CN108376792A - A kind of fuel battery proton exchange film and preparation method of metal-organic phase modification - Google Patents
A kind of fuel battery proton exchange film and preparation method of metal-organic phase modification Download PDFInfo
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- CN108376792A CN108376792A CN201810113035.4A CN201810113035A CN108376792A CN 108376792 A CN108376792 A CN 108376792A CN 201810113035 A CN201810113035 A CN 201810113035A CN 108376792 A CN108376792 A CN 108376792A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- 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
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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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
The present invention relates to fuel cell fields, disclose a kind of fuel battery proton exchange film and preparation method of metal-organic phase modification.Including following preparation process：（1）Benzene sulfonic acid will be added behind zirconium source and ligand dissolving, heating crystallization is made with sulfonic 66 SO of metal-organic phase UiO3H；（2）It will be compound with sulfonic metal-organic phase and Nafion perfluoro sulfonic acid membranes progress hydro-thermal, it takes out, is dry, compound proton exchange membrane is made, proton exchange membrane produced by the present invention passes through strongly hydrophilic with sulfonic metal-organic phase and low swellability compared with common perfluoro sulfonic acid membrane, improve adaptability of the perfluoro sulfonic acid membrane under high temperature low moisture environments, swelling ratio in water is low, and proton transfer rate is high, and conductivity is good, mechanical performance is good, and effectively extends the service life of membrane material.
Description
Technical field
The present invention relates to fuel cell fields, disclose a kind of fuel battery proton exchange film of metal-organic phase modification
And preparation method.
Background technology
Fuel cell is a kind of the chemical energy of fuel and oxidant to be directly changed into electric energy by electrochemical reaction mode
Efficient electric installation, energy conversion rate is high, is a kind of environmental-friendly novel energy.There are many type of fuel cell, proton
Exchange film fuel battery is one such, and biggest advantage is that it can work near room temperature, and start battery is fast,
Energy conversion rate is high, it can not only substitute common secondary cell, but also can be as the power source of automobile, to subtract significantly
Few environmental pollution, application prospect are fabulous.
Core element of the proton exchange membrane as fuel cell, it is different from diaphragm used in general electrochmical power source.It is first
First, it is not only a kind of diaphragm material separating anode and cathode, but also is the base of electrolyte and electrode active material
Bottom.In addition, proton exchange membrane or a kind of permselectivity membrane, and it is all porous membrane to lead to common diaphragm.That is, matter
The effect of proton exchange is dual, provides proton channel as electrolyte and polarization response gas, mesh is isolated as diaphragm
Most common preceding application is perfluoro sulfonic acid membrane.
The main chain of perfluorinated sulfonic acid membrane molecule has polytetrafluoroethylene (PTFE) structure, and the fluorine atom in molecule can be tight by carbon carbon bond
Close covering, and carbon-fluorine bond bond distance is short, bond energy is high, polarizable degree is small, and molecule is made to have excellent thermal stability, chemical stability
With higher mechanical strength, the long life of polymer film is ensured that;Hydrophilic sulfonic acid group energy on molecule branch
Enough adsorbed water molecules, have excellent ionic conduction characteristic.Studies have shown that the quantity of sulfonic acid group in film is improved, with water imbibition
Metal oxide or the other materials such as inorganic solid proton conductor carry out compound, film high-temp. electric conductivity can be improved and reduce film combustion
Expect permeability, this is also the developing Main Topics of current perfluoro sulfonic acid membrane.
Chinese invention patent application number 201610330517.6, which discloses in a kind of perfluoro sulfonic acid membrane (Nafion), mixes sulphur
The method of graphite alkene (SGO), is prepared into SGO/Nafion composite membranes, improves the ionic conductivity of Nafion membrane.The invention is closed
At SGO addition to the water absorption rate of SGO/Nafion composite membranes, swellbility and ionic conductivity are significantly improved.Water suction
Rate increases to the 89% of composite membrane from the 30% of pure Nafion membrane, and swellbility increases to composite membrane from the 75% of pure Nafion membrane
142%, the ionic conductivity of pure Nafion membrane is 57.89Mscm-1, with the increase of SGO contents, the ion-conductance of composite membrane
Conductance gradually increases, the ionic conductivity 125.70Mscm- of highest Nafion-8%-SGO composite membranes1, it is more than pure
Nafion membrane is more than 2 times.
Chinese invention patent application number 200810014151.7 discloses a kind of intercrossed enhanced full fluorin proton adulterated exchange film
And preparation method thereof, belong to field of functional polymer composites, this full fluorin proton exchange film is made with perfluorinated sulfonic resin
For film-forming resin, inorganic matter is added, carries out cross-linking reaction under certain condition, forms the enhancing compound ion with network structure
Exchange membrane.Perfluoro sulfonic acid membrane prepared by the present invention has higher proton conductivity and higher mechanical performance.
According to above-mentioned, the perfluorosulfonic acid proton exchange film working environment harshness in existing scheme, to high temperature and low humidity item
The bad adaptability of part, proton transfer rate is low, and conductivity is low, is swollen in water larger, and service life is short, and traditional raising sulphur
The MATERIALS METHODSs effect such as acid groups and addition water imbibition oxide is undesirable, and exists to membrane material mechanical performance and adversely affect.This
Invention proposes a kind of fuel battery proton exchange film and preparation method of metal-organic phase modification, can effectively solve above-mentioned skill
Art problem.
Invention content
The wider perfluorosulfonic acid proton exchange film of application is to the bad adaptability of high temperature and low-moisture conditions, proton transfer at present
Rate is low, and conductivity is low, is swollen in water larger, and service life is short, and the method effect of traditional raising and modification is undesirable,
And exist to membrane material mechanical performance and adversely affect, prepare difficulty and of high cost.
To solve the above problems, the present invention uses following technical scheme：
A kind of preparation method of the fuel battery proton exchange film of metal-organic phase modification, the fuel battery proton exchange film
Preparation process be：
（1）Preparation with sulfonic metal-organic phase：First zirconium source and ligand are added in organic solvent, benzene is added after dissolving
Sulfonic acid reheats crystallization, is made with sulfonic metal-organic phase UiO-66-SO3H；
（2）The preparation of compound proton exchange membrane：It will first be soaked together with Nafion perfluoro sulfonic acid membranes with sulfonic metal-organic phase
Enter in water, hydrothermal reaction kettle is added, then heating progress hydro-thermal is compound, further takes out, dries, and compound proton exchange membrane is made.
Preferably, step（1）The zirconium source is zirconium chloride.
Preferably, step（1）The ligand is terephthalic acid (TPA).
Preferably, step（1）It is dimethylformamide to state organic solvent.
Preferably, the step（1）In, by weight, wherein：30 ~ 35 parts of zirconium source, 4 ~ 6 parts of ligand, organic solvent 39
~ 51 parts, 15 ~ 20 parts of benzene sulfonic acid.
Preferably, step（1）The temperature of the heating crystallization is 110 ~ 125 DEG C.
Preferably, step（2）The hydrothermal temperature is 180 ~ 190 DEG C, and the time is 150 ~ 200min.
Preferably, step（2）In the compound proton exchange membrane, accounts for composite proton with sulfonic metal-organic phase and hand over
Change the 15-20% of film quality.
A kind of fuel battery proton exchange film of the metal being prepared by the above method-organic phase modification, uses chlorination
Zirconium is dissolved in ligand terephthalic acid (TPA) in solvent dimethylformamide, while benzene sulfonic acid is added as zirconium source, brilliant at 120 DEG C
Change is prepared with sulfonic metal-organic phase UiO-66-SO3It is multiple to carry out hydro-thermal with Nafion perfluoro sulfonic acid membranes later by H
It closes, obtains ionic exchange film for fuel cell.By strongly hydrophilic with sulfonic metal-organic phase and low swelling type,
Adaptability and proton transfer rate of the Nafion membrane under high temperature low moisture environments are improved, while reducing its swelling in aqueous solution,
To improve the environmental suitability and service life of Nafion membrane.
It is and existing the present invention provides the fuel battery proton exchange film and preparation method of a kind of modification of metal-organic phase
Technology is compared, and the feature and excellent effect protruded is：
1, it proposes using with sulfonic metal-organic phase UiO-66-SO3H prepares the fuel cell of metal-organic phase modification
The method of proton exchange membrane.
2, by the strongly hydrophilic with sulfonic metal-organic phase, perfluoro sulfonic acid membrane is improved in high temperature low humidity ring
Adaptability under border, proton transfer rate is high, and conductivity is good.
3, the low swelling type with sulfonic metal-organic phase is crossed, its swellability in aqueous solution is reduced, is improved
The mechanical performance of membrane material, and effectively extend the service life of membrane material.
4, preparation process of the invention is simple, and easy to operate, production cost is low, can be widely used for fuel cell field.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）The detailed process of preparation with sulfonic metal-organic phase is：
First zirconium source and ligand are added in organic solvent, benzene sulfonic acid is added after dissolving, reheats crystallization, is made with sulfonic gold
Category-organic phase UiO-66-SO3H；Zirconium source is zirconium chloride；Ligand is terephthalic acid (TPA)；Organic solvent is dimethylformamide；Add
The temperature of thermal crystallisation is 118 DEG C；
By weight, wherein：33 parts of zirconium source, 5 parts of ligand, 44 parts of organic solvent, 18 parts of benzene sulfonic acid；
（2）The detailed process of the preparation of compound proton exchange membrane is：
It will be first immersed in the water together with Nafion perfluoro sulfonic acid membranes with sulfonic metal-organic phase, and hydrothermal reaction kettle be added, so
Heating progress hydro-thermal is compound afterwards, further takes out, dries, and compound proton exchange membrane is made；Hydrothermal temperature is 185 DEG C, and the time is
180min；
In compound proton exchange membrane, the 15% of compound proton exchange membrane quality is accounted for sulfonic metal-organic phase.
Proton exchange membrane made from embodiment 1, swelling ratio is such as in the minimum relative humidity effectively used at 120 DEG C, water
Shown in table 1.
Embodiment 2
（1）The detailed process of preparation with sulfonic metal-organic phase is：
First zirconium source and ligand are added in organic solvent, benzene sulfonic acid is added after dissolving, reheats crystallization, is made with sulfonic gold
Category-organic phase UiO-66-SO3H；Zirconium source is zirconium chloride；Ligand is terephthalic acid (TPA)；Organic solvent is dimethylformamide；Add
The temperature of thermal crystallisation is 110 DEG C；
By weight, wherein：30 parts of zirconium source, 4 parts of ligand, 51 parts of organic solvent, 15 parts of benzene sulfonic acid；
（2）The detailed process of the preparation of compound proton exchange membrane is：
It will be first immersed in the water together with Nafion perfluoro sulfonic acid membranes with sulfonic metal-organic phase, and hydrothermal reaction kettle be added, so
Heating progress hydro-thermal is compound afterwards, further takes out, dries, and compound proton exchange membrane is made；Hydrothermal temperature is 180 DEG C, and the time is
200min；
In compound proton exchange membrane, the 20% of compound proton exchange membrane quality is accounted for sulfonic metal-organic phase.
Proton exchange membrane made from embodiment 2, swelling ratio is such as in the minimum relative humidity effectively used at 120 DEG C, water
Shown in table 1.
Embodiment 3
（1）The detailed process of preparation with sulfonic metal-organic phase is：
First zirconium source and ligand are added in organic solvent, benzene sulfonic acid is added after dissolving, reheats crystallization, is made with sulfonic gold
Category-organic phase UiO-66-SO3H；Zirconium source is zirconium chloride；Ligand is terephthalic acid (TPA)；Organic solvent is dimethylformamide；Add
The temperature of thermal crystallisation is 125 DEG C；
By weight, wherein：35 parts of zirconium source, 6 parts of ligand, 39 parts of organic solvent, 20 parts of benzene sulfonic acid；
（2）The detailed process of the preparation of compound proton exchange membrane is：
It will be first immersed in the water together with Nafion perfluoro sulfonic acid membranes with sulfonic metal-organic phase, and hydrothermal reaction kettle be added, so
Heating progress hydro-thermal is compound afterwards, further takes out, dries, and compound proton exchange membrane is made；Hydrothermal temperature is 190 DEG C, and the time is
150min；
In compound proton exchange membrane, the 18% of compound proton exchange membrane quality is accounted for sulfonic metal-organic phase.
Proton exchange membrane made from embodiment 3, swelling ratio such as 1 institute of table in the minimum relative humidity used under 120, water
Show.
Embodiment 4
（1）The detailed process of preparation with sulfonic metal-organic phase is：
First zirconium source and ligand are added in organic solvent, benzene sulfonic acid is added after dissolving, reheats crystallization, is made with sulfonic gold
Category-organic phase UiO-66-SO3H；Zirconium source is zirconium chloride；Ligand is terephthalic acid (TPA)；Organic solvent is dimethylformamide；Add
The temperature of thermal crystallisation is 115 DEG C；
By weight, wherein：32 parts of zirconium source, 4 parts of ligand, 47 parts of organic solvent, 17 parts of benzene sulfonic acid；
（2）The detailed process of the preparation of compound proton exchange membrane is：
It will be first immersed in the water together with Nafion perfluoro sulfonic acid membranes with sulfonic metal-organic phase, and hydrothermal reaction kettle be added, so
Heating progress hydro-thermal is compound afterwards, further takes out, dries, and compound proton exchange membrane is made；Hydrothermal temperature is 182 DEG C, and the time is
190min；
In compound proton exchange membrane, the 15% of compound proton exchange membrane quality is accounted for sulfonic metal-organic phase.
Proton exchange membrane made from embodiment 4, swelling ratio is such as in the minimum relative humidity effectively used at 120 DEG C, water
Shown in table 1.
Embodiment 5
（1）The detailed process of preparation with sulfonic metal-organic phase is：
First zirconium source and ligand are added in organic solvent, benzene sulfonic acid is added after dissolving, reheats crystallization, is made with sulfonic gold
Category-organic phase UiO-66-SO3H；Zirconium source is zirconium chloride；Ligand is terephthalic acid (TPA)；Organic solvent is dimethylformamide；Add
The temperature of thermal crystallisation is 122 DEG C；
By weight, wherein：34 parts of zirconium source, 6 parts of ligand, 42 parts of organic solvent, 18 parts of benzene sulfonic acid；
（2）The detailed process of the preparation of compound proton exchange membrane is：
It will be first immersed in the water together with Nafion perfluoro sulfonic acid membranes with sulfonic metal-organic phase, and hydrothermal reaction kettle be added, so
Heating progress hydro-thermal is compound afterwards, further takes out, dries, and compound proton exchange membrane is made；Hydrothermal temperature is 188 DEG C, and the time is
190min；
In compound proton exchange membrane, the 15% of compound proton exchange membrane quality is accounted for sulfonic metal-organic phase.
Proton exchange membrane made from embodiment 5, swelling ratio is such as in the minimum relative humidity effectively used at 120 DEG C, water
Shown in table 1.
Comparative example 1
First zirconium source and ligand are added in organic solvent, reheat crystallization, zirconium source is zirconium chloride；Ligand is terephthalic acid (TPA)；Have
Solvent is dimethylformamide；The temperature of heating crystallization is 117 DEG C；
By weight, wherein：32 parts of zirconium source, 5 parts of ligand, 46 parts of organic solvent；
Then it is immersed in the water with together with Nafion perfluoro sulfonic acid membranes, hydrothermal reaction kettle is added, then heating progress hydro-thermal is compound, then
It takes out, is dry, compound proton exchange membrane is made；Hydrothermal temperature is 186 DEG C, time 170min；
In compound proton exchange membrane, metal-organic phase accounts for the 16% of compound proton exchange membrane quality.
Benzene sulfonic acid is not added for comparative example 1, is not introduced into sulfonic group, proton exchange membrane obtained, is effectively used at 120 DEG C
Swelling ratio is as shown in table 1 in minimum relative humidity, water.
Comparative example 2
Commercially available Nafion perfluoro sulfonic acid membranes.
The test method of above-mentioned performance indicator is：
Under conditions of 120 DEG C of temperature, relative humidity 60%, the proton exchange rate for testing proton exchange membrane changes with time, with
Proton exchange rate is down to 50% time of initial value, as out-of-service time.
At 120 DEG C of temperature, continuously decrease the relative humidity of test environment, test the proton exchange rate of proton exchange membrane with
For proton exchange rate when the variation of relative humidity using relative humidity is 60% as initial value, proton exchange rate is down to initial value
Relative humidity when 50% as effectively uses minimum relative humidity.
The proton exchange membrane that volume is V1 is placed in enough water, volume is dipped to and no longer changes, test volume V2,
By（V2-V1）Swelling ratio in water can be calculated in/V1.
Table 1：
Claims (9)
1. a kind of preparation method of the fuel battery proton exchange film of metal-organic phase modification, which is characterized in that preparation process
For：
（1）Preparation with sulfonic metal-organic phase：First zirconium source and ligand are added in organic solvent, benzene is added after dissolving
Sulfonic acid reheats crystallization, is made with sulfonic metal-organic phase UiO-66-SO3H；
（2）The preparation of compound proton exchange membrane：It will first be soaked together with Nafion perfluoro sulfonic acid membranes with sulfonic metal-organic phase
Enter in water, hydrothermal reaction kettle is added, then heating progress hydro-thermal is compound, further takes out, dries, and compound proton exchange membrane is made.
2. the preparation method of the fuel battery proton exchange film of a kind of metal-organic phase modification according to claim 1, special
Sign is：Step（1）The zirconium source is zirconium chloride.
3. the preparation method of the fuel battery proton exchange film of a kind of metal-organic phase modification according to claim 1, special
Sign is：Step（1）The ligand is terephthalic acid (TPA).
4. the preparation method of the fuel battery proton exchange film of a kind of metal-organic phase modification according to claim 1, special
Sign is：Step（1）It is dimethylformamide to state organic solvent.
5. the preparation method of the fuel battery proton exchange film of a kind of metal-organic phase modification according to claim 1, special
Sign is：The step（1）In, by weight, wherein：30 ~ 35 parts of zirconium source, 4 ~ 6 parts of ligand, 39 ~ 51 parts of organic solvent, benzene
15 ~ 20 parts of sulfonic acid.
6. the preparation method of the fuel battery proton exchange film of a kind of metal-organic phase modification according to claim 1, special
Sign is：Step（1）The temperature of the heating crystallization is 110 ~ 125 DEG C.
7. the preparation method of the fuel battery proton exchange film of a kind of metal-organic phase modification according to claim 1, special
Sign is：Step（2）The hydrothermal temperature is 180 ~ 190 DEG C, and the time is 150 ~ 200min.
8. the preparation method of the fuel battery proton exchange film of a kind of metal-organic phase modification according to claim 1, special
Sign is：Step（2）In the compound proton exchange membrane, compound proton exchange membrane quality is accounted for sulfonic metal-organic phase
15-20%.
9. a kind of fuel cell proton of metal that any one of claim 1 ~ 8 the method is prepared-organic phase modification is handed over
Change film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109524698A (en) * | 2018-09-30 | 2019-03-26 | 中能源工程集团氢能科技有限公司 | One kind being based on thiocarbamide carboxylic acids metal organic frame/Nafion polymer hybrid proton exchange membrane and preparation method thereof |
| CN112838252A (en) * | 2019-11-25 | 2021-05-25 | 嘉应学院 | Proton exchange membrane with high proton conductivity for fuel cell and preparation method and application thereof |
| CN116333526A (en) * | 2023-05-26 | 2023-06-27 | 国家电投集团氢能科技发展有限公司 | Cathode catalytic layer ink, cathode catalytic layer, membrane electrode and fuel cell |
-
2018
- 2018-02-05 CN CN201810113035.4A patent/CN108376792A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109524698A (en) * | 2018-09-30 | 2019-03-26 | 中能源工程集团氢能科技有限公司 | One kind being based on thiocarbamide carboxylic acids metal organic frame/Nafion polymer hybrid proton exchange membrane and preparation method thereof |
| CN112838252A (en) * | 2019-11-25 | 2021-05-25 | 嘉应学院 | Proton exchange membrane with high proton conductivity for fuel cell and preparation method and application thereof |
| CN116333526A (en) * | 2023-05-26 | 2023-06-27 | 国家电投集团氢能科技发展有限公司 | Cathode catalytic layer ink, cathode catalytic layer, membrane electrode and fuel cell |
| CN116333526B (en) * | 2023-05-26 | 2023-08-18 | 国家电投集团氢能科技发展有限公司 | Cathode catalytic layer ink, cathode catalytic layer, membrane electrode and fuel cell |
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