CN114084884A - Preparation method and application of bio-based porous carbon material - Google Patents

Preparation method and application of bio-based porous carbon material Download PDF

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CN114084884A
CN114084884A CN202111233748.2A CN202111233748A CN114084884A CN 114084884 A CN114084884 A CN 114084884A CN 202111233748 A CN202111233748 A CN 202111233748A CN 114084884 A CN114084884 A CN 114084884A
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carbon material
bio
porous carbon
capacitance
based porous
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CN114084884B (en
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何海勇
劳伦
黄昱鑫
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • 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
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • 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
    • H01G11/84—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
    • 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

Abstract

The application discloses a preparation method and application of a bio-based porous carbon material, wherein the preparation method of the bio-based high-capacitance porous carbon material comprises the following steps: (1) mixing fresh plants with KOH, crushing, drying and grinding to obtain a precursor mixture with uniform particles; (2) calcining the precursor mixture to obtain a blocky material; (3) and grinding and crushing the block materials into particles, washing the particles to be neutral by using deionized water, and drying the particles to obtain the high-capacitance porous carbon material. The bio-based high-capacitance porous carbon material based on fresh plants, which is obtained by the invention, has the advantages of simple preparation method, no pollution in process and low commercialization cost. The material is granular, has a multi-level pore structure, is communicated with each other, and is more beneficial to the infiltration and the electron migration of electrolyte. After the material is applied to the electrode material of the super capacitor, the super capacitor electrode material has large capacitance, high capacity retention rate and excellent rate capability, and is a green energy material with great potential.

Description

Preparation method and application of bio-based porous carbon material
Technical Field
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a preparation method and application of a bio-based porous carbon material.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a battery, and has high energy density (10 Wh/kg) and large power density (10 Wh/kg)2～106W/kg), high charge-discharge efficiency (W/kg)>99%) and long life: (>10 thousands times), and the like, and is widely applied to the fields of electronic equipment, transportation, engineering instruments, military equipment, and the like. The super capacitor is used for storing charges by adsorbing ions in electrolyte to the surface of a porous electrode material through the double electric layer effect, so that the specific surface area and the pore structure of the electrode material are main factors influencing the capacitance of the electrode material. With the rapid development of supercapacitor technology, electrode materials of the supercapacitor are developed from activated carbon to novel carbon nanomaterial systems such as carbon nanotubes and graphene.
The bio-based carbon material is low in cost, easy to obtain and simple in preparation process, and is an excellent carbon material source. And the unique cell structure and the internal pipeline structure of the plant are more beneficial to the preparation and synthesis of the porous carbon material. Compared with the common carbon material, the porous carbon material has larger specific surface area, and is beneficial to the storage and the rapid migration of electrolyte ions. The preparation method of the porous carbon with high specific surface area generally uses a KOH activation method or a template method, but the methods are prepared by multi-step operation, and have the disadvantages of high experimental cost, multiple process variables and high commercialization difficulty. Therefore, providing a bio-based high-capacitance porous carbon material prepared by a one-step method is a technical problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of a bio-based porous carbon material. As one aspect of the present application, the present application provides a method for preparing a bio-based porous carbon material, which has the advantages of low raw material price, simple operation, easy process, and easy realization of batch preparation.
A preparation method of a bio-based porous carbon material comprises the following steps:
1) mixing and grinding fresh plant blocks and KOH to obtain a precursor mixture;
2) calcining, carbonizing and activating the precursor mixture in an inert atmosphere to obtain a blocky carbon material;
3) and grinding the massive carbon material, and cleaning to obtain the bio-based porous carbon material.
Optionally, the fresh plant block has a water content of 80-90%.
Optionally, the fresh plant comprises at least one of bamboo shoot, radish, cabbage, celery.
Optionally, the mass ratio of the fresh plants to the KOH in the step 1) is;
optionally, the mass ratio of the fresh plants to the KOH in the step 1) is 15-20: 1.
optionally, in the step 1), the fresh plant block is dried after being mixed with KOH, and then ground after being dried, so as to obtain a precursor mixture.
Optionally, in the step 1), the particle size of the ground plant particles ranges from 0.2 mm to 2mm
Optionally, the drying temperature in the step 1) is 60-100 ℃, and the drying time is 12-48 h.
