CN110668418B - Preparation method of hard carbon microspheres with high specific capacitance - Google Patents
Preparation method of hard carbon microspheres with high specific capacitance Download PDFInfo
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- CN110668418B CN110668418B CN201910981134.9A CN201910981134A CN110668418B CN 110668418 B CN110668418 B CN 110668418B CN 201910981134 A CN201910981134 A CN 201910981134A CN 110668418 B CN110668418 B CN 110668418B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- 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
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- 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 discloses a preparation method of a hard carbon microsphere with high specific capacitance, which comprises the steps of dissolving lignin in water, adding ammonia water to form a solution, and uniformly stirring; spray drying the uniformly stirred solution to obtain lignin microspheres; placing the lignin microspheres in air for pre-oxidation treatment, raising the temperature to 200 ℃ and 400 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 8-12h, and then naturally cooling to room temperature; placing the preoxidized lignin microspheres in an inert atmosphere, and raising the temperature to 250-350 ℃ at a temperature rise rate of 1-5 ℃/min; then raising the temperature to 350-450 ℃ at the temperature rise rate of 1-5 ℃/min, and keeping the temperature for 1-4 h; finally, the temperature is raised to 800-1650 ℃ at the heating rate of 1-10 ℃/min, and the mixture is carbonized at constant temperature for 1-4h, and then is naturally cooled to the room temperature. The invention relates to a preparation method of hard carbon microspheres with high specific capacitance, and the prepared hard carbon microspheres have small specific surface area (less than or equal to 10 m)2The specific capacity can reach up to 402mAh/g) and the capacity retention rate is good (can reach up to 95.5%).
Description
Technical Field
The invention relates to the technical field of high-specific-capacitance carbon materials, in particular to a preparation method of a high-specific-capacitance hard carbon microsphere.
Background
In the present day that the social economy is rapidly developed and the resources are in short supply, novel energy storage elements are rapidly developed. At present, a super capacitor is an energy storage device that is widely focused by researchers due to its rapid charge and discharge, high power density, excellent cycle stability, and high stability. The electrode material is one of the key factors determining the performance of the supercapacitor, and carbon materials such as carbon fiber, activated carbon, carbon nanotubes, graphene and carbon spheres are widely researched electrode materials of the supercapacitor. The spherical carbon material has the characteristics of regular morphology, good fluidity, adjustable particle size and the like, so that the spherical carbon material has a good application prospect when being used as a super capacitor electrode material.
The hard carbon material has high capacity higher than the theoretical capacity (372 mAh/g) of graphite, and excellent rate capability and cycle performance. Currently, carbon microspheres are mainly obtained by direct pyrolysis of spherical carbon precursors (such as glucose, sucrose, polymeric resins, and the like). There are five main methods for synthesizing spherical carbon precursors: hydrothermal reaction, microemulsion polymerization, molecular self-assembly, surface coating polymerization of a spherical template, spray drying and the like. The first four methods have complicated preparation process, high equipment requirement, high pollution, high energy consumption and cost and are difficult to realize large-scale industrial production. The spray drying method can directly dry a suspension (emulsion) or even a solution to obtain powder. Due to a special physical mechanism in the spraying process, the obtained powder has uniform particle size distribution and special morphology, and a material processing process of long-time drying and subsequent crushing is omitted.
The mutually staggered layered structure of the hard carbon materials is beneficial to embedding and removing alkali metal ions from all directions, and the charging and discharging speed is improved; the hard carbon material has larger interlayer spacing than graphite, is beneficial to the embedding and the extraction of ions in the hard carbon material, and is especially suitable for sodium ions with larger size; the nano microporous structure can provide lithium/sodium storage active sites, and the specific capacity of the hard carbon material is increased. Therefore, the hard carbon material used as the lithium storage and sodium storage carbon cathode material has high specific capacity, good high-rate charge and discharge performance and long cycle life.
In recent years, biomass and derivatives thereof have become a novel precursor of carbon materials due to the advantages of large amount, easy availability, reproducibility, environmental friendliness and the like. Lignin, which is the second natural biomass in the global population, is present in the xylem of most terrestrial plants, has a carbon content of about 60%, and is a sustainable carbon material precursor with great potential.
At present, hard carbon materials prepared from resin and plant raw materials are in irregular sheet or block shapes, and chinese patent publication nos. CN1169249C and CN101916845A disclose methods for preparing irregular hard carbon from plant raw materials. However, the tap density of the hard carbon prepared by the prior art is lower, so that the energy density of the battery made of the material is lower.
Disclosure of Invention
The invention aims to provide a preparation method of hard carbon microspheres with high specific capacitance, which has the advantages of simple process, environmental friendliness, low energy consumption and cost and easiness in large-scale industrial production. The prepared hard carbon microspheres have small specific surface area (less than or equal to 10 m)2The specific capacity can reach up to 402mAh/g) and the capacity retention rate is good (can reach up to 95.5%).
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of hard carbon microspheres with high specific capacitance comprises the following steps:
(1) dissolving lignin in water, adding ammonia water to form a solution, and uniformly stirring;
(2) spray drying the uniformly stirred solution to obtain lignin microspheres;
(3) placing the lignin microspheres in air for pre-oxidation treatment, raising the temperature to 200-400 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 8-12h, and then naturally cooling to room temperature;
(4) placing the pre-oxidized lignin microspheres in an inert atmosphere, and raising the temperature to 250-350 ℃ at a temperature rise rate of 1-5 ℃/min; then raising the temperature to 350-450 ℃ at the temperature rise rate of 1-5 ℃/min, and keeping the temperature for 1-4 h; finally, the temperature is raised to 800-1650 ℃ at the heating rate of 1-10 ℃/min, and the mixture is carbonized at constant temperature for 1-4h, and then is naturally cooled to the room temperature.
Preferably, the concentration of the lignin in the solution prepared in step (1) is 5-20%.
Preferably, in step (1), the solution is stirred at room temperature for 1-10 h.
Preferably, in the step (2), the uniformly stirred solution is subjected to spray drying by a spray drying device, wherein the spray drying device adopts a pressure type spray drying mode; in the drying process: the temperature of the air inlet is controlled to be 120-180 ℃, the temperature of the air outlet is controlled to be 80-100 ℃, the pressure of the discharge port is controlled to be 0.1-0.3MPa, and the pressure of the air compressor is controlled to be 0.1-0.3 MPa.
Preferably, in step (4), the inert gas in the inert atmosphere is nitrogen, argon or a mixed gas of the nitrogen and the argon.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the hard carbon microspheres prepared by the method have good spherical morphology and small specific surface area (less than or equal to 10 m)2The hard carbon microsphere material is used for preparing a super capacitor, and the super capacitor prepared from the hard carbon microsphere material has higher specific capacity (up to 402mAh/g) and good capacity retention rate (up to 95.5%);
(2) the method can effectively inhibit the melting of the lignin microspheres by carrying out segmented temperature rise and control on the lignin preoxidation and carbonization processes, thereby reducing the requirements on the quality of the lignin in the production process, further expanding the application range of the lignin and reducing the production and processing cost;
(3) the method has the advantages of simple process, low cost, good reproducibility and easy application.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
(1) Dissolving lignin in water, adding a small amount of ammonia water to form a solution, and stirring for 10 hours, wherein the content of the lignin in the solution is 5%;
(2) spray drying the uniformly stirred solution, and controlling the temperature of an air inlet to be 150 ℃, the temperature of an air outlet to be 80 ℃, the pressure of a discharge hole to be 0.2MPa and the pressure of an air compressor to be 0.2MPa in the drying process to obtain lignin microspheres;
(3) placing the lignin microspheres in air for pre-oxidation treatment, raising the temperature to 200 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 12 hours, and then naturally cooling to room temperature;
(4) placing the pre-oxidized composite microspheres in nitrogen or argon atmosphere, and raising the temperature to 250 ℃ at a heating rate of 2 ℃/min; then the temperature is raised to 450 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 1 h; finally, the temperature is raised to 850 ℃ at the heating rate of 10 ℃/min, and the mixture is carbonized for 2 hours at constant temperature, and then the mixture is naturally cooled to the room temperature.
Performing electrochemical test on the prepared hard carbon microsphere, and calculating according to the nitrogen isothermal adsorption and desorption curve to obtain the hard carbon microsphere with the specific surface area of 4.06m2(ii) in terms of/g. A battery is assembled by using the hard carbon microspheres prepared in the embodiment 1 as electrodes, and is subjected to constant current charge and discharge test at a current density of 0.1C, wherein the specific capacity is 402 mAh/g; the battery was subjected to a cyclic charge and discharge test with a cycle number of 1000 at a current density of 2C, and the battery capacity retention rate was 95.4%.
Example 2
(1) Dissolving lignin in water, adding a small amount of ammonia water to form a solution, and stirring for 8 hours, wherein the content of the lignin in the solution is 15%;
(2) spray drying the uniformly stirred solution, and controlling the temperature of an air inlet to be 150 ℃, the temperature of an air outlet to be 80 ℃, the pressure of a discharge hole to be 0.2MPa and the pressure of an air compressor to be 0.2MPa in the drying process to obtain lignin microspheres;
(3) placing the lignin microspheres in air for pre-oxidation treatment, raising the temperature to 280 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 8 hours, and then naturally cooling to room temperature;
(4) placing the pre-oxidized composite microspheres in nitrogen or argon atmosphere, and raising the temperature to 250 ℃ at a heating rate of 2 ℃/min; then the temperature is raised to 450 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 2 h; finally, the temperature is raised to 1250 ℃ at the heating rate of 7 ℃/min, and the mixture is carbonized for 3 hours at constant temperature, and then the mixture is naturally cooled to the room temperature.
Performing electrochemical test on the prepared hard carbon microsphere, and calculating according to the nitrogen isothermal adsorption and desorption curve to obtain the hard carbon microsphere with the specific surface area of 3.78m2(ii) in terms of/g. The hard carbon microspheres prepared in the example 2 are used as electrodes to assemble a battery, and the battery is subjected to constant current charge and discharge test at the current density of 0.1C, wherein the specific capacity is 399 mAh/g; the battery was subjected to a cyclic charge and discharge test with a cycle number of 1000 at a current density of 2C, and the battery capacity retention rate was 95.5%.
