CN114772588A - Method for modifying activated carbon material and application thereof - Google Patents
Method for modifying activated carbon material and application thereof Download PDFInfo
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- CN114772588A CN114772588A CN202210246399.6A CN202210246399A CN114772588A CN 114772588 A CN114772588 A CN 114772588A CN 202210246399 A CN202210246399 A CN 202210246399A CN 114772588 A CN114772588 A CN 114772588A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 36
- 230000004913 activation Effects 0.000 claims abstract description 49
- 230000004048 modification Effects 0.000 claims abstract description 44
- 238000012986 modification Methods 0.000 claims abstract description 44
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 34
- 238000005530 etching Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000007772 electrode material Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000004146 energy storage Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 239000004744 fabric Substances 0.000 claims description 28
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000004917 carbon fiber Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004153 Potassium bromate Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 229940094037 potassium bromate Drugs 0.000 claims description 6
- 235000019396 potassium bromate Nutrition 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 239000002041 carbon nanotube Substances 0.000 description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
The invention discloses a method for modifying an activated carbon material and application thereof, wherein the method comprises the following steps: 1) dissolving an alkaline substance in deionized water to obtain an alkaline solution; 2) dissolving an oxidizing substance in an alkali solution at normal temperature to obtain an alkaline chemical oxidation etching solution; 3) soaking a carbon material in an alkaline chemical oxidation etching solution at the temperature of 20-80 ℃ for 1-24 h, and carrying out modification and activation treatment; 4) and washing the modified and activated carbon material with deionized water, and drying to obtain the modified and activated carbon material. The carbon material modified and activated by the method has higher specific surface area, good hydrophilic performance and good electrochemical performance, and can be applied to electrode materials of energy storage devices such as alkali metal secondary batteries, super capacitors and flow batteries; in addition, the method has the advantages of simple operation, mild reaction conditions and low energy consumption.
Description
Technical Field
The invention belongs to the field of carbon materials, and particularly relates to a method for modifying an activated carbon material and application thereof.
Background
Carbon materials are widely used as electrode materials for energy storage devices due to their good electronic conductivity and thermal/mechanical stability. However, the low specific surface area and poor hydrophilic performance limit the development and application of the water-based energy storage device. For example, in the application of vanadium flow batteries, the wettability of carbon electrode materials to electrolyte is directly related to the occurrence of vanadium ion redox reaction on the surface of the electrode materials, thereby affecting the energy storage performance of the electrode materials. Therefore, it is necessary to modify and activate the surface of the carbon material. Currently, the activation and modification of carbon-based electrode materials are mainly performed by the following methods: 1) high-temperature heat treatment: the method mainly comprises the steps of activating a carbon material at a high temperature to increase the number of oxygen-containing functional groups on the surface of the carbon material, for example, activating the carbon material at 600-800 ℃ for 1-4 hours in Chinese patent CN 109987604A; 2) strong oxidizing acid treatment: under high temperature conditions such as hydrothermal/solvothermal conditions, oxygen-containing groups are introduced by using a strong oxidizing acid solution to improve the hydrophilic performance of the carbon material, for example, the carbon fiber is subjected to surface modification by using a nitric acid solution in the Chinese patent CN 104018340A; 3) ion sputtering (plasma): bombarding the surface of the carbon material by using a plasma beam under a vacuum condition, and further introducing defects; 4) electrochemical activation method. However, the existing method has the problems of harsh reaction conditions, strict equipment requirements, low modification and activation efficiency and the like. Therefore, it is urgently needed to develop a new method for modifying and activating the surface of the carbon material, which has the advantages of mild reaction conditions, simplicity, convenience and strong operability.
Disclosure of Invention
The invention aims to provide a method for modifying and activating a carbon material and application thereof, wherein alkaline chemical oxidation etching liquid is used for carrying out modification and activation treatment on the carbon material, and the carbon material after the modification and activation treatment has higher specific surface area, good hydrophilic performance and good electrochemical performance; in addition, the method has the advantages of simple operation, mild reaction conditions and low energy consumption.
The technical scheme of the invention is as follows:
the invention provides a method for modifying an activated carbon material, which comprises the following steps:
1) dissolving an alkaline substance in deionized water to obtain an alkaline solution;
2) dissolving an oxidizing substance in an alkali solution at normal temperature to prepare an alkaline chemical oxidation etching solution;
3) soaking a carbon material in an alkaline chemical oxidation etching solution at the temperature of 20-80 ℃ for 1-24 h, and carrying out modification and activation treatment;
4) and washing the modified and activated carbon material with deionized water, and drying to obtain the modified and activated carbon material.
In some embodiments, the alkaline substance is one or a combination of two or more of sodium hydroxide, potassium hydroxide, and ammonia.
In some embodiments, the concentration of the alkali solution is 10-100 g/L.
In some embodiments, the oxidizing species is one or a combination of two or more of sodium persulfate, potassium persulfate, ammonium persulfate, potassium bromate, potassium chlorate, potassium perchlorate, potassium permanganate, and hydrogen peroxide.
In some embodiments, the concentration of the oxidizing substance is 10 to 50 g/L.
In some embodiments, the mass concentration ratio of the alkaline substance to the oxidizing substance in the alkaline chemical oxidation etching solution is 1:1 to 5:1, preferably 3:1 to 4: 1.
In some embodiments, the carbon material is one of graphite felt, carbon fiber paper, carbon cloth, carbon tubes, graphene, carbon black, or a composite thereof.
In some embodiments, the temperature of the soaking in step 3) is 60 ℃ and the time of soaking is 6 hours.
According to the modification method, alkaline chemical oxidation etching liquid is used for modifying and activating the carbon material, on one hand, through liquid-phase chemical oxidation, oxygen-containing hydrophilic functional groups such as sulfonic groups and hydroxyl groups are introduced to the surface of the carbon material, and then the hydrophilic performance of the surface of the carbon material is improved; on the other hand, on the basis of keeping good mechanical properties of the carbon material, the roughness of the surface of the carbon material is increased through the in-situ etching effect, and the specific surface area of the carbon material is improved. Compared with the prior art that the carbon material is modified and activated under the high-temperature condition, the method disclosed by the invention has the advantages that the modification temperature is lower, the carbon material can be modified only under the condition of 20-80 ℃, the method is simpler, the operability is strong, and the requirement on equipment is low.
The invention also provides a modified activated carbon material prepared by the method.
The modified activated carbon material provided by the invention has a high specific surface area, good hydrophilic performance and good electrochemical performance.
The invention also provides application of the modified activated carbon material in preparing an electrode material of an energy storage device.
In some embodiments, the energy storage device is an alkali metal secondary battery, a supercapacitor, or a flow battery.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) compared with the prior art that the carbon material is modified and activated under the high-temperature condition, the modification method disclosed by the invention has the advantages that the modification temperature is lower, the modification and activation treatment is carried out on the carbon material only by using alkaline chemical oxidation etching liquid under the low-temperature condition of 20-80 ℃, oxygen-containing hydrophilic groups can be introduced into the surface of the carbon material, so that the surface hydrophilic performance of the carbon material is improved, meanwhile, the unevenness of the surface of the carbon material is increased and the specific surface area of the carbon material is increased on the premise of keeping the integrity of the main structure of the carbon material.
(2) The method has the advantages of simple process, low requirement on equipment, strong operability, mild reaction conditions and low reaction energy consumption, and is suitable for industrial production.
(3) The carbon material modified and activated by the method has higher specific surface area, good hydrophilic performance and good electrochemical performance, and can be applied to electrode materials of energy storage devices such as alkali metal secondary batteries, super capacitors, flow batteries and the like.
Drawings
Fig. 1 is a contact angle test chart of the carbon cloth of example 1 of the present invention before and after the modification activation treatment.
Fig. 2 is a graph showing the folding performance test of the carbon cloth after the modified activation treatment in example 1 of the present invention.
Fig. 3 is an SEM image of the carbon cloth before the modification activation treatment in example 1 of the present invention.