Optionally, the drying temperature in the step 1) is 60-80 ℃, and the drying time is 18-36 h.
Optionally, said step 2) is performed in a tube furnace.
Alternatively, the reaction conditions for calcination, carbonization and activation in the step 2) are as follows: heating to 600-1300 ℃ at the speed of 1-10 ℃/min, and preserving the heat for 2-6 h.
Optionally, the temperature rise rate in the step 2) is 3-8 ℃/min, the temperature is 600-900 ℃, and the temperature time is 2-4 h.
Optionally, the inert atmosphere comprises at least one of nitrogen, argon, helium.
Alternatively, heating is carried out under an atmosphere of 50-150sccm of an inert gas (sccm refers to Standard Cubic Centimeter per Minute, Standard milliliter per Minute).
Optionally, in the step 3), grinding and crushing the massive carbon material to obtain black particulate carbon particles, washing the black particulate carbon particles to be neutral by using deionized water and ethanol, filtering, and drying to obtain the high-capacitance porous carbon material based on the bio-based material.
Optionally, manual grinding or mechanical grinding is used in the step 3).
Optionally, the ground material is washed to neutral pH in step 3).
Optionally, the step 3) is repeatedly washed to be neutral by using deionized water and ethanol.
Optionally, in the step 3), the ground material powder is dried, and an oven or a vacuum oven is used, wherein the temperature is 60-100 ℃, and the heat preservation time is 12-48 h.
Optionally, the temperature is 60-80 ℃, and the heat preservation time is 18-36 h.
As another aspect of the present application, the present application proposes a bio-based porous carbon material obtained by the above preparation method.
The micro-morphology of the bio-based porous carbon material is a carbon material with interconnected multi-level pore structures, and the specific surface area of the bio-based high-capacitance porous carbon is 1000-3000m2Per g, pore volume of 0.2-2cm3(ii)/g, pore size distribution of 1-3 nm.
Optionally, the specific surface area of the bio-based high-capacitance porous carbon is 1200-1800m2Per g, pore volume of 0.5-1cm3(ii)/g, pore size distribution of 1.5-2.5 nm.
Optionally, the raw material fresh plant of the bio-based porous carbon material contains oxygen-containing functional groups.
Optionally, the bio-based high-capacitance porous carbon material contains 12-25% of oxygen element by mass fraction.
Optionally, the particle size of the bio-based porous carbon material is 20-100 μm.
The term "high capacitance" as used herein refers to the combination of properties of the bio-based porous carbon material, such as high capacitance, high capacity retention, excellent rate capability, and good cycling stability.
As a further aspect of the present application, the present invention also provides the use of the bio-based porous carbon material described above as an electrode material for a supercapacitor. After the bio-based porous carbon material is used as an electrode material of a super capacitor, the material has the advantages of large capacitance, high capacity retention rate, excellent rate performance and good cycle stability.
The invention has the beneficial effects that:
according to the preparation method provided by the invention, fresh plants are used as a bio-based precursor, and carbonization and activation are carried out by using a one-step method after simple treatment, so that the carbon material with a porous structure and a high specific surface area is prepared; after the bio-based porous carbon material is used as an electrode material of a super capacitor, the material has the advantages of large capacitance, high capacity retention rate, excellent rate performance and good cycle stability.
Meanwhile, the preparation method provided by the invention has the advantages of low raw material price, simple operation and easy process, easily realizes batch preparation, can control the morphology, pore structure and specific surface area of the carbon material according to the proportion of the precursor and KOH, and is suitable for industrial production.
Drawings
Fig. 1 is a scanning electron microscope picture of the bio-based high-capacitance porous carbon material prepared in the embodiment 4 of the present invention.
FIG. 2 is a pore distribution curve diagram of the bio-based high-capacitance porous carbon material prepared in example 4 of the present invention.
Fig. 3 is a nitrogen adsorption/desorption curve of the bio-based high-capacitance porous carbon material prepared in example 4 of the present invention.
Fig. 4 is a scanning electron microscope picture of the bio-based high-capacitance porous carbon material prepared in example 5 of the present invention.
FIG. 5 is a pore distribution graph of the bio-based high-capacitance porous carbon material prepared in example 5 of the present invention.
Fig. 6 is a nitrogen adsorption/desorption curve of the bio-based high-capacitance porous carbon material prepared in example 5 of the present invention.
