Mesophase semicoke as well as preparation method and application thereof

Abstract

The invention discloses intermediate-phase semicoke as well as a preparation method and application thereof, and belongs to the technical field of preparation of needle coke. The preparation method of the intermediate-phase semi-coke comprises the following steps: mixing and co-carbonizing organic solvent soluble components of biological asphalt and hydrogenated anthracene oil to obtain the intermediate-phase semi-coke. The method provided by the invention has the advantages of low cost and simple process, and the prepared intermediate phase semicoke has excellent performance and is suitable for production of needle coke.

Description

Technical Field

[0001] The present invention relates to the technical field of needle coke preparation, and particularly relates to a mesophase semicoke, a preparation method thereof, and an application thereof. Background Art

[0002] Mesophase semicoke is a carbonaceous intermediate product with a unique chemical structure and physical properties generated during the pyrolysis process using polycyclic aromatic hydrocarbons such as pitch as raw materials. It can be used in fields such as anode materials for lithium-ion batteries, electrode materials for supercapacitors, adsorption materials, needle coke precursors, and catalyst carriers.

[0003] Currently, mesophase semicoke and needle coke are mainly divided into two types: coal-based and petroleum-based according to their raw materials. Among them, the coal-based type uses high-temperature coal tar pitch as the raw material, while the petroleum-based type mainly uses refinery by-products such as catalytic cracking slurry and ethylene tar as raw materials. Due to the lack or low content of alkane side chains in coal pitch, the viscosity of the system is likely to increase during the mesophase carbonization process, thereby reducing fluidity and being unfavorable for the development of an ordered mesophase structure. Although the content of alkane and cycloalkane components in petroleum pitch is higher than that of coal pitch, which is beneficial to the development of the mesophase, however, the excessively high content of aliphatic hydrocarbons results in too high a reaction activity of the mesophase, making it difficult to reasonably control the coking pressure, time, and temperature, leading to a fast carbonization reaction rate. The mesophase is rapidly generated and rapidly solidified at a lower temperature, forming more mosaic tissue structures, reducing the orderliness of the mesophase semicoke structure, and not being suitable for actual production. Summary of the Invention

[0004] The purpose of the present invention is to provide a mesophase semicoke, a preparation method thereof, and an application thereof to solve the problems existing in the above-mentioned prior art.

[0005] To achieve the above purpose, the present invention provides the following solutions:

[0006] One of the technical solutions of the present invention: A preparation method of a mesophase semicoke, comprising the following steps:

[0007] Mix the organic solvent-soluble component of bio-pitch and hydrogenated anthracene oil for co-carbonization to obtain the mesophase semicoke.

[0008] Further, the mass ratio of the organic solvent-soluble component of bio-pitch to hydrogenated anthracene oil is 3:7.

[0009] Further, the preparation method of the organic solvent-soluble component of bio-pitch comprises the following steps:

[0010] Mix bio-pitch with an organic solvent, heat and stir for reaction, then filter, take the filtrate and remove the organic solvent to obtain the organic solvent-soluble component of bio-pitch.

[0011] Further, the organic solvent includes n-hexane, tetrahydrofuran, or toluene.

[0012] Further, the temperature of the heating and stirring reaction is 70 °C, the time is 1 - 2 h, and the stirring speed is 100 - 200 rpm.

[0013] Further, the preparation method of the hydrogenated anthracene oil includes the following steps:

[0014] Mix anthracene oil and a hydrogenation agent, and perform a heating and stirring reaction to obtain the hydrogenated anthracene oil.

[0015] Further, the hydrogenation agent includes tetralin; the stirring speed of the heating and stirring reaction is 200 - 250 rpm, the temperature is 400 - 430 °C, and the time is 1 h.

[0016] Furthermore, the mass ratio of the anthracene oil to the hydrogenation agent is 400:(10 - 160).

