CN107698914A - A kind of preparation method of flexible memory conductive polymer composite aquogel - Google Patents
A kind of preparation method of flexible memory conductive polymer composite aquogel Download PDFInfo
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- CN107698914A CN107698914A CN201711089697.4A CN201711089697A CN107698914A CN 107698914 A CN107698914 A CN 107698914A CN 201711089697 A CN201711089697 A CN 201711089697A CN 107698914 A CN107698914 A CN 107698914A
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- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 17
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000017 hydrogel Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000003233 pyrroles Chemical class 0.000 claims description 7
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001409 amidines Chemical class 0.000 claims description 2
- FIKFOOMAUXPBJM-UHFFFAOYSA-N hepta-2,5-dienediamide Chemical class NC(=O)C=CCC=CC(N)=O FIKFOOMAUXPBJM-UHFFFAOYSA-N 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 229920000767 polyaniline Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920000128 polypyrrole Polymers 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/48—Conductive polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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 kind of preparation method of flexible memory conductive polymer composite aquogel, comprise the following steps：（1）Pyrrole monomer is dissolved in graphene oxide water solution, stirs and forms solution using ultrasonic wave is scattered, it is standby；（2）By ferrous salt and H2O2Solution sequentially adds step（1）In resulting solution, stir and form reaction system using ultrasonic wave is scattered；（3）Above-mentioned reaction system is reacted into 2h under 0 to 20 DEG C of stirring condition；（4）In step（3）Initiator and N, N ˊ methylene-bisacrylamides are added in gained reactant, stirs and ultrasonic disperse uniformly adds acrylic acid afterwards, continues to stir 5 10min；（5）In 70 DEG C of baking ovens stand reaction, by obtained hydrogel be placed in mass fraction be 45% hydroiodic acid in reduced after, by obtained product in distilled water cleaning and balance, obtain flexible memory conductive polymer composite aquogel.
Description
Technical field
The invention belongs to electrode of super capacitor field of material technology, and in particular to a kind of flexible memory conductive polymer
The preparation method of composite aquogel.
Background technology.
It is flexible, wearable, foldable, just with the fast development of flexible electronic science and miniaturization of electronic products technology
The formula electronic equipment of taking is come out one after another.As one kind of flexible power supply, flexible super capacitor is close because of fast charging and discharging, high power
The excellent chemical property such as degree, long cycle life and the mechanically deform performance such as stretchable, flexible, foldable, meet
Wearable, portable electron device energy demand.Electrode material directly affects as the chief component of ultracapacitor
Its performance.The conventional electrode material of ultracapacitor, the flexibility of carbon material, transition metal oxide and conducting polymer have
Limit, it is stretched and the limit of bending is very small, it is difficult to meets the requirement of flexible super capacitor, generally by means of non-conductive soft
Property base material prepares electrode of the composite as flexible super capacitor.
Hydrogel is a kind of special wet flexible material.It is one kind containing great amount of hydroxy group, amino and carboxyl and moderately handed over
The three-dimensional network polymer of connection, can occur swelling behavior in water, and certain shape can be kept before and after water suction, have excellent
Good elasticity and tensility energy, have tempting application prospect in fields such as insoluble drug release, chemical sensor, artificial muscles.
In recent years, polyalcohol hydrogel is applied in ultracapacitor, has the polymer matrix hydrogel of flexible extensible, such as
Oxidic polyethylene based aquagel, polyacrylic-based hydrogels and polyvinyl alcohol hydrogel, it is mainly used as ultracapacitor electrolysis matter.
Tang etc. immerses the polyacrylic acid hydrogel of crosslinking in aniline monomer, aniline is triggered again after being permeated in polyacrylic acid poly-
Close.Obtained polyaniline/polyacrylic acid 3D interpenetrating net polymers have good electric conductivity, can be as the electricity of ultracapacitor
Matter is solved to use（Tang ZY, Wu J H, Liu Q, Zheng M, Tang QW, Lan Z, Lin JM. Preparation
of poly(acrylic acid)/gelatin/polyaniline gel-electrolyte and its application
in quasi-solid-state dye-sensitized solar cells. J. Power Sources, 2012, 203:
282-287.）.