Fig. 7 is a scanning electron microscope picture of the bio-based high-capacitance porous carbon material prepared in example 6 of the present invention.
FIG. 8 is a cyclic voltammetry curve of the bio-based high-capacitance porous carbon material prepared in example 7 of the present invention as an electrode material of a supercapacitor.
FIG. 9 is a rate performance curve of the bio-based high-capacitance porous carbon material prepared in example 7 of the present invention as an electrode material of a supercapacitor.
Fig. 10 is a constant current charge and discharge curve of the bio-based high-capacitance porous carbon material prepared in example 7 of the present invention as an electrode material of a supercapacitor.
Fig. 11 is a long-cycle charge-discharge efficiency graph of the bio-based high-capacitance porous carbon material prepared in example 7 of the present invention.
FIG. 12 is a cyclic voltammetry curve of the bio-based high-capacitance porous carbon material prepared in example 8 of the present invention as an electrode material of a supercapacitor.
Fig. 13 is a cyclic voltammetry curve of the bio-based high-capacitance porous carbon material prepared in example 9 of the present invention as an electrode material of a supercapacitor.
Fig. 14 is a cyclic voltammetry curve of the bio-based high-capacitance porous carbon material prepared in example 10 of the present invention as an electrode material of a supercapacitor.
FIG. 15 is an X-ray photoelectron spectrum of the bio-based high-capacitance porous carbon material prepared in example 4 of the present invention.
Detailed Description
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The scanning electron microscope picture adopts a Hitachi S4800 field emission scanning electron microscope.
The electrochemical performance test process of the super capacitor adopts a Solartron analytical 1400CellTest System electrochemical workstation, the voltage test interval is 0-1.4V, and the scanning speed is 5-50 mV/s.
The BET test was performed in the following manner: ASAP2020M full-automatic specific surface area and porosity analyzer. Preparation of precursor of bio-based high-capacitance porous carbon material
Example 1
The embodiment provides a preparation method of a precursor of a bio-based high-capacitance porous carbon material, wherein the preparation method comprises the following steps:
using 1000g of bamboo shoots, cutting into small pieces;
weighing 55g of KOH, and fully grinding and uniformly stirring the small bamboo shoots and the KOH by using a mechanical grinder;
putting the mixed precursor into a drying oven, and drying for 48h at 80 ℃;
and grinding the dried precursor by using a mechanical grinder until the dried precursor is crushed, wherein the particle size of the crushed particles is 0.2-2 mm, so as to obtain the precursor of the bio-based high-capacitance porous carbon material.
Example 2
Using 1000g of bamboo shoots, cutting into small pieces;
weighing 60g of KOH, and fully grinding and uniformly stirring the small fresh plants and the KOH by using a mechanical grinder;
putting the mixed precursor into an oven, and drying for 36h at 100 ℃;
and grinding the dried precursor by using a mechanical grinder until the dried precursor is crushed to obtain the precursor of the bio-based high-capacitance porous carbon material.
Example 3
1000g of radish was used and chopped into small pieces;
weighing 58g of KOH, and fully grinding and uniformly stirring the small radish blocks and the KOH by using a mechanical grinder;
putting the mixed precursor into an oven, and drying for 36h at 100 ℃;
and grinding the dried precursor by using a mechanical grinder until the dried precursor is crushed to obtain the precursor of the bio-based high-capacitance porous carbon material.
Preparation of bio-based high-capacitance porous carbon material
Example 4
The embodiment provides a preparation method of a bio-based high-capacitance porous carbon material, wherein the preparation method comprises the following specific steps:
taking 5g of the precursor material prepared in the embodiment 1, transferring the precursor material into a quartz boat, placing the quartz boat in a tube furnace, ventilating for 20 minutes by using 500sccm argon, exhausting air in a quartz tube, then starting to heat at a heating rate of 7 ℃/min to 700 ℃, preserving heat for 4 hours, using 100sccm argon to provide an inert gas atmosphere all the time, naturally cooling to room temperature after the constant-temperature reaction is finished, and then taking out a reaction product;
and grinding the obtained reaction product, repeatedly cleaning the reaction product by using deionized water and ethanol until the pH value is neutral, performing suction filtration, and putting the reaction product into an oven at 80 ℃ for 24 hours to obtain the bio-based high-capacitance porous carbon material, wherein the particle size of the product is 20-100 mu m.