Fig. 4 is an SEM image of the carbon cloth after the modification activation treatment in example 1 of the present invention.
Fig. 5 is a CV curve test chart of the carbon cloth of example 1 of the present invention before and after the modification activation treatment, in which curve (a) is a CV curve of the carbon cloth before the modification activation treatment; curve (b) is the CV curve of the carbon cloth after the modification activation treatment.
FIG. 6 shows modified activated carbon fiber paper prepared by the method of example 2 and the electrolyte (1.6mol/L VOSO) of the modified activated carbon fiber paper prepared by the electrochemical activation method in the positive electrode of the vanadium redox flow battery4) The EIS curve test chart in (1), wherein the curve (a) is the EIS curve of the modified activated carbon fiber paper prepared by the method of example 2 of the present invention; and the curve (b) is an EIS curve of the modified activated carbon fiber paper prepared by the electrochemical activation method.
FIG. 7 shows the electrolyte (1.6mol/L VOSO) of the carbon fiber paper before and after the modification and activation treatment in the vanadium redox flow battery of example 2 of the present invention4) The CV curve test chart in (1), wherein the curve (a) is C of the carbon fiber paper before the modification activation treatmentA V curve; curve (b) is the CV curve of the carbon fiber paper after the modification activation treatment.
Fig. 8 is an EIS curve test chart of the carbon nanotube before and after the modification activation treatment in example 3 of the present invention, in which curve (a) is the EIS curve of the carbon nanotube after the modification activation treatment; curve (b) is the EIS curve of the carbon nanotubes before the modification activation treatment.
Detailed Description
The following detailed description describes embodiments of the invention, which are exemplary and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The embodiment of the invention provides a method for modifying an activated carbon material, which comprises the following steps:
1) dissolving an alkaline substance in deionized water to obtain an alkaline solution;
2) dissolving an oxidizing substance in an alkali solution at normal temperature to prepare an alkaline chemical oxidation etching solution;
3) soaking a carbon material in an alkaline chemical oxidation etching solution at the temperature of 20-80 ℃ for 1-24 h, and carrying out modification activation treatment;
4) and washing the modified and activated carbon material with deionized water, and drying to obtain the modified and activated carbon material.
In some embodiments, the alkaline substance is one or a combination of two or more of sodium hydroxide, potassium hydroxide, and ammonia; the concentration of the alkali solution is 10-100 g/L.
In some embodiments, the oxidizing substance is one or a combination of two or more of sodium persulfate, potassium persulfate, ammonium persulfate, potassium bromate, potassium chlorate, potassium perchlorate, potassium permanganate, and hydrogen peroxide; and the concentration of the oxidizing substance is 10 to 50 g/L.
In some embodiments, the mass concentration ratio of the alkaline substance to the oxidizing substance in the alkaline chemical oxidation etching solution is 1:1 to 5:1, preferably 3:1 to 4: 1.
In some embodiments, the carbon material is one of graphite felt, carbon fiber paper, carbon cloth, carbon tubes, graphene, carbon black, or a composite thereof.
In some embodiments, the temperature of the soaking in step 3) is 60 ℃ and the soaking time is 6 h.
The method for modifying the activated carbon material mainly comprises the steps of preparing alkaline chemical oxidation etching solution, and soaking the carbon material in the alkaline oxidation etching solution for modification and activation, so that oxygen-containing hydrophilic functional groups such as sulfonic acid groups and hydroxyl groups can be introduced to the surface of the carbon material through liquid-phase chemical oxidation, and the hydrophilic performance of the surface of the carbon material is improved; meanwhile, on the basis of keeping good mechanical properties of the carbon material, the roughness of the surface of the carbon material is improved through the in-situ etching effect, so that the specific surface area is increased; in addition, compared with the prior art that the carbon material is modified under the high-temperature condition, the method disclosed by the invention can be used for modifying the carbon material only under the low-temperature condition of 20-80 ℃, and is simple to operate, low in equipment requirement and low in cost.
The embodiment of the invention also provides a modified activated carbon material prepared by the method.
The modified activated carbon material provided by the invention has a high specific surface area, good hydrophilic performance and good electrochemical performance.
The embodiment of the invention also provides application of the modified activated carbon material in preparing an electrode material of an energy storage device.
In some embodiments, the energy storage device is an alkali metal secondary battery, a supercapacitor, or a flow battery.
The present invention is described in further detail below by way of specific examples.
Example 1
A method of modifying an activated carbon material comprising the steps of:
1) weighing 10.0g of sodium hydroxide, and dissolving in 100mL of deionized water to obtain an alkali solution;
2) weighing 2.8g of ammonium persulfate, quickly adding the ammonium persulfate into an alkali solution at normal temperature, continuously stirring until the ammonium persulfate is completely dissolved, and preparing to obtain an alkaline chemical oxidation etching solution;
3) cut 4X 6cm2The carbon cloth is soaked in a water bath at 60 ℃ toOxidizing the etching solution for 6 hours by using alkaline chemistry;
4) and (4) taking out the carbon cloth subjected to the modification and activation treatment in the step 3), washing the carbon cloth with deionized water for 3 times, and drying to obtain the modified and activated carbon cloth.
The carbon cloth before and after the modified activation of example 1 was subjected to a contact angle test as shown in fig. 1. As can be seen from fig. 1, the carbon cloth after the modified activation treatment has a smaller contact angle and better hydrophilic performance than the unmodified carbon cloth.
Fig. 2 is a folding performance test chart of the modified carbon cloth in example 1, and it can be seen from fig. 2 that after the modification and activation treatment, the main structure of the carbon cloth is still intact, and the carbon cloth has good flexibility and mechanical properties.
SEM characterization of the carbon cloth before and after modification activation of example 1 is performed as shown in fig. 3 and 4, wherein fig. 3 is an SEM image of the carbon cloth before modification activation; fig. 4 is an SEM image of the modified activated carbon cloth. Comparing fig. 3 and fig. 4, it can be seen that the roughness of the modified and activated carbon cloth is increased due to the in-situ etching effect of the alkaline chemical oxidation etching solution.
The carbon cloth before and after modification and activation of example 1 was subjected to electrochemical performance characterization, as shown in fig. 5, wherein curve (a) is CV curve of the carbon cloth before modification and activation treatment; curve (b) is the CV curve of the carbon cloth after the modification activation treatment. As can be seen from FIG. 5, after modification and activation, the carbon cloth has better catalytic reaction capability on vanadium ions, shows a larger peak current density, and is expected to be used as an electrode material of a vanadium flow battery.
Example 2
A method of modifying an activated carbon material comprising the steps of:
1) weighing 5.0g of potassium hydroxide, and dissolving the potassium hydroxide in 100mL of deionized water to obtain an alkali solution;
2) weighing 2.4g of potassium persulfate, quickly adding the potassium persulfate into an alkali solution at normal temperature, continuously stirring until the potassium persulfate is completely dissolved, and preparing to obtain an alkaline chemical oxidation etching solution;
3) cut 4X 6cm2The carbon fiber paper is soaked in the alkaline chemical oxidation etching solution for 8 hours at room temperature;
4) and (4) taking out the carbon fiber paper subjected to the modification and activation treatment in the step 3), washing with deionized water for 3 times, and drying to obtain the modified and activated carbon fiber paper.
For comparison, the carbon fiber paper is placed in the positive electrolyte (1.6mol/L VOSO) of the vanadium redox flow battery4) In the method, under the conditions of a scanning speed of 100mV/s and a voltage window of 0-1.4V, the carbon fiber paper is circularly scanned for 100 circles to carry out electrochemical activation.
FIG. 6 shows modified activated carbon fiber paper prepared by the method of example 2 and 1.6mol/L VOSO prepared by electrochemical activation method in vanadium flow battery positive electrolyte4) The EIS curve test chart in (1), wherein curve (a) is the EIS curve of the modified activated carbon fiber paper prepared by the method of example 2 of the present invention; and the curve (b) is an EIS curve of the modified activated carbon fiber paper prepared by the electrochemical activation method. As can be seen from FIG. 6, the carbon fiber paper prepared by the alkaline chemical oxidation etching solution method has higher electronic conductivity and higher modification activation efficiency on the carbon fiber paper.
FIG. 7 shows the electrolyte (1.6mol/L VOSO) of the carbon fiber paper before and after the modification and activation treatment in the vanadium redox flow battery of example 2 of the present invention4) The CV curve test chart in (1), wherein the curve (a) is a CV curve of the carbon fiber paper before the modification activation treatment; curve (b) is the CV curve of the carbon fiber paper after the modification activation treatment. As can be seen from FIG. 7, after modification and activation, the carbon fiber paper has better catalytic reaction capability on vanadium ions, shows larger peak current density, and is expected to be used as an electrode material of a vanadium flow battery.
Example 3
A method of modifying an activated carbon material comprising the steps of:
1) weighing 10.0g of sodium hydroxide, and dissolving in 100mL of deionized water to obtain an alkali solution;
2) weighing 3.2g of potassium bromate, quickly adding the potassium bromate into an alkali solution at normal temperature, continuously stirring until the potassium bromate is completely dissolved, and preparing to obtain an alkaline chemical oxidation etching solution;
3) weighing 1.0g of carbon nano tube, and soaking the carbon nano tube in an alkaline chemical oxidation etching solution for 3 hours in a water bath at the temperature of 80 ℃ under the stirring condition;
4) and (3) washing and filtering the carbon nano tube subjected to the modification and activation treatment in the step 3), washing with deionized water for 3 times, and drying to obtain the modified and activated carbon nano tube.
The electrochemical properties of the carbon nanotubes before and after modification and activation in example 3 were characterized, as shown in fig. 8, wherein curve (a) is an EIS curve of the carbon nanotubes after modification and activation; curve (b) is the EIS curve of the carbon nanotubes before the modification activation treatment. As can be seen from fig. 8, the modified and activated carbon nanotubes have lower resistance and better electronic conductivity.
In the present disclosure, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples" and the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of modifying an activated carbon material, comprising the steps of:
1) dissolving an alkaline substance in deionized water to obtain an alkaline solution;
2) dissolving an oxidizing substance in an alkaline solution at normal temperature to obtain an alkaline chemical oxidation etching solution;
3) soaking a carbon material in an alkaline chemical oxidation etching solution at the temperature of 20-80 ℃ for 1-24 h, and carrying out modification activation treatment;
4) and washing the modified and activated carbon material with deionized water, and drying to obtain the modified and activated carbon material.
2. The method for modifying an activated carbon material according to claim 1, wherein the basic substance is one or a combination of two or more of sodium hydroxide, potassium hydroxide, and ammonia water.
3. The method for modifying an activated carbon material according to any one of claims 1 and 2, wherein the concentration of the alkali solution is 10 to 100 g/L.
4. The method for modifying an activated carbon material according to claim 1, wherein the oxidizing substance is one or a combination of two or more of sodium persulfate, potassium persulfate, ammonium persulfate, potassium bromate, potassium chlorate, potassium perchlorate, potassium permanganate, and hydrogen peroxide.
5. The method for modifying an activated carbon material according to any one of claims 1 and 4, wherein the concentration of the oxidizing substance is 10 to 50 g/L.
6. The method for modifying an activated carbon material as claimed in claim 1, wherein the ratio of the mass concentration of the alkaline substance to the mass concentration of the oxidizing substance in the alkaline chemical oxidation etching solution is 1:1 to 5: 1.
7. The method for modifying an activated carbon material according to claim 1, wherein the carbon material is one of graphite felt, carbon fiber paper, carbon cloth, carbon tube, graphene, carbon black, or a composite thereof.
8. A modified activated carbon material produced by the method according to any one of claims 1 to 7.
9. Use of the modified activated carbon material of claim 8 in the preparation of an electrode material for an energy storage device.
10. Use of the modified activated carbon material of claim 9 in the preparation of an electrode material for an energy storage device, wherein the energy storage device is an alkali metal secondary battery, a supercapacitor, or a flow battery.
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