CN114334474B - Polyurethane sponge of composite phosphorus doped reduced graphene oxide and polypyrrole and preparation method thereof - Google Patents
Polyurethane sponge of composite phosphorus doped reduced graphene oxide and polypyrrole and preparation method thereof Download PDFInfo
- Publication number
- CN114334474B CN114334474B CN202111535610.8A CN202111535610A CN114334474B CN 114334474 B CN114334474 B CN 114334474B CN 202111535610 A CN202111535610 A CN 202111535610A CN 114334474 B CN114334474 B CN 114334474B
- Authority
- CN
- China
- Prior art keywords
- solution
- graphene oxide
- polyurethane sponge
- reduced graphene
- sponge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 23
- 239000011574 phosphorus Substances 0.000 title claims abstract description 23
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 73
- 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
- 239000006185 dispersion Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 17
- 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 13
- 229940012189 methyl orange Drugs 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 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
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 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
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 3
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000004020 conductor Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 description 13
- 230000006835 compression Effects 0.000 description 12
- 238000007906 compression Methods 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000005406 washing Methods 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
- 230000008901 benefit Effects 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 230000006399 behavior Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 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
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002993 sponge (artificial) Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of flexible supercapacitors, and particularly relates to a polyurethane sponge of composite 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 effective combination of the insulating flexible matrix and the conductive material is realized, the excellent electrical performance is realized on the basis of keeping the original compressibility, and the method can be applied to the field of flexible supercapacitors.
Description
Technical Field
The invention belongs to the technical field of flexible supercapacitors, and particularly relates to a polyurethane sponge of composite phosphorus doped reduced graphene oxide and polypyrrole and a preparation method thereof.
Background
Deformable supercapacitors, when deformed, provide a stable power output, are becoming a critical instrument for wearable electronics. The flexible material is used as a compressible matrix, such as polymer sponge, cellulose aerogel and the like, and active materials are loaded, but the insulating matrix seriously influences the electrochemical performance of the electrode material, so that the super capacitor with excellent electrical performance, flexibility, ductility and even repeated compression and bending mechanical performance is very necessary to be prepared.
Polyurethane or melamine sponge having a porous three-dimensional network is used as a compressible substrate due to its excellent water absorption, durability, compressibility properties. The common conductive polymer materials such as polypyrrole, polyaniline and the like are greatly focused by people due to the advantages of easiness in synthesis, excellent specific capacitance, inherent polymer flexibility and the like, and the poor rate performance and the poor cycle stability are unavoidable defects, so that the electrical performance of the material can be effectively improved by combining the conductive polymer with the high conductive material such as the reduced graphene oxide or the activated carbon. Polyurethane sponge has been reported as a three-dimensional carbon network template, and the porous carbon material, iron and ferric oxide are hydrothermally compounded and then calcined at high temperature, but the compressibility of the sponge is greatly affected by the preparation method. It is also reported that the porous carbon nanotube and graphene oxide suspension with opposite charges are alternately absorbed by using sponge in a layer-by-layer assembly mode and then subjected to hydrothermal reduction by using hydrazine hydrate, so that the porous carbon nanotube and graphene oxide suspension can be used as a flexible piezoresistive material, but the method has the advantages that the absorbed graphene oxide cannot be completely reduced by using the hydrazine hydrate along with the increase of a coating period, the electrical property of the porous carbon nanotube and graphene oxide suspension is affected to a certain extent, and the hydrazine hydrate has strong alkalinity and hygroscopicity due to smell in the use process. Reduced graphene oxide adsorbed and acidified by melamine sponge is reported to be polymerized with pyrrole in situ for a compressible supercapacitor, but the method is very easy to settle due to poor dispersibility of the reduced graphene oxide in water, 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, three-dimensional compressible supercapacitors have been rarely studied, and the problem of how to effectively combine an insulating flexible matrix with a conductive filler to obtain a flexible electrode material with stable output is needed to be solved.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a polyurethane sponge of composite phosphorus doped reduced graphene oxide and polypyrrole and a preparation method thereof.
The technical scheme provided by the invention is as follows:
the preparation method of the polyurethane sponge of the composite phosphorus doped reduced graphene oxide and polypyrrole comprises the following steps:
1) Dissolving 0.1-0.6g of methyl orange in 40-300ml of deionized water by taking the weight of the methyl orange as a reference, stirring, adding 0.1-3ml of pyrrole monomer after the methyl orange is completely 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 uniform dispersion, and dissolving to obtain a solution B, wherein the dispersing 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) Pre-cooling 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 the solution to enable the solutions to completely permeate 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, reacting the mixed solution to obtain 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 obtained in the step 3), continuously cleaning 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 airing;
5) And soaking the polyurethane sponge in the dispersion liquid generated by the reaction, taking out, naturally airing, and repeating for 1-4 times to obtain the polyurethane sponge of the composite phosphorus doped reduced graphene oxide and polypyrrole.
The technical scheme is as follows:
compared with the reduced graphene oxide, the phosphorus doped reduced graphene oxide has good dispersion performance in an aqueous solution, 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, electrochemical behaviors and band gaps of the material can be improved by doping phosphorus, so that the material has better performance; the polyurethane sponge has better adsorptivity to the phosphorus doped reduced graphene oxide; the combined action of the two 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), stirring is continued for 18-30 hours after the pyrrole monomer is added.
Specifically, in the step 2), the oxidant is selected from ferric nitrate nonahydrate, ferric trichloride hexahydrate or ammonium persulfate. Preferably, it is 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 prepared by the preparation method.
The outstanding benefits of the invention are mainly represented by the following aspects:
1) The raw materials used in the invention are low in price, and the preparation process is simple and convenient;
2) The dispersion performance of the phosphorus doped reduced graphene oxide in the aqueous solution is good, so that the system is more stable, and a uniform dispersion system can be obtained;
3) The insulating flexible matrix is effectively combined with the conductive material, so that the insulating flexible matrix has excellent electrical property on the basis of keeping the original compressibility, and can be applied to the field of flexible supercapacitors;
4) Along with the change of pressure, the resistance value changes, the current is obviously increased under a certain voltage, and the pressure sensor has a certain sensing performance and can be also used for pressure sensing materials.
Drawings
Fig. 1 is a graph of the performance of a polyurethane sponge electrode of phosphorus doped reduced graphene oxide and polypyrrole. The light-emitting device comprises a super capacitor, a light-emitting device, a display device and a display device, wherein (a) part is a constant current charge-discharge curve of a polyurethane sponge electrode of phosphorus-doped reduced graphene oxide and polypyrrole under different current densities, and (b) part is a linear cyclic voltammogram of the polyurethane sponge electrode of phosphorus-doped reduced graphene oxide and polypyrrole under different scanning speeds, and an embedded graph is a light-emitting graph of a bulb after the super capacitor is assembled.
FIG. 2 is a diagram showing the experimental results of the sponge obtained in example 1. Wherein, part (a) is a graph showing the phenomenon that the lamp emits light after the sponge obtained in example 1 forms a conductive path, and part (b) is a graph showing the phenomenon that the brightness of the lamp light is remarkably increased after a pressure of 50kPa is applied.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
Example 1
(1) 0.1g of methyl orange is dissolved in 40ml of deionized water, stirred, after all dissolution, 0.1ml of pyrrole monomer is added, stirred for 24h and recorded as solution A.
(2) The prepared phosphorus-doped reduced graphene oxide was taken at 0.1g and dispersed in 24ml deionized water. After the dispersion is uniform, 1g of ferric nitrate nonahydrate is added for dissolution, and the solution B is recorded.
(3) The solution A and the solution B are precooled to 4 ℃, the cleaned polyurethane sponge is firstly alternately adsorbed with the solution A and the solution B, the reaction mixture is enabled to be completely permeated into the pores of the sponge by light extrusion, and then the two solutions are mixed, so that the sponge is immersed, and the reaction lasts for 6 hours.
(4) Taking out the sponge, continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out and naturally airing.
(5) Soaking again in the dispersion liquid generated by the reaction, and airing. The specific capacitance of the obtained sponge reaches 400F/g under the current density of 0.5A/g. After the super capacitor is assembled, the specific capacitance is 91%,86% and 80% before compression under the compression ratio of 40%,60% and 80% respectively.
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 connecting passage, and the brightness is obviously increased after the pressure is increased by 50 kPa. It can be seen that this material has a high sensitivity as a piezoresistive pressure sensor, and can be used to detect continuous stress changes. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Example 2
(1) 0.1g of methyl orange is dissolved in 40ml of deionized water, stirred, after all dissolution, 0.1ml of pyrrole monomer is added, stirred for 24h and recorded as solution A.
(2) The prepared phosphorus-doped reduced graphene oxide was taken at 0.1g and dispersed in 24ml deionized water. After the dispersion is uniform, 1g of ferric nitrate nonahydrate is added for dissolution, and the solution B is recorded.
(3) The solution A and the solution B are precooled to 4 ℃, the cleaned polyurethane sponge is firstly alternately adsorbed with the solution A and the solution B, the reaction mixture is enabled to be completely permeated into the pores of the sponge by light extrusion, and then the two solutions are mixed, so that the sponge is immersed, and the reaction lasts for 6 hours.
(4) Taking out the sponge, continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out and naturally airing.
(5) Soaking again in the dispersion liquid generated by the reaction, airing, and repeating twice. The specific capacitance of the obtained sponge reaches 313F/g under the current density of 0.5A/g, and after the sponge is assembled into a super capacitor, the specific capacitance of the sponge is 89%,85% and 84% before compression under the compression ratio of 40%,60% and 80%.
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 the connecting passage, the brightness is obviously increased after the pressure is increased by 50kPa, and the piezoresistive pressure sensor 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 3
(1) 0.1g of methyl orange is dissolved in 40ml of deionized water, stirred, after all dissolution, 0.1ml of pyrrole monomer is added, stirred for 24h and recorded as solution A.
(2) The prepared phosphorus-doped reduced graphene oxide was taken at 0.1g and dispersed in 24ml deionized water. After the dispersion is uniform, 1g of ferric nitrate nonahydrate is added for dissolution, and the solution B is recorded.
(3) The solution A and the solution B are precooled to 4 ℃, the cleaned polyurethane sponge is firstly alternately adsorbed with the solution A and the solution B, the reaction mixture is enabled to be completely permeated into the pores of the sponge by light extrusion, and then the two solutions are mixed, so that the sponge is immersed, and the reaction lasts for 6 hours.
(4) Taking out the sponge, continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out and naturally airing.
(5) Soaking again in the dispersion liquid generated by the reaction, airing, and repeating for three times. The specific capacitance of the obtained sponge reaches 221F/g under the current density of 0.5A/g, and after the sponge is assembled into a super capacitor, the specific capacitance of the sponge is 89%,81% and 80% before compression under the compression ratio of 40%,60% and 80% respectively.
The resistance change rates can reach 24%, 55% and 70% under the pressure of 5kPa, 12.5kPa and 25kPa, the bulb can emit light after the connection passage, and the brightness is obviously increased after the pressure is increased by 50 kPa. Can be used as a piezoresistive pressure sensor for detecting continuous stress changes. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Example 4
(1) 0.1g of methyl orange is dissolved in 40ml of deionized water, stirred, after all dissolution, 0.1ml of pyrrole monomer is added, stirred for 24h and recorded as solution A.
(2) The prepared phosphorus-doped reduced graphene oxide was taken at 0.1g and dispersed in 20ml deionized water. After the dispersion is uniform, 1g of ferric nitrate nonahydrate is added for dissolution, and the solution B is recorded.
(3) The solution A and the solution B are precooled to 4 ℃, the cleaned polyurethane sponge is firstly alternately adsorbed with the solution A and the solution B, the reaction mixture is enabled to be completely permeated into the pores of the sponge by light extrusion, and then the two solutions are mixed, so that the sponge is immersed, and the reaction lasts for 6 hours.
(4) Taking out the sponge, continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out and naturally airing.
(5) Soaking again in the dispersion liquid generated by the reaction, airing, and repeating 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 is 90%,88% and 80% before compression under the compression ratio of 40%,60% and 80% after the sponge is assembled into a super capacitor.
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 being connected with the passage, and the brightness is obviously increased after being pressurized by 50 kPa. Can be used as a piezoresistive pressure sensor for detecting continuous stress changes. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Example 5
(1) 0.1g of methyl orange is dissolved in 40ml of deionized water, stirred, after all dissolution, 0.1ml of pyrrole monomer is added, stirred for 24h and recorded as solution A.
(2) The prepared phosphorus-doped reduced graphene oxide was taken at 0.08g and dispersed in 24ml deionized water. After the dispersion is uniform, 1g of ferric nitrate nonahydrate is added for dissolution, and the solution B is recorded.
(3) The solution A and the solution B are precooled to 4 ℃, the cleaned polyurethane sponge is firstly alternately adsorbed with the solution A and the solution B, the reaction mixture is enabled to be completely permeated into the pores of the sponge by light extrusion, and then the two solutions are mixed, so that the sponge is immersed, and the reaction lasts for 6 hours.
(4) Taking out the sponge, continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out and naturally airing.
(5) Soaking again in the dispersion liquid generated by the reaction, and airing. The specific capacitance of the obtained sponge reaches 263F/g under the current density of 0.5A/g, and after the sponge is assembled into a super capacitor, the specific capacitance of the sponge is 88%,81% and 74% before compression under the compression ratio of 40%,60% and 80%.
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 connecting passage, and the brightness is obviously increased after the pressure is increased by 50 kPa. Can be used as a piezoresistive pressure sensor for detecting continuous stress changes. The composite material with excellent electrochemical and mechanical properties can be widely applied to wearable equipment.
Comparative example 1
(1) 0.1g of methyl orange is dissolved in 40ml of deionized water, stirred, after all dissolution, 0.1ml of pyrrole monomer is added, stirred for 24h and recorded as solution A.
(2) 1g of ferric nitrate nonahydrate was dissolved and solution B was recorded.
(3) The solution A and the solution B are precooled to 4 ℃, the cleaned polyurethane sponge is firstly alternately adsorbed with the solution A and the solution B, the reaction mixture is enabled to be completely permeated into the pores of the sponge by light extrusion, and then the two solutions are mixed, so that the sponge is immersed, and the reaction lasts for 6 hours.
(4) Taking out the sponge, continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the sponge in absolute ethyl alcohol, and naturally airing.
(5) Soaking again in the dispersion liquid generated by the reaction, and airing. The specific capacitance of the obtained sponge was 100F/g at a current density of 0.5A/g.
Comparative example 2
(1) 0.1g of methyl orange is dissolved in 40ml of deionized water, stirred, after all dissolution, 0.1ml of pyrrole monomer is added, stirred for 24h and recorded as solution A.
(2) The prepared phosphorus-doped reduced graphene oxide was taken at 0.08g and dispersed in 24ml deionized water. After the dispersion is uniform, 1g of ferric nitrate nonahydrate is added for dissolution, and the solution B is recorded.
(3) The solution A and the solution B are precooled to 4 ℃, the cleaned polyurethane sponge is firstly alternately adsorbed with the solution A and the solution B, the reaction mixture is enabled to be completely permeated into the pores of the sponge by light extrusion, and then the two solutions are mixed, so that the sponge is immersed, and the reaction lasts for 6 hours.
(4) Taking out the sponge, continuously washing with 0.1M hydrochloric acid and deionized water until the color becomes clear or light yellow, soaking the sponge in absolute ethyl alcohol, taking out and naturally airing. The specific capacitance of the obtained sponge reaches 150F/g under the current density of 0.5A/g.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (5)
1. The preparation method of the polyurethane sponge of the composite phosphorus doped reduced graphene oxide and polypyrrole is characterized by comprising the following steps of:
1) Dissolving 0.1-0.6g of methyl orange in 40-300ml of deionized water by taking the weight of the methyl orange as a reference, stirring, adding 0.1-3ml of pyrrole monomer after the methyl orange is completely 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 uniform dispersion, and dissolving to obtain a solution B, wherein the dispersing 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) Pre-cooling 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 the solution to enable the solutions to completely permeate 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, reacting the mixed solution to obtain 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 obtained in the step 3), continuously cleaning 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 airing;
5) And soaking the polyurethane sponge in the dispersion liquid generated by the reaction, taking out, naturally airing, and repeating for 1-4 times to obtain the polyurethane sponge of the composite phosphorus doped reduced graphene oxide and polypyrrole.
