CN114334474A - Polyurethane sponge compounded with phosphorus-doped reduced graphene oxide and polypyrrole and preparation method thereof - Google Patents
Polyurethane sponge compounded with phosphorus-doped reduced graphene oxide and polypyrrole and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000004814 polyurethane Substances 0.000 title claims abstract description 46
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 71
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 20
- 229940012189 methyl orange Drugs 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 10
- 239000004020 conductor Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000006835 compression Effects 0.000 description 12
- 238000007906 compression Methods 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 238000010277 constant-current charging Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
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Abstract
The invention belongs to the technical field of flexible supercapacitors, and particularly relates to polyurethane sponge compounded with phosphorus-doped reduced graphene oxide and polypyrrole and a preparation method thereof. According to the invention, the phosphorus-doped reduced graphene oxide, polypyrrole and polyurethane sponge are compounded, so that the insulating flexible matrix and the conductive material are effectively combined, the excellent electrical property is realized on the basis of keeping the original compressibility, and the composite material can be applied to the field of flexible super capacitors.
Description
Technical Field
The invention belongs to the technical field of flexible supercapacitors, and particularly relates to polyurethane sponge compounded with phosphorus-doped reduced graphene oxide and polypyrrole and a preparation method thereof.
Background
Deformable supercapacitors, which provide stable power output in case of deformation, are becoming key instruments for wearable electronics. The flexible material is used as a compressible matrix, such as polymer sponge, cellulose aerogel and the like, to load an active material, but the insulating matrix seriously influences the electrochemical performance of an electrode material, so that the preparation of the supercapacitor with excellent mechanical properties, such as excellent electrical properties, flexibility, ductility, repeated compression and bending, is very necessary.
Polyurethane or melamine sponges with a porous three-dimensional network are used as compressible substrates due to their excellent water absorption, durability, and compressibility properties. Common conductive polymer materials such as polypyrrole and polyaniline draw great attention due to the advantages of easy synthesis, excellent specific capacitance, inherent polymer flexibility and the like, and the inevitable defects of poor rate performance and cycling stability are also defects of the common conductive polymer materials, so that the electrical properties of the materials can be effectively improved by combining the conductive polymer with the high conductive materials such as reduced graphene oxide or activated carbon. Polyurethane sponge has been reported as a three-dimensional carbon network template, a porous carbon material, iron and iron oxide are hydrothermally compounded, and then calcined at high temperature, but the compressibility of the sponge is greatly affected by the preparation method. It has also been reported that the flexible piezoresistive material can be used by alternately adsorbing multi-walled carbon nanotubes and graphene oxide suspension with opposite charges by using sponge in a layer-by-layer assembly mode and then performing hydrothermal reduction by using hydrazine hydrate, but the electrical properties of the flexible piezoresistive material are affected to a certain extent because the adsorbed graphene oxide cannot be completely reduced by the hydrazine hydrate with the increase of the coating period, and the hydrazine hydrate is accompanied by odor in the use process and has strong basicity and hygroscopicity. Reduced graphene oxide after being adsorbed and acidified by melamine sponge and pyrrole in-situ polymerization are also reported to be used for the compressible super capacitor, but the reduced graphene oxide in the method has poor dispersibility in water and is extremely easy to settle, and active materials are difficult to uniformly distribute on the sponge. Therefore, although compression is a common mechanical deformation phenomenon of wearable energy storage devices, research on how to effectively combine an insulating flexible matrix and a conductive filler to obtain a flexible electrode material with stable output is still rare.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a polyurethane sponge compounded with phosphorus-doped reduced graphene oxide and polypyrrole and a preparation method thereof.
