CN115117355A - Preparation method and application of negative electrode material for secondary battery - Google Patents
Preparation method and application of negative electrode material for secondary battery Download PDFInfo
- Publication number
- CN115117355A CN115117355A CN202211017842.9A CN202211017842A CN115117355A CN 115117355 A CN115117355 A CN 115117355A CN 202211017842 A CN202211017842 A CN 202211017842A CN 115117355 A CN115117355 A CN 115117355A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- electrode material
- preparation
- natural graphite
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000011280 coal tar Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 16
- 230000004927 fusion Effects 0.000 claims abstract description 13
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract 2
- 238000003763 carbonization Methods 0.000 claims description 21
- 239000010405 anode material Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 238000004898 kneading Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000011331 needle coke Substances 0.000 description 3
- 239000002006 petroleum coke Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007499 fusion processing Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a negative electrode material for a secondary battery, wherein the preparation method comprises the steps of mixing flake natural graphite and medium-temperature coal tar, stirring and fusing the mixture, and then carbonizing the obtained material; the rotating speed of the stirring and fusion treatment is 1000-3000 rpm; the obtained negative electrode material for the secondary battery has a blocky structure; the blocky structure is formed by stacking and agglomerating flaky natural graphite; the particle size of the flaky natural graphite is 2-9 mu m; pyrolytic carbon is arranged in gaps of the flaky natural graphite and on the surface of the blocky structure. The negative electrode material for the secondary battery has high capacity, high rate discharge performance and good processing performance. The invention also provides a preparation method and application of the negative electrode material for the secondary battery.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a preparation method and application of a negative electrode material for a secondary battery.
Background
An electric tool is a new field developed in recent years, and a battery for the electric tool generally requires high-rate discharge, for example, the discharge rate is 5C-10C, and the continuous discharge cycle life is more than 600 times (the capacity retention rate is more than or equal to 80%). Meanwhile, with the popularization of large electric tools, lithium ion batteries for high-energy-density electric tools have become the mainstream development trend.
In the conventional technology, in order to shorten the lithium ion deintercalation path and improve the rate capability of a negative electrode material, the negative electrode material for the electric tool generally adopts small-particle artificial graphite; in order to simplify the preparation method of the negative electrode material, petroleum coke is generally used as a raw material in the conventional process, the raw material is prepared into small-sized powder, and then the negative electrode material with excellent discharge multiplying power is obtained through processes such as granulation, graphitization or shaping, graphitization, coating and the like.
However, the easy graphitization of petroleum coke is relatively poor, so that the energy density of the negative electrode prepared by the preparation method is limited, and the capacity is generally 340-348 mAh/g; and due to the selection of small particle size, the use compaction density of the obtained anode material is limited to 1.55g/cm 3 However, the anode material prepared by the conventional preparation method has difficulty in meeting the requirement of the anode material for the electric tool on energy density.
In the conventional technology, a graphitized product of needle coke or natural graphite is used as a precedent of a negative electrode material of an electric tool, and the negative electrode material has high energy density and is compacted by use due to high plasticity, however, the quick discharge performance of the electric tool firstly requires that the negative electrode material has good quick discharge performance, so that negative electrode enterprises are forced to select a small-sized negative electrode material, and the tap density of the needle coke and the natural graphite under the small size is difficult to improve, so that the corresponding negative electrode piece has poor processability and is difficult to obtain application.
In conclusion, the anode material prepared by the existing preparation method is difficult to have good fast-release performance, high capacity and processability at the same time.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of the negative electrode material for the secondary battery, and the prepared negative electrode material for the secondary battery has high capacity, high rate discharge performance and good processing performance.
The invention also provides application of the negative electrode material for the secondary battery prepared by the preparation method.
According to the embodiment of the first aspect of the invention, the preparation method of the negative electrode material for the secondary battery is provided, and the preparation method comprises the steps of mixing flake natural graphite and medium-temperature coal tar, carrying out stirring and fusing treatment, and then carrying out carbonization treatment on the obtained material;
the rotating speed of the stirring fusion treatment is 1000-3000 rpm;
the negative electrode material has a block structure;
the blocky structure is formed by stacking and agglomerating flaky natural graphite; the particle size of the flaky natural graphite is 2-9 mu m;
pyrolytic carbon is arranged in gaps of the flaky natural graphite and on the surface of the blocky structure.
