Porous carbon material, preparation method therefor and use thereof, and supercapacitor

Abstract

The present invention relates to a porous carbon material, a preparation method therefor and a use thereof. The specific surface area of the porous carbon material is 1500-3000 m2 / g, and the pore size distribution is concentrated in the range 0.6-2.0 nm. The preparation method for the porous carbon material comprises the following steps: (1) acid treatment of montmorillonite; (2) uniformly mixing the acid-treated montmorillonite obtained in step (1) with asphalt and performing carbonization treatment to obtain a carbonized material; and (3) under an inert atmosphere condition, mixing the carbonized material with an activating agent for activation, and then washing and drying. The porous carbon material obtained in the present invention has the advantages of large specific surface area, reasonable pore diameter distribution, high ion transmission speed and the like, and is a supercapacitor carbon material with excellent rate performance.

Description

A porous carbon material, a preparation method thereof, an application thereof, and a supercapacitor

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application 202311534916.0 filed on November 17, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to a porous carbon material and a preparation method thereof, and application of the porous carbon material as supercapacitor carbon in a supercapacitor, as well as a supercapacitor using the porous carbon material. Background Art

[0004] Capacitor carbon is a high-end activated carbon product with a large specific surface area, abundant nano-scale micropores, stable surface physicochemical properties, and high adsorption capacity. It has broad application prospects in emerging technologies such as electronic electrodes, new catalyst supports, energy storage, electric vehicles, and functional adsorbents, and has a particularly high added value as a supercapacitor electrode material. Compared to lithium batteries, supercapacitors have advantages primarily in their superior rate capability, rapid charge-discharge performance, and long-cycle performance. Therefore, improving the performance of supercapacitor carbon in these areas has long been a goal. Because two-dimensional nanosheet carbon materials have continuous electron migration channels and are easily accessible to electrolytes, existing technologies generally employ the addition of conductive materials such as carbon nanotubes and graphene to improve the capacitance performance of supercapacitor carbon. For example, CN114597074A and CN109665523A both improve the conductivity of activated carbon by adding graphene oxide, thereby enhancing the capacitance performance of capacitor carbon. CN106115694A mixes melted matrix asphalt with graphene oxide to prepare a composite asphalt-based activated carbon. The specific surface area of ​​the composite pitch-based activated carbon obtained by this method is 2300-3200m 2 The method has a high specific capacity, a mesoporosity of 6-10 microns, a nitrogen content of 1-3%, and metal impurities of less than 100 ppm. However, the resulting capacitors suffer from poor rate capability and long-term cycling performance. A common drawback of these methods is that the graphene oxide and pitch coke or activated carbon require repeated high-temperature mixing to improve the uniformity of the conductive network in the composite material, a complex process. Furthermore, the graphene oxide and activated carbon are separate particles, making it difficult to ensure product stability and long-term cycling performance.

[0005] Therefore, despite the many modification methods mentioned above, it is difficult to ensure that the product takes into account specific capacity, rate discharge performance and long-cycle performance.

[0006] Summary of the Invention

[0007] In view of the shortcomings of the existing technology, the core purpose of the present invention is to provide a supercapacitor carbon and a preparation method thereof that has good specific capacity, rate performance and long-term cycle performance.

[0008] The first aspect of the present invention provides a porous carbon material, in which the pore volume of pores with a pore diameter of 0.6 to 2 nm is greater than 50 volume %, and the ratio of the pore volume of pores with a pore diameter of 1 to 2 nm to the pore volume of pores with a pore diameter of 0.6 to 1 nm is 1 to 3, preferably 1.9 to 2.6.

[0009] A second aspect of the present invention provides a method for preparing a porous carbon material, which comprises sequentially carbonizing and activating an organic carbon source, wherein the carbonization is performed in the presence of montmorillonite.

[0010] The third aspect of the present invention provides a porous carbon material obtained by the above preparation method.

[0011] A fourth aspect of the present invention provides use of the porous carbon material in a supercapacitor.

[0012] A fifth aspect of the present invention provides a supercapacitor, which uses the above-mentioned porous carbon material as an active electrode material.

[0013] The pores of the porous carbon material provided by the present invention are concentratedly distributed in the range of 0.6 to 2 nm, and the ratio of the pore volume of pores with a pore diameter of 1 to 2 nm to the pore volume of pores with a pore diameter of 0.6 to 1 nm is 1 to 3, thereby greatly improving the specific capacity, rate performance and long-cycle performance of the carbon material when used as a supercapacitor active material. The reason may be that the pores with a pore diameter of 0.6 to 2 nm, especially 1 to 2 nm, are more conducive to the effective infiltration of the electrolyte, shortening the ion and charge transfer distance. The fast charge transfer speed significantly improves the rate performance of the material. A large number of pores with a pore diameter of 1 to 2 nm can also improve the capacitance and long-cycle performance of the material.

[0014] The present invention adds montmorillonite, especially montmorillonite after acidification treatment and single-layer exfoliation, during the carbonization process of organic carbon materials to obtain a porous carbon material with a specific pore structure. The reason may be that the montmorillonite single layer acts as a nanoscale two-dimensional confined unit during the activation process of asphalt, so that the formation process of supercapacitor carbon proceeds along the direction of the two-dimensional layer, hindering the relative movement of asphalt molecules. The structural dimension of the material is fixed by the spatial partitioning effect of the montmorillonite layer, and at the same time plays the role of a hard template, which is beneficial to increase the proportion of pore structures between 1 and 2 nm during the activation process. The pores of the prepared carbon material are concentrated in the range of 0.6 to 2 nm, and have a long-range disordered and short-range ordered structure. When used in supercapacitors, it can ensure that the capacitor has a large capacity, a high rate discharge performance and good long-cycle cycling performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG1 is a pore size distribution diagram of the supercapacitor carbon produced in Example 1 of the present invention.

[0016] FIG2 is an electron microscope photograph of the supercapacitor carbon produced in Example 1 of the present invention.

[0017] FIG3 is a Raman spectrum of the supercapacitor carbon produced in Example 1 of the present invention.

[0018] FIG4 shows the 100,000-cycle charge-discharge performance of the supercapacitor carbon produced in Example 1 of the present invention. DETAILED DESCRIPTION

[0019] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0020] The pores of the porous carbon material provided in the first aspect of the present invention are concentratedly distributed in the range of 0.6 to 2 nm, and the pore volume of pores with a pore diameter of 0.6 to 2 nm in the pore structure is greater than 50 volume%, preferably not less than 60 volume%, and the ratio of the pore volume of pores with a pore diameter of 1 to 2 nm to the pore volume of pores with a pore diameter of 0.6 to 1 nm is 1 to 3, preferably 1.9 to 2.6.

[0021] In the present invention, unless otherwise specified, a pore with a pore diameter of 0.6 to 1 nm refers to a pore with a pore diameter greater than or equal to 0.6 nm and less than 1 nm.