2. The method for preparing the polyurethane sponge by compounding phosphorus-doped reduced graphene oxide and polypyrrole according to claim 1, which is characterized in that: in the step 1), stirring is continued for 18-30h after the pyrrole monomer is added.
3. The method for preparing the polyurethane sponge by compounding phosphorus-doped reduced graphene oxide and polypyrrole according to claim 1, which is characterized in that: in the step 2), the oxidant is selected from ferric nitrate nonahydrate, ferric trichloride hexahydrate or ammonium persulfate.
4. The method for preparing the polyurethane sponge by compounding phosphorus-doped reduced graphene oxide and polypyrrole according to claim 1, which is 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114334474A CN114334474A (en) | 2022-04-12 |
| CN114334474B true CN114334474B (en) | 2024-02-02 |
Family
ID=81052023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111535610.8A Active CN114334474B (en) | 2021-12-15 | 2021-12-15 | Polyurethane sponge of composite phosphorus doped reduced graphene oxide and polypyrrole and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114334474B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117482927B (en) * | 2023-11-03 | 2024-05-28 | 山东大学 | Preparation method and application of polyurethane sponge adsorption material |
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 |
-
2021
- 2021-12-15 CN CN202111535610.8A patent/CN114334474B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114334474A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105175761B (en) | A kind of preparation method and applications of bacteria cellulose/polyaniline/graphene film material | |
| Yu et al. | Scalable preparation of high performance fibrous electrodes with bio-inspired compact core-fluffy sheath structure for wearable supercapacitors | |
| CN107973283B (en) | Elastic carbon aerogel and preparation method and application thereof | |
| CN114334474B (en) | Polyurethane sponge of composite phosphorus doped reduced graphene oxide and polypyrrole and preparation method thereof | |
| CN103450682B (en) | A kind of Carbon nanotube/polypyrrolecomposite composite sponge and preparation method thereof | |
| CN110808175A (en) | Electroactive biomass/polypyrrole hydrogel and preparation method and application thereof | |
| CN101602876A (en) | The multimeshed network compound water congealing glue material and the method for making thereof of high mechanical strength and electrochemical activity | |
| CN105111507A (en) | Preparation method and application of bacterial cellulose/polyaniline/carbon nanotube conducting film material | |
| DE112015000186T5 (en) | Flexible supercapacitor and method of making such | |
| DE102012208636A1 (en) | Hierarchically porous carbon particles for electrochemical applications | |
| CN109216048A (en) | Flexible electrode and preparation method thereof based on bacteria cellulose film | |
| CN111463019B (en) | Preparation method of core-shell structure electrode material | |
| Ren et al. | Nitric acid oxidation of ordered mesoporous carbons for use in electrochemical supercapacitors | |
| CN114156093B (en) | N/O co-doped molybdenum sulfide@porous carbon composite electrode material and preparation method and application thereof | |
| Zhu et al. | Antifreezing ionotronic skin based on flexible, transparent, and tunable ionic conductive nanocellulose hydrogels | |
| CN108624043A (en) | A kind of aerogel composite and preparation method thereof of polypyrrole cladding copper nano-wire | |
| Tao et al. | ATMP doped conductive PANI/CNTs composite hydrogel electrodes toward high energy density flexible supercapacitors | |
| Tang et al. | Fabrication of ferric chloride doped polyaniline/multilayer super-short carbon nanotube nanocomposites for supercapacitor applications | |
| Han et al. | High mechanical properties and excellent anisotropy of dually synergistic network wood fiber gel for human–computer interactive sensors | |
| Wang et al. | Elastic polypyrrole hydrogels reinforced by TEMPO-oxidized cellulose for supercapacitors | |
| Li et al. | One-step electrodeposition of polyaniline nanorods on carbon cloth for high-performance flexible supercapacitors | |
| CN109179365B (en) | High-sensitivity chitosan-based sensing material and preparation method and application thereof | |
| CN114927355B (en) | Preparation method of flexible electrode material of carbon nanotube grafted polyaniline/cellulose nanofiber membrane | |
| Yang et al. | In-situ self-assembly host-guest carbon aerogels for robust electrochemical capacitors | |
| CN108862242B (en) | Preparation method of phosphorus-doped hollow carbon material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |