CN110491676B - Method for preparing high-voltage-resistant electrode material by using porous carbon polyaniline - Google Patents
Method for preparing high-voltage-resistant electrode material by using porous carbon polyaniline Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 76
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 241000209140 Triticum Species 0.000 claims abstract description 9
- 235000021307 Triticum Nutrition 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 235000013312 flour Nutrition 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 235000015110 jellies Nutrition 0.000 claims description 3
- 239000008274 jelly Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 abstract description 15
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 4
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for preparing a high-voltage-resistant electrode material by using porous carbon polyaniline. The invention has the beneficial effects that: the method comprises the steps of taking wheat flour as a carbon source, potassium hydroxide (KOH) and urea as raw materials, wherein the potassium hydroxide is used as an activating agent, obtaining nitrogen-doped hydroxylated porous carbon as a precursor by a high-temperature carbonization-acid treatment method, and then preparing the hydroxylated porous carbon/polyaniline composite material by an in-situ polymerization method; the polyaniline-coated hydroxylated porous carbon composite material prepared by the invention has the advantages of excellent conductivity, large specific surface area and stable physicochemical properties, and can be used as an electrode material of a water system super capacitor with an ultrahigh voltage window.
Description
Technical Field
The invention relates to a method for preparing a high-voltage-resistant electrode material, in particular to a method for preparing a high-voltage-resistant electrode material by using porous carbon polyaniline, and belongs to the technical field of manufacturing of supercapacitors.
Background
In recent years, with the increasing living standard of people and the dependence of industrial development on petroleum, the problem of global petroleum reserve reduction and the problem of global warming become more prominent, and the search for a new clean and renewable energy source or technology is important. In order to deal with the energy crisis and the environmental deterioration, scientists have paid extensive attention to and developed primary energy sources such as solar energy, tidal energy and geothermal energy and secondary energy sources such as electrochemical energy. The lithium ion battery, the traditional capacitor and the super capacitor are common electrochemical energy storage equipment, wherein the super capacitor is one of electrochemical energy storage technologies with great application prospects at present, and is used as an energy storage device bridging the traditional capacitor and the secondary battery.
Currently, the lower energy density of the super capacitor is the biggest disadvantage that limits the development and application of the super capacitor, and therefore, increasing the energy density without losing the power density becomes a difficult point of research. And the formula is as follows: energy density (E ═ C)Asc×ΔV2) Wh/kg), power density (P3600E/. DELTA.t, w/kg), two methods for increasing the energy density of the supercapacitor were known: firstly, the specific capacitance of the electrode active material is improved; and secondly, the electrochemical window of the super capacitor is widened. Polyaniline is a commonly used electrode material of a super capacitor, and has the advantages of low cost, simplicity in preparation, large specific surface area and the like, but most of polyaniline has a low voltage window, a single electrode voltage window is generally 0-1V, and an asymmetric voltage window assembled with a carbon material is generally less than or equal to 1.7V.
Disclosure of Invention
The present invention is directed to solving the above problems and providing a method for preparing a high voltage resistant electrode material using porous carbon polyaniline.
The invention realizes the purpose through the following technical scheme: a method for preparing a high-voltage-resistant electrode material by using porous carbon polyaniline comprises the following steps:
step 1, preparing hydroxylated porous carbon, mixing wheat flour, urea and KOH according to a certain mass ratio, adding distilled water for dissolving, uniformly mixing, carbonizing at high temperature to obtain porous carbon, and adding HNO into a porous carbon sample3After the solution is subjected to ultrasonic treatment, washing the solution with distilled water until the pH value is approximately equal to 7, and drying the solution in vacuum to obtain hydroxylated porous carbon;
step 2, preparing the hydroxylated porous carbon/polyaniline composite material, and sequentially adding 1MH in an ice-water bath2SO4The method comprises the following steps of (1) carrying out in-situ polymerization on the hydroxylated porous carbon prepared in the step (2) by using ammonium persulfate as an initiator, and finishing the reaction after 24 hoursWashing with distilled water until the pH value is approximately equal to 7, and performing vacuum drying to prepare the hydroxylated porous carbon/polyaniline composite material;
step 3, preparing an electrode slice, grinding the hydroxylated porous carbon/polyaniline, the acetylene black and the polyvinylidene fluoride according to a certain mass ratio, coating the ground hydroxylated porous carbon/polyaniline, the acetylene black and the polyvinylidene fluoride on a steel mesh after reaching a micron level, and drying the ground hydroxylated porous carbon/polyaniline, the acetylene black and the polyvinylidene fluoride in vacuum to prepare the electrode slice;
and 4, carrying out electrochemical performance test.
