CN113603086A - Tartary buckwheat-based active carbon material and preparation method and application thereof - Google Patents
Tartary buckwheat-based active carbon material and preparation method and application thereof Download PDFInfo
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- CN113603086A CN113603086A CN202111077348.7A CN202111077348A CN113603086A CN 113603086 A CN113603086 A CN 113603086A CN 202111077348 A CN202111077348 A CN 202111077348A CN 113603086 A CN113603086 A CN 113603086A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 239000012300 argon atmosphere Substances 0.000 description 3
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 3
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- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 239000010902 straw Substances 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- Y02E60/13—Energy storage using capacitors
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- Power Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a tartary buckwheat-based activated carbon material and a preparation method and application thereof; the preparation method of the tartary buckwheat-based activated carbon material comprises the steps of crude carbon preparation, acid cleaning impurity removal, activation, acid cleaning purification, high-temperature carbon supplement and the like. The invention obtains the activated carbon material with low cost, simultaneously improves the purity of the activated carbon, reduces the volatile component and ash content of the material, and reduces the content of oxygen-containing groups, thereby improving the electrochemical circulation stability of the activated carbon material.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a tartary buckwheat-based activated carbon material and a preparation method and application thereof.
Background
With the development of economy, the problem of energy shortage is becoming more severe. The nation also proposes to develop new energy resources vigorously to achieve the aims of 'carbon peak reaching' and 'carbon neutralization'. Therefore, it is urgent to find an energy storage device with low cost, high performance and environmental protection. As a novel energy storage element, the super capacitor attracts people's attention due to the advantages of short charging time, high power density, environmental friendliness and the like.
Compared with a water system, the organic super capacitor has higher voltage and energy density, and can better meet the application requirements of people in the aspect of energy storage. Supercapacitors are classified into electric double layer capacitance types, pseudocapacitance types, and electric double layer/pseudocapacitance hybrid types. The double-electric-layer super capacitor mainly takes the activated carbon as an electrode material, and the biomass carbon is taken as one of the sources of the activated carbon, so that the double-electric-layer super capacitor has the advantages of wide source, environmental friendliness, low cost and the like, and attracts people's attention. Through retrieval, in the prior art, some biomass such as rice hulls, pine nut shells, straws and the like are used as raw materials for preparing the activated carbon of the supercapacitor, but the prepared activated carbon has low purity, high ash content and volatile components, high oxygen-containing groups and poor cycle performance, and the service life of the electric double layer supercapacitor is influenced. Particularly under the organic high-voltage operation condition, the capacity of the carbon material is quickly attenuated, and impurities introduce defects into the carbon material, so that the carbon material cannot resist high voltage and has serious self-discharge phenomenon. In addition, in the initial operation stage, the existing active carbon electrode materials all go through the process of capacity 'rapid attenuation before circulation is stable', which inevitably leads to the specific capacity loss of the electrode materials and the reduction of the utilization efficiency of the materials. In conclusion, the preparation of the supercapacitor activated carbon with low cost, high purity, long cycle performance and high utilization rate and the simple and rapid preparation process are the problems which are urgently solved by the people in the industry at present.
Disclosure of Invention
The invention aims to provide a tartary buckwheat-based activated carbon material, and a preparation method and application thereof, so that the activated carbon material with low cost is obtained, meanwhile, the purity of the activated carbon is improved, the volatile components and ash content of the material are reduced, and the content of oxygen-containing groups is reduced, thereby improving the electrochemical circulation stability of the activated carbon material.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention discloses a preparation method of a tartary buckwheat-based activated carbon material, which comprises the following steps:
(1) preparing crude carbon: heating and carbonizing the tartary buckwheat-based powder under the protection of inert gas to obtain coarse carbon powder;
(2) acid washing for impurity removal: washing the coarse carbon powder in acid liquor;
(3) and (3) activation: mixing the carbon material obtained after acid cleaning with alkali liquor, and then heating and activating under the protection of inert gas;
(4) acid washing and purifying: washing the activated carbon material in acid liquor;
(5) carbon supplement at high temperature: and mixing the activated carbon material obtained after acid washing with a solid carbon supplement agent, and then calcining to obtain the tartary buckwheat-based activated carbon material.
As a preferred technical scheme, in the step (1), the tartary buckwheat-based powder is powder obtained by crushing one or more raw materials of tartary buckwheat, tartary buckwheat stems and tartary buckwheat peels to 80-200 meshes.
As a preferable technical scheme, in the step (1), the temperature for heating and carbonizing is 400-800 ℃, and the time for heating and carbonizing is 1-5 hours.
As a preferable technical scheme, in the step (2), the crude carbon powder is placed in hydrochloric acid solution with the mass fraction of 3% -20%, continuously soaked and washed at 60-95 ℃ for 5-24 hours, washed to be neutral by water, and then dried.
As a preferable technical scheme, in the step (3), the carbon material obtained after acid cleaning is mixed with alkali liquor, soaked and dried, then heated to 600-1300 ℃ under the protection of inert gas for activation for 1-5 hours, then washed with water to be neutral, and then dried.
As a preferable technical scheme, in the step (3), the alkali liquor is one or more of sodium hydroxide solution and potassium hydroxide solution.
As a preferable technical scheme, in the step (4), the activated carbon material obtained after activation is placed in a hydrochloric acid solution with the mass fraction of 3% -20%, continuously soaked and washed at 60-95 ℃ for 5-24 hours, washed to be neutral by water, and then dried.
As a preferable technical scheme, in the step (5), the activated carbon material obtained after acid cleaning and the solid carbon supplement agent are mixed according to the mass ratio of 1:1-1:10, and then the mixture is continuously calcined at the temperature of 300-1300 ℃ for 1-5 hours to obtain the tartary buckwheat-based activated carbon material.
As a preferable technical scheme, in the step (5), the solid carbon supplement agent is one or more of polyethylene, polypropylene and polybutylene.
The invention also discloses the tartary buckwheat-based activated carbon material prepared by the preparation method.
The invention also discloses application of the tartary buckwheat-based activated carbon material in a capacitor energy storage device.
The invention also discloses application of the tartary buckwheat-based activated carbon material in an electrode material.
The invention has the beneficial effects that:
1. the method of the invention comprises the steps of material pulverization, crude carbon preparation, acid cleaning impurity removal, activation, acid cleaning purification and high temperature carbon supplement, and the prepared activated carbon material has highly controllable specific surface area range (conventional range: 1000-2(ii)/g; maximum value: 2280m2/g), the pore distribution is relatively uniform, the number of mesopores is large, the average pore diameter is about 2.03-2.7nm, the ash content of the obtained material is as low as 0.09%, the volatile component is as low as 0.22%, and the oxygen content is low.
2. The invention adopts polyethylene, polypropylene and the like as the solid carbon supplement agent, can greatly simplify the process of adopting dangerous gas carbon sources (such as methane, ethylene and the like) in the traditional high-temperature carbon supplement process, can efficiently reduce the volatile components and the oxygen-containing group content, simultaneously repairs the defect of macropores caused by alkali etching, and improves the electrochemical cycle stability of the carbon material.
3. In the organic supercapacitor test, after 20000 cycles at a constant current density of 1A/g, the coulombic efficiency is 100%, the specific capacitance is 28.4F/g, the capacity maintenance rate is more than 90%, and the application index of the activated carbon of the supercapacitor can be fully met. In the initial stage of the cycle, the assembled super capacitor does not have the phenomenon of rapid specific capacity decay.
4. The carbon raw material of the invention is tartary buckwheat crops (such as tartary buckwheat, tartary buckwheat stems, tartary buckwheat peels and the like) which are planted in large areas in Yunwan areas of Chuanyun, and has low comprehensive cost and market competitiveness, and because the tartary buckwheat contains rich biological flavonoid, amino acid, oleic acid and linoleic acid, and also contains various inorganic elements such as calcium, phosphorus, iron, magnesium, copper, zinc and trace element selenium, the carbon material doped with special elements can be prepared by taking the tartary buckwheat as the raw material, thereby endowing the carbon material with new performance.
Drawings
FIG. 1 is a first scanning electron microscope image of the tartary buckwheat-based activated carbon material obtained in example 1;
FIG. 2 is a scanning electron microscope image II of the tartary buckwheat-based activated carbon material obtained in example 1;
FIG. 3 is a CV diagram of the activated carbon material based on tartary buckwheat obtained in example 1;
fig. 4 is a graph showing the result of the charge and discharge stability test of the tartary buckwheat-based activated carbon material obtained in example 1.
FIG. 5 is a CV diagram of the activated carbon material based on tartary buckwheat obtained in example 2;
FIG. 6 is a graph showing the results of the measurement of the charging and discharging stability of the activated carbon material based on tartary buckwheat obtained in example 2;
FIG. 7 is a CV diagram of the activated carbon material based on tartary buckwheat obtained in example 3;
fig. 8 is a graph showing the result of the measurement of the charge and discharge stability of the activated carbon material based on tartary buckwheat obtained in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described with reference to the accompanying drawings.
Example 1
(1) Preparing crude carbon: under the argon atmosphere, the tartary buckwheat powder with the particle size of 80 meshes is heated to 400 ℃ at the speed of 3 ℃/min and carbonized for 2 hours at constant temperature to obtain coarse carbon powder;
(2) acid washing for impurity removal: naturally cooling the crude carbon powder, taking out, putting the crude carbon powder and 10 wt% hydrochloric acid into a high-pressure reaction kettle, continuously soaking and washing the crude carbon powder and the hydrochloric acid for 24 hours at the temperature of 80 ℃, washing the crude carbon powder to be neutral by using water, and then drying the crude carbon powder;
(3) and (3) activation: mixing and soaking the carbon material obtained after acid cleaning and sodium hydroxide for 2 hours according to the mass ratio of 1:1.5, then drying, heating to 900 ℃ at the speed of 3 ℃/min under the atmosphere of argon, preserving the heat for 2 hours, washing with water to be neutral, and then drying;
(4) acid washing and purifying: placing the activated carbon material and 10 wt% hydrochloric acid into a high-pressure reaction kettle, continuously soaking and washing at 80 ℃ for 24 hours, washing with water to be neutral, and drying;
(5) carbon supplement at high temperature: and mixing the activated carbon material obtained after acid washing with polypropylene according to the mass ratio of 1:8, and calcining at 900 ℃ for 2 hours to obtain the tartary buckwheat-based activated carbon material.
The scanning electron microscope images of the tartary buckwheat-based activated carbon material obtained in the example 1 are shown in the figures 1 and 2, and the specific surface area can reach 2289m through tests2(ii)/g, the average pore diameter is about 2.03nm,
the ash content of the tartary buckwheat-based activated carbon material obtained in the example 1 is tested according to the GB/T1429 method, and the volatile component is tested according to the YB/T5189 method, and the test result shows that the ash content is as low as 0.09% and the volatile component is as low as 0.22%.
Uniformly mixing the tartary buckwheat-based active carbon material obtained in the example 1 with conductive carbon black, sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a certain proportion, adding a water solvent to prepare a negative electrode slurry, and uniformly coating the negative electrode slurry on an aluminum foil (the coating thickness is about 300 mu m; and the surface loading of the active carbon is higher than 5 mg/cm)2) And drying in a vacuum drying oven at 90 ℃ for 12 hours, rolling and blanking to obtain the electrode plate. The obtained electrode plates are respectively a positive electrode and a negative electrode, and are assembled into a full-cell device (comprising 2025/2032 button cells, wound cells, soft package cells and the like) in a glove box with an argon protective atmosphere with water and oxygen both less than 0.1ppm, and the used electrolyte is purchased Nippon 3702 electrolyte. Performing electrochemical test with scan speed of 10mV/s by CHI660D electrochemical workstation, and obtaining cyclic voltammetry curve as shown in FIG. 3; the Wuhan blue battery test system is adopted to carry out constant-current charge and discharge performance test on the full battery, under the running condition of 1A/g, the battery cycle test result is shown in figure 4, and the result shows that after 20000 cycles, the coulomb efficiency is 100%, and the capacity retention rate is more than 90%.
Example 2
(1) Preparing crude carbon: under the argon atmosphere, the tartary buckwheat powder with the particle size of 80 meshes is heated to 400 ℃ at the speed of 3 ℃/min and carbonized for 2 hours at constant temperature to obtain coarse carbon powder;
(2) acid washing for impurity removal: naturally cooling the crude carbon powder, taking out, putting the crude carbon powder and 10 wt% hydrochloric acid into a high-pressure reaction kettle, continuously soaking and washing the crude carbon powder and the hydrochloric acid for 24 hours at the temperature of 80 ℃, washing the crude carbon powder to be neutral by using water, and then drying the crude carbon powder;
(3) and (3) activation: mixing and soaking the carbon material obtained after acid cleaning and sodium hydroxide for 2 hours according to the mass ratio of 1:1.5, then drying, heating to 1100 ℃ at the speed of 3 ℃/min under the atmosphere of argon, preserving heat for 2 hours, washing with water to be neutral, and then drying;
(4) acid washing and purifying: placing the activated carbon material and 10 wt% hydrochloric acid into a high-pressure reaction kettle, continuously soaking and washing at 80 ℃ for 24 hours, washing with water to be neutral, and drying;
(5) carbon supplement at high temperature: and mixing the activated carbon material obtained after acid washing with polypropylene according to the mass ratio of 1:8, and calcining at 1100 ℃ for 2 hours to obtain the tartary buckwheat-based activated carbon material.
Tests prove that the specific surface area of the tartary buckwheat-based activated carbon material obtained in the embodiment 2 can reach 2087m2(ii)/g, the average pore diameter is about 2.10 nm.
The ash content of the tartary buckwheat-based activated carbon material obtained in the example 2 is tested according to the GB/T1429 method, and the volatile component is tested according to the YB/T5189 method, and the test result shows that the ash content is as low as 0.1% and the volatile component is as low as 1.15%.
Uniformly mixing the tartary buckwheat-based active carbon material obtained in the example 2 with conductive carbon black, sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a certain proportion, adding a water solvent to prepare a negative electrode slurry, and uniformly coating the negative electrode slurry on an aluminum foil (the coating thickness is about 300 mu m; and the surface loading of the active carbon is higher than 5 mg/cm)2) And drying in a vacuum drying oven at 90 ℃ for 12 hours, rolling and blanking to obtain the electrode plate. The obtained electrode plates are respectively a positive electrode and a negative electrode, and are assembled into a full-cell device (comprising 2025/2032 button cells, wound cells, soft package cells and the like) in a glove box with an argon protective atmosphere with water and oxygen both less than 0.1ppm, and the used electrolyte is purchased Nippon 3702 electrolyte. Performing electrochemical test with scan speed of 10mV/s by CHI660D electrochemical workstation, and obtaining cyclic voltammetry curve as shown in FIG. 5; the Wuhan blue battery test system is adopted to carry out constant current charge and discharge performance test on the full battery, and the battery is operated under the condition of 1A/gThe cycle test results are shown in fig. 6, and the results show that after 20000 cycles, the coulombic efficiency is 100%, and the capacity retention rate is more than 89%.
Example 3
(1) Preparing crude carbon: under the argon atmosphere, the tartary buckwheat powder with the particle size of 80 meshes is heated to 400 ℃ at the speed of 3 ℃/min and carbonized for 2 hours at constant temperature to obtain coarse carbon powder;
(2) acid washing for impurity removal: naturally cooling the crude carbon powder, taking out, putting the crude carbon powder and 10 wt% hydrochloric acid into a high-pressure reaction kettle, continuously soaking and washing the crude carbon powder and the hydrochloric acid for 24 hours at the temperature of 80 ℃, washing the crude carbon powder to be neutral by using water, and then drying the crude carbon powder;
(3) and (3) activation: mixing and soaking the carbon material obtained after acid cleaning and sodium hydroxide for 2 hours according to the mass ratio of 1:1.5, then drying, heating to 1300 ℃ at the speed of 3 ℃/min under the atmosphere of argon, preserving heat for 2 hours, washing with water to be neutral, and then drying;
(4) acid washing and purifying: placing the activated carbon material and 10 wt% hydrochloric acid into a high-pressure reaction kettle, continuously soaking and washing at 80 ℃ for 24 hours, washing with water to be neutral, and drying;
(5) carbon supplement at high temperature: and mixing the activated carbon material obtained after acid cleaning with polyethylene according to the mass ratio of 1:5, and calcining at 1300 ℃ for 2 hours to obtain the tartary buckwheat-based activated carbon material.
Tests prove that the specific surface area of the tartary buckwheat-based activated carbon material obtained in the embodiment 3 can reach 1565m2(ii)/g, the average pore diameter is about 2.18 nm.
The ash content of the tartary buckwheat-based activated carbon material obtained in the embodiment 3 is tested according to the GB/T1429 method, and the volatile component is tested according to the YB/T5189 method, and the test result shows that the ash content is as low as 0.043% and the volatile component is as low as 1.34%.
Uniformly mixing the tartary buckwheat-based active carbon material obtained in the embodiment 3 with conductive carbon black, sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a certain proportion, adding a water solvent to prepare a negative electrode slurry, and uniformly coating the negative electrode slurry on an aluminum foil (the coating thickness is about 300 mu m; and the surface loading of the active carbon is higher than 5 mg/cm)2) Drying at 90 deg.C for 12 hr in vacuum drying oven, rolling, and blankingAnd obtaining the electrode plate. The obtained electrode plates are respectively a positive electrode and a negative electrode, and are assembled into a full-cell device (comprising 2025/2032 button cells, wound cells, soft package cells and the like) in a glove box with an argon protective atmosphere with water and oxygen both less than 0.1ppm, and the used electrolyte is purchased Nippon 3702 electrolyte. Performing electrochemical test with scan speed of 10mV/s by CHI660D electrochemical workstation, and obtaining cyclic voltammetry curve as shown in FIG. 7; the Wuhan blue battery test system is adopted to carry out constant-current charge and discharge performance test on the full battery, under the running condition of 1A/g, the battery cycle test result is shown in figure 8, and the result shows that after 20000 cycles, the coulomb efficiency is 100%, and the capacity retention rate is more than 90%.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (12)
1. A preparation method of a tartary buckwheat-based activated carbon material is characterized by comprising the following steps: the method comprises the following steps:
(1) heating and carbonizing the tartary buckwheat-based powder under the protection of inert gas to obtain coarse carbon powder;
(2) washing the coarse carbon powder in acid liquor;
(3) mixing the carbon material obtained after acid cleaning with alkali liquor, and then heating and activating under the protection of inert gas;
(4) washing the activated carbon material in acid liquor;
(5) and mixing the activated carbon material obtained after acid washing with a solid carbon supplement agent, and then calcining to obtain the tartary buckwheat-based activated carbon material.
2. A method of preparing a tartary buckwheat-based activated carbon material as defined in claim 1, wherein: in the step (1), the tartary buckwheat-based powder is powder obtained by crushing one or more raw materials of tartary buckwheat, tartary buckwheat stems and tartary buckwheat peels to 80-200 meshes.
3. A method of preparing a tartary buckwheat-based activated carbon material as defined in claim 1, wherein: in the step (1), the temperature for heating and carbonizing is 400-800 ℃, and the time for heating and carbonizing is 1-5 hours.
4. A method of preparing a tartary buckwheat-based activated carbon material as defined in claim 1, wherein: in the step (2), the crude carbon powder is placed in hydrochloric acid solution with the mass fraction of 3% -20%, continuously soaked and washed for 5-24 hours at the temperature of 60-95 ℃, washed to be neutral by water, and then dried.
5. A method of preparing a tartary buckwheat-based activated carbon material as defined in claim 1, wherein: in the step (3), the carbon material obtained after acid cleaning is mixed with alkali liquor, soaked and dried, then heated to 1300 ℃ under the protection of inert gas for activation for 1-5 hours, washed by water to be neutral, and then dried.
6. A method of preparing a tartary buckwheat-based activated carbon material as defined in claim 1, wherein: in the step (3), the alkali liquor is one or more of sodium hydroxide solution and potassium hydroxide solution.
7. A method of preparing a tartary buckwheat-based activated carbon material as defined in claim 1, wherein: in the step (4), the activated carbon material is placed in hydrochloric acid solution with the mass fraction of 3% -20%, and is continuously soaked and washed for 5-24 hours at the temperature of 60-95 ℃, and then is washed to be neutral by water, and then is dried.
8. A method of preparing a tartary buckwheat-based activated carbon material as defined in claim 1, wherein: in the step (5), the activated carbon material obtained after acid cleaning is mixed with a solid carbon supplement agent according to the mass ratio of 1:1-1:10, and then the mixture is continuously calcined at the temperature of 300-1300 ℃ for 1-5 hours to obtain the tartary buckwheat-based activated carbon material.
9. A method of preparing a tartary buckwheat-based activated carbon material as defined in claim 1, wherein: in the step (5), the solid carbon supplement agent is one or more of polyethylene, polypropylene and polybutylene.
10. A tartary buckwheat-based activated carbon material produced by the production method of any one of claims 1 to 9.
11. Use of a tartary buckwheat-based activated carbon material as defined in claim 10 in a capacitor energy storage device.
12. Use of a tartary buckwheat-based activated carbon material as defined in claim 10 in an electrode material.
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| DE102016123166A1 (en) * | 2016-11-30 | 2018-05-30 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung | ACTIVATED CARBON AND ITS USE AS A CAPACITOR ELECTRODE IN A DOUBLE-LAYER CONDENSER |
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| DE102016123166A1 (en) * | 2016-11-30 | 2018-05-30 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung | ACTIVATED CARBON AND ITS USE AS A CAPACITOR ELECTRODE IN A DOUBLE-LAYER CONDENSER |
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| CN116351394A (en) * | 2023-03-13 | 2023-06-30 | 中煤科工清洁能源股份有限公司 | Method for preparing porous adsorption material by utilizing gasified fine ash |
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