CN113979432B - Method for preparing lithium battery anode material by using medium-low temperature coal tar and application thereof - Google Patents
Method for preparing lithium battery anode material by using medium-low temperature coal tar and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention belongs to the technical field of battery materials, and relates to a method for preparing a lithium battery anode material by using medium-low temperature coal tar and application thereof, wherein 1) raw material fraction is cut to obtain 350-520 ℃ fraction section asphalt; 2) Extracting and separating an HS component, an HI-TS component and an TI-QS component from the cut asphalt, and preparing to obtain a prepared raw material; 3) Blending raw materials for secondary carbonization; 4) And further graphitizing to obtain the lithium battery cathode material. The preparation method takes the medium-low temperature coal tar as the raw material, and the preparation is completed through separation, blending, secondary carbonization and graphitization, so that the process is simple and feasible, easy to operate and stable; the obtained lithium battery negative electrode material is used for a lithium battery negative electrode, and has stable battery performance, excellent cycle performance and outstanding attenuation resistance.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a method for preparing a lithium battery anode material by using medium-low temperature coal tar and application thereof.
Background
With the rapid development of modern industry, the demands for energy from countries around the world are explosively increased, and the problems of energy shortage, environmental pollution and the like are gradually and severely increased. The problem of energy shortage will be a great challenge for the sustainable development of world energy over a long period of time in the future. With the development of energy storage technology, technologies such as lithium ion batteries, supercapacitors, lithium sulfur batteries, sodium sulfur batteries, and flow batteries have become important points of attention in recent years. Compared with other energy storage technologies basically in a test stage, the lithium ion battery technology is mature, large-scale commercial application is realized, and the lithium ion battery is almost the most widely used battery in the world. The lithium ion battery has the advantages of high specific energy, weak self-discharge, good cycle performance, no memory effect, environmental protection and the like, and is the secondary battery with the most development prospect at present.
The lithium ion battery is widely applied not only to various electronic products, but also to electric automobiles, signal base stations, energy storage and the like. The impact on human life is becoming more and more important. In recent years, with the development of technology, electric automobiles and energy storage have rapidly developed. Lithium ion batteries using graphite as the negative electrode material are increasingly unable to meet the demands of people for high energy density lithium ion batteries. The energy density of the lithium ion battery is mainly determined by the positive electrode material and the negative electrode material of the lithium ion battery, wherein the energy density of the lithium ion battery is hopefully improved by improving the specific capacity of the negative electrode material. Research on negative electrode materials of lithium ion batteries is important to research and development of power type lithium ion batteries. The current commercialized anode material is mainly graphite anode material, wherein graphitized mesophase carbon microspheres have close packing, can improve the energy density of an energy lithium ion battery, have smooth surfaces, reduce side reactions and improve the first charge and discharge efficiency, but the theoretical gram capacity of graphite as the anode material is 372m & Ah, and can not meet the requirements of people on the high-energy density lithium ion battery
Patent CN109319774 discloses a method for preparing a negative electrode material by using medium-low temperature carbonization coal tar, the method refers to preparing a precursor of the negative electrode material by using refined asphalt, the preparation process is similar to that of needle coke, and the obtained negative electrode material has the same defects as the needle coke in performance, namely, the sphericity of the material is not high, and the regularity of a carbon layer structure is poor; the patent CN105623694A takes impregnant asphalt as a raw material to carry out thermal polymerization to obtain intermediate phase asphalt, and then the intermediate phase asphalt coke is prepared by further carbonization reaction, wherein ash content is less than 0.5%, but the preparation of high-quality intermediate phase asphalt coke is required to be carried out by pretreatment and modulation on the raw material asphalt to obtain the ash impurity removal and proper raw material structure and composition distribution. Patent CN101651199B discloses a lithium battery carbon negative electrode material and a preparation method thereof, wherein coal tar (or coal tar pitch, petroleum pitch) and anthracite are adopted for cladding, and the lithium battery negative electrode material is obtained through polymerization, carbonization and graphitization, but the method for preparing the lithium battery negative electrode material is not beneficial to forming a regular carbon layer structure and uniformly distributed gaps. The preparation method of the anode material has the following problems: the procedures are complex, and the product quality can not be controlled stably.
The Chinese coal has rich resources, wherein the low-rank coal accounts for more than half of the resources, and is mostly distributed in northwest and northeast areas, and the low-rank coal can be converted into high-added-value products such as coal gas, tar, semicoke and the like through a medium-low temperature carbonization (pyrolysis) technology, so that the quality and grading effective utilization of the low-rank coal can be realized. The yield of various kinds of coal tar in China in 2019 is about 2510 multiplied by 10 4 t, wherein the medium and low temperature coal tar is about 560 x 10 4 t, at present, the light component of coal tar is produced into gasoline, diesel oil and special oil products by using a mature process technology, the products belong to light liquid fuel, the asphalt component contains condensed aromatic rings and a plurality of naphthenic and alkyl side chains, and in addition, the asphalt component also contains sulfur, nitrogen, oxygen and various metal heteroatoms, so that the asphalt component is a component which is difficult to process in the structure, and how to process and utilize high added value of up to 20-35% of the asphalt component in the coal tar becomes the bottleneck problem of industrial development to be solved urgently.