As a still further scheme of the invention: the step 1 comprises the following steps:
1.1, taking 5g of wheat flour, and then taking urea and KOH. Mixing wheat flour, urea and KOH according to the mass ratio of 1:1:1, adding 100ml of distilled water, and strongly stirring the mixture by using a glass rod until the mixture is uniform, wherein the mixture is a yellow turbid jelly;
1.2, putting the mixture into an oven, adjusting the temperature to 100 ℃, and completely removing the water in the mixture;
1.3, carbonizing and pore-forming, under the protection of argon, carrying out heat treatment on the dried mixture for 2 hours at 800 ℃ by using a tube furnace, wherein the heating rate is 2 ℃/min, naturally cooling to room temperature after the heat treatment is finished, and taking out a product;
1.4, washing the product with distilled water to remove impurities, and adding a proper amount of 10% HNO into the product3Heating the solution to 70-80 ℃, and carrying out ultrasonic treatment for 30min, wherein 10 percent of HNO is required to be added for multiple times3And (3) solution, ensuring that the mixture is immersed in the solution, washing the mixture with distilled water after the ultrasonic treatment is finished until the pH value is approximately equal to 7, and drying the mixture in an oven at 100 ℃ for 24 hours to obtain the hydroxylated porous carbon.
As a still further scheme of the invention: the step 2 comprises the following steps:
2.1, placing the three-neck flask in an ice-water bath, wherein the device is ensured to be at a lower temperature (0 ℃) in the whole process, and argon is required to be introduced into the device for protection;
2.2 charging 40ml of 1M H into a three-necked flask2SO4And 46.65uL aniline monomer, adding magneton, magnetically stirring for 15min, mixing, adding 100mg hydroxylated porous carbon, and magnetically stirringStirring for 2 hours;
2.3, 0.1142g of APS was dissolved in 40ml of 1M H2SO4Pouring the mixture into a clean and sealed constant-pressure funnel, dropwise adding the mixture into a three-neck flask, keeping magnetic stirring for 24 hours, washing the mixture with distilled water until the pH value is approximately equal to 7, and drying the product in a 100 ℃ oven for 24 hours to finally obtain the hydroxylated porous carbon/polyaniline composite material.
As a still further scheme of the invention: the step 3 comprises the following steps:
3.1, selecting 4 x 1cm2Soaking 200 mesh steel mesh as current collector in acetone for more than 15min, washing with distilled water, and drying in oven;
3.2, putting the hydroxylated porous carbon/polyaniline (active substance), acetylene black and polyvinylidene fluoride (PVDF) prepared in the step 2 into a mortar for grinding according to the mass ratio of 8:1.5:0.5, adding a proper amount of N, N-Dimethylformamide (DMF) solvent to fully mix the materials into paste, uniformly coating the paste on a current collector by using a scraper, wherein the area of the paste is about 1 x 1cm2；
3.3, putting the current collector into a vacuum drying oven at 100 ℃, drying, taking out the pressed sheet, keeping the pressure at 10Mpa for 20s, and obtaining the electrode plate with the load of about 2-3 mg.
As a still further scheme of the invention: the step 4 comprises the following steps:
4.1, performing CV, EIS and GCD tests on the electrode material in sequence by using an electrochemical workstation in a three-electrode method. Wherein the electrolyte is 1M H2SO4The reference electrode is a Saturated Calomel Electrode (SCE), and the counter electrode is a platinum sheet (Pt);
and 4.2, performing CV, EIS and GCD tests on the electrode material in sequence by using an electrochemical workstation in a two-electrode method. Wherein the electrolyte is 1M H2SO4The positive electrode is hydroxylated porous carbon, and the negative electrode is hydroxylated porous carbon/polyaniline, so that the hydroxylated porous carbon// hydroxylated porous carbon/polyaniline supercapacitor is formed.
The invention has the beneficial effects that: the method for preparing the high-voltage water system supercapacitor electrode material by using the hydroxylated porous carbon/polyaniline has reasonable design:
1. when the hydroxylated porous carbon/polyaniline is prepared, the carbon surface can be roughened by acid treatment, so that the reaction active sites are increased, the effective contact surface area is improved, the aniline monomer can be better dispersed on the surface of the porous carbon material, and the polyaniline can be grown in situ on the stable surface of the porous carbon material;
2. the acid treatment can enable the porous carbon to have more hydrophilic functional groups (such as-COOH and-OH) to obtain the hydroxylated porous carbon, so that the hydrophilicity of the porous carbon is improved, and the porous carbon has better wettability in electrolyte. A large number of oxygen-containing functional groups such as-COOH, -OH and the like are easy to generate redox reaction in the electrode charging and discharging process to generate Faraday pseudo-capacitance, so that the specific capacitance of a sample is greatly improved;
3. compared with the method that metal oxide is used as the electrode material of the super capacitor, the hydroxylated porous carbon/polyaniline composite material prepared by the method has the advantages of simple process, low manufacturing cost, excellent cycle performance and rate capability, and the carbon composite material can reach a high voltage window of 2.0V in a safe and green water-based electrolyte, and is an ideal electrode material with high cost performance.
Drawings
FIG. 1 is a SEM and elemental spectrum analysis chart of hydroxylated porous carbon/polyaniline prepared according to the embodiment of the present invention;
FIG. 2 is a charge-discharge diagram of hydroxylated porous carbon/polyaniline prepared in accordance with embodiments of the present invention;
FIG. 3 is a graph of the cycle life (5A/g) of hydroxylated porous carbon/polyaniline prepared according to examples of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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 invention.
Referring to fig. 1 to 3, a method for preparing a high voltage resistant electrode material by using porous carbon polyaniline includes the following steps:
step 1, preparing hydroxylated porous carbon, mixing wheat flour, urea and KOH according to a certain mass ratio, adding distilled water for dissolving, uniformly mixing, carbonizing at high temperature to obtain porous carbon, and adding HNO into a porous carbon sample3After the solution is subjected to ultrasonic treatment, washing the solution with distilled water until the pH value is approximately equal to 7, and drying the solution in vacuum to obtain hydroxylated porous carbon;
wherein, step 1 includes:
1.1, taking 5g of wheat flour, and then taking urea and KOH. Mixing wheat flour, urea and KOH according to the mass ratio of 1:1:1, adding 100ml of distilled water, and strongly stirring the mixture by using a glass rod until the mixture is uniform, wherein the mixture is a yellow turbid jelly;
1.2, putting the mixture into an oven, adjusting the temperature to 100 ℃, and completely removing the water in the mixture;
1.3, carbonizing and pore-forming, under the protection of argon, carrying out heat treatment on the dried mixture for 2 hours at 800 ℃ by using a tube furnace, wherein the heating rate is 2 ℃/min, naturally cooling to room temperature after the heat treatment is finished, and taking out a product;
1.4, washing the product with distilled water to remove impurities, and adding a proper amount of 10% HNO into the product3Heating the solution to 70-80 ℃, and carrying out ultrasonic treatment for 30min, wherein 10 percent of HNO is required to be added for multiple times3And (3) solution, ensuring that the mixture is immersed in the solution, washing the mixture with distilled water after the ultrasonic treatment is finished until the pH value is approximately equal to 7, and drying the mixture in an oven at 100 ℃ for 24 hours to obtain the hydroxylated porous carbon.
Step 2, preparing the hydroxylated porous carbon/polyaniline composite material, and sequentially adding 1MH in an ice-water bath2SO4The method comprises the following steps of (1) carrying out in-situ polymerization on the hydroxylated porous carbon prepared in the step (2) by using ammonium persulfate as an initiator, washing the hydroxylated porous carbon with distilled water until the pH value is approximately equal to 7 after 24 hours of reaction completion, and carrying out vacuum drying to prepare the hydroxylated porous carbon/polyaniline composite material;
wherein, step 2 includes:
2.1, placing the three-neck flask in an ice-water bath, wherein the device is ensured to be at a lower temperature (0 ℃) in the whole process, and argon is required to be introduced into the device for protection;
2.2 charging 40ml of 1M H into a three-necked flask2SO4And 46.65uL aniline monomer, adding magnetons, magnetically stirring for 15min, uniformly mixing, adding 100mg hydroxylated porous carbon, and magnetically stirring for 2 h;
2.3, 0.1142g of APS was dissolved in 40ml of 1M H2SO4Pouring the mixture into a clean and sealed constant-pressure funnel, dropwise adding the mixture into a three-neck flask, keeping magnetic stirring for 24 hours, washing the mixture with distilled water until the pH value is approximately equal to 7, and drying the product in a 100 ℃ oven for 24 hours to finally obtain the hydroxylated porous carbon/polyaniline composite material.
