CN106784942B - A kind of high-intensitive, high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell - Google Patents
A kind of high-intensitive, high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell Download PDFInfo
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- CN106784942B CN106784942B CN201710057801.5A CN201710057801A CN106784942B CN 106784942 B CN106784942 B CN 106784942B CN 201710057801 A CN201710057801 A CN 201710057801A CN 106784942 B CN106784942 B CN 106784942B
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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
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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
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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
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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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- 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-intensitive, 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, obtains casting solution after mixing；Then casting solution is poured on clean glass plate, it is dried 10~15 hours at 80~90 DEG C, it is dried 10~15 hours at 100~110 DEG C, it is dried 10~15 hours at 120~130 DEG C, then at 120~130 DEG C, vacuum degree be 0.1~0.3MPa under the conditions of dry 20~30 hours, the composite membrane is obtained after being cooled to room temperature, may further carry out phosphate-doped, obtains 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 increases substantially the performance of battery, there is extremely wide application prospect.
Description
Technical field
The invention belongs to high temperature proton-conductive films technical fields, and in particular to a kind of high-intensitive, high proton conductivity height
Warm proton conductive composite membrane and its application in high-temperature fuel cell.
Background technique
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of energy source device environmental-friendly, transformation efficiency is high, is not
Carry out ideal energy sources.With being on the rise for China's atmosphere polluting problem, air pollution brought by combustion of fossil fuel
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 atmosphere dirt
The improvement of dye is relatively difficult, even more because the energy resource structure in China is based on fossil fuel, if reductionization rashly in the short time
The usage amount of stone fuel can all cause influence very serious to the stabilization of the energy security in China or even national society.Change
Energy resource structure becomes an extremely urgent demand using the more clean energy.Therefore, Proton Exchange Membrane Fuel Cells has
There is very wide application prospect.By taking now widely used Nafion is the perfluor type sulfonic acid membrane cell of representative as an example,
Most operation temperature is lower than 80 DEG C, so that fuel cell faces CO poor resistance in practical application, the hydro-thermal management of system is stranded
The problems such as difficult.Therefore high temperature proton exchange film fuel cell (HT-PEMFC) just comes into being, and becomes the one of fuel cell technology
A important developing direction.
High temperature proton exchange film fuel cell has the advantages that 1) raising chemical reaction rate, reduces making for catalyst
Dosage；2) since its operating temperature is greater than 120 DEG C, CO will not be generated, to solve the problems, such as electrode material CO poisoning；3) change
The water management of kind system reduces mass transfer polarization, and flow Field Design is also available significantly to be simplified, 4) improve the heat pipe of system
Reason can use the automobile-used cooling system of existing I. C. engine steam, the weight and volume of cooling system is greatly lowered, improve system
Weight and volumetric specific power density.5) since its operating temperature is higher, reactivity is very big, and high-temperature fuel cell is relative to low
The catalyst activity of warm battery, 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 kind of performance.The composite membrane of polybenzimidazoles doping phosphoric acid by
In its high proton conductivity and outstanding thermal stability, become the hot spot of high temperature proton exchange film research.Polyphenyl and miaow
There are the bonding actions 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, transmit proton by the hydrogen bond network that phosphoric acid and imidazole group are formed in film, to get rid of
Dependence of the proton transfer to water, improves the operating temperature of fuel cell.
The film of polyphenyl imidazoles is mainly immersed in phosphoric acid by the method for conventional doping phosphoric acid to be inhaled at a certain temperature
It is attached.Since the free volume between polybenzimidazoles strand is limited, the adsorbance of phosphoric acid is become 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
Method such as uses pore creating material, and (common perforating agent has repefral, diethyl phthalate, two fourth of phthalic acid
Ester, diphenyl phthalate etc.) porous polybenzimidazole membrane is prepared, its advantage is that a large amount of pore structure can be generated, rapidly
Polybenzimidazoles is improved to the adsorption capacity of phosphoric acid；However, the gap of this method manufacture is often very big, so that doping enters benzene
And the phosphoric acid in imidazoles hole is lost rapidly, high proton conductivity can not long-time stable keep, conductivity decline also pole when high temperature
It is serious.Therefore introducing pore structure come the doping and proton conductivity for increasing phosphoric acid is not an effective method.