[0017] Further, the co - carbonization includes: first heating to 360 °C at a rate of 3 °C / min and holding for 2 h, then heating to 420 °C at a rate of 1.5 °C / min and holding for 3 h, while maintaining the pressure at 2 Mpa; then reducing the pressure to 0.5 Mpa and holding at 400 - 430 °C for 3 - 5 h.

[0018] The second technical solution of the present invention: A mesophase semicoke prepared by the above - mentioned preparation method.

[0019] The third technical solution of the present invention: An application of the above - mentioned mesophase semicoke as a negative electrode material for lithium - ion batteries, an electrode material for supercapacitors, an adsorption material, a precursor for needle coke, or a catalyst support.

[0020] The present invention discloses the following technical effects:

[0021] The method of the present invention has the advantages of low cost and simple process. The optical texture of the prepared mesophase semicoke is mainly composed of fiber structures and domain structures with a relatively high degree of order, and has excellent properties, being suitable for the production of needle coke.

[0022] The present invention utilizes the characteristic of high oxygen content in bio - bitumen, and can rapidly generate mesophase semicoke with hydrogenated activated anthracene oil at a relatively low temperature, which is of great significance for the development and utilization of anthracene oil and biomass. Description of the Drawings

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0024] Figure 1 1H NMR spectra of the hydrogenated anthracene oil prepared in Example 1 at different temperatures; 1 ;

[0025] Figure 2 1H NMR spectra of the hydrogenated anthracene oil prepared in Example 2 with different dosages of hydrogenation agent; 1 ;

[0026] Figure 3 Polarized light photographs of the mesophase semicoke prepared in Example 4;

[0027] Figure 4 Polarized light photographs of the mesophase semicoke prepared in Example 4 after calcination at 1300 °C for 1 h;

[0028] Figure 5 XRD spectra of the mesophase semicoke MC-4 (i.e., MC-420) prepared in Example 4, the mesophase semicoke MC-3 prepared in Example 7, and the mesophase semicoke MC-5 prepared in Example 8;

[0029] Figure 6 XRD spectra of the mesophase semicoke MC-415 prepared in Example 3, the mesophase semicoke MC-420 prepared in Example 4, the mesophase semicoke MC-425 prepared in Example 5, and the mesophase semicoke MC-430 prepared in Example 6;

[0030] Figure 7 Polarized light photographs of the mesophase semicoke prepared in Comparative Example 2;

[0031] Figure 8 Polarized light photographs of the mesophase semicoke prepared in Comparative Example 2 after calcination at 1300 °C for 1 h. Detailed Description of the Invention

[0032] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and embodiments of the present invention.

[0033] It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0034] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although this invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of this invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the said documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0035] Without departing from the scope or spirit of this invention, various improvements and changes can be made to the specific embodiments of the specification of this invention, which are obvious to those skilled in the art. Other embodiments obtained from the specification of this invention are obvious to those skilled in the art. The specification and examples of this invention are merely exemplary.

[0036] Regarding the use of "comprising", "including", "having", "containing", etc. in this article, they are all open-ended terms, meaning including but not limited to.

[0037] Anthracene oil is a primary processed product obtained by high-temperature distillation of coal tar. The fraction with a cutting temperature range of 280 - 360 °C contains bicyclic aromatic hydrocarbons, tricyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons, a small amount of gum, and a small amount of asphaltene, and the aromatic hydrocarbon content is above 90%. Currently, anthracene oil mainly has three uses: one is to concentrate and separate anthracene oil to produce products such as crude anthracene, refined anthracene, phenanthrene oil, and carbazole; the second is to blend and produce carbon black oil, fuel oil, or asphalt as a blending oil; the third is to carry out hydro-upgrading of anthracene oil to produce light fuel oil.

[0038] Bio-asphalt is obtained by chemically processing bio-oil through distillation, extraction, oxidation, etc. It has the advantages of wide sources, low price, renewable, and good economic benefits. Different from coal tar pitch and petroleum asphalt, bio-asphalt has the characteristics of lower aromaticity, higher oxygen content, and larger molecular weight distribution. Currently, most biomass is directly burned for power generation, resulting in serious underutilization of biomass and causing certain pollution to the environment. No technical solution for preparing mesophase semicoke using anthracene oil and bio-asphalt has been found in the prior art.

