CN105778133A - Carbon nanotube/graphene oxide nanoribbon-polymer hybrid proton exchange membrane and preparation method thereof - Google Patents
Carbon nanotube/graphene oxide nanoribbon-polymer hybrid proton exchange membrane and preparation method thereof Download PDFInfo
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- 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
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
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- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2327/00—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 a halogen; Derivatives of such polymers
- C08J2327/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention belongs to the technical field of membranes and particularly relates to a carbon nanotube/graphene oxide nanoribbon-polymer hybrid proton exchange membrane and a preparation method thereof. The proton exchange membrane is prepared by: preparing multi-wall carbon nanotubes into carbon nanotube/graphene oxide nanoribbon composite; blending the carbon nanotube/graphene oxide nanoribbon composite with a polymer solution. The proton exchange membrane prepared herein is introduced with one-dimensional and two-dimensional composite (carbon nanotube/graphene oxide nanoribbons) and thereby has good dispersity and has proton conductivity greatly improved as compared to that of pure-polymer proton exchange membranes and multiply improved particularly in high-temperature low-humidity environment; meanwhile, the invention is low in production cost, easy for batch large-scale production and has good industrial production basis and promising application prospect.
Description
Technical field
The invention belongs to technical field of membrane, be specifically related to a kind of CNT/stannic oxide/graphene nano band-polymer hybrid PEM and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is a kind of without burning, and the chemical energy in fuel and oxidant is directly changed into the TRT of electric energy in electrochemical reaction mode.Proton Exchange Membrane Fuel Cells illustrates wide market prospects as a kind of cleaning, efficient, safe green energy resource, gets the attention.As the crucial composition PEM of fuel cell, its performance quality significantly affects the service behaviour of fuel cell, and migration and conveying that it is proton provide passage, and its combination property plays vital effect for developing high performance fuel cell.But, (generally referring to more than 100 DEG C) under low humidity and/or higher temperature, PEM causes making its proton conduction property drastically decline because of violent dehydration, and the problem such as high methanol permeability all significantly limit its actual application value in addition.In PEM matrix, add some nano inoganic particles, strengthen the hydrophily of film, build the proton nanometer transmission channel in film thus improve it at low humidity and/or high temperature proton conductivity at present, the proton conductivity of raising film.
Carbon nanomaterial is the abundantest in terms of pattern, there is one-dimensional CNT, the Graphene (graphene oxide) of two dimension and compound particle etc. thereof, this be to solve to reduce the difficult problem of methanol permeability while lifting proton exchange polymer membrane proton conductivity to provide the approach of solution.CNT contributes to induced polymer membrane matrix and is internally formed more continuous print proton transmitting channel, it is also possible to suppress methanol crossover to a certain extent；And oxygen-containing functional group abundant on two dimensional oxidation Graphene is conducive to promoting the hydrophilicity of film, its two-dimensional structure is also beneficial to stop methyl alcohol infiltration in film simultaneously.
At present mostly the preparation method of carbon nanomaterial-polymer hybrid PEM is to use and be blended-is cast into embrane method, the carbon nanomaterial (dispersion liquid) that will prepare joins in polymer solution, treat it be uniformly dispersed after in particular mold casting film.The method is simple to operate with it and the advantage such as is easily controlled, and becomes present stage and is widely used in preparing the Main Means of this type of hybrid inorganic-organic PEM.
" nano science and nanometer technology " (Journal
Of Nanoscience and Nanotechnology, 2013,13(11): 7424-7429.) report by multi-walled carbon nano-tubes and NafionTMAdd surfactant when (perfluorinated sulfonic resin) is blended, effectively inhibit multi-walled carbon nano-tubes at NafionTMIn agglomeration, successfully obtained the hybrid proton exchange membrane of favorable dispersibility.CNT is respectively 1 wt% and 0.1 0.5 wt% with the addition of surfactant.The methanol permeability of this hybrid proton exchange membrane is far below pure NafionTMFilm, proton conductivity then with pure NafionFilm is suitable.
" physical chemistry C " (Journal of Physical Chemistry C, 2011,115 (42): 20774-20781) report the silane coupler modified graphene oxide utilized containing sulfydryl, then after hydrogen peroxide oxidation, obtain sulfoxidation Graphene, subsequently with NafionTMFilm forming is blended.Under conditions of 120 DEG C of 25 RH%, the proton conductivity of hybrid proton exchange membrane and the purer Nafion of monocell performanceTMFilm promotes 4 times.
" membrane science " (Journal of
Membrane Science, 2014,458:128-135.) it is prepared for sulfonated polyether-ether-ketone-graphene oxide-Nafion by same methodTMHybrid proton exchange membrane.When sulfonated polyether-ether-ketone mass fraction is 1 wt%, and the mass fraction of graphene oxide is 0.75
During wt%, the proton conductivity of hybridized film is 322.2 mS cm-1, monocell density is 621.2 mW cm-2, voltage be current density during 0.4 V be 1496 mA cm-2。
CNT or graphene oxide are scattered in polymeric matrix by above-mentioned technique by the method being blended, improve the proton conductivity of PEM or reduce methanol permeability, but the carbon nanomaterial-polymer film of single structure does not has can promote both performances the most simultaneously, it is restricted so that film properties promotes optimization.
Summary of the invention
CNT/stannic oxide/graphene nano band-polymer hybrid PEM that it is an object of the invention to provide a kind of excellent performance and preparation method thereof.
The preparation method of CNT/stannic oxide/graphene nano band polymer hybrid PEM that the present invention provides, concretely comprises the following steps:
(1) preparation of CNT/stannic oxide/graphene nano band: multi-walled carbon nano-tubes is scattered in sulfuric acid, stirring 0.1 ~ 4 h, add phosphoric acid, stirring 5 ~ 120 min, it is warming up to 50 ~ 90 DEG C simultaneously, add potassium permanganate with the speed of 0.01 ~ 0.1 g/h, at a temperature of 50 ~ 90 DEG C, react 0.5 ~ 10 h；Then it is cooled to room temperature, reactant liquor is slowly added in the hydrogen peroxide solution of 0 DEG C of 0.5 ~ 5 wt% concentration；Centrifugation, washes with water, after dialysing one week, lyophilized；
(2) preparation of CNT/stannic oxide/graphene nano band-polymer hybrid PEM: a certain amount of CNT/stannic oxide/graphene nano band is added in polymer solution, ultrasonic 0.5 ~ 24 h, obtain dispersion liquid, stand 5 ~ 240 min；It is subsequently poured into film tool, slowly heats up, be dried, remove solvent, film forming；After being removed from the molds by film, successively by hydrogen peroxide solution and acid soak, obtain ultrasonic 0.5 ~ 24 h ,-polymer hybrid PEM.
In the present invention, mixed solution film forming procedure in film has is carried out in vacuum drying oven, i.e. the film filling mixed solution is had and is placed in vacuum drying oven, from the beginning of 65-75 DEG C, is to slowly warm up to 115-125 DEG C, is dried, to remove solvent；Vacuumize, and vacuum drying oven temperature is scheduled on 115-125 DEG C of holding 15-18 h.
In the present invention, described multi-walled carbon nano-tubes is scattered in sulfuric acid, and the concentration of multi-walled carbon nano-tubes is 0.01 ~ 10 mg/ml.
In the present invention, described addition phosphoric acid, phosphoric acid and sulfuric acid volume ratio are 0.05 ~ 0.5.
In the present invention, described addition potassium permanganate, the concentration of potassium permanganate is 0.5 ~ 10 mg/mL.
In the present invention, in the hydrogen peroxide solution of described 0 DEG C of 0.5 ~ 5 wt% concentration of addition, hydrogen peroxide solution is 0.05 ~ 0.5 with the volume ratio of reactant liquor.
In the present invention, described polymer solution is the homogeneous phase solution of perfluorinated sulfonic resin, sulfonated polyether-ether-ketone, sulfonate polybenzimidazole or sulfonated polyimide.
In the present invention, the described heating rate slowly heated up is less than 0.5 DEG C/min.Generally 0.1-0.5 DEG C/min.
In the present invention, described through hydrogen peroxide solution and acid soak, the concentration of hydrogen peroxide is 1 ~ 10 wt%, and acid is the one in the hydrochloric acid of 1 ~ 4 mol/L, sulfuric acid and phosphoric acid, or several mixtures.