The mechanism of the preparation method is as follows:
slice natural graphite can take place certain bending, produce certain radian at the in-process that the stirring fuses, and then can take place to pile up between the multi-disc slice natural graphite, because the stirring fuses the anisotropy that provides power, piles up and also go on along different directions, above-mentioned crooked radian has promoted the compactness between each lamella, finally forms compact structure, single granule, the comparatively level and smooth intermediate particle of outward appearance, forms the cathode material who has block structure after the pyrolysis.
According to the preparation method of the negative electrode material for the secondary battery, at least the following beneficial effects are achieved:
(1) at present, the method for improving the quick release performance, capacity or processability of the negative electrode material is mainly a blending process, namely, a graphitized product of petroleum coke, a needle coke graphitized product, natural graphite and the like are mixed according to a proper proportion. The negative electrode material prepared by the method cannot achieve the effects of the three aspects.
The cathode material provided by the invention meets the requirements (quick release performance, capacity and processing performance) of high-energy-density electric tools through special raw material selection, structural design and process combination, and has the advantage of high cost performance due to wide and cheap raw material sources.
(2) The flaky natural graphite can be promoted to curl by stirring and fusion treatment at a specific rotating speed, and the flaky natural graphite on the surface and the internal structure in the negative electrode material are well attached, so that the tap density of the obtained negative electrode material is improved. Therefore, the cathode material with excellent electrochemical performance can be prepared.
(3) The medium temperature coal tar has good fluidity at room temperature and high carbon residue rate, and the two advantages are that the traditional coating asphalt can not be used simultaneously.
In addition, the medium-temperature coal tar has more heteroatom content, pyrolytic carbon can be formed in the carbonization process to be between hard carbon and soft carbon, on the basis of reasonably controlling the oxygen content, the obtained pyrolytic carbon can form a compact coating layer similar to the soft carbon on the surface of the flaky natural graphite and can also form a volume buffer similar to the hard carbon in the graphite, and the combination of the two results can greatly improve the cycle performance of the flaky natural graphite in a high-power discharge state. And the medium-temperature coal tar has good fluidity and is fully filled in gaps of the flaky natural graphite. This further improves the tap density and electrochemical performance of the resulting anode material.
(4) The active natural graphite flakes in the negative electrode material prepared by the method are controlled in particle size, so that the deintercalation path of lithium ions is shortened, and the quick release performance of the obtained negative electrode material is improved.
Further, the characteristics of the flake natural graphite determine that the anode material provided by the invention has higher energy density compared with the conventional artificial graphite.
Furthermore, the pyrolytic carbon is arranged in the block structure, so that the conductivity of the obtained negative electrode material is improved, and the cycle performance and the rate performance of the obtained negative electrode material are finally improved.
Furthermore, the processing performance of the slurry of the single particles of the natural graphite with small particle size cannot be solved in the traditional technology, and the pyrolytic carbon is arranged in the gaps and the surfaces of the flaky natural graphite, so that the tap density of the obtained negative electrode material is improved (compared with the traditional natural graphite), and the problem of pulping and sedimentation of the obtained negative electrode slurry is avoided.
According to some embodiments of the invention, the negative electrode material has a D50 of 7-9 μm.
According to some embodiments of the invention, the anode material has a compacted density of 1.65 to 1.70g/cm 3 。
According to some embodiments of the invention, the gram specific capacity of the negative electrode material is not less than 357 mAh/g.
The specific capacity of the lithium ion battery is obtained at a voltage of 0-2V (the reduction potential of lithium ion is zero potential).
According to some embodiments of the invention, the capacity retention rate of the negative electrode material after 800 weeks of 1C/10C charge-discharge cycle is more than or equal to 85%.
According to the second aspect of the invention, the preparation method of the negative electrode material for the secondary battery is provided, which comprises the steps of mixing the flaky natural graphite and the medium-temperature coal tar, carrying out stirring and fusing treatment, and then carrying out carbonization treatment on the obtained material;
the rotating speed of the stirring and fusion treatment is 1000-3000 rpm.
According to some embodiments of the invention, the flake natural graphite is a waste powder from processing of spheroidal graphite.
Therefore, the waste powder is recycled, and the economic benefit of the preparation method is improved.
The flake natural graphite is also called flake graphite, is flake and is one of raw materials for manufacturing natural spherical graphite. Under the action of external force, the flake natural graphite can be bent to a certain degree.
In other words, the cathode material provided by the invention has low price of the preparation raw materials, and accords with the trends of environmental protection, energy conservation and emission reduction.
According to some embodiments of the invention, the flake natural graphite has a particle size of 2 to 9 μm.
Therefore, the small particles are bent step by step and are densely stacked and wrapped to form the anode material with larger particle size.
According to some embodiments of the invention, the flake natural graphite has a purity of 99.9% or more.
According to some embodiments of the present invention, QI ≦ 0.1% of the medium temperature coal tar (QI being the mass content of quinoline insolubles).
According to some embodiments of the invention, the medium temperature coal tar contains oxygen atoms in an amount of 8% or more by mass.
According to some embodiments of the invention, the medium temperature coal tar contains less than or equal to 0.3% of sulfur.
According to some embodiments of the invention, the mass ratio of the flaky natural graphite to the medium-temperature coal tar is 100: 5-10. For example, it may be 100: 6.
In the temperature range, the medium-temperature coal tar mainly plays a role in coating the flaky natural graphite and filling the flaky natural graphite between layers without granulation; specifically, the formed anode material is a whole body, rather than being formed by agglomerating a plurality of particles.
According to some embodiments of the invention, the method of mixing is kneading.
According to some embodiments of the invention, the temperature of the mixing is 200 to 400 ℃.
Within the temperature range, the bonding force between the flaky natural graphite and the medium-temperature coal tar is improved, and the granulation effect is not achieved.
Within the above temperature range, semi-solidification (to solid) of medium temperature coal tar can also be achieved. Thereby, classification can be performed after the agitation and fusion treatment.
According to some embodiments of the invention, the mixing time is 2-5 h. For example, it may be 4 h.
Therefore, the mixing effect between the flaky natural graphite and the medium-temperature coal tar can be improved, and the uniformity among the obtained negative electrode material particles is finally improved. The binding force between the flaky natural graphite and the medium-temperature coal tar can be improved, and the problem of structural collapse of the obtained negative electrode material in the using process is solved.
According to some embodiments of the invention, the duration of the stirring and fusing treatment is 2-5 h.
According to some embodiments of the invention, the temperature of the stir-fusion process is 10 to 50 ℃. For example, the temperature may be 20 to 30 ℃.
Namely, the anode material with excellent performance can be obtained by carrying out the stirring and fusing treatment in a common environment temperature range.
According to some preferred embodiments of the present invention, the rotation speed of the stirring and fusing process is 2500 to 3000 rpm.
According to some embodiments of the invention, the duration of the stirring and fusing treatment is 3-10 min.
According to some preferred embodiments of the invention, the duration of the stirring and fusing treatment is 7-8 min.
According to some embodiments of the invention, the apparatus used for the agitation fusion process is a fusion machine for negative electrodes.
Therefore, in the stirring and fusing process, the flaky natural graphite can be curled under the action of mechanical force, and further the flaky natural graphite with a certain bending radian is formed, so that the attaching matching degree of the flaky natural graphite is improved, and the tap density of the obtained negative electrode material is improved.
According to some embodiments of the invention, the method further comprises classifying the material obtained by the blending treatment before the carbonizing treatment.
According to some embodiments of the invention, the material obtained after the classification treatment has a D50 of 7-9 μm.