Step 3, preparing an electrode slice, grinding the hydroxylated porous carbon/polyaniline, the acetylene black and the polyvinylidene fluoride according to a certain mass ratio, coating the ground hydroxylated porous carbon/polyaniline, the acetylene black and the polyvinylidene fluoride on a steel mesh after reaching a micron level, and drying the ground hydroxylated porous carbon/polyaniline, the acetylene black and the polyvinylidene fluoride in vacuum to prepare the electrode slice;
wherein, step 3 includes:
3.1, selecting 4 x 1cm2Soaking 200 mesh steel mesh as current collector in acetone for more than 15min, washing with distilled water, and drying in oven;
3.2, putting the hydroxylated porous carbon/polyaniline (active substance), acetylene black and polyvinylidene fluoride (PVDF) prepared in the step 2 into a mortar for grinding according to the mass ratio of 8:1.5:0.5, adding a proper amount of N, N-Dimethylformamide (DMF) solvent to fully mix the materials into paste, uniformly coating the paste on a current collector by using a scraper, wherein the area of the paste is about 1 x 1cm2；
3.3, putting the current collector into a vacuum drying oven at 100 ℃, drying, taking out the pressed sheet, keeping the pressure at 10Mpa for 20s, and obtaining the electrode plate with the load of about 2-3 mg.
And 4, carrying out electrochemical performance test.
Wherein, step 4 includes:
and 4.1, performing CV, EIS and GCD tests on the electrode material in sequence by using an electrochemical workstation in a three-electrode method. Wherein the electrolyte is 1M H2SO4The reference electrode is a Saturated Calomel Electrode (SCE), and the counter electrode is a platinum sheet (Pt);
and 4.2, performing CV, EIS and GCD tests on the electrode material in sequence by using an electrochemical workstation in a two-electrode method. Wherein the electrolyte is 1M H2SO4The capacitor is formed by the hydroxylated porous carbon/polyaniline capacitor with the hydroxylated porous carbon porous polyaniline as the anode and the hydroxylated porous carbon polyaniline as the cathode.
As can be seen from fig. 1, in the SEM image, it can be observed that the prepared hydroxylated porous carbon/polyaniline has uniform pore size, and the surface of the porous carbon is uniformly coated with a layer of small particulate matter, while the N element (characteristic element of polyaniline) spectrum peak in the elemental energy spectrum analysis chart is obvious, which indicates that the existing material is polyaniline and uniformly grows on the surface of the hydroxylated porous carbon.
As can be seen from fig. 2, the supercapacitor made of the hydroxylated porous carbon/polyaniline can be charged with a small current and discharged with a large current, has a symmetrical distribution of charging and discharging curves, has the characteristic of the electric double layer capacitance of the supercapacitor, can reach a high voltage window of 2.0V, and has a power density of 998.5W/kg (at an energy density of 29.4 Wh/kg) calculated from the charging and discharging curves at a current density of 1A/g.
As can be seen from fig. 3, the coulombic efficiency of the hydroxylated porous carbon// hydroxylated porous carbon/polyaniline can still reach 100% after ten thousand cycles, and the fluctuation part of the coulombic efficiency around 100% is caused by external factors such as temperature, humidity, noise, vibration and the like.
The working principle is as follows: in the water system super capacitor, the porous carbon material can provide electric double layer capacitance for the super capacitor due to the developed pore structure, the conductivity is excellent, and the self resistance of the electrode material is small; under the acidic test condition, polyaniline can be caused by oxidation-reduction reaction and shows faradaic pseudo-capacitance behavior, and self-NH of the polyaniline can form hydrogen bond action with-OH and-COOH of porous carbon and stably exist. Due to hydroxylation of the porous carbon material, the synergistic effect between the porous carbon and the polyaniline enables the composite material to have good hydrophilicity and chemical stability, meanwhile, the uniform pore diameter and the three-dimensional porous structure have high contact area in electrolyte, ionic mobility and electron transfer efficiency are accelerated, solution resistance is reduced, polarization of the electrode in the solution is weakened, and further a potential window in the electrode charging and discharging process is improved. The polyaniline-coated hydroxylated porous carbon composite material prepared by the invention has the advantages of excellent conductivity, large specific surface area and stable physicochemical properties, and can be used as an electrode material of a water system super capacitor with an ultrahigh voltage window.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (1)
1. A method for preparing a high-voltage-resistant electrode material by using porous carbon polyaniline is characterized by comprising the following steps: step 1:
1.1, taking 5g of wheat flour, and then taking urea and KOH; mixing wheat flour, urea and KOH according to the mass ratio of 1:1:1, adding 100ml of distilled water, and strongly stirring the mixture by using a glass rod until the mixture is uniform, wherein the mixture is observed to be yellow turbid jelly;
1.2, putting the mixture into an oven, adjusting the temperature to 100 ℃, and completely removing the water in the mixture;
1.3, carbonizing and pore-forming, under the protection of argon, carrying out heat treatment on the dried mixture for 2 hours at 800 ℃ by using a tube furnace, wherein the heating rate is 2 ℃/min, naturally cooling to room temperature after the heat treatment is finished, and taking out a product;
1.4 washing the product with distilled water to remove its impurities, and adding 10% HNO to the product3Heating the solution to 70-80 ℃, and carrying out ultrasonic treatment for 30min, wherein 10% HNO is added for multiple times3The solution is ensured to immerse the mixture, the mixture is washed by distilled water after the ultrasonic treatment is finished until the pH value is approximately equal to 7, and the mixture is dried in an oven at 100 ℃ for 24 hours to obtain hydroxylated porous carbon;
step 2:
2.1, placing the three-neck flask in an ice-water bath, wherein the device is ensured to be at a lower temperature in the whole process, and argon is kept to be introduced into the device for protection;
2.2 charging 40ml of 1M H into a three-necked flask2SO4And 46.65uL aniline monomer, adding magnetons, magnetically stirring for 15min, uniformly mixing, adding 100mg hydroxylated porous carbon, and magnetically stirring for 2 h;
2.3, dissolving 0.1142g of APS in 40ml of 1M H2SO4Pouring the mixture into a clean and closed constant-pressure funnel, dropwise adding the mixture into a three-neck flask, keeping magnetic stirring for 24 hours, washing the mixture with distilled water until the pH value is approximately equal to 7, and drying the product in a 100 ℃ oven for 24 hours to finally obtain the hydroxylated porous carbon/polyaniline composite material;
and step 3:
3.1, selecting 4 x 1cm2Soaking 200 mesh steel mesh as current collector in acetone for more than 15min, washing with distilled water, and drying in oven;
3.2, putting the hydroxylated porous carbon/polyaniline, acetylene black and polyvinylidene fluoride prepared in the step 2 into a mortar for grinding according to the mass ratio of 8:1.5:0.5, adding a proper amount of N, N-dimethylformamide solvent to fully mix the materials into paste, and uniformly coating the paste on a current collector by a scraper, wherein the area of the paste is 1 x 1cm2；
3.3, putting the current collector into a vacuum drying oven at 100 ℃, drying, taking out the pressed sheet, keeping the pressure at 10Mpa for 20s, and obtaining the capacity of the electrode plate of 2-3 mg;
and 4, step 4:
4.1, performing CV, EIS and GCD tests on the electrode material in sequence by using an electrochemical workstation in a three-electrode method; wherein the electrolyte is 1M H2SO4The reference electrode is a saturated calomel electrode, and the counter electrode is a platinum sheet;
4.2, performing CV, EIS and GCD tests on the electrode material in sequence by using an electrochemical workstation in a two-electrode method; wherein the electrolyte is 1M H2SO4The positive electrode is hydroxylated porous carbon, and the negative electrode is hydroxylated porous carbon/polyaniline to form the hydroxylated porous carbon/polyaniline supercapacitor.
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Application publication date: 20191122 Assignee: Guilin Qi Hong Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044172 Denomination of invention: A method for preparing high-voltage electrode materials using porous carbon polyaniline Granted publication date: 20210709 License type: Common License Record date: 20231024 |