The technical scheme provided by the invention is as follows:
a preparation method of polyurethane sponge compounded with phosphorus-doped reduced graphene oxide and polypyrrole comprises the following steps:
1) taking the weight of methyl orange as a reference, dissolving 0.1-0.6g of methyl orange in 40-300ml of deionized water, stirring, adding 0.1-3ml of pyrrole monomer after all methyl orange is dissolved, and continuously stirring to obtain a solution A;
2) dispersing the prepared phosphorus-doped reduced graphene oxide in deionized water, adding an oxidant after the phosphorus-doped reduced graphene oxide is uniformly dispersed, and dissolving to obtain a solution B, wherein the dispersed concentration of the phosphorus-doped reduced graphene oxide is 3-10mg/ml, and the weight ratio of the phosphorus-doped reduced graphene oxide to the oxidant is (0.15-0.5): 1;
3) precooling the solution A obtained in the step 1) and the solution B obtained in the step 2) to 0-4 ℃, then alternately adsorbing the solution A and the solution B by using the cleaned polyurethane sponge, extruding to enable the solutions to be completely permeated into the polyurethane sponge, mixing the solution A and the solution B to obtain a mixed solution, immersing the polyurethane sponge into the mixed solution for reaction, and obtaining a dispersion liquid generated by the reaction, wherein the weight ratio of pyrrole used in the solution A to oxidant used in the solution B is 1 (0.3-0.4);
4) taking out the polyurethane sponge in the dispersion liquid generated by the reaction in the step 3), continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the polyurethane sponge in absolute ethyl alcohol, taking out and naturally drying;
5) and soaking the polyurethane sponge in the dispersion liquid generated by the reaction, taking out the polyurethane sponge, naturally airing the polyurethane sponge, and repeating the step for 1 to 4 times to obtain the polyurethane sponge of the composite phosphorus-doped reduced graphene oxide and polypyrrole.
In the above technical scheme:
compared with reduced graphene oxide, the phosphorus-doped reduced graphene oxide has good dispersibility in an aqueous solution and is not easy to settle, so that the system is more stable, the obtained dispersion system is more uniform, and the physical and chemical properties, the electrochemical behavior and the band gap of the material can be improved by doping phosphorus, so that the performance is better; the polyurethane sponge has better adsorbability to phosphorus-doped reduced graphene oxide; the combined action of the two components ensures that the phosphorus-doped reduced graphene oxide is uniformly distributed on the polyurethane sponge, thereby ensuring the stable output performance of the material.
Specifically, in the step 1), the pyrrole monomer is added and then the stirring is continued for 18-30 h.
Specifically, in the step 2), the oxidant is selected from ferric nitrate nonahydrate, ferric trichloride hexahydrate or ammonium persulfate. Preferably, ferric nitrate nonahydrate.
Specifically, the reaction time is 1 to 6 hours.
The invention also provides the polyurethane sponge of the composite phosphorus-doped reduced graphene oxide and polypyrrole, which is prepared by the preparation method.
The outstanding benefits of the invention are mainly reflected in the following aspects:
1) the raw materials used in the invention have low price and the preparation process is simple and convenient;
2) the phosphorus-doped reduced graphene oxide has good dispersibility in an aqueous solution, so that the system is more stable, and a uniform dispersion system can be obtained;
3) the insulating flexible substrate is effectively combined with the conductive material, so that the conductive material has excellent electrical properties on the basis of keeping the original compressibility, and can be applied to the field of flexible super capacitors;
4) along with the change of pressure, the resistance value changes, the current obviously increases under a certain voltage, and the piezoelectric ceramic has certain sensing performance and can also be used for pressure sensing materials.
Drawings
Fig. 1 is a performance diagram of a polyurethane sponge electrode doped with phosphorus reduced graphene oxide and polypyrrole. The lamp bulb comprises a super capacitor, a polyurethane sponge electrode, a phosphorus-doped reduced graphene oxide, polypyrrole and a linear cyclic voltammetry curve, wherein (a) part of the constant current charging and discharging curve is a constant current charging and discharging curve of the polyurethane sponge electrode with the phosphorus-doped reduced graphene oxide and the polypyrrole under different current densities, and (b) part of the linear cyclic voltammetry curve is a linear cyclic voltammetry curve of the polyurethane sponge electrode with the phosphorus-doped reduced graphene oxide and the polypyrrole under different scanning rates, and an embedded graph is a luminous graph of the lamp bulb after the super capacitor is assembled.
FIG. 2 is a graph showing the test results of the sponge obtained in example 1. Wherein, part (a) is a phenomenon graph of the lamp bulb shining after the sponge obtained in the embodiment 1 forms a conductive path, and part (b) is a phenomenon graph of the lamp bulb brightness obviously increasing after the pressure of 50kPa is applied.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
(1) Dissolving 0.1g of methyl orange in 40ml of deionized water, stirring, adding 0.1ml of pyrrole monomer after all the methyl orange is dissolved, stirring for 24h, and recording the solution A.
(2) 0.1g of the prepared phosphorus-doped reduced graphene oxide is taken and dispersed in 24ml of deionized water. After dispersing uniformly, adding 1g ferric nitrate nonahydrate, dissolving and recording the solution B.
(3) Precooling the solution A and the solution B to 4 ℃, adsorbing the solution A and the solution B alternately by the cleaned polyurethane sponge, slightly extruding to enable the reaction mixture to be completely permeated into sponge pores, mixing the two solutions, immersing the sponge, and reacting for 6 hours.
