CN106674563A - High-performance and light-reduced graphene oxide composite proton exchange membrane and preparation method thereof - Google Patents
High-performance and light-reduced graphene oxide composite proton exchange membrane and preparation method thereof Download PDFInfo
- Publication number
- CN106674563A CN106674563A CN201611155939.0A CN201611155939A CN106674563A CN 106674563 A CN106674563 A CN 106674563A CN 201611155939 A CN201611155939 A CN 201611155939A CN 106674563 A CN106674563 A CN 106674563A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene oxide
- preparation
- polymer
- proton
- 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.)
- Pending
Links
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K7/00—Use of ingredients characterised by shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
-
- 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
- C08J2325/00—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 aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Carbon And Carbon Compounds (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of membranes and particularly relates to a high-performance and light-reduced graphene oxide composite proton exchange membrane and a preparation method thereof. The preparation method comprises the following steps: carrying out ultrasonic standing operation on a polymer solution and a graphene oxide sheet nano dispersion solution to obtain a polymer modified graphene oxide nano composite; drawing the composite into a graphene oxide nano composite membrane; treating the obtained membrane in a hydroiodic acid solution for short time, so as to obtain a light-reduced graphene oxide nano composite membrane which is stable in water; and finally, carrying out acidification treatment on the membrane. An extremely continuous proton transferring channel is constructed in the membrane through a polymer long-distance proton transferring channel which is hundreds of nanometers long in the graphene oxide nano composite and the transferring of protons in layers between the layers is extremely improved. Meanwhile, layer-to-layer conduction of the protons is enhanced through light reduction. The method is simple and convenient to operate and environmentally friendly, and batch production and scale production are easy to realize; and the method has a good industrial production foundation and a wide application prospect.
Description
Technical field
The invention belongs to technical field of membrane, and in particular to a kind of graphene oxide compound proton exchange membrane and its preparation side
Method.
Background technology
Proton Exchange Membrane Fuel Cells is a kind of without burning, directly in electrochemical reaction mode by fuel and oxidation
Chemical energy in agent is changed into the TRT of electric energy.Proton Exchange Membrane Fuel Cells as a kind of cleaning, efficiently, safety it is green
The color energy illustrates wide market prospect, gets the attention.As the key composition of fuel cell --- proton friendship
Film is changed, the service behaviour of its performance quality appreciable impact fuel cell, it provides passage for the migration and conveying of proton, its synthesis
Performance plays vital effect for the high performance fuel cell of exploitation.But due to methanol and the common transmission channel of proton,
Thus for traditional polymer film, improve proton conductivity and generally require to pay the elevated cost of methanol permeability, so as to serious
Have impact on battery economy.These problems all significantly limit its actual application prospect.Thus exploitation high-performance proton exchange
Film has very necessary.
In recent years, the two-dimentional carbon nanomaterial with graphene oxide as representative is with its unique two-dimensional appearance and uniqueness
Obstructing capacity and be widely used in hybrid proton exchange membrane field.Graphene oxide-polymer hybrid the matter reported at present
The preparation method of proton exchange be mostly using being blended-be cast into embrane method, the carbon nanomaterial that will be prepared（Dispersion liquid）Add
To in polymer solution, treat its casting film in particular mold being uniformly dispersed.《Carbon》（Carbon, 2012, 50
(15): 5395-5402.）By graphene oxide and NafionTMBlending prepares hybrid proton exchange membrane, the methanol crossover of hybridized film
The purer Nafion of rateTMFilm reduces half, but proton conductivity has declined.《Membrane science》（Journal of Membrane
Science, 2014, 458: 128-135.）Sulfonated polyether-ether-ketone-graphene oxide-Nafion is prepared for same methodTMHydridization
PEM.It is miscellaneous when sulfonated polyether-ether-ketone mass fraction is 1 wt%, and the mass fraction of graphene oxide is 0.75 wt%
The proton conductivity for changing film is 322.2 mS cm-1, monocell density is 621.2 mW cm-2, electric current when voltage is 0.4 V
Density is 1496 mA cm-2.But be difficult based on the blending and modifying of traditional polymer film while significantly lifting proton conductivity
Rate and methanol permeability.Thus exploitation novel proton exchange membranes, using new proton transport mechanism lifted film transmission performance and
Selectivity tool is of great significance.《Advanced function material》（Advanced Functional Materials, 2015,
25(48): 7502 – 7511）Using polymerization reaction on the solid surface on stannic oxide/graphene nano piece modified polymer layer, be prepared for oxygen
Graphite alkene/polymer core-shell structure nanometer sheet and sucking filtration film forming.80 DEG C of -100 %RH bar of compound proton exchange membrane of gained
Proton conductivity under part is 0.1 Scm-1, slightly below commercialization NafionTm117 films, but its methanol permeability compared with
NafionTm117 films reduce an order of magnitude.Present the applications well prospect of graphene oxide substrate proton exchange.
The present invention stands operation, profit by the easy ultrasound of polymer solution and stannic oxide/graphene nano piece dispersion liquid first
With amphipathic nature polyalcohol self aggregation behavior in a solvent and the hydrophobe non-covalent bond between polymer and graphene oxide
Act on and long title polymer proton transmission channel is constructed on stannic oxide/graphene nano piece, so as to obtain that there is special three dimensional structure
Polymer-modified stannic oxide/graphene nano composite；Then the stannic oxide/graphene nano composite of gained is configured to necessarily
The dispersion liquid of concentration, under pressure auxiliary stannic oxide/graphene nano composite film is pumped into.Subsequently by gained film in hydroiodic acid solution
The middle short time is processed, and has obtained stable slight redox graphene nano-complex film in water.Finally film is carried out into acid
Change is processed.Polymer long-range proton transmitting channel in stannic oxide/graphene nano composite up to hundreds of nanometers is constructed in film
Extremely continuous proton transmitting channel, greatly improve proton in lamella and piece interlayer transmission.Gone back by slight simultaneously
Original, the interlamellar spacing between film internal oxidition graphene nanometer composite is reduced, and this interlayer that also further enhancing proton is passed
Lead.Proton conductivity of the resulting slight redox graphene nano-complex film under high temperature low humidity conditions is compared to business
Product NafionTm117 films have the lifting of decades of times；The outstanding resistance alcohol ability of slight redox graphene nanometer sheet also makes
The methanol permeability for obtaining slight redox graphene nano-complex film is greatly reduced.At 40 DEG C, slight oxygen reduction fossil
The methanol permeability of black alkene nano-complex film is compared with commercialization NafionTm117 films have the reduction of 2 orders of magnitude.The inventive method
It is easy to operate, environmental friendliness, it is easy to mass, large-scale production, with the basic and wide application of good industrialized production
Prospect.
The content of the invention
It is an object of the invention to provide a kind of slight oxygen reduction of high-performance containing long-range polymer proton transmission channel
Graphite alkene compound proton exchange membrane and preparation method thereof
The slight redox graphene composite proton of the high-performance containing long-range polymer proton transmission channel that the present invention is provided
The preparation method of exchange membrane, concretely comprises the following steps：
（1）1 ~ 100 mL graphene oxides aqueous dispersions are mixed with 0.01 ~ 10 mL polymer solutions, 0.5 ~ 3 h of ultrasound；
0.5 ~ 3 h is stood, stannic oxide/graphene nano composite dispersion liquid is obtained；
（2）By gained stannic oxide/graphene nano composite dispersion liquid sucking filtration film forming under 0.05 ~ 1 Mpa pressure, subsequently by oxygen
Graphite alkene nano-complex film is removed from basement membrane；It is placed in 5 ~ 55 wt% hydriodic acid aqueous solutions and soaks 1 ~ 20
min；Again 0.5 ~ 4 h is processed at 20 ~ 90 DEG C with acid, obtain the high performance light containing long-range polymer proton transmission channel
Degree redox graphene compound proton exchange membrane.
Step of the present invention（1）Described in Graphene aqueous dispersions concentration be 0.1 ~ 10 mg/mL.
