CN112830472B - Preparation method of porous carbon, porous carbon obtained by preparation method and application of porous carbon - Google Patents
Preparation method of porous carbon, porous carbon obtained by preparation method and application of porous carbon Download PDFInfo
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- 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- H01G11/84—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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Abstract
The invention provides a preparation method of porous carbon, porous carbon obtained by the preparation method and application of the porous carbon. The preparation method of the porous carbon comprises the following steps: and mixing petroleum asphalt with a template, calcining, and removing the rest template after calcining to obtain the porous carbon, wherein the template is basic magnesium carbonate and/or magnesium oxide. The invention particularly provides a preparation method of petroleum-based two-dimensional porous carbon nano-sheets and three-dimensional graded porous carbon and application of the petroleum-based two-dimensional porous carbon nano-sheets and the three-dimensional graded porous carbon in lithium ion capacitors. The double-carbon composite lithium ion capacitor constructed by the electrode active material prepared by the invention has high energy density, high power density and excellent cycling stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion capacitor preparation, and particularly relates to a preparation method of porous carbon, porous carbon obtained by the preparation method and application of the porous carbon, in particular to a preparation method of petroleum-based two-dimensional porous carbon nano sheets and three-dimensional graded porous carbon and application of the porous carbon in an energy storage electrode.
Background
With further developments in the energy storage field, the demand for new energy storage devices of the next generation capable of satisfying both higher energy density and power density has increased. In view of this, a new type of electrochemical energy storage device, a metal ion capacitor, has been developed. Lithium ion capacitors are one of the metal ion capacitors, because the more sophisticated lithium ion secondary battery development technology is the fastest growing new energy storage device. Lithium ion capacitors generally comprise three parts: a battery-type negative electrode, a capacitor-type positive electrode, and a lithium-containing organic electrolyte. Thus, there are two different electrochemical energy storage mechanisms within lithium ion capacitors, namely: ion intercalation/deintercalation on the negative side and anion adsorption/desorption on the positive side. Therefore, the lithium ion capacitor exhibits a higher power density than the conventional secondary battery and a higher energy density than the conventional supercapacitor.
Currently, commercial lithium ion capacitors are mainly made of commercial graphite as the negative electrode material and activated carbon as the positive electrode material. But the increase in energy density of lithium ion capacitor systems is greatly limited due to the lower specific capacity and poor cycle life of commercial graphite and activated carbon. In general, the energy density of an electrochemical energy storage device is primarily determined by the energy storage behavior of the electrode material. Therefore, the development is cheap and easy to obtain, the operation is simple and convenient, and the high-performance electrode material with low cost is an effective measure for constructing the high-performance lithium ion capacitor and a future development trend.
The petroleum heavy oil is used as an intermediate product in the petroleum refining process, has low price, huge yield and higher carbon content, and is an ideal carbon precursor for preparing the high-performance electrode material. Direct activation is generally carried out using KOH, naOH, H 3 PO 4 The activator is used for etching the precursor at high temperature, the requirement on corrosion resistance of equipment is high, and meanwhile, the product isThe yield of the product is also lower, and the pore canal of the product is single and is mainly micropores and mesopores. The soft template method has higher requirements on the carbon precursor, generally requires that the carbon precursor and the surfactant or the block copolymer can be self-assembled, and has higher production cost and complex preparation flow and high requirements on the precursor, so that the method is limited to be further popularized and applied even though an acid reagent is not required to be added to remove the template.
CN109321211a discloses a graphitized hierarchical porous carbon composite phase change energy storage material and a preparation method thereof, wherein a low-cost carbon precursor, a graphitizing catalyst and a pore-forming agent are adopted as raw materials, and graphitized hierarchical porous carbon is prepared through ball milling, mixing, carbonization and other processes; and then the prepared graphitized hierarchical porous carbon is used as a supporting material and is compounded with a phase change material to obtain the graphitized hierarchical porous carbon composite phase change energy storage material.
CN106430144a discloses a method for preparing asphalt-based hierarchical pore carbon sheet by using a sheet magnesium oxide template and application thereof, the method comprises the following steps: and (3) dropwise adding the asphalt solution into the magnesium oxide suspension, stirring, drying to obtain brown powder, carbonizing, grinding, adding potassium hydroxide for grinding, carbonizing for the second time, adding dilute hydrochloric acid into the product, carrying out ultrasonic vibration, washing and drying to obtain the hierarchical pore carbon material.
CN109292750a discloses a preparation method of a cross-linked three-dimensional porous carbon sheet for a supercapacitor, which is characterized in that: the method comprises the steps of taking viscous petroleum asphalt as a carbon source, taking potassium citrate as a template agent, carrying out pyrolysis to enable carboxylic acid in the potassium citrate and hydroxyl in the petroleum asphalt to form ester bond combination, carrying out ester bond pyrolysis to generate gas to form a bubbling structure, and carrying out further pyrolysis to prepare the nano-sheet porous carbon material.
Therefore, developing a method to increase the yield of porous carbon and improve the single problem of the pore canal of the product is the focus of research in the field.
