CN108163832B - Preparation method and application of asphalt-based carbon nanosheet - Google Patents

Preparation method and application of asphalt-based carbon nanosheet Download PDF

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CN108163832B
CN108163832B CN201711299432.7A CN201711299432A CN108163832B CN 108163832 B CN108163832 B CN 108163832B CN 201711299432 A CN201711299432 A CN 201711299432A CN 108163832 B CN108163832 B CN 108163832B
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sodium chloride
template agent
based carbon
asphalt
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CN108163832A (en
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邱介山
肖南
王玉伟
郝明远
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Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of carbon material preparation, in particular to a preparation method and application of an asphalt-based carbon nanosheet, wherein the preparation method comprises the following steps: (1) sequentially adding medium-temperature coal pitch, a tetrahydrofuran solvent and a simple substance of iodine into a flask, stirring to obtain a completely dissolved mixed solution, (2) dropwise adding a saturated sodium chloride aqueous solution into absolute ethyl alcohol, filtering white precipitate, placing in a drying oven for drying to obtain a sodium chloride template agent, (3) adding the sodium chloride template agent into the mixed solution obtained in the step (1), evaporating tetrahydrofuran in an oil bath, placing in a tubular furnace, carbonizing under the protection of inert gas, cooling, taking out, dissolving the sodium chloride template agent in deionized water, filtering, and drying in the drying oven to obtain the pitch-based carbon nanosheet. The sodium chloride template agent and the tetrahydrofuran solvent used in the invention can be recycled, the production cost is reduced, and the prepared asphalt-based carbon nanosheet as the potassium ion battery negative electrode material has the advantages of high specific capacity, good rate capability and the like.

Description

Preparation method and application of asphalt-based carbon nanosheet
Technical Field
The invention relates to a preparation method and application of an asphalt-based carbon nanosheet, and belongs to the technical field of carbon material preparation.
Background
With the consumption of traditional energy sources, new clean energy sources such as wind energy, solar energy, nuclear energy and the like occupy more and more important positions in an energy system. The effective utilization of clean energy needs a matched energy storage system to convert the clean energy into electric energy and continuously and stably output the electric energy, and a novel energy storage technology is related to the sustainable development of human society. Among the energy storage technologies used at present, lithium ion batteries are widely used in electric devices such as electric vehicles, notebook computers, and mobile phones due to their advantages of high energy density, long cycle life, and good safety. However, the problem of lithium resource shortage seriously restricts the larger-scale application of the lithium ion battery, and the development of a lithium ion battery substitute becomes an important direction for the development of an energy storage technology.
The sodium and potassium elements in the same main group with lithium have physical and chemical characteristics similar to those of lithium, and can be used for preparing 'rocking chair type' secondary batteries. Compared with sodium, the abundance of elements of potassium in the earth crust is similar, but is closer to the standard reduction potential of the lithium ion battery, and the potassium ion battery is expected to obtain the energy density close to that of the lithium ion battery. Meanwhile, potassium ions have good affinity with negative electrodes such as carbon materials used by the traditional lithium ion battery, and the potassium ion battery is conveniently developed based on the existing lithium ion battery technology. Because the radius of potassium ions is larger than that of lithium ions, the common negative electrode materials such as graphite in the lithium ion battery are directly applied to the potassium ion battery and have the defects of low capacity, poor rate performance and the like, and the research and development of the high-performance negative electrode of the potassium ion battery is a key link for the practicability of the potassium ion battery. The carbon material with larger carbon layer spacing has higher reversible potassium storage capacity, the two-dimensional nano-sheet and other nano-structures can effectively shorten the potassium ion transmission path and further improve the electrochemical performance, and the existing method for preparing the carbon material with the two characteristics is still to be developed.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method and application of an asphalt-based carbon nanosheet. The method has the advantages of simple preparation process and rich raw material sources, and the prepared carbon nanosheet used as the potassium ion battery cathode has the advantages of high specific capacity, good rate capability, excellent cycle performance and the like.