[0039] The main components and contents of the anthracene oil used in the specific embodiments of this invention are shown in Table 1.

[0040] Table 1 Main components and contents of anthracene oil

[0041]

[0042] The bio-asphalt used in the specific embodiments of this invention is a by-product of the high-temperature pyrolysis of pine wood, and then is obtained through chemical processes for preparing conventional bio-asphalt such as distillation and extraction.

[0043] Example 1

[0044] Preparation method of hydrogenated anthracene oil:

[0045] Mix 400 g of refined anthracene oil and 120 g of tetralin and place them in a high-pressure reactor for continuous stirring at a stirring speed of 250 rpm. Heat the temperature to 400 °C, 410 °C, 420 °C or 430 °C respectively, and keep for 1 h to obtain 4 kinds of hydrogenated anthracene oil.

[0046] The 1 1H NMR spectra of the hydrogenated anthracene oil prepared in this example are shown in Figure 1 .

[0047] It can be seen from Figure 1 that the hydrogen atoms in anthracene oil can be divided into aliphatic hydrogen and aromatic hydrogen according to the 1 chemical shift of 1H NMR spectra. The chemical shift value of aromatic hydrogen H ar is in the range of 9.0 - 6.0 ppm, and the chemical shift value of aliphatic hydrogen H al is distributed in the region of 4.5 - 0.5 ppm. Among them, the chemical shift of 4.5 - 3.3 ppm is the hydrogen atom H F on the methylene group connecting two aromatic carbons, the chemical shift of 2.0 - 1.5 ppm is the α-position hydrogen atom H α of the methyl or methylene group connected to the benzene ring, the chemical shift of 1.5 - 1.0 ppm is the β-position hydrogen atom H β of the methyl or methylene group connected to the benzene ring, and the chemical shift of 1.0 - 0.5 ppm is the γ-position hydrogen atom H γ of the methyl or methylene group connected to the benzene ring. And it can be seen from Figure 1 that the highest aliphatic hydrogen content is obtained at 410 °C.

[0048] Example 2

[0049] Preparation method of hydrogenated anthracene oil:

[0050] Mix 400 g of refined anthracene oil and tetralin (0 g (0%), 40 g (10%), 80 g (20%), 120 g (30%) or 160 g (40%)) and place them in a high-pressure reactor for continuous stirring at a stirring speed of 250 rpm. Heat to 410 °C and keep for 1 h to obtain hydrogenated anthracene oil.

[0051] The 1 1H NMR spectra of the hydrogenated anthracene oil prepared in this example are shown in Figure 2 .

[0052] It can be seen from Figure 2 that the highest aliphatic hydrogen content and the longest aliphatic side chain can be obtained when the content of tetralin is 30%.

[0053] Example 3

[0054] A preparation method of mesophase semicoke:

[0055] (1) Mix 400 g of refined anthracene oil and 120 g of tetralin and put them into a high-pressure reactor, continuously stir at a stirring speed of 250 rpm, raise the heating temperature to 410 °C, and keep for 1 h to obtain hydrogenated anthracene oil.

[0056] (2) Mix the bio-asphalt with an organic solvent (tetrahydrofuran), heat to 70 °C, stir and react for 2 h at a stirring speed of 200 rpm, filter to remove insoluble components, distill the soluble components at 120 °C to recover the organic solvent, and the remaining product is the organic solvent soluble component of bio-asphalt (i.e., refined bio-asphalt).

[0057] (3) Load the refined bio-asphalt and hydrogenated anthracene oil into a 1 L high-pressure reactor according to a mass ratio of 3:7, close the high-pressure reactor, and repeatedly purge the air in the reactor with nitrogen. First, raise the temperature to 360 °C at a rate of 3 °C / min, keep for 2 h, then raise the temperature to 420 °C at a rate of 1.5 °C / min, keep for 3 h, and maintain the pressure at 2 Mpa; then reduce the pressure to 0.5 Mpa, keep at 415 °C for 4 h, and take out the bottom material, which is mesophase semicoke MC-415.