(4) And taking out the sponge, continuously washing the sponge by using 0.1M hydrochloric acid and deionized water until the color is clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out the sponge, and naturally drying the sponge.
(5) And soaking the mixture in the dispersion liquid generated by the reaction again and airing. The specific capacitance of the obtained sponge reaches 400F/g at the current density of 0.5A/g. After the super capacitor is assembled, the specific capacitance under the compression ratios of 40%, 60% and 80% is respectively 91%, 86% and 80% before compression.
The resistance change rate can reach 24%, 85% and 93% under the pressure of 5kPa, 12.5kPa and 25kPa, the bulb can emit light after the circuit is connected, and the brightness is obviously increased after the circuit is pressurized by 50 kPa. The material has high sensitivity as a piezoresistive pressure sensor and can be used for detecting continuous stress change. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Example 2
(1) Dissolving 0.1g of methyl orange in 40ml of deionized water, stirring, adding 0.1ml of pyrrole monomer after all the methyl orange is dissolved, stirring for 24h, and recording the solution A.
(2) 0.1g of the prepared phosphorus-doped reduced graphene oxide is taken and dispersed in 24ml of deionized water. After dispersing uniformly, adding 1g ferric nitrate nonahydrate, dissolving and recording the solution B.
(3) Precooling the solution A and the solution B to 4 ℃, adsorbing the solution A and the solution B alternately by the cleaned polyurethane sponge, slightly extruding to enable the reaction mixture to be completely permeated into sponge pores, mixing the two solutions, immersing the sponge, and reacting for 6 hours.
(4) And taking out the sponge, continuously washing the sponge by using 0.1M hydrochloric acid and deionized water until the color is clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out the sponge, and naturally drying the sponge.
(5) Soaking in the dispersion liquid generated by the reaction again, drying in the air, and repeating twice. The specific capacitance of the obtained sponge reaches 313F/g under the current density of 0.5A/g, and the specific capacitance under the compression ratios of 40%, 60% and 80% after the sponge is assembled into the super capacitor is respectively 89%, 85% and 84% before compression.
The resistance change rate can reach 36%, 71% and 82% under the pressure of 5kPa, 12.5kPa and 25kPa, the bulb can emit light after being connected with the channel, the brightness is obviously increased after the pressure of 50kPa, and the sensor can be used as a piezoresistive pressure sensor for detecting continuous stress change. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Example 3
(1) Dissolving 0.1g of methyl orange in 40ml of deionized water, stirring, adding 0.1ml of pyrrole monomer after all the methyl orange is dissolved, stirring for 24h, and recording the solution A.
(2) 0.1g of the prepared phosphorus-doped reduced graphene oxide is taken and dispersed in 24ml of deionized water. After dispersing uniformly, adding 1g ferric nitrate nonahydrate, dissolving and recording the solution B.
(3) Precooling the solution A and the solution B to 4 ℃, adsorbing the solution A and the solution B alternately by the cleaned polyurethane sponge, slightly extruding to enable the reaction mixture to be completely permeated into sponge pores, mixing the two solutions, immersing the sponge, and reacting for 6 hours.
(4) And taking out the sponge, continuously washing the sponge by using 0.1M hydrochloric acid and deionized water until the color is clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out the sponge, and naturally drying the sponge.
(5) Soaking in the dispersion liquid generated by the reaction again, drying in the air, and repeating for three times. The specific capacitance of the obtained sponge reaches 221F/g under the current density of 0.5A/g, and the specific capacitance under the compression ratios of 40%, 60% and 80% after the sponge is assembled into a super capacitor is respectively 89%, 81% and 80% before compression.
The resistance change rate can reach 24%, 55% and 70% under the pressure of 5kPa, 12.5kPa and 25kPa, the bulb can emit light after the circuit is connected, and the brightness is obviously increased after the circuit is pressurized by 50 kPa. Can be used as a piezoresistive pressure sensor for detecting continuous stress change. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Example 4
(1) Dissolving 0.1g of methyl orange in 40ml of deionized water, stirring, adding 0.1ml of pyrrole monomer after all the methyl orange is dissolved, stirring for 24h, and recording the solution A.
(2) 0.1g of the prepared phosphorus-doped reduced graphene oxide is taken and dispersed in 20ml of deionized water. After dispersing uniformly, adding 1g ferric nitrate nonahydrate, dissolving and recording the solution B.
(3) Precooling the solution A and the solution B to 4 ℃, adsorbing the solution A and the solution B alternately by the cleaned polyurethane sponge, slightly extruding to enable the reaction mixture to be completely permeated into sponge pores, mixing the two solutions, immersing the sponge, and reacting for 6 hours.
(4) And taking out the sponge, continuously washing the sponge by using 0.1M hydrochloric acid and deionized water until the color is clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out the sponge, and naturally drying the sponge.
(5) The reaction mixture was immersed again in the dispersion, dried and repeated four times. The specific capacitance of the obtained sponge reaches 203F/g under the current density of 0.5A/g, and the specific capacitance of the sponge after being assembled into a super capacitor is respectively 90 percent, 88 percent and 80 percent before compression under the compression ratios of 40 percent, 60 percent and 80 percent.
The resistance change rate can reach 58%, 77% and 85% under the pressure of 5kPa, 12.5kPa and 25kPa, the bulb can emit light after the circuit is connected, and the brightness is obviously increased after the circuit is pressurized by 50 kPa. Can be used as a piezoresistive pressure sensor for detecting continuous stress change. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Example 5
(1) Dissolving 0.1g of methyl orange in 40ml of deionized water, stirring, adding 0.1ml of pyrrole monomer after all the methyl orange is dissolved, stirring for 24h, and recording the solution A.
(2) 0.08g of prepared phosphorus-doped reduced graphene oxide is taken and dispersed in 24ml of deionized water. After dispersing uniformly, adding 1g ferric nitrate nonahydrate, dissolving and recording the solution B.
(3) Precooling the solution A and the solution B to 4 ℃, adsorbing the solution A and the solution B alternately by the cleaned polyurethane sponge, slightly extruding to enable the reaction mixture to be completely permeated into sponge pores, mixing the two solutions, immersing the sponge, and reacting for 6 hours.
(4) And taking out the sponge, continuously washing the sponge by using 0.1M hydrochloric acid and deionized water until the color is clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out the sponge, and naturally drying the sponge.
(5) And soaking the mixture in the dispersion liquid generated by the reaction again and airing. The specific capacitance of the obtained sponge reaches 263F/g under the current density of 0.5A/g, and the specific capacitance under the compression ratios of 40%, 60% and 80% after the sponge is assembled into the super capacitor is respectively 88%, 81% and 74% before compression.
The resistance change rate can reach 54%, 77% and 88% under the pressure of 5kPa, 12.5kPa and 25kPa, the bulb can emit light after the connection of the channel, and the brightness is obviously increased after the pressure of 50 kPa. Can be used as a piezoresistive pressure sensor for detecting continuous stress change. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Comparative example 1
(1) Dissolving 0.1g of methyl orange in 40ml of deionized water, stirring, adding 0.1ml of pyrrole monomer after all the methyl orange is dissolved, stirring for 24h, and recording the solution A.
(2) 1g of ferric nitrate nonahydrate was dissolved, and the solution B was recorded.
(3) Precooling the solution A and the solution B to 4 ℃, adsorbing the solution A and the solution B alternately by the cleaned polyurethane sponge, slightly extruding to enable the reaction mixture to be completely permeated into sponge pores, mixing the two solutions, immersing the sponge, and reacting for 6 hours.
(4) And taking out the sponge, continuously washing the sponge by using 0.1M hydrochloric acid and deionized water until the color is clear or light yellow, soaking the sponge in absolute ethyl alcohol, and naturally airing the sponge.
(5) And soaking the mixture in the dispersion liquid generated by the reaction again and airing. The specific capacitance of the obtained sponge at a current density of 0.5A/g was 100F/g.
Comparative example 2
(1) Dissolving 0.1g of methyl orange in 40ml of deionized water, stirring, adding 0.1ml of pyrrole monomer after all the methyl orange is dissolved, stirring for 24h, and recording the solution A.
(2) 0.08g of prepared phosphorus-doped reduced graphene oxide is taken and dispersed in 24ml of deionized water. After dispersing uniformly, adding 1g ferric nitrate nonahydrate, dissolving and recording the solution B.
(3) Precooling the solution A and the solution B to 4 ℃, adsorbing the solution A and the solution B alternately by the cleaned polyurethane sponge, slightly extruding to enable the reaction mixture to be completely permeated into sponge pores, mixing the two solutions, immersing the sponge, and reacting for 6 hours.
(4) And taking out the sponge, continuously washing the sponge by using 0.1M hydrochloric acid and deionized water until the color is clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out the sponge, and naturally drying the sponge. The specific capacitance of the obtained sponge reaches 150F/g at the current density of 0.5A/g.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A preparation method of polyurethane sponge compounded with phosphorus-doped reduced graphene oxide and polypyrrole is characterized by comprising the following steps:
1) taking the weight of methyl orange as a reference, dissolving 0.1-0.6g of methyl orange in 40-300ml of deionized water, stirring, adding 0.1-3ml of pyrrole monomer after all methyl orange is dissolved, and continuously stirring to obtain a solution A;
2) dispersing the prepared phosphorus-doped reduced graphene oxide in deionized water, adding an oxidant after the phosphorus-doped reduced graphene oxide is uniformly dispersed, and dissolving to obtain a solution B, wherein the dispersed concentration of the phosphorus-doped reduced graphene oxide is 3-10mg/ml, and the weight ratio of the phosphorus-doped reduced graphene oxide to the oxidant is (0.15-0.5): 1;
3) precooling the solution A obtained in the step 1) and the solution B obtained in the step 2) to 0-4 ℃, then alternately adsorbing the solution A and the solution B by using the cleaned polyurethane sponge, extruding to enable the solutions to be completely permeated into the polyurethane sponge, mixing the solution A and the solution B to obtain a mixed solution, immersing the polyurethane sponge into the mixed solution for reaction, and obtaining a dispersion liquid generated by the reaction, wherein the weight ratio of pyrrole used in the solution A to oxidant used in the solution B is 1 (0.3-0.4);
4) taking out the polyurethane sponge in the dispersion liquid generated by the reaction in the step 3), continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the polyurethane sponge in absolute ethyl alcohol, taking out and naturally drying;
5) and soaking the polyurethane sponge in the dispersion liquid generated by the reaction, taking out the polyurethane sponge, naturally airing the polyurethane sponge, and repeating the step for 1 to 4 times to obtain the polyurethane sponge of the composite phosphorus-doped reduced graphene oxide and polypyrrole.
2. The preparation method of the polyurethane sponge of composite phosphorus-doped reduced graphene oxide and polypyrrole according to claim 1, characterized in that: in the step 1), the pyrrole monomer is added and then the stirring is continued for 18 to 30 hours.
3. The preparation method of the polyurethane sponge of composite phosphorus-doped reduced graphene oxide and polypyrrole according to claim 1, characterized in that: in the step 2), the oxidant is selected from ferric nitrate nonahydrate, ferric trichloride hexahydrate or ammonium persulfate.
4. The preparation method of the polyurethane sponge of composite phosphorus-doped reduced graphene oxide and polypyrrole according to claim 1, characterized in that: the reaction time is 1-6 hours.
5. A polyurethane sponge of composite phosphorus-doped reduced graphene oxide and polypyrrole prepared according to the preparation method of any one of claims 1 to 4.
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| CN202111535610.8A CN114334474B (en) | 2021-12-15 | 2021-12-15 | Polyurethane sponge of composite phosphorus doped reduced graphene oxide and polypyrrole and preparation method thereof |
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| CN114334474B CN114334474B (en) | 2024-02-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188610A (en) * | 2016-07-11 | 2016-12-07 | 武汉纺织大学 | A kind of preparation method and application of polypyrrole/polyurethane sponge conducing composite material |
| CN106531462A (en) * | 2016-11-08 | 2017-03-22 | 铜陵市启动电子制造有限责任公司 | Polypyrrole carbon electrode material with added lithium iron phosphate and graphene composite material |
| CN110323073A (en) * | 2019-06-28 | 2019-10-11 | 中国地质大学（北京） | A kind of oxygen doping phosphatization cobalt nickel-redox graphene composite material and its application |
| CN111403182A (en) * | 2020-04-08 | 2020-07-10 | 福州大学 | Graphene oxide hybrid polyaniline-based flexible electrode material and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188610A (en) * | 2016-07-11 | 2016-12-07 | 武汉纺织大学 | A kind of preparation method and application of polypyrrole/polyurethane sponge conducing composite material |
| CN106531462A (en) * | 2016-11-08 | 2017-03-22 | 铜陵市启动电子制造有限责任公司 | Polypyrrole carbon electrode material with added lithium iron phosphate and graphene composite material |
| CN110323073A (en) * | 2019-06-28 | 2019-10-11 | 中国地质大学（北京） | A kind of oxygen doping phosphatization cobalt nickel-redox graphene composite material and its application |
| CN111403182A (en) * | 2020-04-08 | 2020-07-10 | 福州大学 | Graphene oxide hybrid polyaniline-based flexible electrode material and preparation method and application thereof |
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