According to some embodiments of the invention, the tapped density of the material obtained after the classification treatment is more than or equal to 0.8g/cm 3 。
According to some embodiments of the invention, the specific surface area of the material obtained after the classification treatment is less than or equal to 3m 2 /g。
According to some embodiments of the invention, the temperature of the carbonization treatment is 1400 ± 200 ℃.
According to some embodiments of the invention, the temperature of the carbonization treatment is 1440 ℃ to 1550 ℃.
According to some embodiments of the invention, the temperature increase rate of the carbonization treatment is 1 to 5 ℃/min.
According to some embodiments of the invention, the temperature increase rate of the carbonization treatment is 1.5 to 2 ℃/min.
According to some embodiments of the invention, the duration of the heat preservation time of the carbonization treatment is 1-3 h. For example, it may be 2 h.
According to some embodiments of the invention, the atmosphere of the carbonization treatment does not react with the material obtained by the agitation and fusion treatment during the carbonization treatment.
According to some embodiments of the invention, the atmosphere of the carbonization process comprises at least one of nitrogen or an inert gas.
According to some embodiments of the invention, the method further comprises cooling the resultant material after the carbonizing treatment.
According to some embodiments of the invention, the means of cooling comprises water cooling.
According to some embodiments of the invention, the cooling mode comprises cooling to less than or equal to 100 ℃ in 4 hours with water, and then naturally cooling to room temperature (within the range of 10-50 ℃).
According to some embodiments of the invention, the preparation method further comprises performing conventional operations of crushing, sieving, demagnetizing and the like after the cooling.
The sieving removes large particles produced by the carbonization process.
According to an embodiment of the third aspect of the present invention, there is provided a secondary battery whose raw material for preparation includes the negative electrode material.
The secondary battery according to the embodiment of the invention has at least the following beneficial effects:
the secondary battery also has all the advantages of the negative electrode material because the negative electrode material is adopted.
According to some embodiments of the invention, the secondary battery is a cylindrical battery.
According to some embodiments of the invention, the cylindrical battery is model number 18650.
According to an embodiment of the fourth aspect of the present invention, an application of the secondary battery in the field of power batteries is proposed.
The application of the embodiment of the invention has at least the following beneficial effects:
since the negative electrode material has excellent electrochemical properties, the secondary battery prepared therefrom can be applied to power tools with high energy density.
According to some embodiments of the invention, the field of power batteries includes at least one of electric vehicles and unmanned aerial vehicles.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a scanning electron micrograph of an anode material obtained in example 2 of the present invention;
FIG. 2 is a scanning electron micrograph of flake natural graphite used in an example of the present invention;
FIG. 3 is a scanning electron micrograph of a negative electrode material obtained in comparative example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the description of the present invention, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and larger, smaller, larger, etc. are understood as excluding the present numbers, and larger, smaller, inner, etc. are understood as including the present numbers. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
The flake natural graphite used in the embodiment of the present invention is, unless otherwise specified, a waste powder produced from the production of spherical natural graphite, which is generally used in the production of dry batteries, and has a particle size (D50) of 6.3 μm and a purity of 99.92%; the SEM image of the waste powder is shown in FIG. 2, which shows that the flake natural graphite used in the present invention has a flake structure.
The average value of the oxygen atom content of the medium temperature coal tar is 8.9 percent, the QI is less than or equal to 0.04 percent, and the average value of the sulfur content is 0.24 percent.
Example 1
The embodiment prepares the negative electrode material for the secondary battery, and the specific steps are as follows:
s1, mixing flake natural graphite and medium-temperature coal tar according to a weight ratio of 100:10, wherein the mixing equipment is conventional kneading equipment, the kneading temperature is 400 ℃, and the kneading time is 5 hours;
s2, stirring and fusing the material obtained in the step S1 by using a fusing machine, wherein the fusing temperature is room temperature, the rotating speed of the fusing machine is 3000rpm, and the fusing time is 8 min;
s3, grading the material obtained in the step S2;
s4, carbonizing the material obtained in the step S3 in a nitrogen atmosphere, wherein the highest carbonization temperature is 1550 ℃, the carbonization temperature rise speed is 1.5 ℃/min, and the highest temperature heat preservation time is 3 h;
s5, cooling the material obtained in the step S4, wherein the cooling mode is water cooling, specifically, the temperature is reduced to 100 ℃ within 4h, and then the temperature is naturally reduced to the room temperature;
s6, conventionally scattering (crushing), screening, demagnetizing and packaging the material obtained in the step S5.
Example 2
The embodiment prepares the negative electrode material for the secondary battery, and the specific steps are as follows:
s1, mixing flake natural graphite and medium-temperature coal tar according to a weight ratio of 100:6, wherein the mixing equipment is conventional kneading equipment, the kneading temperature is 400 ℃, and the kneading time is 4 hours;
s2, stirring and fusing the materials obtained in the step S1 by using a fusion machine, wherein the rotating speed of the fusion machine is 2500rpm, and the fusion time is 7 min;
s3, grading the material obtained in the step S2;
s4, carbonizing the material obtained in the step S3 in a nitrogen atmosphere, wherein the highest carbonization temperature is 1440 ℃, the carbonization temperature rise speed is 2 ℃/min, and the highest temperature heat preservation time is 2 h;
s5, cooling the material obtained in the step S4, wherein the cooling mode is water cooling, specifically, the temperature is reduced to 100 ℃ within 4h, and then the temperature is naturally reduced to the room temperature;
s6, conventionally scattering (crushing), screening, demagnetizing and packaging the material obtained in the step S5.
Example 3
The embodiment prepares the negative electrode material for the secondary battery, and the specific steps are as follows:
s1, mixing flake natural graphite and medium-temperature coal tar according to a weight ratio of 100:6, wherein the mixing equipment is conventional kneading equipment, the kneading temperature is 300 ℃, and the kneading time is 3 hours;
s2, stirring and fusing the materials obtained in the step S1 by using a fusing machine, wherein the fusing temperature is room temperature, the rotating speed of the fusing machine is 2000rpm, and the fusing time is 5 min;
s3, grading the material obtained in the step S2;
s4, carbonizing the material obtained in the step S3 in a nitrogen atmosphere, wherein the highest carbonization temperature is 1440 ℃, the carbonization temperature rise speed is 4 ℃/min, and the highest temperature heat preservation time is 2 h;
s5, cooling the material obtained in the step S4, wherein the cooling mode is water cooling, specifically, the temperature is reduced to 100 ℃ within 4h, and then the temperature is naturally reduced to the room temperature;
s6, conventionally scattering (crushing), screening, demagnetizing and packaging the material obtained in the step S5.
Example 4
The embodiment prepares the negative electrode material for the secondary battery, and the specific steps are as follows:
s1, mixing flake natural graphite and medium-temperature coal tar according to a weight ratio of 100:5, wherein the mixing equipment is conventional kneading equipment, the kneading temperature is 200 ℃, and the kneading time is 2 hours;
s2, stirring and fusing the material obtained in the step S1 by using a fusing machine, wherein the fusing temperature is room temperature, the rotating speed of the fusing machine is 1000rpm, and the fusing time is 4 min;
s3, grading the material obtained in the step S2;
s4, carbonizing the material obtained in the step S3 in a nitrogen atmosphere, wherein the highest carbonization temperature is 1250 ℃, the carbonization temperature rise speed is 5 ℃/min, and the highest temperature heat preservation time is 1 h;
s5, cooling the material obtained in the step S4, wherein the cooling mode is water cooling, and specifically, the temperature is reduced to 100 ℃ within 4 hours, and then the temperature is naturally reduced to the room temperature;
s6, conventionally scattering (crushing), screening, demagnetizing and packaging the material obtained in the step S5.
Comparative example 1
The comparative example prepares a negative electrode material for a secondary battery, and the specific steps are different from those of example 2 in that:
the method does not include steps S2 to S3.
Test example
The first aspect of the test example tests the morphology of the natural graphite flakes used in example 2, the obtained negative electrode material, and the negative electrode material obtained in comparative example 1, and the results show that: the flake natural graphite used in example 2 and comparative example 1 indeed had a flake structure of 2 to 9 μm; after the preparation of the embodiment 2, the obtained negative electrode material has a curled sheet structure, the accommodating cavity formed by curling is filled with a material different from the sheet structure, the surface of the accommodating cavity is similar to a coating (whether the material is the same or not is observed according to the loosening degree of the material), if the preparation raw materials are not subjected to fusion treatment, the obtained negative electrode material is still mainly in the sheet structure, and the curling, stacking and agglomeration of the natural graphite sheets do not occur, which indicates that the fusion treatment has a decisive influence on the appearance of the negative electrode material obtained by the invention. Specific test results are shown in fig. 1 to 3.
In the second aspect of the test example, other physical and chemical properties and electrochemical properties of the negative electrode materials obtained in examples 1 to 4 and comparative example 1 are also tested, the specific test results are shown in table 1, and the test method refers to the corresponding standard in GB/T245332019.
TABLE 1 Performance results of the anode materials obtained in examples 1 to 4 and comparative example 1
In Table 1, "-" indicates that the obtained pole piece had too poor processability to be detected.
The capacity retention rate is the ratio of the discharge capacity at the 800 th week and the first week after the cycle of the charge-discharge mechanism of 1C/10C. The test voltage is 0-2V (the reduction potential of lithium ion is 0 potential).
Table 1 the results show that: from the comparison of the above table, the preparation method provided by the invention solves the processing performance of small-size natural graphite (the tap density is improved, more uniform cathode slurry can be obtained), also realizes the aims of high energy density and long cycle life, and meets the requirements of high energy density and high power output of the lithium ion battery for the electric tool.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (9)
1. A preparation method of a negative electrode material for a secondary battery is characterized by comprising the steps of mixing flake natural graphite and medium-temperature coal tar, stirring and fusing the mixture, and carbonizing the obtained material;
the rotating speed of the stirring fusion treatment is 1000-3000 rpm;
the negative electrode material has a block structure;
the blocky structure is formed by stacking and agglomerating flaky natural graphite; the particle size of the flaky natural graphite is 2-9 mu m;
pyrolytic carbon is arranged in gaps of the flaky natural graphite and on the surface of the blocky structure.
2. The preparation method according to claim 1, wherein the D50 of the negative electrode material is 7-9 μm.
3. The preparation method of claim 1, wherein the compacted density of the anode material is 1.65-1.70 g/cm 3 。
4. The preparation method of claim 1, wherein the capacity retention rate of the negative electrode material after 800 weeks of 1C/10C charge-discharge cycle is not less than 85%.
5. The preparation method according to claim 1, wherein the mass ratio of the flaky natural graphite to the medium-temperature coal tar is 100: 5-10.
6. The preparation method according to claim 1, wherein the duration of the stirring and fusing treatment is 2 to 5 hours.
7. The production method according to any one of claims 1 to 6, wherein the temperature of the carbonization treatment is 1400 ± 200 ℃.
8. A secondary battery, characterized in that the raw material for preparation comprises the negative electrode material prepared by the preparation method of any one of claims 1 to 7.
