CN113149007A - Olive pomace-based porous carbon material and preparation method thereof - Google Patents
Olive pomace-based porous carbon material and preparation method thereof Download PDFInfo
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- CN113149007A CN113149007A CN202110468990.1A CN202110468990A CN113149007A CN 113149007 A CN113149007 A CN 113149007A CN 202110468990 A CN202110468990 A CN 202110468990A CN 113149007 A CN113149007 A CN 113149007A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 90
- 238000000034 method Methods 0.000 claims description 45
- 238000003763 carbonization Methods 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 20
- 150000007529 inorganic bases Chemical class 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
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- 229910052786 argon Inorganic materials 0.000 claims description 13
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- 238000002156 mixing Methods 0.000 claims description 9
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
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- 239000007789 gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 239000011148 porous material Substances 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
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- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000268590 Euryale ferox Species 0.000 description 1
- 235000006487 Euryale ferox Nutrition 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application relates to an olive pomace-based porous carbon material and a preparation method thereof, and belongs to the technical field of preparation of porous carbon materials. The preparation method comprises the following steps: (1) and carbonizing the olive pomace under anaerobic condition to obtain carbide. (2) And activating the carbide under the anaerobic condition to obtain an activated substance. (3) And acid washing the activated substance to obtain the porous activated carbon material. The obtained olive pomace-based porous carbon material has high specific capacitance under the current density of 1A/g and good electrical properties.
Description
Technical Field
The application relates to the technical field of preparation of porous carbon materials, and in particular relates to an olive pomace-based porous carbon material and a preparation method thereof.
Background
The porous carbon material has the characteristics of developed pores, good conductivity, low density, good stability and the like due to the large specific surface area, and is widely applied to the aspect of capacitors.
The raw materials for preparing the porous carbon material at present are rich in variety, and can be summarized into the following two main categories: (1) a biomass-based material comprising: coconut shells, corn stalks, fruit pits, bamboo, and the like; (2) fossil fuels, including: pitch, coal, phenolic resin, carbon fiber and the like.
However, after the biomass material is used to prepare a porous carbon material, the electrical properties of the obtained porous carbon material need to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the embodiment of the application provides the olive pomace-based porous carbon material and the preparation method thereof, so that the porous carbon material with better electrical property can be obtained.
In a first aspect, an embodiment of the present application provides a preparation method of an olive pomace-based porous carbon material, including: (1) and carbonizing the olive pomace under anaerobic condition to obtain carbide. (2) And activating the carbide under the anaerobic condition to obtain an activated substance. (3) And acid washing the activated substance to obtain the porous activated carbon material.
In some embodiments of the present application, in step (1), the temperature of the carbonization treatment is 600-.
In some examples of the present application, in step (1), the carbonization treatment is performed in a tube furnace, and argon gas is introduced into the tube furnace at a flow rate of 200-.
In some examples of the present application, in step (2), the carbide and the solid inorganic base are mixed and activated under anaerobic conditions at a temperature of 500-700 ℃ for 0.5-5 h.
In some embodiments of the present application, the method of mixing the carbide and the solid inorganic base is an aqueous solution method.
In some examples of the present application, the mass ratio of solid inorganic base to carbide is 2:1 to 3: 1.
In some embodiments of the present application, the solid inorganic base is sodium hydroxide or/and potassium hydroxide.
In some examples of the present application, in the step (3), the acid-washing solution is a weak inorganic acid solution, and the volume concentration of the weak inorganic acid solution is 3-10%.
In some embodiments herein, the acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
In some embodiments of the present application, before step (1), further comprising: and (3) crushing the olive pomace.
In a second aspect, the embodiment of the application provides an olive pomace-based porous carbon material prepared by the above method, and the specific capacitance of the olive pomace-based porous carbon material at a current density of 1A/g is 200-.
The olive pomace-based porous carbon material and the preparation method thereof provided by the embodiment of the application have the beneficial effects that:
the raw material for preparing the porous carbon material is olive pomace, on one hand, the olive pomace can be recycled, and on the other hand, the obtained porous carbon material has high specific capacitance and good electrical properties.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a process flow diagram of a preparation method of an olive pomace-based porous carbon material provided in an embodiment of the present application;
fig. 2 is a constant current charge-discharge spectrogram of the olive pomace-based porous carbon material (carbonized at 600 ℃, and manually ground) provided in this example 1, obtained in a 6M KOH electrolyte at different charge-discharge densities;
fig. 3 is a constant current charging and discharging spectrogram of the olive pomace-based porous carbon material (carbonized at 600 ℃ and obtained by an aqueous solution method) provided in this example 3, obtained in a 6M KOH electrolyte solution at different charging and discharging densities;
FIG. 4 is an XRD diffraction pattern of the olive pomace-based porous carbon material (carbonization at 600 ℃ C., aqueous solution method) provided in this example 3;
FIG. 5 is an AC impedance spectrum of the olive pomace-based porous carbon material (carbonization at 600 ℃ C., aqueous solution method) provided in this example 3 under 6M KOH electrolyte;
FIG. 6 is a SEM photograph of the olive pomace-based porous carbon material (carbonization at 600 ℃ C., aqueous solution method) provided in this example 3;
fig. 7 is a cyclic voltammogram of the olive pomace-based porous carbon material (carbonization at 600 ℃, aqueous solution method) provided in this embodiment 3 in 6M KOH electrolyte at different magnifications;
FIG. 8 is an XPS survey of olive pomace-based porous carbon material (600 ℃ C. carbonization, aqueous solution method) provided in this example 3;
FIG. 9 is an enlarged view of the peak C1s of FIG. 8;
FIG. 10 is an enlarged view of the O1s peak of FIG. 8;
fig. 11 is a constant current charging and discharging spectrogram of the olive pomace-based porous carbon material (carbonization at 800 ℃ and aqueous solution method) provided in this example 4, obtained in 6M KOH electrolyte at different charging and discharging densities;
FIG. 12 is a SEM photograph of the olive pomace-based porous carbon material (carbonization at 800 ℃ C., aqueous solution method) provided in this example 4;
FIG. 13 is an AC impedance spectrum of the olive pomace-based porous carbon material (carbonization at 800 ℃ C., aqueous solution method) provided in this example 4 under 6M KOH electrolyte;
fig. 14 is a cycle chart of a button cell prepared from the olive pomace-based porous carbon material (carbonization at 800 ℃ in an aqueous solution) provided in this example 4;
FIG. 15 is the AC impedance spectrum of the broad-charge porous carbon material (carbonization at 600 ℃ C., aqueous solution method) provided in comparative example 1 in 6M KOH electrolyte;
FIG. 16 is a constant current charging/discharging spectrum of the broad-charge-based porous carbon material (carbonized at 600 ℃ C., aqueous solution method) provided in comparative example 1, obtained in 6M KOH electrolyte at different charging/discharging densities.
Detailed Description
The olive pomace is olive pomace after olive oil pressing, is generally directly used as feed, and has low additional value. In the application, the olive pomace is used for preparing the porous carbon material, so that the additional value of the porous carbon material can be effectively improved.
The application provides a preparation method of an olive pomace-based porous carbon material, and fig. 1 is a process flow chart of the preparation method. Referring to fig. 1, the preparation method includes the following steps:
and S10, pretreating olive pomace. Optionally, the olive pomace is crushed into powder for subsequent full carbonization. Further, drying olive pomace, crushing by a crusher, and crushing to powder with a particle size of 7-12 μm. For example: drying olive pomace at about 120 ℃, and then crushing the olive pomace into powder by a crusher.
And S20, carbonizing the olive pomace powder under anaerobic conditions to obtain carbide, so that the olive pomace can be carbonized, and most of organic matters in the olive pomace can be removed.
Optionally, the carbonization treatment is performed in a tube furnace, and in order to realize an oxygen-insulated environment in the tube furnace, inert gas with the flow rate of 200-300mL/min is introduced into the tube furnace. For example: the inert gas may be argon or/and nitrogen. Illustratively, the flow rate of argon (argon purity 99.999%) introduced into the tube furnace is 200mL/min, 220mL/min, 240mL/min, 260mL/min, 280mL/min, or 300 mL/min.
Further, the temperature of the carbonization treatment is 600-800 ℃, and the time of the carbonization treatment is 1h or more. Illustratively, the temperature of the carbonization treatment is 600 ℃, and the time of the carbonization treatment is 4 h; or the temperature of the carbonization treatment is 800 ℃, and the time of the carbonization treatment is 1 h; or the temperature of the carbonization treatment is 700 ℃, and the time of the carbonization treatment is 2 h; or the temperature of the carbonization treatment is 650 ℃, and the time of the carbonization treatment is 3 h.
