CN112908725A - Preparation method and application of nitrogen-phosphorus double-doped activated carbon - Google Patents
Preparation method and application of nitrogen-phosphorus double-doped activated carbon Download PDFInfo
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- CN112908725A CN112908725A CN202110110279.9A CN202110110279A CN112908725A CN 112908725 A CN112908725 A CN 112908725A CN 202110110279 A CN202110110279 A CN 202110110279A CN 112908725 A CN112908725 A CN 112908725A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 229920001634 Copolyester Polymers 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011363 dried mixture Substances 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- -1 2-carboxyethyl phenyl hypophosphorous acid Chemical compound 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002743 phosphorus functional group Chemical group 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 13
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 33
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
-
- 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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- 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
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Abstract
The invention discloses a preparation method of nitrogen-phosphorus double-doped activated carbon, which comprises the steps of synthesizing phosphorus-containing copolyester by diacid, diol and phosphorus-containing comonomer; carrying out chain extension reaction on phosphorus-containing copolyester and diisocyanate to synthesize a nitrogen-and phosphorus-containing group copolymer, and then carrying out high-temperature pyrolysis and activation to obtain nitrogen-and phosphorus-double-doped activated carbon; the nitrogen-phosphorus double-doped active carbon is applied to a super capacitor. The preparation of the invention can be carried out by using the existing polyester preparation equipment and processing equipment, the preparation process is simple, and the large-scale production is easy; the obtained activated carbon can be used as an electrode material of a super capacitor. The invention provides a preparation method and application of nitrogen and phosphorus co-doped activated carbon by taking a phosphorus-containing copolymer as a precursor, and solves the problems of lower material specific capacitance, lower energy density and narrower working voltage window of the conventional undoped activated carbon or nitrogen and phosphorus double-doped activated carbon super-capacitor.
Description
Technical Field
The invention belongs to the technical field of nano activated carbon preparation, and particularly relates to a preparation method and application of nitrogen-phosphorus double-doped activated carbon.
Background
The super capacitor has the advantages of high power density and long cycle service life, and is widely applied to the fields of automobiles, aerospace, military industry and the like. The activated carbon material has the advantages of large specific surface area, high chemical stability, good conductivity and the like, so that the activated carbon material becomes the most widely applied supercapacitor material at present. However, it is known that an activated carbon supercapacitor belongs to an electric double layer capacitor, and has a drawback of low specific capacitance and low energy density. In addition, the working voltage window of the activated carbon super capacitor using the water system electrolyte is narrow, and the improvement of the energy density is further limited. Therefore, it is necessary to improve the energy density and specific capacitance of the super capacitor and widen the operating voltage window of the super capacitor.
At present, raw materials for preparing the activated carbon material mainly come from biomass materials, coal and petroleum substances, however, the natural substances contain more ash. The ash can reduce the specific surface area of the activated carbon, so that the activated carbon material generates excessive leakage current under an electric field, and the energy storage performance of the activated carbon material is reduced.
In comparison, the activated carbon material prepared by taking the synthetic polymer as the precursor through carbonization and activation has higher purity and lower ash content, so the method is suitable for being applied to the fields of biomedicine and high-performance supercapacitors.
In addition, nitrogen atoms are doped into the activated carbon, so that the effects of improving the conductivity of the material and providing an additional pseudo capacitor can be achieved. And the phosphorus atoms are doped into the activated carbon, so that the effects of improving the hydrophilicity of the material, providing an additional pseudocapacitance and widening the working voltage window of the super capacitor in the suixi 1 electrolyte can be achieved. The nitrogen and phosphorus atoms are doped into the activated carbon material together, so that the energy density of the super capacitor can be effectively improved through a synergistic effect.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a preparation method and application of nitrogen-phosphorus double-doped activated carbon.
The invention is realized by the following technical scheme:
the invention provides a preparation method of nitrogen-phosphorus double-doped activated carbon, which comprises the following specific steps:
s1, putting adipic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and a catalyst of tetrabutyl titanate into a polymerization kettle, mechanically stirring for 3-4 hours at the reaction temperature of 140-180 ℃ under the protection of a nitrogen environment, carrying out esterification reaction, raising the temperature to 200-230 ℃ after the esterification reaction is finished, reducing the pressure to 20-70 Pa, and mechanically stirring for 1-2 hours to obtain the low-molecular-weight phosphorus-containing copolyester;
s2, banburying and blending the phosphorus-containing copolyester prepared in the S1 and 4, 4' -diphenylmethane diisocyanate (MDI) at 100-120 ℃ for 15-30min to obtain a nitrogen-phosphorus group-containing copolymer;
and S3, putting the copolymer containing nitrogen and phosphorus groups prepared in the step S2 into a tubular furnace for high-temperature pyrolysis to obtain the nitrogen-phosphorus double-doped activated carbon.
Preferably, in the step S1, the molar ratio of adipic acid to the glycol is 1: 1.3-1: 1.05, wherein the molar ratio of adipic acid to the 2-carboxyethylphenylphosphinic acid is 1: 0.04-1: 0.1; the content of tetrabutyl titanate is 1-2% of the total mass of reactants.
Preferably, the mass of MDI in the step S2 is 1-4% of the mass of the phosphorus-containing copolyester.
Preferably, the high-temperature pyrolysis method in the step S3 is: placing the phosphorus-containing polyurethane copolymer in a porcelain boat, and then placing the porcelain boat in a tube furnace; introducing nitrogen or argon into the tubular furnace to remove oxygen for 0.1-0.5 h, taking the nitrogen or argon as a protective gas, heating the tubular furnace to 400-500 ℃ at the speed of 2-5 ℃/min, heating to 600-900 ℃ at the speed of 1-3 ℃/min, and keeping for 2-4 h; and then cooling to room temperature at the speed of 3-5 ℃/min to complete high-temperature pyrolysis.
The invention also provides application of the nitrogen-phosphorus double-doped activated carbon, which is characterized in that the nitrogen-phosphorus double-doped activated carbon is applied to a super capacitor. The specific application method comprises the following steps:
(1) cutting the foamed nickel plate into 1 × 2cm2The square of (2) is used as a current collector;
(2) preparing 4% polyvinylidene fluoride emulsion as a binder;
(3) mixing the nitrogen-phosphorus double-doped activated carbon, the acetylene black and the binder according to a mass ratio of 8:1:1, placing the mixture in a container, magnetically stirring for 2-4 h, uniformly blade-coating the mixture on a current collector, vacuum-drying the mixture at 110 ℃ for 12h, placing the dried mixture in an oil press, and compacting the dried mixture under a pressure of 3-8 MPa to obtain a working electrode for the supercapacitor;
(4) and assembling the two same working electrodes and the electrolyte into a symmetrical supercapacitor.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a preparation method and application of nitrogen and phosphorus co-doped activated carbon by taking a phosphorus-containing copolymer as a precursor, and solves the problems of lower material specific capacitance, lower energy density and narrower working voltage window of the conventional undoped activated carbon or nitrogen and phosphorus double-doped activated carbon super-capacitor.
(2) The preparation of the invention can be carried out by using the existing polyester preparation equipment and processing equipment, the preparation process is simple, and the large-scale production is easy; the obtained activated carbon can be used as an electrode material of a super capacitor.
Drawings
Fig. 1 is a schematic diagram of a working electrode prepared from nitrogen-phosphorus double-doped activated carbon according to the present invention.
FIG. 2 is a schematic diagram of a symmetrical supercapacitor made according to the present invention after use.
FIG. 3 is a constant current charge and discharge curve for different current densities through a three-electrode system in 6M potassium hydroxide electrolyte for a working electrode prepared in example 1; wherein a is 1A/g and b is 10A/g.
FIG. 4 is a cyclic voltammogram of the assembled symmetrical supercapacitor of example 1 at different operating voltage windows in 6M potassium hydroxide electrolyte; wherein a is 0-0.8V, b is 0-1V, and c is 0-1.2V.
FIG. 5 is a constant current charge and discharge curve of a symmetrical supercapacitor assembled in accordance with example 2 of the present invention in 6M potassium hydroxide electrolyte; wherein a is 1A/g, b is 2A/g, c is 5A/g, and d is 10A/g.
FIG. 6 is a specific capacitance curve calculated from a constant current discharge curve in 6M potassium hydroxide electrolyte for a symmetrical supercapacitor assembled in accordance with example 2 of the present invention.
FIG. 7 is a graph of the power density of a symmetrical supercapacitor assembled in accordance with example 2 of the present invention in a 6M KOH electrolyte versus the corresponding energy density.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
A preparation method of nitrogen-phosphorus double-doped activated carbon comprises the following steps:
firstly, putting 1mol of adipic acid, 1.1mol of ethylene glycol and 0.05mol of 2-carboxyethyl phenyl hypophosphorous acid into a polymerization kettle, adding a catalyst of tetrabutyl titanate accounting for 1% of the total mass of reactants, introducing nitrogen for environmental protection, mechanically stirring for 3 hours at 170 ℃, then heating to 220 ℃, reducing the pressure to 50Pa, and mechanically stirring for 1 hour to obtain phosphorus-containing copolyester;
carrying out banburying and blending on phosphorus-containing copolyester and 4, 4' -diphenylmethane diisocyanate (MDI) at 100 ℃ for 20min, wherein the mass of the MDI is 2% of that of the phosphorus-containing copolyester, and obtaining a nitrogen-phosphorus group-containing copolymer;
thirdly, placing the phosphorus-containing polyurethane copolymer in a porcelain boat, and then placing the porcelain boat in a tube furnace; introducing nitrogen or argon into the tubular furnace to remove oxygen for 0.5h, taking the nitrogen or argon as a protective gas, heating the tubular furnace to 400 ℃ at the speed of 5 ℃/min, then heating to 700 ℃ at the speed of 3 ℃/min, and keeping for 2 h; then cooling to room temperature at the speed of 3 ℃/min to obtain the nitrogen-phosphorus double-doped active carbon.
The prepared nitrogen-phosphorus double-doped active carbon is used in a super capacitor, and the specific application method comprises the following steps:
firstly, cutting a foamed nickel plate into 1 multiplied by 2cm2The square of (2) is used as a current collector;
secondly, 4% polyvinylidene fluoride (PVDF) emulsion is used as a binder;
thirdly, mixing nitrogen-phosphorus double-doped activated carbon, acetylene black and PVDF according to the mass ratio of 8:1:1, placing the mixture in a container, magnetically stirring the mixture for 2 hours, uniformly coating the mixture on a current collector, drying the mixture in vacuum at 110 ℃ for 12 hours, placing the dried mixture in an oil press, and compacting the dried mixture under the pressure of 5MPa to obtain a working electrode for the supercapacitor, wherein the working electrode is marked as NPAC-1 in figure 1;
and fourthly, assembling two pieces of the same working electrode and electrolyte (6M potassium hydroxide) into a symmetrical super capacitor, as shown in figure 2, wherein the symmetrical super capacitor is marked as NPAC-1// NPAC-1, and in figure 2, the picture is a picture of three super capacitors which are connected in series and the series LED lamp which is lighted by the three super capacitors.
The working electrode for the supercapacitor made of the activated carbon obtained in this example was subjected to constant current charge and discharge tests at different current densities in a 6M potassium hydroxide electrolyte using a three-electrode system (the working electrode, the counter electrode and the reference electrode in this example), and the results are shown in fig. 3, where a is 1A/g and b is 10A/g, and there are curves similar to isosceles shapes at different current densities. According to the working electrode capacitance calculated by the discharge curve, the NPAC-1 working electrode has the specific capacitance of 277F/g at the current density of 1A/g, and when the current density is increased to 10A/g, the specific capacitance is still maintained at 190F/g, so that the NPAC-1 working electrode shows better rate performance.
The supercapacitor NPAC-1// NPAC-1 (two groups of working electrodes in the embodiment) assembled by the working electrodes in the embodiment is subjected to cyclic voltammetry tests in 6M potassium hydroxide electrolyte at a rate of 10mV/s, the test voltage ranges are 0-0.8V, 0-1.0V and 0-1.2V respectively, and the results show that the cyclic voltammetry curve of the supercapacitor still maintains a regular shape in the 0-1.2V working voltage range, which indicates that the working voltage window of the supercapacitor is wide, see FIG. 4, wherein a is 0-0.8V, b is 0-1V and c is 0-1.2V. The super capacitor assembled by the embodiment has high specific capacitance of 51.0F g-1。
In the embodiment, the specific capacitance of the working electrode NPAC-1 under the three-electrode test system is 190F/g, and after two identical NPAC-1 are assembled into a symmetrical supercapacitor, the specific capacitance of the supercapacitor is 51.0F/g. The two are numerically different due to the fact that in a symmetrical supercapacitor, the two working electrodes areThe electrodes are connected in series, and the relation between the total capacitance and the working electrode capacitance is as followsGeneral assembly＝1/CWork by+1/CWork by。
And the mass of the energy storage active substance in the super capacitor is the sum of the masses of the energy storage active substances in the two working electrodes. According to the above quantitative relationship, when the working electrodes are assembled into a supercapacitor device, the total capacitance of the supercapacitor device should be about one fourth of the capacitance of a single working electrode.