FIG. 1 is a scanning electron micrograph of a carbon material according to example 4 of the present invention, in which the structure of the material can be seen and the pores are interconnected.
FIGS. 2 and 3 show BET test data of the carbon material of example 4 of the present invention having a specific surface area of 1367m2And the pore structure is microporous, so that the electrolyte can be infiltrated and ions can be adsorbed easily.
Fig. 15 is an X-ray photoelectron spectrum of the bio-based porous carbon material prepared in this example, which shows that the material contains 79.92% of carbon, 19.37% of oxygen and 0.71% of nitrogen.
Example 5
Taking 5g of the precursor material prepared in the embodiment 2, transferring the precursor material into a quartz boat, placing the quartz boat in a tube furnace, ventilating for 20 minutes by using 500sccm argon, exhausting air in the quartz tube, then starting to heat at the heating rate of 2 ℃/min to 800 ℃, preserving heat for 2 hours, using 100sccm argon to provide inert gas atmosphere all the time, naturally cooling to room temperature after the constant-temperature reaction is finished, and then taking out a reaction product;
and (3) grinding the obtained reaction product, repeatedly washing the reaction product by using deionized water and ethanol until the pH value is neutral, performing suction filtration, and putting the reaction product into a 100 ℃ oven for 24 hours to obtain the bio-based high-capacitance porous carbon material.
FIG. 4 is a scanning electron micrograph of a carbon material obtained by the preparation method described in example 5 of the present invention, which has a more porous structure as the sample of example 3.
FIGS. 5 and 6 show a carbon material obtained by the production method described in example 5 of the present inventionThe BET specific surface area of the sample is as high as 1950m2The pore structure is mainly microporous.
Example 6
Taking 5g of the precursor material prepared in the embodiment 3, transferring the precursor material into a quartz boat, placing the quartz boat in a tube furnace, ventilating for 20 minutes by using 500sccm argon, exhausting air in the quartz tube, then starting to heat at the heating rate of 2 ℃/min to 700 ℃, preserving heat for 3 hours, using 100sccm argon to provide inert gas atmosphere all the time, naturally cooling to room temperature after the constant-temperature reaction is finished, and then taking out a reaction product;
and grinding the obtained reaction product, repeatedly cleaning the reaction product by using deionized water and ethanol until the pH value is neutral, performing suction filtration, and putting the reaction product into an oven at 80 ℃ for 24 hours to obtain the bio-based high-capacitance porous carbon material.
FIG. 7 is a scanning electron micrograph of a carbon material obtained by the preparation method described in example 6 of the present invention, which has a more porous structure as the samples of examples 4 and 5.
Supercapacitor performance testing
Example 7
The application example provides a supercapacitor which takes the bio-based high-capacitance porous carbon material provided in the embodiment 4 as an electrode material, and the assembly of the supercapacitor comprises the following specific steps:
1) according to the following steps of 8: 1: weighing the bio-based high-capacitance porous carbon material prepared in the embodiment 4 of the invention, conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 1, using nitrogen-methyl pyrrolidone (NMP) as a dispersing agent, and uniformly mixing by magnetic stirring to obtain slurry;
2) uniformly coating the slurry on a foam nickel pole piece with the diameter of 16mm, drying in a 60 ℃ drying oven for 12h, and drying in a 60 ℃ vacuum drying oven for 12h to obtain a super capacitor pole piece;
3) the electrode plate with 2 active substances of the same mass is adopted to assemble a button type symmetrical electrode super capacitor, 6MKOH is used as electrolyte, and a 19mm glass fiber membrane is used as a diaphragm.
And (3) carrying out electrochemical performance test on the obtained super capacitor, wherein a Solartron analytical 1400CellTest System electrochemical workstation is adopted in the test process, the voltage test interval is 0-1V, and the scanning speed is 5 mV/s.
FIG. 8 is a plot of the cyclic voltammetry performance of the carbon material of example 4 of the invention as the supercapacitor electrode material of example 7. The parallelogram CV curve shows that the material has good performance and less polarization.
