CN110993998A - Polybenzimidazole proton exchange membrane containing naphthalene ring and preparation method and application thereof - Google Patents
Polybenzimidazole proton exchange membrane containing naphthalene ring and preparation method and application thereof Download PDFInfo
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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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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- 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
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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
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Abstract
The invention discloses a polybenzimidazole proton exchange membrane containing naphthalene rings, a preparation method and application thereof, belongs to the technical field of ion exchange membrane and membrane material preparation processes, and mainly solves the technical problems of low polymerization activity, high reaction temperature, poor solubility, difficult film formation and the like of the existing polybenzimidazole resin. The main chain of the polybenzimidazole polymer molecule contains a naphthalene ring structure or functional groups, and the polybenzimidazole polymer has the advantages of mild preparation conditions, good solubility and simple film forming process, and is expected to realize industrial production. The prepared polybenzimidazole proton exchange membrane has high mechanical stability and high proton conductivity.
Description
Technical Field
The invention belongs to the technical field of ion exchange membranes and membrane material preparation processes, and particularly relates to a polybenzimidazole proton exchange membrane containing naphthalene rings and a preparation method and application thereof.
Background
With the increasing tension of fossil energy and the problem of emission of various pollutants, hydrogen energy has received worldwide attention as a final solution to energy and environmental problems. By 2030, the global hydrogen energy ratio will reach 10%, and the output value will reach 12 trillion yuan. The utilization of hydrogen energy is critically dependent on fuel cell technology, and proton exchange membrane fuel cell technology (PEMFC) is currently the most mainstream fuel cell technology, and the development is relatively mature.
As a core component inside the fuel cell, the proton exchange membrane accounts for 10% -20% of the total cost of the whole fuel cell, and the performance of the proton exchange membrane has a decisive influence on the service performance, the service life, the cost and the like of the PEMFC, so the proton exchange membrane is recognized as a preferred energy source of electric automobiles, fixed power stations and the like.
The operating temperature of the current commercialized perfluorinated sulfonic acid proton exchange membrane (such as Nafion) battery is lower (less than or equal to 80 ℃), so that the PEMFC catalyst is easy to be poisoned by CO, the requirement on the purity of hydrogen is extremely high (the requirement on the purity is 99.9999%), the use cost is high, and simultaneously, the water management of a fuel cell stack is complex, and the efficiency of the fuel cell is reduced. Compared with a medium-low temperature fuel cell, the high-temperature proton exchange membrane fuel cell (HT-PEMFC) has higher electrochemical reaction activity and higher CO tolerance (the concentration can reach 3 percent), so that methanol, natural gas and other reformed hydrogen or coal chemical industry byproduct hydrogen and the like can be adopted as fuels, and the hydrogen purification cost is greatly reduced. Furthermore, simple hydrothermal management fundamentally simplifies the operation and management of the fuel cell system. Therefore, HT-PEMFCs are considered to be the next generation of revolutionary fuel cell technology. As the "heart" part of fuel cells, high temperature proton exchange membranes are the key material of the core of the revolutionary fuel cell technology. Therefore, the development of high-temperature proton exchange membrane materials meeting the requirements of fuel cell applications has become a first problem that the development of HT-PEMFCs must solve. Only German Bassff (BASF) and Danish electric (Danish Power System) have matured their prototypes for years due to their arrangement on polybenzimidazole based high temperature proton exchange membranes. The phosphoric acid-doped PBI high-temperature proton exchange membrane shows excellent chemical stability at the temperature of 140 ℃ and 180 ℃, and can realize the stable operation of a high-temperature fuel cell (180 ℃) with the temperature of over 12000 and 20000 h.
PBI is an aromatic heterocyclic polymer containing benzimidazole repeating units in a high-molecular main chain, and the aromatic main chain enables the PBI to have higher mechanical stability and chemical stability. The ion exchange group of PBI is located on the main chain, and the nitrogen atom on the imidazole ring is easily protonated under acidic conditions (J.electrochem.Soc.1995,7,121-123), forming a network-like electropositive structure, and possessing a proton conductive material base. After the alkaline imidazole ring is doped with phosphoric acid, the conductive material has higher conductive capability and shows the capability of conducting ions under the high-temperature anhydrous condition. Currently, the polybenzimidazole resin is commercialized as poly [2,2 '- (m-phenylene) -5, 5' -dibenzoimidazole ] (mPBI). The chemical structural formula is as follows:
the polymer synthetic monomer has low activity, needs to react for a long time at high temperature (200 ℃), has a main chain structure of full aromaticity, is tightly arranged among molecules, has more internal hydrogen bonds, causes poor solubility and processability of the resin, and limits large-scale production and preparation of the resin, so that the preparation of the PBI with high synthetic activity, low reaction temperature, good solubility and high molecular weight is needed.
