CN114132923A - Preparation method of fast-charging graphite cathode material, product and application thereof - Google Patents
Preparation method of fast-charging graphite cathode material, product and application thereof Download PDFInfo
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Abstract
The invention relates to the field of lithium ion battery cathode materials, in particular to a quick-charging type lithium ion battery graphite cathode material and a preparation method and application thereof. It includes: grading or shaping the carbon material to obtain carbon micro powder A with certain particle shape characteristics; putting the carbon micro powder A into a graphitization furnace, and performing high-temperature graphitization treatment to obtain a graphitized material; screening the graphitized material to obtain a graphitized material B; in an acid aqueous solution system, carrying out micro-expansion treatment on the graphitized material B; putting ethylene cracking tar into a reactor, and adding benzaldehyde and p-toluenesulfonic acid according to a certain proportion to obtain a polynuclear aromatic-rich solid carbon material; mixing the dried micro-expanded graphite micro-powder with the polynuclear aromatic-rich carbon powder material, carbonizing in a carbonization furnace to obtain a carbonized material, cooling the carbonized material, and then sieving to obtain the fast-charging graphite cathode material. The lithium ion battery of the graphite cathode material has good quick charging performance, good rate capability and excellent cycle performance.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a preparation method of a graphite cathode material for a quick-charging lithium ion battery, and a product and application thereof.
Background
After more than twenty years of industrial cultivation and development, new energy technology and industry are greatly developed. According to statistics, in 2020, the new energy automobile sales volume of the China market is 131 thousands, the permeability is 5.2%, and the new energy automobile sales volume and the permeability both present accelerated development situations. However, the charging performance of the electric vehicle cannot meet the travel requirements of daily people, and the electric vehicle has higher and higher requirements on the quick charging performance. As a negative electrode material graphite material of a lithium ion battery, the graphite material has the advantages of low cost, environmental friendliness, low charge-discharge voltage and good stability, and becomes the negative electrode material with the highest commercialization degree at present. However, the interlayer spacing of the graphite material is small, the charging requirement of high-rate current cannot be met, the lithium separation phenomenon is easy to occur, and the quick charging performance of the lithium ion battery is seriously influenced.
The concept of improving the rapid charging performance is based on material structure design and coating optimization, so that the lithium ion inlet and outlet channel is improved, the internal resistance is reduced, the polarization is reduced, and the better dynamic performance is realized. For example, the structure of the material directly affects the lithium ion solid phase diffusion process, especially the crystallinity of the material, the crystallite grain boundaries and the defects existing in the structure. Therefore, on the one hand, in terms of material structure and selection, the grains of the material body are small, and the porosity is large so as to increase the passage of lithium ions, thereby being beneficial to the rapid insertion of the lithium ions in the material. On the other hand, the material has high conductivity, which is beneficial to high lithium ion extraction rate. Although various graphite cathode materials exist at present, the requirements of electric automobiles on quick charging performance cannot be completely met.
Therefore, the development of a graphite negative electrode material for a lithium ion battery, which has ideal fast charge performance, good cycle performance and simple preparation process, is urgently needed in the field.
Disclosure of Invention
The invention aims to solve the technical problems that the quick charge performance of the lithium ion battery cathode material prepared by adopting the structural design of graphite particles and various surface modification in the prior art can not meet the requirement of the quick charge performance of an electric vehicle and the quick charge performance is not ideal enough; the first technical purpose of the invention is to provide a preparation method of a surface-coated modified quick-charging graphite negative electrode material; the second technical purpose of the invention is to provide application of a new structural design and surface coating modified quick-charging graphite negative electrode material.
The lithium ion battery adopting the structural design and the graphite cathode material with the surface coated and modified has good quick charge performance, good rate performance and excellent cycle performance, and can meet the quick charge requirement when being used as a power battery of a passenger vehicle.
The first technical purpose of the invention is solved by the following technical scheme:
the invention provides a preparation method of a quick-charging graphite cathode material, which comprises the following steps:
1) taking petroleum coke or needle coke or mesocarbon microbeads or a mixture of the petroleum coke and the needle coke or the mesocarbon microbeads and the green pellets, and crushing, grading or shaping the petroleum coke or the needle coke or the mesocarbon microbeads by a mechanical mill, an air flow mill or a rolling mill to obtain carbon micropowder A with certain particle shape (sphericity, length-diameter ratio and convexity);
wherein the mass ratio range of the two mixtures is 4: 6-7: 3;
wherein the sphericity is defined as S10: 0.7500-0.7700, S50: 0.8200-0.8300, S90: 0.8600-0.8700;
wherein the width-to-length ratio is defined as S10: 0.650-0.700, S50: 0.800-0.840, S90: 0.900-0.950;
wherein the convexity is defined as S10: 0.9000-0.9100, S50: 0.9300-0.9400, S90: 0.9700-0.9800;
wherein the median particle diameter D50 of the carbon micropowder A is 5.0-15.0 um;
2) putting the carbon micro powder A into a graphitization furnace, and performing high-temperature graphitization treatment to obtain a graphitized material; screening the graphitized material by a 325-mesh sieve to obtain a graphitized material B required by the invention;
wherein, the graphitization furnace equipment is selected from any one of an Acheson furnace, an inner series furnace and a box furnace; more preferably a graphitization furnace specified in the present invention;
wherein the highest constant temperature of the graphitization furnace is set to 3000 ℃, and the graphitization time at 3000 ℃ is 4 h;
3) in an acid aqueous solution system, carrying out micro-expansion treatment on the graphitized material B: adding the graphitized material B into an acid solution system, reacting in a water bath kettle at 30-40 ℃ for 25-35 min, filtering, washing and drying to obtain micro-expanded graphite;
wherein the acidic aqueous solution system is a mixed acid system of inorganic acid and organic acid, the inorganic acid is sulfuric acid, and the organic acid is sulfonic acid (R-SO 3H) or perhalogenated carboxylic acid which can be dissolved in the aqueous solution system;
wherein, the graphite micro powder after micro-expansion treatment is washed by water for many times until the pH value is 6.5-7.0, and then is dried;
wherein the interlayer spacing d002 value of the dried micro-expanded graphite powder is 0.3390-0.3495 nm;
wherein the ratio of the inorganic and organic mixed acid is as follows: 1: 1-1: 3;
4) putting ethylene cracking tar into a reactor, adding benzaldehyde and p-toluenesulfonic acid according to a certain proportion, reacting under the protection of inert gas and under the conditions of a certain heating rate and temperature under continuous stirring until the viscosity of a reaction system is gradually increased and stirring cannot be carried out, and stopping the reaction to obtain the polynuclear aromatic-rich solid carbon material. Crushing the solid carbon material to obtain a powdery carbon material;
wherein, the grading equipment adopts the conventional grading equipment or shaping equipment in the industry to grade or shape the carbon material;
wherein the reactor is any conventional reactor as long as the reactor can be stirred and heated;
wherein the ethylene cracking tar can be ethylene cracking tar conventionally used in the field, and can be ethylene cracking oil slurry produced by Daqing petrochemical, Fushun petrochemical, Jinzhou petrochemical and Qilu petrochemical;
wherein the ratio of benzaldehyde to p-toluenesulfonic acid is 1: 1-0.5: 1; the proportion of the benzaldehyde and p-toluenesulfonic acid mixed agent to ethylene cracking tar is 4-8%;
wherein the inert gas is nitrogen or argon, preferably nitrogen;
wherein the certain heating rate is 3 ℃/min-5 ℃/min, and the preferred heating rate is 3 ℃/min;
wherein the reaction temperature is 130-180 ℃, and the preferable reaction temperature is 150 ℃;
wherein the crushing equipment is mechanical crushing and air flow crushing, preferably air flow crushing;
wherein the median particle diameter of the powder carbon material is D50: 4.0-6.0 um, preferably median particle diameter D50: 5.0 um;
5) mixing the dried micro-expanded graphite micro powder in the step 3) and the polynuclear aromatic-rich carbon powder prepared in the step 4) according to a certain proportion, and carbonizing in a carbonization furnace; cooling the carbonized material and then sieving to obtain the fast-charging graphite cathode material;
wherein the proportion of the micro-expanded graphite micro powder to the polynuclear aromatic-rich carbon powder is as follows: 95: 8-95: 20;
wherein the carbonization furnace is the conventional condition and method for the operation in the field, and can be generally carried out in a tubular furnace, a box furnace, a muffle furnace and a crucible furnace;
wherein the carbonization temperature is 1000-1300 ℃, and preferably 1000-1100 ℃;
wherein the carbonization time is 3-5 h, preferably 3 h;
and screening the carbonized material, wherein the used standard sieve adopts a standard sieve with 325-400 meshes, taking the material to be screened, and screening the obtained carbonized material with a median particle size D50: 7.0-16.0 um, preferably 8.0-12.0 um;
wherein, more preferably, the graphite micro powder is taken and added into an acid solution system, and the mixture reacts for 30 min at 35 ℃ in a water bath kettle, and then the micro expanded graphite is obtained after filtration, washing and drying.
The special graphitization furnace comprises a furnace mechanism and a cover sealing mechanism, wherein the cover sealing mechanism is arranged on one side of the furnace mechanism;
the furnace mechanism comprises a furnace cover, a furnace body, a support frame and a vacuum pump, wherein a first fixing ring is fixedly connected to the top of the outer side of the furnace body, a second fixing ring is fixedly connected to the bottom of the outer side of the furnace cover, the support frame is installed at the bottom of the furnace body, and the air suction end of the vacuum pump is communicated with the furnace body through a pipeline;
the capping mechanism comprises a side frame, a first motor, a rotating shaft, a driving gear, a driven wheel, a hydraulic oil cylinder, a hydraulic rod, a lifting plate, a second motor, a screw rod, a pressing block and a pressing rod, wherein the first motor is fixedly connected to the side frame through a bolt, the rotating shaft is welded with an output shaft of the first motor, the driving gear is welded to the rotating shaft, the top of the side frame is rotatably connected with the driven wheel, the driving gear is meshed with the driven wheel, the driven wheel is fixedly connected with the bottom of the hydraulic oil cylinder through a bolt, an output shaft of the hydraulic oil cylinder is fixedly connected with the hydraulic rod, one end of the lifting plate is welded to the hydraulic rod, the second motor is installed on the lifting plate through a bolt, an output shaft of the second motor penetrates through the lifting plate and is welded with the screw rod, and the screw rod is in threaded connection with the pressing block, the pressure rod is welded on the pressure block; the graphitization effect of the graphitized material is improved.
As a preferable technical scheme of the invention, the number of the pressure levers is four, the four pressure levers are distributed in a rectangular shape, and the bottom ends of the pressure levers are welded with the top of the furnace cover.
As a preferable technical scheme of the invention, a limiting rod is welded at the top of the furnace cover, and the top end of the limiting rod penetrates through the lifting plate and is in sliding connection with the lifting plate.