FIG. 9 is a rate test of the carbon material of example 4 of the present invention as the supercapacitor electrode material of example 7. at a sweep rate of 5mV/s, the capacity of the material of the present invention reaches 327F/g, and at a sweep rate of 100mV/s, the capacity of 254F/g is still present, indicating that the rate performance of the material is good.
FIG. 10 shows a GCD test of constant current charging and discharging of the carbon material of example 4 as the electrode material of the supercapacitor of example 7.
FIG. 11 shows that the carbon material of example 4 of the present invention is used as the electrode material of the supercapacitor of example 7 in a long cycle test, and after the carbon material is cycled for 10000 cycles at a current density of 1A/g, the supercapacitor has a capacity retention rate of 95%, which indicates that the material of the present invention has good long cycle performance.
Example 8
The application example provides a supercapacitor which takes the bio-based high-capacitance porous carbon material provided in the embodiment 5 as an electrode material, and the assembly of the supercapacitor comprises the following specific steps:
according to the following steps of 8: 1: weighing the bio-based high-capacitance porous carbon material prepared in the embodiment 5 of the invention, conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 1, using nitrogen-methyl pyrrolidone (NMP) as a dispersing agent, and uniformly mixing by magnetic stirring to obtain slurry;
uniformly coating the slurry on a foam nickel pole piece with the diameter of 16mm, drying in a 60 ℃ drying oven for 12h, and drying in a 60 ℃ vacuum drying oven for 12h to obtain a super capacitor pole piece;
2 electrode plates with the same active material mass are adopted to assemble a buckle type symmetrical electrode super capacitor, and 2MLi is used2SO4As an electrolyte, a 19mm glass fiber membrane was used as a separator.
And (3) carrying out electrochemical performance test on the obtained super capacitor, wherein a Solartron analytical 1400CellTest System electrochemical workstation is adopted in the test process, the voltage test interval is 0-1.4V, and the scanning speed is 5-50 mV/s.
FIG. 12 is a plot of the cyclic voltammetry performance of the carbon material of example 5 of the invention as the supercapacitor electrode material of example 8 using 2MLi2SO4After the electrolyte is used, the voltage interval is increased to 1.4V, and the CV curve of a parallelogram is also formed at the moment, which shows that the material has good performance and small polarization.
Example 9
The embodiment provides a supercapacitor which takes the bio-based high-capacitance porous carbon material provided in the embodiment 5 as an electrode material, and the assembly of the supercapacitor comprises the following specific steps:
according to the following steps of 8: 1: weighing the bio-based high-capacitance porous carbon material prepared in the embodiment 5 of the invention, conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 1, using nitrogen-methyl pyrrolidone (NMP) as a dispersing agent, and uniformly mixing by magnetic stirring to obtain slurry;
uniformly coating the slurry on a foamed nickel pole piece with the diameter of 16mm, placing the foamed nickel pole piece in a drying oven at 100 ℃ for drying for 12h, and then placing the foamed nickel pole piece in a vacuum drying oven at 100 ℃ for drying for 12h to obtain a super capacitor pole piece;
the electrode plates with the same mass of 2 active substances are adopted to assemble the button type symmetrical electrode super capacitor, the electrolyte of the commercial super capacitor is used as the electrolyte, and a 19mm glass fiber membrane is used as a diaphragm.
And (3) carrying out electrochemical performance test on the obtained super capacitor, wherein a Solartron analytical 1400CellTest System electrochemical workstation is adopted in the test process, the voltage test interval is 0-2.5V, and the scanning speed is 5-50 mV/s.
Fig. 13 is a cyclic voltammetry performance curve of the carbon material of example 5 of the present invention as the supercapacitor electrode material of example 9, the voltage range is increased to 2.5V using the organic commercial supercapacitor electrolyte, and the material of the present invention still has a relatively good CV curve, which illustrates that the material is suitable for use in both aqueous electrolyte systems and organic electrolyte systems of supercapacitors.
Example 10
The application example provides a supercapacitor which takes the bio-based high-capacitance porous carbon material provided in example 6 as an electrode material, and the assembly of the supercapacitor comprises the following specific steps:
1) according to the following steps of 8: 1: weighing the bio-based high-capacitance porous carbon material prepared in the embodiment 6 of the invention, conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 1, using nitrogen-methyl pyrrolidone (NMP) as a dispersing agent, and uniformly mixing by magnetic stirring to obtain slurry;
2) uniformly coating the slurry on a foam nickel pole piece with the diameter of 16mm, drying in a 60 ℃ drying oven for 12h, and then drying in a 120 ℃ vacuum drying oven for 12h to obtain a super capacitor pole piece;
3) the electrode plate with 2 active substances of the same mass is adopted to assemble a button type symmetrical electrode super capacitor, 6MKOH is used as electrolyte, and a 19mm glass fiber membrane is used as a diaphragm.