Example 2
A preparation method of nitrogen-phosphorus double-doped activated carbon comprises the following steps:
firstly, putting 1mol of adipic acid, 1.2mol of ethylene glycol and 0.08mol of 2-carboxyethyl phenyl hypophosphorous acid into a polymerization kettle, adding a catalyst of tetrabutyl titanate with the total mass of 2% of reactants, introducing nitrogen for environmental protection, mechanically stirring for 4 hours at 180 ℃, then heating to 230 ℃, reducing the pressure to 60Pa, and mechanically stirring for 1.5 hours to obtain phosphorus-containing copolyester;
carrying out banburying and blending on phosphorus-containing copolyester and 4, 4' -diphenylmethane diisocyanate (MDI) at 120 ℃ for 18min, wherein the mass of the MDI is 4% of that of the phosphorus-containing copolyester, and obtaining a nitrogen-phosphorus group-containing copolymer;
thirdly, placing the phosphorus-containing polyurethane copolymer in a porcelain boat, and then placing the porcelain boat in a tube furnace; introducing nitrogen or argon into the tubular furnace to remove oxygen for 0.5h, taking the nitrogen or argon as a protective gas, heating the tubular furnace to 400 ℃ at the speed of 3 ℃/min, then heating to 800 ℃ at the speed of 2 ℃/min, and keeping the temperature for 1 h; then cooling to room temperature at the speed of 3 ℃/min to obtain nitrogen-phosphorus double-doped active carbon;
the application method of the prepared nitrogen-phosphorus double-doped activated carbon applied to the super capacitor is the same as that of the embodiment 1, and specifically comprises the following steps: the preparation method comprises the steps of adopting foamed nickel as a current collector, adopting 4% polyvinylidene fluoride (PVDF) emulsion as a binder, mixing nitrogen-phosphorus double-doped activated carbon, acetylene black and PVDF according to the mass ratio of 8:1:1, placing the mixture in a container, magnetically stirring the mixture for 2 hours, then uniformly coating the mixture on the current collector, drying the mixture in vacuum at 110 ℃ for 12 hours, then placing the mixture in an oil press, compacting the mixture by using the pressure of 8MPa, preparing a working electrode, and assembling two identical electrodes into a symmetrical supercapacitor.
The working electrode prepared above is shown in FIG. 1 and labeled as NPAC-2; two sheets of the same working electrode and electrolyte (6M KOH) were assembled into a symmetrical supercapacitor as shown in FIG. 2, which is labeled NPAC-2// NPAC-2, and FIG. 2 is a photograph of a series LED lamp that was lit after the supercapacitor was mounted in series.
When tested in the working electrode 6M potassium hydroxide electrolyte prepared from the nitrogen-phosphorus double-doped activated carbon obtained in example 2 (a three-electrode system consisting of the working electrode, the counter electrode and the reference electrode in this example), the specific capacitance of the working electrode can reach 220F/g at a current density of 1A/g.
In a constant current charging and discharging curve diagram of the symmetrical supercapacitor assembled by the working electrode prepared from the nitrogen-phosphorus double-doped activated carbon obtained in the embodiment 2 in a 6M potassium hydroxide electrolyte, the curve shows a good isosceles triangle without obvious voltage drop, which indicates that the internal resistance is low, and the curve is shown in fig. 5, wherein a is 1A/g, b is 2A/g, c is 5A/g, and d is 10A/g.
Under a two-electrode system (two groups of working electrodes in the embodiment), the specific capacitance of the symmetrical supercapacitor can reach 60.2F/g at a current density of 1A/g, and when the current density is increased and is 10A/g, the specific capacitance is still kept at 41.6F/g, so that the symmetrical supercapacitor shows better rate performance, and the reference figure 6 shows that the specific capacitance is higher than that of the symmetrical supercapacitor.
