CN118270778A - Artificial graphite negative electrode material, preparation method thereof, negative electrode plate and lithium ion battery - Google Patents
Artificial graphite negative electrode material, preparation method thereof, negative electrode plate and lithium ion battery Download PDFInfo
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- CN118270778A CN118270778A CN202211739899.XA CN202211739899A CN118270778A CN 118270778 A CN118270778 A CN 118270778A CN 202211739899 A CN202211739899 A CN 202211739899A CN 118270778 A CN118270778 A CN 118270778A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 31
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- 239000010405 anode material Substances 0.000 claims abstract description 70
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- 238000010438 heat treatment Methods 0.000 claims abstract description 21
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Abstract
The application provides an artificial graphite negative electrode material and a preparation method thereof, a negative electrode plate and a lithium ion battery, and relates to the technical field of lithium ion batteries. The interior of the particles of the artificial graphite anode material presents a honeycomb spherical structure; the porosity X 1, the tap density X 2, the sphericity X 3 and the orientation index X 4 of the negative electrode plate of the artificial graphite negative electrode material and the rapid charge and discharge capacity value Y of the artificial graphite negative electrode material meet the following relations: y=4x 1+X2+2X3-0.1X4, Y is 0-4; the negative electrode plate comprises the artificial graphite negative electrode material. The preparation method of the artificial graphite anode material comprises the following steps: spheroidizing and granulating the fine powder of the carbon-containing raw materials, and performing carbonization heat treatment to obtain carbonized particles; then crushing and spheroidizing and graphitizing are carried out to obtain the artificial graphite anode material with the honeycomb spherical structure in the particles. The artificial graphite particles prepared by the method have specific internal morphology and meet the performance requirements on multiplying power, circulation and the like of lithium batteries.
Description
Technical Field
The application relates to the technical field of lithium ions, in particular to an artificial graphite negative electrode material and a preparation method thereof, a negative electrode plate and a lithium ion battery.
Background
With the rapid expansion of new energy markets at home and abroad, the performance requirements on the automobile power EV battery are gradually increased, especially the power density requirements of the battery are increased again, and further the charge-discharge multiplying power of the battery becomes an urgent market demand. The graphite cathode which is an important component in the lithium ion battery is a key material for determining the charge and discharge multiplying power of the lithium ion battery.
The artificial graphite occupies more than 80% of the market share of the cathode due to the superior cycle performance, safety performance and the like of the artificial graphite. However, the cost of preparing the artificial graphite is not low, a lot of waste materials are generated, and resources are wasted, and meanwhile, the multiplying power performance of the battery does not reach the expected effect after the artificial graphite material finally prepared by using various different processes is applied to the lithium ion battery. In a lithium ion power battery system taking artificial graphite as a negative electrode material, the key for determining the charge and discharge multiplying power of the battery is the artificial graphite material of the negative electrode, and various technical parameters of the artificial graphite negative electrode material have a plurality of interactions and interactions. Therefore, the preparation of the artificial graphite anode material for meeting the requirements of lithium ion batteries is an urgent problem to be solved.
Disclosure of Invention
The application aims to provide an artificial graphite negative electrode material, a preparation method thereof, a negative electrode plate and a lithium ion battery, and the artificial graphite negative electrode material meeting the requirements of the lithium ion battery on cycle performance, multiplying power performance, capacity and initial effect is prepared by reducing the resource waste of raw materials.
In order to achieve the above object, the technical scheme of the present application is as follows:
in a first aspect, the present application provides an artificial graphite anode material, the inside of particles of which is in a honeycomb spherical structure;
The porosity X 1, the tap density X 2, the sphericity X 3 and the orientation index X 4 of the negative electrode plate of the artificial graphite negative electrode material and the rapid charge and discharge capacity value Y of the artificial graphite negative electrode material meet the following relations:
y=4x 1+X2+2X3-0.1X4, wherein Y has a value of 0 to 4;
the negative electrode piece comprises the artificial graphite negative electrode material.
With reference to the first aspect, in some optional embodiments of the present application, the artificial graphite anode material meets at least one of the following conditions:
a. The porosity X 1 of the artificial graphite anode material is 10% -45%;
b. the tap density X 2 of the artificial graphite anode material is 0.9g/cm 3-1.2g/cm3;
c. The sphericity X 3 of the artificial graphite anode material is 0.7-0.95;
d. The orientation index X 4 of the negative electrode plate is 5-40.
