 10 mu m1≤30μm，0.5μm≤D2≤6μm；D1≥5D2；0.5≤P≤1。
2. The negative electrode active material according to claim 1, wherein 20D is2≥D1≥5D2。
3. The negative electrode active material according to claim 1, wherein the negative electrode active material is formed by binding a plurality of particles with a coating layer.
4. The negative electrode active material according to claim 3, wherein the mass ratio of the fine particles to the coating layer is 100 (15 to 40).
5. The negative active material of claim 1, wherein a surface of the plurality of particles is coated with a coating layer.
6. The negative electrode active material according to claim 1, wherein the composition of the fine particles comprises a carbon material selected from one or more of natural graphite, artificial graphite, soft carbon, and hard carbon;
and/or the tap density of the particles is less than or equal to 0.7g/cm3；
And/or the specific surface area of the particles is less than or equal to 20m2/g。
7. The negative active material of any one of claims 3 to 5, wherein the coating layer is formed by one or more substances selected from hard carbon, soft carbon, graphene and 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 carboxymethylcellulose.
8. The negative electrode active material according to claim 1, wherein the negative electrode active material has a lithium ion diffusion coefficient of 10-14～10-12cm2/S；
And/or the intensity D of the crystal face 004 of the anode active material004Intensity D with crystal plane 110110The ratio of (A) to (B) is 1 to 5.
9. A negative electrode sheet comprising the negative electrode active material according to any one of claims 1 to 8.
10. A battery comprising the negative electrode active material of any one of claims 1 to 8 or the negative electrode sheet of claim 9.
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