[0022] In the present invention, the pores of the porous carbon material are concentrated in the range of 0.6 to 2 nm. The pores with a pore diameter of 0.6 to 2 nm, especially 1 to 2 nm, are conducive to the effective infiltration of the electrolyte, shortening the ion and charge transmission distance. The rapid charge transmission speed significantly improves the material's rate performance, specific capacity and long-cycle performance.

[0023] Furthermore, the specific surface area of ​​the porous carbon material can be 1500 to 3000 m 2 / g, preferably 1800-2700m 2 / g. A suitable specific surface area can better meet the rate performance, capacity and long cycle performance requirements of supercapacitors.

[0024] In the present invention, the specific surface area and the pore distribution curve are measured by using a nitrogen adsorption-desorption curve on a Micromeritics ASAP 2020 adsorption instrument.

[0025] According to a preferred embodiment of the present invention, the D of the porous carbon material 50 The D of porous carbon materials is 5 to 10 microns. 50 For example, it can be 5 microns, 6 microns, 7 microns, 8 microns, 9 microns, 10 microns, or a range consisting of any two of the above points.

[0026] According to a preferred embodiment of the present invention, the carbon content of the porous carbon material is 99 wt% or more.

[0027] The Raman spectrum of the porous carbon material provided by the present invention is in the range of 800-2000 wavenumbers / cm -1 The range is only between 1300-1600 wavenumber / cm -1 The spectrum peak appears in the range of 1350 wave number / cm -1 The spectral peak ratio near 1580 wavenumber / cm -1 The peak width of the spectral peak near the spectral peak is larger and the peak height is smaller. Preferably, 1350 wave number / cm -1 The spectral peak ratio near 1580 wavenumber / cm -1 The peak width ratio of the nearby peaks is 1:0.5-0.95, and the peak height ratio is 1:1.05-1.5. In the present invention, unless otherwise specified, the nearby refers to the error caused by factors such as instruments / operations that are acceptable to the present invention, for example, ±10 wavenumbers / cm -1 .

[0028] Furthermore, the size La value of the aromatic sheet layer of the porous carbon material is between 4.4 and 6 nm, preferably between 4.6 and 5.8 nm.

[0029] The size La value of the aromatic layer of the porous carbon material refers to the diameter of the carbon graphite microcrystalline aromatic layer. A larger La value within the above range is conducive to shortening the ion and charge transmission distance and accelerating the charge transmission speed, thereby further ensuring that the capacitor has good rate performance, capacity and long cycle performance. In the present invention, the size La value of the aromatic layer is calculated by the Scherrer formula L using the X-ray diffraction results of the porous carbon material. a =0.89×0.15406 / (B (100) cosθ (100) ) is calculated, where B (100) is the half-peak width corresponding to the (100) peak porous carbon material; θ (100) is the Bragg angle corresponding to the (100) peak.

[0030] The porous carbon material provided by the present invention has a large number of pores of 0.6 to 2 nm, especially 1 to 2 nm, and has a large specific surface area and a high La value, so it is suitable as a supercapacitor carbon for use in supercapacitors.

[0031] The preparation method of the porous carbon material provided by the second aspect of the present invention comprises carbonizing and activating the organic carbon source in the presence of montmorillonite in sequence, and then removing the montmorillonite and other impurities. The obtained porous carbon material has a large number of 0.6-2nm pores and a large specific surface area and a high La value. When used as a supercapacitor carbon in a supercapacitor, a higher rate discharge type can be obtained. The reason may be that the lamellar structure of montmorillonite can effectively limit the delocalization of the organic carbon source during the carbonization process, and can realize the preferential formation of a planar structure of the components in the carbon source, thereby promoting the growth of the material in the two-dimensional direction. At the same time, the spatial partitioning effect of the montmorillonite layer fixes the structural dimension of the material, and at the same time acts as a hard template, increasing the proportion of pore structures between 1 and 2nm in the porous carbon.

[0032] The inventors of the present invention have discovered that acidification modification of montmorillonite not only increases its surface acidity, enhancing its catalytic activity for polycondensation reactions with organic carbon sources, such as asphalt, but also increases the specific surface area and porosity of the montmorillonite, facilitating its dispersion in organic carbon sources, such as asphalt, ultimately improving the rate discharge performance of the carbon material. Therefore, according to a preferred embodiment of the present invention, the montmorillonite is acid-treated prior to carbonization with the organic carbon source. Specifically, the montmorillonite is preferably acid-treated.

[0033] Preferably, the conditions for acidification modification of montmorillonite are such that the specific surface area of ​​the acidified montmorillonite is 50 to 1000 m 2 / g, preferably 150~600m 2 / g.

[0034] According to a specific embodiment of the present invention, the acidification treatment comprises fully contacting the montmorillonite raw material with an organic acid and / or an inorganic acid under stirring or without stirring. The contact conditions include a temperature of 20 to 100° C., preferably 30 to 70° C., and an acid treatment time of 2 to 48 hours, preferably 5 to 30 hours, and more preferably 5 to 24 hours. The acid is then filtered and washed to remove any residual acid on the surface of the montmorillonite.

[0035] For the sake of convenience, the present invention refers to montmorillonite that has not been acidified as montmorillonite raw material. The montmorillonite raw material can be any of various existing montmorillonite products, such as at least one selected from sodium montmorillonite, calcium montmorillonite, sodium-calcium montmorillonite, lithium montmorillonite, magnesium montmorillonite, and hydrogen montmorillonite, preferably sodium montmorillonite.

[0036] Preferably, the montmorillonite has a nano-layered aluminosilicate structure.

[0037] In the preferred embodiment of the present invention, the silicon-oxygen tetrahedrons and the aluminum-oxygen tetrahedrons in the montmorillonite are connected by sharing oxygen atoms.

[0038] It is further preferred that the thermal decomposition temperature of the montmorillonite is not less than 650°C.

[0039] The montmorillonite satisfying the above conditions may be, for example, at least one of sodium montmorillonite (Na-MMT), calcium montmorillonite, magnesium montmorillonite and hydrogen montmorillonite produced by MacLean.

[0040] It is further preferred that the specific surface area of ​​the montmorillonite raw material is 20 to 300 m 2 / g, preferably 20 to 250 m 2 / g.

[0041] It is further preferred that the particle diameter of the montmorillonite is 0.1 to 20 μm, preferably 0.3 to 15 μm, and more preferably 10 to 15 μm.

[0042] The acid used for the acid treatment can be selected from inorganic acids and / or organic acids, preferably inorganic acids; and can be one or more of strong acids, medium-strong acids, and weak acids. The inorganic acid can be selected from one or a mixture of two or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid, preferably nitric acid. The organic acid can be a monobasic acid or a polybasic acid with a dibasic or higher acid content, for example, it can be one or a mixture of two or more of formic acid, acetic acid, succinic acid, oxalic acid, citric acid, tartaric acid, salicylic acid, and malic acid. The acid is preferably H + The concentration is 0.1 to 6 mol / L, preferably 0.5 to 3 mol / L in the form of an aqueous solution.

[0043] Preferably, the liquid-to-solid ratio of montmorillonite to the acid solution is 5 to 50 mL / g, preferably 8 to 30 mL / g, and more preferably 15 to 30 mL / g. The liquid-to-solid ratio of montmorillonite to the acid solution can be 5 mL / g, 8 mL / g, 10 mL / g, 12 mL / g, 15 mL / g, 17 mL / g, 19 mL / g, 21 mL / g, 23 mL / g, 25 mL / g, 30 mL / g, 40 mL / g, 50 mL / g, or ranges consisting of any two of the foregoing.

[0044] To remove free acid from the acidified montmorillonite, the method of the present invention preferably further comprises washing the montmorillonite after the acidification treatment. The washing step is preferably performed several times with deionized water until the filtrate is neutral. After washing, the acid-treated montmorillonite is dried. The drying conditions are as follows: a drying temperature of 40-150°C, preferably 40-110°C, and a drying time of 1-48 hours, preferably 6-24 hours.

[0045] In the present invention, the organic carbon source can be any organic matter that can obtain a carbon material with a porous structure after carbonization, preferably petroleum-based carbon, more preferably asphalt, and further preferably the asphalt is one or more of petroleum asphalt and coal asphalt, especially preferably petroleum asphalt.

[0046] Preferably, the softening point of the asphalt is 80-350°C, preferably 100-300°C.

[0047] Preferably, the density of the asphalt is 0.6 to 1.4 g / cm 3 , preferably 0.9~1.25g / cm 3 .

[0048] According to a preferred embodiment of the present invention, the mass ratio of the organic carbon source to montmorillonite is 100 to 1:1, preferably 50 to 3:1, and more preferably 20 to 3:1. The mass ratio of the organic carbon source to montmorillonite can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 15:1, 20:1, 30:1, 40:1, 50:1, 60:1, 80:1, 100:1, and ranges consisting of any two of the above.

[0049] Before carbonization, the organic carbon source and montmorillonite or acid-treated montmorillonite can be uniformly mixed by melt blending, shearing, ball milling, etc., preferably melt blending and high-speed shearing. Furthermore, the shear rate of the high-speed shearing machine during shear mixing is 2000 to 20000 r / min, preferably 3000 to 8000 r / min. The inventors of the present invention have found that the use of melt blending and high-speed shearing can make the montmorillonite have a larger number of monolithic structures, thereby better confining the organic carbon source during the carbonization process, obtaining a porous carbon material with a larger La value and a larger specific surface area, thereby further improving the capacity, rate performance and long-term cycle performance of the supercapacitor.

[0050] Furthermore, the temperature when the organic carbon source is mixed with the montmorillonite or acid-treated montmorillonite can be 100-350° C., preferably 150-300° C.; the mixing time can be 0.2-3 h, preferably 0.5-2 h.

[0051] In the present invention, the carbonization treatment is carried out in the absence of oxygen, preferably in an inert atmosphere, wherein the inert atmosphere may be nitrogen and / or an inert gas, wherein the inert gas is one or more of helium, neon, argon, krypton, and xenon.

[0052] The carbonization treatment conditions include: a carbonization temperature of 200-650°C, preferably 300-600°C; a heating rate of 1-20°C / min, preferably 5-15°C / min; and a carbonization time of 40-500 minutes. The carbonization time herein refers to the constant temperature carbonization time, excluding the time for heating and cooling.

[0053] The carbonization treatment can be carried out at one temperature or in stages at two temperatures, preferably at two temperatures.

[0054] When the carbonization treatment is carried out at one temperature, the treatment temperature can be 200-650°C, preferably 300-600°C; further, the heating rate can generally be controlled to be 1-20°C / min, preferably 2-15°C / min; further, the gas flow rate can be 50-500 mL / min, preferably 200-500 mL / min; and the carbonization treatment time can be 20-300 min, preferably 60-300 min.

[0055] When the carbonization treatment is carried out in stages at two temperatures, the carbonization temperature of the first stage can be 300-550°C, preferably 450-520°C; the heating rate can generally be controlled to be 1-15°C / min, preferably 5-15°C / min; the gas flow rate can be 100-500mL / min, preferably 200-500mL / min; the carbonization treatment time can be 10-100min, preferably 20-60min.

[0056] The carbonization temperature of the second stage can be 400-650°C, preferably 500-600°C; the heating rate can generally be controlled to be 5-20°C / min, preferably 5-15°C / min; the gas flow rate can be 100-500mL / min, preferably 200-300mL / min; the carbonization treatment time can be 40-200min, preferably 60-200min.

[0057] According to a preferred embodiment of the present invention, the temperature of the first stage carbonization is 50-150°C lower than that of the second stage, and the duration is 20-180 minutes shorter. This method can further improve the specific capacity, rate charge-discharge performance, and long-term cycle performance of the resulting carbon material.

[0058] Since the solid material obtained after the carbonization treatment is completed does not undergo obvious two-phase separation and is a uniform black mixture, in order to obtain the desired porous carbon material, it is necessary to perform activation treatment after carbonization.

[0059] Preferably, after the carbonization treatment is completed, it is first cooled to room temperature or ambient temperature. There is no limitation on the cooling method. It can be cooled naturally or cooled with an external heat exchange means. After cooling, the obtained solid material is further preferably crushed to a particle size of 10 to 100 μm, preferably 10 to 30 μm, and then activated.

[0060] The activator used for the activation is preferably at least one of a hydroxide or carbonate containing an alkali metal and / or alkaline earth metal. Preferably, the activator is a granular solid with a particle size generally ranging from 10 to 300 μm. Specifically, the activator can be one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, calcium hydroxide, and magnesium hydroxide, preferably one or more of sodium hydroxide, potassium hydroxide, and potassium carbonate.

[0061] Preferably, the activation treatment conditions include an activation temperature of 600-1000°C, preferably 700-900°C; further, the activation heating rate is generally controlled to be 1-10°C / min, preferably 8-10°C / min; the activation time can be 20-180 min, preferably 20-120 min. Further preferably, the activation is carried out in the absence of oxygen, preferably under an inert atmosphere, and the inert atmosphere can be nitrogen and / or an inert gas, wherein the inert gas is one or more of helium, neon, argon, krypton, and xenon. The gas flow rate can be 100-500 mL / min, preferably 200-500 mL / min.

[0062] Further preferably, the weight ratio of the carbonized material to the activator is 1:0.2 to 10, preferably 1:1.5 to 3, and more preferably 1:2 to 3. The weight ratio of the carbonized material to the activator can be 1:0.2, 1:1, 1:1.5, 1:1.7, 1:1.8, 1:2, 1:2.1, 1:2.2, 1:2.5, 1:2.6, 1:2.8, 1:3, 1:4, 1:5, 1:10, and ranges consisting of any two of the above.

[0063] According to a preferred embodiment of the present invention, the method further includes washing the activated product. The primary purpose of washing is to remove residual montmorillonite and alkaline substances produced by the reaction, thereby revealing the rich pore structure formed during the activation process. The washing process can include a first water wash, a second acid wash, and a third water wash. The temperature of the first water wash is 30-100°C, preferably 60-100°C. The first water wash is preferably carried out under condensation reflux with stirring. The first water wash duration is 2-48 hours, preferably 5-24 hours. The liquid-to-solid ratio of the first water wash is 10-50:1, preferably 10-30:1. The acid solution used in the second acid wash can be one or more of hydrochloric acid, nitric acid, sulfuric acid, and acetic acid. The mass fraction of the acid solution can be 0.5-20%, preferably 1-10%. The liquid-to-solid ratio of the acid solution to the solid material can be 5-30:1, preferably 5-20:1. The three-stage water washing is performed by washing with deionized water or ultrapure water for several times. The liquid-solid mass ratio of water to solid phase material during the water washing can be 10-50:1, preferably 10-30:1. The three-stage water washing is performed at room temperature.

[0064] According to a preferred embodiment of the present invention, the method further comprises drying the washed product at a temperature of 60 to 150° C., preferably 60 to 120° C., and for a drying time of 1 to 24 hours, preferably 4 to 12 hours.

[0065] According to a specific embodiment of the present invention, the method for preparing the porous carbon material comprises the following steps:

[0066] (1) Under inert atmosphere conditions, the organic carbon material is carbonized in the presence of montmorillonite to obtain a carbonized material;

[0067] (2) The carbonized material is contacted with an activator for activation, and then washed and dried.

[0068] According to a particularly preferred embodiment of the present invention, the method for preparing the porous carbon material comprises the following steps:

[0069] (1) contacting montmorillonite with an acid solution to perform acid treatment to obtain acid-treated montmorillonite;

[0070] (2) under an inert atmosphere, mixing the acid-treated montmorillonite obtained in step (1) with an organic carbon source, preferably asphalt, and carbonizing the mixture to obtain a carbonized material;

[0071] (3) Under an inert atmosphere, the carbonized material is mixed with an activator for activation, and then washed and dried.

[0072] The third aspect of the present invention provides a porous carbon material obtained by the above preparation method.

[0073] The porous carbon material obtained by the above method has a large number of pores of 0.6 to 2 nm, especially 1 to 2 nm, and has a large specific surface area and La value, making it suitable for use as a supercapacitor carbon in supercapacitors. Therefore, a fourth aspect of the present invention provides the use of the above porous carbon material in a supercapacitor, preferably as an active electrode material.

[0074] A fifth aspect of the present invention provides a supercapacitor, which uses the above-mentioned porous carbon material as an active electrode material.

[0075] When the obtained supercapacitor is an organic buckled supercapacitor, at a current density of 1 A / g, the mass specific capacitance can be 25 to 45 F / g, preferably 35 to 45 F / g; when the current density increases to 15 A / g, the mass specific capacitance of the organic buckled supercapacitor can be 20 to 40 F / g, preferably 30 to 39 F / g, and the specific capacitance retention rate after 100,000 charge and discharge cycles can be 78-95%, preferably 85-95%.

[0076] The present invention will be further described below by way of examples.

[0077] In the Examples, the specific surface area and pore size distribution curves of the samples were obtained by nitrogen adsorption-desorption curves on a Micromeritics ASAP 2020 adsorption instrument at an operating temperature of -196°C (liquid nitrogen temperature). The samples were pretreated by dehydration at 300°C under nitrogen protection before testing. The specific surface area and pore size distribution were calculated using the BET method and the DFT method, respectively.

[0078] The electron microscope was tested using a Japan Electron Field Emission Scanning Electron Microscope JEM7500M; the Raman spectrometer was tested using a HR-800 Raman spectrometer produced by HORIBA JobinYvon of France.

[0079] The electrochemical test method is as follows: activated carbon, conductive agent acetylene black, and binder PVDF (polyvinylidene fluoride) are mixed evenly in a mass ratio of 8:1:1, coated on carbon-coated aluminum foil, dried, and sliced. The electrode surface density is 2.6 mg / cm 2 (Electrode area density = (weight after coating - weight before coating) / coating area) Organic buckled supercapacitors were assembled using a 1 mol / L tetraethylammonium tetrafluoroborate dissolved in propylene carbonate electrolyte. Electrochemical performance and long-term cycling performance were then tested on a Newway electrochemical tester (model BTS-5V50mA).

[0080] Example 1

[0081] Accurately weigh montmorillonite (Na-MMT, produced by Maclean, with a specific surface area of ​​240m 2 / g, average particle size is 10μm) 5g was placed in a 250mL single-necked flask, 150mL of 2mol / L nitric acid solution was added, and the mixture was stirred at a constant temperature of 50℃ for 24h for acidification. The mixture was cooled to room temperature (25℃, the same below) and filtered. The mixture was washed with deionized water until neutral, dried at 110℃ for 12h, ground and sieved to obtain acidified montmorillonite with a particle size of less than 15μm and a specific surface area of ​​485m 2 / g.

[0082] Weigh 20g of petroleum asphalt (softening point 190℃, density 1.12g / cm 3 ), heated to a molten state, 4 g of the above-mentioned acidified montmorillonite was weighed and added to the molten asphalt under stirring, and the molten blend was sheared at a shear rate of 6000 r / min using a high-speed shearing machine for 1 hour. After cooling to room temperature, it was taken out in a solid state to obtain the first material.

[0083] The first material was loaded into a quartz ark and placed in a carbonization furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500 mL / min for 20 minutes. Then, the temperature was raised to 480°C at a rate of 5°C / min at a nitrogen flow rate of 300 mL / min, and carbonized at a constant temperature for 40 minutes. Then, the temperature was raised to 590°C at a rate of 10°C / min, and carbonized at a constant temperature for 60 minutes. After cooling to room temperature, the carbonized product was crushed to micron level in a jet crusher and used as the second material.

[0084] 15g of the second material and 45g of KOH were evenly mixed and loaded into a corundum ark, which was then placed in an activation furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500mL / min for 20min, and then the temperature was raised to 900℃ at a rate of 10℃ / min at a nitrogen flow rate of 200mL / min. Constant temperature activation was performed for 40min, the heating was turned off, and the mixture was taken out after cooling to room temperature to obtain the activated product. The activated product was transferred to a flask, deionized water was added according to a liquid-solid mass ratio of 15:1, heated to 100℃ and condensed and refluxed, magnetically stirred for 5h, filtered, and then washed with water at a liquid-solid mass ratio of 40:1. Then, 5% dilute hydrochloric acid was used for filtering and washing according to a liquid-solid mass ratio of 15:1, and then washed with water at a liquid-solid mass ratio of 40:1. The resulting filter cake was dried in a blast drying oven at 105℃ for 8h to obtain porous carbon. The porous carbon was ball-milled into D 50 The particle size is 8 to 10 μm, and the metal ions are removed by a magnetic separator to obtain asphalt-based supercapacitor carbon.

[0085] The pore size distribution diagram, electron microscope photograph and Raman spectrum of the obtained supercapacitor carbon are shown in Figure 1, Figure 2 and Figure 3 respectively. As can be seen from Figure 1, the total proportion of pores <0.6nm and pores >2.0nm is 28% by volume, and the proportion of pores of 1.0-2.0nm is 1.9 times that of micropores of 0.6-1.0nm. As can be seen from Figure 2, the prepared porous carbon material has a clear lamellar structure, with long-range disorder and short-range order. As can be seen from Figure 3, the Raman spectrum of the porous carbon material is in the range of 800-2000 wavenumbers / cm -1 The range is only between 1300-1600 wavenumber / cm -1 The spectrum peak appears in the range of 1350 wave number / cm -1 The spectral peak ratio near 1580 wavenumber / cm -1 The peak width near the peak is larger and the peak height is smaller; specifically, 1300 wavenumber / cm -1 The spectral peak near 1600 wavenumber / cm -1 The peak width ratio of the nearby peaks is 1:0.71, and the peak height ratio is 1:1.11.

[0086] In addition, the specific surface area of ​​the obtained supercapacitor carbon was measured to be 2363m 2 / g, and the size La of the aromatic layer is 4.9nm.

[0087] Electrochemical testing showed that the mass specific capacitance of the organic buckled supercapacitor was 42.5 F / g at a current density of 1 A / g. When the current density increased to 15 A / g, the mass specific capacitance of the organic buckled supercapacitor was 39.0 F / g. The specific capacitance retention rate was 91.8%, and the specific capacitance retention rate was 89.7% after 100,000 charge and discharge cycles (see Figure 4).

[0088] Example 2

[0089] Accurately weigh montmorillonite (Ca-MMT, produced by Maclean, with a specific surface area of ​​190m 2 / g, average particle size is 15μm) 5g was placed in a 150mL single-necked flask, 75mL of 3mol / L hydrochloric acid solution was added, stirred and acidified at a constant temperature of 70℃ for 15h, cooled to room temperature, filtered, washed with deionized water until neutral, dried at 110℃ for 12h, ground and sieved to obtain acidified montmorillonite with a particle size of less than 15μm and a specific surface area of ​​369m 2 / g.

[0090] Weigh 20g of asphalt (softening point 280℃, density 1.21g / cm 3 ), heated to 300°C, weighed 1g of acidified montmorillonite and added to the molten asphalt under stirring, and sheared the molten blend at a shear rate of 3000r / min using a high-speed shearing machine for 2h. After cooling to room temperature, it was taken out in a solid state to obtain the first material.

[0091] The first material was loaded into a quartz ark and placed in a carbonization furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500 mL / min for 20 minutes. Then, the temperature was raised to 450°C at a rate of 2°C / min at a nitrogen flow rate of 300 mL / min, and carbonized at a constant temperature for 60 minutes. Then, the temperature was raised to 550°C at a rate of 15°C / min, and carbonized at a constant temperature for 120 minutes. After cooling to room temperature, the carbonized product was crushed to micron level in a jet crusher and used as the second material.

[0092] 15g of the second material and 38g of KOH were evenly mixed, loaded into a corundum ark, and placed in an activation furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500mL / min for 20 minutes, and then the temperature was raised to 800℃ at a rate of 8℃ / min at a nitrogen flow rate of 300mL / min. Constant temperature activation was performed for 120 minutes, the heating was turned off, and the mixture was taken out after cooling to room temperature to obtain the activated product. The activated product was transferred to a flask, deionized water was added according to a liquid-solid ratio of 10:1, heated to 70℃ and condensed under reflux, magnetically stirred for 10 hours, hot filtered, and then washed with ultrapure water with a liquid-solid mass ratio of 40:1. Finally, it was filtered and washed with 5% dilute hydrochloric acid at a liquid-solid mass ratio of 15:1, and then washed with ultrapure water with a liquid-solid mass ratio of 40:1. The filter cake was dried in a blast drying oven at 120℃ for 4 hours to obtain porous carbon. The porous carbon was ball-milled into D 50 The particles were 8 to 10 μm in size, and excess metal ions were removed by a magnetic separator to obtain pitch-based supercapacitor carbon. The electron microscope image and Raman spectrum of the obtained supercapacitor carbon are basically consistent with Figures 2 and 3, respectively.

[0093] The specific surface area of ​​the obtained supercapacitor carbon is 2162m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 25%, the proportion of pores of 1.0-2.0nm is 2.1 times that of micropores of 0.6-1.0nm, and the size of the aromatic sheet is 4.6nm.

[0094] After electrochemical testing, the mass specific capacitance of the organic buckled supercapacitor was 39.3F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic buckled supercapacitor was 35.3F / g, and the specific capacitance retention rate was 89.8%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 87.6%.

[0095] Example 3

[0096] Accurately weigh montmorillonite (Na-MMT, produced by Maclean, with a specific surface area of ​​240m 2 / g, average particle size is 10μm) 5g was placed in a 100mL single-necked flask, 50mL of 1.5mol / L sulfuric acid solution was added, stirred and acidified at a constant temperature of 40℃ for 30h, cooled to room temperature, filtered, washed with deionized water until neutral, dried at 105℃ for 12h, ground and sieved to obtain acidified montmorillonite with a particle size of less than 15μm and a specific surface area of ​​503m 2 / g.

[0097] Weigh 20g of petroleum asphalt (softening point 240℃, density 1.18g / cm 3), heated to 250°C, weighed 5.7g of acidified montmorillonite and added to the molten asphalt under stirring, and sheared the molten blend with a high-speed shearing machine at a shear rate of 5000r / min for 2h. After cooling to room temperature, it was taken out in a solid state to obtain the first material.

[0098] The first material was loaded into a quartz ark and placed in a carbonization furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500 mL / min for 20 minutes. Then, the temperature was raised to 520°C at a rate of 8°C / min at a nitrogen flow rate of 200 mL / min, and carbonized at a constant temperature for 20 minutes. Then, the temperature was raised to 600°C at a rate of 5°C / min, and carbonized at a constant temperature for 80 minutes. After cooling to room temperature, the carbonized products were crushed together in a jet crusher to micron level and evenly mixed as the second material.

[0099] 15g of the second material and 30g of KOH were evenly mixed, loaded into a corundum ark, and placed in an activation furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500mL / min for 20 minutes, and then the temperature was raised to 850℃ at a rate of 8℃ / min at a nitrogen flow rate of 300mL / min. Constant temperature activation was performed for 60 minutes, the heating was turned off, and the mixture was taken out after cooling to room temperature to obtain the activated product. The activated product was transferred to a flask, deionized water was added according to a liquid-solid ratio of 30:1, heated to 100℃ and condensed under reflux, magnetically stirred for 12h, hot filtered, and then washed with ultrapure water with a liquid-solid mass ratio of 40:1. Finally, it was filtered and washed with 5% dilute hydrochloric acid at a liquid-solid mass ratio of 15:1, and then washed with ultrapure water with a liquid-solid mass ratio of 40:1. The resulting filter cake was dried in a blast drying oven at 105℃ for 8h to obtain porous carbon. The porous carbon was ball-milled into D 50 The particles were 8 to 10 μm in size, and excess metal ions were removed by a magnetic separator to obtain pitch-based supercapacitor carbon. The electron microscope image and Raman spectrum of the obtained supercapacitor carbon are basically consistent with Figures 2 and 3, respectively.

[0100] The specific surface area of ​​the obtained supercapacitor carbon is 1923m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 30%, the proportion of pores of 1.0-2.0nm is 2.6 times that of micropores of 0.6-1.0nm, and the size of the aromatic sheet is 5.1nm.

[0101] After electrochemical testing, the mass specific capacitance of the organic buckled supercapacitor was 35.4F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic buckled supercapacitor was 31.6F / g, and the specific capacitance retention rate was 89.0%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 88.3%.

[0102] Example 4

[0103] Accurately weigh calcium montmorillonite (Ca-MMT, with a specific surface area of ​​190m 2 / g, average particle size is 15μm) 10g was placed in a 200mL single-necked flask, 120mL of 0.5mol / L hydrochloric acid solution was added, the mixture was stirred and acidified at a constant temperature of 100℃ for 30h, cooled to room temperature, filtered, washed with deionized water until neutral, dried at 105℃ for 12h, ground and sieved to obtain acidified montmorillonite with a particle size of less than 15μm and a specific surface area of ​​352m 2 / g.

[0104] Weigh 30g of petroleum asphalt (softening point 150℃, density 1.08g / cm 3 ), heated to 250 ° C, weighed 0.75 g of acidified montmorillonite and added to the molten asphalt under stirring, mechanically stirred for 2 hours, cooled to room temperature and taken out in a solid state, which is the first material.

[0105] The first material was loaded into a quartz ark and placed in a carbonization furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500 mL / min for 20 minutes. Then, the temperature was raised to 490°C at a rate of 3°C / min at a nitrogen flow rate of 200 mL / min, and carbonized at a constant temperature for 30 minutes. Then, the temperature was raised to 650°C at a rate of 8°C / min, and carbonized at a constant temperature for 100 minutes. After cooling to room temperature, the carbonized product was crushed to micron level in a jet crusher and used as the second material.

[0106] 20g of the second material and 36g of KOH were evenly mixed, loaded into a corundum ark, and placed in an activation furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500mL / min for 20 minutes, and then the temperature was raised to 820℃ at a rate of 10℃ / min at a nitrogen flow rate of 250mL / min. Constant temperature activation was performed for 100min, the heating was turned off, and the mixture was taken out after cooling to room temperature to obtain the activated product. The activated product was transferred to a flask, deionized water was added according to a liquid-solid ratio of 30:1, heated to 100℃ and condensed under reflux, magnetically stirred for 12h, hot filtered, and then washed with ultrapure water with a liquid-solid mass ratio of 30:1. Finally, it was filtered and washed with 5% dilute hydrochloric acid at a liquid-solid mass ratio of 15:1, and then washed with ultrapure water with a liquid-solid mass ratio of 30:1. The resulting filter cake was dried in a blast drying oven at 105℃ for 6h to obtain porous carbon. The porous carbon was ball-milled into D 50 The particle size is 8 to 10 μm, and the excess metal ions are removed by a magnetic separator to obtain asphalt-based supercapacitor carbon.

[0107] The specific surface area of ​​the obtained supercapacitor carbon is 1787m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 39%, the proportion of pores from 1.0 to 2.0nm is 1.7 times that of micropores from 0.6 to 1.0nm, and the size of the aromatic sheet is 4.4nm.

[0108] After electrochemical testing, the mass specific capacitance of the organic buckled supercapacitor was 27.1F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic buckled supercapacitor was 22.6F / g, and the specific capacitance retention rate was 83.3%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 80.5%.

[0109] Example 5

[0110] Weigh 15g of petroleum asphalt (softening point 215℃, density 1.14g / cm 3 ), heated to 260 ° C, under stirring conditions, weighed 1.5g hydrogen montmorillonite (H-MMT, specific surface area is 485m 2 / g, with an average particle size of 15μm) is added to the molten asphalt, and the molten blend is sheared at a shear rate of 4000r / min by a high-speed shearing machine for 2h. After cooling to room temperature, it is taken out in a solid state to obtain the first material.

[0111] The first material was loaded into a quartz ark and placed in a carbonization furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500 mL / min for 20 minutes. Then, the temperature was raised to 500°C at a rate of 6°C / min at a nitrogen flow rate of 300 mL / min, and carbonized at a constant temperature for 80 minutes. Then, the temperature was raised to 610°C at a rate of 12°C / min, and carbonized at a constant temperature for 150 minutes. After cooling to room temperature, the carbonized product was crushed to micron level in a jet crusher and used as the second material.

[0112] 10g of the second material and 28g of KOH were evenly mixed, loaded into a corundum ark, and placed in an activation furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500mL / min for 20min, and then the temperature was raised to 750℃ at a rate of 10℃ / min at a nitrogen flow rate of 200mL / min. Constant temperature activation was performed for 90min, the heating was turned off, and the mixture was taken out after cooling to room temperature to obtain the activated product. The activated product was transferred to a flask, deionized water was added according to a liquid-to-solid ratio of 30:1, heated to 100℃ and condensed under reflux, magnetically stirred for 12h, hot filtered, and then washed with ultrapure water with a liquid-to-solid mass ratio of 40:1. Finally, it was filtered and washed with 5% dilute hydrochloric acid at a liquid-to-solid mass ratio of 20:1, and then washed with ultrapure water with a liquid-to-solid mass ratio of 30:1. The resulting filter cake was dried in a blast drying oven at 105℃ for 6h to obtain porous carbon. The porous carbon was ball-milled into D 50The particle size is 8 to 10 μm, and the excess metal ions are removed by a magnetic separator to obtain asphalt-based supercapacitor carbon.

[0113] The specific surface area of ​​the obtained supercapacitor carbon is 2069m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 38%, the proportion of pores of 1.0-2.0nm is 2.0 times that of micropores of 0.6-1.0nm, and the size of the aromatic sheet is 4.7nm.

[0114] After electrochemical testing, the mass specific capacitance of the organic button-type supercapacitor was 35.2F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic button-type supercapacitor was 29.6F / g, and the specific capacitance retention rate was 84.1%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 82.6%.

[0115] Example 6

[0116] Accurately weigh magnesium-based montmorillonite (Mg-MMT, with a specific surface area of ​​190m 2 / g, average particle size is 8μm) 10g was placed in a 150mL single-necked flask, 80mL of 3mol / L acetic acid solution was added, stirred and acidified at a constant temperature of 60℃ for 18h, cooled to room temperature, filtered, washed with deionized water until neutral, dried at 110℃ for 12h, ground and sieved to obtain acidified montmorillonite with a particle size of less than 15μm and a specific surface area of ​​367m 2 / g.

[0117] Weigh 20g of petroleum asphalt (softening point 230℃, density 1.17g / cm 3 ), heated to 270 ° C, under stirring conditions, weighed 5g of acidified montmorillonite was added to the molten asphalt, and the molten blend was sheared at a shear rate of 8000r / min using a high-speed shearing machine for 0.5h. After cooling to room temperature, it was taken out in a solid state to obtain the first material.

[0118] The first material was loaded into a quartz ark and placed in a carbonization furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500 mL / min for 20 minutes. Then, the temperature was raised to 580°C at a rate of 5°C / min at a nitrogen flow rate of 250 mL / min. The material was carbonized at a constant temperature for 300 minutes and cooled to room temperature. The carbonized product was crushed to micron level in a jet crusher and used as the second material.

[0119] 16g of the second material and 35g of KOH were evenly mixed, loaded into a corundum ark, and placed in an activation furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500mL / min for 20 minutes, and then the temperature was raised to 880℃ at a rate of 8℃ / min at a nitrogen flow rate of 200mL / min. Constant temperature activation was performed for 60 minutes, the heating was turned off, and the mixture was taken out after cooling to room temperature to obtain the activated product. The activated product was transferred to a flask, deionized water was added according to a liquid-to-solid ratio of 30:1, heated to 100℃ and condensed under reflux, magnetically stirred for 12h, hot filtered, and then washed with ultrapure water with a liquid-to-solid mass ratio of 40:1. Finally, it was filtered and washed with 5% dilute hydrochloric acid at a liquid-to-solid mass ratio of 15:1, and then washed with ultrapure water with a liquid-to-solid mass ratio of 40:1. The resulting filter cake was dried in a blast drying oven at 105℃ for 8h to obtain porous carbon. The porous carbon was ball-milled into D 50 The particle size is 8 to 10 μm, and the excess metal ions are removed by a magnetic separator to obtain asphalt-based supercapacitor carbon.

[0120] The specific surface area of ​​the obtained supercapacitor carbon is 1982m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 28%, the proportion of pores of 1.0-2.0nm is 1.8 times that of micropores of 0.6-1.0nm, and the size of the aromatic sheet is 4.4nm.

[0121] After electrochemical testing, the mass specific capacitance of the organic buckled supercapacitor was 28.7F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic buckled supercapacitor was 23.1F / g, and the specific capacitance retention rate was 80.5%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 79.2%.

[0122] Example 7

[0123] Weigh 8g of asphalt (softening point 260℃, density 1.20g / cm 3 ), heated to 280 ° C, and weighed 1g Na-MMT (produced by Maclean, with a specific surface area of ​​240m 2 / g, with an average particle size of 10 μm) was added to the molten asphalt, and the molten blend was sheared at a shear rate of 6000 r / min using a high-speed shearing machine for 1.5 hours. After cooling to room temperature, the mixture was taken out in a solid state to obtain the first material.

[0124] The first material was loaded into a quartz ark and placed in a carbonization furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500 mL / min for 20 minutes. Then, the temperature was raised to 300°C at a rate of 5°C / min at a nitrogen flow rate of 250 mL / min, and carbonized at a constant temperature for 80 minutes. Then, the temperature was raised to 550°C at a rate of 10°C / min, and carbonized at a constant temperature for 100 minutes. After cooling to room temperature, the carbonized product was crushed to micron level in a jet crusher and used as the second material.

[0125] 8g of the second material and 32g of KOH were evenly mixed, loaded into a corundum ark, and placed in an activation furnace. Nitrogen was used to replace the air in the activation furnace at a flow rate of 500mL / min for 20 minutes, and then the temperature was raised to 800℃ at a rate of 7℃ / min at a nitrogen flow rate of 300mL / min. Constant temperature activation was performed for 70 minutes, the heating was turned off, and the mixture was taken out after cooling to room temperature to obtain the activated product. The activated product was transferred to a flask, deionized water was added according to a liquid-to-solid ratio of 30:1, heated to 100℃ and condensed under reflux, magnetically stirred for 12h, hot filtered, and then washed with ultrapure water with a liquid-to-solid mass ratio of 40:1. Finally, it was filtered and washed with 5% dilute hydrochloric acid at a liquid-to-solid mass ratio of 15:1, and then washed with ultrapure water with a liquid-to-solid mass ratio of 40:1. The resulting filter cake was dried in a blast drying oven at 105℃ for 8h to obtain porous carbon. The porous carbon was ball-milled into D 50 The particle size is 8 to 10 μm, and the excess metal ions are removed by a magnetic separator to obtain asphalt-based supercapacitor carbon.

[0126] The specific surface area of ​​the obtained supercapacitor carbon is 1832m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 40%, the proportion of pores of 1.0-2.0nm is three times that of micropores of 0.6-1.0nm, and the size of the aromatic sheet is 4.5nm.

[0127] After electrochemical testing, the mass specific capacitance of the organic buckled supercapacitor was 24.3F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic buckled supercapacitor was 19.4F / g, and the specific capacitance retention rate was 79.7%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 78.6%.

[0128] Comparative Example 1

[0129] The method of Example 1 is followed, except that no montmorillonite is added during the carbonization process, the step of acidifying the montmorillonite is not included, and the supercapacitor carbon is obtained after the petroleum asphalt is directly carbonized and activated.

[0130] The specific surface area of ​​the obtained supercapacitor carbon is 2184m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 51%, the proportion of pores from 1.0 to 2.0nm is 1.7 times that of micropores from 0.6 to 1.0nm, and the size of the aromatic sheet is 4.3nm.

[0131] After electrochemical testing, the mass specific capacitance of the organic button-type supercapacitor was 38.7F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic button-type supercapacitor was 28.7F / g, and the specific capacitance retention rate was 74.2%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 68.5%.

[0132] Comparative Example 2

[0133] The method of Example 1 is followed, except that the mixed system of acidified montmorillonite and asphalt is directly activated to obtain supercapacitor carbon without undergoing a carbonization step.

[0134] The specific surface area of ​​the obtained supercapacitor carbon is 2008m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 42%, the proportion of pores of 1.0-2.0nm is 3.5 times that of micropores of 0.6-1.0nm, and the size of the aromatic sheet is 4.1nm.

[0135] After electrochemical testing, the mass specific capacitance of the organic button-type supercapacitor was 36.9F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic button-type supercapacitor was 26.6F / g, and the specific capacitance retention rate was 72.1%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 67.8%.

[0136] Comparative Example 3

[0137] The method of Example 1 was followed, except that the montmorillonite was replaced by silicon dioxide of the same weight, to obtain supercapacitor carbon.

[0138] The specific surface area of ​​the obtained supercapacitor carbon is 648m 2 / g, the total proportion of pores <0.6nm and pores >2.0nm is 52%, the proportion of pores of 1.0-2.0nm is 3.4 times that of micropores of 0.6-1.0nm, and the size of the aromatic sheet is 4.0nm.

[0139] After electrochemical testing, the organic buckled supercapacitor had a mass specific capacitance of 12 F / g at a current density of 1 A / g; when the current density increased to 15 A / g, the mass specific capacitance of the organic buckled supercapacitor was 5.3 F / g, with a specific capacitance retention rate of 41.7%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 23.2%.

[0140] Comparative Example 4

[0141] A porous carbon material was prepared according to the method of Example 1 of CN106115694A. The specific surface area of ​​the obtained porous carbon material was 3167 square meters / gram, the mesoporosity of 2-50 nm was 63% by volume, the total proportion of pores <0.6 nm and pores >2.0 nm was 82%, the proportion of pores of 1.0-2.0 nm was 1.1 times that of micropores of 0.6-1.0 nm, and the size of the aromatic layer was 4.0 nm.

[0142] After electrochemical testing, the mass specific capacitance of the organic buckled supercapacitor was 45F / g at a current density of 1A / g; when the current density increased to 15A / g, the mass specific capacitance of the organic buckled supercapacitor was 29.9F / g, and the specific capacitance retention rate was 66.4%. After 100,000 charge and discharge cycles, the specific capacitance retention rate was 68.5%.

[0143] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A porous carbon material, wherein the pore volume of pores with a pore diameter of 0.6 to 2 nm is greater than 50 volume %, preferably not less than 60 volume %, and the ratio of the pore volume of pores with a pore diameter of 1 to 2 nm to the pore volume of pores with a pore diameter of 0.6 to 1 nm is 1 to 3, preferably 1.9 to 2.

6.

2. The porous carbon material according to claim 1, wherein The specific surface area of ​​the porous carbon material is 1500-3000m 2 / g, preferably 1800-2700m 2 / g.

3. The porous carbon material according to claim 1 or 2, wherein: The size La value of the aromatic sheet layer of the porous carbon material is between 4.4 and 6 nm, preferably between 4.6 and 5.8 nm.

4. The porous carbon material according to claim 1, 2 or 3, wherein: The D of the porous carbon material 50 The particle size is 5 to 10 microns, and the carbon content is more than 99% by weight.

5. The porous carbon material according to any one of claims 1 to 4, wherein: The Raman spectrum of the porous carbon material is between 800 and 2000 wavenumbers / cm -1 The range is only between 1300 and 1600 wavenumbers / cm -1 The peak appears in the range of 1350 wavenumber / cm -1 The spectral peak near 1580 wavenumber / cm -1 The peak width near the peak is larger and the peak height is smaller; preferably, 1350 wavenumber / cm -1 The peak near 1580 wavenumber / cm -1 The peak width ratio of the nearby spectral peaks is 1:0.5-0.95, and the peak height ratio is 1:1.05-1.

5.

6. A method for preparing a porous carbon material, the method comprising sequentially carbonizing and activating an organic carbon source, characterized in that: The carbonization is carried out in the presence of montmorillonite.

7. The preparation method according to claim 6, wherein: The specific surface area of ​​the montmorillonite is 50-1000m 2 / g, preferably 150-600m 2 / g.

8. The preparation method according to claim 7, wherein: The montmorillonite is an acid-treated montmorillonite, wherein the acid-treated montmorillonite raw material is contacted with an acid solution, wherein the liquid-to-solid ratio of the montmorillonite raw material to the acid solution is 5 to 50 mL / g, preferably 8 to 30 mL / g; + The concentration is 0.1 to 6 mol / L, preferably 0.5 to 3 mol / L.

9. The preparation method according to claim 8, wherein: The contacting temperature is 20 to 100° C., preferably 30 to 70° C.; the contacting time is 2 to 48 hours, preferably 5 to 30 hours.

10. The preparation method according to claim 8 or 9, wherein: The average particle diameter of the montmorillonite raw material is 0.1 to 20 μm, preferably 0.3 to 15 μm; the specific surface area of ​​the montmorillonite raw material is 20 to 300 m 2 / g preferably 20 to 250 m 2 / g.

11. The preparation method according to any one of claims 6 to 10, wherein: The carbonization temperature is 200-650° C., preferably 300-600° C., and the carbonization time is 40-500 minutes, preferably 50-200 minutes.

12. The preparation method according to any one of claims 6 to 11, wherein: The carbonization method includes firstly performing the carbonization at 300-550°C, preferably 450-520°C, for 10-100 min, preferably 20-60 min; and then performing the carbonization at 400-650°C, preferably 500-600°C, for 40-200 min, preferably 60-200 min.

13. The preparation method according to any one of claims 6 to 12, wherein: The mass ratio of the organic carbon source to montmorillonite is 100 to 1:1, preferably 50 to 3:

1.

14. The preparation method according to any one of claims 6 to 13, wherein: The weight ratio of the carbonized material to the activating agent used for activation is 1:0.2-10, preferably 1:1.5-3; the activation temperature is 600-1000°C, preferably 700-900°C; the activation time is 20-180min, preferably 20-120min; preferably, the activating agent is NaOH and / or KOH.

15. The porous carbon material obtained by the preparation method according to any one of claims 6 to 14.

16. Use of the porous carbon material according to any one of claims 1 to 5 and 15 in a supercapacitor, preferably as an active electrode material.

17. A supercapacitor, characterized in that: The supercapacitor uses the porous carbon material described in any one of claims 1 to 5 and 15 as an active electrode material.

18. The supercapacitor according to claim 17, wherein: The supercapacitor is an organic button-type supercapacitor. When the current density is 1A / g, the mass specific capacitance is 25-45F / g, preferably 35-45F / g; when the current density increases to 15A / g, the mass specific capacitance of the organic button-type supercapacitor is 20-40F / g, preferably 30-39F / g, and the specific capacitance retention rate after 100,000 charge and discharge cycles is 78-95%, preferably 85-95%.

Images