[0058] Example 4

[0059] A preparation method of mesophase semicoke:

[0060] (1) Mix 400 g of refined anthracene oil and 120 g of tetralin and put them into a high-pressure reactor, continuously stir at a stirring speed of 250 rpm, raise the heating temperature to 410 °C, and keep for 1 h to obtain hydrogenated anthracene oil.

[0061] (2) Mix the bio-asphalt with an organic solvent (tetrahydrofuran), heat to 70 °C, stir and react for 2 h at a stirring speed of 200 rpm, filter to remove insoluble components, distill the soluble components at 120 °C to recover the organic solvent, and the remaining product is the organic solvent soluble component of bio-asphalt (i.e., refined bio-asphalt).

[0062] (3) Load the refined bio-asphalt and hydrogenated anthracene oil into a 1 L high-pressure reactor according to a mass ratio of 3:7, close the high-pressure reactor, and repeatedly purge the air in the reactor with nitrogen. First, raise the temperature to 360 °C at a rate of 3 °C / min, keep for 2 h, then raise the temperature to 420 °C at a rate of 1.5 °C / min, keep for 3 h, and maintain the pressure at 2 Mpa; then reduce the pressure to 0.5 Mpa, keep at 420 °C for 4 h, and take out the bottom material, which is mesophase semicoke MC-420 (i.e., MC-4).

[0063] Example 5

[0064] A preparation method of mesophase semicoke:

[0065] (1) Mix 400 g of refined anthracene oil and 120 g of tetralin and put them into a high-pressure reactor for continuous stirring at a stirring speed of 250 rpm. Heat the temperature to 410 °C and keep it for 1 h to obtain hydrogenated anthracene oil.

[0066] (2) Mix bio-asphalt with an organic solvent (tetrahydrofuran), heat it to 70 °C, stir and react for 2 h at a stirring speed of 200 rpm. Filter to remove insoluble components. The soluble components are distilled at 120 °C to recover the organic solvent, and the remaining product is the organic solvent-soluble component of bio-asphalt (i.e., refined bio-asphalt).

[0067] (3) Load refined bio-asphalt and hydrogenated anthracene oil into a 1 L high-pressure reactor according to a mass ratio of 3:7. Seal the high-pressure reactor and repeatedly purge the air in the reactor with nitrogen. First, heat it to 360 °C at a rate of 3 °C / min and keep it for 2 h, then heat it to 420 °C at a rate of 1.5 °C / min and keep it for 3 h, keeping the pressure at 2 Mpa; then reduce the pressure to 0.5 Mpa and keep it at 425 °C for 4 h. Take out the bottom material, which is mesophase semicoke MC-425.

[0068] Example 6

[0069] A preparation method of mesophase semicoke:

[0070] (1) Mix 400 g of refined anthracene oil and 120 g of tetralin and put them into a high-pressure reactor for continuous stirring at a stirring speed of 250 rpm. Heat the temperature to 410 °C and keep it for 1 h to obtain hydrogenated anthracene oil.

[0071] (2) Mix bio-asphalt with an organic solvent (tetrahydrofuran), heat it to 70 °C, stir and react for 2 h at a stirring speed of 200 rpm. Filter to remove insoluble components. The soluble components are distilled at 120 °C to recover the organic solvent, and the remaining product is the organic solvent-soluble component of bio-asphalt (i.e., refined bio-asphalt).

[0072] (3) Load refined bio-asphalt and hydrogenated anthracene oil into a 1 L high-pressure reactor according to a mass ratio of 3:7. Seal the high-pressure reactor and repeatedly purge the air in the reactor with nitrogen. First, heat it to 360 °C at a rate of 3 °C / min and keep it for 2 h, then heat it to 420 °C at a rate of 1.5 °C / min and keep it for 3 h, keeping the pressure at 2 Mpa; then reduce the pressure to 0.5 Mpa and keep it at 430 °C for 4 h. Take out the bottom material, which is mesophase semicoke MC-430.

[0073] Example 7

[0074] A preparation method of mesophase semicoke:

[0075] (1) Mix 400 g of refined anthracene oil and 120 g of tetralin and place them in a high-pressure reactor for continuous stirring. The stirring speed is 250 rpm. Heat the temperature to 410 °C and maintain for 1 h to obtain hydrogenated anthracene oil.

[0076] (2) Mix bio-asphalt with an organic solvent (tetrahydrofuran) and heat to 70 °C, stir and react for 2 h, with a stirring speed of 200 rpm. Filter to remove insoluble components. Distill the soluble components at 120 °C to recover the organic solvent. The remaining product is the organic solvent-soluble component of bio-asphalt (i.e., refined bio-asphalt).

[0077] (3) Load refined bio-asphalt and hydrogenated anthracene oil into a 1 L high-pressure reactor according to a mass ratio of 3:7. Seal the high-pressure reactor and repeatedly purge the air in the reactor with nitrogen. First, heat to 360 °C at a rate of 3 °C / min and hold for 2 h. Then, heat to 420 °C at a rate of 1.5 °C / min and hold for 3 h, maintaining the pressure at 2 Mpa. Then, reduce the pressure to 0.5 Mpa and hold at 420 °C for 3 h. Take out the bottom material, which is mesophase semi-coke MC-3.

[0078] Example 8

[0079] A method for preparing mesophase semi-coke:

[0080] (1) Mix 400 g of refined anthracene oil and 120 g of tetralin and place them in a high-pressure reactor for continuous stirring. The stirring speed is 250 rpm. Heat the temperature to 410 °C and maintain for 1 h to obtain hydrogenated anthracene oil.

[0081] (2) Mix bio-asphalt with an organic solvent (tetrahydrofuran) and heat to 70 °C, stir and react for 2 h, with a stirring speed of 200 rpm. Filter to remove insoluble components. Distill the soluble components at 120 °C to recover the organic solvent. The remaining product is the organic solvent-soluble component of bio-asphalt (i.e., refined bio-asphalt).

[0082] (3) Load refined bio-asphalt and hydrogenated anthracene oil into a 1 L high-pressure reactor according to a mass ratio of 3:7. Seal the high-pressure reactor and repeatedly purge the air in the reactor with nitrogen. First, heat to 360 °C at a rate of 3 °C / min and hold for 2 h. Then, heat to 420 °C at a rate of 1.5 °C / min and hold for 3 h, maintaining the pressure at 2 Mpa. Then, reduce the pressure to 0.5 Mpa and hold at 420 °C for 5 h. Take out the bottom material, which is mesophase semi-coke MC-5.

[0083] Table 2

[0084] Sample Mf Mm Mc Ff Fc L All Example 3 (415 °C) 12 23 34 3 6 15 85 Example 4 (420 °C) 4 15 19 21 10 32 100 Example 5 (425 °C) 20 25 23 4 0 7 79 Example 6 (430 °C) 53 14 8 0 0 0 75 Example 7 (3 h) 15 27 12 7 4 30 95 Example 8 (5 h) 60 13 10 0 0 0 83

[0085] In Table 2, Mf represents fine-grained mosaic structure; Mm represents medium mosaic structure; Mc represents coarse-grained mosaic structure; Ff represents fine fiber structure; Fc represents coarse fiber structure; L represents domain structure; All represents total content.

[0086] It can be seen from Table 2 that when the reaction temperature and time increase, both the fibrous and night structures of the mesophase semicoke show a trend of first increasing and then decreasing, and the best texture (i.e., mosaic structure, fiber structure, and domain structure) can be obtained under the reaction conditions of 420 °C and 4 h.

[0087] Among them, the mosaic structure: can provide a relatively high specific surface area and porosity, and can be used for adsorption, catalytic carriers, or thermal insulation materials.