In some alternative embodiments of the present application, the artificial graphite anode material further satisfies at least one of the following conditions:
e. The particle diameter D50 of the artificial graphite anode material is 10-20 mu m;
f. the specific surface area of the artificial graphite anode material is 1.0m 2/g-4.0m2/g.
In a second aspect, the application provides a method for preparing an artificial graphite anode material, which comprises the following steps:
spheroidizing and granulating the fine powder of the carbon-containing raw material, and then performing carbonization heat treatment to obtain carbonized particles;
And crushing and spheroidizing the carbonized particles, and graphitizing to obtain the artificial graphite anode material with the honeycomb spherical structure inside the particles.
With reference to the second aspect, in some alternative embodiments of the application, the preparation method satisfies at least one of the following conditions:
A. The carbonaceous raw material fine powder includes at least one of a coke raw material pulverized fine powder and a granulating pulverized fine powder;
B. The pulverized fine powder of the coke raw material comprises by-product fine powder obtained by pulverizing the coke raw material, wherein the particle size D50 of the by-product fine powder is 1-6 mu m;
C. The coke raw material comprises at least one of petroleum coke, pitch coke and needle coke;
D. The granulating and crushing fine powder comprises fine powder produced by performing secondary granulation, shaping and classification on the crushed product of the coke raw material, wherein the D50 of the fine powder is 4-13 mu m.
Further preferably, the preparation method further satisfies at least one of the following conditions:
E. The carbon-containing raw material fine powder comprises coke raw material crushed fine powder and granulating crushed fine powder, and before spheroidizing and granulating, the carbon-containing raw material fine powder further comprises: mixing the crushed fine powder of the coke raw material and the granulated and crushed fine powder to obtain mixed aggregate;
F. The mixing comprises stirring at a speed of 50rpm-600rpm for 10min-60min;
G. The mass ratio of the crushed fine powder of the coke raw materials in the mixed aggregate is 0-100%, and the mass ratio of the granulated crushed fine powder is 0-100%.
With reference to the second aspect, in some alternative embodiments of the application, the preparation method satisfies at least one of the following conditions:
H. When the spheroidizing granulation is carried out, a binder is added into the fine powder of the carbon-containing raw materials;
I. The binder comprises at least one of petroleum asphalt, coal asphalt, liquid asphalt, anthracene oil, wash oil, phenolic resin, epoxy resin, furan resin, furfural resin, starch and polyethylene glycol;
J. the mass ratio of the fine powder of the carbon-containing raw material to the binder is 10: (0.1-2);
K. the spheroidizing and granulating time is 5-60 min;
And L, performing carbonization heat treatment, wherein the carbonization heat treatment comprises the following steps: the method is carried out under the atmosphere of protective gas, wherein the protective gas comprises at least one of argon, nitrogen and helium;
m, the temperature for carbonization heat treatment is 300-1400 ℃;
N, the time for performing carbonization heat treatment is 8-50 h;
And O, the particle size D50 of the product obtained after the crushing and sphericizing treatment is 10-20 mu m.
With reference to the second aspect, in some alternative embodiments of the application, the graphitization treatment is performed at a temperature of 2800 ℃ to 3000 ℃.
In a third aspect, the application also provides a negative electrode plate, the raw materials of which comprise the artificial graphite negative electrode material in the first aspect or the artificial graphite negative electrode material prepared by the preparation method in the second aspect.
In a fourth aspect, the application also provides a lithium ion battery, which comprises the negative electrode plate in the third aspect.
The application has the beneficial effects that:
The interior of the particles of the artificial graphite anode material is in a honeycomb spherical structure, so that the anode material ensures that pores are uniformly distributed from inside to outside, the porosity is adjusted, the tap density can be adjusted, the high tap density requirement of the anode material is met, isotropy is improved, and the particle expansion is small; the contact area with the electrolyte is large, the lithium ion deintercalation path is effectively shortened, and the performance with more excellent multiplying power performance and cycle performance is obtained. Through the honeycomb spherical structure, a relational expression between different technical parameters of the artificial graphite anode material and the charge and discharge capacity of the lithium ion battery is formed, and the cycle performance, the multiplying power performance, the capacity and the first effect requirements of the lithium ion battery are met.
The preparation method of the artificial graphite anode material uses the byproduct coke raw material fine powder produced in the process of processing the coke raw material, the quantity of the fine powder is rapidly increased along with the continuous expansion of the market of the artificial graphite anode material, and the fine powder is secondarily utilized, so that the utilization rate of the coke raw material can be improved, the purposes of improving quality and reducing cost can be achieved, the artificial graphite anode material with excellent performance can be obtained, and the preparation method has huge economic benefit. In addition, after spheroidizing and granulating, the secondary particles of the anode material are compacted and the sphericizing of the particles is realized.
The negative electrode plate containing the artificial graphite negative electrode material is used in a lithium ion battery, and the first charge capacity is more than or equal to 340mAh/g under the condition that the charge and discharge multiplying power is more than or equal to 10C; the first discharge efficiency is more than or equal to 88 percent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is a schematic diagram of spheroidizing granulation;
FIG. 2 is a cross-sectional SEM image of an artificial graphite anode material of example 3;
FIG. 3 is a cross-sectional SEM image of an artificial graphite anode material of comparative example 1;
FIG. 4 is an SEM image of an artificial graphite anode material of example 3;
Fig. 5 is an SEM image of the artificial graphite anode material of comparative example 1.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"Parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g, 2.689g, or the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. or the mass of the A component is aK, the mass of the B component is bK (K is any number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"And/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
In a first aspect, the present application provides an artificial graphite anode material having a honeycomb spherical structure in the inside of particles thereof.
In addition, the porosity X 1, the tap density X 2, the sphericity X 3 and the orientation index X 4 of the negative electrode plate of the artificial graphite negative electrode material and the rapid charge and discharge capacity value Y of the artificial graphite negative electrode material meet the following relation: y=4x 1+X2+2X3-0.1X4, wherein Y has a value of 0 to 4; the negative electrode piece comprises the artificial graphite negative electrode material.
It should be noted that, when Y is less than 0, X 1、X2、X3 must have one or more smaller index values, or X 4 is larger, and at this time, the internal porosity, sphericity, tap density and isotropy of the material are reduced, which means that the honeycomb spherical structure of the material is also changed, which may cause deterioration of the rate capability, reduction of the energy density and the like of the battery, and further affect the charging and discharging performance. When Y > 4, it means that the index value in X 1、X2、X3、X4 is changed, for example, the internal porosity exceeds 45%, and the honeycomb structure in the material is further enriched, and the tap density is reduced, so that the battery cycle performance is deteriorated and the energy density is reduced.
With reference to the first aspect, in some optional embodiments of the present application, the porosity X 1 of the artificial graphite anode material is 10% -45%, for example, may be 10%, 20%, 30%, 40%, 45% or any value between 10% -45%.
In some alternative embodiments of the application, the bulk density X 2 of the artificial graphite anode material is 0.9g/cm 3-1.2g/cm3, which may be, for example, 0.9g/cm 3、1.0g/cm3、1.1g/cm3、1.2g/cm3 or any value between 0.9g/cm 3-1.2g/cm3.
The higher the porosity X 1 inside the negative electrode material is, the electrolyte can be filled inside the particles, and the lithium ion intercalation and deintercalation paths are effectively shortened. At the same time, the porosity increases and the tap density X 2 decreases. Therefore, the application ensures that the porosity X 1 of the artificial graphite anode material is more than or equal to 10 percent and less than or equal to 45 percent, and the tap density X 2 of the artificial graphite anode material is more than or equal to 0.9 and less than or equal to 2 and less than or equal to 1.2.
In some alternative embodiments of the application, the sphericity X 3 of the artificial graphite anode material is 0.7-0.95, which may be, for example, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or any value between 0.7-0.95.
In some embodiments of the application, the tap density X 2 is required to be 0.9- 2 -1.2, but if the particle size of the anode material is too small, the tap density of the material is lower, so that the sphericity X 3 is required to be 0.7- 3 -0.95 at the same time, and the tap density of the anode material can be improved to a required range.
In some alternative embodiments of the application, the negative pole piece orientation index X 4 is 5-40, which may be, for example, 5, 10, 15, 20, 25, 30, 35, 40 or any value between 5 and 40.
The orientation index of the negative electrode sheet is a test result of orientation (004)/(110) when the compacted density of the negative electrode sheet is 1.5g/cm 3. In general, the higher the pole piece orientation value is, the weaker the isotropy of the expressed material is, and the rate performance of the material is correspondingly deteriorated.
In some alternative embodiments of the application, the particle size D50 of the artificial graphite anode material is 10 μm to 20 μm, and may be, for example, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, or any value between 10 μm and 20 μm.
In some alternative embodiments of the application, the specific surface area of the artificial graphite anode material is 1.0m 2/g-4.0m2/g, which may be 1.0m2/g、1.5m2/g、2.0m2/g、2.5m2/g、3.0m2/g、3.5m2/g、4.0m2/g or any value between 1.0m 2/g-4.0m2/g, for example.
In a second aspect, the application provides a method for preparing an artificial graphite anode material, which comprises the following steps:
s1, performing spheroidization granulation on fine powder of a carbon-containing raw material, and performing carbonization heat treatment to obtain carbonized particles;
S2, crushing and spheroidizing the carbonized particles, and graphitizing to obtain the artificial graphite anode material with the inside of the particles in a honeycomb spherical structure.
With reference to the second aspect, in some alternative embodiments of the application, the carbonaceous raw material fine powder in S1 includes at least one of a coke raw material pulverized fine powder and a granulated pulverized fine powder.
In some preferred embodiments, the pulverized fine powder of the coke raw material includes a by-product fine powder obtained by pulverizing the coke raw material, the particle diameter D50 of which is 1 μm to 6 μm, and may be, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm or any value between 1 μm and 6 μm.
Further, the coke raw material comprises at least one of petroleum coke, pitch coke and needle coke.
In some preferred embodiments, the granulated and pulverized fine powder includes a fine powder produced by subjecting a pulverized product of the coke raw material to secondary granulation, shaping, classification, and the D50 of the fine powder may be 4 μm to 13 μm, for example, 4 μm, 6 μm, 8 μm, 10 μm, 125 μm, 13 μm, or any value between 4 μm and 13 μm.
In the production process of the artificial graphite anode material, crushing is an important process, and whether the raw coke (including petroleum coke, needle coke and the like) or the raw coke is pelletized, the raw coke is crushed to a required granularity index through a crusher, the crushed raw coke is subjected to spheroidization through a shaper again, and then fine powder is removed through classification, so that a qualified crushed or pelletized product is obtained. At present, the process of crushing, spheroidizing and grading generally has the yield of 65-95%, which leads to 5-35% of fine powder in the production process, and the fine powder has the characteristics of small granularity, low tap density, large specific surface area and the like, and is contrary to the requirements of conventional crushed products, so that the fine powder cannot be directly utilized, is generally treated as waste, and causes great waste of coke raw materials. In the production process of the artificial graphite negative electrode material, the fine powder of the waste materials is used as the raw material, so that the waste material treatment cost is reduced, the artificial graphite negative electrode material is prepared, and great economic benefits are generated.
In some preferred embodiments, when the carbonaceous raw material fine powder in S1 includes the coke raw material pulverized fine powder and the pelletization pulverized fine powder, and before the spheroidization granulation is performed, further comprising: and mixing the crushed fine powder of the coke raw materials and the granulated and crushed fine powder to obtain mixed aggregate.
Further preferably, the mixing comprises stirring at a speed of 50rpm-600rpm, which may be, for example, 50rpm, 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, 600rpm or any value between 50rpm-600rpm, for 10min-60min, which may be, for example, 10min, 20min, 30min, 40min, 50min, 60min or any value between 10min-60 min.
Further preferably, the mass ratio of the pulverized fine powder of the raw coke in the mixed aggregate is 0 to 100%, the mass ratio of the pulverized fine powder of the granulated is 0 to 100%, for example, the mass ratio of the pulverized fine powder of the raw coke may be 10%, and the mass ratio of the pulverized fine powder of the granulated is 90%; the mass ratio of the crushed fine powder of the coke raw material is 30 percent, and the mass ratio of the crushed fine powder of the pelletization is 70 percent; the mass ratio of the crushed fine powder of the coke raw material is 50 percent, and the mass ratio of the granulated and crushed fine powder is 50 percent.
In some preferred embodiments, the spheroidizing granulation in S1 further comprises adding a binder to the carbonaceous feedstock fines.
Further preferably, the binder comprises at least one of petroleum asphalt, coal asphalt, liquid asphalt, anthracene oil, wash oil, phenolic resin, epoxy resin, furan resin, furfural resin, starch, polyethylene glycol.
Further preferably, the mass ratio of the coke raw material fine powder to the binder is 10: (0.1-2), for example, may be 10:0.1, 10:0.5, 10:1. 10:1.5, 10:2 or 10: (0.1-2).
In some preferred embodiments, the time for spheroidizing granulation in S1 is 5min-60min, and may be, for example, 5min, 10min, 20min, 30min, 40min, 50min, 60min, or any value between 5min-60 min.
It should be noted that, compared with the conventional granulation methods such as a vertical kettle, a horizontal kettle, and a continuous kettle, the spheroidizing granulation of the present application is that the material forms three-dimensional flow under the high-speed rotation of the inclined rotor, and impact force, compression force, shearing force, etc. generated by the collision among the rotor, the wall surface, and the material continuously applies the acting force to the material, as shown in fig. 1.
The raw material fine powder particles are continuously collided to generate a spheroidizing effect, and the micro powder is adhered to the surface of a parent body layer by layer in a snowball-like manner with the aid of a binder, so that the particle size is gradually increased, and the sphericizing of the secondary particles is realized while the material is tightly densified. Meanwhile, the used binder is preferably liquid, so that the liquid binder has cohesiveness, and the materials are inlaid through deformation, so that the granulating effect can be achieved without heating. The process also has the advantages of short granulating time, reduced binder consumption and the like.
In some preferred embodiments, the temperature at which the carbonization heat treatment is performed in S1 is 300 ℃ to 1400 ℃, for example, may be 300 ℃,500 ℃, 800 ℃, 1000 ℃, 1200 ℃, 1400 ℃, or any value between 300 ℃ and 1400 ℃.
In some preferred embodiments, the carbonization heat treatment is performed in S1 for a period of 8h to 50h, for example, 8h, 10h, 20h, 30h, 40h, 50h, or any value between 8h and 50 h.
In some preferred embodiments, the particle size D50 of the product obtained after the broken-spherical treatment in S2 is 10 μm to 20. Mu.m, for example, it may be 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm or any value between 10 μm and 20. Mu.m.
In some preferred embodiments, the temperature of the graphitization treatment in S2 is from 2800 ℃ to 3000 ℃, e.g., can be 2800 ℃, 2850 ℃, 2900 ℃, 2950 ℃, 3000 ℃, or any value between 2800 ℃ and 3000 ℃.
In a third aspect, the application also provides a negative electrode plate, the raw materials of which comprise the artificial graphite negative electrode material in the first aspect or the artificial graphite negative electrode material prepared by the preparation method in the second aspect.
In a fourth aspect, the application also provides a lithium ion battery, which comprises the negative electrode plate in the third aspect.
Embodiments of the present invention will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides an artificial graphite anode material, and the specific preparation method comprises the following steps:
(1) Raw material screening: pulverizing the coke raw material into fine powder with D50 particle size of 2-3 μm, preferably granulating the pulverized fine powder with D50 particle size of 5-7 μm;
(2) Mixing: the mixing ratio of the crushed fine powder of the coke raw material and the granulated and crushed fine powder is 4:6, mixing for 20min at a speed of 100r/min in a device with a mixing function;
(3) Spheroidizing and granulating: the mass ratio of the mixed aggregate to the epoxy resin is 10: adding epoxy resin in a proportion of 0.3, mixing and granulating for 10min, and then performing carbonization heat treatment for 16h at 1300 ℃ under the protection of inert gas to obtain carbonized particles;
(4) Crushing and grading: crushing and spheroidizing the carbonized particles in the step (3), wherein the particle size D50 is between 12 and 16 mu m;
(5) Graphitizing: and (3) graphitizing the material subjected to the sphericizing treatment in the step (4) at a high temperature of 3000 ℃ to obtain the artificial graphite anode material. Half battery capacity is 355.3mAh/g;
Example 2
The embodiment provides an artificial graphite anode material, and the specific preparation method comprises the following steps:
(1) Raw material screening: pulverizing the coke raw material into fine powder with D50 particle size of 2-3 μm, preferably granulating the pulverized fine powder with D50 particle size of 5-7 μm;
(2) Mixing: the mixing proportion of the crushed fine powder of the coke raw material and the crushed fine powder of the pelletization is 3:7, mixing for 20min at a speed of 100r/min in a device with a mixing function;
(3) Spheroidizing and granulating: the mass ratio of the mixed aggregate to the epoxy resin is 10: adding epoxy resin in a proportion of 0.3, mixing and granulating for 10min, and then performing carbonization heat treatment for 16h at 1300 ℃ under the protection of inert gas to obtain carbonized particles;
(4) Crushing and grading: crushing and spheroidizing the carbonized particles in the step (3), wherein the particle size D50 is between 12 and 16 mu m;
(5) Graphitizing: and (3) graphitizing the material subjected to the sphericizing treatment in the step (4) at a high temperature of 3000 ℃ to obtain the artificial graphite anode material.
Example 3
The embodiment provides an artificial graphite anode material, and the specific preparation method comprises the following steps:
(1) Raw material screening: pulverizing the coke raw material into fine powder with D50 particle size of 2-3 μm, preferably granulating the pulverized fine powder with D50 particle size of 5-7 μm;
(2) Mixing: the mixing ratio of the crushed fine powder of the coke raw material and the granulated and crushed fine powder is 2:8, mixing for 20min at a speed of 100r/min in a device with a mixing function;
(3) Spheroidizing and granulating: the mass ratio of the mixed aggregate to the epoxy resin is 10: adding epoxy resin in a proportion of 0.3, mixing and granulating for 10min, and then performing carbonization heat treatment for 16h at 1300 ℃ under the protection of inert gas to obtain carbonized particles;
(4) Crushing and grading: crushing and spheroidizing the carbonized particles in the step (3), wherein the particle size D50 is between 12 and 16 mu m;
(5) Graphitizing: and (3) graphitizing the material subjected to the sphericizing treatment in the step (4) at a high temperature of 3000 ℃ to obtain the artificial graphite anode material.
Example 4
The embodiment provides an artificial graphite anode material, and the specific preparation method comprises the following steps:
(1) Raw material screening: pulverizing the coke raw material into fine powder with D50 particle size of 2-3 μm, preferably granulating and pulverizing into fine powder with D50 particle size of 6-10 μm;
(2) Mixing: the mixing ratio of the crushed fine powder of the coke raw material and the granulated and crushed fine powder is 3.5:6.5, mixing for 20min at a speed of 100r/min in a device with a mixing function;
(3) Spheroidizing and granulating: the mass ratio of the mixed aggregate to the starch to the water is 10:0.3:2, adding starch and water in proportion, mixing and granulating for 10min, and then carrying out carbonization heat treatment for 16h at 1300 ℃ under the protection of inert gas to obtain carbonized particles;
(4) Crushing and grading: crushing and spheroidizing the carbonized particles in the step (3), wherein the particle size D50 is between 12 and 16 mu m;
(5) Graphitizing: and (3) graphitizing the material subjected to the sphericizing treatment in the step (4) at a high temperature of 3000 ℃ to obtain the artificial graphite anode material.
Example 5
The embodiment provides an artificial graphite anode material, and the specific preparation method comprises the following steps:
(1) Raw material screening: pulverizing the coke raw material into fine powder with D50 particle size of 2-4 μm, preferably granulating and pulverizing into fine powder with D50 particle size of 6-10 μm;
(2) Mixing: the mixing proportion of the crushed fine powder of the coke raw material and the crushed fine powder of the pelletization is 3:7, mixing for 20min at a speed of 100r/min in a device with a mixing function;
(3) Spheroidizing and granulating: the mass ratio of the mixed aggregate to the liquid asphalt is 10:1, adding liquid asphalt in proportion, mixing and granulating for 10min, and then performing carbonization heat treatment for 16h at 1300 ℃ under the protection of inert gas to obtain carbonized particles;
(4) Crushing and grading: crushing and spheroidizing the carbonized particles in the step (3), wherein the particle size D50 is between 12 and 16 mu m;
(5) Graphitizing: and (3) graphitizing the material subjected to the sphericizing treatment in the step (4) at a high temperature of 3000 ℃ to obtain the artificial graphite anode material.
Example 6
The embodiment provides an artificial graphite anode material, and the specific preparation method comprises the following steps:
(1) Raw material screening: pulverizing the coke raw material into fine powder with D50 particle size of 2-4 μm, preferably granulating and pulverizing into fine powder with D50 particle size of 6-10 μm;
(2) Mixing: the mixing ratio of the crushed fine powder of the coke raw material and the granulated and crushed fine powder is 2:8, mixing for 20min at a speed of 100r/min in a device with a mixing function;
(3) Spheroidizing and granulating: according to the mass ratio of the mixed aggregate to the anthracene oil of 10:2, adding anthracene oil in proportion, mixing and granulating for 25min, and then performing carbonization heat treatment for 16h at 1300 ℃ under the protection of inert gas to obtain carbonized particles;
(4) Crushing and grading: crushing and spheroidizing the carbonized particles in the step (3), wherein the particle size D50 is between 12 and 16 mu m;
(5) Graphitizing: and (3) carrying out high-temperature graphitization on the material subjected to the crushing and sphericizing treatment in the step (4) at 3000 ℃ to obtain the artificial graphite anode material.
Comparative example 1
The comparative example provides an artificial graphite anode material, which specifically comprises the following preparation method:
(1) Raw material screening: selecting needle coke raw materials, and crushing the needle coke raw materials to a particle size D50 of 8-10 mu m;
(2) Mixing: the mixing proportion of the needle coke crushed material and the asphalt is 90:10, mixing for 20min at a speed of 100r/min in a device with a mixing effect;
(3) Granulating: granulating by using a vertical kettle;
(4) Crushing and grading: crushing and sphericizing the granulated material, wherein the particle diameter D50 is between 12 and 16 mu m;
(5) Graphitizing: and (3) carrying out high-temperature graphitization on the material subjected to the crushing and sphericizing treatment in the step (4) at 3000 ℃ to obtain the artificial graphite anode material.
And (3) manufacturing a button cell: the negative electrode materials prepared in examples 1 to 6 and comparative example 1 were respectively mixed with a conductive paste (cmc+sp) and SBR in a mass ratio of 95:3:2 are uniformly mixed in N-methyl pyrrolidone and coated on a copper foil current collector, vacuum drying is carried out at 130 ℃ to obtain a negative electrode plate, then a button cell is assembled in a glove box for testing, wherein a lithium metal is adopted as a counter electrode, a diaphragm is a PP-PE-PP composite film, the diameter is 19.2mm, and an electrolyte is LB5315C.
The results of the relevant test properties of the artificial graphite anode materials prepared in examples 1 to 6 and comparative example 1 are shown in table 1, and the relevant electrochemical properties of the button cell after the artificial graphite anode materials prepared in examples 1 to 6 and comparative example 1 were used for button cell fabrication are shown in table 2.
TABLE 1
TABLE 2
Fig. 2 is a cross-sectional SEM view of the artificial graphite anode material of example 3, fig. 3 is a cross-sectional SEM view of the artificial graphite anode material of comparative example 1, fig. 4 is a SEM view of the artificial graphite anode material of example 3, and fig. 5 is a SEM view of the artificial graphite anode material of comparative example 1.
By combining the table 1, the table 2 and the figures 2-5, the artificial graphite material prepared by spheroidizing, granulating and graphitizing is shown that when Y is more than or equal to 0 and less than or equal to 4, the interior of the secondary particle artificial graphite presents a compact embedded honeycomb spherical structure, so that the porosity of the material is ensured, the high compaction requirement of the material is met, the isotropy of the material is improved, the expansion of particles is reduced, the contact area with electrolyte is large, the lithium ion deintercalation path is effectively shortened, and the purposes of improving the multiplying power performance and the cycle performance of the material are achieved. Because the primary particles during spheroidizing and granulating are continuously bonded layer by layer, the particle size of the secondary particles formed by spheroidizing and granulating is gradually increased, the outer surfaces of the secondary particles can always bear larger acting force, the primary particles are always firm and compact when inlaid, uniform pore distribution can be reserved from inside to outside, and meanwhile, the primary particles can be fully contacted with the binder. The spheroidizing granulation of the application not only can realize uniform coating, but also has a certain filling effect on macropores, and the finally prepared compact inlaid honeycomb spherical structure meets the requirements of the lithium ion battery on cycle performance, rate capability, capacity and first effect of the secondary particle artificial graphite.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. An artificial graphite anode material, characterized in that the inside of particles of the artificial graphite anode material is in a honeycomb spherical structure;
The porosity X 1, the tap density X 2, the sphericity X 3 and the orientation index X 4 of the negative electrode plate of the artificial graphite negative electrode material and the rapid charge and discharge capacity value Y of the artificial graphite negative electrode material meet the following relations:
y=4x 1+X2+2X3-0.1X4, wherein Y has a value of 0 to 4;
the negative electrode piece comprises the artificial graphite negative electrode material.
2. The artificial graphite anode material of claim 1, wherein at least one of the following conditions is satisfied:
a. The porosity X 1 of the artificial graphite anode material is 10% -45%;
b. the tap density X 2 of the artificial graphite anode material is 0.9g/cm 3-1.2g/cm3;
c. The sphericity X 3 of the artificial graphite anode material is 0.7-0.95;
d. The orientation index X 4 of the negative electrode plate is 5-40.
3. The artificial graphite anode material according to claim 1 or 2, wherein at least one of the following conditions is satisfied:
e. The particle diameter D50 of the artificial graphite anode material is 10-20 mu m;
f. the specific surface area of the artificial graphite anode material is 1.0m 2/g-4.0m2/g.
4. The preparation method of the artificial graphite anode material is characterized by comprising the following steps of:
spheroidizing and granulating the fine powder of the carbon-containing raw material, and then performing carbonization heat treatment to obtain carbonized particles;
And crushing and spheroidizing the carbonized particles, and graphitizing to obtain the artificial graphite anode material with the honeycomb spherical structure inside the particles.
5. The method of manufacturing of claim 4, wherein at least one of the following conditions is satisfied:
A. The carbonaceous raw material fine powder includes at least one of a coke raw material pulverized fine powder and a granulating pulverized fine powder;
B. The pulverized fine powder of the coke raw material comprises by-product fine powder obtained by pulverizing the coke raw material, wherein the particle size D50 of the by-product fine powder is 1-6 mu m;
C. The coke raw material comprises at least one of petroleum coke, pitch coke and needle coke;
D. The granulating and crushing fine powder comprises fine powder produced by performing secondary granulation, shaping and classification on the crushed product of the coke raw material, wherein the D50 of the fine powder is 4-13 mu m.
6. The method of manufacturing according to claim 5, wherein at least one of the following conditions is satisfied:
E. The carbon-containing raw material fine powder comprises coke raw material crushed fine powder and granulating crushed fine powder, and before spheroidizing and granulating, the carbon-containing raw material fine powder further comprises: mixing the crushed fine powder of the coke raw material and the granulated and crushed fine powder to obtain mixed aggregate;
F. the mixing includes: stirring at 50-600 rpm for 10-60 min;
G. The mass ratio of the crushed fine powder of the coke raw materials in the mixed aggregate is 0-100%, and the mass ratio of the granulated crushed fine powder is 0-100%.
7. The method of manufacturing of claim 4, wherein at least one of the following conditions is satisfied:
H. When the spheroidizing granulation is carried out, a binder is added into the fine powder of the carbon-containing raw materials;
I. The binder comprises at least one of petroleum asphalt, coal asphalt, liquid asphalt, anthracene oil, wash oil, phenolic resin, epoxy resin, furan resin, furfural resin, starch and polyethylene glycol;
J. the mass ratio of the fine powder of the carbon-containing raw material to the binder is 10: (0.1-2);
K. the spheroidizing and granulating time is 5-60 min;
And L, performing carbonization heat treatment, wherein the carbonization heat treatment comprises the following steps: the method is carried out under the atmosphere of protective gas, wherein the protective gas comprises at least one of argon, nitrogen and helium;
m, the temperature for carbonization heat treatment is 300-1400 ℃;
N, the time for performing carbonization heat treatment is 8-50 h;
And O, the particle size D50 of the product obtained after the crushing and sphericizing treatment is 10-20 mu m.
8. The method of any one of claims 4-7, wherein the graphitization treatment is at a temperature of 2800 ℃ to 3000 ℃.
9. A negative electrode sheet, characterized in that the raw material thereof comprises the artificial graphite negative electrode material according to any one of claims 1 to 3 or the artificial graphite negative electrode material prepared by the preparation method according to any one of claims 4 to 8.
10. A lithium ion battery comprising the negative electrode tab of claim 9.
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| CN118270778A true CN118270778A (en) | 2024-07-02 |
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