Disclosure of Invention
The invention aims to provide a preparation method of porous carbon, porous carbon obtained by the preparation method and application of the porous carbon. The preparation method of the porous carbon further improves the yield of the obtained porous carbon product, and ensures that the porous carbon has a rich mesoporous structure.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing porous carbon, the method comprising the steps of: and mixing petroleum asphalt with a template, calcining, and removing the rest template after calcining to obtain the porous carbon, wherein the template is basic magnesium carbonate and/or magnesium oxide.
The preparation method of the porous carbon further improves the yield of the obtained porous carbon product, and ensures that the porous carbon has a rich mesoporous structure, so that compared with graphite of a commercial lithium ion battery/capacitor cathode and active carbon of a commercial super capacitor/lithium ion capacitor anode, the porous carbon material prepared by the preparation method of the invention has more excellent lithium storage capacity, shows higher specific capacity, and can greatly improve the energy density and the cycling stability of the commercial lithium ion battery and the super capacitor.
Preferably, the mass ratio of petroleum asphalt to template is (3-5): 1, e.g., 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, etc.
Preferably, the petroleum asphalt is a hard asphalt having an initial weight loss temperature of greater than 300 ℃ (e.g., 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, etc.), the petroleum asphalt having a weight loss of greater than 75wt% (e.g., 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, etc.) between 300-635 ℃ (e.g., 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 635 ℃, etc.), and the petroleum asphalt having a weight loss of greater than 95wt% (e.g., 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, etc.) at greater than 750 ℃ (e.g., 755 ℃, 760 ℃, 765 ℃, 770 ℃, 775 ℃, etc.).
Preferably, the basic magnesium carbonate is not pretreated, the initial weight loss stage is 34-300 ℃, and the weight loss ratio is 19.3wt% due to the removal of water. The second weight loss stage was 300-600℃and the weight loss ratio due to CO2 removal was 37.4wt%. The total weight loss ratio of the two stages was 56.7wt%.
Preferably, the calcination is carried out in a horizontal high temperature tube furnace.
Preferably, the temperature of the calcination is 700-900 ℃ (e.g., 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, etc.), the temperature rise rate of the calcination is 2-5 ℃/min (e.g., 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, etc.), and the time of the calcination is 200-510min (e.g., 200min, 250min, 300min, 350min, 400min, 450min, 500min, 510min, etc.).
Preferably, the specific steps of removing the template remaining after calcination are as follows: the template remaining after calcination was removed by washing with hydrochloric acid.
Preferably, the hydrochloric acid is used in an amount of 10 to 150mL/g of asphalt, for example, 10mL/g of asphalt, 20mL/g of asphalt, 40mL/g of asphalt, 60mL/g of asphalt, 80mL/g of asphalt, 100mL/g of asphalt, 120mL/g of asphalt, 140mL/g of asphalt, 150mL/g of asphalt, etc., and the hydrochloric acid has a concentration of 1 to 10mol/L, for example, 1mol/L, 2mol/L, 4mol/L, 6mol/L, 8mol/L, 10mol/L, etc. The amount of hydrochloric acid used herein refers to the volume of hydrochloric acid used per gram of asphalt, e.g. "10mL/g asphalt" refers to the need to wash 10mL hydrochloric acid per 1g asphalt to remove the template remaining after calcination.
Preferably, the hydrochloric acid is washed with water for 1-2 times, and the water consumption is 500-1000mL/g of asphalt, such as 500mL/g of asphalt, 600mL/g of asphalt, 700mL/g of asphalt, 800mL/g of asphalt, 900mL/g of asphalt, 1000mL/g of asphalt, etc. Wherein the amount of water used refers to the volume of water used per gram of bitumen, e.g. "500mL/g bitumen" means that 500mL of water is required for washing per 1g bitumen.
Preferably, the porous carbon is a two-dimensional porous carbon nano sheet, and the preparation method of the two-dimensional porous carbon nano sheet comprises the following steps:
(1) Mixing petroleum asphalt and basic magnesium carbonate in a grinding and mixing mode;
(2) Calcining the mixed substance obtained in the step (1) in a high-temperature tube furnace in a nitrogen atmosphere;
(3) Washing the product obtained by calcining in the step (2) by hydrochloric acid to remove the residual template after calcining, and washing by water to obtain the two-dimensional porous carbon nano sheet.
Preferably, the porous carbon is a porous carbon having a three-dimensional hierarchical porous structure, and the method for preparing the porous carbon having the three-dimensional hierarchical porous structure comprises the steps of:
(1') mixing petroleum asphalt and magnesium oxide by a grinding mixing mode;
(2 ') calcining the mixed material obtained in the step (1') in a high-temperature tube furnace under a nitrogen atmosphere;
(3 ') washing the product obtained by calcining in the step (2') by hydrochloric acid to remove the residual template after calcining, and washing by water to obtain intermediate porous carbon;
(4 ') mixing the intermediate porous carbon obtained in the step (3') with an activator by a grinding mixing mode;
(5 ') calcining the mixed material obtained in the step (4') in a high-temperature tube furnace under the nitrogen atmosphere;
(6) Washing the product obtained by calcining in the step (5') by hydrochloric acid to remove the residual template after calcining, and washing by water to obtain the porous carbon with the three-dimensional hierarchical porous structure.
Preferably, in step (4'), the activator is potassium hydroxide.
Preferably, in step (4'), the mass ratio of the activator to the intermediate porous carbon is (3-5): 1, e.g., 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, etc.
Preferably, in step (5'), the temperature of the calcination is 700-900 ℃ (e.g., 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, etc.), the temperature rise rate of the calcination is 2-5 ℃/min (e.g., 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, etc.), and the time of the calcination is 200-510min (e.g., 200min, 250min, 300min, 350min, 400min, 450min, 500min, 510min, etc.).
Preferably, in step (6'), the hydrochloric acid is used in an amount of 2 to 30mL/g of asphalt, for example, 2mL/g of asphalt, 4mL/g of asphalt, 6mL/g of asphalt, 8mL/g of asphalt, 10mL/g of asphalt, 12mL/g of asphalt, 14mL/g of asphalt, 16mL/g of asphalt, 18mL/g of asphalt, 20mL/g of asphalt, 22mL/g of asphalt, 24mL/g of asphalt, 26mL/g of asphalt, 28mL/g of asphalt, 30mL/g of asphalt, etc., and the hydrochloric acid is used in an amount of 1 to 10mol/L, for example, 1mol/L, 2mol/L, 4mol/L, 6mol/L, 8mol/L, 10mol/L, etc.
Preferably, in step (6'), the number of times of washing with water is 1 to 2, and the amount of water used is 100 to 200mL/g of asphalt, for example, 100mL/g of asphalt, 120mL/g of asphalt, 140mL/g of asphalt, 160mL/g of asphalt, 180mL/g of asphalt, 200mL/g of asphalt, etc.
In a second aspect, the present invention provides a porous carbon obtained by the method for producing a porous carbon according to the first aspect. Preferably, the porous carbon is a two-dimensional porous carbon nano-sheet or a porous carbon having a three-dimensional hierarchical porous structure.
In a third aspect, the present invention provides the use of a porous carbon as described in the second aspect for the preparation of a lithium ion capacitor.
In a fourth aspect, the present invention provides a lithium ion electrode sheet comprising porous carbon as described in the second aspect. Preferably, the electrode sheet is a positive electrode sheet, and the electrode sheet is porous carbon as described in the second aspect. Preferably, the electrode plate is a negative electrode plate, and the preparation raw materials of the negative electrode plate include: the porous carbon, the conductive agent, and the binder as described in the second aspect.
Preferably, the mass ratio of the porous carbon to the conductive agent to the binder is (6-8): 1-2;
wherein "6-8" is, for example, 6, 6.5, 7, 7.5, 8, etc., the first "1-2" is, for example, 1, 1.2, 1.4, 1.6, 1.8, 2, etc., and the second "1-2" is, for example, 1, 1.2, 1.4, 1.6, 1.8, 2, etc.
Preferably, the conductive agent is conductive carbon black.
Preferably, the binder is an aqueous solution of sodium carboxymethyl cellulose.
In a fifth aspect, the present invention provides a lithium ion capacitor, which includes the lithium ion electrode sheet according to the fourth aspect.
Preferably, in the lithium ion capacitor, the mass ratio of the positive electrode sheet to the negative electrode sheet is (1-3): 1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.2:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the active carbon and graphite raw materials prepared industrially, the raw materials used in the invention are the byproduct hard petroleum asphalt in the petroleum refining process, and compared with the active carbon and graphite raw materials prepared industrially, the raw materials are low in cost, wide in source, higher in yield and higher in carbon content, so that the prepared porous carbon product has higher yield and is a carbon precursor with low added value.
(2) The preparation method of the material used by the invention is simple to operate, the used chemical reagent is low in price, the production cost is greatly reduced, and the material has objective large-scale application prospect.
(3) Compared with graphite of a commercial lithium ion battery/capacitor cathode and active carbon of a commercial supercapacitor/lithium ion capacitor anode, the porous carbon material prepared by the method has more excellent lithium storage capacity, shows higher specific capacity, and can greatly improve the energy density and the cycle stability of the commercial lithium ion battery and the supercapacitor.
(4) The two-dimensional porous carbon nano sheet and the three-dimensional graded porous carbon prepared by the method can be respectively used as active materials of the anode and the cathode of the lithium ion capacitor, and have ultrahigh specific capacity and outstanding cycle stability; the lithium ion capacitor assembled by the two materials has higher energy density and power density than those of commercial lithium ion capacitors, and has good long-cycle stability and great popularization and application values.
Drawings
FIG. 1 is a scanning electron microscope image of HCNs-5 provided in example 1, scale bar 1 μm.
FIG. 2 is a scanning electron microscope image of HCNs-5 provided in example 1, scale 200nm.
FIG. 3 is a projection electron microscope image of HCNs-5 provided in example 1, scale 500nm.
FIG. 4 is a projection electron microscope image of HCNs-5 provided in example 1, scale 50nm.
FIG. 5 is an X-ray diffraction (XRD) pattern of HCNs-5 provided in example 1.
FIG. 6 is a Raman spectrum of HCNs-5 provided in example 1.
FIG. 7 is a scanning electron microscope image of HCNs-4 provided in example 2, scale 1 μm.
FIG. 8 is a scanning electron microscope image of HCNs-4 provided in example 2, scale 200nm.
FIG. 9 is an X-ray diffraction (XRD) pattern of HCNs-4 provided in example 2.
Fig. 10 is a raman spectrum of HCNs-4 provided in example 2.
FIG. 11 is a scanning electron microscope image of HCNs-6 provided in example 3, scale 1 μm.
FIG. 12 is a scanning electron microscope image of HCNs-6 provided in example 3, scale 200nm.
FIG. 13 is an X-ray diffraction (XRD) pattern of HCNs-6 provided in example 3.
FIG. 14 is a Raman spectrum of HCNs-6 provided in example 3.
FIG. 15 is a scanning electron microscope image of 3DHPC-5 provided in example 5, with a scale of 500nm.
FIG. 16 is a scanning electron microscope image of 3DHPC-5 provided in example 5, scale 100nm.
FIG. 17 is a projection electron microscope image of 3DHPC-5 provided in example 5, with a scale of 500nm.
FIG. 18 is a projection electron microscope image of 3DHPC-5 provided in example 5, scale 100nm.
FIG. 19 is a scanning electron microscope image of basic magnesium carbonate with a scale of 1. Mu.m.
FIG. 20 is a scanning electron microscope image of basic magnesium carbonate with a scale of 200nm.
FIG. 21 is a scanning electron micrograph of magnesium oxide with a scale of 2. Mu.m.
FIG. 22 is a scanning electron micrograph of magnesium oxide with a scale of 500nm.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The sources of the components in the following embodiments are as follows: petroleum asphalt (manufacturer: jiujiang petrochemical Co., ltd., brand: hard asphalt), basic magnesium carbonate (manufacturer: national drug group chemical reagent Co., ltd., brand: 20023717), conductive carbon black (manufacturer: dongguan City road laboratory equipment science and technology Co., brand: MA-EN-CO-03) and sodium carboxymethylcellulose (manufacturer: shanghai Alasdine Biochemical technology Co., ltd., brand: C104977).
Example 1
The present embodiment provides a method for preparing porous carbon (HCNs-4), comprising the steps of:
(1) 1.0g of petroleum asphalt and 4.0g of basic magnesium carbonate are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Transferring to a 20mL corundum boat, placing in a horizontal tube furnace filled with nitrogen, heating from room temperature to 800 ℃ at a heating rate of 5 ℃/min, and keeping for 120min;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product which is named as HCNs-4.
Fig. 1 and fig. 2 are sem charts of HCNs-4 provided in example 1, and as shown in fig. 1 and fig. 2, it can be seen that the prepared material has a two-dimensional lamellar structure, which can provide an enlarged interlayer distance for intercalation and diffusion of lithium ions, effectively reduce diffusion resistance of lithium ions, and improve transmission kinetics of lithium ions. Meanwhile, the stable two-dimensional lamellar structure can effectively relieve volume change caused in the process of lithium ion intercalation and deintercalation, and the circulation stability of the material is improved.
FIGS. 3 and 4 are transmission electron microscope diagrams of HCNs-4 provided in example 1, and from FIG. 3, it can be seen that the HCNs-4 material has a layered structure rich in defects, and can provide rich active sites and storage space for adsorption and storage of lithium ions; as shown in figure 4, the surface of the two-dimensional sheet layer is provided with abundant mesopores, so that the specific surface area of the material is effectively improved, the diffusion path of lithium ions is further shortened, the transmission rate of the lithium ions in the bulk phase of the material is accelerated, meanwhile, a rich space is provided for the adsorption of the lithium ions, the surface capacitance contribution ratio of the lithium ions is increased, the rapid reaction kinetics is shown, and the material is an ideal high-performance lithium ion capacitor anode active material.
Fig. 5 is an X-ray diffraction (XRD) pattern of HCNs-4 provided in example 1, and two diffraction peaks corresponding to 002 and 100 crystal planes of graphite at about 23 ° and 43 ° can be seen in the powder X-ray diffraction pattern of HCNs-4 shown in fig. 5, indicating that the prepared example exhibits amorphous carbon characteristics.
FIG. 6 is a Raman spectrum of HCNs-4 provided in example 1, from which it can be seen that the spectrum is located at 1350cm, as shown in FIG. 6 -1 And 1590cm -1 The two peaks at the point correspond to the D peak (sp 2 ) And G peak (sp) 3 ) Peak intensity ratio I of D peak and G peak D /I G The embodiment has a higher defect level as shown by=0.894, which is favorable for providing rich electrochemical lithium storage active sites for lithium ion storage, greatly improves the lithium storage capacity of the material, and increases the capacitance contribution ratio of the material capacity.
Example 2
The present embodiment provides a method for preparing porous carbon (HCNs-3), comprising the steps of:
(1) 1.0g of petroleum asphalt and 3.0g of basic magnesium carbonate are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Transferring to a 20mL corundum boat, placing in a horizontal tube furnace filled with nitrogen, heating from room temperature to 800 ℃ at a heating rate of 5 ℃/min, and keeping for 120min;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product, which is named as HCNs-3.
Fig. 7 and 8 are scanning electron microscope diagrams of HCNs-3 provided in example 2, and as shown in fig. 7 and 8, the prepared material can be seen to have a blocky shape, lack pore channels, small specific surface area, being unfavorable for rapid transmission of lithium ions on the surface and bulk phase of the material, large transmission resistance, limited effective lithium storage, and greatly limited lithium storage capacity of the material. The lower template addition amount results in poorer coating effect of the template, and the regulation and activation effects of the template are not effectively exerted.
FIG. 9 is an X-ray diffraction (XRD) spectrum of HCNs-3 provided in example 2. As shown in FIG. 9, two diffraction peaks corresponding to 002 and 100 crystal planes of graphite at about 23℃and 43℃were observed in the powder X-ray diffraction pattern of HCNs-3, exhibiting amorphous carbon characteristics consistent with those of example 1.
Fig. 10 is a raman spectrum of HCNs-3 provided in example 2, and from the raman spectrum of HCNs-3 shown in fig. 10, it can be seen that the similar spectrum characteristics of example 2 to those of example 1, namely, defect peak (D peak) and graphitization peak (G peak) corresponding to the carbon material are exhibited, and ID/ig=0.895, and the defect degree is high.
Example 3
The present embodiment provides a method for preparing porous carbon (HCNs-5), comprising the steps of:
(1) 1.0g of petroleum asphalt and 5.0g of basic magnesium carbonate are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Transferring to a 20mL corundum boat, placing in a horizontal tube furnace filled with nitrogen, heating from room temperature to 800 ℃ at a heating rate of 5 ℃/min, and keeping for 120min;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product which is named as HCNs-5.
Fig. 11 and fig. 12 are sem images of HCNs-5 provided in example 3, and as can be seen from the sem images of fig. 11 and fig. 12, the prepared material has a stacked structure of sheets, and the channel structure is severely deficient. The template addition amount is too high, so that the prepared lamellar structure deforms and convolves, the adsorption of lithium ions on the surface of the material and the intercalation and deintercalation of lithium ions in a bulk phase are not facilitated, the lithium storage space is deficient, and the lithium storage capacity is weak.
FIG. 13 is an X-ray diffraction (XRD) pattern of HCNs-5 provided in example 3; in the powder X-ray diffraction pattern of HCNs-5, two diffraction peaks corresponding to 002 and 100 crystal planes of graphite were observed at about 23℃and 43℃and exhibited amorphous carbon characteristics consistent with example 1.
FIG. 14 is a Raman spectrum of HCNs-5 provided in example 3; from the raman spectra of HCNs-5, it can be seen that the similar spectral features of example 3 to example 1, i.e. exhibiting a defect peak (D-peak) and graphitization peak (G-peak) corresponding to the carbon material, with ID/ig=0.859, have the lowest defect level and the highest graphitization level compared to examples 1 and 2. According to the electrochemical test results, the lithium storage capacity of this example was the worst, which is due to the lowest defect level and the deformed two-dimensional lamellar structure.
Example 4
The present embodiment provides a method for producing porous carbon (SHC-4), comprising the steps of:
(1) 1.0g of petroleum asphalt and 4.0g of magnesium oxide are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 120min to obtain the final product, which is named SHC-4.
Example 5
The present embodiment provides a method for producing porous carbon (3 DHPC-4), the method for producing porous carbon (3 DHPC-4) comprising the steps of:
(1) Respectively weighing 0.1g of SHC-5 prepared in example 4 and 0.4g of KOH, grinding and mixing uniformly in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) And (3) reducing the temperature of the tubular furnace to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual KOH after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product which is named as 3DHPC-4.
Comparative example 1
This comparative example provides a method for producing porous carbon (HPC-4), the method for producing porous carbon (HPC-4) comprising the steps of:
(1) 1.0g of petroleum asphalt and 4.0g of potassium citrate are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product, namely HPC-4.
Comparative example 2
The present comparative example provides a method for preparing porous carbon (MCC-4), comprising the steps of:
(1) 1.0g of petroleum asphalt and 4.0g of magnesium citrate are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product, which is named as MCC-4.
Comparative example 3
The present comparative example provides a method for preparing porous carbon (MAC-4), the method for preparing porous carbon (MAC-4) comprising the steps of:
(1) 1.0g of petroleum asphalt and 4.0g of magnesium acetate are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product, which is named as MAC-4.
Comparative example 4
This comparative example provides a method for preparing a porous carbon (PAC-4), the method for preparing the porous carbon (PAC-4) comprising the steps of:
(1) 1.0g of petroleum asphalt and 4.0g of potassium acetate are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product, which is named PAC-4.
Comparative example 5
This comparative example provides a method for preparing porous carbon (IOC-4), comprising the steps of:
(1) 1.0g of petroleum asphalt and 4.0g of ferric oxide are respectively weighed and ground and uniformly mixed in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) When the temperature of the tube furnace is reduced to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove residual templates after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product, namely the IOC-4.
Comparative example 6
This comparative example provides a method for producing porous carbon (HPAC-4), comprising the steps of:
(1) 0.1g of HPC-4 prepared in comparative example 1 and 0.4g of KOH are respectively weighed and ground and mixed uniformly in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) And (3) reducing the temperature of the tubular furnace to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove the residual template after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product which is named as HPAC-4.
Comparative example 7
This comparative example provides a method for producing porous carbon (MCAC-4), which comprises the steps of:
(1) Respectively weighing 0.1g of MCC-4 prepared in comparative example 2 and 0.4g of KOH, grinding and uniformly mixing in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) And (3) reducing the temperature of the tubular furnace to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove the residual template after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 120min to obtain the final product, which is named MCAC-5.
Comparative example 8
The present comparative example provides a method for preparing porous carbon (MAAC-4), comprising the steps of:
(1) Respectively weighing 0.1g of the MAC-4 prepared in the comparative example 3 and 0.4g of KOH, and grinding and mixing uniformly in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) And (3) reducing the temperature of the tubular furnace to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove the residual template after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product which is named MAAC-4.
Comparative example 9
The present comparative example provides a method for preparing porous carbon (hacnts-4), comprising the steps of:
(1) Respectively weighing 0.1g of HCNs-4 prepared in example 1 and 0.4g of KOH, and grinding and mixing uniformly in a 250mL agate mortar;
(2) Then transferring the mixture to a 20mL corundum boat, placing the corundum boat in a horizontal tube furnace filled with nitrogen, and heating the corundum boat from room temperature to 800 ℃ at a heating rate of 5 ℃ per minute and keeping the corundum boat for 120 minutes;
(3) And (3) reducing the temperature of the tubular furnace to room temperature, transferring the calcined product into a 250mL beaker, adding a proper amount of hydrochloric acid to remove the residual template after calcination, washing for multiple times, transferring a sample obtained through vacuum filtration into a 60 ℃ oven, and drying for 24 hours to obtain the final product, namely HACNs-4.
Application example 1
The embodiment provides a metal ion capacitor, wherein the capacitor negative electrode material comprises the following components: 32mg of HCNs-4 active material of example 1, 6mg of conductive carbon black and an aqueous solution containing 2mg of sodium carboxymethylcellulose.
The present embodiment provides a method for manufacturing a secondary battery, including the steps of:
32mg of HCNs-4 active material, 6mg of conductive carbon black and an aqueous solution containing 2mg of sodium carboxymethyl cellulose. Fully grinding and uniformly mixing in a 100mL mortar, coating on a copper foil, and controlling the electrode area loading on the copper foil to be 1.0mg/cm 2 Then transferring into a vacuum oven, drying at 80 ℃ for 120min, cutting into round electrode plates and assembling with metal lithium plates to obtain the button secondary battery.
Application example 2
The present application example provides a metal ion capacitor differing from application example 1 only in that the HCNs-3 provided in example 2 is contained in the negative electrode material of the capacitor, and the remaining raw material amounts and the preparation method of the battery are the same as application example 1.
Application example 3
The present application example provides a metal ion capacitor differing from application example 1 only in that the HCNs-5 provided in example 3 is contained in the negative electrode material of the capacitor, and the remaining raw material amounts and the preparation method of the battery are the same as application example 1.
Application example 4
The present application example provides a metal ion capacitor differing from application example 1 only in that the capacitor negative electrode material contains SHC-4 provided in example 4, and the remaining raw material amounts and the preparation method of the battery are the same as application example 1.
Application example 5
The embodiment provides a metal ion capacitor, wherein the positive electrode material of the capacitor comprises the following components: 32mg of 3DHPC-4 active material of example 4, 6mg of conductive carbon black and an aqueous solution containing 2mg of sodium carboxymethylcellulose.
A method for manufacturing a secondary battery, comprising the steps of:
32mg of 3DHPC-4 active material, 4mg of conductive carbon black and an aqueous solution containing 2mg of sodium carboxymethylcellulose are fully ground and uniformly mixed in a 100mL mortar and then coated on an aluminum foil, and the area loading of an electrode on the aluminum foil is controlled to be 2.0mg/cm 2 Then transferring into a vacuum oven, drying at 80 ℃ for 120min, cutting into round electrode plates and assembling with metal lithium plates to obtain the button secondary battery.
Application example 6
The present example provides a metal ion capacitor, wherein the negative electrode plate is the electrode plate prepared in example 1, and the positive electrode plate is the electrode plate prepared in application example 5. The mass ratio of the negative electrode plate to the positive electrode plate is 1:1, and the pre-lithiated negative electrode plate and the positive electrode plate are assembled into a complete lithium ion capacitor.
Application example 7
The present example provides a metal ion capacitor, wherein the negative electrode plate is the electrode plate prepared in example 1, and the positive electrode plate is the electrode plate prepared in application example 5. The mass ratio of the negative electrode plate to the positive electrode plate is 1:2, and the pre-lithiated negative electrode plate and the positive electrode plate are assembled into a complete lithium ion capacitor.
Application example 8
The present example provides a metal ion capacitor, wherein the negative electrode plate is the electrode plate prepared in example 1, and the positive electrode plate is the electrode plate prepared in application example 5. The mass ratio of the negative electrode plate to the positive electrode plate is 1:3, and the pre-lithiated negative electrode plate and the positive electrode plate are assembled into a complete lithium ion capacitor.