[0088] Fiber structure: The molecules are highly oriented along the axial direction, forming a fibrous or needle-like structure, with high mechanical strength and conductivity, and can be used in applications such as anode materials for lithium-ion batteries, electrode materials for supercapacitors, adsorption materials, needle coke precursors, or catalyst carriers.

[0089] Domain structure: Its uniformity and orientation affect the intercalation / deintercalation behavior of lithium ions, and after optimization, it can improve the cycle stability and rate performance of the battery.

[0090] The polarized light photograph of the mesophase semicoke prepared in Example 4 is shown in Figure 3 ; The polarized light photograph of the mesophase semicoke prepared in Example 4 after calcination at 1300 °C for 1 h is shown in Figure 4 .

[0091] From Figure 3 and Figure 4 it can be seen that most of the textures after calcination are fibrous and coarse-grained mosaic structures, with high structural orderliness, which is conducive to obtaining high-quality needle coke.

[0092] Effect Example 1

[0093] The XRD spectra of the mesophase semicoke MC-4 (i.e., MC-420) prepared in Example 4, the mesophase semicoke MC-3 prepared in Example 7, and the mesophase semicoke MC-5 prepared in Example 8 are shown in Figure 5 ; The XRD spectra of the mesophase semicoke MC-415 prepared in Example 3, the mesophase semicoke MC-420 prepared in Example 4, the mesophase semicoke MC-425 prepared in Example 5, and the mesophase semicoke MC-430 prepared in Example 6 are shown in Figure 6 .

[0094] From Figure 5 and Figure 6It can be seen that the mesophase semicokes prepared in Examples 3 to 8 all have obvious absorption peaks near 26° and 43°, indicating that the six mesophase semicokes all have a certain degree of graphitization performance. By comparing the characteristic diffraction absorption peaks of the six mesophase semicokes, it can be seen that the peak intensity of the mesophase semicoke MC-4 (i.e., MC-420) is sharper and the absorption intensity of the diffraction peak is significantly increased, indicating that the aromatic sheet order degree of the MC-4 product is the best and the graphitization degree is the highest.

[0095] Comparative Example 1

[0096] Same as Example 4, the difference is only that step (3) is specifically: loading the refined bio-asphalt and hydrogenated anthracene oil into a 1L high-pressure reactor according to a mass ratio of 3:7, sealing the high-pressure reactor, and repeatedly purging the air in the reactor with nitrogen. First, heat it to 360°C at a rate of 3°C / min, hold for 2h, then heat it to 420°C at a rate of 1.5°C / min, hold for 3h, and keep the pressure at 2Mpa; then keep it at 420°C for 4h under a pressureless state to obtain the product.

[0097] The product obtained by the method of this comparative example is liquid asphalt, and mesophase semicoke cannot be obtained.

[0098] Comparative Example 2

[0099] A preparation method of mesophase semicoke:

[0100] (1) Mix the bio-asphalt with an organic solvent (tetrahydrofuran) and heat to 70°C, stir and react for 2h, the stirring speed is 200rpm, filter to remove the insoluble components, and distill the soluble components at 120°C to recover the organic solvent, and the remaining product is the organic solvent soluble component of the bio-asphalt (i.e., refined bio-asphalt).

[0101] (2) Load the refined bio-asphalt and anthracene oil into a 1L high-pressure reactor according to a mass ratio of 3:7, seal the high-pressure reactor, and repeatedly purge the air in the reactor with nitrogen. First, heat it to 360°C at a rate of 3°C / min, hold for 2h, then heat it to 420°C at a rate of 1.5°C / min, hold for 3h, and keep the pressure at 2Mpa; then reduce the pressure to 0.5Mpa and hold at 420°C for 3h, and take out the bottom material to obtain mesophase semicoke MC-AO.

[0102] The polarized light photo of the mesophase semicoke prepared in this comparative example is shown in Figure 7 ; The polarized light photo of the mesophase semicoke prepared in this comparative example after calcination at 1300°C for 1h is shown in Figure 8 .

[0103] From Figure 7 and Figure 8It can be seen that the mesophase semicoke obtained from the co-carbonization reaction of unhydrogenated anthracene oil and bio-bitumen is in a fine-grained mosaic structure. This is because the reaction activity of the raw material anthracene oil is relatively low, and the reaction with bio-bitumen is insufficient, making it difficult to form a planar structure of aromatic macromolecules.

[0104] Effect Example 2

[0105] The mesophase semicoke was activated by the KOH activation method to prepare activated mesophase semicoke, which was used as an electrode to prepare a supercapacitor, and its electrochemical performance was characterized.

[0106] KOH activation method: The mesophase semicoke was immersed in a KOH (1 g / mL) solution, maintained at 80 °C in a vacuum drying oven for 4 h, and then the immersed mesophase semicoke was heated to 750 °C in a tubular furnace at a heating rate of 7 °C / min, held at a constant temperature for 1 h, and naturally cooled to room temperature. The KOH was washed away with hydrochloric acid solution and deionized water until the washing solution was neutral to obtain activated mesophase semicoke.

[0107] The activated mesophase semicoke, conductive graphite, and 70 wt% polytetrafluoroethylene emulsion (PTFE) were mixed evenly in a mass ratio of 80:15:5, ultrasonicated for 30 min, and dried in a vacuum drying oven for 2 h. The mixture was pressed into tablets at 5 MPa for 1 min, and then pressed into tablets with known mass of nickel foam at 5 MPa for 5 min. After weighing, subtracting the mass of the nickel foam was the mass of the electrode sheet, and each electrode sheet was on average 25 mg. A supercapacitor was assembled and its electrochemical performance was characterized. The results are shown in Table 3.

[0108] Table 3 Electrochemical Performance

[0109]

[0110]

[0111] The above-described embodiments are only descriptions of the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention should fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing mesophase semi-coke, characterized in that: The following steps are involved: The organic solvent soluble components of the bio-asphalt and hydrogenated anthracene oil are mixed and co-carbonized to obtain the mesophase semi-coke.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the organic solvent soluble component of the bio-asphalt to the hydrogenated anthracene oil is 3:

7.

3. The preparation method according to claim 2, characterized in that: The method for preparing the organic solvent soluble component of the bio-asphalt comprises the following steps: The bio-asphalt is mixed with an organic solvent, heated and stirred for reaction, and then filtered. The filtrate is taken and the organic solvent is removed to obtain the organic solvent-soluble component of the bio-asphalt.

4. The preparation method according to claim 3, characterized in that: The organic solvent includes n-hexane, tetrahydrofuran or toluene.

5. The preparation method according to claim 3, characterized in that: The temperature of the heating and stirring reaction is 70° C., the time is 1 to 2 hours, and the stirring speed is 100 to 200 rpm.

6. The preparation method according to claim 1, characterized in that: The preparation method of the hydrogenated anthracene oil comprises the following steps: Anthracene oil and a hydrogenating agent are mixed, heated and stirred for reaction, to obtain the hydrogenated anthracene oil.

7. The preparation method according to claim 6, characterized in that: The hydrogenating agent includes tetralin; the stirring speed of the heating and stirring reaction is 200-250 rpm, the temperature is 400-430° C., and the time is 1 hour.

8. The preparation method according to claim 1, characterized in that: The co-carbonization comprises: firstly heating to 360°C at 3°C / min, keeping the temperature for 2h, then heating to 420°C at 1.5°C / min, keeping the temperature for 3h, and maintaining the pressure at 2Mpa; then reducing the pressure to 0.5Mpa, and keeping the temperature at 400-430°C for 3-5h.

9. A mesophase semi-coke prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the mesophase semi-coke according to claim 9 as a negative electrode material for lithium-ion batteries, an electrode material for supercapacitors, an adsorption material, a needle coke precursor or a catalyst carrier.

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