It is the polymer that a kind of polymer itself has microcellular structure from tool microporous polymer.General polymer is due to it
Intermolecular powerful active force, strand can be bent and be reversed to increase intermolecular interaction, thus can effectively into
Row steric bulk.There is the nonplanar structure of rigid element and distortion from the strand of tool microporous polymer itself, main chain cannot
It is enough freely rotated, each section cannot adequately occupy inner space in molecule, and the rigid element of recess forms continuous micropore.When
It, can be to polybenzimidazoles point due to its huge rigidity and nonplanarity when this polymer is incorporated into polybenzimidazoles
Huge free volume is brought between son, and good compatibility will not destroy its mechanical property between organic structure；These are huge
Big free volume can accommodate a large amount of phosphoric acid, and the functional group introduced is close phosphoric acid, can make the loss of phosphoric acid significantly
Slow down, further enhances composite membrane to the ability containing control of phosphoric acid.
Summary of the invention
The object of the present invention is to provide a kind of high-intensitive, 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, to improve the adsorbance of phosphoric acid.And by the variation to functional group is modified in proton conduction enhancer, so that phosphoric acid
Ability containing control and proton conductivity be obviously improved.
The present invention is the basis material adulterated with polybenzimidazoles, is random copolymer, structural formula is as follows:
Ar is with one of flowering structure
N is positive integer, indicates the degree of polymerization；
Proton conduction enhancer PIMs of the present invention, structural formula are as follows:
M is positive integer, indicates the degree of polymerization；
R1It can be-H or-SO3H；R2Can be-CN ,-COOH,Or
The present invention carries out the preparation of proton-conductive films by solution casting, and is directed to different proton conduction enhancers
The polybenzimidazoles of PIMs and different structure screen casting film agent and cast film processes condition, and suitable casting film agent can
To be dimethyl acetamide, dimethylformamide, dimethyl sulfoxide, trifluoroacetic acid, N-Methyl pyrrolidone, Loprazolam or chlorine
One or more of imitate.
The present invention also explores cast film process and has been improved.Proton conduction enhancer PIMs is specifically added to casting
In film, polybenzimidazoles is added, obtains casting solution after mixing；Wherein proton conduction enhancer PIMs and polyphenyl and miaow
The quality of azoles and be 1g:5~15mL, proton conduction enhancer PIMs and two kinds of polybenzimidazoles polymerizations with the amount ratio of casting film agent
In object, the mass percentage of proton conduction enhancer PIMs is 5~15%；Then casting solution is poured over to clean glass plate
On, it is small that 10~15 are dried at drying 10~15 hours, 120~130 DEG C at drying 10~15 hours, 100~110 DEG C at 80~90 DEG C
When, then at 120~130 DEG C, vacuum degree to dry 20~30 hours under the conditions of 0.1~0.3MPa, polyphenyl is obtained after being cooled to room temperature
And imidazoles is the composite membrane of high-intensitive, the big free volume of the incorporation proton conduction enhancer of matrix, the enhancing of phosphate adsorption ability.
Proton conduction enhancer PIMs (PIM-1, C-PIMs, S-PIMs etc.) is incorporated into polybenzimidazoles by the present invention,
C-PIMs, S-PIMs not only have a big free volume and rigid structure of PIM-1 after modification, and the group of functionalization with
There is very strong affinity between phosphoric acid；After being mixed polybenzimidazoles, it can not only improve polybenzimidazoles to phosphoric acid
The ability containing control, and the functional group of its modification can also participate in the proton conduction of hydrogen bond network, upgrade to proton conductivity
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 of phosphate-doped polybenzimidazoles high temperature proton conduction fuel cell is improved greatly.
Further, obtained composite membrane is immersed in the culture dish for filling the phosphoric acid that mass concentration is 80~90%, and
It is carried out phosphate adsorption 8~180 hours at 120~150 DEG C, the composite membrane of taking-up is wiped to the phosphoric acid on surface with filter paper, then
5~8h of baking at 100~120 DEG C is put into vacuum drying oven, to obtain the phosphate-doped high temperature polyphenyl of high proton conductivity
And imidazoles/PIMs composite membrane.The present invention constructs polyphenyl and miaow by introducing phosphorus acid monomer in composite membrane, by the doping of phosphoric acid
The hydrogen bond network of azoles and phosphoric acid prepares the high high temperature proton exchange film of proton conduction property.
Composite membrane is applied to high-temperature fuel cell field and is being kept due to the introducing of proton conduction enhancer by the present invention
While polybenzimidazoles overwhelming majority mechanics performance, its proton conductivity is greatly improved and then increases substantially battery
Performance, have extremely important application prospect.
Detailed description of the invention
Fig. 1: the nmr spectrum of the S-PIM synthesized in embodiment 1；
Fig. 2: from tool pore polymer PIM-1 (synthetic method and characterization referring to Macromol.Rapid Commun.2008,
29,783-788) and the infrared absorption pattern of the PIMs of different functional groups functionalization (PIM-1, C-PIMs, S-PIMs), three
In the comparison of the infared spectrum of a 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 characterization are shown in Macromolecules 2009,42,6038-6043) doping
It can curve；From the figure we can see that the OPBI film (see embodiment 2,3,4) of C-PIM is doped with, with incorporation C-PIM's
Increase, mechanical property gradually increases.
Fig. 4: the proton conductivity curve of 8 product of embodiment；
Fig. 5: the proton conductivity curve of 9 product of embodiment.
Specific embodiment
Embodiment 1；The synthesis of S-PIM
It takes and prepares 100 grams of PIM-1 according to document (Macromol.Rapid Commun.2008,29,783-788) method,
Be added 1 mass per liter score be 98% the concentrated sulfuric acid, mechanical stirring speed 300 revs/min lower room temperature sulfonation 8 hours, then fall
Enter into 10 liters of mixture of ice and water, is then washed with deionized for several times until all removals of remaining sulfuric acid, is obtained by filtration solid
Body is dried in vacuo 24 hours for 120 DEG C in vacuum drying oven, obtains S-PIM solid.Its nuclear magnetic spectrogram is as shown in Figure 1.Infrared absorption
Spectrogram is as shown in Fig. 2, we clearly see the characteristic absorption peak of various functional groups in the figure, it was demonstrated that various different functional groups
Be successfully introduced into.
Embodiment 2: the preparation for C-PIM and the OPBI composite membrane that the mass fraction for adulterating C-PIM is 5%
0.05g C-PIM polymer is taken, is added in 10mL DMSO and is sufficiently dissolved into homogeneous and transparent casting solution, then
0.95g OPBI is added into resulting solution, continues 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 at being dried 12 hours, 120 DEG C at being dried 12 hours, 100 DEG C at 80 DEG C
It 12 hours, dries 24 hours under 120 DEG C of vacuum, the saturating of the C-PIM and OPBI that incorporation mass fraction is 5% is obtained after being cooled to room temperature
Bright composite membrane.The thermal weight loss temperature of its 5wt% is 307.5 DEG C.
Embodiment 3: the preparation for C-PIM and the OPBI composite membrane that the mass fraction for adulterating C-PIM is 10%
0.10g C-PIM polymer is taken, is added in 10mL DMSO and is sufficiently dissolved into homogeneous and transparent casting solution, then
0.90g OPBI will be added in resulting solution, 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 at being dried 12 hours, 120 DEG C at being dried 12 hours, 100 DEG C at 80 DEG C
It 12 hours, dries 24 hours under 120 DEG C of vacuum, obtains the C-PIM's and OPBI that incorporation 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 preparation for C-PIM and the OPBI composite membrane that the mass fraction for adulterating C-PIM is 15%
0.15g C-PIM polymer is taken, is added in 10mL DMSO and is sufficiently dissolved into homogeneous and transparent casting solution, then
0.85g OPBI will be added in resulting solution, 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 at being dried 12 hours, 12 DEG C at being dried 12 hours, 100 DEG C at 80 DEG C
It 12 hours, dries 24 hours under 120 DEG C of vacuum, obtains the C-PIM's and OPBI that incorporation 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 preparation for S-PIM and the OPBI composite membrane that the mass fraction for adulterating S-PIM is 5%
0.05g S-PIM polymer is taken, is added in 10mL DMSO and is sufficiently dissolved into homogeneous and transparent casting solution, then
0.95g OPBI will be added in resulting solution, 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 at being dried 12 hours, 120 DEG C at being dried 12 hours, 100 DEG C at 80 DEG C
It 12 hours, dries 24 hours under 120 DEG C of vacuum, the saturating of the S-PIM and OPBI that incorporation mass fraction is 5% is obtained after being cooled to room temperature
Bright composite membrane.The thermal weight loss temperature of its 5wt% is 290.22 DEG C.
