CN106009444B - A kind of preparation method of polypyrrole-graphene-polyvinyl alcohol composite aerogel - Google Patents
A kind of preparation method of polypyrrole-graphene-polyvinyl alcohol composite aerogel Download PDFInfo
- Publication number
- CN106009444B CN106009444B CN201610559587.9A CN201610559587A CN106009444B CN 106009444 B CN106009444 B CN 106009444B CN 201610559587 A CN201610559587 A CN 201610559587A CN 106009444 B CN106009444 B CN 106009444B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- graphene
- preparation
- graphene oxide
- composite aerogel
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
Abstract
The present invention discloses a kind of preparation method of polypyrrole-graphene-polyvinyl alcohol composite aerogel, comprising: (1) graphene oxide is distributed in dispersing agent, obtains certain density graphene oxide dispersion；(2) graphene oxide dispersion for taking step (1) to obtain, sequentially adds pyrroles, glutaraldehyde solution, poly-vinyl alcohol solution, after mixing evenly, stands a period of time；(3) compound for obtaining step (2) circulating frozen under low temperature and room temperature thaws for several times, obtains pyrroles-graphene oxide-polyvinyl alcohol composite aerogel；(4) composite aerogel that step (3) obtains is sequentially placed into oxidant, in hydrazine hydrate, obtains polypyrrole-graphene-polyvinyl alcohol composite aerogel.Preparation process of the present invention is simple, and obtained composite aerogel has good chemical property and compression and back renaturation, can be used for constructing the Novel electronic devices such as compressible supercapacitor.
Description
Technical field
The invention belongs to field of material preparation, are related to a kind of preparation of polypyrrole-graphene-polyvinyl alcohol composite aerogel
Method.
Background technique
Polyvinyl alcohol is a kind of widely used water soluble polymer, nontoxic, nonirritant, containing a large amount of in strand
Hydroxyl, polarity is strong, easily formation hydrogen bond, therefore have good hydrophilic, performance is between rubber and plastics.But it is poly-
Vinyl alcohol intensity itself is low, heat-resisting, poor water resistance, is restricted polyvinyl alcohol in very various applications.
The big pi bond system of the conjugation formed is built in representative of the polypyrrole as conducting polymer by alternate Dan Shuan, and it is special to have
Physical and chemical performance, in opto-electronic device, there is good application prospect in the fields such as sensor.But pure polypyrrole indissoluble
Yu Shui, poor ductility, processing difficulties.
Surface of graphene oxide contains the functional groups such as a large amount of carboxyl, hydroxyl and carbonyl, can be dispersed in water or organic solvent
In.The graphene obtained after being restored has high ratio table and accumulates, good conductivity, excellent electronic conduction ability and machine
Tool performance.Therefore it is added in polymer as packing material, can effectively improve electricity, the heat, mechanical performance of polymer,
Substantially increase the properties of compound.But graphene hydrophilicity is poor, and lamella be easy reunite, being stacked makes
It obtains its specific surface area to reduce significantly, reduces performance in the composite.
The complex method of high molecular material and graphene is generally divided into chemical method and electrochemical method at present.With usual system
The blend method of standby composite material is compared, and chemical copolymerization method can use the conjugated structure of high molecular structure and graphene, real
Existing macromolecule and graphene are in macroscopic view and combining closely on microcosmic level.How by polyvinyl alcohol, graphene, polypyrrole three
Effectively compound, forming one kind has compression and back renaturation, and the good polypyrrole-graphene-polyvinyl alcohol of chemical property is compound
Aeroge is the critical issue in preparing.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of polypyrrole-graphene-polyvinyl alcohol composite aerogel, should
Method reaction condition is mild, and simple process, production cost is low, polypyrrole-graphene obtained-polyvinyl alcohol composite aerogel tool
There are good electric conductivity and compression and back renaturation.
To achieve the goals above, The technical solution adopted by the invention is as follows: a kind of polypyrrole-graphene-polyvinyl alcohol
The preparation method of composite aerogel, it is characterised in that it includes the following steps:
(1) graphene oxide solid is added in dispersing agent, certain density oxidation is obtained by stirring, ultrasonic disperse
Graphene dispersing solution, it is spare；
(2) graphene oxide dispersion prepared and obtained in step (1) is taken, pyrroles, glutaraldehyde solution, poly- second are sequentially added
Enolate solution stands a period of time after mixing evenly；
(3) compound for obtaining step (2) circulating frozen under low temperature and room temperature thaws for several times, obtains pyrroles-oxidation
Graphene-polyvinyl alcohol gel；
(4) pyrroles-graphene oxide-polyvinyl alcohol gel for obtaining step (3) is sequentially placed into oxidant, hydrazine hydrate
In, obtain polypyrrole-graphene-polyvinyl alcohol composite aerogel.
According to the above scheme, it is preferable that dispersing agent described in step (1) is distilled water, alcohol, dimethylformamide, chlorine
Imitative, n-butanol, propyl alcohol one or more kinds of mixture.
According to the above scheme, it is preferable that the concentration of graphene oxide dispersion described in step (1) is 0.01~10mg/
mL。
According to the above scheme, it is preferable that the concentration of glutaraldehyde solution described in step (2) is 10~25wt%.
According to the above scheme, it is preferable that the concentration of poly-vinyl alcohol solution described in step (2) is 10~200mg/mL.
According to the above scheme, it is preferable that the dosage of graphene oxide dispersion described in step (2) is 1~100mL, pyrrole
Coughing up dosage is 10~200 μ L, and glutaraldehyde solution dosage is 0.1~10mL, and poly-vinyl alcohol solution dosage is 0.1~10mL.
According to the above scheme, it is preferable that mixing time described in step (2) be 0.5~12h, time of repose be 0.5~
12h。
According to the above scheme, it is preferable that low temperature range described in step (3) is -70~-10 DEG C.
According to the above scheme, it is preferable that the number that circulating frozen described in step (3) thaws is 1~20 time.
According to the above scheme, it is preferable that oxidant described in step (4) is ferric trichloride, ferric nitrate, ferric sulfate or over cure
Sour ammonium.
According to the above scheme, it is preferable that the substance of pyrroles described in oxidant described in step (4) and step (2)
The ratio between amount is 0.5~14, and the dosage of hydrazine hydrate described in step (4) is 10~200 μ L.
According to the above scheme, it is preferable that pyrroles-graphene oxide-polyvinyl alcohol gel described in step (4) is placed in oxidation
Time in agent is 5~50h, the time being placed in hydrazine hydrate is 4~for 24 hours.
Compared with prior art, the present invention has following prominent effect:
1) there is porous structure, tool according to polypyrrole-graphene-polyvinyl alcohol composite aerogel made of the method for the present invention
There are good amphipathic property, electric conductivity and compression and back renaturation, has in fields such as biomaterial, compressible capacitors and preferably answer
Use prospect；
2) in preparation method, first graphene oxide and pyrrole monomer are dispersed in polyvinyl alcohol, then pyrrole polymerization list
It is evenly dispersed in polyvinyl alcohol matrix to realize polypyrrole and graphene for body and redox graphene；
3) preparation process of the invention is very simple, is suitble to industrialized production, and each component in controllable composite aerogel
Content.
Detailed description of the invention
Fig. 1 is polypyrrole-graphene-compression of the polyvinyl alcohol composite aerogel under ballast load prepared by embodiment 1
Reply figure.Wherein left figure is the reset condition placed before counterweight, and middle graph is compressive state when placing counterweight, and right figure is to remove
Recoil state after counterweight.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
(1) 5g pva powder is dissolved in 500mL distilled water, obtains the poly-vinyl alcohol solution that concentration is 10mg/mL；
(2) 50mg graphene oxide solid is added in 50mL distilled water, obtains concentration by stirring, ultrasonic disperse and be
The finely dispersed graphene oxide solution of 1mg/mL.
(3) 20 μ L pyrrole monomers (0.28mmol) are sequentially added into 20mL graphene oxide dispersion, 0.2mL concentration is
10wt% glutaraldehyde solution, 5mL poly-vinyl alcohol solution after stirring 0.5h, stand 1h；By obtained compound at -60 DEG C and often
The lower circulating frozen of temperature thaws 8 times, obtains pyrroles-graphene oxide-polyethylene gel.
(4) pyrroles-graphene oxide-polyvinyl alcohol gel is placed in 6h in the ammonium persulfate solution of 12mL 0.1mol/L,
It is placed in 120 μ L hydrazine hydrates lower 6h again, obtains polypyrrole-graphene-polyvinyl alcohol composite aerogel.
The test of compression and back renaturation is carried out to obtained polypyrrole-graphene-polyvinyl alcohol composite aerogel, by 1000g weight
Code is placed in above the composite aerogel, observes the compression reaction situation of the composite aerogel, the result is shown in Figure 1.
Measuring the polypyrrole-graphene-polyvinyl alcohol composite aerogel conductivity using four probe method is 1.24*10-5S/
cm。
Embodiment 2
(1) 5g pva powder is dissolved in 250mL distilled water, obtains the poly-vinyl alcohol solution that concentration is 20mg/mL；
(2) 50mg graphene oxide solid is added in 25mL distilled water, obtains concentration by stirring, ultrasonic disperse and be
The finely dispersed graphene oxide solution of 2mg/mL.
(3) 30 μ L pyrrole monomers (0.43mmol) are sequentially added into 20mL graphene oxide dispersion, 1mL concentration is
The glutaraldehyde solution of 15wt%, 2mL poly-vinyl alcohol solution after stirring 1h, stand 1h；By obtained compound at -10 DEG C and often
The lower circulating frozen of temperature thaws 5 times, obtains pyrroles-graphene oxide-polyethylene gel；
(4) pyrroles-graphene oxide-polyvinyl alcohol gel is placed in 6h in the ammonium persulfate solution of 15mL 0.1mol/L,
It is placed in 12h in 120 μ L hydrazine hydrates again, obtains polypyrrole-graphene-polyvinyl alcohol composite aerogel.
Measuring polypyrrole-graphene-polyvinyl alcohol composite aerogel conductivity using four probe method is 2.52*10- 5S/cm。
Embodiment 3
(1) 5g pva powder is dissolved in 100mL distilled water, obtains the poly-vinyl alcohol solution that concentration is 50mg/mL；
(2) 50mg graphene oxide solid is added in 25mL alcohol, obtains concentration by stirring, ultrasonic disperse and be
The finely dispersed graphene oxide solution of 2mg/mL.
(3) 40 μ L pyrrole monomers (0.57mmol) are sequentially added into 15mL graphene oxide dispersion, 0.5mL concentration is
The glutaraldehyde solution of 20wt%, 2mL poly-vinyl alcohol solution after stirring 1h, stand 5h；By obtained compound at -30 DEG C and often
The lower circulating frozen of temperature thaws 5 times, obtains pyrroles-graphene oxide-polyethylene gel；
(4) pyrroles-graphene oxide-polyvinyl alcohol gel is placed in the ammonium persulfate solution of 20mL 0.1mol/L
12h, then it is placed in 18h in 60 μ L hydrazine hydrates, obtain polypyrrole-graphene-polyvinyl alcohol composite aerogel.
Measuring polypyrrole-graphene-polyvinyl alcohol composite aerogel conductivity using four probe method is 4.65*10- 5S/cm。
Embodiment 4
(1) 5g pva powder is dissolved in 250mL distilled water, obtains the poly-vinyl alcohol solution that concentration is 20mg/mL；
(2) 50mg graphene oxide solid is added in 25mL distilled water, obtains concentration by stirring, ultrasonic disperse and be
The finely dispersed graphene oxide solution of 2mg/mL.
(3) 100 μ L pyrrole monomers (1.44mmol) are sequentially added into 50mL graphene oxide dispersion, 1mL concentration is
The glutaraldehyde solution of 25wt%, 2mL poly-vinyl alcohol solution after stirring 1h, stand 1h；By obtained compound at -50 DEG C and often
The lower circulating frozen of temperature thaws 3 times, obtains pyrroles-graphene oxide-polyethylene gel；
(4) pyrroles-graphene oxide-polyvinyl alcohol gel is placed in the liquor ferri trichloridi of 15mL 0.2mol/L
12h, then it is placed in 10h in 120 μ L hydrazine hydrates, obtain polypyrrole-graphene-polyvinyl alcohol composite aerogel.
Measuring polypyrrole-graphene-polyvinyl alcohol composite aerogel conductivity using four probe method is 6.57*10- 5S/cm。
Embodiment 5
(1) 5g pva powder is dissolved in 50mL distilled water, obtains the poly-vinyl alcohol solution that concentration is 100mg/mL；
(2) 5mg graphene oxide solid is added in 1mL dimethylformamide, is obtained by stirring, ultrasonic disperse dense
Degree is the finely dispersed graphene oxide solution of 5mg/mL.
(3) 200 μ L pyrrole monomers (2.89mmol) are sequentially added into 30mL graphene oxide dispersion, 2mL concentration is
10wt% glutaraldehyde solution, 0.5mL poly-vinyl alcohol solution after stirring 1h, stand 1h；By obtained compound at -65 DEG C and often
The lower circulating frozen of temperature thaws 5 times, obtains pyrroles-graphene oxide-polyethylene gel；
(4) pyrroles-graphene oxide-polyvinyl alcohol gel is placed in 12h in 5mL 0.4mol/L ammonium persulfate solution, then
It is placed in 20h in 100 μ L hydrazine hydrates, obtains polypyrrole-graphene-polyvinyl alcohol composite aerogel.
Measuring polypyrrole-graphene-polyvinyl alcohol composite aerogel conductivity using four probe method is 1.32*10- 4S/cm。
Embodiment 6
(1) 5g pva powder is dissolved in 27.8mL distilled water, it is molten obtains the polyvinyl alcohol that concentration is 180mg/mL
Liquid；
(2) 5mg graphene oxide solid is added in 100mL chloroform, obtains concentration by stirring, ultrasonic disperse and be
The finely dispersed graphene oxide solution of 0.05mg/mL.
(3) 150 μ L pyrrole monomers (2.17mmol), 10mL concentration are sequentially added into 100mL graphene oxide dispersion
For 15wt% glutaraldehyde solution, 10mL poly-vinyl alcohol solution after stirring 11h, stands 12h；By obtained compound at -25 DEG C and
Circulating frozen thaws 18 times under room temperature, obtains pyrroles-graphene oxide-polyethylene gel；
(4) pyrroles-graphene oxide-polyvinyl alcohol gel is placed in 48h in 50mL 0.4mol/L ammonium persulfate solution,
It is placed in 4h in 180 μ L hydrazine hydrates again, obtains polypyrrole-graphene-polyvinyl alcohol composite aerogel.
Measuring polypyrrole-graphene-polyvinyl alcohol composite aerogel conductivity using four probe method is 4.82*10- 5S/cm。
Embodiment 7
(1) 5g pva powder is dissolved in 33.3mL distilled water, it is molten obtains the polyvinyl alcohol that concentration is 150mg/mL
Liquid；
(2) 5mg graphene oxide solid is added in 0.7mL dimethylformamide, is obtained by stirring, ultrasonic disperse
Concentration is the finely dispersed graphene oxide solution of 7mg/mL.
(3) 100 μ L pyrrole monomers (1.44mmol) are sequentially added into 80mL graphene oxide dispersion, 5mL concentration is
20wt% glutaraldehyde solution, 8mL poly-vinyl alcohol solution after stirring 5h, stand 0.5h；By obtained compound at -45 DEG C and often
The lower circulating frozen of temperature thaws 2 times, obtains pyrroles-graphene oxide-polyethylene gel；
(4) pyrroles-graphene oxide-polyvinyl alcohol gel is placed in 30h in 50mL 0.4mol/L ammonium persulfate solution,
It is placed in 15 μ L hydrazine hydrates again for 24 hours, obtains polypyrrole-graphene-polyvinyl alcohol composite aerogel.
Measuring polypyrrole-graphene-polyvinyl alcohol composite aerogel conductivity using four probe method is 8.95*10- 5S/cm。
Each raw material cited by the present invention can realize that the bound value of the present invention and each raw material, interval value can
Realize the present invention；Embodiment numerous to list herein.The bound value of technological parameter (such as temperature, time) of the invention,
Interval value can realize the present invention, embodiment numerous to list herein.
Claims (10)
1. a kind of preparation method of polypyrrole-graphene-polyvinyl alcohol composite aerogel, which is characterized in that it includes following step
It is rapid:
(1) graphene oxide solid is added in dispersing agent, certain density graphite oxide is obtained by stirring, ultrasonic disperse
Alkene dispersion liquid, it is spare；
(2) graphene oxide dispersion prepared and obtained in step (1) is taken, pyrroles, glutaraldehyde solution, polyvinyl alcohol are sequentially added
Solution stands a period of time after mixing evenly；
(3) compound for obtaining step (2) circulating frozen under low temperature and room temperature thaws for several times, obtains pyrroles-graphite oxide
Alkene-polyvinyl alcohol gel；
(4) pyrroles-graphene oxide-polyvinyl alcohol gel for obtaining step (3) is sequentially placed into oxidant, in hydrazine hydrate, obtains
To polypyrrole-graphene-polyvinyl alcohol composite aerogel.
2. preparation method according to claim 1, it is characterised in that: dispersing agent described in step (1) is distilled water, wine
The mixtures of essence, the one or more of dimethylformamide, chloroform, n-butanol, propyl alcohol.
3. preparation method according to claim 1, it is characterised in that: graphene oxide dispersion described in step (1)
Concentration be 0.01~10mg/mL.
4. preparation method according to claim 1, it is characterised in that: the concentration of glutaraldehyde solution described in step (2)
For 10~25wt%；The concentration of poly-vinyl alcohol solution described in step (2) is 10~200mg/mL.
5. preparation method according to claim 1, it is characterised in that: graphene oxide dispersion described in step (2)
Dosage be 1~100mL, pyrroles's dosage be 10~200 μ L, glutaraldehyde solution dosage be 0.1~10mL, poly-vinyl alcohol solution use
Amount is 0.1~10mL.
6. preparation method according to claim 1, it is characterised in that: mixing time described in step (2) be 0.5~
12h, time of repose are 0.5~12h.
7. preparation method according to claim 1, it is characterised in that: low temperature range described in step (3) be -70~-
10 DEG C, the number that the circulating frozen thaws is 1~20 time.
8. preparation method according to claim 1, it is characterised in that: oxidant described in step (4) be ferric trichloride,
Ferric nitrate, ferric sulfate or ammonium persulfate.
9. preparation method according to claim 1, it is characterised in that: in oxidant described in step (4) and step (2)
The ratio between described amount of substance of pyrroles is 0.5~14, and the dosage of hydrazine hydrate described in step (4) is 10~200 μ L.
10. preparation method according to claim 1, it is characterised in that: gel described in step (4) is placed in oxidant
Time be 5~50h, be placed in time in hydrazine hydrate be 4~for 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610559587.9A CN106009444B (en) | 2016-07-15 | 2016-07-15 | A kind of preparation method of polypyrrole-graphene-polyvinyl alcohol composite aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610559587.9A CN106009444B (en) | 2016-07-15 | 2016-07-15 | A kind of preparation method of polypyrrole-graphene-polyvinyl alcohol composite aerogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106009444A CN106009444A (en) | 2016-10-12 |
| CN106009444B true CN106009444B (en) | 2018-12-14 |
Family
ID=57118279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610559587.9A Expired - Fee Related CN106009444B (en) | 2016-07-15 | 2016-07-15 | A kind of preparation method of polypyrrole-graphene-polyvinyl alcohol composite aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106009444B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633105A (en) * | 2016-10-27 | 2017-05-10 | 山东科技大学 | Preparation method of high-elasticity ternary composite hydrogel |
| CN107365427A (en) * | 2017-03-21 | 2017-11-21 | 李阳阳 | A kind of method that Frozen-thawed cycled method prepares aeroge |
| CN107840971A (en) * | 2017-10-27 | 2018-03-27 | 华南理工大学 | It is a kind of that from adhering to, wearable power is quick to sense composite aquogel and preparation method thereof |
| CN108242341A (en) * | 2017-12-21 | 2018-07-03 | 华北电力大学 | A kind of preparation of multifunctional graphite vinyl sill and its application in terms of ultracapacitor and water process |
| CN110157143A (en) * | 2018-02-05 | 2019-08-23 | 北京欧美中科学技术研究院 | A kind of superelevation conductive polymer aerogel based on graphene |
| CN108711522B (en) * | 2018-04-26 | 2020-10-23 | 武汉工程大学 | Boron-doped graphene/polyaniline composite aerogel and preparation method thereof |
| CN109280540A (en) * | 2018-09-20 | 2019-01-29 | 赵建平 | It is a kind of using graphene aerogel as energy storage material of matrix and preparation method thereof |
| CN109925981B (en) * | 2019-03-13 | 2022-02-11 | 太原理工大学 | Preparation method of graphene composite aerogel with high compressive strength |
| CN110105591B (en) * | 2019-05-09 | 2022-03-15 | 武汉工程大学 | Preparation method of polyvinyl alcohol-polypyrrole composite conductive hydrogel with tensile property |
| CN110105592A (en) * | 2019-05-09 | 2019-08-09 | 武汉工程大学 | A kind of preparation method of high strength poly vinyl alcohol-graphene oxide-polypyrrole composite hydrogel |
| CN110563966B (en) * | 2019-08-26 | 2022-05-10 | 武汉工程大学 | Preparation method of MXene/graphene/polyvinyl alcohol composite gel |
| CN110698856A (en) * | 2019-09-23 | 2020-01-17 | 江苏理工学院 | Graphene/polypyrrole/water-soluble polymer ternary composite material and preparation method thereof |
| CN113926397B (en) * | 2020-07-14 | 2022-11-01 | 厦门大学 | Graphene pyrrole aerogel and preparation method and application thereof |
| CN112210177B (en) * | 2020-10-12 | 2022-10-25 | 广安长明高端产业技术研究院 | 3D printing antibacterial conductive composite material and preparation method thereof |
| CN113480847B (en) * | 2021-07-22 | 2023-08-01 | 广东石油化工学院 | Preparation method of composite board with strong mechanical property and energy storage property |
| CN115744888A (en) * | 2022-11-08 | 2023-03-07 | 江苏永达电源股份有限公司 | Preparation process of graphene negative electrode material of high-capacity battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
-
2016
- 2016-07-15 CN CN201610559587.9A patent/CN106009444B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
Non-Patent Citations (1)
| Title |
|---|
| "石墨烯复合气凝胶的结构控制合成及性能研究";孙瑞;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20151215;B020-218 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106009444A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106009444B (en) | A kind of preparation method of polypyrrole-graphene-polyvinyl alcohol composite aerogel | |
| Lin et al. | One-pot synthesis of a double-network hydrogel electrolyte with extraordinarily excellent mechanical properties for a highly compressible and bendable flexible supercapacitor | |
| Yu et al. | Highly conductive and mechanically robust cellulose nanocomposite hydrogels with antifreezing and antidehydration performances for flexible humidity sensors | |
| CN103897183B (en) | Binary carbon material-conductive composite nano-polymers air-sensitive film and preparation method thereof | |
| CN107522269B (en) | Preparation method of porous graphene/polypyrrole electrode material | |
| Zhu et al. | High‐performance supercapacitor electrode materials from chitosan via hydrothermal carbonization and potassium hydroxide activation | |
| Li et al. | In situ synthesis of conductive nanocrystal cellulose/polypyrrole composite hydrogel based on semi-interpenetrating network | |
| Liu et al. | Swelling, pH sensitivity, and mechanical properties of poly (acrylamide‐co‐sodium methacrylate) nanocomposite hydrogels impregnated with carboxyl‐functionalized carbon nanotubes | |
| Lei et al. | Soft template interfacial growth of novel ultralong polypyrrole nanowires for electrochemical energy storage | |
| CN110105592A (en) | A kind of preparation method of high strength poly vinyl alcohol-graphene oxide-polypyrrole composite hydrogel | |
| Fan et al. | A hierarchical porous carbon membrane from polyacrylonitrile/polyvinylpyrrolidone blending membranes: Preparation, characterization and electrochemical capacitive performance | |
| CN103112238B (en) | Preparation method of conducting polymer composite thin film | |
| CN104934237B (en) | A kind of preparation method of nitrating porous charcoal/graphene two dimension combination electrode material | |
| CN108659422A (en) | A kind of polyaniline/graphene/polyvinyl alcohol plural gel and preparation method thereof | |
| CN104130540A (en) | Cellulose based conductive hydrogel and preparation method and application thereof | |
| CN100558815C (en) | High conductive polyamide/graphite nano conductive composite material and preparation method thereof | |
| CN103146231A (en) | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid | |
| Sheng et al. | Boosting PEDOT energy storage with redox dopant and electrolyte additive | |
| Fu et al. | Novel non-covalent sulfonated multiwalled carbon nanotubes from p-toluenesulfonic acid/glucose doped polypyrrole for electrochemical capacitors | |
| CN105244190A (en) | Preparation method of graphene/carbon nano tube co-reinforced conducting polymer hydrogel | |
| Dhibar et al. | Copper chloride‐doped polyaniline/multiwalled carbon nanotubes nanocomposites: Superior electrode material for supercapacitor applications | |
| CN108039283B (en) | A kind of rich N doping multi-stage porous carbon material and the preparation method and application thereof based on in-situ polymerization | |
| Wang et al. | Rational design of modified fluororubber-based quasi-solid-state electrolyte for flexible supercapacitors with enhanced performance | |
| Lu et al. | Flexible Polypyrrole Nanotube–Polyethylene Glycol–Polyvinyl Alcohol Hydrogels for Enhanced Electromagnetic Shielding | |
| RU2462485C2 (en) | Method of improving conductivity of conducting polymer product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181214 Termination date: 20210715 |