CN111943184B - Preparation method and device of low-cost short-range ordered sheet-like structure negative electrode material - Google Patents
Preparation method and device of low-cost short-range ordered sheet-like structure negative electrode material Download PDFInfo
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- CN111943184B CN111943184B CN202010650185.6A CN202010650185A CN111943184B CN 111943184 B CN111943184 B CN 111943184B CN 202010650185 A CN202010650185 A CN 202010650185A CN 111943184 B CN111943184 B CN 111943184B
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Abstract
The invention relates to a preparation method and a device of a low-cost short-range ordered sheet-shaped structure negative electrode material. The coke structure of the anode material precursor prepared by the invention is isotropic, a granulation process can be omitted in the production of the anode material, and lithium ions can be inserted from multiple directions and dispersed in all directions after being used for the lithium ion battery, so that high multiplying power, low expansion and long cycle life are realized. The volume reduction and density increase of the heat treatment process can effectively improve the utilization rate of the graphitization furnace, the process can realize low cost of raw materials, simple process, isotropy of the cathode Jiao Gexiang, and excellent rate capability of the formed cathode material.
Description
Technical Field
The invention belongs to the technical field of production of lithium ion battery cathode materials, and particularly relates to a preparation method and a device of a low-cost short-range ordered sheet-shaped cathode material.
Background
The lithium ion battery is widely applied to the fields of consumer electronics, electric automobiles, energy storage materials and the like, and along with the updating and upgrading of consumer electronics products, the vigorous development of new energy automobile industry, the rapid popularization of smart grids and the vigorous demand of other technical fields on high-performance batteries, the lithium ion battery industry is bound to continuously develop at a high speed for a long time in the future, so that great opportunity is provided for the development of the lithium battery cathode material industry, and higher requirements are provided at the same time.
The negative electrode material is an important component of the lithium ion battery, and the performance of the negative electrode material affects the safety, specific capacity, rate capability, cycle life, high and low temperature performance and other key indexes of the lithium ion battery, and is one of the key materials of the lithium ion battery. With the increasing requirements of power batteries and electronic products on battery capacity, service life, safety and the like, the demands of high-performance and low-cost cathode materials will become the development trend in the future. In the production process of the graphite negative electrode material, the orientation and the cyclic expansion of the artificial graphite are reduced through a granulation process, and a lithium ion diffusion channel is increased, so that the rate capability and the capacity are improved. The granulation process is to crush large-particle coke and then bond the large-particle coke with binders such as asphalt to form large coke particles again, so that the powder material achieves isotropy. If the coke structure for the negative electrode material is isotropic, a granulation process can be omitted in the production of the negative electrode material, lithium ions can be similarly inserted from multiple directions after the lithium ion battery is formed, and stress is also dispersed in all directions, so that high multiplying power, low expansion and long cycle life are realized. With the adjustment of the policies related to new energy automobiles, the negative electrode material industry chain is under the cost reduction pressure, the graphitization cost in the cost composition of the artificial graphite product accounts for more than 50% of the direct cost, and the most direct method is to optimize the graphitization process or improve the graphitization product yield in order to reduce the negative electrode material cost. Therefore, on the basis of ensuring the capacity of the lithium ion battery, the development of the lithium ion battery cathode material with excellent rate capability, good cycle performance and low cost has great significance.
In addition, the trend of oil heaviness is increasing, the heavy components which are more than 10 percent of the total oil can not be converted into light components by the prior art, and the conversion of the heavy components with high hydrocarbon content into carbon materials is an important utilization way. The heavy petroleum components mainly comprise colloid and asphaltene and are composed of macromolecules with high carbon-hydrogen ratio, and the full utilization and high-efficiency conversion of the heavy petroleum components are increasingly important for the comprehensive configuration and the reasonable utilization of resources of petroleum refining processes.
Disclosure of Invention
The invention provides a preparation method and a device of a low-cost short-range ordered sheet-shaped structure cathode material, wherein the coke structure of a precursor of the prepared cathode material is isotropic, a granulation process can be omitted in the production of the cathode material, lithium ions can be inserted from multiple directions and the stress can be dispersed to all directions after the anode material is used for a lithium ion battery, and high multiplying power, low expansion and long cycle life are realized. The volume reduction and the density increase of the heat treatment process can effectively improve the utilization rate of the graphitization furnace, the process can realize low cost of raw materials, the process is simple, the cathode Jiao Gexiang has the same polarity, and the formed cathode material has excellent multiplying power performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a low-cost short-range ordered sheet-structure negative electrode material is characterized in that asphalt is used as a raw material, the asphalt and a petroleum heavy component are mixed, the mixture is sent into a coking tower to be coked, negative electrode coke with a short-range ordered sheet-structure is obtained, the negative electrode coke is crushed and screened, enters a heat treatment process to reduce the volume and increase the density, and finally is graphitized, so that the negative electrode material for a lithium ion battery is obtained.
The method specifically comprises the following steps:
1) Formation of negative electrode coke: feeding a mixed material of asphalt and heavy petroleum components into a heating furnace for heating, feeding generated oil gas into a coking tower from the bottom of the coking tower for coking reaction to obtain short-range ordered sheet-structured negative coke, feeding the oil gas generated at the top of the coking tower into a flash distillation fractionating tower, cooling high-temperature oil gas at the top of the flash distillation fractionating tower to realize partial reflux, feeding light components at the top of the fractionating tower into a light oil receiving tank, and feeding heavy distillate oil at the bottom of the fractionating tower into a heavy oil receiving tank or circularly conveying the heavy distillate oil to an asphalt raw material tank;
2) Reducing volume and increasing density of the negative electrode coke: crushing the negative electrode coke obtained in the step 1), screening to obtain coke powder with D50 of 10-20 microns, conveying the coke powder to a carbonization furnace, arranging a graphite baffle at the upper end of the coke powder material, connecting a displacement sensor above the graphite baffle, enabling the coke powder material to shrink in volume (as the temperature rises, a part of volatile components in the coke powder can be discharged, so that the volume can shrink), monitoring the volume change of the coke powder material in real time by the displacement sensor, ending carbonization when the volume of the coke powder material stops changing, and realizing the effects of reducing the volume and increasing the density of the negative electrode coke;
3) Graphitizing the coke powder: finally graphitizing the carbonized coke powder material in a graphitizing furnace at 2600-3000 ℃, scattering and demagnetizing to obtain the short-distance ordered sheet-shaped structure cathode material.
The asphalt is one or more of coal asphalt, petroleum asphalt, spinnable asphalt and mesophase asphalt; the petroleum heavy component is a petroleum component which contains asphaltene, aromatic components or colloid, does not contain saturated components and has an initial boiling point of more than or equal to 150 ℃; the mixing ratio of the asphalt to the petroleum heavy component is as follows: (80 wt% -95 wt%): (20 wt% to 5 wt%).
In the step 1), the outlet temperature of the heating furnace is 420-520 ℃, the reaction temperature of the coking tower is 520-590 ℃, and the control range of the top pressure of the coking tower is 0.3-1.0 MPa.
In the step 2), the temperature of the carbonization furnace is 550-1000 ℃, the carbonization time is 1-10 h, and the carbonization temperature rise rate is 0.2-10 ℃/min.
A device used in a preparation method of a low-cost short-range ordered sheet-like structure cathode material comprises an asphalt raw material tank, a petroleum heavy component raw material tank, a mixer, a mixed material tank, a heating furnace, a coking tower, a crusher, a screening machine, a carbonization furnace, a graphitization furnace and a flash distillation fractionating tower; asphalt head tank and petroleum heavy ends head tank pass through the entry of blender connection mixing material jar, the exit linkage heating furnace entry of mixing material jar, heating furnace exit linkage coking tower, the light phase exit linkage flash distillation fractionating tower of coking tower, the heavy phase export of coking tower pay-off to the breaker, and the breaker pay-off to the screening machine, and the screening machine pay-off to retort, and the retort pay-off to graphitizing furnace.