Conducting polymer and the flexible hydro-gel electrode of the compound preparation of polyalcohol hydrogel can be obtained into good electrochemistry
Activity.For example, Li et al. can prepare the three-dimensional network skeleton of electrically conductive polyaniline introducing polyvinyl alcohol in the supermolecule water of high intensity
Gel, it, which is used as flexible super capacitor electrode material, can obtain good electro-chemical activity（Li WW, Gao FX, Wang
XQ, Zhang N,Ma MM. Strong and robust polyaniline-based supramolecular
hydrogels for flexible supercapacitors. Angew. Chem. Int. Ed., 2016, 55: 1-
8.).Conducting polymer monomer is placed in the PAHG being crosslinked by Hao etc., using " two-step method ", is first prepared poly-
Acrylamide gel, after be soaked in aniline monomer solution, prepare polyacrylamide/conducting polyaniline of flexible extensible
Aqueous amine gel electrode, the alpha-cyclodextrin induction aniline with amphiphilic structure is introduced in hydrogel 3D loose structure interior polymerics, its
Superior electrochemical capacitance characteristic be attributed to the connected loose structure of the polymer chain of flexibility, height and matrix and electrically conductive polyaniline it
Between good contact（Hao GP, Hippauf F, Oschatz M, Wisser FM, Leifert A, Nicel W,
Mohamed-Noriega N,Zheng ZK, Kaskel S. Stretchable and semitransparent
conductive hybrid hydrogels for flexible supercapacitors. ACS Nano, 2014, 7:
7138-7146.）.To sum up, the conductive compound water congealing gel electrode of flexible extensible has possessed certain basis, but current flexible electrode
The conduction and mechanical property of material（Stretching, flexible bending performance）The needs of future portable electronic product can not still be met.
The content of the invention
In order to solve problem above, the purpose of the present invention be by with high electrochemical activity, high conductivity graphene, lead
Electric polymer introduces the three-dimensional net structure of flexible polypropylene acid hydrogel.On the one hand, the introducing of graphene can be formed appropriate
Conductive crosslinking points, so as to further regulate and control the mechanical property and chemical property of flexible compound hydrogel；On the other hand, by double electricity
Layer capacitance is combined the total specific capacitance that can improve electrode material with the faraday's electric capacity provided by electroactive material, so as to further carry
Its high energy density.There is not been reported both at home and abroad for such a method.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is as follows：
A kind of preparation method of flexible memory conductive polymer composite aquogel, comprises the following steps：
（1）Pyrrole monomer is dissolved in graphene oxide water solution, stirs and forms solution using ultrasonic wave is scattered, standby, oxygen
The concentration of graphite alkene is 0.1-2mg/mL, and the concentration of pyrrole monomer is 0.01M-0.3M；
（2）By ferrous salt and H2O2Solution sequentially adds step（1）In resulting solution, stir and formed instead using ultrasonic wave is scattered
Answer system；Described ferrous salt is ferrous sulfate, one kind of frerrous chloride, H2O2Mol ratio with pyrroles is 20:1-2:1, H2O2
Mol ratio with ferrous salt is 1000:1-100:1 ；
（3）By step（2）Gained reaction system reacts 2h under 0-20 DEG C of stirring condition；
（4）In step（3）Initiator and N, N ˊ-methylene-bisacrylamide are added in gained reactant, stirs simultaneously ultrasonic disperse
Acrylic acid is added after uniformly, continues to stir 5-10min；Described initiator is ammonium persulfate, azo diisobutyl amidine hydrochloride
In one kind, the concentration of acrylic acid is 5-20mg/mL, and the mass ratio of ammonium persulfate and acrylic acid is 10:1-100:1, acrylic acid
With N, the mass ratio of N ˊ-methylene-bisacrylamide is 200:1-50:1,
（5）Reaction 6-24h is stood in 70 DEG C of baking ovens, obtained hydrogel is placed in the hydroiodic acid that mass fraction is 45%
After row reduction, by obtained product, cleaning and balance 12-24h, every 6h change a water and obtain flexible memory macromolecule in distilled water
Conductive composite aquogel.