9. Use of the secondary battery according to claim 8 in the field of power batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211017842.9A CN115117355B (en) | 2022-08-24 | 2022-08-24 | Preparation method and application of negative electrode material for secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211017842.9A CN115117355B (en) | 2022-08-24 | 2022-08-24 | Preparation method and application of negative electrode material for secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115117355A true CN115117355A (en) | 2022-09-27 |
| CN115117355B CN115117355B (en) | 2022-11-15 |
Family
ID=83336082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211017842.9A Active CN115117355B (en) | 2022-08-24 | 2022-08-24 | Preparation method and application of negative electrode material for secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115117355B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086343A (en) * | 1998-09-09 | 2000-03-28 | Sec Corp | Carbon composite material and its production |
| JP2001357849A (en) * | 2000-06-13 | 2001-12-26 | Sec Corp | Material for negative electrode of lithium secondary battery, method for producing the same, and lithium secondary battery |
| CN1547278A (en) * | 2003-12-12 | 2004-11-17 | 天津大学 | Core-shell carbon negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN102255077A (en) * | 2010-05-21 | 2011-11-23 | 深圳市比克电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN102299307A (en) * | 2011-09-03 | 2011-12-28 | 深圳市贝特瑞新能源材料股份有限公司 | Electrode anode material and preparation method thereof |
| WO2012000201A1 (en) * | 2010-07-02 | 2012-01-05 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery negative electrode material and preparing method therefor |
| CN202977594U (en) * | 2012-11-27 | 2013-06-05 | 天津市贝特瑞新能源科技有限公司 | Coating device applied to coating preparation of negative electrode material of lithium ion battery |
| CN103633307A (en) * | 2013-12-20 | 2014-03-12 | 大连宏光锂业股份有限公司 | Method for producing silicon-carbon composite negative electrode material of lithium ion battery |
| CN104600313A (en) * | 2014-12-30 | 2015-05-06 | 东莞市凯金新能源科技有限公司 | High-capacity graphite composite material of lithium-ion battery and preparation method of composite material |
| JP2015095455A (en) * | 2013-11-08 | 2015-05-18 | 深▲セン▼市貝特瑞新能源材料股▲ふん▼有限公司 | Negative electrode material of on-vehicle energy storage lithium ion battery, and manufacturing method thereof |
| CN104733705A (en) * | 2013-12-20 | 2015-06-24 | 上海杉杉科技有限公司 | Negative pole material for lithium ion power cell and preparation method thereof |
| CN106654235A (en) * | 2017-02-08 | 2017-05-10 | 深圳市贝特瑞新能源材料股份有限公司 | Composite graphite material and preparation method thereof and lithium-ion battery comprising composite graphite material |
| CN110723729A (en) * | 2019-09-26 | 2020-01-24 | 湖南中科星城石墨有限公司 | Kish graphite cathode material for lithium ion battery and modification process of Kish graphite cathode material |
| WO2021004204A1 (en) * | 2019-07-08 | 2021-01-14 | 宁波杉杉新材料科技有限公司 | Natural graphite negative electrode material and preparation method therefor, and lithium-ion battery |
| US20210020941A1 (en) * | 2018-12-17 | 2021-01-21 | Btr New Material Group Co., Ltd. | Low-swelling graphite anode material, preparation method thereof and lithium ion battery |
-
2022
- 2022-08-24 CN CN202211017842.9A patent/CN115117355B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086343A (en) * | 1998-09-09 | 2000-03-28 | Sec Corp | Carbon composite material and its production |
| JP2001357849A (en) * | 2000-06-13 | 2001-12-26 | Sec Corp | Material for negative electrode of lithium secondary battery, method for producing the same, and lithium secondary battery |
| CN1547278A (en) * | 2003-12-12 | 2004-11-17 | 天津大学 | Core-shell carbon negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN102255077A (en) * | 2010-05-21 | 2011-11-23 | 深圳市比克电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
| WO2012000201A1 (en) * | 2010-07-02 | 2012-01-05 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery negative electrode material and preparing method therefor |
| CN102299307A (en) * | 2011-09-03 | 2011-12-28 | 深圳市贝特瑞新能源材料股份有限公司 | Electrode anode material and preparation method thereof |
| WO2013029211A1 (en) * | 2011-09-03 | 2013-03-07 | 深圳市贝特瑞新能源材料股份有限公司 | Negative electrode material and preparation method therefor |
| CN202977594U (en) * | 2012-11-27 | 2013-06-05 | 天津市贝特瑞新能源科技有限公司 | Coating device applied to coating preparation of negative electrode material of lithium ion battery |
| JP2015095455A (en) * | 2013-11-08 | 2015-05-18 | 深▲セン▼市貝特瑞新能源材料股▲ふん▼有限公司 | Negative electrode material of on-vehicle energy storage lithium ion battery, and manufacturing method thereof |
| CN103633307A (en) * | 2013-12-20 | 2014-03-12 | 大连宏光锂业股份有限公司 | Method for producing silicon-carbon composite negative electrode material of lithium ion battery |
| CN104733705A (en) * | 2013-12-20 | 2015-06-24 | 上海杉杉科技有限公司 | Negative pole material for lithium ion power cell and preparation method thereof |
| CN104600313A (en) * | 2014-12-30 | 2015-05-06 | 东莞市凯金新能源科技有限公司 | High-capacity graphite composite material of lithium-ion battery and preparation method of composite material |
| CN106654235A (en) * | 2017-02-08 | 2017-05-10 | 深圳市贝特瑞新能源材料股份有限公司 | Composite graphite material and preparation method thereof and lithium-ion battery comprising composite graphite material |
| US20210020941A1 (en) * | 2018-12-17 | 2021-01-21 | Btr New Material Group Co., Ltd. | Low-swelling graphite anode material, preparation method thereof and lithium ion battery |
| WO2021004204A1 (en) * | 2019-07-08 | 2021-01-14 | 宁波杉杉新材料科技有限公司 | Natural graphite negative electrode material and preparation method therefor, and lithium-ion battery |
| CN110723729A (en) * | 2019-09-26 | 2020-01-24 | 湖南中科星城石墨有限公司 | Kish graphite cathode material for lithium ion battery and modification process of Kish graphite cathode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115117355B (en) | 2022-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112201776B (en) | Natural graphite negative electrode material, preparation method thereof and lithium ion battery | |
| US8728668B2 (en) | Negative electrode active material for lithium ion rechargeable battery and negative electrode using the same | |
| US20120015249A1 (en) | Lithium phosphorus complex oxide-carbon composite, method for producing same, positive electrode active material for lithium secondary battery, and lithium secondary battery | |
| CN102117911B (en) | Graphite cathode material for lithium ion battery and preparation method thereof | |
| CN106486669A (en) | A kind of high-discharge-rate lithium ion battery graphite cathode material and preparation method thereof | |
| CN102255077B (en) | Lithium ion battery negative material and preparation method | |
| CN112670461B (en) | Natural graphite carbon coated negative electrode material, preparation method thereof and lithium ion battery | |
| KR101612603B1 (en) | Carbon-silicon complex, negative active material for secondary battery including the same and method for preparing the same | |
| KR101631735B1 (en) | Anode active material for lithium secondary battery and preparation method of thereof | |
| CN111403693A (en) | Negative active material and negative electrode sheet, electrochemical device and electronic device using the same | |
| CN114597326B (en) | Negative electrode active material, negative electrode plate containing same and battery | |
| CN111370654A (en) | Composite graphite negative electrode material, lithium ion battery and preparation method and application thereof | |
| CN114314580A (en) | Composite graphite negative electrode material and preparation method and application thereof | |
| CN112542587A (en) | Graphite material, secondary battery, and electronic device | |
| CN110970599B (en) | Graphene-based composite negative electrode material, preparation method thereof and lithium ion battery | |
| JP6592156B2 (en) | Negative electrode material for lithium ion secondary battery and method for producing the same, negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| CN113697805A (en) | Quick-charging high-compaction high-capacity artificial graphite negative electrode material and preparation method thereof | |
| CN110350178A (en) | A kind of preparation method of lithium ion battery composite graphite negative electrode material | |
| CN115893403A (en) | Artificial graphite negative electrode material and preparation method and application thereof | |
| JP2010257982A (en) | Anode active material for lithium secondary battery, and lithium secondary battery including the same | |
| US20240387804A1 (en) | Negative electrode active material, and negative electrode plate and battery including negative electrode active material | |
| CN118016857B (en) | A negative electrode active material and a lithium ion battery using the same | |
| CN114156446A (en) | Negative electrode active material, negative plate containing negative electrode active material and lithium ion battery | |
| CN116902973B (en) | Lithium ion battery graphite negative electrode material and preparation method thereof | |
| CN115117355B (en) | Preparation method and application of negative electrode material for secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |