CN117844263A - Preparation method and device of binder asphalt for granulating lithium ion battery cathode material - Google Patents
Preparation method and device of binder asphalt for granulating lithium ion battery cathode material Download PDFInfo
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- CN117844263A CN117844263A CN202410096723.XA CN202410096723A CN117844263A CN 117844263 A CN117844263 A CN 117844263A CN 202410096723 A CN202410096723 A CN 202410096723A CN 117844263 A CN117844263 A CN 117844263A
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- ion battery
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- 239000010426 asphalt Substances 0.000 title claims abstract description 109
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 239000011230 binding agent Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010406 cathode material Substances 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000011269 tar Substances 0.000 claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 22
- 239000011280 coal tar Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000000199 molecular distillation Methods 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 16
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 15
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000007773 negative electrode material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 239000011305 binder pitch Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011295 pitch Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000004939 coking Methods 0.000 abstract description 7
- 238000005469 granulation Methods 0.000 abstract description 7
- 230000003179 granulation Effects 0.000 abstract description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910021383 artificial graphite Inorganic materials 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 239000002006 petroleum coke Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
The invention relates to a preparation method and a device of binder asphalt for granulating a lithium ion battery anode material, wherein the method is used for a granulating process in the production process of the anode material in a mode of mixing coal-based asphalt and oil-based tar. The binder asphalt for granulating the lithium ion battery with high cohesiveness is obtained by taking medium-low temperature coal tar pitch and ethylene tar as raw materials and polyacrylic acid as a modifier through pressurizing polymerization, oxidative crosslinking and molecular distillation processes in sequence. The invention uses medium-low temperature coal tar and ethylene tar as raw materials, is easy to obtain, has low cost and high cohesiveness, and is an adhesive asphalt material for granulating lithium ion batteries, so that the asphalt realizes high value-added utilization, and the obtained adhesive asphalt product has low quinoline insoluble content, good cohesiveness and high coking value, and obviously improves the performance of the anode material after granulation. Simple process, good product quality and high enterprise profit.
Description
Technical Field
The invention belongs to the technical field of asphalt, and particularly relates to a preparation method and a device of binder asphalt for granulating a lithium ion battery anode material.
Background
Binder pitch is an important raw material for the production of carbon products, and has high carbon content and excellent binding property. The quality of the binder asphalt directly influences the technical indexes of the product such as strength, thermal shock resistance, electric conduction and heat conduction. With the rapid development of the metallurgical industry, the quality requirements of carbon products are continuously improved, and the quality requirements of asphalt binders are correspondingly improved. The asphalt binder with improved quality can reduce the resistivity of products, and improve the mechanical strength, oxidation resistance and thermal stability of the products. Two requirements of a binder for producing a carbon material are that a certain plasticity is given to a paste in the process of kneading and forming; and secondly, carbon film bonding bridges are formed among the particle aggregates in the roasting process, and the fixed carbon particles are combined into a whole, so that the carbon film has certain mechanical strength. Among the various indexes of binder asphalt, the most important indexes are TI and QI, and the beta resin is truly representative of the binder component.
In lithium ion batteries, the negative electrode material is one of the important factors affecting the capacity and service life of the battery, and the negative electrode material is mainly artificial graphite. The compatibility of the artificial graphite in the lithium ion battery and the electrolyte is not high, and the phenomenon of co-intercalation of solvent molecules can occur during the intercalation/deintercalation of lithium ions, so that the cycle life of the battery is not high; meanwhile, due to the fact that the microstructure is different in the artificial graphite process, a graphite microcrystalline structure cannot be completely formed in the graphitization process, a plurality of active sites can be generated on the surface of the artificial graphite, the specific capacity of the negative electrode material is seriously affected, the applicability of the artificial graphite is reduced, and the artificial graphite is relatively complete in lamellar structure, so that lithium ions can only be inserted in the direction perpendicular to the Z axis, the migration path of the lithium ions is increased, and the rate performance is poor. At the moment, the binder for granulating the negative electrode material with high coking value, low QI, high beta resin and low ash content can be directionally prepared, and the artificial graphite secondary particles with uniform and stable void structure and excellent microstructure can be prepared on the basis of ensuring the mutual penetration of the graphite lamellar frameworks.
Disclosure of Invention
The invention provides a preparation method and a device of binder asphalt for granulating a lithium ion battery anode material, which are used for preparing binder asphalt with high coking value, low QI, high beta resin and low ash content for granulating the anode material, and on the basis of ensuring that graphite lamellar frameworks are mutually communicated, the artificial graphite secondary particles with uniform and stable void structure and excellent microstructure are prepared.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the method is used for granulating the anode material production process in a mode of mixing coal-based asphalt and oil-based tar. The binder asphalt for granulating the lithium ion battery with high cohesiveness is obtained by taking medium-low temperature coal tar pitch and ethylene tar as raw materials and polyacrylic acid as a modifier through pressurizing polymerization, oxidative crosslinking and molecular distillation processes in sequence.
The method specifically comprises the following steps:
1) Adding ethylene tar into medium-low temperature coal tar, and placing the mixture into a pressurized reaction kettle and stirring the mixture for 1 to 1.5 hours at 180 to 200 ℃ to obtain the mixed asphalt.
2) The mixed asphalt is polymerized in a pressurizing reaction kettle under pressure, the temperature is raised to 350-400 ℃ at the heating rate of 3-5 ℃/min, nitrogen is introduced to pressurize to 0.5-1.0 MPa, and the polymerization reaction is carried out for 2-8 h at constant temperature, thus obtaining the pressurizing polymerized asphalt.
3) And (3) further carrying out oxidative crosslinking on the pressurized polymerized asphalt obtained in the step (2), wherein the temperature is 330-380 ℃, and the air flow is regulated and controlled according to the total amount of materials (100L/min-600L/min) to carry out oxidation for 2-6 h, so as to obtain the oxidized asphalt.
4) Molecular distillation is carried out on the mixed asphalt oxide obtained in the step 3) through a molecular distillation device, the temperature is 230-280 ℃, the vacuum pressure of a short-path molecular distillation device is controlled, under the rotating condition, the mixed asphalt oxide is distilled, and the high-softening-point asphalt material with high cohesiveness is prepared through a molecular distillation method; the vacuum pressure of the short-path molecular distiller is 30-200 Pa, and the rotating speed is 200-400 rpm.
5) Adding modifier polyacrylic acid into the high softening point asphalt material obtained in the step 4) for mixing, wherein the mixing temperature is 220-270 ℃, and the mixing time is 0.5-2 h, so as to obtain the binder asphalt for granulating the lithium ion battery.
In the mixture raw material of the medium-low temperature coal tar and the ethylene tar, the ethylene tar accounts for 10-30wt% of the medium-low temperature coal tar.
The addition amount of the modifier is 0.5-2 wt% of the mixture raw material of the medium-low temperature coal tar and ethylene tar.
The softening point of the prepared binder asphalt for granulating the lithium ion battery is 170-250 ℃, the QI value is <1%, the TI value is >31%, the CV is >60%, the moisture is <1%, and the ash content is <1%.
The device comprises a pressurizing reaction kettle, an oxidation device, a short-range molecular distiller and a polymerization reaction kettle, wherein a discharge port of the pressurizing reaction kettle is connected with a feed port of the oxidation device, a discharge port of the oxidation device is connected with a feed port of the short-range molecular distiller, a heavy component outlet of the short-range molecular distiller is connected with the polymerization reaction kettle, and a discharge port of the polymerization reaction kettle is connected with a raw material collecting device.
The device also comprises a light component collecting tank and a byproduct collecting tank, wherein a gas phase outlet of the oxidation device is connected with the light component collecting tank, and a light component outlet of the short-path molecular distiller is connected with the byproduct collecting tank.
The oxidation device is a reaction kettle with a stirrer, and the bottom of the reaction kettle is connected with an air pump.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention uses medium-low temperature coal tar and ethylene tar as raw materials, is easy to obtain, has low cost and high cohesiveness, and is an adhesive asphalt material for granulating lithium ion batteries, so that the asphalt realizes high value-added utilization, and the obtained adhesive asphalt product has low quinoline insoluble content, good cohesiveness and high coking value, and obviously improves the performance of the anode material after granulation. Simple process, good product quality and high enterprise profit.
2) Polyacrylic acid (PAA) is a water-soluble high molecular polymer, and an aliased acrylic acid homopolymer is a chain-shaped high molecular water-based adhesive, and is a weak acid, colorless or light yellow liquid. The polyacrylic acid serving as a binder asphalt additive is used for granulating the negative electrode of the lithium battery, can better inhibit the volume expansion of an active material, form a more stable thin SEI film, effectively prevent the corrosion of electrolyte to the active material, reduce the impedance of an electrode, particularly the charge transfer impedance, and improve the diffusion rate of lithium ions, thus having a vital effect on improving the service performance of the battery.
3) Asphalt is a black solid substance with extremely high carbon content and in a glass phase form at normal temperature, and is widely used as a raw material of artificial carbon materials. The coated asphalt prepared by the oxidation method has the characteristics of high carbon residue value, low QI content, good thermal stability and isotropy. The asphalt component is complicated, and light and heavy components can be separated by a molecular distillation method, so that the material performance is improved.
4) The asphalt is subjected to polycondensation reaction through the raw material mixing and pressurizing polymerization process, the softening point of the reacted asphalt is greatly reduced under the condition that the coking value of the reacted asphalt is unchanged, and the coking value of the asphalt is greatly improved compared with the conventional process after the softening point is improved through the molecular distillation process. The coking value is improved in that less volatile is discharged in the granulating process of the cathode material, and the yield is improved. The oxidation process improves the content of beta resin and greatly improves the cohesiveness.
Drawings
FIG. 1 is a process scheme of the present invention.
FIG. 2 is a scanning electron microscope image of the binder pitch and petroleum coke of example 1 after pelletization.
FIG. 3 is a scanning electron microscope image of the binder pitch and petroleum coke of example 2 after pelletization.
FIG. 4 is a scanning electron microscope image of the binder pitch and petroleum coke of example 3 after pelletization.
FIG. 5 is a scanning electron microscope image of the binder pitch and petroleum coke of example 4 after pelletization.
In the figure: 1-pressurizing reaction kettle, 2-oxidizing device, 3-light component collecting tank, 4-short-path molecular distiller, 5-byproduct collecting tank, 6-polymerizing reaction kettle, 7-raw material collecting device and 8-air pump.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method is used for granulating the anode material production process in a mode of mixing coal-based asphalt and oil-based tar. The binder asphalt for granulating the lithium ion battery with high cohesiveness is obtained by taking medium-low temperature coal tar pitch and ethylene tar as raw materials and polyacrylic acid as a modifier through pressurizing polymerization, oxidative crosslinking and molecular distillation processes in sequence. In the mixture raw materials of the medium-low temperature coal tar and the ethylene tar, the ethylene tar accounts for 10-30wt% of the medium-low temperature coal tar. The addition amount of the modifier polyacrylic acid is 0.5-2 wt% of the mixture raw material of the medium-low temperature coal tar and ethylene tar.
The method specifically comprises the following steps:
1) Adding ethylene tar into medium-low temperature coal tar, and placing the mixture into a pressurized reaction kettle and stirring the mixture for 1 to 1.5 hours at 180 to 200 ℃ to obtain the mixed asphalt.
2) The mixed asphalt is polymerized in a pressurizing reaction kettle under pressure, the temperature is raised to 350-400 ℃ at the heating rate of 3-5 ℃/min, nitrogen is introduced to pressurize to 0.5-1.0 MPa, and the polymerization reaction is carried out for 2-8 h at constant temperature, thus obtaining the pressurizing polymerized asphalt.
3) And (3) further carrying out oxidative crosslinking on the pressurized polymerized asphalt obtained in the step (2), wherein the temperature is 330-380 ℃, and the air flow is regulated and controlled according to the total amount of materials (100L/min-600L/min) to carry out oxidation for 2-6 h, so as to obtain the oxidized asphalt.
4) Molecular distillation is carried out on the mixed asphalt oxide obtained in the step 3) through a molecular distillation device, the temperature is 230-280 ℃, the vacuum pressure of a short-path molecular distillation device is controlled, under the rotating condition, the mixed asphalt oxide is distilled, and the high-softening-point asphalt material with high cohesiveness is prepared through a molecular distillation method; the vacuum pressure of the short-path molecular distiller is 30-200 Pa, and the rotating speed is 200-400 rpm.
5) Adding modifier polyacrylic acid into the high softening point asphalt material obtained in the step 4) for mixing, wherein the mixing temperature is 220-270 ℃, and the mixing time is 0.5-2 h, so as to obtain the binder asphalt for granulating the lithium ion battery.
The softening point of the prepared binder asphalt for granulating the lithium ion battery is 170-250 ℃, the QI value is <1%, the TI value is >31%, the CV is >60%, the moisture is <1%, and the ash content is <1%.
As shown in figure 1, the device adopted by the preparation method of the binder asphalt for granulating the lithium ion battery cathode material comprises a pressurizing reaction kettle 1, an oxidation device 2, a short-range molecular distiller 4 and a polymerization reaction kettle 5, wherein a discharge port of the pressurizing reaction kettle 1 is connected with a feed port of the oxidation device 2, a discharge port of the oxidation device 2 is connected with a feed port of the short-range molecular distiller 4, a heavy component outlet of the short-range molecular distiller 4 is connected with the polymerization reaction kettle 6, and a discharge port of the polymerization reaction kettle 6 is connected with a raw material collecting device 7.
The device also comprises a light component collecting tank 3 and a byproduct collecting tank 5, wherein a gas phase outlet of the oxidation device 2 is connected with the light component collecting tank 3, and a light component outlet of the short-path molecular distiller 4 is connected with the byproduct collecting tank 5.
The oxidation device 2 is a reaction kettle with a stirrer, the bottom of the reaction kettle is connected with an air pump 8, and air is fed into the oxidation device 2 through the air pump 8.
The process according to the invention will be further illustrated by means of several examples.
Example 1:
uniformly mixing medium-low temperature coal tar with a certain mass and ethylene tar accounting for 20wt% of the medium-low temperature coal tar, placing the mixture into a pressurized reaction kettle 1, and stirring the mixture at 180 ℃ for 1.5 hours to ensure that the two raw materials are fully mixed. And (3) pressurizing and polymerizing the mixed asphalt in a pressurizing reaction kettle 1, heating to 380 ℃ at a speed of 5 ℃/min, introducing nitrogen and pressurizing to 1Mpa for polymerization reaction for 2 hours to obtain the pressurizing polymerized asphalt. And (3) carrying out oxidative crosslinking on the pressurized polymerized asphalt, wherein the air flow is 100L/min, the oxidative crosslinking temperature is 370 ℃, and the temperature is kept for 3 hours to obtain the oxidized asphalt. Adding the oxidized asphalt into a short-path molecular distiller 5, setting the temperature to 250 ℃, controlling the vacuum pressure of the short-path molecular distiller 5 to be 100Pa, controlling the rotating speed to be 200rpm, and distilling for 3 hours to obtain the high-softening-point asphalt material with high cohesiveness through a molecular distillation method. And adding polyacrylic acid accounting for 1 weight percent of the raw material asphalt into the high-softening-point asphalt material, and mixing at the temperature of 250 ℃ to obtain the binder asphalt for granulating the lithium ion battery. The performance index is shown in Table 1. The performance indexes of the asphalt and petroleum coke after granulation are shown in table 2 (granularity in table 2), a scanning electron microscope image is shown in fig. 2, a negative electrode material is prepared and assembled into a button type lithium ion battery for electrochemical test, and the battery test results are shown in table 2 compared with the negative electrode material prepared from common granulated asphalt.
Example 2:
uniformly mixing medium-low temperature coal tar with a certain mass and ethylene tar accounting for 25wt% of the medium-low temperature coal tar, placing the mixture into a pressurized reaction kettle 1, and stirring the mixture for 1h at 190 ℃ to ensure that the two raw materials are fully mixed. And (3) pressurizing and polymerizing the mixed asphalt in a pressurizing reaction kettle 1, heating to 370 ℃ at a speed of 4 ℃/min, introducing nitrogen to pressurize to 0.9Mpa, and polymerizing for 6 hours to obtain the pressurizing polymerized asphalt. And (3) carrying out oxidative crosslinking on the pressurized polymerized asphalt, wherein the air flow is 200L/min, the oxidative crosslinking temperature is 360 ℃, and the temperature is kept for 5 hours to obtain the oxidized asphalt. Adding the oxidized asphalt into a short-path molecular distiller 5, setting the temperature to 270 ℃, controlling the vacuum pressure of the short-path molecular distiller 5 to be 150Pa, controlling the rotating speed to be 300rpm, and distilling for 3 hours to obtain the asphalt material with high cohesiveness and high softening point by a molecular distillation method. Polyacrylic acid accounting for 1.5 weight percent of the raw material asphalt is added into the high softening point asphalt material and mixed at 240 ℃ to prepare the binder asphalt for lithium ion battery granulation. The performance indexes of the asphalt and petroleum coke after granulation are shown in table 2, a scanning electron microscope image is shown in fig. 3, a negative electrode material is prepared and assembled into a button type lithium ion battery for electrochemical test, and the test result of the battery is shown in table 2 compared with the negative electrode material prepared from common granulated asphalt.
Example 3:
uniformly mixing medium-low temperature coal tar with a certain mass and ethylene tar accounting for 15wt% of the medium-low temperature coal tar, placing the mixture into a pressurized reaction kettle 1, and stirring the mixture at 185 ℃ for 1.5 hours to ensure that the two raw materials are fully mixed. And (3) pressurizing and polymerizing the mixed asphalt in a pressurizing reaction kettle 1, heating to 360 ℃ at a speed of 5 ℃/min, introducing nitrogen to pressurize to 0.8Mpa, and polymerizing for 4 hours to obtain the pressurizing polymerized asphalt. And (3) carrying out oxidative crosslinking on the pressurized polymerized asphalt, wherein the air flow is 100L/min, the oxidative crosslinking temperature is 380 ℃, and the temperature is kept for 6 hours to obtain the oxidized asphalt. Adding the oxidized asphalt into a short-path molecular distiller 5, setting the temperature to 260 ℃, controlling the vacuum pressure of the short-path molecular distiller 5 to 90Pa, controlling the rotating speed to 250rpm, and distilling for 3 hours to obtain the high-softening-point asphalt material with high cohesiveness through a molecular distillation method. And adding polyacrylic acid accounting for 0.9 weight percent of the raw material asphalt into the high-softening-point asphalt material, and mixing at 230 ℃ to obtain the binder asphalt for granulating the lithium ion battery. The performance indexes of the asphalt and petroleum coke after granulation are shown in table 2, a scanning electron microscope image is shown in fig. 4, a negative electrode material is prepared and assembled into a button type lithium ion battery for electrochemical test, and the test results of the battery are shown in table 2 compared with the negative electrode material prepared from common granulated asphalt.
Example 4:
uniformly mixing medium-low temperature coal tar with a certain mass and ethylene tar accounting for 28wt% of the medium-low temperature coal tar, placing the mixture into a pressurized reaction kettle 1, and stirring the mixture for 1.5h at the temperature of 195 ℃ to ensure that the two raw materials are fully mixed. And placing the mixed asphalt into a pressurizing reaction kettle for pressurizing and polymerizing, heating to 390 ℃ at the speed of 3 ℃/min, introducing nitrogen and pressurizing to 0.5Mpa for polymerizing for 1 hour to obtain the pressurizing polymerized asphalt. And (3) carrying out oxidative crosslinking on the pressurized polymerized asphalt, wherein the air flow rate is 300L/min, the oxidative crosslinking temperature is 350 ℃, and the temperature is kept for 4 hours to obtain the oxidized asphalt. Adding the oxidized asphalt into a short-path molecular distiller 5, setting the temperature to 240 ℃, controlling the vacuum pressure of the short-path molecular distiller 5 to 80Pa, the rotating speed to 400rpm, and the distillation time to 3 hours, and preparing the asphalt material with high cohesiveness and high softening point by a molecular distillation method. And adding polyacrylic acid accounting for 1.8 weight percent of the raw material asphalt into the high-softening-point asphalt material, and mixing at 260 ℃ to obtain the binder asphalt for granulating the lithium ion battery. The performance indexes of the asphalt and petroleum coke after granulation are shown in table 2, a scanning electron microscope image is shown in fig. 5, a negative electrode material is prepared and assembled into a button type lithium ion battery for electrochemical test, and the test results of the battery are shown in table 2 compared with the negative electrode material prepared from common granulated asphalt.
Table 1 example performance index
| Sequence number | Softening point/. Degree.C | QI/％ | TI/％ | CV/％ | Moisture/% | Ash/% |
| 1 | 180.9 | 0.10 | 31.2 | 66.2 | 0.04 | 0.02 |
| 2 | 183.0 | 0.13 | 36.5 | 68.1 | 0.03 | 0.05 |
| 3 | 201.7 | 0.21 | 37.0 | 72.3 | 0.03 | 0.03 |
| 4 | 186.2 | 0.68 | 32.2 | 67.1 | 0.02 | 0.03 |
TABLE 2 Performance index after granulating and assembling the cathode materials into button cell
The above description is only of the preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art will be able to make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof within the scope of the present invention.
Claims (10)
1. The preparation method of the binder pitch for granulating the lithium ion battery cathode material is characterized in that medium-low temperature coal tar pitch and ethylene tar are used as raw materials, polyacrylic acid is used as a modifier, and the binder pitch for granulating the lithium ion battery is obtained through pressurized polymerization, oxidative crosslinking and molecular distillation processes in sequence.
2. The preparation method of the binder asphalt for granulating the negative electrode material of the lithium ion battery as claimed in claim 1, which is characterized by comprising the following specific method steps:
1) Adding ethylene tar into medium-low temperature coal tar, and placing the mixture in a pressurized reaction kettle for stirring to obtain mixed asphalt;
2) Pressurizing and polymerizing the mixed asphalt in a pressurizing reaction kettle, heating to 350-400 ℃ at a heating rate of 3-5 ℃/min, introducing nitrogen to pressurize to 0.5-1.0 MPa, and maintaining the polymerization temperature for 2-8 h to obtain pressurized polymerized asphalt;
3) Oxidizing and crosslinking the pressurized polymerized asphalt obtained in the step 2), wherein the temperature is 330-380 ℃ and the oxidizing time is 2-6 h, so as to obtain oxidized asphalt;
4) Carrying out molecular distillation on the oxidized asphalt obtained in the step 3) through a molecular distillation device, wherein the temperature is 230-280 ℃, and obtaining an asphalt material;
5) Adding polyacrylic acid serving as a modifier into the asphalt material obtained in the step 4) for mixing, wherein the mixing temperature is 220-270 ℃, and the adhesive asphalt for granulating the lithium ion battery is prepared.
3. The method for preparing binder pitch for granulating negative electrode material of lithium ion battery according to claim 1 or 2, wherein the ethylene tar accounts for 10-30wt% of the medium-low temperature coal tar in the mixture raw material of the medium-low temperature coal tar and the ethylene tar.
4. The method for preparing binder pitch for granulating negative electrode material of lithium ion battery according to any one of claims 1-3, wherein the addition amount of the modifier is 0.5-2 wt% of the mixture raw material of medium-low temperature coal tar and ethylene tar.
5. The method for preparing binder pitch for granulating negative electrode material of lithium ion battery according to claim 2, wherein in the step 1), the stirring temperature is 180-200 ℃ and the stirring time is 1-1.5 h.
6. The method for producing binder pitch for granulating negative electrode material of lithium ion battery according to claim 2, wherein in the step 3), the flow rate of the oxidative crosslinking reaction is 100L/min to 600L/min.
7. The method for producing binder pitch for granulating negative electrode material of lithium ion battery according to claim 2, wherein in the step 4), the vacuum pressure of the short-path molecular still is 30 to 200Pa, and the rotational speed is 200 to 400rpm.
8. The method for preparing binder pitch for granulating negative electrode material of lithium ion battery as claimed in claim 2, wherein the mixing time of the pitch material of step 5) and the modifier polyacrylic acid is 0.5-2 h.
9. The method for producing a binder pitch for granulating negative electrode materials for lithium ion batteries according to claim 1 or 2, wherein the softening point of the binder pitch for granulating lithium ion batteries is 170 ℃ to 250 ℃, QI value <1%, TI value >31%, CV >60%, moisture <1%, ash <1%.
10. The apparatus for preparing binder asphalt for granulating negative electrode materials of lithium ion batteries according to any one of claims 1-8, comprising a pressurized reaction kettle, an oxidation device, a short-path molecular distiller and a polymerization reaction kettle, wherein a discharge port of the pressurized reaction kettle is connected with a feed port of the oxidation device, a discharge port of the oxidation device is connected with a feed port of the short-path molecular distiller, a heavy component outlet of the short-path molecular distiller is connected with the polymerization reaction kettle, and a discharge port of the polymerization reaction kettle is connected with a raw material collecting device.
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