In order to make the temperature in the tube furnace reach 600-800 ℃, the temperature can be raised at the temperature raising rate of 8-12 ℃/min so as to carry out carbonization after reaching a certain temperature.
In order to make the carbide more porous, the carbide may be ground to make the carbide grain-free. For example: the carbide was ground to a particle size of nanometer scale with a mortar.
And S30, activating the carbide under anaerobic condition to obtain an activator, and forming pores on the carbide to increase the specific surface area and improve the electrical properties of the carbide. Alternatively, the manner of the activation treatment is: mixing carbide and solid inorganic alkali, and activating for 0.5-5h under the anaerobic condition at the temperature of 500-700 ℃. The method for mixing the carbide and the solid inorganic base can be a manual grinding or ball milling method or an aqueous solution method, wherein the aqueous solution method comprises the following steps: and putting the carbide and the solid inorganic base into water, fully stirring to form a solution, dissolving the solid inorganic base into the water, and drying the solution to obtain a mixture of the carbide and the solid inorganic base which are mixed more uniformly.
Illustratively, the temperature of activation is 500 ℃ and the time of activation is 5 h; or the activation temperature is 700 ℃, and the activation time is 0.5 h; or the activation temperature is 600 ℃, and the activation time is 2 h; or the activation temperature is 700 ℃, and the activation time is 3 h.
In order to make pores better for the carbide, the mass ratio of the solid inorganic base to the carbide is 2:1-3: 1. Illustratively, the mass ratio of solid inorganic base to carbide is 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, or 3: 1.
Optionally, the solid inorganic base is sodium hydroxide or/and potassium hydroxide. For example: the solid inorganic base is sodium hydroxide, the solid inorganic base is potassium hydroxide, or the solid inorganic base is a mixture of sodium hydroxide and potassium hydroxide.
Alternatively, the device for activation treatment can be a tubular furnace for carbonization treatment, and inert gas with the flow rate of 200-300mL/min is introduced into the tubular furnace in order to realize the oxygen-insulated environment in the tubular furnace. For example: the inert gas may be argon or/and nitrogen. Illustratively, the flow rate of argon (argon purity 99.999%) introduced into the tube furnace is 200mL/min, 220mL/min, 240mL/min, 260mL/min, 280mL/min, or 300 mL/min. In other embodiments, the activation device may be another tube furnace, and the present application is not limited thereto.
And S40, acid washing the activated substance to obtain the porous activated carbon material, wherein inorganic impurities in the activated substance can be removed, and the porous activated carbon material with better electrical property is obtained. Optionally, the acid-washing solution is a weak inorganic acid solution, and the volume concentration of the weak inorganic acid solution is 3-10%. Further, the acid includes one or more of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
For example: the volume concentration of the hydrochloric acid is 3-7%; the volume concentration of the sulfuric acid is 3-6%; the volume concentration of the nitric acid is 3-5%; the volume concentration of the phosphoric acid is 5-10%.
Before the acid washing, the activated product may be washed with water (e.g., ultrapure water), optionally, the ultrasonic treatment is performed for about 30min by using ultrapure water, then the centrifugal treatment is performed (the number of revolutions of the centrifugal treatment is 10000rad/min, and the time of the centrifugal treatment is 5min), and then the steps are repeated three times.
Then the activated substance after being washed by water is placed in an inorganic acid solution with the volume concentration of 3-10 percent to be subjected to ultrasonic cleaning for about 30 min.
After acid washing, the inorganic acid in the activator can be washed clean with water (e.g., ultrapure water), such as: and cleaning the activated material subjected to acid washing by using ultrapure water, then performing suction filtration, repeating the process for many times, and then drying to obtain the olive pomace-based porous activated carbon material.
The specific capacitance of the olive pomace-based porous carbon material at a current density of 1A/g is 200-420F/g. Illustratively, the olive pomace based porous carbon material has a specific capacitance of 200F/g, 250F/g, 300F/g, 350F/g, or 420F/g.