In order to achieve the above purpose and solve the problems existing in the prior art, the invention adopts the technical scheme that: a preparation method of asphalt-based carbon nanosheets comprises the following steps:
step 1, sequentially adding medium-temperature coal pitch and a tetrahydrofuran solvent into a flask, uniformly mixing, adding an iodine simple substance, and stirring to obtain a completely dissolved mixed solution, wherein the mass ratio of the medium-temperature coal pitch to the tetrahydrofuran solvent is 1:5-50, and the mass ratio of the medium-temperature coal pitch to the iodine simple substance is 1: 0.1-0.5;
step 2, dropwise adding a saturated sodium chloride aqueous solution into absolute ethyl alcohol, filtering white precipitate, placing the filtered white precipitate in a 50-150 ℃ oven, and drying for 2-24 hours to obtain a sodium chloride template agent, wherein the mass ratio of the saturated sodium chloride aqueous solution to the absolute ethyl alcohol is 1: 2-8;
step 3, adding the sodium chloride template agent prepared in the step 2 into the mixed solution prepared in the step 1, placing the mixed solution in an oil bath at 50-150 ℃ to evaporate tetrahydrofuran to dryness, then placing the mixture in a tubular furnace, raising the temperature to 600-1000 ℃ at a heating rate of 5-10 ℃/min under the protection of inert gas for carbonization treatment for 1-3h, wherein the mass ratio of the medium-temperature coal pitch to the sodium chloride template agent is 1:6-25, and the inert gas is selected from one of nitrogen or argon;
and 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, putting the sample into an oven at the temperature of 80-160 ℃, and drying for 2-24 hours to obtain the target material asphalt-based carbon nanosheet.
The method and the application of the prepared asphalt-based carbon nanosheet in the potassium ion battery.
The invention has the beneficial effects that: a preparation method of asphalt-based carbon nanosheets comprises the following steps: (1) sequentially adding medium-temperature coal pitch and a tetrahydrofuran solvent into a flask, uniformly mixing, adding an iodine simple substance, stirring to obtain a completely dissolved mixed solution, (2) dropwise adding a saturated sodium chloride aqueous solution into absolute ethyl alcohol, filtering a white precipitate, placing in an oven, and drying to obtain a sodium chloride template, (3) adding the sodium chloride template prepared in the step 2 into the mixed solution prepared in the step 1, placing in an oil bath, evaporating tetrahydrofuran to dryness, placing the mixture in a tubular furnace, and carrying out carbonization treatment under the protection of inert gas, (4) cooling a sample carbonized in the step 3 to room temperature, placing in deionized water, dissolving the sodium chloride template, filtering, placing in the oven, and drying to obtain the target material pitch-based carbon nanosheet. Compared with the prior art, the preparation method provided by the invention is simple to operate, can remove the sodium chloride template agent by simple water washing, and is green and environment-friendly; the sodium chloride template agent and the tetrahydrofuran solvent can be recycled, so that the production cost is reduced; the raw materials and the template agent have rich sources, and large-scale production is easy to realize; the asphalt-based carbon nanosheet prepared by the method has the characteristics of high specific capacity, good rate capability, excellent cycle performance and the like when being used as a potassium ion battery cathode material.
Drawings
Fig. 1 is a scanning electron micrograph of pitch-based carbon nanosheets prepared in example 1 of the present invention.
Fig. 2 is a transmission electron micrograph of the pitch-based carbon nanosheet prepared in example 1 of the present invention.
Fig. 3 is an X-ray diffraction pattern of the asphalt-based carbon nanosheet prepared in example 1 of the present invention.