Comparative application example 1
The comparative example provided a metal ion capacitor differing from example 1 only in that the negative electrode material of the capacitor contained HPC-4 provided in comparative example 1, and the remaining raw material amounts and the battery manufacturing method were the same as those of example 1.
Comparative application example 2
The comparative example provided a metal ion capacitor differing from example 1 only in that the capacitor negative electrode material contained MCC-4 provided in comparative example 2, and the remaining raw material amounts and the battery preparation method were the same as example 1.
Comparative application example 3
The comparative example provided a metal ion capacitor differing from example 1 only in that the negative electrode material of the capacitor contained MAC-4 provided in comparative example 3, and the remaining raw material amounts and the battery manufacturing method were the same as example 1.
Comparative application example 4
The comparative example provided a metal ion capacitor differing from example 1 only in that PAC-4 provided in comparative example 4 was contained in the negative electrode material of the capacitor, and the remaining raw material amounts and the preparation method of the battery were the same as example 1.
Comparative application example 5
The comparative example provided a metal ion capacitor differing from example 1 only in that the IOC-4 provided in comparative example 5 was contained in the negative electrode material of the capacitor, and the remaining raw material amounts and the preparation method of the battery were the same as example 1.
Comparative application example 6
The comparative example provided a metal ion capacitor differing from example 5 only in that the capacitor positive electrode material contained HPAC-4 provided in comparative example 6, and the remaining raw material amounts and the battery manufacturing method were the same as example 5.
Comparative application example 7
The comparative example provided a metal ion capacitor differing from example 5 only in that MCAC-4 provided in comparative example 7 was contained in the positive electrode material of the capacitor, and the remaining raw material amounts and the preparation method of the battery were the same as example 5.
Comparative application example 8
The comparative example provided a metal ion capacitor differing from example 5 only in that the positive electrode material of the capacitor contained MAAC-4 provided in comparative example 8, and the remaining raw material amounts and the battery manufacturing method were the same as example 5.
Comparative application example 9
The comparative example provided a metal ion capacitor differing from example 5 only in that the positive electrode material of the capacitor contained HACNs-4 provided in comparative example 9, and the remaining raw material amounts and the battery manufacturing method were the same as example 5.
Performance testing
Each electrochemical lithium storage performance test was performed on the secondary batteries and the metal ion capacitors provided in the above application examples 1 to 8 and comparative application examples 1 to 9, and the specific test methods are as follows:
(1) Lithium storage performance: positive or negative electrode lithium storage performance test: carrying out lithium storage performance test on blue electric test equipment, wherein the voltage range of the negative electrode test is 0.01-3.0V, and the current density of the test is 1Ag-1; the voltage range of the positive electrode test is 2.0-4.5V, and the current density of the test is 2Ag-1; the lithium storage specific capacity obtained by the test is based on the mass of the single electrode active material;
(2) Lithium storage performance test of lithium ion capacitor:
(1) constant current charge and discharge tests under different current densities are carried out on Shanghai chemical electrochemical workstations, namely: 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0Ag-1, the tested voltage ranges from 0.5V to 4.2V, and the discharge time Deltat/s under different current densities is recorded according to the following calculation formulas of the energy density (E) and the power density (P) of the metal ion capacitor: p= [ i× (vmax+vmin) ×1000 ]/(m×2); e= (p×Δt)/3600, wherein: i/m is current density, and the unit is Ag-1; (vmax+vmin)/2 is the average voltage in V; Δt is the discharge time in s. (2) And (3) carrying out a test on the cycling stability of the blue electric testing equipment, wherein the tested voltage range is 0.5-4.2V, the tested current density is 1Ag-1, and the specific lithium storage capacity obtained by the test is based on the total mass of active substances of the positive electrode and the negative electrode.
The specific test results are shown in tables 1-3 below:
TABLE 1
From table 1, it can be seen that the two-dimensional porous carbon nano-sheet with abundant mesopores prepared by the invention has excellent lithium storage performance, and the HCNs-5 prepared by example 1 shows the most excellent lithium storage capacity of the negative electrode, and compared with the commercial graphite negative electrode, the lithium storage performance of the negative electrode is significantly improved.
TABLE 2
It can be seen from table 2 that the porous carbon with three-dimensional hierarchical framework prepared by the invention has excellent lithium storage performance, and the 3DHPC-5 prepared in example 4 shows the most excellent positive electrode lithium storage capability, which is significantly improved compared with the commercial active carbon positive electrode.
TABLE 3 Table 3
By comparing the lithium storage performance of the anode and the cathode of the application example, the anode adopts HCNs-4, the cathode adopts 3DHPC-4 as an electrode active material, a double-carbon mixed lithium ion capacitor HCNs-4//3DHPC-4 is constructed, different anode-cathode mass ratios are researched, and the lithium ion capacitor constructed when the anode and the cathode have the same mass ratio is determined to have optimal electrochemical performance.
Fig. 19 and 20 are scanning electron microscope diagrams of basic magnesium carbonate, and the basic magnesium carbonate is shown in fig. 19 and 20, and shows irregular stacked lamellar morphology, so that the porous nano-sheet morphology with higher specific surface area can be obtained by petroleum asphalt. Fig. 21 and 20 are scanning electron microscope diagrams of magnesium oxide, and as shown in fig. 21 and 22, the magnesium oxide shows a dispersed block morphology, so that petroleum asphalt can obtain a porous morphology, the specific surface area of the material is increased, and the diffusion distance of electrolyte ions is shortened.
The applicant states that the present invention is illustrated by the above examples as well as porous carbon and applications derived therefrom, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must be practiced in dependence upon the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (18)
1. The preparation method of the porous carbon is characterized in that when the porous carbon is a two-dimensional porous carbon nano sheet, the preparation method of the two-dimensional porous carbon nano sheet comprises the following steps:
(1) Mixing petroleum asphalt and basic magnesium carbonate in a mass ratio of 1:3, 1:4 or 1:5 in a grinding and mixing mode;
(2) Calcining the mixed substance obtained in the step (1) in a high-temperature tube furnace in a nitrogen atmosphere;
(3) Washing the product obtained by calcining in the step (2) by hydrochloric acid to remove the residual template after calcining, and washing by water to obtain the two-dimensional porous carbon nano sheet;
when the porous carbon is a porous carbon with a three-dimensional hierarchical porous structure, the preparation method of the porous carbon with the three-dimensional hierarchical porous structure comprises the following steps:
(1') mixing petroleum asphalt and magnesium oxide in a mass ratio of 1:4 by a grinding mixing mode;
(2 ') calcining the mixed material obtained in the step (1') in a high-temperature tube furnace under a nitrogen atmosphere;
(3 ') washing the product obtained by calcining in the step (2') by hydrochloric acid to remove the residual template after calcining, and washing by water to obtain intermediate porous carbon;
(4 ') mixing the intermediate porous carbon obtained in the step (3') with potassium hydroxide in a mass ratio of (3-5) 1 by a grinding mixing mode;
(5 ') calcining the mixed material obtained in the step (4') in a high-temperature tube furnace under the nitrogen atmosphere;
and (6 ') washing the product obtained by calcining in the step (5') by hydrochloric acid to remove the residual template after calcining, and washing by water to obtain the porous carbon with the three-dimensional hierarchical porous structure.
2. The method of producing porous carbon according to claim 1, wherein the petroleum pitch is a hard pitch, the initial weight loss temperature of the petroleum pitch is more than 300 ℃, the weight loss of the petroleum pitch is more than 75wt% between 300 ℃ and 635 ℃, and the petroleum pitch is 95% or more wt% at more than 750 ℃.
3. The method for producing a porous carbon according to claim 1, wherein the temperature of the calcination in the step (2) is 700 to 900 ℃, the temperature rise rate of the calcination is 2 to 5 ℃/min, and the time of the calcination is 200 to 510 min.
4. The method for producing porous carbon according to claim 1, wherein the amount of hydrochloric acid used in the step (3) is 10 to 150mL/g pitch, and the concentration of hydrochloric acid is 1 to 10 mol/L.
5. The method for producing porous carbon according to claim 1, wherein the hydrochloric acid washing in step (3) or step (6') is followed by water washing, the number of times of water washing is 1 to 2, and the amount of water used is 500 to 1000mL/g pitch.
6. The method for producing a porous carbon according to claim 1, wherein,
in the step (5'), the temperature of the calcination is 700-900 ℃, the temperature rising rate of the calcination is 2-5 ℃/min, and the time of the calcination is 200-510 min.
7. The method for producing a porous carbon according to claim 1, wherein in the step (6'), the amount of the hydrochloric acid is 2 to 30mL/g pitch and the concentration of the hydrochloric acid is 1 to 10 mol/L.
8. A porous carbon, characterized in that it is obtained by the method for producing a porous carbon according to any one of claims 1 to 7.
9. The porous carbon according to claim 8, wherein the porous carbon is a two-dimensional porous carbon nanoplatelet or a porous carbon having a three-dimensional hierarchical porous structure.
10. Use of the porous carbon according to claim 8 for the preparation of a lithium ion capacitor.
11. A lithium-ion electrode sheet comprising the porous carbon of claim 8.
12. The lithium-ion electrode sheet of claim 11, wherein the electrode sheet is a positive electrode sheet and the electrode sheet is the porous carbon of claim 8.
13. The lithium-ion electrode sheet according to claim 11, wherein the electrode sheet is a negative electrode sheet, and the preparation raw materials of the negative electrode sheet include: the porous carbon, conductive agent, and binder of claim 8.
14. The lithium-ion electrode sheet according to claim 13, wherein the mass ratio of the porous carbon, the conductive agent and the binder is (6-8): (1-2): (1-2).
15. The lithium-ion electrode sheet of claim 13, wherein the conductive agent is conductive carbon black.
16. The lithium ion electrode sheet of claim 13, wherein the binder is an aqueous solution of sodium carboxymethyl cellulose.
17. A lithium ion capacitor comprising the lithium ion electrode sheet of claim 11.
18. The lithium ion capacitor according to claim 17, wherein the mass ratio of the positive electrode tab to the negative electrode tab is (1-3): 1.
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