In the application, the preparation method of the olive pomace-based porous carbon material comprises the following steps: pulverizing olive pomace into powder with particle size of 7-12 μm, and carbonizing the olive pomace powder for 1.5-2.5h under anaerobic condition and temperature of 780-800 deg.C to obtain carbide; grinding carbide to nano level to obtain carbide powder; adding carbide powder and KOH powder with the carbon-alkali ratio of 1:2.5-1:3 into water, stirring and mixing, then drying to obtain mixed powder, and performing activation treatment on the mixed powder for 1-1.5h under the anaerobic condition and at the temperature of 580-620 ℃ to obtain an activated substance; washing the activated substance with water, washing the activated substance with inorganic acid with the volume concentration of 3-10%, washing with water, and drying to obtain the olive pomace-based porous carbon material. When the olive pomace-based porous carbon material prepared by the method is used as a negative electrode material of a battery, the comprehensive performance of the battery is better, and the olive pomace-based porous carbon material is suitable for being used as the negative electrode material of the battery.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
And putting the dried and crushed olive pomace into a nickel boat, and carbonizing in an argon atmosphere (the flow rate of argon is 250mL/min) to obtain carbide. Wherein the carbonization temperature is 600 ℃, the heating rate is 10 ℃/min, and the carbonization heat preservation time is 120 min.
Putting carbide into a mortar, grinding the carbide until the carbide has no granular sensation to obtain carbide powder, respectively weighing 2.0g of carbide powder and 4.44g of KOH powder (the KOH purity is 90 percent and the carbon-base ratio is 1:2), fully and manually grinding the carbide powder and the KOH powder for 30min, putting the ground finished product into a nickel boat, and activating at 600 ℃ under the argon protection atmosphere (the argon flow rate is 250mL/min) to obtain the activator. Wherein the activation heating rate is 10 ℃/min, the activation temperature is 600 ℃, and the activation heat preservation time is 60 min.
And (3) ultrasonically treating the activated substance for 30min by using ultrapure water, centrifuging (the rotation is 10000rad/min, the time is 5min), repeating for three times, adding an HCl solution with the volume concentration of 5%, ultrasonically treating for 30min, performing suction filtration until the solution is neutral, and drying the sample to obtain the olive pomace-based porous carbon material.
Grinding and mixing the olive pomace-based porous carbon material dried in vacuum, the conductive agent Super P and the binder (PVDF) according to the mass ratio of 8:1:1, grinding the mixture into thin slices, coating and pressing the thin slices on a foamed nickel substrate, drying the thin slices in a blast drying oven at 120 ℃ for 12 hours, and drying the thin slices in a vacuum drying oven for 2 hours to obtain the electrode slice. And then detecting the constant current charge and discharge conditions obtained under different charge and discharge densities.
Fig. 2 is a constant current charge-discharge spectrum obtained by using the olive pomace-based porous carbon material (carbonized at 600 ℃, and manually ground) provided by this example in 6M KOH electrolyte at different charge-discharge densities. As can be seen from FIG. 2, the specific capacitance of the olive pomace-based porous carbon material at a current density of 1A/g is 280F/g.
Example 2
Example 2 is a modification of example 1, and example 2 differs from example 1 in that: the mass ratio of the carbide to the solid KOH is 1: 2.5.
The specific capacitance of the olive pomace-based porous carbon material provided by the embodiment can reach 280F/g at a current density of 1A/g. As can be seen from the comparison of example 1 and example 2, the carbon-to-base ratio of 1:2.5 or 1:2 has little effect on the specific capacitance of the olive pomace-based porous carbon material.
Example 3
Example 3 is a modification of example 1, and example 3 differs from example 1 in that: putting carbide into a mortar, grinding the carbide until no granular sensation exists to obtain carbide powder, respectively weighing 2g of carbonized sample and 6.66g of KOH powder (the KOH purity is 90 percent, and the carbon-alkali ratio is 1:3), pouring the carbonized sample and the 6.66g of KOH powder into a beaker, uniformly mixing, adding 5mL of deionized water into the beaker, fully stirring, stirring by using magnetic force for about 10min, pouring the raw materials into a nickel boat after mixing is finished, drying for 4h (120 ℃), and activating at 600 ℃ under the protection of argon (the flow rate of argon is 250mL/min) to obtain an activated substance. Wherein the activation heating rate is 10 ℃/min, the activation temperature is 600 ℃, and the activation heat preservation time is 60 min.
Fig. 3 is a constant current charge-discharge spectrum obtained by the olive pomace-based porous carbon material (carbonization at 600 ℃ and aqueous solution method) in 6M KOH electrolyte at different charge-discharge densities. As can be seen from FIG. 3, the specific capacitance of the olive pomace-based porous carbon material at a current density of 1A/g is 419F/g, and the specific capacitance of the prepared activated carbon material at a current density of 1A/g is maintained at about 400F/g in the case of multiple experiments. It can be seen from the comparison between example 1 and example 3 that the mixing mode of the aqueous solution method can ensure that the potassium hydroxide and the carbide are mixed more fully, and is beneficial to improving the specific capacitance of the olive pomace-based porous carbon material.
Fig. 4 is an XRD diffraction pattern of the olive pomace-based porous carbon material (carbonization at 600 ℃, aqueous solution method) provided in this example. As can be seen from FIG. 4, diffraction peaks of graphite appear at about 26 ℃ 2. theta. which correspond exactly to the (002) and (001) crystal planes of graphite (PDF #41-1487), indicating that example 3 succeeded in producing a porous carbon material.
Fig. 5 is an ac impedance spectrum of the olive pomace-based porous carbon material (carbonized at 600 ℃, aqueous solution method) provided by this example under 6M KOH electrolyte. It can be seen from fig. 5 that the material has high conductivity and low equivalent series resistance, indicating good capacitor performance.
Fig. 6 is an SEM image of the olive pomace-based porous carbon material (carbonization at 600 ℃, aqueous solution method) provided in this example. As can be seen from fig. 6, the material is a porous material.
Fig. 7 is a cyclic voltammogram of the olive pomace-based porous carbon material (carbonized at 600 ℃, aqueous solution method) provided by this embodiment under different multiplying factors in 6M KOH electrolyte, and the specific data are shown in the figure.
FIG. 8 is an XPS survey spectrum of an olive pomace-based porous carbon material (600 ℃ C. carbonization, aqueous solution method) according to this example; fig. 9 is an enlarged view of the peak C1s in fig. 8, fig. 10 is an enlarged view of the peak O1s in fig. 8, and as can be seen from fig. 8-10, C, O two elements mainly exist in the sample, wherein the content of the C element is 90.5%, and the content of the O element is 9.5%, which proves that the material is a porous carbon material, and the presence of the O element in the material can increase the pseudocapacitance of the material.
Example 4
Example 4 is a modification of example 3, and example 4 differs from example 3 in that: the carbonization temperature of the olive pomace is 800 ℃.
Fig. 11 is a constant current charge/discharge spectrum obtained by the olive pomace-based porous carbon material (carbonization at 800 ℃ and aqueous solution method) in 6M KOH electrolyte at different charge/discharge densities. As can be seen from FIG. 11, the specific capacitance of the olive pomace-based porous carbon material at a current density of 1A/g is about 272F/g. As can be seen from the correspondence between fig. 3 and fig. 11, in example 3 and example 4, although the specific capacitance of the material provided in example 4 is reduced, the rate capability is significantly improved, and the material is more suitable for being used as a battery negative electrode material and has a longer service life.
Fig. 12 is an SEM image of the olive pomace-based porous carbon material (carbonization at 800 ℃, aqueous solution method) provided in this example. As can be seen from fig. 12, the material is a porous material.
Fig. 13 is an ac impedance spectrum of the olive pomace-based porous carbon material (carbonized at 800 ℃, aqueous solution method) provided by this example under 6M KOH electrolyte. It can be seen from fig. 13 that the material has high conductivity, low resistance and good conductivity. And as can be seen from comparison between example 3 and example 4, the carbonization temperature is higher, and the combination of the carbonization temperature and the aqueous solution method can reduce the resistance of the olive pomace-based porous carbon material and ensure better conductivity.
Fig. 14 is a cycle chart of a button cell prepared from the olive pomace-based porous carbon material (carbonization at 800 ℃ and aqueous solution method) provided in this embodiment; according to the technical scheme, the preparation method comprises the steps of obtaining slurry from an olive pomace-based porous carbon material, a conductive agent Super P, a binder (PVDF) and a solvent (N-methyl pyrrolidone) according to the mass ratio of 8:1:1:2, then respectively coating the slurry on a copper foil and an aluminum foil to form pole pieces, then assembling a button cell and testing the cycle performance of the cell to obtain a figure 14, wherein as can be seen from the figure 14, the capacity loss is small after 10000 charge-discharge cycles, which shows that the material provided by the embodiment has good stability and long service life as a negative electrode material of the cell.
Compared with example 3, although the olive pomace-based porous carbon material provided by the application has a reduced specific capacitance value, the olive pomace-based porous carbon material has good conductivity, and when the olive pomace-based porous carbon material is used as a negative electrode material of a battery, the battery has good rate capability and stability, and the comprehensive performance of the battery is better.
Example 5
Example 5 is a modification of example 3, and example 5 differs from example 3 in that: the carbonization temperature of the olive pomace is 700 ℃.
The specific capacitance of the olive pomace-based porous carbon material provided by the embodiment can reach 359F/g at a current density of 1A/g. It can be seen from the comparison of examples 3, 4 and 5 that the values of specific capacitance of the olive pomace-based porous carbon material at a current density of 1A/g gradually decrease when the carbonization temperature of olive pomace is 600 ℃, 700 ℃ or 800 ℃, respectively.
Comparative example 1
Comparative example 1 is identical to the preparation process of example 3, with the difference that: in comparative example 1, olive pomace raw material was replaced with euryale ferox.
FIG. 15 shows the AC impedance spectrum of the broad-charge porous carbon material (600 ℃ C. for carbonization and aqueous solution method) provided in comparative example 1 in 6M KOH electrolyte. As can be seen from fig. 15, the porous carbon material has a low electric resistance and a good electric conductivity. FIG. 16 is a constant current charging/discharging spectrum of the broad-charge-based porous carbon material (carbonized at 600 ℃ C., aqueous solution method) provided in comparative example 1, obtained in 6M KOH electrolyte at different charging/discharging densities. As can be seen from FIG. 16, the specific capacitance of the broad-charge-based porous carbon material at a current density of 1A/g was 183F/g. As can be seen from comparison of comparative example 1 and example 3, the raw material for preparing the porous activated carbon is widely loaded, and the specific capacitance value of the obtained porous carbon material is very small, so that the requirements of the capacitor can not be met basically. Therefore, when a porous carbon material is prepared using a wide charge as a raw material, although the porous carbon material has good conductivity, the specific capacitance of the porous carbon material is small, and thus the porous carbon material cannot meet the demand of a capacitor and cannot be used as a negative electrode material of a battery.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
1. A preparation method of an olive pomace-based porous carbon material is characterized by comprising the following steps of:
(1) carbonizing olive pomace under anaerobic condition to obtain carbide;
(2) activating the carbide under the anaerobic condition to obtain an activator;
(3) and acid-washing the activated substance to obtain the porous activated carbon material.
2. The method as set forth in claim 1, wherein the carbonization temperature in step (1) is 600 ℃ and 800 ℃, and the carbonization time is 1 hour or more.
3. The method as claimed in claim 2, wherein in the step (1), the carbonization treatment is performed in a tube furnace, and argon gas is introduced into the tube furnace at a flow rate of 200-300 mL/min.
4. The method as claimed in claim 1, wherein in the step (2), the carbide and the solid inorganic base are mixed and activated under the anaerobic condition at a temperature of 500-700 ℃ for 0.5-5 h.
5. The method according to claim 4, wherein the method of mixing the carbide and the solid inorganic base is an aqueous solution method.
6. The production method according to claim 4, wherein the mass ratio of the solid inorganic base to the carbide is 2:1 to 3: 1.
7. The method according to claim 6, wherein the solid inorganic base is sodium hydroxide or/and potassium hydroxide.
8. The method according to claim 1, wherein in the step (3), the acid-washing solution is a weak inorganic acid solution, and the weak inorganic acid solution has a volume concentration of 3-10%.
9. The method of claim 8, wherein the acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
10. The olive pomace-based porous carbon material prepared by the preparation method as defined in any one of claims 1-9, wherein the specific capacitance of the olive pomace-based porous carbon material at a current density of 1A/g is 200-420F/g.
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Application publication date: 20210723 |