The device comprises a carbonization furnace and is characterized in that a graphitizing baffle is arranged on the upper part of the carbonization furnace, the graphitizing baffle is arranged at the upper end of a coke powder material, and a displacement sensor is mounted on the graphitizing baffle.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention takes the asphalt and the petroleum heavy component as raw materials, and the raw materials are easy to obtain and have low price. The petroleum crude oil contains extremely heavy components which account for about 10 percent of the total mass of the crude oil and are difficult to be hydrotreated to obtain light oil products, and the petroleum heavy components which mainly comprise asphaltene and colloid have higher reaction activity and can promote the polymerization of the asphalt at low temperature to generate isotropic short-range ordered flake-structure negative coke. Therefore, the method for preparing the cathode coke by adopting the heavy petroleum components has important technical and economic values.
(2) According to the invention, the cathode coke with the short-range ordered flake structure is obtained, the cathode coke is isotropic, lithium ions can be embedded from multiple directions after the cathode coke is used for a lithium ion battery, stress is dispersed to all directions, the number of lithium ion transmission channels is large, the problems of few inlets for embedding and releasing in an anisotropic structure and low diffusion rate are solved, low expansion and long cycle life are realized, and the multiplying power performance is good.
(3) According to the invention, the volume of the cathode Jiao Jiaofen is reduced and the density of the cathode is increased through a heat treatment process, the monitoring of the volume change of the coke powder in the heat treatment process is realized by adding a displacement sensor at the upper end of the carbonization furnace, the shrinkage condition of the coke powder is monitored in real time through the displacement sensor, and the graphitization is carried out after the coke powder is shrunk in volume, so that the Jiao Fenliang can be accommodated in the graphitization furnace in unit volume and is increased by 25-50 wt%, and the utilization rate of the graphitization furnace is greatly increased. In the cost composition of the artificial graphite product, the graphitization cost accounts for more than 50% of the direct cost, and by the method, the production cost of the cathode material is effectively reduced, the process is simple, the product performance is excellent, and the enterprise profit is high.
Drawings
FIG. 1 is a process scheme of the present invention;
FIG. 2 is a polarizing microscope picture of the short range ordered sheet structure negative electrode focal of the present invention;
fig. 3 is a scanning electron microscope image of the negative electrode material of the present invention.
In the figure: the system comprises a 1-asphalt raw material tank, a 2-petroleum heavy component raw material tank, a 3-mixer, a 4-mixed material tank, a 5-heating furnace, a 6-coking tower, a 7-crusher, an 8-sieving machine, a 9-spiral feeder, a 10-carbonization furnace, a 11-graphitization baffle, a 12-displacement sensor, a 13-graphitization furnace, a 14-scattering machine, a 15-demagnetizing machine, a 16-finished product bin, a 17-flash distillation fractionating tower, a 18-light oil receiving tank and a 19-heavy oil receiving tank.
Detailed Description
The following examples are included to further illustrate embodiments of the invention:
a preparation method of a low-cost short-range ordered sheet-structure negative electrode material is characterized in that asphalt is used as a raw material, the asphalt and a petroleum heavy component are mixed, the mixture is sent into a coking tower to be coked, negative electrode coke with a short-range ordered sheet-structure is obtained, the negative electrode coke is crushed and screened, enters a heat treatment process to reduce the volume and increase the density, and finally is graphitized, so that the negative electrode material for a lithium ion battery is obtained.
The method specifically comprises the following steps:
mixing of bitumen with petroleum heavy components: respectively conveying the asphalt and the heavy petroleum components from a raw material storage tank to a mixer by a pump for mixing, and conveying the uniformly mixed asphalt and the heavy petroleum components to a raw material mixing tank to obtain a mixed material;
1) Formation of negative electrode coke: the mixed material is sent into a heating furnace for heating, the outlet temperature of the heating furnace is controlled in an operation mode of program temperature change, the generated high-temperature oil gas is sent into a coking tower from the bottom of the coking tower through an oil transfer line for coking reaction to obtain short-range ordered sheet-structured negative coke, the reaction temperature of the material in the coking tower is controlled in the process of program temperature change in the operation mode, and the top pressure of the coking tower is controlled by a pressure control valve; high-temperature oil gas generated at the top of the coking tower enters a flash distillation fractionating tower, the temperature of the bottom of the fractionating tower is controlled, the high-temperature oil gas is cooled at the top of the flash distillation fractionating tower, partial reflux is realized, accurate cutting of fractions is achieved, light components at the top of the fractionating tower enter a light oil receiving tank, heavy distillate oil at the bottom of the fractionating tower enters a heavy oil receiving tank or is circularly conveyed to an asphalt raw material tank;
2) Reducing volume and increasing density of the negative electrode coke: crushing the negative electrode coke obtained in the step 1) by using a mechanical mill, screening to obtain coke powder with D50 of 10-20 mu m, and carbonizing the coke powder by using a carbonization furnace through a heat treatment process to realize volume reduction and density increase of the material; conveying the coke powder to a carbonization furnace by a spiral feeder, arranging a graphite baffle plate on the upper part of the coke powder material, connecting a displacement sensor above the graphite baffle plate, enabling the coke powder material to contract in volume along with the rise of temperature, monitoring the change of the coke powder material in volume in real time by the displacement sensor, ending carbonization when the volume of the coke powder material stops changing, and realizing the effect of reducing the volume and increasing the density of cathode coke;
3) Graphitizing the coke powder: finally graphitizing the carbonized coke powder material in a graphitizing furnace at 2600-3000 ℃, scattering and demagnetizing to obtain the short-distance ordered sheet-shaped structure cathode material.
The asphalt is one or more of coal asphalt, petroleum asphalt, spinnable asphalt and mesophase asphalt; the petroleum heavy component is a petroleum component which contains asphaltene, aromatic components or colloid, does not contain saturated components and has an initial boiling point of more than or equal to 150 ℃; the mixing ratio of the asphalt to the petroleum heavy component is as follows: (80-95 wt%): (20-5 wt%).
The heavy petroleum component without saturated component and with initial boiling point not lower than 150 deg.c has high reaction activity and can promote the low temperature polymerization of asphalt to form short range ordered intermediate phase structure, and the short range ordered intermediate phase structure produces isotropic short range ordered small piece structure negative coke after coking reaction. In the process, the petroleum heavy component plays a key role, the formation of a short-range ordered small-piece structure is promoted, and after the negative electrode coke of the structure forms a negative electrode material, lithium ions can be inserted from multiple directions, so that the shuttling of the lithium ions is easy, and the high-rate performance is achieved.
In the step 1), the heating furnace heats the material from 150-200 ℃ to 380-520 ℃ at the heating rate of 5-15 ℃/h, the outlet temperature of the heating furnace is 420-520 ℃, and the reaction time is 16-40 h; the reaction temperature of the coking tower is 520-590 ℃, the heating rate is 2 ℃/h-10 ℃/h, the coking time is 16 h-40 h, and the tower top pressure of the coking tower is controlled within the range of 0.3-1.0 MPa through a pressure control valve. The temperature system of the coking tower is controlled, which is beneficial to the formation of the short-distance ordered flake structure negative coke.
In the step 2), the temperature of the carbonization furnace is 550-1000 ℃, the carbonization time is 1-10 h, and the carbonization temperature rise rate is 0.2-10 ℃/min. The carbonization furnace is a vertical furnace.
The cathode Jiao Jiaofen is subjected to heat treatment in a carbonization furnace at 550-1000 ℃, the volume shrinkage is large, the volume change of materials tends to be smooth along with the rise of temperature, a displacement sensor is added at the upper end of the carbonization furnace to monitor the shrinkage condition of the coke powder in real time, and the purposes of reducing the volume and increasing the density of the coke powder are achieved after the volume of the coke powder is shrunk.
A device used in a preparation method of a low-cost short-range ordered sheet-shaped structure cathode material comprises an asphalt raw material tank 1, a petroleum heavy component raw material tank 2, a mixer 3, a mixture material tank 4, a heating furnace 5, a coking tower 6, a crusher 7, a sieving machine 8, a carbonization furnace 10, a graphitization furnace 13, a scattering machine 14, a demagnetizer 15 and a flash distillation fractionating tower 17; asphalt head tank 2 and petroleum heavy component head tank 1 pass through the entry of 3 connection mixing material jars 4 of blender, 5 entrys of exit linkage heating furnace of mixture material jar 4, 5 exit linkage coking tower 6 of heating furnace, 6 light phase exit linkage flash distillation fractionating tower 17 of coking tower, the heavy phase export of coking tower 6 pay-off to breaker 7, and breaker 7 pay-off to screening machine 8, and screening machine 8 is through the pay-off of screw feeder 9 to retort 10, and retort 10 pay-off to graphitizing furnace 13. And a light phase outlet of the flash fractionating tower 17 is connected with a light oil receiving tank 18, and a heavy phase outlet of the flash fractionating tower 17 is connected with a heavy oil receiving tank 19 or connected with the asphalt raw material tank 1. The materials in the inking furnace 13 are sent into a finished product bin 16 after passing through a scattering machine 14 and a demagnetizing machine 15.
The upper portion of retort 10 is equipped with graphitization baffle 11, graphitization baffle 11 is arranged in the fine coke material upper end, graphitization baffle 11 is last to be installed displacement sensor 12. After the coke powder material is fed into the carbonization furnace 10, the graphitized baffle 11 is placed on the coke powder material from the upper end of the carbonization furnace 10.
Example 1:
mixing coal tar pitch and petroleum heavy component by 90wt%: mixing 10wt% in a mixer, transferring into a mixed material tank after mixing, feeding the mixed material into a heating furnace, heating the heating furnace from 150 ℃ to 300 ℃ at a heating rate of 15 ℃/h, and then heating at a heating rate of 5 ℃/hHeating from 300 ℃ to 410 ℃, wherein the feeding time is 32h, heating from 410 ℃ to 520 ℃ at the heating rate of 5 ℃/h after entering a coking tower, the pressure is 0.5MPa, and the reaction time is 24h, thus obtaining the short-range ordered platelet-structured negative electrode coke. Crushing the negative electrode coke by a crusher to obtain coke powder, and sieving the coke powder, wherein the granularity D50 of the sieved coke powder is 15-20 mu m, and the bulk density of the coke powder is 0.40g/cm 3 . The screened coke powder is not subjected to heat treatment of a carbonization furnace, the coke powder is directly graphitized under the protection of inert gas at 2800 ℃, and the volume of a graphitized crucible is 0.186m 3 The weight of the coke powder capable of being contained is 74.4kg, the short-range ordered sheet-shaped structure negative electrode material is obtained after the coke powder is graphitized, and the negative electrode material and the lithium sheet are used as the positive electrode to assemble the button cell to test the electrochemical performance of the button cell. The negative electrode material and the property index after assembling the button cell are shown in table 1. This example was not treated to reduce the volume and increase the density in the carbonization furnace and is discussed as a comparative condition for the following examples.