CNT prepared by the present invention/stannic oxide/graphene nano band polymer hybrid PEM, introduces one-dimensional/Two-dimensional Composites (CNT/stannic oxide/graphene nano band), favorable dispersibility in PEM.
Compared with traditional handicraft, the present invention first passes through CNT/stannic oxide/graphene nano band compound that the method for in-situ chemical cutting is prepared for having one-dimensional/two dimension composite construction.CNT/stannic oxide/graphene nano band the compound obtained by the method is had stronger π-π and interacts, and CNT is high with the size matching degree of stannic oxide/graphene nano band, this all ensure that CNT/stannic oxide/graphene nano band compound in conjunction with the advantage of a peacekeeping Two-dimensional Carbon nano material, can improve the combination property of hybrid proton exchange membrane.Subsequently, by obtained CNT/stannic oxide/graphene nano band compound and polymer solution blend, hybrid proton exchange membrane is prepared.The synergy of CNT/stannic oxide/graphene nano band can induce the ion cluster in PEM matrix to build long-range proton transport nanochannel, so that the proton conductivity that the hybrid proton exchange membrane of gained is under high temperature low humidity conditions promotes notable.Additionally, the composite construction of one-dimensional/two dimension makes methanol crossover passage tortuosity increase thus inhibits the methanol crossover phenomenon of PEM.Proton conductivity relatively straight polymer PEM thereby through the CNT obtained by this technique/stannic oxide/graphene nano band-polymer hybrid PEM is obviously improved, especially increase exponentially in the environment of high temperature and/or low humidity, methanol permeability has the decline of an order of magnitude simultaneously, has finally given high performance inorganic hybridization PEM.
Additionally, production cost of the present invention is relatively low, it is easy to mass, large-scale production, there is the application prospect that good industrialized production is basic and wide.
Detailed description of the invention
Further describe preparation and the proton conduction property thereof of CNT of the present invention/stannic oxide/graphene nano band polymer hybrid PEM by the following examples.But, this embodiment is merely possible to provide explanation rather than limit the present invention.
Embodiment 1:
(1) preparation of CNT/stannic oxide/graphene nano band: 0.1 g multi-walled carbon nano-tubes is scattered in 35 ml sulfuric acid, stirs 1.5 h；Add phosphoric acid 5 mL, stir 20 min, be warming up to 70 DEG C simultaneously, add potassium permanganate 0.2 g with the speed of 0.1 g/h, at a temperature of 70 DEG C, react 2 h；Then it is cooled to room temperature, reactant liquor is slowly added in the hydrogen peroxide solution of 100 0 DEG C of 3wt% concentration of mL；Centrifugation, washes with water, after dialysing one week, lyophilized, obtains CNT/stannic oxide/graphene nano band compound；
(2) preparation of CNT/stannic oxide/graphene nano band-polymer hybrid PEM: 1 mg CNT/stannic oxide/graphene nano band is added the commercially available Nafion of 4 mlTMSolution, ultrasonic 20 min；Gained mixed liquor is added after rotation is evaporated off major part solvent 4 ml DMFs, and continues rotation steaming 20min；After standing 1.5h, by above-mentioned NafionTMSolution is poured in the mould of 2cm × 5cm size, is placed in vacuum drying oven, is to slowly warm up to 120 DEG C to remove solvent from 70 DEG C of beginnings after 2 h；Vacuumize and this vacuum drying oven temperature is scheduled on 120 DEG C and keeps 16 h, then film is removed from the molds, by this film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, subsequently with 1 M H2SO4At 80 DEG C, through 1 h, film is converted into H+Type, the most i.e. can get CNT/stannic oxide/graphene nano band NafionTMBase hybrid proton exchange membrane.
The proton conduction property of this PEM is tested in the case of " 100/120 DEG C of-40 RH% humidity ".
It can thus be seen that the CNT/stannic oxide/graphene nano band Nafion prepared by new technologyTMBase hybrid proton exchange membrane proton conductivity under high temperature low humidity conditions, compared to pure NafionTMFilm, is greatly enhanced.
The methanol permeability of this PEM is tested in the case of " 40 DEG C ".
It can thus be seen that the CNT/stannic oxide/graphene nano band Nafion prepared by new technologyTMThe methanol permeability of base hybrid proton exchange membrane, compared to pure NafionTMFilm, has greatly reduction.
Embodiment 2:
(1) preparation of CNT/stannic oxide/graphene nano band: 0.1 g multi-walled carbon nano-tubes is scattered in 35 ml sulfuric acid, stirs 1.5 h；Add phosphoric acid 5 mL, stir 20 min, be warming up to 70 DEG C simultaneously, add potassium permanganate 0.1 g with the speed of 0.1 g/h, at a temperature of 70 DEG C, react 2 h；Then it is cooled to room temperature, reactant liquor is slowly added in the hydrogen peroxide solution of 100 0 DEG C of 3wt% concentration of mL；Centrifugation, washes with water, after dialysing one week, lyophilized, obtains CNT/stannic oxide/graphene nano band compound；
(2) preparation of CNT/stannic oxide/graphene nano band-polymer hybrid PEM: 1 mg CNT/stannic oxide/graphene nano band is added the commercially available Nafion of 4 mlTMSolution, ultrasonic 20 min；Gained mixed liquor is added after rotation is evaporated off major part solvent 4 ml DMFs, and continues rotation steaming 20min；After standing 1.5h, by above-mentioned NafionTMSolution is poured in the mould of 2cm × 5cm size, is placed in vacuum drying oven, is to slowly warm up to 120 DEG C to remove solvent from 70 DEG C of beginnings after 2 h；Vacuumize and this vacuum drying oven temperature is scheduled on 120 DEG C and keeps 16 h, then film is removed from the molds, by this film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, subsequently with 1 M H2SO4At 80 DEG C, through 1 h, film is converted into H+Type, the most i.e. can get CNT/stannic oxide/graphene nano band NafionTMBase hybrid proton exchange membrane.
The proton conduction property of this PEM is tested in the case of " 100/120 DEG C of-40 RH% humidity ".
It can thus be seen that the CNT/stannic oxide/graphene nano band Nafion prepared by new technologyTMBase hybrid proton exchange membrane proton conductivity under high temperature low humidity conditions, compared to pure NafionTMFilm, is greatly enhanced.
The methanol permeability of this PEM is tested in the case of " 40 DEG C ".
It can thus be seen that the CNT/stannic oxide/graphene nano band Nafion prepared by new technologyTMThe methanol permeability of base hybrid proton exchange membrane, compared to pure NafionTMFilm, greatly reduces.
Embodiment 3:
(1) preparation of CNT/stannic oxide/graphene nano band: 0.1 g multi-walled carbon nano-tubes is scattered in 35 ml sulfuric acid, stirs 1.5 h；Add phosphoric acid 5 mL, stir 20 min, be warming up to 70 DEG C simultaneously, add potassium permanganate 0.3 g with the speed of 0.1 g/h, at a temperature of 70 DEG C, react 3 h；Then it is cooled to room temperature, reactant liquor is slowly added in the hydrogen peroxide solution of 100 0 DEG C of 3wt% concentration of mL；Centrifugation, washes with water, after dialysing one week, lyophilized, obtains CNT/stannic oxide/graphene nano band compound；
(2) preparation of CNT/stannic oxide/graphene nano band-polymer hybrid PEM: 1 mg CNT/stannic oxide/graphene nano band is added the commercially available Nafion of 4 mlTMSolution, ultrasonic 20 min；Gained mixed liquor is added after rotation is evaporated off major part solvent 4 ml DMFs, and continues rotation steaming 20min；After standing 1.5h, by above-mentioned NafionTMSolution is poured in the mould of 2cm × 5cm size, is placed in vacuum drying oven, is to slowly warm up to 120 DEG C to remove solvent from 70 DEG C of beginnings after 2 h；Vacuumize and this vacuum drying oven temperature is scheduled on 120 DEG C and keeps 16 h, then film is removed from the molds, by this film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, subsequently with 1 M H2SO4At 80 DEG C, through 1 h, film is converted into H+Type, the most i.e. can get CNT/stannic oxide/graphene nano band NafionTMBase hybrid proton exchange membrane.
Embodiment 4:
(1) preparation of CNT/stannic oxide/graphene nano band: 0.1 g multi-walled carbon nano-tubes is scattered in 35 ml sulfuric acid, stirs 1.5 h；Add phosphoric acid 5 mL, stir 20 min, be warming up to 70 DEG C simultaneously, add potassium permanganate 0.2 g with the speed of 0.1 g/h, at a temperature of 70 DEG C, react 2 h；Then it is cooled to room temperature, reactant liquor is slowly added in the hydrogen peroxide solution of 100 0 DEG C of 3wt% concentration of mL；Centrifugation, washes with water, after dialysing one week, lyophilized, obtains CNT/stannic oxide/graphene nano band compound；
(2) preparation of CNT/stannic oxide/graphene nano band-polymer hybrid PEM: 0.5 mg CNT/stannic oxide/graphene nano band is added the commercially available Nafion of 4 mlTMSolution, ultrasonic 20 min；Gained mixed liquor is added after rotation is evaporated off major part solvent 4 ml DMFs, and continues rotation steaming 20min；After standing 1.5 h, by above-mentioned NafionTMSolution is poured in the mould of 2cm × 5cm size, is placed in vacuum drying oven, is to slowly warm up to 120 DEG C to remove solvent from 70 DEG C of beginnings after 2 h；Vacuumize and this vacuum drying oven temperature is scheduled on 120 DEG C and keeps 16 h, then film is removed from the molds, by this film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, subsequently with 1 M H2SO4At 80 DEG C, through 1 h, film is converted into H+Type, the most i.e. can get CNT/stannic oxide/graphene nano band NafionTMBase hybrid proton exchange membrane.
Embodiment 5:
(1) preparation of CNT/stannic oxide/graphene nano band: 0.1 g multi-walled carbon nano-tubes is scattered in 35 ml sulfuric acid, stirs 1.5 h；Add phosphoric acid 5 mL, stir 20 min, be warming up to 70 DEG C simultaneously, add potassium permanganate 0.2 g with the speed of 0.1 g/h, at a temperature of 70 DEG C, react 2 h；Then it is cooled to room temperature, reactant liquor is slowly added in the hydrogen peroxide solution of 100 0 DEG C of 3wt% concentration of mL；Centrifugation, washes with water, after dialysing one week, lyophilized, obtains CNT/stannic oxide/graphene nano band compound；
(2) preparation of CNT/stannic oxide/graphene nano band-polymer hybrid PEM: 2 mg CNTs/stannic oxide/graphene nano band is added the commercially available Nafion of 4 mlTMSolution, ultrasonic 20 min；Gained mixed liquor is added after rotation is evaporated off major part solvent 4 ml DMFs, and continues rotation steaming 20min；After standing 1.5 h, by above-mentioned NafionTMSolution is poured in the mould of 2cm × 5cm size, is placed in vacuum drying oven, is to slowly warm up to 120 DEG C to remove solvent from 70 DEG C of beginnings after 2 h；Vacuumize and this vacuum drying oven temperature is scheduled on 120 DEG C and keeps 16 h, then film is removed from the molds, by this film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, subsequently with 1 M H2SO4At 80 DEG C, through 1 h, film is converted into H+Type, the most i.e. can get CNT/stannic oxide/graphene nano band NafionTMBase hybrid proton exchange membrane.
Embodiment 6:
(1) preparation of CNT/stannic oxide/graphene nano band: 0.1 g multi-walled carbon nano-tubes is scattered in 35 ml sulfuric acid, stirs 1.5 h；Add phosphoric acid 5 mL, stir 20 min, be warming up to 70 DEG C simultaneously, add potassium permanganate 0.2 g with the speed of 0.1 g/h, at a temperature of 70 DEG C, react 2 h；Then it is cooled to room temperature, reactant liquor is slowly added in the hydrogen peroxide solution of 100 0 DEG C of 3wt% concentration of mL；Centrifugation, washes with water, after dialysing one week, lyophilized, obtains CNT/stannic oxide/graphene nano band compound；
(2) preparation of CNT/stannic oxide/graphene nano band-polymer hybrid PEM: 4 mg CNTs/stannic oxide/graphene nano band is added the commercially available Nafion of 4 mlTMSolution, ultrasonic 20 min；Gained mixed liquor is added after rotation is evaporated off major part solvent 4 ml DMFs, and continues rotation steaming 20min；After standing 1.5 h, by above-mentioned NafionTMSolution is poured in the mould of 2cm × 5cm size, is placed in vacuum drying oven, is to slowly warm up to 120 DEG C to remove solvent from 70 DEG C of beginnings after 2 h；Vacuumize and this vacuum drying oven temperature is scheduled on 120 DEG C and keeps 16 h, then film is removed from the molds, by this film first with the H of 3 wt%2O2Solution soaks 2h in 70 DEG C, subsequently with 1 M H2SO4At 80 DEG C, through 1 h, film is converted into H+Type, the most i.e. can get CNT/stannic oxide/graphene nano band NafionTMBase hybrid proton exchange membrane.
Claims (10)
1. the preparation method of CNT/stannic oxide/graphene nano band-polymer hybrid PEM, it is characterised in that concretely comprise the following steps:
(1) preparation of CNT/stannic oxide/graphene nano band: multi-walled carbon nano-tubes is scattered in sulfuric acid, stirring 0.1 ~ 4 h, add phosphoric acid, stirring 5 ~ 120 min, it is warming up to 50 ~ 90 DEG C simultaneously, add potassium permanganate with the speed of 0.01 ~ 0.1 g/h, at a temperature of 50 ~ 90 DEG C, react 0.5 ~ 10 h；Then it is cooled to room temperature, reactant liquor is slowly added in the hydrogen peroxide solution that 0 DEG C of concentration is 0.5 ~ 5 wt%；Centrifugation, washes with water, after dialysis, lyophilized；
(2) preparation of CNT/stannic oxide/graphene nano band-polymer hybrid PEM: CNT/stannic oxide/graphene nano band is added in polymer solution, ultrasonic 0.5 ~ 24 h, obtain dispersion liquid, stand 5 ~ 240 min；It is subsequently poured into mould, slowly heats up, be dried, remove film forming after solvent；Film is removed from the molds, successively by hydrogen peroxide solution and acid soak, i.e. obtains CNT/stannic oxide/graphene nano band-polymer hybrid PEM.
Preparation method the most according to claim 1, it is characterised in that described in step (1), multi-walled carbon nano-tubes is scattered in sulfuric acid, the concentration of multi-walled carbon nano-tubes is 0.01 ~ 10 mg/ml.
Preparation method the most according to claim 1 and 2, it is characterised in that in step (1), phosphoric acid and sulfuric acid volume ratio are 0.05 ~ 0.5.
Preparation method the most according to claim 3, it is characterised in that described in step (1), the concentration of potassium permanganate is 0.5 ~ 10 mg/mL.
5. according to the preparation method described in claim 1,2 or 4, it is characterised in that hydrogen peroxide solution described in step (1) is 0.05 ~ 0.5 with the volume ratio of reactant liquor.
Preparation method the most according to claim 5, it is characterised in that described in step (2), polymer solution is the one in perfluorinated sulfonic resin, sulfonated polyether-ether-ketone, sulfonate polybenzimidazole or sulfonated polyimide, or the homogeneous phase solution of several mixing.
7. according to the preparation method described in claim 1,2,4 or 6, it is characterised in that the heating rate slowly heated up described in step (2) is less than 0.5 DEG C/min.
Preparation method the most according to claim 7, it is characterised in that the film forming procedure in film has of mixed solution described in step (2) is carried out in vacuum drying oven, i.e. has the film filling mixed solution and is placed in vacuum drying oven, from the beginning of 65-75 DEG C, it is warming up to 115-125 DEG C, is dried, to remove solvent；Vacuumize, and vacuum drying oven temperature is scheduled on 115-125 DEG C of holding 15-18 h.
9. according to the preparation method described in claim 1,2,4,6 or 8, it is characterised in that described in step (2), the concentration of hydrogen peroxide is 1 ~ 10
Wt%, acid is the one of the hydrochloric acid of 1 ~ 4 mol/L, sulfuric acid or phosphoric acid, or several mixtures.
10. one kind by the preparation-obtained CNT of one of claim 1-9 preparation method/stannic oxide/graphene nano band-polymer hybrid PEM.
