CN112670504A - Modified resistance material, graphite negative electrode material containing modified resistance material, and preparation method and application of graphite negative electrode material - Google Patents
Modified resistance material, graphite negative electrode material containing modified resistance material, and preparation method and application of graphite negative electrode material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000010439 graphite Substances 0.000 title claims abstract description 49
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000007773 negative electrode material Substances 0.000 title claims description 23
- 239000010406 cathode material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002699 waste material Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 41
- 238000007493 shaping process Methods 0.000 claims description 40
- 238000005087 graphitization Methods 0.000 claims description 33
- 238000012545 processing Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011329 calcined coke Substances 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 10
- 238000010298 pulverizing process Methods 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 230000005389 magnetism Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005056 compaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
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- 230000014759 maintenance of location Effects 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
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- 239000006253 pitch coke Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a modified resistance material, a graphite cathode material containing the same, and a preparation method and application thereof. The preparation method of the modified resistance material comprises the following steps: the resistance material is crushed, graded and shaped to obtain the resistance material; the parameters of the equipment used for crushing are set as follows: the frequency of a main machine is 25-50Hz, the frequency of a grader is 20-35Hz, and the frequency of a fan is 20-40 Hz; hierarchical plastic all-in-one equipment is adopted in hierarchical, the operation of plastic, and the parameter setting of hierarchical plastic all-in-one equipment is: the frequency of the main machine is 30-60Hz, the frequency of the grader is 10-40Hz, and the frequency of the fan is 30-50 Hz. The method changes waste into valuable, utilizes the waste resistance materials as raw materials, is used for preparing the graphite cathode material, has simple working procedures and low production cost, and can be produced in a large scale; the prepared graphite cathode material has high tap density and good capacity efficiency, multiplying power and expansion performance of the battery.
Description
Technical Field
The invention relates to a modified resistance material, a graphite negative electrode material containing the same, and a preparation method and application thereof.
Background
The lithium ion battery processed and manufactured by using the artificial graphite cathode material has remarkable advantages, high energy density, excellent rate capability, low expansion, excellent quick charging capability, high cycle ratio, no memorability effect, safety, no pollution and the like. At present, lithium ion batteries are mainly applied to steering energy storage equipment and power equipment of consumer electronic equipment, and the market demand is increased geometrically times year by year.
With the market popularization, the requirements of power energy sources on cathode materials compared with consumer electronics at present are focused on the middle-low end broad population of the general public in addition to excellent physical and electrochemical properties, and high requirements are put forward on cost control. At present, the processing cost of the electric hybrid new energy automobile in the market is generally higher, and the electric hybrid new energy automobile is not beneficial to the popularization of EV power automobiles. Therefore, in recent years, low-cost, high-performance and high-safety research on the negative electrode material of artificial graphite has become a general research direction.
The resistance material is a crucible or an electrode which is matched as an auxiliary material in the graphitization processing procedure and is generally used for conducting and heating the processed crucible or electrode, after the resistance material is graphitized for the first time, the powder resistance of the resistance material is greatly reduced, the conductivity is poor, and as a result, the resistance material cannot be used as the graphitization auxiliary material after being processed, and the conventional processing mode is used as a carburant or scrapping processing.
Chinese patent application CN106981657A discloses a method for preparing graphite cathode material, which uses one or more of petroleum coke, pitch coke and resistor as raw materials to prepare graphite cathode material, but its process route is long, the raw materials need to be baked many times, the pollution is large, and the resistor has high ash/volatile/sulfur content; in the working procedure, a certain proportion of catalyst is added for mixing to generate pollution, the loss of a crucible or an electrode in the graphitization working procedure is increased, the service life of the graphite electrode is shortened, and the cost is high.
Disclosure of Invention
The invention aims to overcome the defects of high cost or complex preparation method of a graphite cathode material in the prior art, and provides a modified resistance material, a graphite cathode material containing the modified resistance material, a preparation method and application of the graphite cathode material. The preparation method of the modified resistance material provided by the invention is simple, the cost of the modified resistance material for preparing the graphite cathode material is low, the method is simple, and the prepared graphite cathode material has excellent performance.
The graphite cathode material is prepared by taking the processed resistance material waste as the raw material and changing the structure of the processed resistance material into valuable, the texture becomes hard, the processing is difficult, and the process cost is high if the graphite cathode material is granulated for two times or more.
The invention solves the technical problems through the following technical scheme:
the invention provides a preparation method of a modified resistance material, which comprises the following steps: the resistance material is crushed, graded and shaped to obtain the resistance material; wherein the content of the first and second substances,
the parameters of the equipment used for crushing are set as follows: the frequency of a main machine is 25-50Hz, the frequency of a grader is 20-35Hz, and the frequency of a fan is 20-40 Hz;
the operation of grading and shaping adopts grading and shaping all-in-one machine equipment, and the parameters of the grading and shaping all-in-one machine equipment are set as follows: the frequency of the main machine is 30-60Hz, the frequency of the grader is 10-40Hz, and the frequency of the fan is 30-50 Hz.
In the invention, the electric resistance material refers to electric resistance material waste obtained after one or more of petroleum calcined coke, coal calcined coke, asphalt calcined coke and metallurgical calcined coke is subjected to primary or multiple graphitization processing. The graphitization processing generally refers to a processing procedure that the resistance material is usually used as an auxiliary material to be matched around a crucible or an electrode in a conventional graphitization processing procedure in the field, and is used for conducting electricity and heating the processed crucible or electrode.
In the invention, the electric resistance material is preferably obtained by carrying out primary graphitization on petroleum calcined coke.
In the present invention, the resistance material preferably has the following characteristics: the particle size is 2-25mm, the powder resistance is 30-120 mu omega mu m, the sulfur content is 0.01-0.15%, and the ash content is 0.1-0.6%, wherein the percentages are mass percentages of the resistance material.
In the present invention, the pulverization may be carried out in a conventional manner in the art. The comminution apparatus may be conventional in the art, preferably a mechanical mill, a roll mill or a jet mill.
In the present invention, the classification means may be a classification means conventional in the art. The classification apparatus may be a classification apparatus conventional in the art. The grading equipment can be used for adjusting the particle size distribution and the fine powder content of the powder.
In the present invention, the shaping means may be conventional in the art. The shaping device may be a shaping device conventional in the art. The shaping machine can be used for modifying the surface appearance of the material and improving the tap density of the material.
In the present invention, the device used for the pulverization, classification, and shaping treatment is preferably a pulverization, classification, and shaping integrated device. The crushing, grading and shaping integrated equipment can be conventional crushing, grading and shaping integrated equipment in the field, can be continuously produced and can reduce dust pollution. For example, when the crushing and grinding bin is hung with 1000kg of package materials of 300-.
Wherein, the crushing, grading and shaping integrated equipment generally comprises three discharge ports: a cyclone classification port F1, a normal material discharge port F2 and a dust removal powder receiving port F3.
The crushing, grading and shaping integrated device preferably comprises a crushing device and a grading and shaping integrated device; the parameter settings of the comminution apparatus are preferably: the frequency of a main machine is 25-50Hz, the frequency of a grader is 20-35Hz, and the frequency of a fan is 20-40 Hz; the parameter setting of the grading and shaping integrated device is preferably as follows: the frequency of the main machine is 30-60Hz, the frequency of the grader is 10-40Hz, and the frequency of the fan is 30-50 Hz.
The invention also provides a modified resistance material prepared by the preparation method of the modified resistance material.
The invention also provides a modified resistance material, wherein the D50 particle size of the modified resistance material is 6-25 mu m, and the tap density is 0.85-0.95g/cm3。
In the present invention, the particle size of the modified resistor is preferably 6 to 19 μm, such as 6 to 11 μm or 11 to 17.5 μm, and further such as 9, 13 or 17 μm; or the particle size of the modified resistance material is preferably 17.5-25 μm;
in the invention, the tap density of the modified resistance material is preferably 0.9g/cm3。
The invention also provides a graphite negative electrode material containing the modified resistance material.
The invention also provides a preparation method of the graphite cathode material, which comprises the following steps: and graphitizing the modified resistance material, and screening and demagnetizing the mixed material to obtain the modified resistance material.
In the present invention, the graphitization treatment temperature may be a graphitization temperature conventional in the art, and is preferably 2400 to 2800 ℃, for example 2600 ℃. The graphitization treatment time is preferably 35-55 h, such as 45 h.
In the present invention, the graphitization treatment apparatus may be an apparatus conventionally used for graphitization in the art, preferably an Acheson furnace.
In the invention, the material obtained after the graphitization treatment has the following properties:
the D50 particle size is preferably 8-16.5 μm, for example 8.5, 12, 12.5 or 16 μm;
the true density is preferably 0.9 to 1.1g/cm3；
Proportion tableThe area is preferably 1 to 3g/cm2E.g. 1.5, 2 or 2.5g/cm2；
The compacted density is preferably 1.5 to 1.7g/cm2E.g. 1.55, 1.6 or 1.65g/cm2；
The capacity is preferably 340-350mAh/g, for example 345 mAh/g.
In the invention, the operation of the material mixing sieve for demagnetizing can be the operation of the material mixing sieve for demagnetizing which is conventional in the field.
In the invention, the mixed material sieving and demagnetizing equipment can be equipment which is conventionally used for demagnetizing the mixed material sieving in the field, and is preferably a vertical or horizontal mixed sieving machine.
In the invention, the material obtained after the mixed material screening and demagnetizing treatment has the following characteristics:
the particle size is preferably 8-16.5 μm, for example 8.5, 12, 12.5 or 16 μm;
the tap density is preferably 1 to 1.1g/cm3For example 1.05g/cm3；
The specific surface area is preferably 1 to 3g/cm2E.g. 1.5, 2 or 2.5g/cm2；
The compacted density is preferably 1.5 to 1.7g/cm2For example 1.55 or 1.65g/cm2；
The capacity is preferably 340-350mAh/g, such as 345 mAh/g;
the magnetic content is preferably 700ppb or less.
In a preferred embodiment of the present invention, the preparation method comprises the steps of:
(1) crushing, grading and shaping treatment: pulverizing the resistance material in a pulverizing, grading and shaping integrated equipment to obtain D50 with particle diameter of 6-19 μm and tap density of 0.85-0.95g/cm3The material A of (1);
(2) graphitization treatment: graphitizing the material A obtained in the step (1) in a graphitizing furnace, wherein the graphitizing temperature is 2400-2800 ℃, and the graphitizing time is 35-55 hours, so as to obtain a graphite cathode material D50 with the particle size of 6-25 mu m;
(3) screening and demagnetizing the mixed material: and (3) fully and uniformly mixing the materials prepared in the step (2) in a mixing and screening device to remove magnetism.
The invention also provides the graphite cathode material prepared by the preparation method.
Wherein, the graphite cathode material preferably has the following characteristics:
the particle size is preferably 8.2-16.2 μm, for example 12.6 μm;
the ash content is preferably 0.01-0.03%, e.g. 0.02%;
the true density is preferably 2.24-2.25g/cm3；
The specific surface area is preferably 1.5 to 2.7g/cm2E.g. 2.1g/cm2；
The tap density is preferably 0.87 to 1.07g/cm2E.g. 1.01g/cm2。
The invention also provides an application of the graphite negative electrode material in preparation of a lithium battery.
The invention also provides a lithium battery containing the graphite negative electrode material.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1) the preparation method uses the processed resistance material as a raw material to prepare the artificial graphite cathode material, and uses the resistance material subjected to high-temperature treatment to replace the current calcined needle coke as the raw material, so that waste is changed into valuable, and the cost is greatly reduced. Compared with the existing preparation process of the cathode material, the preparation method provided by the invention has the advantages of simple process, low production cost, short manufacturing takt, capability of greatly shortening the production process and the production period, high efficiency, safety and capability of realizing large-scale production.
2) According to the invention, the resistance material is taken as a raw material, the resistance material is crushed to prepare powder to form single-particle micro powder, then grading and shaping treatment is carried out, the appearance modification of the particles is regular and smooth, fine powder is broken up in a grading way to enable the particle size distribution of the particles to be better, and then the resistance material is crushed and graphitized to remove impurities and increase the graphitization degree; and finally, screening and homogenizing the mixed material, and further demagnetizing to remove magnetic substances in the graphite powder. The shaping treatment in the crushing all-in-one machine can not only modify the appearance of the product and the surface smoothness of product particles, but also improve the tap density of the product. For materials with high requirements on tap density, serial shaping equipment can be added, and the invention can finely control the tap density by a serial graphitization treatment process after shaping, realize granulation without coating asphalt and improve tap density.
3) The graphite cathode material prepared by the invention has higher tap density which is the key for manufacturing a high-capacity battery, and the higher the tap density is, the larger the capacity loaded in the battery is, and the larger the specific energy is, thus being beneficial to improving the electrical property of the battery material. The battery prepared by the graphite cathode material prepared by the invention has capacity efficiency, rate capability and expansion coefficient which meet the requirements of the current consumer electronic batteries/power batteries and energy storage batteries, and the electrochemical performance can reach as follows: the first discharge capacity is more than 345mAh/g, and the first efficiency is more than 92.0 percent; the discharge plateau and the plateau retention rate are higher; the cycle performance is good, and the capacity retention rate is more than 90% after 800 cycles; the processing performance is better.
Drawings
FIG. 1 is a graph showing the 30-cycle capacity retention rate of batteries prepared from the graphite negative electrode materials obtained in examples 1 to 3 and comparative example 1.
FIG. 2 is a graph showing charge and discharge curves of a battery 1C prepared from the graphite negative electrode materials obtained in examples 1 to 3 and comparative example 1.
Fig. 3 is an SEM image of the graphite anode material obtained in example 1 (a: 500 × magnification; b: 1000 × magnification).
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples, the sources of the electrical resistance material were: the resistance material purchased from Yixing Yongchun graphite GmbH is used as an auxiliary material for a graphitization processing procedure, matched around a crucible or an electrode, and subjected to graphitization processing once (at 2300-3200 ℃ for more than 32 hours) and then discarded.
Example 1
A preparation method of a graphite negative electrode material comprises the following preparation steps:
(1) feeding 8-25mm resistance material into a mechanical grinding, crushing, grading and shaping all-in-one machine (wherein the parameters of the equipment are set as the main machine frequency of 25Hz, the classifier frequency of 30Hz and the fan frequency of 30Hz, and the parameters of the grading and shaping all-in-one machine are set as the main machine frequency of 37Hz, the classifier frequency of 28Hz and the fan frequency of 40Hz), controlling the powder particle diameter D50 to be about 17.0 mu m and controlling the tap density to be 0.95g/cm3Left and right;
(2) graphitizing at 2800 deg.C in Acheson furnace for 45 hr to obtain graphitized semi-finished product with particle size of 16-16.5 μm and BET of 1.0-2.0g/cm2The compaction density in one pass is 1.650g/cm3The capacity is about 350 mAh/g;
(3) the semi-finished graphite powder prepared by graphitization is screened and demagnetized by mixing materials, the particle size of the finished product is 16-16.5 mu m, and the tap density TD is 1.0g/cm3About 1.0-2.0g/cm BET2The compaction density in one pass is 1.65g/cm3The capacity is about 3500mAh/g, and the magnetic content is below 700 ppb.
Example 2
A preparation method of a graphite negative electrode material comprises the following preparation steps:
(1) feeding 8-25mm resistance material into a grinding, crushing, grading and shaping all-in-one machine (wherein the parameters of the equipment are set as the main machine frequency of 15Hz, the grader frequency of 35Hz and the fan frequency of 25Hz, and the parameters of the grading and shaping all-in-one machine are set as the main machine frequency of 65Hz, the grader frequency of 55Hz and the fan frequency of 30Hz), controlling the powder particle diameter D50 to be about 13.0 mu m and controlling the tap density to be 0.90g/cm3Left and right:
(2) graphitizing for 55h in Acheson furnace at 2600 deg.C, the particle diameter of graphitized semi-finished product is 12.0-12.5 μm, and TD is 1.1g/cm3About 1.5-2.5g/cm BET2The density of the two times of compaction is 1.70g/cm3The capacity is about 350 mAh/g;
(3) the semi-finished graphite powder prepared by graphitization is screened and demagnetized by mixing materials, the grain diameter of the graphitized semi-finished product is 12.0-12.5 mu m, and the tap density TD is 1.1g/cm3About 1.5-2.5g/cm BET2The density of the two times of compaction is 1.70g/cm3About 350mAh/g in capacity and 700ppb or less in magnetic content.
Example 3
A preparation method of a graphite negative electrode material comprises the following preparation steps:
(1) feeding 8-25mm resistance material into a rolling, grinding, crushing, grading and shaping all-in-one machine (wherein the parameters of the equipment are that the frequency of a main machine is 55Hz, the frequency of a grader is 40Hz, and the frequency of a fan is 45Hz, and the parameters of the grading and shaping all-in-one machine are that the frequency of the main machine is 15Hz, the frequency of the grader is 30Hz, and the frequency of the fan is 45Hz), controlling the powder particle diameter D50 to be about 9.0 mu m, and controlling the tap density to be 0.85g/cm3Left and right:
(2) graphitizing in Acheson furnace at 2400 deg.C for 55 hr to obtain graphitized semi-finished product with particle diameter of 8.0-8.5 μm and tap density TD of 0.9g/cm3About 2.0-3.0g/cm BET2The density of the second compaction is about 1.55, and the capacity is about 345 mAh/g;
(3) the semi-finished graphite powder prepared by graphitization is screened and demagnetized by mixing materials, the particle size of the finished product is 8.0-8.5 mu m, and the tap density TD is 1.0g/cm3About 2.0-3.0g/cm BET2The two-pass compaction density is about 1.55, the capacity is about 345mAh/g, and the magnetic content is below 700 ppb.
Comparative example 1 preparation of graphite negative electrode using calcined Petroleum Coke processing
(1) Putting the calcined petroleum coke material into a jaw crusher or a hammer crusher, crushing the large calcined coke into particles with the particle size of less than 25mm, putting the particles into a rolling, grinding and grading shaping integrated machine, controlling the particle size D50 of powder to be about 16.0 mu m, and controlling the tap density to be about 0.97;
(2) graphitizing for 60h in Acheson furnace at 3000 deg.C to obtain graphitized semi-finished product with particle diameter of 15.0-15.5 μm, tap density TD at 1.05g/cm3About 1.0-2.0g/cm BET2The density of the second compaction is about 1.73, and the capacity is about 345 mAh/g;
(3) the semi-finished graphite powder prepared by graphitization is screened and demagnetized by mixing materials, the particle size of the finished product is 15.0-15.5um, and the tap density TD is 1.05g/cm3About 1.0-2.0g/cm BET2The two-pass compaction density is about 1.73, the capacity is about 345mAh/g, and the magnetic content is below 700 ppb.
Comparative example 2
The resistance material is treated by the crushing, grading and shaping integrated machine, and when the D50 particle size of the resistance material exceeds 25 mu m, the tap density of the prepared graphite powder is found to be extremely high (more than 1.2 g/cm)3) And the particle size distribution of the whole graphite powder is too narrow, the follow-up expansion and the cycle performance are judged not to meet the requirements, the later-stage verification is not carried out, and the test is terminated.
When the D50 particle size of the resistance material is less than 6 μm, the tap density of the graphite powder is extremely small (less than 0.5 g/cm)3) The particle size distribution of the whole graphite powder is too wide, the electric capacity is judged to be not in accordance with the requirement, the later-stage verification is not carried out, and the test is terminated.
Effects of the embodiment
The graphite negative electrode materials prepared in examples 1 to 3 and comparative example were subjected to a physical and electrochemical performance test, and the obtained physical and electrochemical performances are shown in table 1:
table 1 results of physical and electrochemical properties of graphite negative electrode material
As can be seen from table 1, fig. 2, and fig. 3, after the primary graphitization resistor is used and is subjected to pulverization, shaping, graphitization, material mixing, screening, and demagnetization, the graphite cathode manufactured by using the primary graphitization resistor is compared with the graphite cathode processed by using calcined petroleum coke, so that the electrochemical performance index of the manufactured product is not greatly different, and the cathode is round in appearance. And the evaluation of the battery manufactured by the same process at the later stage has small capacity retention rate and charge-discharge curve difference. Therefore, the auxiliary material for graphitizing processing is secondarily utilized to reduce the cost of the raw material, and the graphite cathode can be completely processed by taking calcined petroleum coke as the raw material.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. The preparation method of the modified resistance material is characterized by comprising the following steps of: the resistance material is crushed, graded and shaped to obtain the resistance material;
the parameters of the equipment used for crushing are set as follows: the frequency of a main machine is 25-50Hz, the frequency of a grader is 20-35Hz, and the frequency of a fan is 20-40 Hz;
the operation of grading and shaping adopts grading and shaping all-in-one machine equipment, and the parameters of the grading and shaping all-in-one machine equipment are set as follows: the frequency of the main machine is 30-60Hz, the frequency of the grader is 10-40Hz, and the frequency of the fan is 30-50 Hz.
2. The method for preparing the modified electric resistance material according to claim 1, wherein the electric resistance material is waste of electric resistance material after primary or multiple graphitization processing of one or more of petroleum calcined coke, coal-based calcined coke, asphalt calcined coke and metallurgical calcined coke; preferably, the electric resistance material is obtained by carrying out primary graphitization on petroleum calcined coke;
and/or the electric resistance material has the following characteristics: the granularity is 2-25mm, the powder resistance is 30-120 mu omega mu m, the sulfur content is 0.01-0.15%, and the ash content is 0.1-0.6%, wherein the percentages are mass percentages of the resistance material;
and/or the equipment used for crushing is a mechanical crusher, a roller mill or a jet mill;
and/or the equipment used for crushing, grading and shaping is crushing, grading and shaping integrated equipment; wherein, the crushing, grading and shaping integrated equipment preferably comprises three discharge ports: a cyclone classification port F1, a normal material discharge port F2 and a dust removal powder receiving port F3;
the crushing, grading and shaping integrated device preferably comprises a crushing device and a grading and shaping integrated device.
3. A modified electric resistance material prepared by the method for preparing a modified electric resistance material according to claim 1 or 2.
4. The modified electric resistance material is characterized in that the D50 particle size of the modified electric resistance material is 6-25 mu m, and the tap density is 0.85-0.95g/cm3；
The particle size of the modified resistor material is preferably 6-19 μm, such as 6-11 μm or 11-17.5 μm, and is further such as 9, 13 or 17 μm; or the particle size of the modified resistance material is preferably 17.5-25 μm;
and/or the tap density of the modified resistance material is 0.9g/cm3。
5. A graphite negative electrode material comprising the modified electric resistance material as claimed in claim 3 or 4.
6. The preparation method of the graphite negative electrode material is characterized by comprising the following steps of: the modified resistor material as claimed in claim 3 or 4 is obtained by graphitization treatment and sieving and demagnetizing treatment of the mixed material.
7. The preparation method of the graphite cathode material as claimed in claim 6, wherein the graphitization treatment temperature is 2400-2800 ℃, such as 2600 ℃; the graphitization treatment time is preferably 35-55 h, such as 45 h;
and/or the graphitization treatment equipment is an Acheson furnace;
and/or the material obtained after the graphitization treatment has the following properties:
d50 has a particle size of 8-16.5 μm, for example 8.5, 12, 12.5 or 16 μm;
the true density is preferably 0.9 to 1.1g/cm3；
The specific surface area is preferably 1 to 3g/cm2E.g. 1.5, 2 or 2.5g/cm2；
The compacted density is preferably 1.5 to 1.7g/cm2E.g. 1.55, 1.6 or 1.65g/cm2；
The capacity is preferably 340-350mAh/g, such as 345 mAh/g;
and/or the mixed material screening and demagnetizing equipment is a vertical or horizontal mixed screening machine;
and/or the material obtained after the mixed material is sieved and demagnetized has the following characteristics:
particle size is 8-16.5 μm, for example 8.5, 12, 12.5 or 16 μm;
the tap density is preferably 1 to 1.1g/cm3For example 1.05g/cm3；
The specific surface area is preferably 1 to 3g/cm2E.g. 1.5, 2 or 2.5g/cm2；
The compacted density is preferably 1.5 to 1.7g/cm2For example 1.55 or 1.65g/cm2；
The capacity is preferably 340-350mAh/g, such as 345 mAh/g;
the magnetic content is preferably 700ppb or less;
preferably, the preparation method of the graphite negative electrode material comprises the following steps:
(1) crushing, grading and shaping treatment: pulverizing the resistance material in a pulverizing, grading and shaping integrated equipment to obtain D50 with particle diameter of 6-19 μm and tap density of 0.85-0.95g/cm3The material A of (1);
(2) graphitization treatment: graphitizing the material A obtained in the step (1) in a graphitizing furnace, wherein the graphitizing temperature is 2400-2800 ℃, and the graphitizing time is 35-55 hours, so as to obtain a graphite cathode material D50 with the particle size of 6-25 mu m;
(3) screening and demagnetizing the mixed material: and (3) fully and uniformly mixing the materials prepared in the step (2) in a mixing and screening device to remove magnetism.
8. A graphite negative electrode material prepared by the method for preparing a graphite negative electrode material according to claim 7;
wherein, the graphite cathode material preferably has the following characteristics:
the particle size is preferably 8.2-16.2 μm, for example 12.6 μm;
the ash content is preferably 0.01-0.03%, e.g. 0.02%;
the true density is preferably 2.24-2.25g/cm3；
The specific surface area is preferably 1.5 to 2.7g/cm2E.g. 2.1g/cm2；
The tap density is preferably 0.87 to 1.07g/cm2E.g. 1.01g/cm2。
9. Use of the graphitic negative electrode material according to claim 8 for the preparation of lithium batteries.
10. A lithium battery comprising the graphite negative electrode material of claim 8.
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