Step of the present invention（1）Described in polymer solution be perfluorinated sulfonic resin, sulfonated polyether-ether-ketone, polystyrene sulphur
The homogeneous phase solution of one or more mixing of acid, polyacrylic acid, sulfonate polybenzimidazole or sulfonated polyimide, concentration is 0.1
~ 100 mg/mL。
Step of the present invention（2）Described in acid for the hydrochloric acid, sulphuric acid or phosphoric acid of 1 ~ 4 mol/L one or more mixed
Compound.
Compared with traditional handicraft, the present invention is first by polymer solution and stannic oxide/graphene nano piece dispersion liquid simplicity
Ultrasound stands operation, using between amphipathic nature polyalcohol self aggregation behavior in a solvent and polymer and graphene oxide
Hydrophobe non-covalent bond effect constructs long title polymer proton transmission channel on stannic oxide/graphene nano piece, so as to be had
There is the polymer-modified stannic oxide/graphene nano composite of special three dimensional structure；Then the stannic oxide/graphene nano of gained is answered
Compound is configured to certain density dispersion liquid, and under pressure auxiliary stannic oxide/graphene nano composite film is pumped into.Subsequently by gained
Film short time in hydroiodic acid solution is processed, and has obtained stable slight redox graphene nano-complex film in water.
Finally film is carried out into acidification.Polymer long-range proton transport in stannic oxide/graphene nano composite up to hundreds of nanometers is led to
Road constructs extremely continuous proton transmitting channel in film, greatly improve proton in lamella and piece interlayer transmission.
Simultaneously by slight reduction, the interlamellar spacing between film internal oxidition graphene nanometer composite is reduced, and this is also further enhanced
The interlayer conductive of proton.Proton of the resulting slight redox graphene nano-complex film under high temperature low humidity conditions
Conductivity is compared to commercialization NafionTm117 films have the lifting of decades of times；Slightly redox graphene nanometer sheet is outstanding
Resistance alcohol ability the methanol permeability of slight redox graphene nano-complex film is greatly reduced.At 40 DEG C,
The methanol permeability of slight redox graphene nano-complex film is compared with commercialization NafionTm117 films have 2 orders of magnitude
Reduce.The inventive method is easy to operate, environmental friendliness, it is easy to mass, large-scale production, with good industrialized production base
Plinth and wide application prospect.
Specific embodiment
The high-performance containing long-range polymer proton transmission channel of the invention is further described by the following examples
The preparation of slight redox graphene compound proton exchange membrane and its performance.However, the embodiment is merely possible to provide saying
The bright rather than restriction present invention.
Embodiment 1：
（1）By the graphene oxide aqueous dispersions of the mg/mL of 30 mL 0.5 and the commercially available Nafion of the mg/mL of 0.3 mL 50Tm
Solution mixes, ultrasonic 0.5 h；0.5 h is stood, stannic oxide/graphene nano composite dispersion liquid is obtained；
（2）By gained stannic oxide/graphene nano composite dispersion liquid sucking filtration film forming under 0.1 Mpa pressure, subsequently by graphite oxide
Alkene nano-complex film is removed from basement membrane；It is placed in 55 wt% hydriodic acid aqueous solutions and soaks 6 min；It is molten with 1 M sulphuric acid again
Liquid processes 2 h at 80 DEG C, obtains the slight redox graphene matter of the high-performance containing long-range polymer proton transmission channel
Proton exchange.
The proton conduction property of the PEM is tested in the case of " 100 DEG C of -40 %RH humidity ".
。
It can thus be seen that the high-performance containing long-range polymer proton transmission channel that the present invention is prepared is slightly also
Proton conductivity of the former graphene oxide compound proton exchange membrane under high temperature low humidity conditions is compared with commercialization NafionTM117 film films
Lift 20 times.
The methanol permeability of the PEM is tested in the case of " 40 DEG C ".
。
It can thus be seen that the high-performance containing long-range polymer proton transmission channel that the present invention is prepared is slightly also
The methanol permeability of former graphene oxide compound proton exchange membrane, compared to commercialization NafionTM117 films reduce by two quantity
Level.
Embodiment 2：
（1）By the graphene oxide aqueous dispersions of the mg/mL of 50 mL 0.3 and the commercially available Nafion of the mg/mL of 0.5 mL 50Tm
Solution mixes, ultrasonic 1 h；1 h is stood, stannic oxide/graphene nano composite dispersion liquid is obtained；
（2）By gained stannic oxide/graphene nano composite dispersion liquid sucking filtration film forming under 0.2 Mpa pressure, subsequently by graphite oxide
Alkene nano-complex film is removed from basement membrane；It is placed in 30 wt% hydriodic acid aqueous solutions and soaks 5 min；It is molten with 2 M sulphuric acid again
Liquid processes 2.5 h at 60 DEG C, obtains the slight redox graphene of high-performance containing long-range polymer proton transmission channel
PEM.
Embodiment 3：
（1）By the graphene oxide aqueous dispersions of the mg/mL of 20 mL 1 and the sulfonated polyether-ether-ketone solution of the mg/mL of 1 mL 10
Mixing, ultrasonic 1.5 h；1 h is stood, stannic oxide/graphene nano composite dispersion liquid is obtained；
（2）By gained stannic oxide/graphene nano composite dispersion liquid sucking filtration film forming under 0.3 Mpa pressure, subsequently by graphite oxide
Alkene nano-complex film is removed from basement membrane；It is placed in 30 wt% hydriodic acid aqueous solutions and soaks 6 min；It is molten with 3 M sulphuric acid again
Liquid processes 2 h at 30 DEG C, obtains the slight redox graphene matter of the high-performance containing long-range polymer proton transmission channel
Proton exchange.
Embodiment 4：
（1）By the graphene oxide aqueous dispersions of the mg/mL of 100 mL 0.4 and the polyvinylbenzenesulfonic acid sodium of the mg/mL of 10 mL 1
Solution mixes, ultrasonic 2 h；1.5 h are stood, stannic oxide/graphene nano composite dispersion liquid is obtained；
（2）By gained stannic oxide/graphene nano composite dispersion liquid sucking filtration film forming under 0.1 Mpa pressure, subsequently by graphite oxide
Alkene nano-complex film is removed from basement membrane；It is placed in 35 wt% hydriodic acid aqueous solutions and soaks 7 min；It is molten with 2 M sulphuric acid again
Liquid processes 3 h at 35 DEG C, obtains the slight redox graphene matter of the high-performance containing long-range polymer proton transmission channel
Proton exchange.
Embodiment 5：
（1）The graphene oxide aqueous dispersions of the mg/mL of 50 mL 0.3 are mixed with the polyacrylic acid solution of the mg/mL of 10 mL 3
Close, ultrasonic 1 h；0.5 h is stood, stannic oxide/graphene nano composite dispersion liquid is obtained；
（2）By gained stannic oxide/graphene nano composite dispersion liquid sucking filtration film forming under 0.4 Mpa pressure, subsequently by graphite oxide
Alkene nano-complex film is removed from basement membrane；It is placed in 55 wt% hydriodic acid aqueous solutions and soaks 4 min；It is molten with 4 M sulphuric acid again
Liquid processes 1 h at 25 DEG C, obtains the slight redox graphene matter of the high-performance containing long-range polymer proton transmission channel
Proton exchange.
Embodiment 6：
（1）The graphene oxide aqueous dispersions of the mg/mL of 30 mL 0.5 are molten with the sulfonate polybenzimidazole of the mg/mL of 5 mL 1
Liquid mixes, ultrasonic 1.2 h；0.8 h is stood, stannic oxide/graphene nano composite dispersion liquid is obtained；
（2）By gained stannic oxide/graphene nano composite dispersion liquid sucking filtration film forming under 0.1 Mpa pressure, subsequently by graphite oxide
Alkene nano-complex film is removed from basement membrane；It is placed in 50 wt% hydriodic acid aqueous solutions and soaks 6 min；It is molten with 2 M sulphuric acid again
Liquid processes 2 h at 60 DEG C, obtains the slight redox graphene matter of the high-performance containing long-range polymer proton transmission channel
Proton exchange.
PEM prepared by embodiment 2-6, with same or similar with the PEM prepared by embodiment 1
Characteristic.
Claims (5)
1. a kind of preparation method of the slight redox graphene compound proton exchange membrane of high-performance, it is characterised in that concrete step
Suddenly it is：
（1）5 ~ 100 mL graphene oxides aqueous dispersions are mixed with 0.5 ~ 10 mL polymer solutions, 0.5 ~ 3 h of ultrasound；
0.5 ~ 3 h is stood, stannic oxide/graphene nano composite dispersion liquid is obtained；
（2）By gained stannic oxide/graphene nano composite dispersion liquid sucking filtration film forming under 0.05 ~ 1 Mpa pressure, subsequently by oxygen
Graphite alkene nano-complex film is removed from basement membrane；It is placed in 5 ~ 55 wt% hydriodic acid aqueous solutions and soaks 1 ~ 20
min；Again 0.5 ~ 4 h is processed at 20 ~ 90 DEG C with acid, obtain the high performance light containing long-range polymer proton transmission channel
Degree redox graphene PEM.
2. preparation method according to claim 1, it is characterised in that step（1）Described in Graphene aqueous dispersions
Concentration is 0.01 ~ 10 mg/mL.
3. preparation method according to claim 1, it is characterised in that step（1）Described in polymer solution be perfluor
The one of sulfonate resin, sulfonated polyether-ether-ketone, polystyrolsulfon acid, polyacrylic acid, sulfonate polybenzimidazole or sulfonated polyimide
Kind or the homogeneous phase solution of several mixing, concentration is 0.1 ~ 100 mg/mL.
4. preparation method according to claim 1, it is characterised in that step（2）Described in acid be 1 ~ 4 mol/L
Hydrochloric acid, sulphuric acid or phosphoric acid the mixture of one or more.
5. a kind of slight redox graphene of high-performance prepared by one of claim 1-4 preparation method is combined
PEM, the compound proton exchange membrane contains long-range polymer proton transmission channel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611155939.0A CN106674563A (en) | 2016-12-14 | 2016-12-14 | High-performance and light-reduced graphene oxide composite proton exchange membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611155939.0A CN106674563A (en) | 2016-12-14 | 2016-12-14 | High-performance and light-reduced graphene oxide composite proton exchange membrane and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106674563A true CN106674563A (en) | 2017-05-17 |
Family
ID=58868293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611155939.0A Pending CN106674563A (en) | 2016-12-14 | 2016-12-14 | High-performance and light-reduced graphene oxide composite proton exchange membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674563A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110157016A (en) * | 2019-06-10 | 2019-08-23 | 浙江鹏孚隆科技股份有限公司 | A kind of preparation method of polyether-ether-ketone aqueous dispersion liquid |
| CN111925544A (en) * | 2020-07-16 | 2020-11-13 | 江苏科润膜材料有限公司 | High-strength water-retention perfluorinated sulfonic acid proton exchange membrane, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897093A (en) * | 2014-04-04 | 2014-07-02 | 武汉理工大学 | Graphene/polymer composite hydrogel thin film and preparation method thereof |
| WO2015038570A3 (en) * | 2013-09-11 | 2015-05-07 | Indiana University Research And Technology Corporation | Covalently-grafted polyaniline on graphene oxide for supercapacitors |
| CN104672481A (en) * | 2015-02-13 | 2015-06-03 | 复旦大学 | Metal-organic framework (MOF) modified graphene/polymer hybrid proton exchange membrane and preparation method thereof |
-
2016
- 2016-12-14 CN CN201611155939.0A patent/CN106674563A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015038570A3 (en) * | 2013-09-11 | 2015-05-07 | Indiana University Research And Technology Corporation | Covalently-grafted polyaniline on graphene oxide for supercapacitors |
| CN103897093A (en) * | 2014-04-04 | 2014-07-02 | 武汉理工大学 | Graphene/polymer composite hydrogel thin film and preparation method thereof |
| CN104672481A (en) * | 2015-02-13 | 2015-06-03 | 复旦大学 | Metal-organic framework (MOF) modified graphene/polymer hybrid proton exchange membrane and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110157016A (en) * | 2019-06-10 | 2019-08-23 | 浙江鹏孚隆科技股份有限公司 | A kind of preparation method of polyether-ether-ketone aqueous dispersion liquid |
| CN111925544A (en) * | 2020-07-16 | 2020-11-13 | 江苏科润膜材料有限公司 | High-strength water-retention perfluorinated sulfonic acid proton exchange membrane, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Duan et al. | Enhancing proton conductivity and methanol resistance of SPAEK membrane by incorporating MOF with flexible alkyl sulfonic acid for DMFC | |
| Yu et al. | CNT@ polydopamine embedded mixed matrix membranes for high-rate and long-life vanadium flow batteries | |
| CN102146204B (en) | Acid and alkali crosslinking proton exchange membrane and preparation thereof | |
| CN105778133A (en) | Carbon nanotube/graphene oxide nanoribbon-polymer hybrid proton exchange membrane and preparation method thereof | |
| CN110256913A (en) | A kind of preparation method of antioxidant, water-retaining agent, mixture, denatured fuel cell membrane-electrode | |
| CN106046404B (en) | NafionTMModifiedTwo-dimensional layered material nanosheet-polymer hybrid proton exchange membrane and preparation method thereof | |
| Xu et al. | Graphene quantum dot reinforced hyperbranched polyamide proton exchange membrane for direct methanol fuel cell | |
| TW200843168A (en) | Catalyst layer and process for preparation thereof, and membrane electrode assembly and polymer electrolyte fuel cell using the catalyst layer | |
| CN102838777B (en) | Recovery method of sulfonated polyether ether ketone (SPEEK) / polyaniline (PANI) / propylene glycol monomethyl acetate (PMA) composite proton exchange membrane | |
| Yin et al. | Improved proton conduction of sulfonated poly (ether ether ketone) membrane by sulfonated covalent organic framework nanosheets | |
| CN106158405A (en) | A kind of nickel hydroxide/graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor | |
| WO2016124052A1 (en) | Proton exchange membrane for fuel cells and preparation method therefor | |
| Gao et al. | Carbon nanotubes reinforced proton exchange membranes in fuel cells: An overview | |
| CN103012824A (en) | Graphene oxide-polymer hybrid proton exchange membrane and preparation method thereof | |
| CN106532091B (en) | NafionTMThe carbon quantum dot of modification-polymer hybrid proton exchange membrane and preparation method thereof | |
| CN103435828A (en) | Sulfonated graphene oxide-silicon dioxide compound/polymer hybridization proton exchange membrane and preparation method thereof | |
| CN105085913A (en) | Preparation method of sulfonated polyimide (SPI) proton conducting membrane containing branched structure | |
| WO2023197787A1 (en) | Conductive polyaniline/graphene oxide-modified nafion composite proton exchange membrane and use thereof | |
| CN102895997A (en) | Preparation method for direct methanol fuel cell supported Pt-based anode catalyst | |
| CN113527684B (en) | Oxygen reduction catalytic layer based on grafted polybenzimidazole as proton conductor and preparation method thereof | |
| Liu et al. | Revisiting Nafion membranes by introducing ammoniated polymer with norbornene to improve fuel cell performance | |
| CN106674563A (en) | High-performance and light-reduced graphene oxide composite proton exchange membrane and preparation method thereof | |
| Soleimani et al. | Enhanced performance of nanocomposite membrane developed on sulfonated poly (1, 4-phenylene ether-ether-sulfone) with zeolite imidazole frameworks for fuel cell application | |
| Ye et al. | Simple acid etched graphene oxide constructing high-performance sandwich structural hybrid membrane for redox flow battery | |
| Yan et al. | MXene: A two-dimensional nanomaterial for enhancing start-up performance of high temperature proton exchange membranes |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170517 |