Disclosure of Invention
Aiming at the technical problems in the background art, the invention provides a method for preparing a lithium battery cathode material by using medium-low temperature coal tar and application thereof, wherein the preparation is finished by taking the medium-low temperature coal tar as a raw material through separation, blending, carbonization and graphitization, and the process is simple and feasible, easy to operate and stable; when the prepared lithium battery negative electrode material is used as a lithium battery negative electrode, the battery performance is stable, the cycle performance is excellent, and the attenuation resistance is outstanding.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the method for preparing the lithium battery anode material by using the medium-low temperature coal tar comprises the following steps:
1) Pretreatment of raw materials
Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2) Separation and blending
2.1 Sequentially adopting normal alkane solution, monocyclic hydrocarbon aromatic hydrocarbon solution and quinoline solution to extract and separate the fraction section asphalt of 350-520 ℃ in the step 1) for three times, and respectively correspondingly obtaining normal alkane soluble HS component, normal alkane insoluble monocyclic aromatic hydrocarbon soluble HI-TS component and monocyclic aromatic hydrocarbon insoluble quinoline soluble TI-QS component;
2.2 Preparing an normal alkane soluble matter HS component, an normal alkane insoluble monocyclic aromatic hydrocarbon soluble matter HI-TS component and a monocyclic aromatic hydrocarbon insoluble quinoline soluble matter TI-QS component which are obtained in the step 2.1);
3) The prepared raw materials obtained in the step 2) are subjected to carbonization reaction to generate semicoke;
4) And (3) graphitizing the semicoke obtained in the step (3) to obtain the lithium battery anode material.
Further, in the step 2.1), the specific process of extraction and separation is as follows:
2.1.1 Mixing the fraction asphalt at 350-520 ℃ with normal alkane solution, carrying out primary extraction reaction under the stirring condition, and standing to obtain primary supernatant and lower asphalt HI; separating normal alkane soluble substances HS from the primary supernatant, and drying the lower asphalt HI;
2.1.2 Mixing the lower asphalt HI obtained in the step 2.1.1) with a monocyclic hydrocarbon aromatic hydrocarbon solution, carrying out secondary extraction reaction under the stirring condition, standing to obtain a secondary supernatant and lower asphalt TI, and separating an n-alkane insoluble monocyclic aromatic hydrocarbon soluble HI-TS from the secondary supernatant; drying the lower asphalt TI;
2.1.3 Mixing the lower asphalt TI obtained in the step 2.1.2) with a quinoline solution, carrying out three extraction reactions under the stirring condition, and standing to obtain three supernatant and lower asphalt; separating monocyclic aromatic hydrocarbon insoluble quinoline soluble TI-QS from the third supernatant; and taking the lower asphalt layer and drying to obtain quinoline insoluble QI.
Further, in the steps 2.1.1) to 2.1.3), the conditions of the three extraction reactions are the same, and the conditions are as follows: the extraction temperature is 60-80 ℃, the stirring rotation speed is 1800-2200 r/min, the stirring time is 10-60 min, and the standing time is 0.5-3 h.
Further, in the step 2.1.1), the normal alkane is one or more of C7-C10 normal alkanes.
Further, in the step 2.1.2), the monocyclic hydrocarbon aromatic hydrocarbon is one or more of benzene, toluene and xylene.
Further, in the step 2.2), the mass ratio of the normal paraffin soluble HS component, the normal paraffin insoluble monocyclic aromatic hydrocarbon soluble HI-TS component and the monocyclic aromatic hydrocarbon insoluble quinoline soluble TI-QS component is 20% -40%: 60% -75%: 1 to 10 percent.
Further, in the step 3), the carbonization conditions are: heating to 380-440 ℃ at the temperature rising rate of 3-5 ℃/min under the pressure of 3-5 MPa, and keeping the temperature for 6-10 h; then heating to 480-520 ℃ at the temperature rising rate of 0.5-1.5 ℃/min under the pressure of 0.2-1 MPa, and keeping the temperature for 8-12 h.
Further, in the step 4), the temperature of the graphitization reaction is 2800-3200 ℃, the heating rate is 5-8 ℃/min, and the graphitization time is 6-12 h.
A lithium battery negative electrode material prepared by a method for preparing a lithium battery negative electrode material by using medium-low temperature coal tar.
An application of a lithium battery anode material as an anode in a lithium battery.
The beneficial effects of the invention are as follows:
1. according to the method for preparing the anode material by using the medium-low temperature tar, the medium-low temperature tar is used as a raw material, and the structure of the anode material is controlled by adjusting the composition of the raw material, regulating and controlling the viscosity of a system in the carbonization process and the like, so that the high-quality anode material is prepared. The invention realizes the quality control of the product by blending the raw material composition, and the preparation process is simple and feasible, easy to operate and has strong product stability.
