CN106784942A - A kind of high intensity, the high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell - Google Patents
A kind of high intensity, the high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell Download PDFInfo
- Publication number
- CN106784942A CN106784942A CN201710057801.5A CN201710057801A CN106784942A CN 106784942 A CN106784942 A CN 106784942A CN 201710057801 A CN201710057801 A CN 201710057801A CN 106784942 A CN106784942 A CN 106784942A
- Authority
- CN
- China
- Prior art keywords
- proton
- composite membrane
- hours
- dried
- temperature
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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]
-
- 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
Abstract
A kind of high intensity, the high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell, belong to high temperature proton-conductive films technical field.It is that proton conduction enhancer PIMs is added in casting film agent, adds polybenzimidazoles, and casting solution is obtained after being well mixed；Then casting solution is poured on clean glass plate, dried 10~15 hours at 80~90 DEG C, dried 10~15 hours at 100~110 DEG C, dried 10~15 hours at 120~130 DEG C, it is baking 20~30 hours under the conditions of 0.1~0.3MPa then at 120~130 DEG C, vacuum, the composite membrane is obtained after being cooled to room temperature, can further carry out phosphate-doped, obtain phosphate-doped composite membrane.Composite membrane is applied to high-temperature fuel cell field by the present invention, due to the introducing of proton conduction enhancer, the mechanical property of polybenzimidazoles is enhanced, while its proton conductivity is greatly improved and then the performance of battery is increased substantially, with extremely wide application prospect.
Description
Technical field
The invention belongs to high temperature proton-conductive films technical field, and in particular to a kind of high intensity, the height of high proton conductivity
Warm proton conductive composite membrane and its application in high-temperature fuel cell.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of high energy source device of environment-friendly, transformation efficiency, is not
Carry out preferable energy sources.With being on the rise for China's atmosphere polluting problem, the air pollution that combustion of fossil fuel is brought
Problem is also outstanding day by day.Control atmosphere pollution is more and more important, and difficulty of governance is also increasing.It is not only due to air dirty
The improvement of dye is relatively difficult, even more because the energy resource structure of China is based on fossil fuel, if reductionization rashly in the short time
The usage amount of stone fuel, the stabilization of energy security or even national society to China can all cause very serious influence.Change
Energy resource structure, an extremely urgent demand is become using the energy for more cleaning.Therefore, Proton Exchange Membrane Fuel Cells tool
There is very wide application prospect.As a example by perfluor type sulfonic acid membrane cell with now widely used Nafion as representative,
Most operation temperature is less than 80 DEG C so that fuel cell faces CO poor resistances in practical application, the hydro-thermal management of system is stranded
Difficult the problems such as.Therefore high temperature proton exchange film fuel cell (HT-PEMFC) just arises at the historic moment, and as fuel cell technology one
Individual important developing direction.
High temperature proton exchange film fuel cell has the following advantages that：1) chemical reaction rate is improved, making for catalyst is reduced
Consumption；2) because its operating temperature is more than 120 DEG C, CO will not be generated, so as to solve the problems, such as that electrode material CO is poisoned；3) change
The water management of kind system, reduces mass transfer polarization, and flow Field Design can also significantly be simplified, 4) heat pipe of system is improved
Reason, can use the automobile-used cooling system of existing I. C. engine steam, and the weight and volume of cooling system is greatly lowered, and improve system
Weight and volumetric specific power density.5) because its operating temperature is higher, reactivity is very big, and high-temperature fuel cell is relative to low
Warm battery, the catalyst activity of demand is relatively low, and the selection space of catalyst is no longer confined to noble metal field, reduces
Production cost prospect is more considerable.
Polybenzimidazoles is the extremely excellent fire resistant resin of a class performance.The composite membrane of polybenzimidazoles doping phosphoric acid by
In its high proton conductivity and outstanding heat endurance, the focus as high temperature proton exchange film research.Polyphenyl and miaow
There is the bonding action of soda acid complexing between the acid hydroxy group in basic amine group and phosphoric acid molecules on azoles molecule so that polyphenyl is simultaneously
Imidazoles can adsorb phosphoric acid, and the hydrogen bond network that is formed in film by phosphoric acid and imidazole group transmits proton, so as to break away from
Dependence of the proton transfer to water, improves the operating temperature of fuel cell.
The method of conventional doping phosphoric acid is mainly to be immersed in the film of polyphenyl imidazoles in phosphoric acid is inhaled at a certain temperature
It is attached.Because the free volume between polybenzimidazoles strand is limited, the adsorbance of phosphoric acid is turned into and limits its proton-conducting
One bottleneck of energy.The adsorbance of phosphoric acid can be increased by introducing pore structure in polybenzimidazole membrane.Conventional pore-forming side
Such as using pore creating material, (conventional perforating agent has repefral, diethyl phthalate, the fourth of phthalic acid two to method
Ester, diphenyl phthalate etc.) porous polybenzimidazole membrane is prepared, its advantage is can to produce substantial amounts of pore structure, rapidly
Improve adsorption capacity of the polybenzimidazoles to phosphoric acid；However, the space of this method manufacture is often very big so that doping enters benzene
And the phosphoric acid in imidazoles hole is lost in rapidly, high proton conductivity cannot long-time stable keep, conductivity declines also pole during high temperature
For serious.Therefore pore structure is introduced to increase the doping and proton conductivity of phosphoric acid be not an effective method.
It is a kind of polymer polymer with microcellular structure in itself from tool microporous polymer.General polymer is due to it
Intermolecular powerful active force, strand can bend and reverse to increase intermolecular interaction, thus can effectively enter
Row steric bulk.There is the nonplanar structure of rigid element and distortion from tool microporous polymer strand in itself, main chain can not
Enough freely to rotate, each several part can not sufficiently occupy inner space in molecule, and the rigid element of depression forms continuous micropore.When
When this polymer is incorporated into polybenzimidazoles, due to its huge rigidity and nonplanarity, can be to polybenzimidazoles point
Huge free volume is brought between son, and compatibility good between organic structure will not destroy its mechanical property；These are huge
Big free volume can accommodate substantial amounts of phosphoric acid, and the functional group for introducing is close phosphoric acid, can make the loss of phosphoric acid significantly
Slow down, composite membrane is further enhanced phosphoric acid ability containing control.
The content of the invention
It is an object of the invention to provide a kind of high intensity, the high temperature proton conductive composite membrane of high proton conductivity and its in height
Application in temp fuel battery.
The present invention increases the free body of polymer by mixing proton conduction enhancer PIMs in polybenzimidazoles
Product, so as to improve the adsorbance of phosphoric acid.And by the change to modifying functional group in proton conduction enhancer so that phosphoric acid
Ability containing control and proton conductivity be obviously improved.
With the matrix material that polybenzimidazoles is doping, it is random copolymer to the present invention, and its structural formula is as follows：
Ar is one of following structure
N is positive integer, represents the degree of polymerization；
Proton conduction enhancer PIMs of the present invention, its structural formula is as follows：
M is positive integer, represents the degree of polymerization；
R1Can be-H or-SO3H；R2Can be-CN ,-COOH,Or
The present invention carries out the preparation of proton-conductive films by solution casting, and for different proton conduction enhancers
The polybenzimidazoles of PIMs and different structure, is screened to casting film agent and cast film processes condition, and suitable casting film agent can
Being dimethylacetylamide, dimethylformamide, dimethyl sulfoxide (DMSO), trifluoroacetic acid, 1-METHYLPYRROLIDONE, Loprazolam or chlorine
One or more of imitate.
The present invention is also explored and improved to cast film process.Proton conduction enhancer PIMs is specifically added to casting
In film, polybenzimidazoles is added, casting solution is obtained after being well mixed；Wherein proton conduction enhancer PIMs and polyphenyl and miaow
The quality of azoles and be 1g with the amount ratio of casting film agent：5~15mL, proton conduction enhancer PIMs and two kinds of polymerizations of polybenzimidazoles
In thing, the weight/mass percentage composition of proton conduction enhancer PIMs is 5~15%；Then casting solution is poured over clean glass plate
On, dried 10~15 hours at 80~90 DEG C, dried 10~15 hours at 100~110 DEG C, 10~15 are dried at 120~130 DEG C small
When, then at 120~130 DEG C, vacuum to be dried 20~30 hours under the conditions of 0.1~0.3MPa, polyphenyl is obtained after being cooled to room temperature
And imidazoles is high intensity, big free volume, the enhanced composite membrane of phosphate adsorption ability of the incorporation proton conduction enhancer of matrix.
Be incorporated into proton conduction enhancer PIMs (PIM-1, C-PIMs, S-PIMs etc.) in polybenzimidazoles by the present invention,
By C-PIMs, S-PIMs after modification not only with PIM-1 big free volume and rigid structure, and the group of functionalization with
There is very strong affinity between phosphoric acid；After being mixed polybenzimidazoles, can not only improve polybenzimidazoles to phosphoric acid
The ability containing control, and its functional group modified can also participate in the proton conduction of hydrogen bond network, and proton conductivity is upgraded
Good dual facilitation is arrived, (mass fraction is less than 15%) also can be excessively enough big in the case that even incorporation is less high
The performance that phosphate-doped polybenzimidazoles high temperature proton conducts fuel cell is improved greatly.
Further, resulting composite membrane is immersed in the culture dish for filling the phosphoric acid that mass concentration is 80~90%, and
Phosphate adsorption is carried out at 120~150 DEG C 8~180 hours, the composite membrane filter paper of taking-up is wiped into the phosphoric acid on surface, then
It is put into vacuum drying oven and 5~8h is dried at 100~120 DEG C, so as to obtains the phosphate-doped high temperature polyphenyl of high proton conductivity
And imidazoles/PIMs composite membranes.The present invention constructs polyphenyl and miaow by introducing phosphorus acid monomer in composite membrane by the doping of phosphoric acid
Azoles and the hydrogen bond network of phosphoric acid, prepare the high high temperature proton exchange film of proton conduction property.
Composite membrane is applied to high-temperature fuel cell field by the present invention, due to the introducing of proton conduction enhancer, is being kept
While polybenzimidazoles overwhelming majority mechanics performance, its proton conductivity is greatly improved and then battery is increased substantially
Performance, with extremely important application prospect.
Brief description of the drawings
Fig. 1：The nmr spectrum of the S-PIM synthesized in embodiment 1；
Fig. 2：From tool pore polymer PIM-1 (synthetic method and characterize referring to Macromol.Rapid Commun.2008,
29,783-788) and different functional groups functionalization PIMs (PIM-1, C-PIMs, S-PIMs) infrared absorption pattern, three
In the comparing of the infared spectrum of individual structure, we can be clearly seen that the characteristic absorption peak for introducing functional group, it was demonstrated that different functions
Group is successfully introduced into.
Fig. 3：OPBI (its synthetic method is shown in RSC Adv., 2015,5,53870-53873, in polybenzimidazoles described herein
The mechanical property of structure b) and C-PIM (synthetic method and sign are shown in Macromolecules 2009,42,6038-6043) doping
Can curve；It will be seen that being doped with the OPBI films (see embodiment 2,3,4) of C-PIM from figure, with incorporation C-PIM's
Increase, its mechanical property gradually strengthens.
Fig. 4：The proton conductivity curve of the product of embodiment 8；
Fig. 5：The proton conductivity curve of the product of embodiment 9.
Specific embodiment
Embodiment 1；The synthesis of S-PIM
Take and prepare 100 grams of PIM-1 according to document (Macromol.Rapid Commun.2008,29,783-788) method,
Add the concentrated sulfuric acid that 1 mass per liter fraction is 98%, then mechanical agitation speed fell in 300 revs/min of lower normal temperature sulfonation 8 hours
Enter in 10 liters of mixture of ice and water, be then washed with deionized for several times until remaining sulfuric acid is all removed, be filtrated to get solid
Body, 120 DEG C are vacuum dried 24 hours in vacuum drying oven, obtain S-PIM solids.Its nuclear magnetic spectrogram is as shown in Figure 1.INFRARED ABSORPTION
Spectrogram is as shown in Fig. 2 in figure, we are clearly visible that the characteristic absorption peak of various functional groups, it was demonstrated that various different functional groups
Be successfully introduced into.
Embodiment 2：The mass fraction of doping C-PIM is the preparation of 5% C-PIM and OPBI composite membrane
0.05g C-PIM polymer is taken, is added in 10mL DMSO and is fully dissolved into the casting solution of transparent and homogeneous, then
To 0.95g OPBI are added in the solution of gained, continue to stir until two kinds of polymer is uniformly mixed into sticky solution, then
It is poured on the glass plate of clean 10cm × 10cm, and is dried 12 hours at 80 DEG C, dried 12 hours at 100 DEG C, is dried at 120 DEG C
12 hours, dried 24 hours under 120 DEG C of vacuum, be cooled to after room temperature obtain mixing the C-PIM that mass fraction is 5% it is saturating with OPBI
Bright composite membrane.The thermal weight loss temperature of its 5wt% is 307.5 DEG C.
Embodiment 3：The mass fraction of doping C-PIM is the preparation of 10% C-PIM and OPBI composite membrane
0.10g C-PIM polymer is taken, is added in 10mL DMSO and is fully dissolved into the casting solution of transparent and homogeneous, then
0.90g OPBI will be added in the solution of gained, continue to stir until two kinds of polymer is uniformly mixed into sticky solution, then
It is poured on the glass plate of clean 10cm × 10cm, and is dried 12 hours at 80 DEG C, dried 12 hours at 100 DEG C, is dried at 120 DEG C
12 hours, dried 24 hours under 120 DEG C of vacuum, obtain mixing the C-PIM and OPBI that mass fraction is 10% after being cooled to room temperature
Transparent composite membrane.The thermal weight loss temperature of its 5wt% is 287.76 DEG C.
Embodiment 4：The mass fraction of doping C-PIM is the preparation of 15% C-PIM and OPBI composite membrane
0.15g C-PIM polymer is taken, is added in 10mL DMSO and is fully dissolved into the casting solution of transparent and homogeneous, then
0.85g OPBI will be added in the solution of gained, continue to stir until two kinds of polymer is uniformly mixed into sticky solution, then
It is poured on the glass plate of clean 10cm × 10cm, and is dried 12 hours at 80 DEG C, dried 12 hours at 100 DEG C, is dried at 12 DEG C
12 hours, dried 24 hours under 120 DEG C of vacuum, obtain mixing the C-PIM and OPBI that mass fraction is 15% after being cooled to room temperature
Transparent composite membrane.The thermal weight loss temperature of its 5wt% is 294.6 DEG C.
Embodiment 5：The mass fraction of doping S-PIM is the preparation of 5% S-PIM and OPBI composite membrane
0.05g S-PIM polymer is taken, is added in 10mL DMSO and is fully dissolved into the casting solution of transparent and homogeneous, then
0.95g OPBI will be added in the solution of gained, continue to stir until two kinds of polymer is uniformly mixed into sticky solution, then
It is poured on the glass plate of clean 10cm × 10cm, and is dried 12 hours at 80 DEG C, dried 12 hours at 100 DEG C, is dried at 120 DEG C
12 hours, dried 24 hours under 120 DEG C of vacuum, be cooled to after room temperature obtain mixing the S-PIM that mass fraction is 5% it is saturating with OPBI
Bright composite membrane.The thermal weight loss temperature of its 5wt% is 290.22 DEG C.
Embodiment 6：The mass fraction of doping S-PIM is the preparation of 10% S-PIM and OPBI composite membrane
0.10g S-PIM polymer is taken, is added in 10mL DMSO and is fully dissolved into the casting solution of transparent and homogeneous, then
0.90g OPBI will be added in the solution of gained, continue to stir until two kinds of polymer is uniformly mixed into sticky solution, then
It is poured on the glass plate of clean 10cm × 10cm, and is dried 12 hours at 80 DEG C, dried 12 hours at 100 DEG C, is dried at 120 DEG C
12 hours, dried 24 hours under 120 DEG C of vacuum, obtain mixing the S-PIM and OPBI that mass fraction is 10% after being cooled to room temperature
Transparent composite membrane.The thermal weight loss temperature of its 5wt% is 281.14 DEG C.
Embodiment 7：The mass fraction of doping S-PIM is the preparation of 15% S-PIM and OPBI composite membrane
0.15g S-PIM polymer is taken, is added in 10mL DMSO and is fully dissolved into the casting solution of transparent and homogeneous, then
0.95g OPBI will be added in the solution of gained, continue to stir until two kinds of polymer is uniformly mixed into sticky solution, then
It is poured on the glass plate of clean 10cm × 10cm, and is dried 12 hours at 80 DEG C, dried 12 hours at 100 DEG C, is dried at 120 DEG C
12 hours, dried 24 hours under 120 DEG C of vacuum, obtain mixing the S-PIM and OPBI that mass fraction is 15% after being cooled to room temperature
Transparent composite membrane.The thermal weight loss temperature of its 5wt% is 258.66 DEG C.
Embodiment 8：A series of preparation of the phosphate-doped film of the OPBI films of doping C-PIM
C-PIM the and OPBI composite membranes immersion of doping C-PIM different quality containings prepared by embodiment 2,3,4 fills matter
In the culture dish of the phosphoric acid for measuring fraction 85%, and phosphate adsorption is carried out under 120 DEG C of high temperature 36 hours.Composite membrane is wiped with filter paper
The phosphoric acid on surface, is then placed in vacuum drying oven vacuum drying 5 hours at 100 DEG C, so that it is different to obtain a series of doping C-PIM
The phosphate-doped films of OPBI/ of mass fraction.After the doping absorption phosphoric acid for wherein being prepared based on embodiment 3, at 200 DEG C
Proton conductivity is up to 0.200S/cm-1。
Embodiment 9：A series of preparation of the phosphate-doped film of the OPBI films of doping S-PIM
S-PIM the and OPBI composite membranes immersion of doping S-PIM different quality containings prepared by embodiment 5,6,7 fills matter
In the culture dish of the phosphoric acid for measuring fraction 85%, and phosphate adsorption is carried out under 120 DEG C of high temperature 36 hours.Composite membrane is wiped with filter paper
The phosphoric acid on surface, is then placed in being dried 5 hours at 100 DEG C in vacuum drying oven, so as to obtain a series of doping S-PIM different qualities divide
The phosphate-doped films of several OPBI/.After the doping absorption phosphoric acid for wherein being prepared based on embodiment 6, at 200 DEG C, proton is passed
Conductance is up to 0.264S/cm-1。
Claims (7)
1. a kind of high intensity, the preparation method of the high temperature proton conductive composite membrane of high proton conductivity, it is characterised in that：It is by matter
Sub- conduction enhancer PIMs is added in casting film agent, adds polybenzimidazoles, and casting solution is obtained after being well mixed；Wherein proton
The quality of conduction enhancer PIMs and polybenzimidazoles and be 1g with the amount ratio of casting film agent：5~15mL, proton conduction enhancer
In PIMs and polybenzimidazoles two kinds of polymer, the weight/mass percentage composition of proton conduction enhancer PIMs is 5~15%；Then will
Casting solution is poured on clean glass plate, is dried 10~15 hours at 80~90 DEG C, is dried 10~15 hours at 100~110 DEG C,
Dried 10~15 hours at 120~130 DEG C, it is small to dry 20~30 under the conditions of 0.1~0.3MPa then at 120~130 DEG C, vacuum
When, obtain composite membrane after being cooled to room temperature；
Wherein, the structural formula of polybenzimidazoles is as follows,
Ar is one of following structure,
N is positive integer, represents the degree of polymerization；
The structural formula of proton conduction enhancer PIMs is as follows,
M is positive integer, represents the degree of polymerization；
R1It is-H or-SO3H；R2Be-CN ,-COOH,
2. as claimed in claim 1 a kind of high intensity, the preparation method of the high temperature proton conductive composite membrane of high proton conductivity,
It is characterized in that：Casting film agent is dimethylacetylamide, dimethylformamide, dimethyl sulfoxide (DMSO), trifluoroacetic acid, N- crassitudes
One or more of ketone, Loprazolam or chloroform.
3. the high temperature proton conductive composite membrane of a kind of high intensity, high proton conductivity, it is characterised in that：It is by claim 1 or 2
Described method is prepared.
4. high intensity, the high temperature proton conductive composite membrane of high proton conductivity described in claim 3 is in high-temperature fuel cell
Application.
5. a kind of high intensity, the preparation method of the phosphate-doped high temperature proton exchange film of high proton conductivity, it is characterised in that：
It is in being 80~90% phosphoric acid by the composite membrane immersion mass concentration described in claim 3, phosphorus to be carried out at 120~150 DEG C
Acid absorption 8~180 hours, then wipes the phosphoric acid on surface by the composite membrane filter paper of taking-up, places into vacuum drying oven 100
5~8h is dried at~120 DEG C, so as to obtain the phosphate-doped high temperature proton exchange film of high intensity, high proton conductivity.
6. the phosphate-doped high temperature proton exchange film of a kind of high intensity, high proton conductivity, it is characterised in that：Being will by right
The method described in 5 is asked to prepare.
7. high intensity, the phosphate-doped high temperature proton exchange film of high proton conductivity described in claim 6 is in high-temperature fuel
Application in battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710057801.5A CN106784942B (en) | 2017-01-23 | 2017-01-23 | A kind of high-intensitive, high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710057801.5A CN106784942B (en) | 2017-01-23 | 2017-01-23 | A kind of high-intensitive, high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106784942A true CN106784942A (en) | 2017-05-31 |
| CN106784942B CN106784942B (en) | 2019-08-06 |
Family
ID=58943055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710057801.5A Active CN106784942B (en) | 2017-01-23 | 2017-01-23 | A kind of high-intensitive, high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106784942B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503491A (en) * | 2018-11-12 | 2019-03-22 | 吉林大学 | A kind of imidazole radicals phosphotungstate, preparation method and its preparing the application in proton exchange membrane used for high-temperature fuel cell |
| CN111682248A (en) * | 2020-06-29 | 2020-09-18 | 香港科技大学 | PBI membrane activation treatment method with high proton conductivity and ion selectivity |
| CN112063010A (en) * | 2020-07-27 | 2020-12-11 | 浙江晨阳新材料有限公司 | Phosphoric acid-doped porous polybenzimidazole electrolyte membrane and preparation method and application thereof |
| CN113299959A (en) * | 2021-06-04 | 2021-08-24 | 中国科学院化学研究所 | Composite proton exchange membrane and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338072A (en) * | 2008-08-15 | 2009-01-07 | 同济大学 | Organic/inorganic composite enhancement type anhydrous proton conducting film and method for preparing same |
| CN102643421A (en) * | 2012-04-23 | 2012-08-22 | 天津师范大学 | Novel polymer containing phosphonate group and preparation method and application of novel polymer |
| CN103408796A (en) * | 2013-07-23 | 2013-11-27 | 常州大学 | Preparation method of polymer composite membrane used for methanol fuel cells |
| CN103897179A (en) * | 2014-04-01 | 2014-07-02 | 天津师范大学 | Efficient preparation method of polymers containing phosphonic acid groups and salts |
| CN104341607A (en) * | 2014-09-04 | 2015-02-11 | 吉林大学 | Application of polybenzimidazole polymer containing side group in proton exchange membrane |
| CN105008028A (en) * | 2013-03-06 | 2015-10-28 | 沙特基础工业公司 | Polymeric membranes |
| CN105024084A (en) * | 2015-08-19 | 2015-11-04 | 哈尔滨工业大学 | High-temperature proton exchange membrane fuel cell membrane electrode and preparation method thereof |
| CN105680079A (en) * | 2016-04-19 | 2016-06-15 | 合肥工业大学 | Preparation method of layered composite proton exchange membrane for fuel cell |
-
2017
- 2017-01-23 CN CN201710057801.5A patent/CN106784942B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338072A (en) * | 2008-08-15 | 2009-01-07 | 同济大学 | Organic/inorganic composite enhancement type anhydrous proton conducting film and method for preparing same |
| CN102643421A (en) * | 2012-04-23 | 2012-08-22 | 天津师范大学 | Novel polymer containing phosphonate group and preparation method and application of novel polymer |
| CN105008028A (en) * | 2013-03-06 | 2015-10-28 | 沙特基础工业公司 | Polymeric membranes |
| CN103408796A (en) * | 2013-07-23 | 2013-11-27 | 常州大学 | Preparation method of polymer composite membrane used for methanol fuel cells |
| CN103897179A (en) * | 2014-04-01 | 2014-07-02 | 天津师范大学 | Efficient preparation method of polymers containing phosphonic acid groups and salts |
| CN104341607A (en) * | 2014-09-04 | 2015-02-11 | 吉林大学 | Application of polybenzimidazole polymer containing side group in proton exchange membrane |
| CN105024084A (en) * | 2015-08-19 | 2015-11-04 | 哈尔滨工业大学 | High-temperature proton exchange membrane fuel cell membrane electrode and preparation method thereof |
| CN105680079A (en) * | 2016-04-19 | 2016-06-15 | 合肥工业大学 | Preparation method of layered composite proton exchange membrane for fuel cell |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503491A (en) * | 2018-11-12 | 2019-03-22 | 吉林大学 | A kind of imidazole radicals phosphotungstate, preparation method and its preparing the application in proton exchange membrane used for high-temperature fuel cell |
| CN109503491B (en) * | 2018-11-12 | 2021-05-25 | 吉林大学 | Imidazolyl phosphotungstate, preparation method and application thereof in preparation of proton exchange membrane for high-temperature fuel cell |
| CN111682248A (en) * | 2020-06-29 | 2020-09-18 | 香港科技大学 | PBI membrane activation treatment method with high proton conductivity and ion selectivity |
| CN112063010A (en) * | 2020-07-27 | 2020-12-11 | 浙江晨阳新材料有限公司 | Phosphoric acid-doped porous polybenzimidazole electrolyte membrane and preparation method and application thereof |
| CN113299959A (en) * | 2021-06-04 | 2021-08-24 | 中国科学院化学研究所 | Composite proton exchange membrane and preparation method and application thereof |
| CN113299959B (en) * | 2021-06-04 | 2022-07-08 | 中国科学院化学研究所 | Composite proton exchange membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106784942B (en) | 2019-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110336052B (en) | Mixed matrix type cation exchange membrane and preparation method thereof | |
| CN106784942B (en) | A kind of high-intensitive, high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell | |
| CN102146204B (en) | Acid and alkali crosslinking proton exchange membrane and preparation thereof | |
| CN109065926A (en) | Mineralising legal system in situ has machine-Inorganic multilayer compound proton exchange membrane preparation method | |
| Du et al. | Semi-interpenetrating network anion exchange membranes based on quaternized polyvinyl alcohol/poly (diallyldimethylammonium chloride) | |
| CN105085913A (en) | Preparation method of sulfonated polyimide (SPI) proton conducting membrane containing branched structure | |
| CN104629081A (en) | Preparation method of pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as base | |
| CN107383404A (en) | A kind of preparation method of fluorine-containing branched sulphonated polyimides proton conductive membrane | |
| Qaisrani et al. | Facile and green fabrication of polybenzoxazine-based composite anion-exchange membranes with a self-cross-linked structure | |
| CN105070933A (en) | Composite proton-exchange membrane for fuel cell and preparation method of composite proton-exchange membrane | |
| CN102838777B (en) | Recovery method of sulfonated polyether ether ketone (SPEEK) / polyaniline (PANI) / propylene glycol monomethyl acetate (PMA) composite proton exchange membrane | |
| CN110071313B (en) | Polybenzimidazole multi-component nano high-temperature proton exchange composite membrane, preparation method and application thereof | |
| CN101510615A (en) | Semi-interpenetrating network type composite proton exchange film based on crosslinkable medlin and preparation method thereof | |
| CN106549171A (en) | A kind of cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity and preparation method thereof | |
| Zeng et al. | Construction of ordered OH− migration channels in anion exchange membrane by synergizes of cationic metal‐organic framework and quaternary ammonium groups | |
| Ju et al. | Construction of effective transmission channels by anchoring metal‐organic framework on side‐chain sulfonated poly (arylene ether ketone sulfone) for fuel cells | |
| CN108987774A (en) | A kind of stable type MOFs fuel battery proton exchange film and preparation method thereof | |
| CN110176617B (en) | Method for improving alcohol resistance selectivity of NAFION membrane | |
| CN104966845B (en) | Semi-hyper branched semi-cross-linking type sulfonated polyimide composite proton exchange membrane and preparation method thereof | |
| CN115536885B (en) | Preparation method of submicron phase separation anion exchange membrane | |
| CN111342095B (en) | High-temperature fuel cell proton exchange membrane and preparation method thereof | |
| CN100499238C (en) | Organic-inorganic compoiste proton exchange film and preparing method | |
| CN101777656B (en) | Solid fluorine-containing high polymer proton exchange membrane for fuel cell and preparation method thereof | |
| CN103560259A (en) | POSS (Polyhedral Oligomeric Silsesquioxane) crosslinking type sulfonated polyimide proton exchange membrane as well as preparation method thereof | |
| CN116613362A (en) | Composite amphoteric ion exchange membrane for vanadium battery and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |