CN104151587A - Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane - Google Patents
Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane Download PDFInfo
- Publication number
- CN104151587A CN104151587A CN201310180337.0A CN201310180337A CN104151587A CN 104151587 A CN104151587 A CN 104151587A CN 201310180337 A CN201310180337 A CN 201310180337A CN 104151587 A CN104151587 A CN 104151587A
- Authority
- CN
- China
- Prior art keywords
- proton exchange
- exchange membrane
- cross
- linking
- polybenzimidazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a preparation method of a covalent cross-linking polybenzimidazole high-temperature proton exchange membrane. The preparation method comprises the following steps: carrying out covalent cross-linking by taking polybenzimidazole resin as a raw material and taking bivariate or multivariate halides and epoxy compounds as cross-linking agents, and forming the membrane through a solvent volatilization method. The covalent cross-linking polybenzimidazole high-temperature proton exchange membrane prepared by utilizing the method disclosed by the invention has the advantages of better dimensional stability, thermodynamic stability and chemical stability, high phosphoric acid doping level and higher proton conducting property and can be used within a range of 20-200 DEG C. The preparation process disclosed by the invention is simple and low in raw material cost; and the prepared cross-linking proton exchange membrane has potential of being applied to a high-temperature fuel cell.
Description
Technical field
The invention belongs to the preparation method of the preparation field of used for high-temperature fuel cell proton exchange membrane, particularly a kind of novel crosslinked polybenzimidazole membrane.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFCs) is a kind ofly by electrochemical reaction, directly chemical energy to be converted to the power generation assembly of electric energy.Owing to having, efficiency is high, startup is fast and pollute the characteristics such as little, and since late nineteenth century, the development of PEMFCs receives much attention always.Proton exchange membrane is the important component part of fuel cell membrane electrode, has following major function: (1), as the medium of proton transfer, (2), as the barrier of separating reactant gases, (3) are as the carrier of cell catalyst.At present, business-like perfluoro sulfonic acid membrane (PFSA), as the Nafion film of E.I.Du Pont Company's production, it embodies higher proton conductivity, good chemistry and mechanical stability [Lu J L during lower than 100 ℃ in working temperature, Fang Q H, Li S L, Jiang S P.A novel phosphotungstic acid impregnated meso-Nafion multilayer membrane for proton exchange membrane fuel cells.Journal of Membrane Science.2013,427:101-107].Research shows, under high temperature (>100 ℃), it is poisoning that PEMFCs has resistance to CO, fast electrode kinetics, without negative electrode, flood, the cooling system of simplifying, can effectively utilize the advantages such as used heat [Chandan A, Hattenberger M, El-kharouf A, et al.High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC) – A review.Journal of Power Sources.2013, 231:264-278], and Nafion film is in the working temperature of PEMFCs during higher than 100 ℃, humidity reduces, cause its electroconductibility sharply to decline.Therefore, exploring a kind of novel proton exchange membranes that is applicable to high temperature proton exchange film fuel cell (HT-PEMFCs) is determined to win.
Polybenzimidazole (PBI) film becomes because having the features such as high glass-transition temperature (Tg=425～435 ℃), high mechanical strength, low gas permeation rate the proton exchange membrane material that the is applied to HT-PEMFCs [Han Kefei etc. that have potentiality, Chinese patent, 201210144585.5,2012], [Han Kefei etc., Chinese patent, 201110121715.9,2011].At present, studying more is the PBI film of phosphoric acid (PA) doping, and high doped level can improve the proton conductivity of PBI film, but the highly doped problems such as the high swelling of low mechanical strength that cause have seriously restricted the widespread commercial of PA doping PBI film.Existing more report aspect preparation modification PBI proton exchange membrane, as prepare organic/inorganic composite film [Xing Danmin etc., Chinese patent, 200710157517.1,2007], nano-material modified film [Yan Liuming etc., Chinese patent, 201010227608.X, 2010], sulfonation modifying film [A enlightening gram etc., Chinese patent, 00804418.X, 2000], [Joachim base not etc. for bridging modifying polymer film, Chinese patent, 02816024.X, 2002] etc.Wherein, cross-linking modified physical strength and the chemical stability that can significantly strengthen PBI film, room Jian Hua etc. has been prepared containing amino cross-linking modified PBI film [room Jian Hua etc., Chinese patent, 200710171865.4,2007], Betty S.J etc. are with 1,4-bis-(brooethyl) benzene is linking agent, has prepared crosslinked PBI film [Betty S.J, et al, United States Patent (USP), US2004/0261616,2004], cross-linking modified PBI film is prepared as it and is used widely and lays a good foundation in HT-PEMFCs.
Summary of the invention
The object of this invention is to provide and a kind ofly can be applied to proton exchange membrane of high-temperature fuel cell and preparation method thereof, the cross linking membrane of preparing by this law can be used at room temperature to 200 ℃.
The concrete technical scheme that the present invention adopts is:
A) prepared polybenzimidazole resin is dissolved in polar solvent, the homogeneous macromolecular solution that is made into massfraction and is 0.1wt.%～50wt.% is standby;
B) in above-mentioned macromolecular solution, adding massfraction is binary or polynary halides or the epoxy compounds of 0.1wt.%～50wt.%, and magnetic agitation obtains homogeneous containing the proton exchange coating solution of linking agent;
C) adopt traditional casting filming therapy, the proton exchange coating solution by gained containing linking agent falls in dull and stereotyped container, to be cross-linked film forming.
The chemical structural formula general formula of linking agent involved in the present invention is as shown in formula I～(VI):
Wherein: the X in general formula is Cl, Br, I.
(1) R
1for alkyl, aryl, heteroaryl, ether oxygen base;
(2) R
1in alkyl be straight chained alkyl, branched-chain alkyl, cycloalkyl.Wherein, chain-like alkyl carbonatoms is 2 to 10 integer; Cycloalkyl carbonatoms is less than 18; Ether oxygen base carbonatoms is 2 to 10 integer, and between adjacent oxygen atom, carbon atom number is 1 to 5 integer;
(3) R
1in aryl be phenyl, naphthyl, anthryl, phenanthryl and benzyl, the position of substitution is thought and two is replaced ortho position, a position, contraposition, and on aryl, is connected with the substituting groups such as halogen atom, alkyl, amino;
(4) R
1in heteroaryl preferably from imidazolyl, oxazolyl, pyridyl, quinolyl and Macrocyclic polyamine class heterocycle.Wherein, in Macrocyclic polyamine class heterocycle, the number of nitrogen is 2 to 10 integer, and the carbon atom number between adjacent nitrogen atom is 1 to 5 integer;
Compare with existing high-temperature fuel cell proton exchange membrane material, technology of preparing of the present invention and mould material have following advantage:
1, the acid of proton exchange membrane doping ability is strong, and proton conductivity is high.The repetition polybenzimidazole unit that the present invention contains many basic groups by preparation, has effectively improved the doping of phosphoric acid, by covalent cross-linking modification, effectively reduces the loss of institute's doping phosphoric acid, to obtaining high proton conductivity film; Utilize the proton exchange membrane that the present invention makes all to there is good proton conductivity at low temperature and high temperature.
2, proton exchange membrane has higher physical strength and good antioxidant property.The present invention, by covalent cross-linking modification, makes polymer backbone have fenestral fabric on the one hand, effectively raises the physical strength of film; The formation of covalent linkage has effectively replaced the hydrogen bond of original copolymer interchain on the other hand, has strengthened bond energy, reduced free radical attack-NH-group site, thereby improved the antioxidant property of film.
3, cross linking membrane preparation technology simple possible, with low cost.The present invention mixes linking agent with macromolecular solution, natural covalent cross-linking in the process of casting film-forming solvent flashing, and technique is simple, and raw materials cost is low, is easy to industrialization.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
A certain amount of polybenzimidazole resin is added to N, in N-dimethylacetamide solution, low-grade fever is dissolved, obtaining massfraction is the preferred 0.1wt.%-10wt.% of 0.1wt.%-50wt.%() macromolecular solution, then adding wherein massfraction is the preferred 0.1wt.%-10wt.% of 0.1wt.%-50wt.%() 1,2-ethylene dibromide, magnetic agitation mixes it; Decompress filter, obtains homogeneous containing the proton exchange coating solution of linking agent; Adopt casting filming therapy, temperature programming, volatilization, except desolventizing, obtains required cross-linked proton exchange membrane.
Embodiment 2
A certain amount of polybenzimidazole resin is added to N, in N-dimethylacetamide solution, low-grade fever is dissolved, obtaining massfraction is the preferred 0.1wt.%-10wt.% of 0.1wt.%-50wt.%() macromolecular solution, then adding wherein massfraction is the preferred 0.1wt.%-10wt.% of 0.1wt.%-50wt.%() epoxy chloropropane, magnetic agitation mixes it; Decompress filter, obtains homogeneous containing the proton exchange coating solution of linking agent; Adopt casting filming therapy, temperature programming, volatilization, except desolventizing, obtains required cross-linked proton exchange membrane.
Embodiment 3
A certain amount of polybenzimidazole resin is added to N, in N-dimethylacetamide solution, low-grade fever is dissolved, obtaining massfraction is the preferred 0.1wt.%-10wt.% of 0.1wt.%-50wt.%() macromolecular solution, then adding wherein massfraction is the preferred 0.1wt.%-10wt.% of 0.1wt.%-50wt.%() 1,2,5,6-diepoxy hexane, magnetic agitation mixes it; Decompress filter, obtains homogeneous containing the proton exchange coating solution of linking agent; Adopt casting filming therapy, temperature programming, volatilization, except desolventizing, obtains required cross-linked proton exchange membrane.
Embodiment 4
The preparation of the proton exchange membrane of other linking agent modifications can be with reference to above embodiment.
Claims (6)
1. a preparation method for novel crosslinked polybenzimidazole membrane, is characterized in that preparing according to the following steps:
A) polybenzimidazole resin is dissolved in polar organic solvent, the homogeneous macromolecular solution that is made into massfraction and is 0.1wt.%～50wt.% is standby;
B) in above-mentioned macromolecular solution, adding massfraction is the binary of 0.1wt.%～50wt.% or polynary halides, epoxy compounds, and magnetic agitation, obtains homogeneous containing the proton exchange coating solution of linking agent;
C) adopt traditional casting filming therapy, the proton exchange coating solution by gained containing linking agent falls in culture dish, dry out solvent in convection oven, crosslinked film forming.
2. cross-linked proton exchange membrane according to claim 1, is characterized in that: when obtaining homogeneous containing the proton exchange coating solution of linking agent, first linking agent is dissolved in to polar organic solvent wiring solution-forming, then adds polybenzimidazole resin to dissolve.
3. cross-linked proton exchange membrane according to claim 1, is characterized in that: while preparing cross-linked proton exchange membrane, the chemical structural formula of related linking agent is at least one in the compound of formula I～(VI):
Wherein: the X in general formula is Cl, Br, I.
(1) R
1for alkyl, aryl, heteroaryl, ether oxygen base;
(2) R
1in alkyl be straight chained alkyl, branched-chain alkyl, cycloalkyl; Wherein, chain-like alkyl carbonatoms is 2 to 10 integer; Cycloalkyl carbonatoms is less than 18; Ether oxygen base carbonatoms is 2 to 10 integer, and between adjacent oxygen atom, carbon atom number is 1 to 5 integer;
(3) R
1in aryl be phenyl, naphthyl, anthryl, phenanthryl and benzyl, the position of substitution is two to replace ortho position, a position, contraposition, and on aryl, is connected with the substituting groups such as halogen atom, alkyl, amino;
(4) R
1in heteroaryl preferably from imidazolyl, oxazolyl, pyridyl, quinolyl and Macrocyclic polyamine class heterocycle.Wherein, in Macrocyclic polyamine class heterocycle, the number of nitrogen is 2 to 10 integer, and the carbon atom number between adjacent nitrogen atom is 1 to 5 integer.
4. cross-linked proton exchange membrane according to claim 1, it is characterized in that: polybenzimidazole resin is dissolved in polar organic solvent, preferably be dissolved in N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-Methyl pyrrolidone (NMP).
5. cross-linked proton exchange membrane according to claim 1, is characterized in that: the temperature range while dissolving polybenzimidazole resin is 25-200 ℃, preferably 25-100 ℃.
6. cross-linked proton exchange membrane according to claim 1, is characterized in that: temperature programming scope during casting method dry out solvent is 25-200 ℃, preferably 40-150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310180337.0A CN104151587A (en) | 2013-05-15 | 2013-05-15 | Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310180337.0A CN104151587A (en) | 2013-05-15 | 2013-05-15 | Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104151587A true CN104151587A (en) | 2014-11-19 |
Family
ID=51877227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310180337.0A Pending CN104151587A (en) | 2013-05-15 | 2013-05-15 | Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104151587A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543459A (en) * | 2016-11-10 | 2017-03-29 | 常州大学 | A kind of preparation method of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane |
| CN106633864A (en) * | 2016-09-01 | 2017-05-10 | 宁波群力紧固件制造有限公司 | High-intensity screw and preparation method thereof |
| CN106684415A (en) * | 2016-12-27 | 2017-05-17 | 深圳大学 | High temperature proton exchange membrane and preparation method thereof |
| CN107248583A (en) * | 2017-05-24 | 2017-10-13 | 长春工业大学 | Polybenzimidazoles poly ion liquid is crosslinked compound high temperature proton exchange film and preparation method thereof |
| CN107887626A (en) * | 2017-11-09 | 2018-04-06 | 中国科学院上海有机化学研究所 | One kind is crosslinked compound high temperature proton exchange film and preparation method thereof |
| CN108384170A (en) * | 2018-05-29 | 2018-08-10 | 中国科学院上海有机化学研究所 | A kind of cross-linking type organic phospho acid high temperature proton exchange film and preparation method thereof |
| CN108417871A (en) * | 2018-03-13 | 2018-08-17 | 中国科学院上海有机化学研究所 | A kind of high temperature proton exchange film for fuel cell and preparation method thereof |
| CN108493469A (en) * | 2018-03-13 | 2018-09-04 | 中国科学院上海有机化学研究所 | A kind of cross-linking type high temperature proton exchange film and preparation method thereof |
| CN108539235A (en) * | 2018-03-19 | 2018-09-14 | 同济大学 | A kind of polybenzimidazoles proton conductive membrane and preparation method thereof with dual network structure |
| CN108832161A (en) * | 2018-05-29 | 2018-11-16 | 中国科学院上海有机化学研究所 | It is a kind of to be crosslinked compound organic phospho acid high temperature proton exchange film and preparation method thereof |
| CN112126105A (en) * | 2020-09-18 | 2020-12-25 | 上海交通大学 | Polybenzimidazole/phosphoric acid composite membrane prepared by online crosslinking method and preparation method thereof |
| CN112803052A (en) * | 2021-04-07 | 2021-05-14 | 常州创氢能源科技有限公司 | Preparation method of crosslinked polybenzimidazole proton exchange membrane |
| CN112940306A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Porous ion conduction membrane for flow battery and preparation and application thereof |
| CN112940321A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Cross-linked composite membrane for flow battery and preparation and application thereof |
| CN114400355A (en) * | 2021-12-02 | 2022-04-26 | 佛山仙湖实验室 | High-performance proton exchange membrane and preparation method and application thereof |
-
2013
- 2013-05-15 CN CN201310180337.0A patent/CN104151587A/en active Pending
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633864A (en) * | 2016-09-01 | 2017-05-10 | 宁波群力紧固件制造有限公司 | High-intensity screw and preparation method thereof |
| CN106543459A (en) * | 2016-11-10 | 2017-03-29 | 常州大学 | A kind of preparation method of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane |
| CN106543459B (en) * | 2016-11-10 | 2019-06-04 | 常州大学 | A kind of preparation method of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane |
| CN106684415A (en) * | 2016-12-27 | 2017-05-17 | 深圳大学 | High temperature proton exchange membrane and preparation method thereof |
| CN107248583A (en) * | 2017-05-24 | 2017-10-13 | 长春工业大学 | Polybenzimidazoles poly ion liquid is crosslinked compound high temperature proton exchange film and preparation method thereof |
| CN107887626A (en) * | 2017-11-09 | 2018-04-06 | 中国科学院上海有机化学研究所 | One kind is crosslinked compound high temperature proton exchange film and preparation method thereof |
| CN107887626B (en) * | 2017-11-09 | 2020-12-29 | 中国科学院上海有机化学研究所 | Cross-linked composite high-temperature proton exchange membrane and preparation method thereof |
| CN108417871A (en) * | 2018-03-13 | 2018-08-17 | 中国科学院上海有机化学研究所 | A kind of high temperature proton exchange film for fuel cell and preparation method thereof |
| CN108493469A (en) * | 2018-03-13 | 2018-09-04 | 中国科学院上海有机化学研究所 | A kind of cross-linking type high temperature proton exchange film and preparation method thereof |
| CN108493469B (en) * | 2018-03-13 | 2020-08-07 | 中国科学院上海有机化学研究所 | Cross-linked high-temperature proton exchange membrane and preparation method thereof |
| CN108417871B (en) * | 2018-03-13 | 2020-03-10 | 中国科学院上海有机化学研究所 | High-temperature proton exchange membrane for fuel cell and preparation method thereof |
| CN108539235A (en) * | 2018-03-19 | 2018-09-14 | 同济大学 | A kind of polybenzimidazoles proton conductive membrane and preparation method thereof with dual network structure |
| CN108384170B (en) * | 2018-05-29 | 2020-03-10 | 中国科学院上海有机化学研究所 | Cross-linked organic phosphonic acid high-temperature proton exchange membrane and preparation method thereof |
| CN108832161B (en) * | 2018-05-29 | 2020-03-10 | 中国科学院上海有机化学研究所 | Cross-linked composite organic phosphonic acid high-temperature proton exchange membrane and preparation method thereof |
| CN108832161A (en) * | 2018-05-29 | 2018-11-16 | 中国科学院上海有机化学研究所 | It is a kind of to be crosslinked compound organic phospho acid high temperature proton exchange film and preparation method thereof |
| CN108384170A (en) * | 2018-05-29 | 2018-08-10 | 中国科学院上海有机化学研究所 | A kind of cross-linking type organic phospho acid high temperature proton exchange film and preparation method thereof |
| CN112940306A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Porous ion conduction membrane for flow battery and preparation and application thereof |
| CN112940321A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Cross-linked composite membrane for flow battery and preparation and application thereof |
| CN112940321B (en) * | 2019-12-10 | 2022-04-15 | 中国科学院大连化学物理研究所 | Cross-linked composite membrane for flow battery and preparation and application thereof |
| CN112126105A (en) * | 2020-09-18 | 2020-12-25 | 上海交通大学 | Polybenzimidazole/phosphoric acid composite membrane prepared by online crosslinking method and preparation method thereof |
| CN112803052A (en) * | 2021-04-07 | 2021-05-14 | 常州创氢能源科技有限公司 | Preparation method of crosslinked polybenzimidazole proton exchange membrane |
| CN112803052B (en) * | 2021-04-07 | 2021-06-25 | 常州创氢能源科技有限公司 | Preparation method of crosslinked polybenzimidazole proton exchange membrane |
| CN114400355A (en) * | 2021-12-02 | 2022-04-26 | 佛山仙湖实验室 | High-performance proton exchange membrane and preparation method and application thereof |
| CN114400355B (en) * | 2021-12-02 | 2024-02-23 | 佛山仙湖实验室 | High-performance proton exchange membrane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104151587A (en) | Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane | |
| Park et al. | Chemically durable polymer electrolytes for solid-state alkaline water electrolysis | |
| Wang et al. | Side-chain-type poly (arylene ether sulfone) s containing multiple quaternary ammonium groups as anion exchange membranes | |
| CN110224166B (en) | Phosphoric acid-doped cross-linked polybenzimidazole high-temperature proton exchange membrane and preparation method thereof | |
| Subianto | Recent advances in polybenzimidazole/phosphoric acid membranes for high‐temperature fuel cells | |
| Mader et al. | Polybenzimidazole/acid complexes as high-temperature membranes | |
| CN101367903B (en) | Enhancement type composite proton exchanging film based on semi-interpenetrating network and preparation method thereof | |
| Iulianelli et al. | Sulfonated PEEK-based polymers in PEMFC and DMFC applications: A review | |
| CN101003637B (en) | Polymer electrolyte membrane, method of preparing the same and fuel cell employing the same | |
| CN103087337B (en) | A kind of poly-pyrrole throat/sulfonated polymer composite proton exchange membrane material and preparation method thereof and application | |
| Wang et al. | Synthesis and characterization of a fluorinated cross-linked anion exchange membrane | |
| Yao et al. | Highly sulfonated co-polyimides containing hydrophobic cross-linked networks as proton exchange membranes | |
| Seo et al. | Preparation and characterization of sulfonated amine-poly (ether sulfone) s for proton exchange membrane fuel cell | |
| Gao et al. | Anion exchange membranes with" rigid-side-chain" symmetric piperazinium structures for fuel cell exceeding 1.2 W cm− 2 at 60° C | |
| Zhao et al. | Design and application of covalent organic frameworks for ionic conduction | |
| Li et al. | Cross-linked fully aromatic sulfonated polyamide as a highly efficiency polymeric filler in SPEEK membrane for high methanol concentration direct methanol fuel cells | |
| EP3229302A1 (en) | Polymer electrolyte membrane | |
| Zhou et al. | Phenolate anion-based branched/cross-linked poly (arylene ether sulfone) hydroxide exchange membranes | |
| Salma et al. | A mini-review on alkaline stability of imidazolium cations and imidazolium-based anion exchange membranes | |
| Qian et al. | Quaternary ammonium-functionalized crosslinked poly (aryl ether sulfone) s anion exchange membranes with enhanced alkaline stability for water electrolysis | |
| Meng et al. | Semi‐interpenetrating Network Membrane from Polyethyleneimine‐Epoxy Resin and Polybenzimidazole for HT‐PEM Fuel Cells | |
| Moorthy et al. | Neoteric advancements in polybenzimidazole based polymer electrolytes for high-temperature proton exchange membrane fuel cells-A versatile review | |
| CN112126105A (en) | Polybenzimidazole/phosphoric acid composite membrane prepared by online crosslinking method and preparation method thereof | |
| Wu et al. | Thermal cure-induced crosslinked polybenzimidazole containing 4, 5-diazafluorene and pyridine for high-temperature proton exchange membrane | |
| Che et al. | The effect of grafted alkyl side chains on the properties of poly (terphenyl piperidinium) based high temperature proton exchange membranes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141119 |