Disclosure of Invention
The invention of the invention is: in order to overcome the defects in the prior art and solve the technical problems of low polymerization activity, high reaction temperature, poor solubility, difficult film formation and the like of the existing polybenzimidazole resin, the invention provides polybenzimidazole of which the main chain contains naphthalene rings, and the polymerization activity, the phosphoric acid doping rate and the solubility of the polybenzimidazole are improved, so that the proton exchange membrane for the high-temperature hydrogen-oxygen fuel cell is prepared.
The design concept of the invention is as follows: the polybenzimidazole main chain in the invention contains a naphthalene ring structure, so that the distance between high molecular chains is increased, phosphoric acid doping is facilitated, the interaction with nitrogen heterocycles on the main chain of the polymer is facilitated, the proton conductivity is increased, the hydrogen bond effect among polymer molecules is reduced, and the solubility of the polymer is improved. The invention is prepared by using diacid with different structures and biphenyltetramine through nucleophilic polycondensation reaction.
The invention is realized by the following technical scheme.
A polybenzimidazole type proton exchange membrane containing naphthalene rings, wherein: the main chain of the polybenzimidazole molecule contains a naphthalene ring structure, and the polybenzimidazole has a general formula:
the polymer is a homopolymer, a block copolymer or a random copolymer; n represents the polymerization degree of the polymer, n is a positive integer greater than 0, and the weight average molecular weight of the polymer is between 3000 and 800000;
in the general structural formula, R is one or more of the following structures:
Wherein the R structure is characterized in that: the diacid containing naphthalene ring has higher reaction activity, is beneficial to reducing the temperature and time of polymerization reaction, and the naphthalene ring is positioned in the main chain, thereby being beneficial to increasing the distance between macromolecules, leading phosphoric acid to be easily doped, improving the transmission of protons, simultaneously reducing the effect of hydrogen bonds between molecules and being beneficial to improving the solubility.
Further, the proton exchange membrane is synthesized by polycondensation, and the monomer of the polycondensation reaction is any one of 3, 3' -diaminobenzidine and the following diacid containing naphthalene ring:
A preparation method of a polybenzimidazole proton exchange membrane containing naphthalene rings comprises the following steps:
s1, firstly, adding diacid containing a naphthalene ring structure and biphenyltetramine into a polyphosphoric acid solvent in a nitrogen atmosphere, heating to 120-180 ℃, reacting for 2-24 hours, and pouring the hot solution into deionized water to obtain a filamentous polymer; then, washing the filamentous polymer for multiple times, adding sodium bicarbonate to adjust the pH value of the solution to be neutral, and filtering to obtain a solid polymer; finally, boiling the obtained solid polymer with water, filtering and drying the obtained polymer; in the reaction system, the monomer concentration of diacid monomer containing naphthalene ring structure and biphenyl tetramine in polyphosphoric acid solvent is 1-25 wt%, and the molar usage of the diacid monomer containing naphthalene ring structure and biphenyl tetramine is the same;
s2, dissolving the dried polymer in a polar solvent at 20-140 ℃, controlling the concentration of the solution at 2-20 wt%, directly casting the obtained polymer solution on a glass plate or a stainless steel plate, flattening by using a casting knife, drying for 5-24h at 60-100 ℃ to form a film, and then drying for 1-24h at 80-150 ℃ in vacuum to prepare the polybenzimidazole proton exchange membrane containing naphthalene rings, wherein the thickness of the proton exchange membrane is 10-200 μm.
Further, in the step S2, the polar solvent is one or more of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide.
The application of polybenzimidazole proton exchange membrane containing naphthalene ring comprises the following steps:
s1, immersing the polybenzimidazole proton exchange membrane containing naphthalene ring in 85% phosphoric acid for 1-48h, wherein the immersion temperature is 20-120 ℃;
s2, installing the proton exchange membrane soaked in the step S1 in a high-temperature proton exchange membrane fuel cell, hot-pressing the proton exchange membrane and two pieces of carbon paper sprayed with a catalyst together to prepare a membrane electrode, then clamping the membrane electrode by a graphite electrode plate with a gas flow channel, fixing the membrane electrode by a high-temperature heating end plate, and introducing hydrogen and oxygen into the proton exchange membrane fuel cell through the gas flow channel.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polybenzimidazole polymer containing a naphthalene ring structure synthesized by the invention has mild preparation conditions and low synthesis temperature;
(2) the prepared polymer has good solubility and film-forming property;
(3) the obtained ion exchange membrane has good thermal stability and mechanical property;
(4) the ion exchange membrane has excellent proton conductivity when applied to a high-temperature fuel cell.
Drawings
Fig. 1 is a graph showing the basic performance of a fuel cell of the polymer membrane prepared in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, which are merely representative examples to clearly and completely explain the present invention, but the scope of the present invention is not limited by these examples.
Example 1
Adding 30g of polyphosphoric acid (PPA) into a 100ml three-neck flask, introducing nitrogen, heating to 100 ℃, mechanically stirring for 15 minutes, removing air in the three-neck flask, cooling to 50 ℃, adding 5mmol of biphenyltetramine and 5mmol of 1', 4-naphthalenedicarboxylic acid, stirring, heating to 140 ℃, reacting for 7 hours, cooling, and pouring into a solution containing 5% of sodium bicarbonate. After standing for 24 hours, the solution was washed well with water until the solution was neutral. Filtering and drying. The prepared polymer was dissolved in NMP to prepare a 6% solution, which was cast onto a glass plate and flattened with a cast film knife. After drying at 80 ℃ for 20 hours, the film was removed from the glass plate. The dry polymer membrane was immersed in 85% phosphoric acid solution at room temperature for 10 hours to obtain a polybenzimidazole ion exchange membrane having a thickness of about 90 μm.
Example 2
Adding 60g of polyphosphoric acid (PPA) into a 100ml three-neck flask, introducing nitrogen, heating to 100 ℃, mechanically stirring for 15 minutes, removing air in the three-neck flask, cooling to 50 ℃, adding 5mmol of biphenyltetramine and 5mmol of 2', 6-naphthalene dicarboxylic acid, stirring, heating to 160 ℃, reacting for 10 hours, cooling, and pouring into a solution containing 5% of sodium bicarbonate. After standing for 24 hours, the solution was washed well with water until the solution was neutral. Filtering and drying. The prepared polymer was dissolved in NMP to prepare a 5% solution, which was cast onto a glass plate and flattened with a casting knife. After drying at 80 ℃ for 20 hours, the film was removed from the glass plate. The dry polymer membrane was immersed in 85% phosphoric acid solution at room temperature for 24 hours to obtain a polybenzimidazole ion exchange membrane having a thickness of about 80 μm.
Example 3
Adding 60g of polyphosphoric acid (PPA) into a 100ml three-neck flask, introducing nitrogen, heating to 100 ℃, mechanically stirring for 15 minutes, removing air in the three-neck flask, cooling to 50 ℃, adding 5mmol of biphenyltetramine and 5mmol of 2', 6-naphthalene dicarboxylic acid, stirring, heating to 160 ℃, reacting for 10 hours, cooling, and pouring into a solution containing 5% of sodium bicarbonate. After standing for 24 hours, the solution was washed well with water until the solution was neutral. Filtering and drying. The prepared polymer was dissolved in NMP to prepare a 5% solution, which was cast onto a glass plate and flattened with a casting knife. After drying at 80 ℃ for 20 hours, the film was removed from the glass plate. The dry polymer membrane was immersed in 85% phosphoric acid solution at room temperature for 24 hours to obtain a polybenzimidazole ion exchange membrane having a thickness of about 80 μm.
Example 4
Adding 80g of polyphosphoric acid (PPA) into a 100ml three-neck flask, introducing nitrogen, heating to 100 ℃, mechanically stirring for 15 minutes, removing air in the three-neck flask, cooling to 50 ℃, adding 6mmol of biphenyltetramine and 6mmol of 1', 5-naphthalene dicarboxylic acid, stirring, heating to 180 ℃, reacting for 24 hours, cooling, and pouring into a solution containing 5% of sodium bicarbonate. After standing for 24 hours, the solution was washed well with water until the solution was neutral. Filtering and drying. The prepared polymer was dissolved in NMP to prepare a 5% solution, which was cast onto a glass plate and flattened with a casting knife. After drying at 80 ℃ for 20 hours, the film was removed from the glass plate. The dry polymer membrane was immersed in 85% phosphoric acid solution at room temperature for 48 hours to obtain a polybenzimidazole ion exchange membrane having a thickness of about 60 μm.
Example 5
Adding 80g of polyphosphoric acid (PPA) into a 100ml three-neck flask, introducing nitrogen, heating to 100 ℃, mechanically stirring for 15 minutes, removing air in the three-neck flask, cooling to 50 ℃, adding 6mmol of biphenyltetramine, 3mmol of 1 ', 4-naphthalenedicarboxylic acid and 3mmol of 1', 5-naphthalenedicarboxylic acid, stirring, heating to 160 ℃, reacting for 8 hours, cooling, and pouring into a solution containing 5% of sodium bicarbonate. After standing for 24 hours, the solution was washed well with water until the solution was neutral. Filtering and drying. The prepared polymer was dissolved in NMP to prepare a 5% solution, which was cast onto a glass plate and flattened with a casting knife. After drying at 80 ℃ for 20 hours, the film was removed from the glass plate. The dry polymer membrane was immersed in 85% phosphoric acid solution at room temperature for 48 hours to obtain a polybenzimidazole ion exchange membrane having a thickness of about 70 μm.
Example 6
Adding 60g of polyphosphoric acid (PPA) into a 100ml three-neck flask, introducing nitrogen, heating to 100 ℃, mechanically stirring for 15 minutes, removing air in the three-neck flask, cooling to 50 ℃, adding 5mmol of biphenyltetramine and 5mmol of 1', 6-naphthalene dicarboxylic acid, stirring, heating to 160 ℃, reacting for 8 hours, cooling, and pouring into a solution containing 5% of sodium bicarbonate. After standing for 24 hours, the solution was washed well with water until the solution was neutral. Filtering and drying. The prepared polymer was dissolved in NMP to prepare a 5% solution, which was cast onto a glass plate and flattened with a casting knife. After drying at 80 ℃ for 20 hours, the film was removed from the glass plate. The dry polymer membrane was immersed in 85% phosphoric acid solution at room temperature for 48 hours to obtain a polybenzimidazole ion exchange membrane having a thickness of about 70 μm.
Example 7
Adding 80g of polyphosphoric acid (PPA) into a 100ml three-neck flask, introducing nitrogen, heating to 100 ℃, mechanically stirring for 15 minutes, removing air in the three-neck flask, cooling to 50 ℃, adding 6mmol of biphenyltetramine, 3mmol of 1 ', 4-naphthalenedicarboxylic acid and 3mmol of 12', 6-naphthalenedicarboxylic acid, stirring, heating to 160 ℃, reacting for 12 hours, cooling, and pouring into a solution containing 5% of sodium bicarbonate. After standing for 24 hours, the solution was washed well with water until the solution was neutral. Filtering and drying. The prepared polymer was dissolved in NMP to prepare a 5% solution, which was cast onto a glass plate and flattened with a casting knife. After drying at 80 ℃ for 20 hours, the film was removed from the glass plate. The dry polymer membrane was immersed in 85% phosphoric acid solution at 80 ℃ for 24 hours to obtain a polybenzimidazole ion exchange membrane having a thickness of about 70 μm.
Example 8
The polybenzimidazole proton exchange membrane prepared in example 1 was assembled in a high temperature fuel cell using 40% platinum on carbon catalyst with a platinum loading of 0.5mg/cm2The hydrogen and oxygen flux is 200ccm, the battery shows better performance at 160 ℃, and the maximum power density reaches 110mW/cm2The polybenzimidazole proton exchange membrane shows good electrochemical performance and has wide application prospect.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (5)
1. A polybenzimidazole proton exchange membrane containing naphthalene ring is characterized in that: the main chain of the polybenzimidazole molecule contains a naphthalene ring structure, and the polybenzimidazole has a general formula:
the polymer is a homopolymer, a block copolymer or a random copolymer; n represents the polymerization degree of the polymer, n is a positive integer greater than 0, and the weight average molecular weight of the polymer is between 3000 and 800000;
in the general structural formula, R is one or more of the following structures:
2. The polybenzimidazole type proton exchange membrane containing naphthalene ring according to claim 1, wherein: the proton exchange membrane is synthesized by polycondensation, and the monomer of the polycondensation reaction is any one of 3, 3' -diaminobenzidine and the following diacid containing naphthalene ring:
3. The preparation method of polybenzimidazole type proton exchange membrane containing naphthalene ring according to claim 1, which is characterized by comprising the following steps:
s1, firstly, adding diacid containing a naphthalene ring structure and biphenyltetramine into a polyphosphoric acid solvent in a nitrogen atmosphere, heating to 120-180 ℃, reacting for 2-24 hours, and pouring the hot solution into deionized water to obtain a filamentous polymer; then, washing the filamentous polymer for multiple times, adding sodium bicarbonate to adjust the pH value of the solution to be neutral, and filtering to obtain a solid polymer; finally, boiling the obtained solid polymer with water, filtering and drying the obtained polymer; in the reaction system, the monomer concentration of diacid monomer containing naphthalene ring structure and biphenyl tetramine in polyphosphoric acid solvent is 1-25 wt%, and the molar usage of the diacid monomer containing naphthalene ring structure and biphenyl tetramine is the same;
s2, dissolving the dried polymer in a polar solvent at 20-140 ℃, controlling the concentration of the solution at 2-20 wt%, directly casting the obtained polymer solution on a glass plate or a stainless steel plate, flattening by using a casting knife, drying for 5-24h at 60-100 ℃ to form a film, and then drying for 1-24h at 80-150 ℃ in vacuum to prepare the polybenzimidazole proton exchange membrane containing naphthalene rings, wherein the thickness of the proton exchange membrane is 10-200 μm.
4. The method for preparing polybenzimidazole type proton exchange membrane containing naphthalene ring according to claim 3, wherein: in the step S2, the polar solvent is one or more of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide.
5. The use of a polybenzimidazole type proton exchange membrane containing naphthalene rings according to claim 1, characterized in that it comprises the following steps:
s1, immersing the polybenzimidazole proton exchange membrane containing naphthalene ring in 85% phosphoric acid for 1-48h, wherein the immersion temperature is 20-120 ℃;
s2, installing the proton exchange membrane soaked in the step S1 in a high-temperature proton exchange membrane fuel cell, hot-pressing the proton exchange membrane and two pieces of carbon paper sprayed with a catalyst together to prepare a membrane electrode, then clamping the membrane electrode by a graphite electrode plate with a gas flow channel, fixing the membrane electrode by a high-temperature heating end plate, and introducing hydrogen and oxygen into the proton exchange membrane fuel cell through the gas flow channel.
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| CN112142980A (en) * | 2020-09-18 | 2020-12-29 | 珠海冠宇电池股份有限公司 | Hyperbranched polybenzimidazole-polysiloxane block copolymer and preparation method and application thereof |
| CN113527685A (en) * | 2021-06-10 | 2021-10-22 | 中国科学院山西煤炭化学研究所 | Polybenzimidazole ion solvent membrane and preparation method and application thereof |
| CN114395251A (en) * | 2021-12-24 | 2022-04-26 | 寰泰储能科技股份有限公司 | Soluble polybenzimidazole anion exchange membrane material and synthesis and application thereof |
| CN114685794A (en) * | 2022-05-05 | 2022-07-01 | 寰泰储能科技股份有限公司 | Synthesis and application of naphthalene-containing polybenzimidazole material |
| CN115594847A (en) * | 2022-09-06 | 2023-01-13 | 上海四羿科技有限公司（Cn） | High-oxidation-resistance polybenzimidazole ion exchange membrane and preparation method and application thereof |
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| CN115594847A (en) * | 2022-09-06 | 2023-01-13 | 上海四羿科技有限公司（Cn） | High-oxidation-resistance polybenzimidazole ion exchange membrane and preparation method and application thereof |
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