Fig. 4 is a discharge specific capacity diagram of the asphalt-based carbon nanosheets prepared in example 1 of the present invention at different current densities in a potassium ion battery.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Step 1, sequentially adding 1g of medium-temperature coal tar pitch and 30g of tetrahydrofuran solvent into a flask, uniformly mixing, adding 0.3g of iodine simple substance, and stirring to obtain a completely dissolved mixed solution; step 2, dropwise adding 100g of saturated sodium chloride aqueous solution into 500g of absolute ethyl alcohol, filtering white precipitate, placing the white precipitate in an oven at 80 ℃, and drying for 12 hours to obtain a sodium chloride template agent; step 3, weighing 10g of the sodium chloride template agent prepared in the step 2, adding the sodium chloride template agent into the mixed solution prepared in the step 1, placing the mixed solution into an oil bath at 80 ℃ to evaporate tetrahydrofuran to dryness, then placing the mixture into a tubular furnace, and raising the temperature to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon to perform carbonization treatment for 2 hours; and 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, putting the sample into a drying oven at 110 ℃, drying for 5 hours to obtain the target material asphalt-based carbon nanosheet, and XRD (X-ray diffraction) characterization shows that the carbon layer spacing of the asphalt-based carbon nanosheet can reach 0.371 nm. Preparing a negative electrode material from an asphalt-based carbon nanosheet, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, a metal potassium sheet is a counter electrode, and assembling a potassium ion battery in a glove box. The electrochemical performance of the battery is tested on a Land CT2001A type battery test system, and the charge-discharge voltage range is0.01-2.5V, and the charging and discharging rate of the asphalt-based carbon nano sheet is measured to be 0.05A g-1Under the condition, the first reversible capacity reaches 275mAh g-1。
Example 2
Step 1, sequentially adding 1g of medium-temperature coal tar pitch and 20g of tetrahydrofuran solvent into a flask, uniformly mixing, adding 0.2g of iodine simple substance, and stirring to obtain a completely dissolved mixed solution; step 2, dropwise adding 100g of saturated sodium chloride aqueous solution into 400g of absolute ethyl alcohol, filtering white precipitate, placing the white precipitate in a 100 ℃ oven, and drying for 10 hours to obtain a sodium chloride template agent; step 3, weighing 10g of the sodium chloride template agent prepared in the step 2, adding the sodium chloride template agent into the mixed solution prepared in the step 1, placing the mixed solution into an oil bath at 90 ℃ to evaporate tetrahydrofuran to dryness, then placing the mixture into a tubular furnace, and raising the temperature to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon to perform carbonization treatment for 2 hours; and 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, putting the sample into a drying oven at 110 ℃, drying for 5 hours to obtain the target material asphalt-based carbon nanosheet, and XRD (X-ray diffraction) characterization shows that the carbon layer spacing of the asphalt-based carbon nanosheet can reach 0.369 nm. Preparing a negative electrode material from an asphalt-based carbon nanosheet, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, a metal potassium sheet is a counter electrode, and assembling a potassium ion battery in a glove box. Testing the electrochemical performance of the battery on a Land CT2001A battery test system, wherein the charging and discharging voltage range is 0.01-2.5V, and the charging and discharging rate of the asphalt-based carbon nano sheet is 0.05Ag-1Under the condition of the first reversible capacity of 268mAh g-1。
Example 3
Step 1, sequentially adding 1g of medium-temperature coal tar pitch and 30g of tetrahydrofuran solvent into a flask, uniformly mixing, adding 0.4g of iodine simple substance, and stirring to obtain a completely dissolved mixed solution; step 2, dropwise adding 100g of saturated sodium chloride aqueous solution into 600g of absolute ethyl alcohol, filtering white precipitate, placing the white precipitate in a 90 ℃ oven, and drying for 12 hours to obtain a sodium chloride template agent; step 3, weighing 8g of sodium chloride template agent prepared in the step 2, adding the sodium chloride template agent into the mixed solution prepared in the step 1, placing the mixed solution into an oil bath at the temperature of 80 ℃, evaporating tetrahydrofuran to dryness, and placing the mixture into a containerIn a tube furnace, under the protection of argon, raising the temperature to 700 ℃ at the heating rate of 5 ℃/min, and carrying out carbonization treatment for 2 h; and 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, putting the sample into a 100 ℃ oven, and drying for 8 hours to obtain the target material asphalt-based carbon nanosheet, wherein XRD (X-ray diffraction) characterization shows that the carbon layer spacing of the asphalt-based carbon nanosheet can reach 0.373 nm. Preparing a negative electrode material from a carbon nanosheet, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, a metal potassium sheet is a counter electrode, and assembling a potassium ion battery in a glove box. Testing the electrochemical performance of the battery on a Land CT2001A battery test system, wherein the charging and discharging voltage range is 0.01-2.5V, and the charging and discharging rate of the asphalt-based carbon nano sheet is 0.05A g-1Under the condition of (1), the first reversible capacity reaches 284mAh g-1。