The present invention uses H2O2-Fe2+The mol ratio of system, hydrogen peroxide and ferrous salt is 1000:1-100:1, peroxidating
Hydrogen is significantly excessive, H is used alone2O2Pyrroles can not be polymerize, Fe2+In this as promotion H2O2Aoxidize the catalyst of pyrroles.H2O2
During addition preferentially and FeCl2Reaction, makes Fe2+It is changed into Fe3+, while generate OH.The Fe during the entire process of polymerization3+Can be slow
Aoxidize pyrroles and generate pyrroles's polymer.Fe3+While polypyrrole is aoxidized itself Fe is reduced to again2+, Fe2+Again with H2O2Reaction
Generate Fe3+And OH, so circulation is repeatedly until H2O2Exhaust, and pyrroles is polymerized to polypyrrole.Whole course of reaction pyrroles's
Polymerization speed is slower, and the nanometer polypyrrole of acquisition can be dispersed in graphene oxide solution well.Meanwhile in course of reaction
Hydrogen bond and the pi-conjugated effects of p- between OH and graphene oxide and polypyrrole be present caused by constantly, make the polypyrrole of generation can be
Stable dispersion in graphene oxide solution, give full play to its electrochemistry in the flexible hydro-gel 3D network structures being subsequently formed
Activity.Beneficial effects of the present invention are as follows：
1st, the present invention assigns it in the good dispersiveness of hydrogel, graphite oxide using the oxygen-containing functional group of surface of graphene oxide
Graphene assigns composite aquogel good mechanical property as the physical crosslinking point of conduction after alkene reduction；Meanwhile use is compound
Oxidizer system regulates and controls stabilization of the electric polypyrrole strand in 3D cross-linked network structures, dispersed, assigns compound water congealing
The good electro-chemical activity of glue, at home and abroad there is not been reported in document.
2nd, the conductive composite aquogel for preparing of the present invention, has good flexibility, bending and tensile property, will wherein moisture
Volume-diminished is hardened after drying, and volume increases and recovers flexible after reuptaking moisture, and its 3D network structure has good note
Recall effect.
3rd, the present invention carries out polymerisation under normal temperature, static state, and equipment is simple, operation is easy, easily expansion scale metaplasia
Production.
Brief description of the drawings
Fig. 1 is hydrogel stress-strain curve prepared by the present invention；
Fig. 2 is the SEM photograph of the flexible recovery of composite aquogel prepared by the present invention and loose structure change.
Embodiment
The present invention is described in further detail below by way of specific embodiment.
Embodiment 1
A kind of preparation method of flexible memory conductive polymer composite aquogel, step are as follows：
（1）By 14 μ L（0.2mmol）Pyrrole monomer is dissolved in 20mL (0.1mg/mL) graphene oxide water solution, is stirred and sharp
Solution is formed with ultrasonic wave is scattered；
（2）By 0.5mg frerrous chlorides（4×10-6mol）、122μL 30%H2O2 (4mmol) solution sequentially adds above-mentioned steps
（1）In resulting solution, and disperseed using ultrasonic wave；
（3）By step（2）Gains react 2h under 0 DEG C of stirring condition；
（4）In step（3）0.1g ammonium persulfates are added in gained reactant, 5mg N, N ˊ-methylene-bisacrylamides, stirring is simultaneously
Ultrasonic disperse uniformly adds 1g acrylic acid afterwards, continues to stir 10min；
（5）Reaction 6h is stood in 70 DEG C of baking ovens, obtained hydrogel is placed in the hydroiodic acid that mass fraction is 45% and carried out
After reduction, by obtained product in distilled water cleaning and balance 12h, change a water per 6h and obtain flexible memory conductive polymer and answer
Heshui gel.
Embodiment 2
A kind of preparation method of flexible memory conductive polymer composite aquogel, its difference from Example 1 are 14 μ L
（0.2mmol）Pyrrole monomer is changed into 420 μ L（6mmol）, the concentration of graphene oxide is changed into 2mg/mL, 0.5mg from 0.1mg/mL
Frerrous chloride（4×10-6mol）It is changed into 0.0152g（1.2×10-4 mol）, 122 μ L 30%H2O2 (4mmol) is changed into 366 μ L
30%H2O2 (12mmol), 0.1g ammonium persulfates are changed into 0.04g ammonium persulfates, and 5mg N, N ˊ-methylene-bisacrylamides are changed into
0.08gN, N ˊ-methylene-bisacrylamide, the quality of acrylic acid are changed into 4g from 1g.Step（3）In 0 DEG C be changed into 5 DEG C, step
（5）In standing reaction 6h be changed into 24h, the cleaning and balance time is changed into 24h from 12h.
Embodiment 3
A kind of preparation method of flexible memory conductive polymer composite aquogel, its difference from Example 1 are 14 μ L
（0.2mmol）Pyrrole monomer is changed into 70 μ L（1mmol）, the concentration of graphene oxide is changed into 0.5mg/mL from 0.1mg/mL,
0.5mg frerrous chlorides（4×10-6mol）It is changed into 2.4mg（1.88×10-5 mol）, 122 μ L 30%H2O2 (4mmol) is changed into 432 μ
L 30%H2O2 (15mmol), 0.1g ammonium persulfates are changed into 0.08g azo diisobutyl amidine hydrochlorides, 5mg N, N ˊ-di-2-ethylhexylphosphine oxides
Acrylamide is changed into 0.0106gN, N ˊ-methylene-bisacrylamide, and the quality of acrylic acid is changed into 1.6g from 1g.Step（3）In
0 DEG C is changed into 10 DEG C, step（5）In standing reaction 6h be changed into 12h, the cleaning and balance time is changed into 18h from 12h.
Embodiment 4
A kind of preparation method of flexible memory conductive polymer composite aquogel, its difference from Example 1 are 14 μ L
（0.2mmol）Pyrrole monomer is changed into 140 μ L（2mmol）, the concentration of graphene oxide is changed into 1mg/mL, 0.5mg from 0.1mg/mL
Frerrous chloride（4×10-6mol）It is changed into 6.1mg（5×10-5 mol）, 122 μ L 30%H2O2 (4mmol) is changed into 613 μ L 30%
H2O2 (20mmol), 0.1g ammonium persulfates are changed into 0.06g azo diisobutyl amidine hydrochlorides, 5mg N, N ˊ-methylene bisacrylamides
Acid amides is changed into 0.024gN, N ˊ-methylene-bisacrylamide, and the quality of acrylic acid is changed into 2.4g from 1g.Step（3）In 0 DEG C change
For 15 DEG C, step（5）In standing reaction 6h be changed into 18h, the cleaning and balance time is changed into 18h from 12h.
Embodiment 5
A kind of preparation method of flexible memory conductive polymer composite aquogel, its difference from Example 1 are 14 μ L
（0.2mmol）Pyrrole monomer is changed into 280 μ L（4mmol）, the concentration of graphene oxide is changed into 1.5mg/mL from 0.1mg/mL,
0.5mg frerrous chlorides（4×10-6mol）It is changed into 0.0102g（6.7×10-5 mol）Ferrous sulfate, 122 μ L 30%H2O2
(4mmol) is changed into 613 μ L 30%H2O2 (20mmol), 0.1g ammonium persulfates are changed into 0.0375g ammonium persulfates, 5mg N, N ˊ-Asias
Bisacrylamide is changed into 0.0375gN, N ˊ-methylene-bisacrylamide, and the quality of acrylic acid is changed into 3g from 1g.Step（3）
In 0 DEG C be changed into 20 DEG C, step（5）In standing reaction 6h be changed into 24h, the cleaning and balance time is changed into 24h from 12h
The performance parameter of composite prepared by embodiment 1-5 is as shown in table 1.
Table 1
Elongation is calculated according to below equation：
Wherein, δ is elongation, and L is maximum elongation length, and s is former long
Fig. 1 is the load-deformation curve of composite aquogel prepared by the embodiment of the present invention 1, from curve, its elongation at break
Up to 400%, tensile strength shows good flexible extensible performance up to 0.2MPa.
Fig. 2 is the SEM photograph of the flexible recovery of composite aquogel prepared by the embodiment of the present invention 1 and loose structure change.This
Kind hydrogel dries after-contraction, and being immersed in again in water can recover flexible again（As shown in Fig. 2 upper right corner）, there is flexible memory
Function, it is convenient to electrolyte is drawn to inside its loose structure, can also regulate and control its loose structure by regulating and controlling its water absorption
Change.
Technical scheme is described in detail above-described embodiment.It is apparent that the present invention is not limited retouched
The embodiment stated.Based on the embodiment in the present invention, those skilled in the art can also make a variety of changes accordingly, but appoint
What is equal with the present invention or similar change belongs to the scope of protection of the invention.
Claims (7)
1. a kind of preparation method of flexible memory conductive polymer composite aquogel, it is characterised in that comprise the following steps：
(1) pyrrole monomer is dissolved in graphene oxide water solution, stirs and form solution using ultrasonic wave is scattered, it is standby；
(2) by ferrous salt and H2O2Solution is sequentially added in step (1) resulting solution, is stirred and is formed instead using ultrasonic wave is scattered
Answer system；
(3) reaction system obtained by step (2) is reacted into 2h under 0 to 20 DEG C of stirring condition；
(4) initiator and N, N ˊ-methylene-bisacrylamide are added in step (3) gained reactant, stirs simultaneously ultrasonic disperse
Acrylic acid is added after uniformly, continues to stir 5-10min；
(5) reaction is stood in 70 DEG C of baking ovens, obtained hydrogel is placed in the hydroiodic acid that mass fraction is 45% and gone back
After original, by obtained product in distilled water cleaning and balance, obtain flexible memory conductive polymer composite aquogel.
2. preparation method according to claim 1, it is characterised in that the concentration of graphene oxide is described in step (1)
0.1-2mg/mL, the concentration of the pyrrole monomer is 0.01M-0.3M.
3. preparation method according to claim 1, it is characterised in that the ferrous salt described in step (2) is ferrous sulfate
Or frerrous chloride.
4. preparation method according to claim 1, it is characterised in that H described in step (2)2O2Mol ratio with pyrroles is
20:1-2:1, the H2O2Mol ratio with ferrous salt is 1000:1-100:1.
5. preparation method according to claim 1, it is characterised in that the initiator described in step (4) is ammonium persulfate
Or azo diisobutyl amidine hydrochloride, the concentration of described acrylic acid is 5-20mg/mL, acrylic acid and N, N ˊ-di-2-ethylhexylphosphine oxide third
The mass ratio of acrylamide is 200:1-50:1,
6. preparation method according to claim 1, it is characterised in that the initiator described in step (4) is ammonium persulfate,
The mass ratio of ammonium persulfate and acrylic acid is 10:1-100:1.
7. preparation method according to claim 1, it is characterised in that the time that reaction is stood described in step (5) is 6-
24h, cleaning and balance time are 12-24h, and a water is changed per 6h.
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| CN108586664A (en) * | 2018-04-24 | 2018-09-28 | 华中科技大学 | A kind of method and the capacitor preparing the stretchable ultracapacitor of full hydrogel |
| CN109942747A (en) * | 2019-04-01 | 2019-06-28 | 福州大学 | A kind of compliant conductive hydrogel and preparation method thereof |
| CN113461971A (en) * | 2021-06-28 | 2021-10-01 | 广州大学 | Conductive hydrogel and preparation method and application thereof |
| CN114343650A (en) * | 2021-12-09 | 2022-04-15 | 中国科学院深圳先进技术研究院 | Electro-polymerization modified flexible contact, and semi-dry electrode and electroencephalogram cap containing flexible contact |
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| CN102863617A (en) * | 2011-07-04 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of polypyrrole nanometer microspheres |
| CN103390511A (en) * | 2013-07-30 | 2013-11-13 | 河海大学 | Preparation method for graphene oxide/polypyrrole composite material of lamellar microstructure |
| CN106633105A (en) * | 2016-10-27 | 2017-05-10 | 山东科技大学 | Preparation method of high-elasticity ternary composite hydrogel |
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| CN102863617A (en) * | 2011-07-04 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of polypyrrole nanometer microspheres |
| CN103390511A (en) * | 2013-07-30 | 2013-11-13 | 河海大学 | Preparation method for graphene oxide/polypyrrole composite material of lamellar microstructure |
| CN106633105A (en) * | 2016-10-27 | 2017-05-10 | 山东科技大学 | Preparation method of high-elasticity ternary composite hydrogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108586664A (en) * | 2018-04-24 | 2018-09-28 | 华中科技大学 | A kind of method and the capacitor preparing the stretchable ultracapacitor of full hydrogel |
| CN109942747A (en) * | 2019-04-01 | 2019-06-28 | 福州大学 | A kind of compliant conductive hydrogel and preparation method thereof |
| CN113461971A (en) * | 2021-06-28 | 2021-10-01 | 广州大学 | Conductive hydrogel and preparation method and application thereof |
| CN113461971B (en) * | 2021-06-28 | 2023-12-26 | 广州大学 | Conductive hydrogel and preparation method and application thereof |
| CN114343650A (en) * | 2021-12-09 | 2022-04-15 | 中国科学院深圳先进技术研究院 | Electro-polymerization modified flexible contact, and semi-dry electrode and electroencephalogram cap containing flexible contact |
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