According to the test data of the two-electrode system, the energy density of the symmetrical supercapacitor prepared in example 2 is higher and is 602W kg-1The energy density can reach 12.4Wh Kg-1See fig. 7.
The preparation equipment of the embodiment 1-2 is simple and is easy for large-scale production; the obtained nitrogen-phosphorus double-doped activated carbon can be used as an electrode material of a super capacitor and has higher energy density.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A preparation method of nitrogen-phosphorus double-doped activated carbon is characterized by comprising the following specific steps:
s1, putting adipic acid, ethylene glycol, 2-carboxyethyl phenyl hypophosphorous acid and a catalyst of tetrabutyl titanate into a polymerization kettle, mechanically stirring for 3-4 hours at the reaction temperature of 140-180 ℃ under the protection of a nitrogen environment, carrying out esterification reaction, raising the temperature to 200-230 ℃ after the esterification reaction is finished, reducing the pressure to 20-70 Pa, and mechanically stirring for 1-2 hours to obtain the low-molecular-weight phosphorus-containing copolyester;
s2, banburying and blending the phosphorus-containing copolyester prepared in the S1 and 4, 4' -diphenylmethane diisocyanate (MDI) at 100-120 ℃ for 15-30min to obtain a nitrogen-phosphorus group-containing copolymer;
and S3, putting the copolymer containing nitrogen and phosphorus groups prepared in the step S2 into a tubular furnace for high-temperature pyrolysis to obtain the nitrogen-phosphorus double-doped activated carbon.
2. The preparation method of nitrogen-phosphorus double-doped activated carbon according to claim 1, wherein in the step of S1, the molar ratio of the adipic acid to the glycol is 1: 1.3-1: 1.05, wherein the molar ratio of the adipic acid to the 2-carboxyethylphenylphosphinic acid is 1: 0.04-1: 0.1; the content of the tetrabutyl titanate is 1-2% of the total mass of the reactants.
3. The preparation method of nitrogen-phosphorus double-doped activated carbon according to claim 1, wherein the mass of MDI in the step S2 is 1-4% of the mass of the phosphorus-containing copolyester.
4. The method for preparing nitrogen-phosphorus double-doped activated carbon according to claim 1, wherein the high-temperature pyrolysis method in the step S3 is as follows: placing the phosphorus-containing polyurethane copolymer in a porcelain boat, and then placing the porcelain boat in a tube furnace; introducing nitrogen or argon into the tubular furnace to remove oxygen for 0.1-0.5 h, taking the nitrogen or argon as a protective gas, heating the tubular furnace to 400-500 ℃ at the speed of 2-5 ℃/min, heating to 600-900 ℃ at the speed of 1-3 ℃/min, and keeping for 2-4 h; and then cooling to room temperature at the speed of 3-5 ℃/min to complete high-temperature pyrolysis.
5. Use of the nitrogen-phosphorus double-doped activated carbon prepared by the method of any one of claims 1 to 4, wherein the nitrogen-phosphorus double-doped activated carbon is used in a supercapacitor; the application method comprises the following steps: the method comprises the steps of preparing working electrodes by using foamed nickel as a current collector and nitrogen-phosphorus double-doped active carbon, acetylene black and PVDF according to the mass ratio of 8:1:1, and assembling two identical working electrodes into a symmetrical supercapacitor.
6. The application of the nitrogen-phosphorus double-doped activated carbon as claimed in claim 5, wherein the step of preparing the supercapacitor from the nitrogen-phosphorus double-doped activated carbon comprises the following steps:
(1) cutting the foamed nickel plate into 1 × 2cm2The square of (2) is used as a current collector;
(2) preparing 4% polyvinylidene fluoride emulsion as a binder;
(3) mixing the nitrogen-phosphorus double-doped activated carbon, the acetylene black and the binder according to a mass ratio of 8:1:1, placing the mixture in a container, magnetically stirring for 2-4 h, uniformly blade-coating the mixture on a current collector, vacuum-drying the mixture at 110 ℃ for 12h, placing the dried mixture in an oil press, and compacting the dried mixture under a pressure of 3-8 MPa to obtain a working electrode for the supercapacitor;
(4) and assembling the two same working electrodes and the electrolyte into a symmetrical supercapacitor.
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