2. According to the invention, during carbonization, the carbonization process is controlled through two different carbonization conditions, the prepared and optimized blending raw materials are carbonized under proper reaction conditions, and the prepared semicoke is used as a precursor of the anode material, so that the stability of the precursor is ensured, the subsequent graphitization and subsequent treatment are facilitated, and the performance and stability of the final anode material are ensured.
3. The lithium ion battery cathode material prepared by the method has stable electrical property and has the specific capacity of more than 340mAh in a lithium battery cathode; the first charge and discharge efficiency is high and can reach 97.68 percent at most; the cycle performance is excellent, the cycle retention rate is 96.23% after 300 weeks, and the attenuation resistance is outstanding.
4. According to the invention, the medium-low temperature coal tar is used as a raw material to prepare the lithium battery anode material, so that not only is the stability and electrical performance of the preparation of the anode material improved, but also a new way is provided for deep processing of the medium-low temperature coal tar, and the added value of the medium-low temperature coal tar is improved.
Drawings
FIG. 1 is a scanning electron microscope picture of the negative electrode material of the lithium battery prepared in example 2;
fig. 2 is a scanning electron microscope picture of the negative electrode material of the lithium battery prepared in example 5.
Detailed Description
The invention will now be described in detail with reference to the drawings and examples.
The method for preparing the negative electrode material by using the medium-low temperature coal tar is characterized in that the medium-low temperature coal tar raw material is cut by fractions, and the negative electrode material of the lithium battery can be obtained by blending the raw material, carbonizing and graphitizing.
The preparation method provided by the invention comprises the following specific steps:
1) Pretreatment of raw materials
Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2) Separation and blending
2.1 Sequentially adopting normal alkane solution, monocyclic hydrocarbon aromatic hydrocarbon solution and quinoline solution to extract and separate the fraction section asphalt of 350-520 ℃ in the step 1) for three times, and respectively correspondingly obtaining normal alkane soluble HS component, normal alkane insoluble monocyclic aromatic hydrocarbon soluble HI-TS component and monocyclic aromatic hydrocarbon insoluble quinoline soluble TI-QS component;
the specific separation method comprises the following steps:
2.1.1 Mixing the fraction asphalt at 350-520 ℃ with normal alkane solution, carrying out primary extraction reaction under the stirring condition, and standing to obtain primary supernatant and lower asphalt HI; separating normal alkane soluble substances HS from the primary supernatant, and drying the lower asphalt HI;
2.1.2 Mixing the lower asphalt HI obtained in the step 2.1.1) with a monocyclic hydrocarbon aromatic hydrocarbon solution, carrying out secondary extraction reaction under the stirring condition, standing to obtain a secondary supernatant and lower asphalt TI, and separating an n-alkane insoluble monocyclic aromatic hydrocarbon soluble HI-TS from the secondary supernatant; drying the lower asphalt TI;
2.1.3 Mixing the lower asphalt TI obtained in the step 2.1.2) with a quinoline solution, carrying out three extraction reactions under the stirring condition, and standing to obtain three supernatant and lower asphalt; separating monocyclic aromatic hydrocarbon insoluble quinoline soluble TI-QS from the third supernatant; taking the lower asphalt layer and drying to obtain quinoline insoluble QI;
2.2 Preparing an normal alkane soluble matter HS component, an normal alkane insoluble monocyclic aromatic hydrocarbon soluble matter HI-TS component and a monocyclic aromatic hydrocarbon insoluble quinoline soluble matter TI-QS component which are obtained in the step 2.1);
in the steps 2.1.1) to 2.1.3), the conditions of the three extraction reactions are the same; the method comprises the following steps: the extraction temperature is 60-80 ℃; stirring speed is 1800-2200 r/min, stirring time is 10-40 min, and standing time is 0.5-1.5 h.
In the step 2.1.1) of the invention, the normal alkane is one of C7-C10 normal alkanes. In particular to one or more of n-heptane, n-octane, nonane and decane.
In the step 2.1.2) of the invention, the monocyclic hydrocarbon aromatic hydrocarbon is one of C7-C9. In particular to one or more of benzene, toluene and xylene.