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| CN106390748A (en) * | 2016-09-28 | 2017-02-15 | 天津工业大学 | Preparation method of high-throughput and multilayer sandwich type composite nano-filtration membrane |
| CN106450395A (en) * | 2016-12-07 | 2017-02-22 | 黄河科技学院 | Polybenzimidazole-high-conductivity graphene layered composite high-temperature proton exchange membrane with high conductivity and stability and preparation method of polybenzimidazole-high-conductivity graphene layered composite high-temperature proton exchange membrane |
| CN106532091A (en) * | 2016-11-15 | 2017-03-22 | 复旦大学 | NafionTM-modified carbon quantum dot-polymer hybrid proton exchange membrane and preparing method thereof |
| CN106977753A (en) * | 2017-03-28 | 2017-07-25 | 天津大学 | A kind of bionical ultrathin membrane of high intensity solid electrolyte and preparation method thereof |
| CN108134118A (en) * | 2017-12-25 | 2018-06-08 | 宁波卡尔新材料科技有限公司 | A kind of preparation method of triazole graphene modification sulphonation polyphenylene oxide proton membrane and mating film-forming process |
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| CN111193054A (en) * | 2020-01-09 | 2020-05-22 | 安徽师范大学 | Preparation method of proton exchange membrane |
| CN113506904A (en) * | 2021-06-02 | 2021-10-15 | 华南理工大学 | Proton exchange membrane and preparation method and application thereof |
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| CN103012824A (en) * | 2012-12-27 | 2013-04-03 | 复旦大学 | Graphene oxide-polymer hybrid proton exchange membrane and preparation method thereof |
| CN104072979A (en) * | 2014-07-18 | 2014-10-01 | 福州大学 | Oxidized graphene nano-ribbon/polymer composite film and preparation method thereof |
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| CN106390748A (en) * | 2016-09-28 | 2017-02-15 | 天津工业大学 | Preparation method of high-throughput and multilayer sandwich type composite nano-filtration membrane |
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| CN106532091A (en) * | 2016-11-15 | 2017-03-22 | 复旦大学 | NafionTM-modified carbon quantum dot-polymer hybrid proton exchange membrane and preparing method thereof |
| CN106450395A (en) * | 2016-12-07 | 2017-02-22 | 黄河科技学院 | Polybenzimidazole-high-conductivity graphene layered composite high-temperature proton exchange membrane with high conductivity and stability and preparation method of polybenzimidazole-high-conductivity graphene layered composite high-temperature proton exchange membrane |
| CN106977753A (en) * | 2017-03-28 | 2017-07-25 | 天津大学 | A kind of bionical ultrathin membrane of high intensity solid electrolyte and preparation method thereof |
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| CN108878933B (en) * | 2018-06-20 | 2021-01-22 | 湖南国昶能源科技有限公司 | Preparation method of Nafion/lignin composite proton exchange membrane |
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| CN109903998A (en) * | 2019-02-26 | 2019-06-18 | 内蒙古科技大学 | A kind of combination electrode and its preparation method and application |
| CN109824929A (en) * | 2019-03-18 | 2019-05-31 | 山东星火科学技术研究院 | The preparation method of sulfonated polyether-ether-ketone and carbon nano-tube compound film |
| CN111193054A (en) * | 2020-01-09 | 2020-05-22 | 安徽师范大学 | Preparation method of proton exchange membrane |
| CN113506904A (en) * | 2021-06-02 | 2021-10-15 | 华南理工大学 | Proton exchange membrane and preparation method and application thereof |
| CN114634642A (en) * | 2022-02-23 | 2022-06-17 | 华中科技大学 | PCNT (prestressed concrete) and PGO (PGO) synergistically modified polymer hybrid proton exchange membrane and preparation method thereof |
| CN114634642B (en) * | 2022-02-23 | 2023-03-10 | 华中科技大学 | PCNT (prestressed concrete) and PGO (PGO) synergistically modified polymer hybrid proton exchange membrane and preparation method thereof |
| CN115124030A (en) * | 2022-08-02 | 2022-09-30 | 武汉市碳翁科技有限公司 | Method for preparing flexible self-supporting carbon nanotube film on large scale |
| CN115124030B (en) * | 2022-08-02 | 2023-12-22 | 武汉市碳翁科技有限公司 | Method for preparing flexible self-supporting carbon nano tube film on large scale |
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