As a preferred technical scheme of the present invention, a sealing ring is bonded to the bottom of the second fixing ring, a positioning column is welded to the bottom of the second fixing ring, a positioning hole is formed in the first fixing ring, and the positioning column is matched with the positioning hole.
As a preferable technical scheme of the invention, the bottom of the furnace body is communicated with a waste discharge pipe, and the top of the furnace cover is communicated with an air inlet pipe.
As a preferred technical scheme of the invention, the inner side wall of the furnace body is fixedly connected with a heat preservation shell through a bottom plate, the inner side of the heat preservation shell is provided with a graphite crucible, and the outer side wall of the heat preservation shell is provided with a heating coil.
The invention also provides application of the coated and granulated modified graphite material as a negative electrode material in the field of lithium ion batteries.
The invention also provides a lithium ion battery, and the negative electrode material of the lithium ion battery comprises the coated and granulated modified graphite material.
The invention also provides application of the lithium ion battery as a power battery in the field of passenger vehicles.
On the basis of the common knowledge in the field, the above conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the special graphite cathode material has the advantages that the special structural design is adopted, the aggregate graphite powder with a certain sphericity is preferably selected, and the special granulation and coating modes are combined, so that the lithium ion battery of the prepared special graphite cathode material has good quick charge performance, good rate performance and excellent cycle performance, can be used as a power battery of a passenger vehicle, and can meet the requirement of quick charge.
Drawings
FIG. 1 is a particle size distribution diagram of graphite powder A used in example 1;
FIG. 2 is a schematic structural view of a graphitization furnace of the present invention;
FIG. 3 is an enlarged structural view of the region A of FIG. 2 according to the present invention;
FIG. 4 is an enlarged structural view of the region B shown in FIG. 2 according to the present invention.
In the figure: 10. a furnace cover; 11. a furnace body; 12. a heat preservation shell; 13. a graphite crucible; 14. a heating coil; 15. a waste discharge pipe; 16. a support frame; 17. a vacuum pump; 18. an air inlet pipe; 111. a first retaining ring; 112. positioning holes; 121. a second retaining ring; 122. a seal ring; 123. a positioning column; 21. a side frame; 22. a first motor; 23. a rotating shaft; 24. a driving gear; 25. a driven wheel; 26. a hydraulic cylinder; 27. a hydraulic lever; 28. a lifting plate; 29. a limiting rod; 210. a second motor; 211. a screw rod; 212. briquetting; 213. a pressure lever.
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.
Example 1
(1) Taking petroleum coke and mesocarbon microbeads, and mixing the raw materials in a mass ratio of 6: 4, adding mechanical grinding powder
Shaping to obtain carbon micropowder A with certain sphericity, length-diameter ratio and convexity characteristics; sphericity S10: 0.7602, S50: 0.82590, S90: 0.8650, respectively; width-to-length ratio S10: 0.655, S50: 0.820, S90: 0.930; convexity S10: 0.9050, S50: 0.9320, S90: 0.9710; the median particle diameter D50 of the carbon micropowder A is 10.0 um;
(2) putting the carbon micro powder A into an Acheson furnace, carrying out high-temperature graphitization treatment, keeping the temperature of 3000 ℃ for 4 hours, cooling, discharging, sieving by a 325-mesh sieve, and obtaining graphitization powder B;
(3) taking sulfuric acid and beta-aminoethanesulfonic acid according to the mass ratio of 1: 1 preparing an acidic aqueous solution. Adding the graphite powder B prepared in the step (2) into an acidic aqueous solution, reacting in a water bath kettle at 35 ℃ for 30 min, filtering, washing and drying to obtain micro-expanded graphite, wherein the pH value of the micro-expanded graphite is 7.0, and the interlayer spacing d002 value is 0.3390 nm;
(4) ethylene cracking tar (Qilu petrochemical industry of manufacturer) is taken and added with benzaldehyde and p-methyl benzene sulfonic acid mixed acid. Wherein the ratio of the mixed acid of benzaldehyde and p-toluenesulfonic acid to ethylene cracking tar is 4%, and the ratio of benzaldehyde to p-toluenesulfonic acid is 1: 1. and under the protection of nitrogen atmosphere, starting stirring, heating to 150 ℃ at a speed of 3 ℃/min, continuously stirring in the heating process, continuously stirring at a constant temperature of 150 ℃ until the viscosity of the reaction system is gradually increased and stirring cannot be carried out, and stopping reaction. And (3) mechanically crushing the cross-linked polymer to obtain the polynuclear aromatic carbon-rich powder material with the median particle size of D50: 4.0 um;
(5) mixing the micro-expanded graphite micro-powder dried in the step 3) and the polynuclear aromatic carbon-rich powder prepared in the step 4) according to a ratio of 95: 8, and carbonizing in a muffle furnace under the nitrogen atmosphere. Heating to 1000 deg.C at 3 deg.C/min, and maintaining for 3 hr. Cooling the carbonized material, then sieving, adopting a standard sieve with 400 meshes, taking the sieved material, and sieving to obtain the carbonized material with the median particle size D50: 14.0um to obtain the fast-charging graphite cathode material.
Referring to fig. 1-3, a graphitization furnace includes a furnace mechanism and a capping mechanism disposed at one side of the furnace mechanism; the capping mechanism compresses and seals the furnace mechanism through a mechanical automation structure.
Referring to fig. 1 and 3, the furnace mechanism includes a furnace cover 10, a furnace body 11, a support frame 16 and a vacuum pump 17, the top of the outer side of the furnace body 11 is fixedly connected with a first fixing ring 111, the bottom of the outer side of the furnace cover 10 is fixedly connected with a second fixing ring 121, the support frame 16 is installed at the bottom of the furnace body 11, and the suction end of the vacuum pump 17 is communicated with the furnace body 11 through a pipeline; first solid fixed ring 111 and the laminating of the solid fixed ring 121 of second compress tightly the back, can make bell 10 compress tightly the top of furnace body 11, the bottom of the solid fixed ring 121 of second bonds and has sealed circle 122, sealed circle 122 is used for improving the leakproofness, the bottom welding of the solid fixed ring 121 of second has reference column 123, has seted up locating hole 112 on the solid fixed ring 111 of first, reference column 123 and locating hole 112 phase-match for the position of location bell 10 prevents bell 10 skew center.
Referring to fig. 1 and 2, the capping mechanism includes a side frame 21, a first motor 22, a rotating shaft 23, a driving gear 24, a driven wheel 25, a hydraulic cylinder 26, a hydraulic rod 27, a lifting plate 28, a second motor 210, a screw rod 211, a pressing block 212 and a pressing rod 213, the first motor 22 is fixedly connected to the side frame 21 through a bolt, the rotating shaft 23 is welded to an output shaft of the first motor 22, the driving gear 24 is welded to the rotating shaft 23, the top of the side frame 21 is rotatably connected to the driven wheel 25, the driving gear 24 is engaged with the driven wheel 25, the first motor 22 drives the rotating shaft 23 to rotate, and further drives the driving gear 24 to rotate, the driven wheel 25 drives the hydraulic cylinder 26 to rotate, the furnace cover 10 is driven to rotate, the driven wheel 25 is fixedly connected to the bottom of the hydraulic cylinder 26 through a bolt, an output shaft of the hydraulic cylinder 26 is fixedly connected to the hydraulic rod 27, and the hydraulic cylinder 26 drives the hydraulic rod 27 to ascend or descend, and then the furnace cover 10 is driven to ascend or descend, one end of the lifting plate 28 is welded on the hydraulic rod 27, the second motor 210 is installed on the lifting plate 28 through a bolt, an output shaft of the second motor 210 penetrates through the lifting plate 28 and is welded with the screw rod 211, the screw rod 211 is in threaded connection with the pressing block 212, the pressing rod 213 is welded on the pressing block 212, and the second motor 210 drives the screw rod 211 to rotate, so that the pressing block 212 moves up and down, and further the furnace cover 10 is pressed tightly through the pressing rod 213. The number of the four pressing rods 213 is four, the four pressing rods 213 are distributed in a rectangular shape, and the bottom ends of the pressing rods 213 are welded with the top of the furnace cover 10, so that the connection firmness of the furnace cover 10 and the pressing block 212 is improved, and the graphitization effect of the graphitized material of the embodiment of the invention is improved.
Specifically, referring to fig. 1, a limiting rod 29 is welded to the top of the furnace cover 10, and the top end of the limiting rod 29 penetrates through the lifting plate 28 and is slidably connected with the lifting plate 28 for guiding the furnace cover 10 to move.
Specifically, referring to fig. 1, the bottom of the furnace body 11 is communicated with a waste discharge pipe 15, and the top of the furnace cover 10 is communicated with an air inlet pipe 18. The waste discharge pipe 15 is used for discharging impurities and waste gas in the furnace body 11, the inner side wall of the furnace body 11 is fixedly connected with a heat preservation shell 12 through a bottom plate, a graphite crucible 13 is arranged on the inner side of the heat preservation shell 12, a heating coil 14 is arranged on the outer side wall of the heat preservation shell 12, and the heating coil 14 heats the graphite crucible 13.
The working principle is as follows: the capping mechanism compresses and seals the furnace mechanism through a mechanical automation structure. After the material drops into and accomplishes, first motor 22 drives pivot 23 and rotates, and then drive driving gear 24 and rotate, drive hydraulic cylinder 26 through following driving wheel 25 and rotate, it rotates to drive bell 10, make bell 10 be located directly over the furnace body 11, hydraulic cylinder 26 drives hydraulic stem 27 and rises or descends, tentatively drive bell 10 and cover furnace body 11, second motor 210 drives lead screw 211 and rotates, make briquetting 212 reciprocate, make briquetting 212 drive bell 10 push down furnace body 11, further compress tightly bell 10, automatic operation, and is simple and convenient, bell 10 edge each point pressure is the same, reduce the degree of wear of bell 10 edge each point, and the service life is prolonged, and the graphitization effect of graphitizing material is improved.
Example 2
(1) Taking petroleum coke and mesocarbon microbeads, and mixing the raw materials in a mass ratio of 6: 4, adding mechanical grinding powder
Shaping to obtain carbon micropowder A with certain sphericity, length-diameter ratio and convexity characteristics; sphericity S10: 0.7602, S50: 0.82590, S90: 0.8650, respectively; width-to-length ratio S10: 0.655, S50: 0.820, S90: 0.930; convexity S10: 0.9050, S50: 0.9320, S90: 0.9710; the median particle diameter D50 of the carbon micropowder A is 10.0 um;
(2) putting the carbon micro powder A into an Acheson furnace, carrying out high-temperature graphitization treatment, keeping the temperature of 3000 ℃ for 4 hours, cooling, discharging, sieving by a 325-mesh sieve, and obtaining graphitization powder B;
(3) taking sulfuric acid and beta-aminoethanesulfonic acid according to the mass ratio of 1: 3 preparing an acidic aqueous solution. Adding the graphite powder prepared in the step (1) into an acidic aqueous solution, reacting in a water bath kettle at 35 ℃ for 30 min, filtering, washing and drying to obtain micro-expanded graphite, wherein the pH value of the micro-expanded graphite is 6.5, and the interlayer spacing d002 value is 0.3450 nm;
(4) ethylene cracking tar (Qilu petrochemical industry of manufacturer) is taken and added with benzaldehyde and p-methyl benzene sulfonic acid mixed acid. Wherein the ratio of the mixed acid of benzaldehyde and p-toluenesulfonic acid to ethylene cracking tar is 4%, and the ratio of benzaldehyde to p-toluenesulfonic acid is 1: 1. and under the protection of nitrogen atmosphere, starting stirring, heating to 150 ℃ at a speed of 3 ℃/min, continuously stirring in the heating process, continuously stirring at a constant temperature of 150 ℃ until the viscosity of the reaction system is gradually increased and stirring cannot be carried out, and stopping reaction. And (3) mechanically crushing the cross-linked polymer to obtain the polynuclear aromatic carbon-rich powder material with the median particle size of D50: 4.0 um;
(5) mixing the micro-expanded graphite micro-powder dried in the step 3) and the polynuclear aromatic carbon-rich powder prepared in the step 4) according to a ratio of 95: 12, and carbonizing the mixture in a muffle furnace under a nitrogen atmosphere. Heating to 1000 deg.C at 3 deg.C/min, and maintaining for 3 hr. Cooling the carbonized material, then sieving, adopting a standard sieve with 400 meshes, taking the sieved material, and sieving to obtain the carbonized material with the median particle size D50: 15.5um to obtain the quick-charging graphite cathode material.
Example 3
(1) Taking needle coke and a mesocarbon microbead green ball according to the mass ratio of 6: 4, adding mechanical grinding powder
Shaping to obtain carbon micropowder A with certain sphericity, length-diameter ratio and convexity characteristics; sphericity S10: 0.7652, S50: 0.8219, S90: 0.8640, respectively; width-to-length ratio S10: 0.645, S50: 0.830, S90: 0.920; convexity S10: 0.9056, S50: 0.9350, S90: 0.9740, respectively; the median particle diameter D50 of the carbon micropowder A is 8.0 um;
(2) putting the carbon micro powder A into an Acheson furnace, carrying out high-temperature graphitization treatment, keeping the temperature of 3000 ℃ for 4 hours, cooling, discharging, sieving by a 325-mesh sieve, and obtaining graphitization powder B;
(3) taking sulfuric acid and trifluoromethanesulfonic acid according to a mass ratio of 1: 1 preparing an acidic aqueous solution. Adding the graphite powder prepared in the step (1) into an acidic aqueous solution, reacting in a water bath kettle at 35 ℃ for 30 min, filtering, washing and drying to obtain micro-expanded graphite, wherein the pH value of the micro-expanded graphite is 6.9, and the interlayer spacing d002 value is 0.3410 nm;
(4) ethylene cracking tar (Qilu petrochemical industry of manufacturer) is taken and added with benzaldehyde and p-methyl benzene sulfonic acid mixed acid. Wherein the proportion of the mixed acid of benzaldehyde and p-toluenesulfonic acid to ethylene cracking tar is 6%, and the proportion of benzaldehyde to p-toluenesulfonic acid is 1: 1. and under the protection of nitrogen atmosphere, starting stirring, heating to 150 ℃ at a speed of 3 ℃/min, continuously stirring in the heating process, continuously stirring at a constant temperature of 150 ℃ until the viscosity of the reaction system is gradually increased and stirring cannot be carried out, and stopping reaction. And (3) mechanically crushing the cross-linked polymer to obtain the polynuclear aromatic carbon-rich powder material with the median particle size of D50: 4.0 um;
(5) mixing the micro-expanded graphite micro-powder dried in the step 3) and the polynuclear aromatic carbon-rich powder prepared in the step 4) according to a ratio of 95: 8, and carbonizing in a muffle furnace under the nitrogen atmosphere. Heating to 1000 deg.C at 3 deg.C/min, and maintaining for 3 hr. Cooling the carbonized material, then sieving, adopting a standard sieve with 400 meshes, taking the sieved material, and sieving to obtain the carbonized material with the median particle size D50: 12.3um to obtain the fast-charging graphite cathode material.
Example 4
(1) Taking needle coke and a mesocarbon microbead green ball according to the mass ratio of 6: 4, adding mechanical grinding powder
Shaping to obtain carbon micropowder A with certain sphericity, length-diameter ratio and convexity characteristics; sphericity S10: 0.7652, S50: 0.8219, S90: 0.8640, respectively; width-to-length ratio S10: 0.645, S50: 0.830, S90: 0.920; convexity S10: 0.9056, S50: 0.9350, S90: 0.9740, respectively; the median particle diameter D50 of the carbon micropowder A is 8.0 um;
(2) putting the carbon micro powder A into an Acheson furnace, carrying out high-temperature graphitization treatment, keeping the temperature of 3000 ℃ for 4 hours, cooling, discharging, sieving by a 325-mesh sieve, and obtaining graphitization powder B;
(3) taking sulfuric acid and trifluoromethanesulfonic acid according to a mass ratio of 1: 3 preparing an acidic aqueous solution. Adding the graphite powder prepared in the step (1) into an acidic aqueous solution, reacting in a water bath kettle at 35 ℃ for 30 min, filtering, washing and drying to obtain micro-expanded graphite, wherein the pH value of the micro-expanded graphite is 6.5, and the interlayer spacing d002 value is 0.3460 nm;
(4) ethylene cracking tar (Qilu petrochemical industry of manufacturer) is taken and added with benzaldehyde and p-methyl benzene sulfonic acid mixed acid. Wherein the proportion of the mixed acid of benzaldehyde and p-toluenesulfonic acid to ethylene cracking tar is 6%, and the proportion of benzaldehyde to p-toluenesulfonic acid is 1: 1. and under the protection of nitrogen atmosphere, starting stirring, heating to 150 ℃ at a speed of 3 ℃/min, continuously stirring in the heating process, continuously stirring at a constant temperature of 150 ℃ until the viscosity of the reaction system is gradually increased and stirring cannot be carried out, and stopping reaction. And (3) mechanically crushing the cross-linked polymer to obtain the polynuclear aromatic carbon-rich powder material with the median particle size of D50: 4.0 um;
(5) mixing the micro-expanded graphite micro-powder dried in the step 3) and the polynuclear aromatic carbon-rich powder prepared in the step 4) according to a ratio of 95: 12, and carbonizing the mixture in a muffle furnace under a nitrogen atmosphere. Heating to 1000 deg.C at 3 deg.C/min, and maintaining for 3 hr. Cooling the carbonized material, then sieving, adopting a standard sieve with 400 meshes, taking the sieved material, and sieving to obtain the carbonized material with the median particle size D50: 13.5um to obtain the fast-charging graphite cathode material.
Example 5
(1) Taking petroleum coke and needle coke, and mixing the raw materials in a mass ratio of 7: 3, rolling, grinding and shaping to obtain carbon micropowder A with certain sphericity, length-diameter ratio and convexity characteristics; sphericity S10: 0.7632, S50: 0.8239, S90: 0.8670, respectively; width-to-length ratio S10: 0.665, S50: 0.832, S90: 0.940; convexity S10: 0.9046, S50: 0.9360, S90: 0.9762, respectively; the median particle diameter D50 of the carbon micropowder A is 5.5 um;
(2) putting the carbon micro powder A into an Acheson furnace, carrying out high-temperature graphitization treatment, keeping the temperature of 3000 ℃ for 4 hours, cooling, discharging, sieving by a 325-mesh sieve, and obtaining graphitization powder B;
(3) taking sulfuric acid and perchloro aromatic carboxylic acid according to a mass ratio of 1: 1 preparing an acidic aqueous solution. Adding the graphite powder prepared in the step (1) into an acidic aqueous solution, reacting in a water bath kettle at 35 ℃ for 30 min, filtering, washing and drying to obtain micro-expanded graphite, wherein the pH value of the micro-expanded graphite is 6.8, and the interlayer spacing d002 value is 0.3460 nm;
(4) ethylene cracking tar (Qilu petrochemical industry of manufacturer) is taken and added with benzaldehyde and p-methyl benzene sulfonic acid mixed acid. Wherein the ratio of the mixed acid of benzaldehyde and p-toluenesulfonic acid to ethylene cracking tar is 4%, and the ratio of benzaldehyde to p-toluenesulfonic acid is 1: 1. and under the protection of nitrogen atmosphere, starting stirring, heating to 150 ℃ at a speed of 3 ℃/min, continuously stirring in the heating process, continuously stirring at a constant temperature of 150 ℃ until the viscosity of the reaction system is gradually increased and stirring cannot be carried out, and stopping reaction. And (3) mechanically crushing the cross-linked polymer to obtain the polynuclear aromatic carbon-rich powder material with the median particle size of D50: 5.0 um;
(5) mixing the micro-expanded graphite micro-powder dried in the step 3) and the polynuclear aromatic carbon-rich powder prepared in the step 4) according to a ratio of 95: 8, and carbonizing in a muffle furnace under the nitrogen atmosphere. Heating to 1000 deg.C at 3 deg.C/min, and maintaining for 3 hr. Cooling the carbonized material, then sieving, adopting a standard sieve with 400 meshes, taking the sieved material, and sieving to obtain the carbonized material with the median particle size D50: 8.5um to obtain the fast-charging graphite cathode material.
Example 6
(1) Taking petroleum coke and needle coke, and mixing the raw materials in a mass ratio of 7: 3, rolling, grinding and shaping to obtain carbon micropowder A with certain sphericity, length-diameter ratio and convexity characteristics; sphericity S10: 0.7632, S50: 0.8239, S90: 0.8670, respectively; width-to-length ratio S10: 0.665, S50: 0.832, S90: 0.940; convexity S10: 0.9046, S50: 0.9360, S90: 0.9762, respectively; the median particle diameter D50 of the carbon micropowder A is 5.5 um;
(2) putting the carbon micro powder A into an Acheson furnace, carrying out high-temperature graphitization treatment, keeping the temperature of 3000 ℃ for 4 hours, cooling, discharging, sieving by a 325-mesh sieve, and obtaining graphitization powder B;
(3) taking sulfuric acid and perchloro aromatic carboxylic acid according to a mass ratio of 1: 3 preparing an acidic aqueous solution. Adding the graphite powder prepared in the step (1) into an acidic aqueous solution, reacting in a water bath kettle at 35 ℃ for 30 min, filtering, washing and drying to obtain micro-expanded graphite, wherein the pH value of the micro-expanded graphite is 6.5, and the interlayer spacing d002 value is 0.3490 nm;
(4) ethylene cracking tar (Qilu petrochemical industry of manufacturer) is taken and added with benzaldehyde and p-methyl benzene sulfonic acid mixed acid. Wherein the proportion of the mixed acid of benzaldehyde and p-toluenesulfonic acid to ethylene cracking tar is 8%, and the proportion of benzaldehyde to p-toluenesulfonic acid is 1: 1. and under the protection of nitrogen atmosphere, starting stirring, heating to 150 ℃ at a speed of 3 ℃/min, continuously stirring in the heating process, continuously stirring at a constant temperature of 150 ℃ until the viscosity of the reaction system is gradually increased and stirring cannot be carried out, and stopping reaction. And (3) mechanically crushing the cross-linked polymer to obtain the polynuclear aromatic carbon-rich powder material with the median particle size of D50: 5.0 um;
(5) mixing the micro-expanded graphite micro-powder dried in the step 3) and the polynuclear aromatic carbon-rich powder prepared in the step 4) according to a ratio of 95: mixing at a ratio of 16, and carbonizing in a muffle furnace under a nitrogen atmosphere. Heating to 1000 deg.C at 3 deg.C/min, and maintaining for 3 hr. Cooling the carbonized material, then sieving, adopting a standard sieve with 400 meshes, taking the sieved material, and sieving to obtain the carbonized material with the median particle size D50: 12.3um to obtain the fast-charging graphite cathode material.
Comparative example 1
Compared with example (1), the difference is that: the method is characterized in that artificial graphite powder (self-made by new medium steel heat energy golden energy) with the median particle size D50 of 10.0um is taken, sphericity screening and micro-expansion treatment are not carried out. Mixing the stone-taking powdered ink and the medium-temperature asphalt according to the ratio of 95: 8, adding the mixture into a vertical kettle for low-temperature heat treatment, raising the temperature to 550 ℃ at a speed of 3 ℃/min, and preserving the temperature for 3 hours. Cooling and discharging, and carbonizing in a muffle furnace under the condition of nitrogen atmosphere. Heating to 1000 deg.C at 3 deg.C/min, and maintaining for 3 hr. And (4) cooling the carbonized material, then sieving, and taking the sieved material by adopting a standard sieve with 400 meshes.
Comparative example 2
Compared with example (1), the difference is that: the method is characterized in that artificial graphite powder (self-made by new medium steel heat energy golden energy) with the median particle size D50 of 10.0um is taken, sphericity screening and micro-expansion treatment are not carried out. Mixing the stone-taking powdered ink and the medium-temperature asphalt according to the ratio of 95: mixing at a ratio of 18, adding into a vertical kettle, performing low-temperature heat treatment, heating to 550 ℃ at a speed of 3 ℃/min, and keeping the temperature for 3 h. Cooling and discharging, and carrying out carbonization treatment in a muffle furnace under the condition of nitrogen atmosphere. Heating to 1000 deg.C at 3 deg.C/min, and maintaining for 3 hr. And (4) cooling the carbonized material, then sieving, and taking the sieved material by adopting a standard sieve with 400 meshes.
Effects of the embodiment
The particle size, the interlayer spacing d002 value, the first discharge capacity, the coulombic efficiency and the rate capability of the graphite negative electrode material of the lithium ion batteries of the above examples 1 to 6 and comparative examples 1 and 2 are shown in the table 1.
The particle size testing equipment is as follows: laser particle size distribution instrument MS 3000;
the grain shape tester comprises: dynamic particle size granulometer QICPIC-LIXELL M3;
and (3) electrochemical performance testing:
a button cell CR2032 type is adopted, a lithium sheet is taken as a counter electrode, a diaphragm is a Celgard 2300 PP/PE/PP three-layer microporous composite membrane, and a 1M LiPF6/EC + EMC + DMC solution is taken as a supporting electrolyte. The sample after passing through a 350-mesh standard sieve is: mixing SP, CMC and SBR in the ratio of 95.5 to 1.5 to form slurry, coating the slurry on conductive copper foil, drying at 120 deg.c for 2 hr, and rolling and pressing in a roller press under 10 MPa. And (4) assembling the positive and negative electrode plates, the diaphragm and the electrolyte, and then punching and sealing. All assembly processes were performed in a dry glove box filled with argon.
The lithium ion cell constructed as described above was allowed to incubate overnight at room temperature. The battery charge and discharge performance was tested using an Arbin charge/discharge tester. The current density of charge and discharge is tested to be 0.6mA/cm2The cut-off charge-discharge voltage is 0.005-1.500V.
And (3) rate performance test: discharging to 5mV with a constant current of 0.6mA in the first period, then discharging at a constant voltage, stopping discharging with a current of 0.06mA, and charging to 2V with a constant current of 0.1C; discharging to 5mV at constant current of 0.1C, then discharging at constant voltage, stopping current of 0.06mA, charging to 2V at constant current of 0.2C, and then discharging at multiplying power by 0.2C, 0.5C, 1C, 2C and 3C; after 3C, the current returns to 0.2C, and the multiplying power charging current is 0.1C.
TABLE 1
The above data illustrate that:
1. in the embodiments 1-6 of the invention, a special structural design is adopted, the aggregate graphite powder with a certain particle shape structure (sphericity, width-length ratio and convexity) is preferably selected, and a special granulation and coating mode is combined, so that the lithium ion battery of the prepared special graphite cathode material has good quick charge performance, good rate performance and excellent cycle performance, and can meet the requirement of quick charge;
2. comparative examples 1 to 2 the fast charging performance of the graphite anode material prepared without the grain structure treatment and the micro-expansion treatment was much lower than that of examples 1 to 6 of the present invention.
Claims (10)
1. A preparation method of a quick-charging graphite cathode material is characterized by comprising the following steps:
1) grading or shaping the carbon material to obtain carbon micro powder A with certain particle shape characteristics;
wherein the median particle diameter D50 of the carbon material is 5.0-15.0 um;
putting the carbon micro powder A into a graphitization furnace, and performing high-temperature graphitization treatment to obtain a primary graphitized material; screening the primary graphitized material to obtain a graphitized material B;
3) in an acid aqueous solution system, carrying out micro-expansion treatment on the graphitized material B;
4) putting ethylene cracking tar into a reactor, adding benzaldehyde and p-toluenesulfonic acid according to a certain proportion, continuously stirring under the protection of inert gas, reacting at a certain heating rate and temperature condition until the viscosity of a reaction system is gradually increased until stirring cannot be carried out, and stopping the reaction to obtain a polynuclear aromatic-rich solid carbon material; crushing the solid carbon material to obtain a powdery carbon material;
5) mixing the micro-expanded graphite micro-powder obtained in the step 3) with the polynuclear aromatic-rich carbon powder material prepared in the step 4) according to a certain proportion, carbonizing in a carbonization furnace to obtain a carbonized material, cooling the carbonized material, and then sieving to obtain the fast-charging graphite cathode material.
2. The preparation method of the fast-charging graphite anode material according to claim 1, characterized by comprising the following steps:
the carbon material in the step 1) is petroleum coke or needle coke or intermediate phase carbon microsphere green pellets or a mixture of the petroleum coke or the needle coke or the intermediate phase carbon microsphere green pellets, and the mass ratio of the two mixtures is 4: 6-7: 3.
3. the preparation method of the fast-charging graphite anode material according to claim 1, characterized by comprising the following steps: the particle shape characteristics of the step 1) comprise sphericity, length-diameter ratio and convexity;
the sphericity is defined as S10: 0.7500-0.7700, S50: 0.8200-0.8300, S90: 0.8600-0.8700;
the width-to-length ratio is defined as S10: 0.650-0.700, S50: 0.800-0.840, S90: 0.900-0.950;
the convexity is defined as S10: 0.9000-0.9100, S50: 0.9300-0.9400, S90: 0.9700-0.9800.
4. The preparation method of the fast-charging graphite anode material according to claim 1, characterized by comprising the following steps:
the micro-expansion treatment in the step 3) specifically comprises the steps of taking graphite micro powder, adding the graphite micro powder into an acid solution system, reacting for 25-35 min at 30-40 ℃ in a water bath kettle, filtering, washing and drying to obtain micro-expansion graphite;
wherein the acidic aqueous solution system is an inorganic and organic mixed acid system, and the ratio of the inorganic and organic mixed acid is as follows: 1: 1-1: 3;
wherein, the reaction is carried out for 30 min at 35 ℃ in a water bath, the filtration and the multiple water washing are carried out until the pH value is 6.5 to 7.0, and the drying is carried out;
wherein the interlayer spacing d002 value of the dried micro-expanded graphite powder is 0.3390-0.3495 nm.
5. The preparation method of the fast-charging graphite anode material according to claim 4, characterized by comprising the following steps:
the inorganic acid is sulfuric acid, and the organic acid is sulfonic acid (R-SO 3H) or perhalogenated carboxylic acid which is soluble in an aqueous solution system.
6. The preparation method of the fast-charging graphite anode material according to claim 1, characterized by comprising the following steps: the ethylene cracking tar in the step 4) is ethylene cracking slurry produced by Daqing petrochemical, Fushun petrochemical, Jinzhou petrochemical and Qilu petrochemical; the mass ratio of the benzaldehyde to the p-toluenesulfonic acid is 1: 1-0.5: 1; the mass ratio of the benzaldehyde and p-toluenesulfonic acid mixed agent to the ethylene cracking tar is 4-8%.
7. The preparation method of the fast-charging graphite anode material according to claim 1, characterized by comprising the following steps: the inert gas in the step 4) is nitrogen or argon;
the certain heating rate is 3 ℃/min-5 ℃/min, and the preferred heating rate is 3 ℃/min;
wherein the reaction temperature is 130-180 ℃, and the preferable reaction temperature is 150 ℃.
8. The preparation method of the fast-charging graphite anode material according to claim 1, characterized by comprising the following steps:
the mass ratio of the micro-expanded graphite micropowder in the step 5) to the polynuclear aromatic-rich carbon powder is as follows: 95: 8-95: 20;
the carbonization temperature is 1000-1300 ℃, and preferably 1000-1100 ℃;
the carbonization time is 3-5 h, preferably 3 h;
and (3) cooling the carbonized material, then sieving, wherein a standard sieve of 325-400 meshes is adopted as the standard sieve, taking the sieved material, and sieving to obtain the carbonized material with the median particle size D50: 7.0-16.0 um, preferably 8.0-12.0 um.
9. A lithium ion battery, wherein the negative electrode material of the lithium ion battery comprises the coated and granulated modified graphite material prepared by the preparation method of the quick-charging graphite negative electrode material as defined in any one of claims 1 to 8.
10. Use of the lithium ion battery according to claim 9 as a power battery in the field of passenger vehicles.
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