CN115521425A - Covalent organic framework proton-conducting electrolyte material and preparation method and application thereof - Google Patents
Covalent organic framework proton-conducting electrolyte material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115521425A CN115521425A CN202211070551.6A CN202211070551A CN115521425A CN 115521425 A CN115521425 A CN 115521425A CN 202211070551 A CN202211070551 A CN 202211070551A CN 115521425 A CN115521425 A CN 115521425A
- Authority
- CN
- China
- Prior art keywords
- proton
- electrolyte material
- tpbd
- sulfonic acid
- organic framework
- 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
- 239000013310 covalent-organic framework Substances 0.000 title abstract description 47
- 239000000463 material Substances 0.000 title abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000012078 proton-conducting electrolyte Substances 0.000 title abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 51
- 239000002001 electrolyte material Substances 0.000 claims abstract description 35
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 28
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 19
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 19
- 229960001553 phloroglucinol Drugs 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 31
- 239000011521 glass Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- CRLGCNXKBJGMDX-UHFFFAOYSA-N 3-[2-amino-5-[4-amino-3-(3-sulfopropoxy)phenyl]phenoxy]propane-1-sulfonic acid Chemical compound C1=C(OCCCS(O)(=O)=O)C(N)=CC=C1C1=CC=C(N)C(OCCCS(O)(=O)=O)=C1 CRLGCNXKBJGMDX-UHFFFAOYSA-N 0.000 description 2
- IBWKBGGKOXVOFZ-UHFFFAOYSA-N 4-[2-amino-5-[4-amino-3-(4-sulfobutoxy)phenyl]phenoxy]butane-1-sulfonic acid Chemical compound C1=C(OCCCCS(O)(=O)=O)C(N)=CC=C1C1=CC=C(N)C(OCCCCS(O)(=O)=O)=C1 IBWKBGGKOXVOFZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- 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]
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the technical field of electrolyte materials, in particular to a covalent organic framework proton conduction electrolyte material and a preparation method and application thereof. The electrolyte material is a polymer with a structural unit shown in the following general formula I:
in the general formula I, x is selected from 0, 1, 2 or 3,R and is selected from sulfonic acid group or C with sulfonic acid group 1 To C 4 An alkoxy group of (2). The invention develops a new polymer skeleton by introducing sulfonic acid groups into covalent organic framework pore channels and fixing in a covalent bond form, prepares a series of covalent organic framework proton-conducting electrolyte materials, a preparation method and application thereof, and a proton-conducting membrane consisting of the electrolyte materialsHigh conductivity, and proton conductivity of 0.19S cm at 80 deg.C and 95% relative humidity ‑1 Above, up to 0.217S cm ‑1 。
Description
Technical Field
The invention relates to the technical field of electrolyte materials, in particular to a covalent organic framework proton conduction electrolyte material and a preparation method and application thereof.
Background
In the fields of energy storage and conversion, brine desalination, catalysis and the like, the conduction of cations plays a very key role. Especially in fuel cells, protons (H) + ) The conductivity directly affects the performance of the entire cell, and the pem is one of the core components of a pem fuel cell. Currently, commercial proton-conducting electrolyte materials mainly use polytetrafluoroethylene as a skeleton, and perfluorosulfonic acid resin with a proton-conducting sulfonic acid group as a side chain (for example, nafion of dupont, with the structure of
) The material has stable physical and chemical structure, good mechanical performance and proton conductivity up to 0.1 S.cm -1 . However, the chemical synthesis of perfluorosulfonic acid resin molecules is complicated, environmentally polluting, and the cost of the resin solution is about 30% or more of the cost of fuel cells (document: progress in Polymer Science,2011,36 (11): 1443-1498). In addition, in the process of forming the film by the perfluorinated sulfonic acid resin solution, the film in the film is composed of linear resin macromolecules and is in an amorphous state, so hydrophilic and hydrophobic micro areas are formed by intrinsic structures (hydrophobic skeleton and hydrophilic side chain) of resin molecules in the film structure, and the communicated hydrophilic areas are main channels for proton transmission in the film. Therefore, after such electrolyte materials are formed into a film, the dependence on humidity during operation is also very high, and when the temperature is too high, the water content of the film is reduced, which leads to a sharp decrease in the proton conductivity. For this reason, it is necessary to develop a novel material to solve these problems.