Example 3
(1) Dissolving lignin in water, adding a small amount of ammonia water to form a solution, and stirring for 5 hours, wherein the content of the lignin in the solution is 10%;
(2) spray drying the uniformly stirred solution, and controlling the temperature of an air inlet to be 150 ℃, the temperature of an air outlet to be 80 ℃, the pressure of a discharge hole to be 0.2MPa and the pressure of an air compressor to be 0.2MPa in the drying process to obtain lignin microspheres;
(3) placing the lignin microspheres in air for pre-oxidation treatment, raising the temperature to 200 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 10 hours, and then naturally cooling to room temperature;
(4) placing the pre-oxidized composite microspheres in nitrogen or argon atmosphere, and raising the temperature to 250 ℃ at a temperature rise rate of 5 ℃/min; then the temperature is raised to 450 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 3 hours; and finally, heating to 1650 ℃ at the heating rate of 5 ℃/min, carbonizing for 1h at constant temperature, and naturally cooling to room temperature.
Performing electrochemical test on the prepared hard carbon microsphere, and calculating according to the nitrogen isothermal adsorption and desorption curve to obtain the hard carbon microsphere with the specific surface area of 3.51m2(ii) in terms of/g. The hard carbon microspheres prepared in the example 3 are used as electrodes to assemble a battery, and the battery is subjected to constant current charge and discharge test at the current density of 0.1C, wherein the specific capacity is 384 mAh/g; the battery was subjected to a cyclic charge and discharge test with a cycle number of 1000 at a current density of 2C, and the battery capacity retention rate was 93%.
The above-mentioned embodiments are merely illustrative of the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the scope of the present invention.
Claims (5)
1. A preparation method of hard carbon microspheres with high specific capacitance is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving lignin in water, adding ammonia water to form a solution, and uniformly stirring;
(2) spray drying the uniformly stirred solution to obtain lignin microspheres;
(3) placing the lignin microspheres in air for pre-oxidation treatment, raising the temperature to 200-400 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 8-12h, and then naturally cooling to room temperature;
(4) placing the pre-oxidized lignin microspheres in an inert atmosphere, and raising the temperature to 250-350 ℃ at a temperature rise rate of 1-5 ℃/min; then raising the temperature to 350-450 ℃ at the temperature rise rate of 1-5 ℃/min, and keeping the temperature for 1-4 h; finally, the temperature is raised to 800-1650 ℃ at the heating rate of 1-10 ℃/min, and the mixture is carbonized at constant temperature for 1-4h, and then is naturally cooled to the room temperature.
2. The method for preparing the hard carbon microsphere with high specific capacitance as claimed in claim 1, wherein the method comprises the following steps: in the solution prepared in the step (1), the concentration of the lignin is 5-20%.
3. The method for preparing the hard carbon microsphere with high specific capacitance as claimed in claim 1, wherein the method comprises the following steps: in step (1), the solution is stirred at room temperature for 1-10 h.
4. The method for preparing the hard carbon microsphere with high specific capacitance as claimed in claim 1, wherein the method comprises the following steps: in the step (2), spray drying is carried out on the uniformly stirred solution through spray drying equipment, wherein the spray drying equipment adopts a pressure type spray drying mode; in the drying process: the temperature of the air inlet is controlled to be 120-180 ℃, the temperature of the air outlet is controlled to be 80-100 ℃, the pressure of the discharge port is controlled to be 0.1-0.3MPa, and the pressure of the air compressor is controlled to be 0.1-0.3 MPa.
5. The method for preparing the hard carbon microsphere with high specific capacitance as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the inert gas in the inert atmosphere is nitrogen, argon or a mixed gas of the nitrogen and the argon.
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| CN111170298B (en) * | 2020-01-19 | 2021-02-05 | 宁波瞬能科技有限公司 | Preparation method and application of lignin-based hard carbon |
| CN111470487A (en) * | 2020-05-11 | 2020-07-31 | 三峡大学 | Preparation method and application of biomass carbon material |
| CN112919449B (en) * | 2021-02-08 | 2022-07-26 | 大连理工大学 | Boron-nitrogen co-doped porous carbon microsphere material and preparation method thereof |
| CN114044508B (en) * | 2021-12-20 | 2023-06-23 | 张家港博威新能源材料研究所有限公司 | Hard carbon microsphere and preparation method and application thereof |
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| CN105819426A (en) * | 2016-04-06 | 2016-08-03 | 华南理工大学 | Alkali lignin carbon nanometer microsphere as well as preparation method and application thereof |
| CN108511204B (en) * | 2018-04-02 | 2020-06-16 | 张家港博威新能源材料研究所有限公司 | Preparation method of oxygen-nitrogen co-doped porous hollow carbon microspheres |
| CN108584952A (en) * | 2018-08-01 | 2018-09-28 | 国家能源投资集团有限责任公司 | Spherical porous charcoal and preparation method thereof |
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