Embodiment 6: the preparation for S-PIM and the OPBI composite membrane that the mass fraction for adulterating S-PIM is 10%
0.10g S-PIM polymer is taken, is added in 10mL DMSO and is sufficiently dissolved into homogeneous and transparent casting solution, then
0.90g OPBI will be added in resulting solution, 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 at being dried 12 hours, 120 DEG C at being dried 12 hours, 100 DEG C at 80 DEG C
It 12 hours, dries 24 hours under 120 DEG C of vacuum, obtains the S-PIM's and OPBI that incorporation 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 preparation for S-PIM and the OPBI composite membrane that the mass fraction for adulterating S-PIM is 15%
0.15g S-PIM polymer is taken, is added in 10mL DMSO and is sufficiently dissolved into homogeneous and transparent casting solution, then
0.95g OPBI will be added in resulting solution, 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 at being dried 12 hours, 120 DEG C at being dried 12 hours, 100 DEG C at 80 DEG C
It 12 hours, dries 24 hours under 120 DEG C of vacuum, obtains the S-PIM's and OPBI that incorporation 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.
A series of embodiment 8: the preparation of the phosphate-doped film of the OPBI film of doping C-PIM
C-PIM the and OPBI composite membrane immersion of doping C-PIM different quality containing prepared by embodiment 2,3,4 is filled into matter
In the culture dish for measuring the phosphoric acid of score 85%, and carried out phosphate adsorption 36 hours under 120 DEG C of high temperature.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 film of the OPBI/ of mass fraction.After the doping absorption phosphoric acid being wherein prepared based on embodiment 3, at 200 DEG C
Proton conductivity is up to 0.200S/cm-1。
A series of embodiment 9: the preparation of the phosphate-doped film of the OPBI film of doping S-PIM
S-PIM the and OPBI composite membrane immersion of doping S-PIM different quality containing prepared by embodiment 5,6,7 is filled into matter
In the culture dish for measuring the phosphoric acid of score 85%, and carried out phosphate adsorption 36 hours under 120 DEG C of high temperature.Composite membrane is wiped with filter paper
The phosphoric acid on surface is then placed in vacuum drying oven at 100 DEG C and dries 5 hours, to obtain a series of doping S-PIM different qualities point
The phosphate-doped film of several OPBI/.After the doping absorption phosphoric acid being wherein 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 preparation method of high-intensitive, high proton conductivity high temperature proton conductive composite membrane, it is characterised in that: be by matter
Sub- conduction enhancer PIMs is added in casting film agent, is added polybenzimidazoles, is obtained casting solution after mixing；Wherein proton
The quality of conduction enhancer PIMs and polybenzimidazoles and be 1g:5~15mL, proton conduction enhancer with the amount ratio of casting film agent
In PIMs and polybenzimidazoles two kinds of polymer, the mass percentage of proton conduction enhancer PIMs is 5~15%；Then will
Casting solution is poured on clean glass plate, is dried 10~15 hours at drying 10~15 hours, 100~110 DEG C at 80~90 DEG C,
It is 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 degree
When, composite membrane is obtained after being cooled to room temperature；
Wherein, the structural formula of polybenzimidazoles is as follows,
Ar be with one of flowering structure,
N is positive integer, indicates the degree of polymerization；
The structural formula of proton conduction enhancer PIMs is as follows,
M is positive integer, indicates the degree of polymerization；
R1It is-SO3H；R2It is-COOH.
2. a kind of preparation method of high-intensitive, high proton conductivity high temperature proton conductive composite membrane as described in claim 1,
It is characterized by: casting film agent is dimethyl acetamide, dimethylformamide, dimethyl sulfoxide, trifluoroacetic acid, N- crassitude
One or more of ketone, Loprazolam or chloroform.
3. a kind of high-intensitive, high proton conductivity high temperature proton conductive composite membrane, it is characterised in that: be by claims 1 or 2
The method is prepared.
4. high-intensitive, high proton conductivity high temperature proton conductive composite membrane as claimed in claim 3 is in high-temperature fuel cell
Application.
5. a kind of preparation method of high-intensitive, high proton conductivity phosphate-doped high temperature proton exchange film, it is characterised in that:
It is to immerse composite membrane as claimed in claim 3 in the phosphoric acid that mass concentration is 80~90%, phosphorus is carried out at 120~150 DEG C
The composite membrane of taking-up, the phosphoric acid on surface is then wiped with filter paper, is placed into vacuum drying oven 100 by acid absorption 8~180 hours
5~8h is dried at~120 DEG C, to obtain high-intensitive, high proton conductivity phosphate-doped high temperature proton exchange film.
6. a kind of high-intensitive, high proton conductivity phosphate-doped high temperature proton exchange film, it is characterised in that: wanted by right
Method described in asking 5 is prepared.
7. high-intensitive, high proton conductivity phosphate-doped high temperature proton exchange film as claimed in claim 6 is in high-temperature fuel
Application in battery.
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| 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 |
| 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 |
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