2.2 Blending the normal alkane soluble substance HS component, the normal alkane insoluble monocyclic aromatic hydrocarbon soluble substance HI-TS component and the monocyclic aromatic hydrocarbon insoluble quinoline soluble substance TI-QS component separated in the step 2.1) to obtain a blending raw material which does not contain original QI and has proper composition; the mass ratio of the normal alkane soluble HS component to the normal alkane insoluble monocyclic aromatic hydrocarbon soluble HI-TS component to the monocyclic aromatic hydrocarbon insoluble quinoline soluble TI-QS component is 20% -40%: 60% -75%: 1% -10%;
3) The prepared raw materials obtained in the step 2) are subjected to carbonization reaction to generate semicoke;
the carbonization conditions are as follows: heating to 380-440 ℃ at the temperature rising rate of 3-5 ℃/min under the pressure of 3-5 MPa, and keeping the temperature for 6-10 h; then heating to 480-520 ℃ at the temperature rising rate of 0.5-1.5 ℃/min under the pressure of 0.2-1 MPa, and keeping the temperature for 8-12 h; the carbonization process adopts two-stage heating carbonization, so that the stability of the carbonized precursor is ensured, and the subsequent graphitization and subsequent treatment are facilitated;
4) And (3) carrying out graphitization reaction on the semicoke in the step (3) to obtain a lithium battery anode material, wherein graphitization conditions are as follows: the temperature is 2800-3200 ℃; the temperature rising rate is 5-8 ℃/min, and the graphitization time is 6-12 h.
In the invention, the reaction equipment of each step, and the extraction reaction is carried out in a reaction kettle; the graphitization reaction is carried out in a graphitization furnace, the carbonization reaction is carried out in a carbonization furnace, and other instruments and equipment participating in the reaction are all conventional products; the adopted reagent and medicine are purchased from the market.
The lithium battery anode material obtained by the preparation method provided by the invention has stable and good electrical property, and the specific capacity of the lithium battery anode material is as high as more than 340 mAh; the first charge and discharge efficiency is high and can reach 97.68 percent at most; the cycle performance is excellent, the cycle retention rate is 96.23% after 300 weeks, the attenuation resistance is outstanding, a new way is provided for deep processing of medium-low temperature coal tar, the added value is improved, and the method has good popularization significance.
The following describes the preparation method of the negative electrode material for lithium batteries according to the present invention in several specific examples.
Example 1
The method for preparing the lithium battery anode material by using the medium-low temperature coal tar provided by the embodiment comprises the following steps:
1) Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2.1 350-520 ℃ fraction section asphalt separation and blending
2.1.1 Weighing 150g of asphalt at the fraction stage of 350-520 ℃, placing the asphalt into a reaction kettle containing 300g of n-heptane solvent, firstly heating the reaction kettle to 65 ℃, stirring for 10min at the rotation speed of 1800r/min for primary extraction reaction, and then standing for 1h to obtain primary supernatant and lower asphalt HI; taking out the supernatant liquid once, and separating out the n-heptane solvent to obtain an n-heptane soluble substance HS; taking out the lower asphalt HI and drying for later use;
2.1.2 Placing the lower asphalt HI of 2.1.1) into a reaction kettle containing 300g of toluene solvent, firstly heating the reaction kettle to 65 ℃, stirring for 10min at the rotation speed of 1800r/min to perform secondary extraction reaction, then standing for 1h to obtain secondary supernatant and lower asphalt TI, and separating the toluene solvent from the secondary supernatant to obtain n-heptane insoluble toluene soluble HI-TS; taking out and drying the lower asphalt TI;
2.1.3 2.1.2) of the lower asphalt TI is put into a reaction kettle containing 100g of quinoline solvent, the temperature of the reaction kettle is firstly increased to 65 ℃, the mixture is stirred for 10min to generate three extraction reactions at the rotation speed of 1800r/min, and then the mixture is stood for 1h to obtain three supernatant and lower asphalt. Finally, taking out the supernatant liquid of three times to separate the quinoline solvent to obtain a toluene insoluble quinoline soluble TI-QS; and taking out and drying the lower asphalt layer to obtain quinoline insoluble QI.
2.2 The obtained n-heptane soluble matter HS, n-heptane insoluble toluene soluble matter HI-TS and toluene insoluble quinoline soluble matter TI-QS are blended according to the mass ratio of 25 percent to 70 percent to 5 percent to obtain a blending raw material;
3) Heating the blended raw materials to 400 ℃ at a heating rate of 3MPa and 5 ℃/min, keeping the temperature for 8 hours for primary carbonization reaction, and then heating to 480 ℃ at a heating rate of 0.5MPa and 1.5 ℃/min for secondary carbonization reaction at a constant temperature for 8 hours to obtain a semicoke product, namely a cathode material precursor;
4) And (3) placing the anode material precursor into a graphitization furnace, heating to 2800 ℃ at a speed of 5 ℃/min, and performing graphitization reaction treatment at a constant temperature for 6 hours to obtain the anode material of the lithium battery.
Example 2
The method for preparing the lithium battery anode material by using the medium-low temperature coal tar provided by the embodiment comprises the following steps:
1) Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2.1 350-520 ℃ fraction section asphalt separation and blending
2.1.1 Weighing 150g of asphalt at the fraction stage of 350-520 ℃, placing the asphalt into a reaction kettle containing 300g of n-heptane solvent, heating the reaction kettle to 75 ℃, stirring for 30min at the rotation speed of 2000r/min for primary extraction reaction, and standing for 1h to obtain primary supernatant and lower asphalt TI; taking out the supernatant liquid once, and separating out the n-heptane solvent to obtain an n-heptane soluble substance HS; taking out the lower asphalt HI and drying for later use;
2.1.2 Placing the lower asphalt HI obtained in 2.1.1) into a reaction kettle containing 300g of toluene solvent, firstly heating the reaction kettle to 75 ℃, stirring for 30min at the rotation speed of 2000r/min to perform secondary extraction reaction, and standing for 1h to obtain secondary supernatant and lower asphalt TI; finally, taking out the secondary supernatant to separate out toluene solvent to obtain an n-heptane insoluble toluene soluble matter HI-TS; taking out the lower asphalt TI and drying for later use;
2.1.3 2.1.2) obtaining lower asphalt TI, putting the lower asphalt TI into a reaction kettle containing 100g of quinoline solvent, firstly heating the reaction kettle to 75 ℃, stirring for 30min at the rotation speed of 2000r/min to perform three extraction reactions, and standing for 1h to obtain three supernatant and lower asphalt QI; finally, taking out the supernatant liquid of three times, and carrying out suction filtration to separate out a quinoline solvent to obtain a toluene insoluble quinoline soluble TI-QS; taking out the lower asphalt QI, and drying the residual solvent to obtain quinoline insoluble QI;
2.2 The obtained n-heptane soluble matter HS, n-heptane insoluble toluene soluble matter HI-TS and toluene insoluble quinoline soluble matter TI-QS are blended according to the mass ratio of 20 percent to 73 percent to 7 percent to obtain a blending raw material;
3) Heating the blended raw materials to 420 ℃ at a heating rate of 4MPa and 3 ℃/min, and keeping the temperature for 10 hours for primary carbonization reaction; then heating to 500 ℃ under the heating rate of 0.2MPa and 0.5 ℃/min, and keeping the temperature for 10 hours for secondary carbonization reaction to obtain a cathode material precursor;
4) And (3) placing the prepared anode material precursor in a graphitization furnace, heating to 2800 ℃ at a speed of 5 ℃/min, and performing graphitization reaction treatment at a constant temperature for 8 hours to obtain the anode material of the lithium battery.
Example 3
The method for preparing the lithium battery anode material by using the medium-low temperature coal tar provided by the embodiment comprises the following steps:
1) Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2.1 350-520 ℃ fraction section asphalt separation and blending
2.1.1 Weighing 150g of asphalt at the fraction stage of 350-520 ℃, placing the asphalt into a reaction kettle containing 300g of n-heptane solvent, firstly heating the reaction kettle to 80 ℃, stirring for 45min at the rotation speed of 2100r/min for primary extraction reaction, and standing for 1h to obtain primary supernatant and lower asphalt HI; taking out the supernatant liquid once, and separating out the n-heptane solvent to obtain an n-heptane soluble substance HS; taking out the lower asphalt HI and drying for later use;
2.1.2 Placing the lower asphalt HI obtained in the step 2.1.1) into a reaction kettle containing 300g of toluene solvent; firstly, heating the temperature of a reaction kettle to 80 ℃, stirring for 45min at a rotation speed of 2100r/min to perform secondary extraction reaction, and standing for 1h to obtain secondary supernatant and lower asphalt TI; taking out the secondary supernatant, and separating out toluene solvent to obtain n-heptane insoluble toluene soluble matter HI-TS; taking out the lower asphalt TI and drying for later use;
2.1.3 Placing the lower asphalt TI obtained in the step 2.1.2) into a reaction kettle containing 100g of quinoline solvent; firstly, heating the temperature of a reaction kettle to 80 ℃, stirring for 45min at a rotation speed of 2100r/min to perform three extraction reactions, and standing for 1h to obtain three supernatant and lower asphalt QI; taking out the supernatant liquid of the three times, and separating out the quinoline solvent to obtain a toluene insoluble quinoline soluble TI-QS; taking out the lower asphalt QI, and drying the residual solvent to obtain quinoline insoluble QI;
2.2 The obtained n-heptane soluble matter HS, n-heptane insoluble toluene soluble matter HI-TS and toluene insoluble quinoline soluble matter TI-QS are blended according to the mass ratio of 30 percent to 65 percent to 5 percent to obtain a blending raw material;
3) Heating the blended raw materials to 400 ℃ at a heating rate of 3MPa and 5 ℃/min, keeping the temperature for 8 hours for primary carbonization reaction, and then heating to 480 ℃ at a heating rate of 0.5MPa and 1.5 ℃/min for secondary carbonization reaction at the temperature for 8 hours to obtain a cathode material precursor;
4) And (3) placing the prepared anode material precursor in a graphitization furnace, heating to 2800 ℃ at a speed of 5 ℃/min, and performing graphitization reaction treatment at a constant temperature for 8 hours to obtain the anode material of the lithium battery.
Example 4
The method for preparing the lithium battery anode material by using the medium-low temperature coal tar provided by the embodiment comprises the following steps:
1) Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2.1 350-520 ℃ fraction section asphalt separation and blending
2.1.1 Weighing 150g of asphalt at the fraction stage of 350-520 ℃, placing the asphalt into a reaction kettle containing 300g of n-heptane solvent, firstly heating the reaction kettle to 75 ℃, stirring for 30min at the rotating speed of 2000r/min for primary extraction reaction, and standing for 1h to obtain primary supernatant and lower asphalt HI; finally taking out the supernatant liquid once, and separating out the n-heptane solvent to obtain an n-heptane soluble substance HS; taking out the lower asphalt HI and drying for later use;
2.1.2 Placing the lower asphalt HI obtained in the step 2.1.1) into a reaction kettle containing 300g of toluene solvent. Firstly, heating the temperature of a reaction kettle to 75 ℃, stirring for 30min at a rotating speed of 2000r/min to perform secondary extraction reaction, and standing for 1h to obtain secondary supernatant and lower asphalt TI; finally taking out the secondary supernatant, and separating out toluene solvent to obtain n-heptane insoluble toluene soluble matter HI-TS; taking out the lower asphalt TI and drying for later use;
2.1.3 Placing the lower asphalt TI obtained in the step 2.1.2) into a reaction kettle containing 100g of quinoline solvent. Firstly, heating the temperature of a reaction kettle to 75 ℃, stirring for 30min at a rotating speed of 2000r/min to perform three extraction reactions, and standing for 1h to obtain three supernatant and lower asphalt QI; finally taking out the supernatant liquid of three times, and separating out the quinoline solvent to obtain a toluene insoluble quinoline soluble TI-QS; taking out the lower asphalt QI, and drying the residual solvent to obtain quinoline insoluble QI;
2.2 Mixing the n-heptane soluble matter HS, the n-heptane insoluble toluene soluble matter HI-TS and the toluene insoluble quinoline soluble matter TI-QS obtained in the step 2.1) according to the mass ratio of 40% to 50% to 10% to obtain a mixed raw material;
3) Heating the blended raw materials to 420 ℃ at a heating rate of 4MPa and 3 ℃/min, keeping the temperature for 10 hours for primary carbonization reaction, and then heating to 500 ℃ at a heating rate of 0.2MPa and 0.5 ℃/min for secondary carbonization reaction at a constant temperature for 8 hours to obtain a cathode material precursor;
4) And (3) placing the prepared anode material precursor in a graphitization furnace, heating to 2800 ℃ at a speed of 5 ℃/min, and performing graphitization reaction treatment at a constant temperature for 8 hours to obtain the anode material of the lithium battery.
Example 5
The method for preparing the lithium battery anode material by using the medium-low temperature coal tar provided by the embodiment comprises the following steps:
1) Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2.1 350-520 ℃ fraction section asphalt separation and blending
2.1.1 150g of asphalt with the cut fraction at 350-520 ℃ is weighed and put into a reaction kettle containing 300g of n-heptane solvent; firstly, heating the temperature of a reaction kettle to 75 ℃, stirring for 45min at a rotating speed of 2000r/min to perform primary extraction reaction, and standing for 3h to obtain primary supernatant and lower asphalt HI; finally taking out the supernatant liquid once, and separating out the n-heptane solvent to obtain an n-heptane soluble substance HS; taking out the lower asphalt HI and drying for later use;
2.1.2 Placing the lower asphalt HI obtained in the step 2.1.1) into a reaction kettle containing 300g of toluene solvent. Firstly, heating the temperature of a reaction kettle to 75 ℃, stirring for 45min at a rotating speed of 2000r/min to perform secondary extraction reaction, and standing for 3h to obtain secondary supernatant and lower asphalt TI; finally taking out the secondary supernatant, and separating out toluene solvent to obtain n-heptane insoluble toluene soluble matter HI-TS; taking out the lower asphalt TI and drying for later use;
2.1.3 Placing the lower asphalt HI obtained in the step 2.1.2) into a reaction kettle containing 100g of quinoline solvent. Firstly, heating the temperature of a reaction kettle to 75 ℃, stirring for 45min at a rotating speed of 2000r/min to perform three extraction reactions, and standing for 3h to obtain three supernatant and lower asphalt QI; finally taking out the supernatant liquid of three times, and separating out the quinoline solvent to obtain a toluene insoluble quinoline soluble TI-QS; taking out the lower asphalt QI, and drying the residual solvent to obtain quinoline insoluble QI;
2.2 Preparing the n-heptane soluble matter HS, the n-heptane insoluble toluene soluble matter HI-TS and the toluene insoluble quinoline soluble matter TI-QS obtained in the step 2.1) according to the mass ratio of 20 percent to 73 percent to 7 percent to obtain a prepared raw material;
3) Heating the blended raw materials to 420 ℃ at a heating rate of 4MPa and 3 ℃/min, keeping the temperature for 10 hours for primary carbonization reaction, and then heating to 480 ℃ at a heating rate of 0.2MPa and 0.5 ℃/min for secondary carbonization reaction at the temperature for 10 hours to obtain a cathode material precursor;
4) And (3) placing the prepared anode material precursor in a graphitization furnace, heating to 2800 ℃ at a speed of 5 ℃/min, and performing graphitization reaction treatment at a constant temperature for 8 hours to obtain the anode material of the lithium battery.
Example 6
The method for preparing the lithium battery anode material by using the medium-low temperature coal tar provided by the embodiment comprises the following steps:
1) Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2.1 350-520 ℃ fraction section asphalt separation and blending
2.1.1 150g of asphalt with the cut fraction at 350-520 ℃ is weighed and put into a reaction kettle containing 300g of n-heptane solvent; firstly, heating the temperature of a reaction kettle to 75 ℃, stirring for 30min at a rotating speed of 2000r/min to perform primary extraction reaction, and standing for 1h to obtain primary supernatant and lower asphalt HI; finally taking out the supernatant liquid once, and separating out the n-heptane solvent to obtain an n-heptane soluble substance HS; taking out the lower asphalt HI and drying for later use;
2.1.2 Placing the lower asphalt HI obtained in the step 2.1.1) into a reaction kettle containing 300g of toluene solvent; firstly, heating the temperature of a reaction kettle to 75 ℃, stirring for 30min at a rotating speed of 2000r/min to perform secondary extraction reaction, and standing for 1h to obtain secondary supernatant and lower asphalt TI; finally taking out the secondary supernatant, and separating out toluene solvent to obtain n-heptane insoluble toluene cocoa HI-TS; taking out the lower asphalt TI and drying for later use;
2.1.3 Placing the lower asphalt HI obtained in the step 2.1.2) into a reaction kettle containing 100g of quinoline solvent; firstly, heating the temperature of a reaction kettle to 75 ℃, stirring for 30min at a rotating speed of 2000r/min to perform three extraction reactions, and standing for 1h to obtain three supernatant and lower asphalt QI; finally taking out the supernatant liquid of three times, and separating out the quinoline solvent to obtain a toluene insoluble quinoline soluble TI-QS; taking out the lower asphalt QI, and drying the residual solvent to obtain quinoline insoluble QI;
2.2 Preparing the n-heptane soluble matter HS, the n-heptane soluble toluene insoluble matter HI-TS and the toluene insoluble quinoline soluble matter TI-QS obtained in the step 2.1) according to the mass ratio of 20 percent to 73 percent to 7 percent to obtain a prepared raw material;
3) Heating the blended raw materials to 420 ℃ at a heating rate of 4MPa and 3 ℃/min, keeping the temperature for 10 hours for primary carbonization reaction, and then heating to 480 ℃ at a heating rate of 0.2MPa and 0.5 ℃/min for secondary carbonization reaction at a constant temperature for 8 hours to obtain a cathode material precursor;
4) And (3) placing the prepared anode material precursor in a graphitization furnace, heating to 2800 ℃ at a speed of 5 ℃/min, and performing graphitization reaction treatment at a constant temperature for 8 hours to obtain the anode material of the lithium battery.
Further, the performance of the anode material prepared by the method of the present invention was studied by the following test.
Test 1 microstructure
The microstructure of the anode materials obtained in example 2 and example 5 was analyzed.
The specific method is as follows:
the microscopic appearance of the product was observed by using a ZEISS SIGMA scanning electron microscope from the two materials prepared in example 2 and example 5, and a scanning electron microscope image of the negative electrode material was obtained, and the results are shown in fig. 1 and 2.
As can be seen from the results of fig. 1 and 2, the materials produced in example 2 and example 5 all had a structure with a main body of stacked and regular layers. When the material with the structure is used as an electrode, the electrode has high integrity and flexibility, is favorable for the transmission of ions/charges between electrode interfaces, and has high capacity and excellent cycle stability.
Test 2 electrochemical Properties
Further, the prepared material is used as a negative electrode, so that a lithium battery is prepared, and the battery performance of the lithium battery is detected.
The specific process is as follows:
6 groups of lithium battery materials prepared in examples 1-6 are selected to be respectively used as negative electrodes, and lithium sheets are adopted as positive electrodes to prepare button lithium batteries; next, button lithium batteries were tested by using a combined battery test system, respectively, to obtain electrical performance parameters of 6 groups of lithium battery materials, and the results are shown in table 1.
Table 1 performance parameters of lithium batteries prepared with negative electrode materials
As can be seen from Table 1, the electrode materials prepared in examples 1 to 6 were discharged for the first time up to 382mAh/g when applied as a negative electrode of a lithium battery; the highest charge and discharge efficiency can reach 97.68 percent for the first time; the retention was 96.23% over 300 weeks of circulation. Compared with the existing similar lithium battery cathode materials in the market, the cathode material has stable electrical property, excellent cycle performance and outstanding attenuation resistance.
The above examples only list several groups of test results, and the lithium battery anode materials prepared by adopting other preparation parameters provided by the invention have the structure of stacked and regular lamellar structures, and the electrochemical performance is in the range shown in Table 1, namely, the first charge is 328-355 mAh/g, and the first discharge is 343-382 mAh/g; the first efficiency is within 93.42-97.68%, the cycle is 300 weeks, the electrochemical performance retention rate is within 91.23-96.23%, and the novel method provided by the invention is capable of preparing the lithium battery anode material from the medium-low temperature coal tar, is novel and excellent, is feasible, not only improves the added value of the medium-low temperature coal tar, but also has popularization and application values.
Claims (7)
1. The method for preparing the lithium battery anode material by using the medium-low temperature coal tar is characterized by comprising the following steps of:
1) Pretreatment of raw materials
Cutting the medium-low temperature coal tar raw material into fractions to obtain 350-520 ℃ fraction section asphalt;
2) Separation and blending
2.1 Sequentially adopting normal alkane solution, monocyclic hydrocarbon aromatic hydrocarbon solution and quinoline solution to extract and separate the fraction section asphalt at the temperature of 350-520 ℃ in the step 1) for three times, and respectively correspondingly obtaining an normal alkane soluble HS component, an normal alkane insoluble monocyclic aromatic hydrocarbon soluble HI-TS component and a monocyclic aromatic hydrocarbon insoluble quinoline soluble TI-QS component;
in the step 2.1), the specific process of extraction and separation is as follows:
2.1.1 Mixing the fraction asphalt at 350-520 ℃ with normal alkane solution, carrying out primary extraction reaction under the stirring condition, and standing to obtain primary supernatant and lower asphalt HI; separating normal alkane soluble substances HS from the primary supernatant, and drying the lower asphalt HI;
2.1.2 Mixing the lower asphalt HI obtained in the step 2.1.1) with a monocyclic hydrocarbon aromatic hydrocarbon solution, carrying out secondary extraction reaction under the stirring condition, standing to obtain a secondary supernatant and lower asphalt TI, and separating an n-alkane insoluble monocyclic aromatic hydrocarbon soluble HI-TS from the secondary supernatant; drying the lower asphalt TI;
2.1.3 Mixing the lower asphalt TI obtained in the step 2.1.2) with a quinoline solution, carrying out three extraction reactions under the stirring condition, and standing to obtain three supernatant and lower asphalt; separating monocyclic aromatic hydrocarbon insoluble quinoline soluble TI-QS from the third supernatant; taking the lower asphalt layer and drying to obtain quinoline insoluble QI;
2.2 Preparing an normal alkane soluble matter HS component, an normal alkane insoluble monocyclic aromatic hydrocarbon soluble matter HI-TS component and a monocyclic aromatic hydrocarbon insoluble quinoline soluble matter TI-QS component which are obtained in the step 2.1);
in the step 2.2), the mass ratio of the normal alkane soluble matter HS component, the normal alkane insoluble monocyclic aromatic hydrocarbon soluble matter HI-TS component and the monocyclic aromatic hydrocarbon insoluble quinoline soluble matter TI-QS component is 20% -40%: 60% -75%: 1% -10%;
3) The prepared raw materials obtained in the step 2) are subjected to carbonization reaction to generate semicoke;
in the step 3), the carbonization conditions are as follows: heating to 380-440 ℃ at the temperature rising rate of 3-5 ℃/min under the pressure of 3-5 MPa, and keeping the temperature for 6-10 h; then heating to 480-520 ℃ at the temperature rising rate of 0.5-1.5 ℃/min under the pressure of 0.2-1 MPa, and keeping the temperature for 8-12 h;
4) And (3) graphitizing the semicoke obtained in the step (3) to obtain the lithium battery anode material.
2. The method for preparing the lithium battery anode material by using the medium-low temperature coal tar according to claim 1, wherein in the steps 2.1.1) to 2.1.3), the conditions of the three extraction reactions are the same, and the conditions are as follows: the extraction temperature is 60-80 ℃, the stirring rotation speed is 1800-2200r/min, the stirring time is 10-60 min, and the standing time is 0.5-3 h.
3. The method for preparing the lithium battery anode material by using the medium-low temperature coal tar according to claim 2, wherein in the step 2.1.1), the normal alkane is one or more of C7-C10 normal alkanes.
4. The method for preparing the lithium battery anode material by using the medium-low temperature coal tar according to claim 2, wherein in the step 2.1.2), the monocyclic hydrocarbon aromatic hydrocarbon is one or more of benzene, toluene and xylene.
5. The method for preparing the lithium battery anode material by using the medium-low temperature coal tar according to claim 1, wherein in the step 4), the graphitization reaction temperature is 2800-3200 ℃, the heating rate is 5-8 ℃/min, and the graphitization time is 6-12 h.
6. A lithium battery anode material prepared by the method for preparing a lithium battery anode material by using medium-low temperature coal tar according to claim 1.
7. Use of the negative electrode material for lithium batteries according to claim 6 as a negative electrode in lithium batteries.
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