Example 4
Step 1, sequentially adding 1g of medium-temperature coal tar pitch and 30g of tetrahydrofuran solvent into a flask, uniformly mixing, adding 0.1g of iodine simple substance, and stirring to obtain a completely dissolved mixed solution; step 2, dropwise adding 100g of saturated sodium chloride aqueous solution into 500g of absolute ethyl alcohol, filtering white precipitate, placing the white precipitate in a 90 ℃ oven, and drying for 10 hours to obtain a sodium chloride template agent; step 3, weighing 10g of the sodium chloride template agent prepared in the step 2, adding the sodium chloride template agent into the mixed solution prepared in the step 1, placing the mixed solution into an oil bath at 90 ℃ to evaporate tetrahydrofuran to dryness, then placing the mixture into a tubular furnace, and raising the temperature to 800 ℃ at a heating rate of 5 ℃/min under the protection of argon to perform carbonization treatment for 1 h; and 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, putting the sample into a 100 ℃ oven, and drying for 8 hours to obtain the target material asphalt-based carbon nanosheet, wherein XRD (X-ray diffraction) characterization shows that the carbon layer spacing of the carbon nanosheet can reach 0.355 nm. Preparing a negative electrode material from an asphalt-based carbon nanosheet, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, a metal potassium sheet is a counter electrode, and assembling a potassium ion battery in a glove box. Testing the electrochemical performance of the battery on a Land CT2001A battery test system, wherein the charging and discharging voltage range is 0.01-2.5V, and the charging and discharging rate of the asphalt-based carbon nano sheet is 0.05A g-1Under the condition of the first reversible capacity of 239mAh g-1。
Example 5
Step 1, sequentially adding 1g of medium-temperature coal tar pitch and 20g of tetrahydrofuran solvent into a flask, uniformly mixing, adding 0.3g of iodine simple substance, and stirring to obtain a completely dissolved mixed solution; step 2, dropwise adding 100g of saturated sodium chloride aqueous solution into 300g of absolute ethyl alcohol, filtering white precipitate, placing the white precipitate in a 100 ℃ oven, and drying for 6 hours to obtain a sodium chloride template agent; step 3, weighing 15g of the sodium chloride template agent prepared in the step 2, adding the sodium chloride template agent into the mixed solution prepared in the step 1, placing the mixed solution into an oil bath at 70 ℃, drying tetrahydrofuran by distillation, placing the mixture into a tubular furnace, and raising the temperature to 700 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen for carbonization treatment for 2 hours; and 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, putting the sample into a drying oven at 110 ℃, drying for 5 hours to obtain the target material asphalt-based carbon nanosheet, and XRD (X-ray diffraction) characterization shows that the carbon layer spacing of the carbon nanosheet can reach 0.370 nm. Preparing a negative electrode material from an asphalt-based carbon nanosheet, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, a metal potassium sheet is a counter electrode, and assembling a potassium ion battery in a glove box. Testing the electrochemical performance of the battery on a Land CT2001A battery test system, wherein the charging and discharging voltage range is 0.01-2.5V, and the charging and discharging rate of the asphalt-based carbon nano sheet is 0.05A g-1Under the condition that the first reversible capacity reaches 271mAh g-1。
Example 6
Step 1, sequentially adding 1g of medium-temperature coal tar pitch and 30g of tetrahydrofuran solvent into a flask, uniformly mixing, adding 0.2g of iodine simple substance, and stirring to obtain a completely dissolved mixed solution; step 2, dropwise adding 100g of saturated sodium chloride aqueous solution into 400g of absolute ethyl alcohol, filtering white precipitate, placing the white precipitate in a 70 ℃ oven, and drying for 12 hours to obtain a sodium chloride template agent; step 3, weighing 20g of the sodium chloride template agent prepared in the step 2, adding the sodium chloride template agent into the mixed solution prepared in the step 1, placing the mixed solution into an oil bath at the temperature of 75 ℃ to evaporate tetrahydrofuran to dryness, then placing the mixture into a tubular furnace, and raising the temperature to 600 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen to perform carbonization2h, processing; and 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, putting the sample into a 100 ℃ oven, and drying for 8 hours to obtain the target material asphalt-based carbon nanosheet, wherein XRD (X-ray diffraction) characterization shows that the carbon layer spacing of the asphalt-based carbon nanosheet can reach 0.366 nm. Preparing a negative electrode material from an asphalt-based carbon nanosheet, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, a metal potassium sheet is a counter electrode, and assembling a potassium ion battery in a glove box. Testing the electrochemical performance of the battery on a Land CT2001A battery test system, wherein the charging and discharging voltage range is 0.01-2.5V, and the charging and discharging rate of the asphalt-based carbon nano sheet is 0.05A g-1Under the condition of the first reversible capacity of 261mAh g-1。
Comparative example 1
Step 1, sequentially adding 1g of medium-temperature coal pitch and 30g of tetrahydrofuran solvent into a flask, and uniformly stirring to obtain a completely dissolved mixed solution; step 2, dropwise adding 100g of saturated sodium chloride aqueous solution into 500g of absolute ethyl alcohol, filtering white precipitate, placing the white precipitate in an oven at 80 ℃, and drying for 12 hours to obtain a sodium chloride template agent; step 3, weighing 10g of the sodium chloride template agent prepared in the step 2, adding the sodium chloride template agent into the solution prepared in the step 1, placing the solution into an oil bath at 80 ℃ to evaporate tetrahydrofuran to dryness, then placing the mixture into a tubular furnace, and raising the temperature to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon to perform carbonization treatment for 2 hours; and 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, putting the sample into a drying oven at 110 ℃, drying for 5 hours to obtain the target material asphalt-based carbon nanosheet, and the XRD (X-ray diffraction) characterization shows that the carbon layer spacing of the asphalt-based carbon nanosheet is 0.342 nm. Preparing a negative electrode material from an asphalt-based carbon nanosheet, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, a metal potassium sheet is a counter electrode, and assembling a potassium ion battery in a glove box. Testing the electrochemical performance of the battery on a Land CT2001A battery test system, wherein the charging and discharging voltage range is 0.01-2.5V, and the charging and discharging rate of the asphalt-based carbon nano sheet is 0.05A g-1Under the condition of (2), the first reversible capacity is only 213mAh g-1。
Compared with the example 1, the comparative example has the advantages that the distance between carbon layers of the prepared asphalt-based carbon nanosheets is obviously reduced without adding iodine. The reversible capacity of the potassium ion battery assembled by taking the asphalt-based carbon nanosheet as the negative electrode is obviously reduced for the first time under the same test condition.
Comparative example 2
Step 1, sequentially adding 1g of medium-temperature coal tar pitch and 30g of tetrahydrofuran solvent into a flask, uniformly mixing, adding 0.3g of iodine simple substance, and stirring to obtain a completely dissolved mixed solution; step 2, placing the mixed solution prepared in the step 1 in an oil bath at the temperature of 80 ℃ to evaporate tetrahydrofuran to dryness, then placing the mixture in a tubular furnace, and raising the temperature to 700 ℃ at the heating rate of 5 ℃/min under the protection of argon to perform carbonization treatment for 2 hours; and 3, cooling the sample carbonized in the step 2 to room temperature, taking out and placing in a drying oven at 110 ℃, drying for 5 hours to obtain the target material asphalt-based carbon particles, wherein XRD (X-ray diffraction) characterization shows that the carbon layer spacing of the asphalt-based carbon particles can reach 0.370 nm. Preparing a negative electrode material by using asphalt-based carbon particles, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 7:2:1, wherein a current collector is a copper foil, a metal potassium sheet is a counter electrode, and assembling a potassium ion battery in a glove box. Testing the electrochemical performance of the battery on a Land CT2001A battery test system, wherein the charging and discharging voltage range is 0.01-2.5V, and the charging and discharging rate of the asphalt-based carbon particles is 0.05A g-1Under the condition of (2), the first reversible capacity is only 256mAh g-1。
This comparative example compares to example 1, without the addition of sodium chloride templating agent, and the resulting material is pitch-based carbon particles. The reversible capacity of the potassium ion battery assembled by taking the asphalt-based carbon particles as the negative electrode is obviously reduced for the first time under the same test condition.

Claims (1)

1. A preparation method of asphalt-based carbon nanosheets for use in potassium ion batteries is characterized by comprising the following steps:
step 1, sequentially adding medium-temperature coal pitch and a tetrahydrofuran solvent into a flask, uniformly mixing, adding an iodine simple substance, and stirring to obtain a completely dissolved mixed solution, wherein the mass ratio of the medium-temperature coal pitch to the tetrahydrofuran solvent is 1:5-50, and the mass ratio of the medium-temperature coal pitch to the iodine simple substance is 1: 0.1-0.5;
step 2, dropwise adding saturated sodium chloride aqueous solution into absolute ethyl alcohol, filtering white precipitate, and placing the white precipitate into a container with the volume of 50-150 DEG CoDrying in a baking oven for 2-24 hours to obtain a sodium chloride template agent, wherein the mass ratio of the saturated sodium chloride aqueous solution to the absolute ethyl alcohol is 1: 2-8;
step 3, adding the sodium chloride template agent prepared in the step 2 into the mixed solution prepared in the step 1, and placing the mixed solution in a range of 50-150oEvaporating tetrahydrofuran in oil bath, placing the mixture in a tube furnace, and under the protection of inert gas, adding 5-10% of tetrahydrofuranoThe temperature rising rate of C/min is increased to 600-1000oC, carrying out carbonization treatment for 1-3h, wherein the mass ratio of the medium-temperature coal pitch to the sodium chloride template agent is 1:6-25, and the inert gas is selected from one of nitrogen or argon;
step 4, cooling the sample carbonized in the step 3 to room temperature, putting the sample into deionized water, dissolving a sodium chloride template agent, filtering, and placing the sample in a place of 80-160 DEG CoAnd C, drying for 2-24h in an oven to obtain the target material asphalt-based carbon nanosheet.
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CN111370655B (en) * 2018-12-26 2021-07-27 浙江工业大学 Iodine-modified spindle-shaped biological carbon material and application thereof in preparation of metal lithium cathode
CN110265645B (en) * 2019-06-25 2021-03-23 郑州中科新兴产业技术研究院 Asphalt-based carbon nanosheet composite negative electrode material, and preparation method and application thereof
CN110823866A (en) * 2019-10-14 2020-02-21 重庆长安工业(集团)有限责任公司 Method for testing copper content in sodium chloride
CN115784198A (en) * 2022-12-01 2023-03-14 中国科学院山西煤炭化学研究所 Method for preparing asphalt-based hard carbon material through iodine crosslinking and application of asphalt-based hard carbon material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784830A (en) * 2016-11-29 2017-05-31 大连理工大学 A kind of preparation method and applications of the Pitch-based Carbon nanometer sheet for anode material of lithium-ion battery
CN106784736A (en) * 2017-02-08 2017-05-31 大连理工大学 A kind of sodium-ion battery negative pole coats the preparation method and application of tin particles nanometer sheet with coal tar pitch resin base amorphous carbon
CN106876702A (en) * 2017-02-08 2017-06-20 大连理工大学 A kind of sodium-ion battery negative pole coal tar pitch resin base amorphous carbon coats the preparation method and application of few layer molybdenum disulfide nano box

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784830A (en) * 2016-11-29 2017-05-31 大连理工大学 A kind of preparation method and applications of the Pitch-based Carbon nanometer sheet for anode material of lithium-ion battery
CN106784736A (en) * 2017-02-08 2017-05-31 大连理工大学 A kind of sodium-ion battery negative pole coats the preparation method and application of tin particles nanometer sheet with coal tar pitch resin base amorphous carbon
CN106876702A (en) * 2017-02-08 2017-06-20 大连理工大学 A kind of sodium-ion battery negative pole coal tar pitch resin base amorphous carbon coats the preparation method and application of few layer molybdenum disulfide nano box

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