Example 2:
mixing coal tar pitch and petroleum heavy component according to the weight ratio of 90 percent: mixing 10wt% in a mixer, conveying the mixture into a mixed material tank, feeding the mixed material into a heating furnace, heating the heating furnace from 150 ℃ to 300 ℃ at a heating rate of 15 ℃/h, then heating from 300 ℃ to 410 ℃ at a heating rate of 5 ℃/h, feeding for 32h, feeding into a coking tower, heating from 410 ℃ to 520 ℃ at a heating rate of 5 ℃/h, controlling the pressure to be 0.5MPa, and controlling the reaction time to be 24h to obtain the short-range ordered platelet structured negative electrode coke. Crushing the negative electrode coke by a crusher to obtain coke powder, and screening the coke powder, wherein the screened granularity D50 is 15-20 mu m. Conveying the coke powder to a carbonization furnace for heat treatment, observing the volume change condition of the displacement sensor in real time, keeping the temperature of the carbonization furnace at 900 ℃ for 2 hours, ensuring that the volume change tends to be gentle, ending carbonization, and ensuring that the bulk density of the coke powder subjected to heat treatment by the carbonization furnace is 0.60g/cm 3 . Graphitizing the heat-treated coke powder at 2800 ℃ under the protection of inert gas, wherein the volume of a graphitizing crucible is 0.186m 3 The weight of the coke powder contained was 111.6kg, which was 50% higher than that in example 1. Graphitizing the coke powder to obtain the short-range ordered sheet-like structure cathode materialAnd assembling the button cell by taking the lithium sheet as the cathode and the lithium sheet as the anode, and testing the electrochemical performance of the button cell. The negative electrode material and the property indexes after assembling the negative electrode material into the button cell are shown in table 1. This example was compared with example 1, and the same conditions as in example 1 were used for the heat treatment step of the coke oven.
Example 3:
mixing petroleum asphalt and petroleum heavy components according to the weight percentage of 95 percent: 5wt% of the raw materials are mixed in a mixer, the mixture is conveyed into a mixed material tank, the mixed material enters a heating furnace, the heating furnace is heated from 150 ℃ to 300 ℃ at a heating rate of 15 ℃/h, then the heating furnace is heated from 300 ℃ to 490 ℃ at a heating rate of 8 ℃/h, the feeding time is 35h, the raw materials enter a coking tower, the heating furnace is heated from 490 ℃ to 550 ℃ at a heating rate of 5 ℃/h, the temperature is kept for 4h, the pressure is 0.7MPa, and the reaction time is 16h, so that the short-range ordered flake structure negative electrode coke is obtained. Crushing the negative electrode coke by a crusher to obtain coke powder, and screening the coke powder, wherein the screened granularity D50 is 10-15 mu m. Conveying the coke powder to a carbonization furnace for heat treatment, observing the volume change condition of the displacement sensor in real time, keeping the temperature of the carbonization furnace at 800 ℃ for 3 hours, ensuring that the volume change tends to be gentle, ending carbonization, and ensuring that the bulk density of the coke powder subjected to heat treatment by the carbonization furnace is 0.56g/cm 3 . Graphitizing the heat-treated coke powder at 2800 ℃ under the protection of inert gas, wherein the volume of a graphitizing crucible is 0.186m 3 The weight of the coke powder contained in the coke oven was 104.2kg, which was 40% higher than that of example 1. And graphitizing the coke powder to obtain a short-range ordered sheet-like structure cathode material, assembling the cathode material serving as a cathode and a lithium sheet serving as an anode into a button battery, and testing the electrochemical performance of the button battery. The negative electrode material and the property index after assembling the button cell are shown in table 1.
Example 4:
mixing petroleum asphalt and petroleum heavy components according to the weight percentage of 85 percent: mixing 15wt% in a mixer, mixing, conveying to a mixed material tank, feeding the mixed material into a heating furnace, heating the heating furnace from 150 ℃ to 350 ℃ at a heating rate of 10 ℃/h, then heating from 350 ℃ to 420 ℃ at a heating rate of 8 ℃/h, feeding for 30h, feeding into a coking tower, heating from 420 ℃ to 420 ℃ at a heating rate of 6 ℃/hKeeping the temperature at 520 ℃ for 2h, keeping the pressure at 0.8MPa and reacting for 19h to obtain the short-range ordered flake-structured negative electrode coke. Crushing the negative electrode coke by a crusher to obtain coke powder, and screening the coke powder, wherein the screened granularity D50 is 10-15 mu m. Conveying the coke powder into a carbonization furnace for heat treatment, observing the volume change condition of the displacement sensor in real time, keeping the temperature of the carbonization furnace at 850 ℃ for 3 hours, keeping the volume change to be gentle, ending carbonization, and controlling the stacking density of the coke powder after heat treatment by the carbonization furnace to be 0.50g/cm 3 . Graphitizing the heat-treated coke powder at 3000 ℃ under the protection of inert gas, wherein the volume of a graphitizing crucible is 0.186m 3 The weight of the coke powder contained therein was 93.0kg, which was 25% higher than that in example 1. And graphitizing the coke powder to obtain a short-range ordered sheet-shaped structure cathode material, assembling the cathode material serving as a cathode and a lithium sheet serving as an anode into a button cell, and testing the electrochemical performance of the button cell. The negative electrode material and the property index after assembling the button cell are shown in table 1.
Example 5:
mixing the mesophase pitch and petroleum heavy components according to the weight percentage of 90 percent: mixing 10wt% in a mixer, conveying the mixture into a mixed material tank, feeding the mixed material into a heating furnace, heating the heating furnace to the temperature of 150 ℃ to 300 ℃ at the heating rate of 10 ℃/h, then heating the mixed material to the temperature of 420 ℃ (the temperature is not right) at the heating rate of 5 ℃/h, feeding the mixed material into a coking tower for 39h, heating the mixed material into the coking tower to the temperature of 530 ℃ from 420 ℃ at the heating rate of 8 ℃/h, keeping the temperature for 5h, keeping the pressure at 0.5MPa (the pressure values are not right), and reacting for 19h to obtain the short-range ordered flake structure negative electrode coke. Crushing the negative electrode coke by a crusher to obtain coke powder, and screening, wherein the screened granularity D50 is 15-20 mu m. Conveying the coke powder to a carbonization furnace for heat treatment, observing the volume change condition of the displacement sensor in real time, keeping the temperature of the carbonization furnace at 800 ℃ for 2 hours, ensuring that the volume change tends to be smooth, ending carbonization, and ensuring that the bulk density of the coke powder subjected to heat treatment by the carbonization furnace is 0.52g/cm 3 . Graphitizing the heat-treated coke powder at 2800 ℃ under the protection of inert gas, wherein the volume of a graphitizing crucible is 0.186m 3 The weight of the coke powder contained in the coke oven was 96.72kg, which was 30% higher than that of example 1. Coke breeze stoneAnd (3) obtaining a short-range ordered sheet-shaped structure cathode material after the ink is formed, assembling a button battery by taking the short-range ordered sheet-shaped structure cathode material as a cathode and a lithium sheet as an anode, and testing the electrochemical performance of the button battery. The negative electrode material and the property index after assembling the button cell are shown in table 1.
TABLE 1 examples negative electrode materials and property indexes after assembling into button cell
Claims (6)
1. A preparation method of a low-cost short-range ordered sheet-structured negative electrode material is characterized in that asphalt is used as a raw material, the asphalt and a petroleum heavy component are mixed, the mixture is sent into a coking tower for coking, negative electrode coke with a short-range ordered sheet-structured structure is obtained, the negative electrode coke is crushed and screened, enters a heat treatment process for reducing the volume and increasing the density, and finally is graphitized, so that the negative electrode material for a lithium ion battery is obtained;
the method specifically comprises the following steps:
1) Formation of negative electrode coke: feeding a mixed material of asphalt and heavy petroleum components into a heating furnace for heating, feeding generated oil gas into a coking tower from the bottom of the coking tower for coking reaction to obtain short-range ordered sheet-structured negative coke, feeding the oil gas generated at the top of the coking tower into a flash distillation fractionating tower, cooling the oil gas at the top of the flash distillation fractionating tower to realize partial reflux, feeding the light components at the top of the fractionating tower into a light oil receiving tank, and feeding the heavy distillate oil at the bottom of the fractionating tower into a heavy oil receiving tank or circularly conveying the heavy distillate oil to an asphalt raw material tank;
2) Reducing volume and increasing density of the negative electrode coke: crushing the negative electrode coke obtained in the step 1), screening to obtain coke powder with D50 of 10-20 microns, conveying the coke powder to a carbonization furnace, arranging a graphite baffle at the upper end of a coke powder material, connecting a displacement sensor above the graphite baffle, enabling the coke powder material to shrink in volume along with the rise of temperature, monitoring the volume change of the coke powder material by the displacement sensor in real time, ending carbonization when the volume of the coke powder material stops changing, and realizing the effect of reducing the volume and increasing the density of the negative electrode coke;
3) Graphitizing the coke powder: finally graphitizing the carbonized coke powder material in a graphitizing furnace at 2600-3000 ℃, scattering and demagnetizing to obtain a short-distance ordered sheet-shaped structure negative electrode material;
the petroleum heavy component is a petroleum component which contains asphaltene, aromatic components or colloid, does not contain saturated components and has an initial boiling point of more than or equal to 150 ℃; the mixing proportion of the asphalt and the petroleum heavy component is as follows: (80 wt% -95 wt%): (20 wt% to 5 wt%).
2. The preparation method of the low-cost short-range ordered sheet structure negative electrode material as claimed in claim 1, wherein the asphalt is one or more of coal asphalt, petroleum asphalt, spinnable asphalt and mesophase asphalt.
3. The preparation method of the low-cost short-range ordered sheet-like structure negative electrode material according to claim 1, characterized in that, in the step 1), the outlet temperature of the heating furnace is 420-520 ℃, the reaction temperature of the coking tower is 520-590 ℃, and the top pressure of the coking tower is controlled within the range of 0.3-1.0 MPa.
4. The preparation method of the low-cost short-range ordered sheet-like structure negative electrode material according to claim 1, wherein in the step 2), the temperature of the carbonization furnace is 550-1000 ℃, the carbonization time is 1-10 h, and the carbonization temperature rise rate is 0.2-10 ℃/min.
5. The device used in the preparation method of the low-cost short-distance ordered sheet structure negative electrode material according to any one of claims 1 to 4 is characterized by comprising an asphalt raw material tank, a petroleum heavy component raw material tank, a mixer, a mixed material tank, a heating furnace, a coking tower, a crusher, a sieving machine, a carbonization furnace, a graphitization furnace, a scattering machine, a demagnetizer and a flash distillation fractionating tower; the asphalt material tank and the petroleum heavy component material tank are connected with an inlet of a mixed material tank through a mixer, an outlet of the mixed material tank is connected with an inlet of a heating furnace, an outlet of the heating furnace is connected with a coking tower, a light phase outlet of the coking tower is connected with a flash distillation fractionating tower, a heavy phase outlet of the coking tower feeds materials to a crusher, the crusher feeds materials to a screening machine, the screening machine feeds materials to a carbonization furnace, and the carbonization furnace feeds materials to a graphitization furnace.
6. The device for preparing the low-cost short-range ordered sheet-like structure negative electrode material according to claim 5 is characterized in that a graphitized baffle is arranged at the upper part of the carbonization furnace, the graphitized baffle is arranged at the upper end of the coke powder material, and a displacement sensor is arranged on the graphitized baffle.
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