CN106450395A - 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 - Google Patents
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 Download PDFInfo
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- CN106450395A CN106450395A CN201611115336.8A CN201611115336A CN106450395A CN 106450395 A CN106450395 A CN 106450395A CN 201611115336 A CN201611115336 A CN 201611115336A CN 106450395 A CN106450395 A CN 106450395A
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- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a polybenzimidazole-high-conductivity graphene layered composite high-temperature proton exchange membrane with high conductivity and stability and a preparation method of the polybenzimidazole-high-conductivity graphene layered composite high-temperature proton exchange membrane. The layered composite high-temperature proton exchange membrane is prepared by the following steps: taking polybenzimidazole as polymer matrix, and uniformly spraying graphene/polybenzimidazole composite layers with high phosphoric acid protection ability on two sides of the matrix respectively to form the dense layered composite membrane. The polybenzimidazole-high-conductivity graphene layered composite high-temperature proton exchange membrane can greatly solve the problem of phosphoric acid loss of a polybenzimidazole/phosphoric acid membrane, improve the conductivity stability of the membrane; has the advantages of better proton conductive capacity and low permeability under the condition without humidification and can be used as a proton exchange membrane in a high-temperature proton exchange membrane fuel cell, a direct alcohol fuel cell, an electrochemical sensor or other electrochemical devices.
Description
Technical field
The invention belongs to fuel cell material technical field is and in particular to have polyphenyl the miaow of high conductivity stability
Azoles-high connductivity Graphene combined high temperature PEM and preparation method layer by layer.
Background technology
Proton Exchange Membrane Fuel Cells（PEMFC）It is a kind of efficient, cleaning, eco-friendly TRT, be electronic vapour
The ideal power source of car, can act also as disperseing the Military Powers or compact power etc. such as power station, submarine and spacecraft, has very
Wide application prospect.But now widely used be perfluor type sulfonic acid membrane cell with Nafion as representative, but
The proton conducting ability of this kind of PEM is affected greatly by water content in film and temperature, and alcohol-rejecting ability is poor, the work of PEMFC
Make temperature and not can exceed that 80 DEG C.Because PEMFC is limited by operating temperature so that it faces CO toleration in practical application
The problems such as difference, hydro-thermal difficult management of system.Therefore PEMFC running temperature is brought up to more than 100 DEG C, just can be efficiently against
The problems referred to above of traditional Nafion base PEMFC, the fuel cell of this type（FC）Normally referred to as high temperature proton exchange film combustion
Material battery（HT-PEMFC）, it is an important developing direction of PEMFC technology.
HT-PEMFC system has the following advantages：1）Electrochemical reaction speed improves, and effectively reduces electrochemical cathode polarization
Overpotential is it is allowed to reduce catalyst load amount it is allowed to use non-platinum catalyst；2）The humidification requirements of reacting gas are reduced；3）Electricity
Pool inner water simplifies hydro-thermal management with gas phase presence；Additionally, HT-PEMFC simplifies FC cooling system to a certain extent.In view of
The tempting development prospect of HT-PEMFC, has extensively carried out the development of HT-PEMFC critical material both at home and abroad, hands over including high temperature proton
Change film, catalyst and carrier etc., and achieve preferable PRELIMINARY RESULTS, wherein high temperature proton exchange film be research focus it
One.
Research for HT-PEMFC PEM is concentrated mainly on polybenzimidazoles at present（PBI）On, it is in 1959
Year is reported in United States Patent (USP) first, and PBI film product is introduced to the market by Hoechst Celanese company of the U.S. within 1988.As
The present, PBI as the most outstanding polymer-based material in engineering thermoplasties, in the high temperature proton exchange as HT-PEMFC
Film aspect shows huge effectiveness and feasibility.But PBI type membrane material is in hot operation（T≥150℃）, meeting can not
Degrade with avoiding.Furthermore, phosphoric acid losing issue is also one of bottleneck of impact PBI type high temp film commercial applications, for this reason,
The conduction of phosphoric acid can be replaced by the ionic liquid of other conducting hydrogen ions, thus solving the problems, such as that phosphoric acid runs off.
In sum, obtain at present such PEM polymeric substrates easily be subject to free radical attack and degrade, phosphoric acid
The difficult problem such as serious that runs off restricts its business-like application, by, preparing in film using the composite bed with absorption phosphoric acid ability
Composite membrane layer by layer, can effectively avoid the losing issue of phosphoric acid, the service life of lifting film, and improve the dimensionally stable of film
Property.
Content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide having polyphenyl the miaow of high conductivity stability
Azoles-high connductivity Graphene combined high temperature PEM and preparation method layer by layer, by with polybenzimidazoles as polymeric substrates,
There is in one layer of substrate both sides even application the Graphene/polybenzimidazoles composite bed of highly protective phosphoric acid ability, formed fine and close
Composite membrane layer by layer.The method can be greatly decreased the phosphoric acid losing issue of polybenzimidazoles/phosphoric acid class film, effectively improves film
Stable conductivity, this film has preferable Proton conducting ability under not humidification conditions, and has the advantages that low-permeable.
To achieve these goals, the technical solution used in the present invention is：
There is the preparation side of the polybenzimidazoles-high connductivity Graphene of high conductivity stability combined high temperature PEM layer by layer
Method, comprises the following steps：
（1）0.2 ~ 1 g polybenzimidazoles is dissolved in 10 ~ 20 mL high boiling solvents, after dissolving is stirred at room temperature, pours glass into
In casting film plate, 80 ~ 120 DEG C of drying 24 h, 2 hs are dried at 150 DEG C, obtain polybenzimidazole polymer substrate, the thickness of this film
Spend for 10 ~ 100 μm；
（2）By the mixed solution of high connductivity Graphene/polybenzimidazoles, ultrasonic 10 ~ 60 min, using spraying process, by polyphenyl simultaneously
Imidazoles polymeric substrates both sides even application one floor height conductive graphene/polybenzimidazoles composite bed, the thickness of spraying is 1 ~ 5 μ
m；Spraying temperature is 50 ~ 120 DEG C；The flow velocity of spraying is 0.1 ~ 2 mL/min, and composite membrane is placed in 60 ~ 100 DEG C of vacuum drying
It is dried in case；
（3）To combined high temperature PEM be immersed in 50 ~ 85 wt% phosphoric acid solutions layer by layer, 80 ~ 120 DEG C are soaked 24 ~ 48
Then film is taken out from solution by h, obtains polybenzimidazoles-high connductivity Graphene combined high temperature PEM layer by layer.
Preferably, step（2）Described in the mixed solution of high connductivity Graphene/polybenzimidazoles in, high connductivity graphite
Alkene is 10 with the mass ratio of polybenzimidazoles:1~3:1, solvent is high boiling solvent, by the high boiling solvent of high connductivity Graphene
In, add polybenzimidazoles, dissolve after stirring.
Preferably, described high boiling solvent is N,N-dimethylacetamide or N-Methyl pyrrolidone.Described high boiling point is molten
Agent is DMAC N,N' dimethyl acetamide and/or N-Methyl pyrrolidone.
Polybenzimidazoles-high connductivity the Graphene with high conductivity stability being obtained using above-mentioned preparation method is layer by layer
Combined high temperature PEM.
Polybenzimidazoles-high connductivity Graphene combined high temperature the matter layer by layer with high conductivity stability that the present invention provides
Proton exchange and preparation method, compared with prior art have the advantages that：
1. the present invention is respectively adopted polybenzimidazoles is polymeric substrates, has highly protective in one layer of substrate both sides even application
The Graphene of phosphoric acid ability/polybenzimidazoles composite bed, the composite membrane that the fine and close composite membrane layer by layer of formation is obtained, even structure,
It is applied to anhydrous system, the high temperature proton exchange film fuel cell that 120 ~ 200 DEG C of operating temperature；
2. the present invention adopts the polybenzimidazoles-high connductivity Graphene composite construction layer by layer of high conductivity stability, can be effective
Solve the losing issue of phosphoric acid, and effectively improve proton conductivity and its stable conductivity of composite membrane；
3. polybenzimidazoles-high connductivity Graphene combined high temperature the matter layer by layer with high conductivity stability proposed by the present invention
Proton exchange and preparation method thereof is applied to high temperature proton exchange film fuel cell, direct alcohol fuel cell, electrochemical sensing
Use as PEM in device or other electrochemical appliance.
Brief description
Fig. 1 is polybenzimidazoles-high connductivity Graphene combined high temperature PEM layer by layer that embodiment 1 is obtained, with biography
The conductance profile figure of system polybenzimidazoles composite membrane；
Fig. 2 is polybenzimidazoles-high connductivity Graphene electrical conductivity in combined high temperature PEM layer by layer that embodiment 2 is obtained
Variation diagram with soaking water number of times.
Specific embodiment
Polybenzimidazoles used in example below（PBI, CAS:25928-81-8）Purchased from FuMA-Tech company；N,N-
Dimethyl acetylamide（DMAC, CAS:127-19-5）, N-Methyl pyrrolidone（NMP, CAS:872-50-4）Big purchased from Tianjin
Luxuriant chemical reagents corporation；High connductivity Graphene NMP slurry, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences；Phosphoric acid is purchased
From Shanghai Aladdin biochemical technology limited company.
Embodiment 1
There is the preparation side of the polybenzimidazoles-high connductivity Graphene of high conductivity stability combined high temperature PEM layer by layer
Method, is prepared by following steps：
（1）By in the N-Methyl pyrrolidone solution of high connductivity Graphene, add polybenzimidazoles, dissolve after stirring, Graphene
Mass ratio with polybenzimidazoles is 10:1, the mass fraction of Graphene is 25 wt%；
（2）0.2 g polybenzimidazoles is dissolved in 20 mL N-Methyl pyrrolidone, after dissolving is stirred at room temperature, pours glass into
In casting film plate, 100 DEG C of drying 24 h, 2 hs are dried at 150 DEG C, obtain polybenzimidazole polymer substrate, the thickness of this film is
30 μm；
（3）By the N-Methyl pyrrolidone mixed solution of high connductivity Graphene/polybenzimidazoles, ultrasonic 60 min, using spraying
Method by polybenzimidazole polymer substrate both sides even application one floor height conductive graphene/polybenzimidazoles composite bed, spraying
Thickness is 5 μm；Spraying temperature is 80 DEG C；The flow velocity of spraying is 0.2 mL/min, and composite membrane is placed in 100 DEG C of vacuum drying
It is dried in case；
（4）To combined high temperature PEM be immersed in 85 wt% phosphoric acid solutions layer by layer, 80 DEG C of immersion 48 h, then by film
Take out from solution, obtain polybenzimidazoles-high connductivity Graphene combined high temperature PEM layer by layer.
Polybenzimidazoles-high connductivity Graphene combined high temperature PEM layer by layer that embodiment 1 is obtained, testing conductivity
Variation with temperature figure.By embodiment 1 be obtained polybenzimidazoles-high connductivity Graphene layer by layer combined high temperature PEM and
Its preparation is cut into the rectangular sheet of a size of 40 mm × 10 mm, the polybenzimidazoles-high connductivity graphite then embodiment 1 being obtained
Combined high temperature PEM is placed in electrical conductivity fixture alkene layer by layer, and fixture is put in vacuum drying oven, keeps 3 at 90 DEG C
H, then temperature rise to 170 DEG C from 90 DEG C, every the electrical conductivity of 10 DEG C of test lower films, result is as shown in Figure 1.
It will be seen from figure 1 that polybenzimidazoles-high connductivity Graphene combined high temperature proton friendship layer by layer that embodiment 1 is obtained
Change membrane conductivity at 150 DEG C, anhydrous condition is issued to 46 mS/cm, far above traditional polybenzimidazoles/phosphoric acid composite membrane
Electrical conductivity, electrical conductivity meets the needs of high temperature proton exchange film fuel cell, illustrates that prepared cross linking membrane has higher electricity
Conductance.
Embodiment 2
There is the preparation side of the polybenzimidazoles-high connductivity Graphene of high conductivity stability combined high temperature PEM layer by layer
Method, is prepared by following steps：
（1）By in the N,N-dimethylacetamide solution of high connductivity Graphene, add polybenzimidazoles, dissolve after stirring, graphite
Alkene is 3 with the mass ratio of polybenzimidazoles:1, the mass fraction of Graphene is 25 wt%；
（2）1 g polybenzimidazoles is dissolved in 20 mL N,N-dimethylacetamide, after dissolving is stirred at room temperature, pours glass into
In casting film plate, 80 DEG C of drying 24 h, 2 hs are dried at 150 DEG C, obtain polybenzimidazole polymer substrate, the thickness of this film is
80 μm；
（3）By the N,N-dimethylacetamide mixed solution of high connductivity Graphene/polybenzimidazoles, ultrasonic 60 min, using spray
Coating, polybenzimidazole polymer substrate both sides even application one floor height conductive graphene/polybenzimidazoles composite bed sprays
Thickness be 1 μm；Spraying temperature is 100 DEG C；The flow velocity of spraying is 0.2 mL/min, composite membrane is placed in 100 DEG C of vacuum and does
It is dried in dry case；
（4）To combined high temperature PEM be immersed in 85 wt% phosphoric acid solutions layer by layer, 80 DEG C of immersion 48 h, then by film
Take out from solution, obtain polybenzimidazoles-high connductivity Graphene combined high temperature PEM layer by layer.
Polybenzimidazoles-high connductivity Graphene that the traditional PBI composite membrane of test, embodiment 1 and embodiment 2 are obtained is multiple layer by layer
Close conductivity variations after water immersion for the high temperature proton exchange film, concrete grammar is as follows：By three kinds of films be separately immersed in from
Take out after 5 min in sub- water, test film, in 150 DEG C of electrical conductivity, repeats this step, record electrical conductivity is with the change soaking number of times
Situation.
Figure it is seen that polybenzimidazoles-high connductivity Graphene combined high temperature the proton exchange layer by layer of present invention preparation
Compared with traditional PBI composite membrane, not only electrical conductivity has been lifted film, and stability in water for the electrical conductivity is more prominent, says
The structure of the bright present invention effectively reduces the ion turnover rate of film.
Embodiment 3
There is the preparation side of the polybenzimidazoles-high connductivity Graphene of high conductivity stability combined high temperature PEM layer by layer
Method, is prepared by following steps：
（1）By in the N-Methyl pyrrolidone solution of high connductivity Graphene, add polybenzimidazoles, dissolve after stirring, Graphene
Mass ratio with polybenzimidazoles is 5:1, the mass fraction of Graphene is 25 wt%；
（2）0.8 g polybenzimidazoles is dissolved in 20 mLN- methyl pyrrolidones, after dissolving is stirred at room temperature, pours glass casting into
In lamina membranacea, 120 DEG C of drying 24 h, 2 hs are dried at 150 DEG C, obtain polybenzimidazole polymer substrate, the thickness of this film is 30
μm；
（3）By the N-Methyl pyrrolidone mixed solution of high connductivity Graphene/polybenzimidazoles, ultrasonic 30 min, using spraying
Method, by polybenzimidazole polymer substrate both sides even application one floor height conductive graphene/polybenzimidazoles composite bed, spraying
Thickness is 3 μm；Spraying temperature is 90 DEG C；The flow velocity of spraying is 0.5 mL/min, and composite membrane is placed in 100 DEG C of vacuum drying
It is dried in case；
（4）To combined high temperature PEM be immersed in 85 wt% phosphoric acid solutions layer by layer, 80 DEG C of immersion 48 h, then by film
Take out from solution, obtain polybenzimidazoles-high connductivity Graphene combined high temperature PEM layer by layer.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, ability
Other modifications or equivalent that domain those of ordinary skill is made to technical scheme, without departing from skill of the present invention
The spirit and scope of art scheme, all should cover in the middle of scope of the presently claimed invention.
Claims (4)
1. a kind of polybenzimidazoles-high connductivity Graphene with high conductivity stability combined high temperature PEM layer by layer
Preparation method is it is characterised in that comprise the following steps：
（1）0.2 ~ 1 g polybenzimidazoles is dissolved in 10 ~ 20 mL high boiling solvents, after dissolving is stirred at room temperature, pours glass into
In casting film plate, 80 ~ 120 DEG C of drying 24 h, 2 hs are dried at 150 DEG C, obtain polybenzimidazole polymer substrate, the thickness of this film
Spend for 10 ~ 100 μm；
（2）By the mixed solution of high connductivity Graphene/polybenzimidazoles, ultrasonic 10 ~ 60 min, using spraying process, by polyphenyl simultaneously
Imidazoles polymeric substrates both sides even application one floor height conductive graphene/polybenzimidazoles composite bed, the thickness of spraying is 1 ~ 5 μ
m；Spraying temperature is 50 ~ 120 DEG C；The flow velocity of spraying is 0.1 ~ 2 mL/min, and composite membrane is placed in 60 ~ 100 DEG C of vacuum drying
It is dried in case；
（3）To combined high temperature PEM be immersed in 50 ~ 85 wt% phosphoric acid solutions layer by layer, 80 ~ 120 DEG C are soaked 24 ~ 48
H, then serous coat take out from solution, obtain polybenzimidazoles-high connductivity Graphene combined high temperature PEM layer by layer.
2. the preparation of polybenzimidazoles according to claim 1-high connductivity Graphene combined high temperature PEM layer by layer
Method it is characterised in that：Step（2）Described in the mixed solution of high connductivity Graphene/polybenzimidazoles in, high connductivity graphite
Alkene is 10 with the mass ratio of polybenzimidazoles:1~3:1, solvent is high boiling solvent, by the high boiling solvent of high connductivity Graphene
In, add polybenzimidazoles, dissolve after stirring.
3. the system of the polybenzimidazoles according to claim 1 and 2-high connductivity Graphene combined high temperature PEM layer by layer
Preparation Method it is characterised in that：Described high boiling solvent is DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.
4. a kind of polybenzimidazoles-high connductivity Graphene combined high temperature PEM layer by layer with high conductivity stability,
It is characterized in that：Described polybenzimidazoles-high connductivity Graphene combined high temperature proton friendship layer by layer with high conductivity stability
Changing film is to be prepared by the method described in claims 1 to 3 any one claim.
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| CN109888348A (en) * | 2019-04-10 | 2019-06-14 | 黑龙江大学 | Fuel cell proton membrane material solid super acids/azacyclo- graphene oxide/2,5- polybenzimidazoles preparation method |
| CN110350222A (en) * | 2019-06-11 | 2019-10-18 | 东旭光电科技股份有限公司 | Compound proton exchange membrane and preparation method thereof, compound proton exchange membrane fuel cell |
| CN111048815A (en) * | 2019-12-24 | 2020-04-21 | 中国科学院青岛生物能源与过程研究所 | Modified fuel cell proton exchange membrane and preparation method thereof |
| CN111244475A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | High-temperature proton exchange membrane fuel cell membrane electrode and preparation method and application thereof |
| CN114628690A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Fuel cell gas diffusion layer and preparation method and application thereof |
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| CN114628690A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Fuel cell gas diffusion layer and preparation method and application thereof |
| CN114628690B (en) * | 2020-12-12 | 2024-02-09 | 中国科学院大连化学物理研究所 | Fuel cell gas diffusion layer and preparation method and application thereof |
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Application publication date: 20170222 |