The covalent organic framework is a novel crystalline porous material which has the characteristics of low density, permanent porosity, high specific surface area and the like, and has a structureCan be designed in advance, and has good application prospect in the aspects of batteries, catalysis, adsorption, separation, energy storage and the like. Most of the covalent organic framework materials currently used in the field of proton conduction are prepared by a post-synthesis method, namely: firstly, a covalent organic framework structure is synthesized, and then proton carriers (phosphoric acid, imidazole and the like) are introduced into the pore channels of the covalent organic framework structure by an impregnation method to improve the proton conductivity. Digambar Balaji Shide et al (J. Mater. Chem. A., 2016,4,2682-2690) synthesized a covalent organic framework material containing pyridine groups on the framework by a simple mechanical grinding method, because the framework has abundant N sites, phosphoric acid can be well loaded in the pore channels by a hydrogen bonding mode, and the conductivity of the loaded material reaches 2.5 multiplied by 10 under the conditions of 120 ℃ and 0 percent relative humidity (0 percent RH) -3 S·cm -1 . Xu et al (Nature Mater 15,722-726 (2016)) synthesized a mesoporous two-dimensional covalent organic framework material with ordered channels by a solvothermal method, and the material has good chemical stability. Then loading triazole and imidazole small molecules in the pore channels respectively, wherein the electrical conductivity reaches 1.1 multiplied by 10 respectively under the anhydrous condition at the temperature of 130 DEG C -3 S·cm -1 And 4.37X 10 - 3 S·cm -1 And excellent proton conductivity is shown. CN112563547A discloses a pyrazinyl porous covalent organic framework material, a preparation method thereof and application thereof in a proton conduction material of a fuel cell, wherein an author conducts sulfonation and phosphoric acid loading modification on the covalent organic framework material, the final material shows excellent proton conduction performance, and the conductivity reaches 8.8 multiplied by 10 -2 S·cm -1 。
However, the proton carrier is introduced into the pore channel of the covalent organic framework by an impregnation method, although the proton conductivity of the material can be improved well, the proton carrier is combined in a hydrogen bond mode, the stability of the load mode is poor, and phosphoric acid, imidazole and the like are water-soluble proton acid and can lose with water when being used as a proton exchange membrane, so that the performance is reduced. In addition, the material mostly exists in a powder form, and a solid electrolyte is required to be prepared in a tabletting mode, so that the obtained solid electrolyte has uneven components, is easy to cause pore channel blockage, has poor stability and compactness, is not beneficial to proton conduction, and has limited improvement on the proton conduction capability of the modified material.
Therefore, it is highly desirable to provide a covalent organic framework proton conducting electrolyte material having a proton conducting membrane with high conductivity and proton conductivity of 0.19S · cm at 80 ℃ and 95% relative humidity -1 The above.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, a covalent organic framework proton conduction electrolyte material, a preparation method and application thereof are provided. By an in-situ polymerization technology, a functional group side chain with a proton conduction function is introduced in situ on a COF (covalent organic framework) skeleton, and a novel covalent organic framework proton conduction electrolyte material with excellent proton conduction capability is developed.
The invention conception of the invention is as follows: the invention develops a new polymer skeleton by introducing sulfonic acid groups into covalent organic framework pore channels and fixing the sulfonic acid groups in a covalent bond form, prepares a series of covalent organic framework proton conduction electrolyte materials and a preparation method and application thereof, and the proton conduction membrane formed by the electrolyte materials has high conductivity, and the proton conductivity is 0.19S-cm under the conditions of 80 ℃ and 95 percent of relative humidity -1 Above, up to 0.217S cm -1 。
The first aspect of the invention provides a covalent organic framework proton-conducting electrolyte material, a preparation method and an application thereof, wherein the electrolyte material is a polymer with a structural unit shown as the following general formula I:
in the general formula I, x is selected from 0, 1, 2 or 3,R is selected from sulfonic acid group (-SO) 3 H) Or C having a sulfonic acid group 1 To C 4 An alkoxy group of (2). The wavy line in the general formula of the invention represents: in the general formula, waves exist on the amino terminalThe key position of the line is connected with the key position of the wavy line on the double-bond end; the bond position of the wavy line at the double bond end and the bond position of the wavy line at the amino end or
The key positions of the wavy lines are connected.
Preferably, the electrolyte material is a polymer having a structural unit represented by the following general formula ii:
in the general formula II, x is selected from 0, 1, 2 or 3,R is selected from sulfonic acid group (-SO) 3 H) Or C having a sulfonic acid group 1 To C 4 An alkoxy group of (2).
Compared with the prior art, the covalent organic framework proton conduction electrolyte material provided by the first aspect of the invention, and the preparation method and the application thereof have the following beneficial effects: the invention develops a new polymer skeleton by introducing sulfonic acid groups into covalent organic framework pore channels and fixing the sulfonic acid groups in a covalent bond form, prepares a series of covalent organic framework proton conduction electrolyte materials and a preparation method and application thereof, and the proton conduction membrane formed by the electrolyte materials has high conductivity, and the proton conductivity is 0.19S-cm under the conditions of 80 ℃ and 95 percent of relative humidity -1 Above, up to 0.217S cm -1 。
Preferably, the alkoxy group is a straight chain alkoxy group, and the substitution position of the sulfonic acid group is the tail end of the alkoxy group; further preferably, R is selected from-SO 3 H、-OCH 2 SO 3 H、-O(CH 2 ) 2 SO 3 H、-O(CH 2 ) 3 SO 3 H or-O (CH) 2 ) 4 SO 3 H。
Preferably, x is 0.
A second aspect of the invention provides a production method of the electrolyte material, the production method including the steps of: in the presence of solvent, 1,3,5-trialdehyde phloroglucinol and biphenylReacting amine monomers to prepare the electrolyte material; the benzidine monomer is shown as a general formula III:
in the general formula III, x is selected from 0, 1, 2 or 3,R is selected from sulfonic acid group (-SO) 3 H) Or C having a sulfonic acid group 1 To C 4 An alkoxy group of (2).
Preferably, the alkoxy group is a straight chain alkoxy group, and the substitution position of the sulfonic acid group is the tail end of the alkoxy group; further preferably, R is selected from-OCH 2 SO 3 H、-O(CH 2 ) 2 SO 3 H、-O(CH 2 ) 3 SO 3 H or-O (CH) 2 ) 4 SO 3 H。
Preferably, the preparation method comprises the following steps:
1,3,5-trialdehyde phloroglucinol is dissolved in a solvent A to prepare a first solution;
the benzidine monomer is dissolved in a solvent B to prepare a second solution;
and mixing the first solution and the second solution, and reacting to prepare the dispersion type solution with the electrolyte material.
Preferably, the solvent A comprises at least one of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, acetonitrile, ethanol, methanol, propanol and butanol.
Preferably, the solvent B comprises at least one of water, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, acetonitrile, ethanol, methanol, propanol and butanol.
Preferably, the dissolving is ultrasonic dissolving, and the time of ultrasonic dissolving is 1-30min.
Preferably, the mixing is ultrasonic mixing, and the time of the ultrasonic mixing is 1-30min.
Preferably, the concentration of the 1,3,5-trialdehyde phloroglucinol in the first solution is 3-200mmol/L; more preferably, the concentration of the 1,3,5-trialdehyde phloroglucinol is 50-150mmol/L.
Preferably, the concentration of the benzidine monomer in the second solution is 3-200mmol/L; further preferably, the concentration of the benzidine monomer is 7.5 to 200mmol/L.
Preferably, the molar ratio of the 1,3,5-trialdehyde phloroglucinol to the benzidine monomers is 2 (3-6).
Preferably, an acid catalyst is added after the first solution and the second solution are mixed; further preferably, the acidic catalyst has a sulfonic acid group thereon; still further preferably, the acidic catalyst comprises p-toluenesulfonic acid.
Preferably, the molar ratio of the acidic catalyst to the benzidine monomer is (1-2): 3.
preferably, the reaction is a standing reaction.
Preferably, the reaction time is 1 to 3 days.
A third aspect of the invention provides a proton-conducting membrane, the composition of which comprises the electrolyte material.
In a fourth aspect, the present invention provides a method for preparing the proton-conducting membrane, the method comprising the steps of:
and pouring the dispersion solution on a horizontal substrate, spreading the dispersion solution, heating the dispersion solution to volatilize the solvent to obtain the proton conduction membrane, putting the substrate in water to separate the proton conduction membrane, and washing the proton conduction membrane.
Preferably, the material of the substrate includes at least one of glass and polytetrafluoroethylene.
Preferably, the substrate has a smooth flat surface.
Preferably, the heating temperature is 40-60 ℃, and the heating time is 3-5 days.
Preferably, the washing solvent comprises at least one of N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and water.
A fifth aspect of the invention provides a fuel cell comprising said proton-conducting membrane.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention develops a new polymer skeleton by introducing sulfonic acid groups into covalent organic framework pore channels and fixing the sulfonic acid groups in a covalent bond form, prepares a series of covalent organic framework proton conduction electrolyte materials and a preparation method and application thereof, and the proton conduction membrane formed by the electrolyte materials has high conductivity, and the proton conductivity is 0.19S-cm under the conditions of 80 ℃ and 95 percent of relative humidity -1 Above, up to 0.217S cm -1 。
(2) The invention realizes simple preparation of the self-supporting covalent organic framework membrane by an in-situ polymerization method, and the prepared membrane has better mechanical strength and flexibility and high stability and compactness.
Drawings
FIG. 1 shows TPBD-SO in example 1 3 A physical photograph of the H film;
FIG. 2 shows TPBD-SO in example 1 3 SEM image of H film;
FIG. 3 shows TPBD-SO obtained in example 1 3 Fourier transform infrared spectroscopy of the H film;
FIG. 4 shows TPBD-SO in example 1 3 H, testing proton conductivity of the membrane;
FIG. 5 shows TPBD-3-SO in example 2 3 A physical photograph of the H film;
FIG. 6 shows TPBD-3-SO obtained in example 2 3 SEM image of H film;
FIG. 7 shows TPBD-3-SO in example 2 3 Fourier transform infrared spectroscopy of the H film;
FIG. 8 shows TPBD-3-SO obtained in example 2 3 H, testing proton conductivity of the membrane;
FIG. 9 shows TPBD-4-SO obtained in example 3 3 A physical photograph of the H film;
FIG. 10 shows TPBD-4-SO in example 3 3 SEM image of H film;
FIG. 11 shows TPBD-4-SO in example 3 3 Fourier transform infrared spectroscopy of the H film;
FIG. 12 shows TPBD-4-SO in example 3 3 H, testing proton conductivity of the membrane;
FIG. 13 is a photograph of an actual implementation of the TPBD-OH film of comparative example 1;
FIG. 14 is an SEM image of a TPBD-OH film in comparative example 1;
FIG. 15 is an XRD pattern of the TPBD-OH film of comparative example 1;
FIG. 16 is a Fourier transform infrared spectrum of the TPBD-OH film of comparative example 1;
FIG. 17 is a proton conductivity test chart of the TPBD-OH film in comparative example 1.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
TPBD-SO 3 H (covalent organic framework proton conducting electrolyte material) and TPBD-SO 3 Preparation method and product performance of H membrane (self-supporting covalent organic frame-based electrolyte membrane).
TPBD-SO 3 The structural formula of H (covalent organic framework proton conducting electrolyte material) is as follows:
dissolving 1,3,5-trialdehyde phloroglucinol as a monomer in N-methyl pyrrolidone, dissolving 3,3 '-disulfonic acid benzidine in dimethyl sulfoxide, and fully dissolving the monomer by ultrasonic treatment for 5 minutes, wherein the concentrations are respectively 50mmol/L (1,3,5-trialdehyde phloroglucinol) and 75mmol/L (3,3' -disulfonic acid benzidine);
mixing 1ml of 1,3,5-trialdehyde phloroglucinol solution and 1ml of 3,3' -disulfonic acid benzidine solution, performing ultrasonic treatment for 5 minutes to uniformly disperse the mixed solution, and standing at room temperature for 1 day to obtain TPBD-SO 3 A dispersion-type solution of H (covalent organic framework proton conducting electrolyte material);
then pouring the electrolyte solution on a cleaned glass plate, naturally spreading the electrolyte solution, heating the glass plate for 4 days at 60 ℃, putting the glass plate in water to separate a membrane after the solvent is volatilized, washing the glass plate by using N, N-dimethylformamide and deionized water, and finally drying the glass plate to obtain TPBD-SO 3 H membrane (self-supporting covalent organic framework based electrolyte membrane).
FIG. 1 shows TPBD-SO in example 1 3 A physical photograph of the H film shows that the H film has better flexibility. FIG. 2 shows TPBD-SO in example 1 3 SEM image of H film, TPBD-SO can be seen from the SEM image of FIG. 2 3 The H film is very uniform and compact. FIG. 3 shows TPBD-SO in example 1 3 Fourier transform infrared spectrum of H film, with Wavenumber (unit cm) on the abscissa -1 ) And the ordinate is the transmission (in a.u.); in the Fourier transform infrared spectrogram of FIG. 3, 1573cm -1 Peak at C = C, 1610cm -1 And 1298cm -1 Peaks at C = O and C-N, respectively, indicating TPBD-SO 3 H film formation was successful at 1186cm -1 And 1023cm -1 Is treated with-SO 3 H peak, indicating successful modification of the sulfonate on the covalent organic framework. FIG. 4 shows TPBD-SO obtained in example 1 3 H membrane proton conductivity test chart, the abscissa is impedance Z '(in Ω), the ordinate is impedance Z' (in Ω), FIG. 4 is TPBD-SO 3 The proton conductivity of the H membrane measured at 80 deg.C and relative humidity of 95% was 0.217S-cm -1 Indicating excellent proton conductivity.
Example 2
TPBD-3-SO 3 H (covalent organic framework proton conducting electrolyte material) and TPBD-3-SO 3 Preparation method and product performance of H membrane (self-supporting covalent organic frame-based electrolyte membrane).
TPBD-3-SO 3 The structural formula of H (covalent organic framework proton conducting electrolyte material) is as follows:
dissolving 1,3,5-trialdehyde phloroglucinol as a monomer in N-methyl pyrrolidone, dissolving 3,3 '-di (3-sulfopropoxy) benzidine in deionized water, and fully dissolving the monomer by ultrasonic treatment for 5 minutes, wherein the concentrations of the monomer are respectively 50mmol/L (1,3,5-trialdehyde phloroglucinol) and 75mmol/L (3,3' -disulfonic acid benzidine);
mixing 1ml of 1,3,5-trialdehyde phloroglucinol solution and 10ml of 3,3' -di (3-sulfopropoxy) benzidine solution, performing ultrasonic treatment for 5 minutes to uniformly disperse the mixed solution, and standing at room temperature for 1 day to obtain TPBD-3-SO 3 A dispersion-type solution of H (covalent organic framework proton conducting electrolyte material);
then pouring the electrolyte solution on a cleaned glass plate, horizontally and naturally spreading, heating at 50 ℃ for 3 days, putting the glass plate into water to separate a membrane after the solvent is volatilized, washing with N, N-dimethylformamide and deionized water, and finally drying to obtain TPBD-3-SO 3 H membrane (self-supporting covalent organic framework based electrolyte membrane).
FIG. 5 shows TPBD-3-SO obtained in example 2 3 A physical photograph of the H film shows that the H film has better flexibility. FIG. 6 shows TPBD-3-SO obtained in example 2 3 SEM image of H film, from the SEM image of FIG. 6, it can be seen that TPBD-3-SO 3 The H film is very uniform and compact. FIG. 7 shows TPBD-3-SO in example 2 3 Fourier transform Infrared Spectroscopy of H film, with the abscissa being the number of wavenumbers (units cm) in the Fourier transform Infrared Spectroscopy of FIG. 7 -1 ) And a transmittance (in a.u.) of 1577cm on the ordinate -1 Peak at C = C, 1611cm -1 And 1303cm -1 Peaks at C = O and C-N, respectively, indicating TPBD-3-SO 3 H film formation was successful at 1184cm -1 And 1030cm -1 Is treated with-SO 3 H peak, indicating successful modification of the sulfonate on the covalent organic framework. FIG. 8 shows TPBD-3-SO obtained in example 2 3 H, proton conductivity test chart of the membrane, wherein the abscissa is impedance Z '(in omega), and the ordinate is impedance Z' (in omega); FIG. 8 is an impedance diagram of a TPBD-3-SO3H film at 80 ℃ and 95% relative humidity, showing a proton conductivity of 0.205 S.cm -1 Thus showing excellent proton conductivity.
Example 3
TPBD-4-SO 3 H (covalent organic framework proton conducting electrolyte material) and TPBD-4-SO 3 Preparation method and product performance of H membrane (self-supporting covalent organic frame-based electrolyte membrane).
TPBD-4-SO 3 The structural formula of H (covalent organic framework proton conducting electrolyte material) is as follows:
dissolving monomers 1,3,5-trialdehyde phloroglucinol and 3,3 '-bis (4-sulfobutoxy) benzidine in N-methylpyrrolidone and deionized water respectively, and performing ultrasonic treatment for 5 minutes to fully dissolve the monomers, wherein the concentrations are 50mmol/L (1,3,5-trialdehyde phloroglucinol) and 75mmol/L (3,3' -disulfonic acid benzidine) respectively;
mixing 1ml of 1,3,5-trialdehyde phloroglucinol solution and 10ml of 3,3' -bis (4-sulfobutoxy) benzidine solution, performing ultrasonic treatment for 5 minutes to uniformly disperse the mixed solution, and standing at room temperature for 1 day to obtain TPBD-4-SO 3 A dispersion-type solution of H (covalent organic framework proton-conducting electrolyte material);
then pouring the electrolyte solution on a cleaned glass plate, naturally spreading the electrolyte solution, heating the glass plate for 3 days at 50 ℃, putting the glass plate in water to separate a membrane after the solvent is volatilized, washing the glass plate by using N, N-dimethylformamide and deionized water, and finally drying the glass plate to obtain TPBD-4-SO 3 H membrane (self-supporting covalent organic framework based electrolyte membrane).
FIG. 9 shows TPBD-4-SO obtained in example 3 3 A physical photograph of the H film shows that the H film has better flexibility. FIG. 10 shows TPBD-4-SO in example 3 3 SEM image of H film, from the SEM image of FIG. 10, it can be seen that TPBD-4-SO 3 The H film is very uniform and compact. FIG. 11 shows TPBD-4-SO in example 3 3 Fourier transform infrared spectrum of H film, with wave number (unit cm) as abscissa -1 ) And the ordinate is the transmission (in a.u.) of the sample; in the Fourier transform infrared spectrogram of FIG. 11, 1577cm -1 Peak at C = C, 1611cm -1 And 1301cm -1 At the branch partPeaks of C = O and C-N, respectively, indicating TPBD-4-SO 3 H film formation success, 1190cm -1 And 1038cm -1 Is treated with-SO 3 H peak, indicating successful modification of the sulfonate on the covalent organic framework. FIG. 12 shows TPBD-4-SO in example 3 3 H, proton conductivity test chart of the membrane, wherein the abscissa is impedance Z '(in omega), and the ordinate is impedance Z' (in omega); FIG. 12 shows TPBD-4-SO 3 The proton conductivity of the H membrane measured at 80 deg.C and relative humidity of 95% is 0.191S-cm -1 Thus showing excellent proton conductivity.
Comparative example 1
TPBD-OH (covalent organic framework proton conductive electrolyte material) and TPBD-OH membrane preparation method and product performance.
Adding 1,3,5-trialdehyde phloroglucinol into an N-methyl pyrrolidone solution, adding 3,3 '-dihydroxy benzidine and p-toluenesulfonic acid into a dimethyl sulfoxide solution, respectively carrying out ultrasonic treatment for 5 minutes to fully dissolve the monomers, wherein the concentrations of 1,3,5-trialdehyde phloroglucinol and 3,3' -dihydroxy benzidine are 100mmol/L and 150mmol/L respectively, and the concentration of p-toluenesulfonic acid is 100mmol/L;
mixing 1ml of 1,3,5-trialdehyde phloroglucinol solution and 1ml of 3,3' -dihydroxybenzidine solution, performing ultrasonic treatment for 5 minutes to uniformly disperse the mixed solution, and standing at room temperature for 1 day to obtain a dispersion type solution of TPBD-OH (covalent organic framework proton conductive electrolyte material);
and then pouring the dispersion solution on a cleaned glass plate, horizontally and naturally spreading the solution, heating the glass plate for 4 days at 60 ℃, putting the glass plate in water to separate the membrane after the solvent is volatilized, washing the membrane by using N, N-dimethylformamide and deionized water, and finally drying the membrane to obtain the TPBD-OH membrane (the self-supporting covalent organic framework-based electrolyte membrane).
FIG. 13 is a photograph of an actual product of the TPBD-OH film in comparative example 1. FIG. 14 is an SEM image of the TPBD-OH film of comparative example 1, and it can be seen from the SEM image of FIG. 14 that the TPBD-OH film is very uniform and dense. Fig. 15 is an XRD pattern of the TPBD-OH film of comparative example 1, and the XRD pattern of fig. 15 can indicate that the TPBD-OH film has a certain crystallinity. FIG. 16 is a Fourier transform infrared spectrum, abscissa, of the TPBD-OH film of comparative example 1Denoted as Wavenumber (Wavenumber, unit cm) -1 ) And the ordinate is the transmission (in a.u.); in the Fourier transform infrared spectrogram of FIG. 16, 1577cm -1 Peak at C = C, 1610cm -1 And 1293cm -1 Peaks at C = O and C-N, respectively, indicate successful formation of TPBD-OH film. FIG. 17 is a test chart of proton conductivity of the TPBD-OH film in comparative example 1, with impedance Z 'on the abscissa (in Ω) and impedance Z' on the ordinate (in Ω); FIG. 17 is an impedance diagram of a TPBD-OH film at 80 ℃ and 95% relative humidity, showing a proton conductivity of 9.28X 10 -5 S·cm -1 。
Comparative example 1 of the present invention includes the proton conductivity of TPBD-OH film and TPBD-4-SO 3 The proton conductivity properties of H-membranes differ greatly. The method specifically comprises the following steps: the TPBD-OH film had a conductivity of 9.28X 10 at 80 ℃ and a relative humidity of 95% -5 S·cm -1 And TPBD-4-SO 3 The conductivity of the H film under the same condition is 0.191S-cm -1 The performance is obviously superior to that of the TPBD-OH film.
Claims (10)
1. An electrolyte material, characterized in that the electrolyte material is a polymer having a structural unit represented by the following general formula I:
in the general formula I, x is selected from 0, 1, 2 or 3,R and is selected from sulfonic acid group or C with sulfonic acid group 1 To C 4 An alkoxy group of (2).
2. The electrolyte material of claim 1, wherein the electrolyte material is a polymer having a structural unit represented by the following general formula ii:
in the general formula II, x is selected from 0, 1, 2 or3,R is selected from sulfonic acid group or C with sulfonic acid group 1 To C 4 An alkoxy group of (2).
3. The electrolyte material of claim 1, wherein R is selected from-SO 3 H、-OCH 2 SO 3 H、-O(CH 2 ) 2 SO 3 H、-O(CH 2 ) 3 SO 3 H or-O (CH) 2 ) 4 SO 3 H。
4. A production method for the electrolyte material according to any one of claims 1 to 3, characterized in that the production method comprises the steps of:
in the presence of a solvent, 1,3,5-trialdehyde phloroglucinol reacts with a benzidine monomer to prepare the electrolyte material;
the benzidine monomer is shown as a general formula III; in the general formula III, x is selected from 0, 1, 2 or 3,R and is selected from sulfonic acid group or C with sulfonic acid group 1 To C 4 Alkoxy group of (2).
5. The method of manufacturing according to claim 4, comprising the steps of:
1,3,5-trialdehyde phloroglucinol is dissolved in a solvent A to prepare a first solution;
the benzidine monomer is dissolved in a solvent B to prepare a second solution;
mixing the first solution and the second solution, and reacting to obtain the electrolyte material;
the electrolyte material is present in the form of a dispersion-type solution.
6. The method according to claim 5, wherein the solvent A comprises at least one of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, tetrahydrofuran, acetonitrile, ethanol, methanol, propanol, and butanol;
the solvent B comprises at least one of water, N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, acetonitrile, ethanol, methanol, propanol and butanol.
7. A proton-conducting membrane, wherein the composition of the proton-conducting membrane comprises the electrolyte material of any of claims 1-3.
8. A method of making a proton conducting membrane, comprising the steps of:
spreading the electrolyte material obtained by the production method according to any one of claims 4 to 6 on a substrate, heating to volatilize the solvent to obtain the proton-conducting membrane, separating the proton-conducting membrane by placing the substrate in water, and washing the proton-conducting membrane.
9. The method according to claim 8, wherein the heating temperature is 40 to 60 ℃ and the heating time is 3 to 5 days.
10. A fuel cell comprising the proton conducting membrane of claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211070551.6A CN115521425A (en) | 2022-09-02 | 2022-09-02 | Covalent organic framework proton-conducting electrolyte material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211070551.6A CN115521425A (en) | 2022-09-02 | 2022-09-02 | Covalent organic framework proton-conducting electrolyte material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115521425A true CN115521425A (en) | 2022-12-27 |
Family
ID=84698270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211070551.6A Pending CN115521425A (en) | 2022-09-02 | 2022-09-02 | Covalent organic framework proton-conducting electrolyte material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115521425A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117638128A (en) * | 2024-01-26 | 2024-03-01 | 杭州德海艾科能源科技有限公司 | High proton conductivity porous membrane for vanadium battery and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305347A (en) * | 2019-06-06 | 2019-10-08 | 中国石油大学(北京) | Modified glycan substrate proton exchange and preparation method thereof |
| CN110336052A (en) * | 2019-06-25 | 2019-10-15 | 大连理工大学 | A kind of mixed-matrix type cation-exchange membrane and preparation method thereof |
| CN112679731A (en) * | 2020-12-21 | 2021-04-20 | 同济大学 | Covalent organic framework material containing sulfonic acid group and preparation and application thereof |
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
| CN113461887A (en) * | 2021-01-28 | 2021-10-01 | 渤海大学 | One-dimensional nanochannel self-supporting covalent organic framework membrane for salt difference power generation and application thereof |
| WO2022061666A1 (en) * | 2020-09-24 | 2022-03-31 | 浙江大学 | Method for preparing hollow covalent organic framework material |
| CN114456339A (en) * | 2022-02-11 | 2022-05-10 | 天津大学浙江研究院 | Covalent organic framework film with high content of ionic groups, preparation method and application thereof |
| CN114976476A (en) * | 2022-05-16 | 2022-08-30 | 北京工业大学 | COFs (carbon-on-glass) based diaphragm for dendrite-free lithium metal battery and preparation method thereof |
-
2022
- 2022-09-02 CN CN202211070551.6A patent/CN115521425A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305347A (en) * | 2019-06-06 | 2019-10-08 | 中国石油大学(北京) | Modified glycan substrate proton exchange and preparation method thereof |
| CN110336052A (en) * | 2019-06-25 | 2019-10-15 | 大连理工大学 | A kind of mixed-matrix type cation-exchange membrane and preparation method thereof |
| WO2022061666A1 (en) * | 2020-09-24 | 2022-03-31 | 浙江大学 | Method for preparing hollow covalent organic framework material |
| CN112679731A (en) * | 2020-12-21 | 2021-04-20 | 同济大学 | Covalent organic framework material containing sulfonic acid group and preparation and application thereof |
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
| CN113461887A (en) * | 2021-01-28 | 2021-10-01 | 渤海大学 | One-dimensional nanochannel self-supporting covalent organic framework membrane for salt difference power generation and application thereof |
| CN114456339A (en) * | 2022-02-11 | 2022-05-10 | 天津大学浙江研究院 | Covalent organic framework film with high content of ionic groups, preparation method and application thereof |
| CN114976476A (en) * | 2022-05-16 | 2022-08-30 | 北京工业大学 | COFs (carbon-on-glass) based diaphragm for dendrite-free lithium metal battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117638128A (en) * | 2024-01-26 | 2024-03-01 | 杭州德海艾科能源科技有限公司 | High proton conductivity porous membrane for vanadium battery and preparation method thereof |
| CN117638128B (en) * | 2024-01-26 | 2024-04-30 | 杭州德海艾科能源科技有限公司 | High proton conductivity porous membrane for vanadium battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110336052B (en) | Mixed matrix type cation exchange membrane and preparation method thereof | |
| Zhang et al. | Cross-linked membranes based on sulfonated poly (ether ether ketone)(SPEEK)/Nafion for direct methanol fuel cells (DMFCs) | |
| Cheng et al. | SGO/SPEN-based highly selective polymer electrolyte membranes for direct methanol fuel cells | |
| Zheng et al. | Nafion-microporous organic polymer networks composite membranes | |
| Sun et al. | Phosphoric acid-loaded covalent triazine framework for enhanced the proton conductivity of the proton exchange membrane | |
| CN114361469A (en) | Fuel cell catalyst layer and fuel cell | |
| CN112133946A (en) | Carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal organic framework composite membrane and preparation method thereof | |
| CN114524919A (en) | Polyaryl anion exchange membrane and preparation method thereof | |
| Sun et al. | Polybenzimidazole dendrimer containing triazine rings-based high-temperature proton exchange membranes with high performances over a wide humidity range | |
| Roshanravan et al. | Incorporating sulfonated MIL-100 (Fe) in sulfonated polysulfone for enhancing microbial fuel cell performance | |
| Wang et al. | Synthesized Geminal-imidazolium-type ionic liquids applying for PVA-FP/[DimL][OH] anion exchange membranes for fuel cells | |
| Xu et al. | Surface modification of heteropoly acid/SPEEK membranes by polypyrrole with a sandwich structure for direct methanol fuel cells | |
| 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 | |
| CN113067022A (en) | Amino-containing sulfonated polyaryletherketone sulfone blended metal organic framework composite membrane and preparation method thereof | |
| CN115521425A (en) | Covalent organic framework proton-conducting electrolyte material and preparation method and application thereof | |
| CN112898539A (en) | Long-side-chain polyaromatic hydrocarbon isatin alkaline membrane for fuel cell and preparation method thereof | |
| Zhang et al. | Microporous and low swelling branched poly (aryl piperidinium) anion exchange membranes for high-performed water electrolyzers | |
| Cheng et al. | NH group-rich dendrimer doped polybenzimidazole composite membrane with consecutive proton transportation channels for HT-PEMFCs | |
| Wang et al. | High-performance proton exchange membranes based on block polybenzimidazole and organic–inorganic fillers with a low acid doping level | |
| Zhao et al. | Fabrication of a 2, 6-diaminopurine-grafted cellulose nanocrystal composite with high proton conductivity | |
| CN115207423A (en) | Preparation method of sodium lignosulfonate modified attapulgite chitosan proton exchange membrane | |
| CN111969232B (en) | Preparation method of fuel cell diaphragm material | |
| CN114395112A (en) | Hydrophobic block-containing polycarbazole anion exchange membrane and preparation method thereof | |
| CN113363541A (en) | POSS covalent hybrid polybenzimidazole ion exchange membrane and preparation method thereof | |
| CN115181286B (en) | Guanidino phosphate hydrogen bond organic framework material, and preparation method and application 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 |