And (3) carrying out electrochemical performance test on the obtained super capacitor, wherein a Solartron analytical 1400CellTest System electrochemical workstation is adopted in the test process, the voltage test interval is 0-1V, and the scanning speed is 5 mV/s.
FIG. 14 is a CV test of the carbon material of example 6 of the present invention as the supercapacitor electrode material of example 10, showing a capacity of 240F/g at a sweep rate of 5 mV/s.
The above embodiments are merely illustrative of the technical ideas 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 protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. A preparation method of a bio-based porous carbon material is characterized by comprising the following steps:
1) mixing and grinding fresh plant blocks and KOH to obtain a precursor mixture;
2) calcining, carbonizing and activating the precursor mixture in an inert atmosphere to obtain a blocky carbon material;
3) and grinding the massive carbon material, and cleaning to obtain the bio-based porous carbon material.
2. The method of claim 1, wherein the fresh pieces of plant material have a moisture content of 80-90%;
preferably, the fresh plant includes at least one of bamboo shoot, radish, cabbage, and celery.
3. The method for preparing a bio-based porous carbon material according to claim 1, wherein the mass ratio of fresh plants to KOH in step 1) is;
preferably, the mass ratio of the fresh plants to the KOH in the step 1) is 15-20: 1.
4. the method for preparing a bio-based porous carbon material according to claim 1, wherein in step 1), the fresh plant pieces are mixed with KOH and then dried, and then ground to obtain a precursor mixture;
preferably, in the step 1), the particle size of the ground plant particles is in the range of 0.2-2 mm.
5. The method for preparing a bio-based porous carbon material according to claim 1, wherein the reaction conditions for the calcination carbonization activation in the step 2) are: heating to 600-1300 ℃ at the speed of 1-10 ℃/min, and preserving the heat for 2-6 h.
6. A bio-based porous carbon material, characterized in that it is prepared by the method of any one of claims 1 to 5.
7. The bio-based porous carbon material as claimed in claim 6, wherein the micro-morphology of the bio-based porous carbon material is a carbon material with interconnected multi-stage pore structures, and the specific surface area of the bio-based high-capacitance porous carbon is 1000-3000m2Per g, pore volume of 0.2-2cm3(ii)/g, pore size distribution is 1-3 nm;
preferably, the specific surface area of the bio-based high-capacitance porous carbon is 1200-1800m2Per g, pore volume of 0.5-1cm3(ii)/g, pore size distribution of 1.5-2.5 nm.
8. The bio-based porous carbon material according to claim 6, wherein the bio-based high-capacitance porous carbon material contains 12 to 25% by mass of oxygen.
9. The bio-based porous carbon material of claim 6, wherein the particle size of the bio-based porous carbon material is 20 to 100 μm.
10. Use of a bio-based porous carbon material according to any one of claims 6 to 9 as an electrode material for a supercapacitor.
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CN106744936A (en) * 2016-12-05 2017-05-31 天津大学 A kind of method that biomass cauline leaf separation prepares absorbent charcoal material
CN112138664A (en) * 2020-09-10 2020-12-29 广州大学 Carbon-based electrocatalyst and preparation method thereof
CN113184849A (en) * 2021-05-14 2021-07-30 西南大学 Activated carbon material derived based on green soy bean hulls as well as preparation method and application thereof

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CN106744936A (en) * 2016-12-05 2017-05-31 天津大学 A kind of method that biomass cauline leaf separation prepares absorbent charcoal material
CN106698427A (en) * 2017-03-09 2017-05-24 深圳市贝特瑞新能源材料股份有限公司 Activated carbon, preparation method thereof, and application of activated carbon in supercapacitor electrode
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CN113184849A (en) * 2021-05-14 2021-07-30 西南大学 Activated carbon material derived based on green soy bean hulls as well as preparation method and application thereof

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