CN112820922B - Ceramic particle reinforced high-temperature proton exchange membrane, manufacturing method thereof and electrochemical equipment - Google Patents
Ceramic particle reinforced high-temperature proton exchange membrane, manufacturing method thereof and electrochemical equipment Download PDFInfo
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- 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
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Abstract
The present disclosure relates to a ceramic particle reinforced high temperature proton exchange membrane for an electrochemical device, comprising: an acidic electrolyte; a polyazole polymer; the ceramic particles are reinforced. The film has good chemical properties and mechanical integrity, and also has low manufacturing cost.
Description
Technical Field
The disclosure relates to the field of fuel cells, in particular to a ceramic particle reinforced high-temperature proton exchange membrane, a manufacturing method thereof and a fuel cell.
Background
In recent years, the demand for clean power from non-fossil fuels has increased dramatically. A fuel cell is a chemical device that can directly convert chemical energy of fuel into electric energy, and is also called an electrochemical generator. The fuel cell uses fuel and oxygen as raw materials, and has no mechanical transmission parts, so that the fuel cell has no pollution and discharges few harmful gases. It follows that fuel cells are the most promising power generation technology from the viewpoint of energy conservation and ecological environment conservation.
This need has focused on many technologies, such as proton exchange membrane fuel cells. Currently, proton exchange membrane fuel cells are generally divided into two categories, namely low-temperature proton exchange membrane fuel cells (working temperature is 60-80 ℃) and high-temperature proton exchange membranes (working temperature is 120-160 ℃).
Low temperature pem fuel cells typically use a covalently bonded sulfate group containing fluoropolymer and water as the electrolyte. Currently, the low temperature proton exchange membrane mainly comprises a Nafion membrane of DuPont and a commercial membrane of Aciplex-S membrane of Dow chemical company. The operating temperature of low temperature proton exchange membrane fuel cells is limited to around 80 c due to the loss of water, which results in a loss of proton conductivity.
This range has several major advantages over low temperature pem fuel cells.
First, the activity of the noble metal catalyst on the electrodes of the pem stack increases in high temperature operating environments. Due to the more effective resistance of noble metal catalysts to carbon monoxide "poisoning" at higher temperatures, the cost of hydrocarbon reforming and purification of fuel cells on natural gas and other hydrocarbon fuels can be effectively simplified and reduced.
Secondly, the use of proton exchange membrane fuel cell electrodes at higher temperatures can also reduce the loading of precious metals in the catalyst layer.
In addition, another advantage of high temperature pem fuel cells is that higher quality heat can be provided. For example, heating at a temperature of 140 ℃ is far more useful and efficient than heat captured only at 80 ℃, whereas low temperature fuel cell operating temperatures based on fluoropolymer water films are only 80 ℃.
Furthermore, very similar systems are generally more electrically efficient when operated at higher temperatures. Based on the above advantages, the high temperature proton exchange membrane fuel cell system is obviously more cost-effective.
The above information in the background section is only for enhancement of understanding of the background of the application and therefore it may contain information that does not constitute prior art that is known to a person of ordinary skill in the art.
Disclosure of Invention
The present disclosure provides a ceramic particle reinforced high temperature proton exchange membrane for a fuel cell having good electrochemical performance and mechanical integrity.
According to one aspect of the present application, there is provided a high temperature proton exchange membrane for an electrochemical device, comprising: an acidic electrolyte; a polyazole polymer accounting for more than 10% of the total weight of the high-temperature proton exchange membrane; the ceramic particles are reinforced.
According to some embodiments of the present application, the polyazole polymer comprises greater than 15% of the total weight of the high temperature proton exchange membrane.
According to some embodiments of the present application, the acidic electrolyte comprises polyphosphoric acid.
According to some embodiments of the present application, the polyazole polymer comprises: a polymer obtained by polymerizing an aromatic tetraamino monomer and a diaminocarboxylic acid monomer, a polymer obtained by polymerizing an aromatic dicarboxylic acid monomer, or a polymer obtained by polymerizing an aromatic tricarboxylic acid and a tetracarboxylic acid monomer. Preferably, the polyazole polymer is a polymer polymerized from aromatic tetraamino monomers, diamino carboxylic acid monomers, and tricarboxylic acid monomers, optionally with the addition of a component of a crosslinking agent.
According to some embodiments of the present application, the high-temperature proton exchange membrane comprises 30% to 55% by weight of polyazole polymer.
According to some embodiments of the present application, the high temperature proton exchange membrane further comprises a cross-linking agent, wherein the cross-linking agent is 0.06% -29% by weight of the membrane. Preferably, the crosslinker comprises 0.09% to 10% by weight of the membrane.
According to some embodiments of the present application, the reinforced ceramic particles comprise: one or more of silicon dioxide, aluminum oxide, zirconium oxide, boron nitride, silicon carbide, silicon nitride, mica, talc and metal nitride.
According to some embodiments of the present application, the reinforced ceramic particles are 10% or less of the total weight of the high temperature proton exchange membrane.
According to some embodiments of the present application, the reinforced ceramic particles are 1 micron or less.
According to some embodiments of the present application, the high temperature proton exchange membrane has a thickness of 25-250 μm.
According to some embodiments of the present application, the proton conductivity of the high temperature proton exchange membrane is 0.07-0.15S/cm.
According to some embodiments of the present application, the high temperature proton exchange membrane has a young's modulus of 85 to 250 mpa.
According to another aspect of the present application, there is also provided a method for preparing a high temperature proton exchange membrane for an electrochemical device, comprising: dissolving a polyazole monomer in polyphosphoric acid; dispersing the reinforced ceramic particles into the polyazole monomer/polyphosphoric acid solution to obtain a dispersion liquid; casting the polyazole monomer/polyphosphoric acid/reinforced ceramic particle dispersion liquid on a plane or an electrode to form a liquid film; heating the liquid film to 250 ℃ in the air or inert gas atmosphere to 200 ℃ so that the liquid film is subjected to polymerization reaction; cooling the liquid film undergoing polymerization; immersing the cooled liquid film into a phosphoric acid solution bath with the concentration of 30-90%.
According to some embodiments of the present application, the phosphoric acid solution bath has a temperature in a range of 0-100 ℃.
According to another aspect of the present application, there is also provided an electrochemical device comprising a high temperature proton exchange membrane as described above.
Application of the scheme of the various embodiments of the present disclosure enables ceramic particle reinforced high temperature proton exchange membranes with high physical properties, high solids content, and excellent chemical properties to be obtained. The addition of the reinforcing ceramic particles results in an increase in viscosity, which allows a good tolerance for low viscosity monomeric polyphosphoric acid solutions, making the preparation process more controllable. The high physical properties of the proton exchange membranes provided in the present disclosure make them good proton conductors for membrane electrode assemblies. Such membranes are also capable of withstanding much higher pressure differentials than the prior art. These excellent properties are not found in the prior art membranes and the manufacturing costs of the membrane electrode are reduced. Membrane electrodes made using the membranes of the present disclosure also exhibit more pronounced durability in use.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art can appreciate, the described embodiments can be modified in various different ways, without departing from the spirit or scope of the present disclosure. Accordingly, the embodiments are to be regarded as illustrative in nature and not as restrictive.
In previous studies, there has been a method for preparing a proton exchange membrane comprising the steps of: firstly, azole monomers are dissolved in polyphosphoric acid; then carrying out high-temperature polymerization on the monomer while stirring the solution in a polymerization reaction vessel; after the polymerization is complete, the very viscous solution is cast on a flat surface and the ready-to-prepare film is then hydrolyzed in an aqueous solution of phosphoric acid of the desired concentration. This process, and the films made therefrom, have considerable limitations. Another problem that remains with this process is the temperature sensitivity during the polymerization process. For example, if the entire system in the reactor is gelated near the end of the reaction, gelation easily occurs in such an exothermic polymerization reaction even if the polymerization monomers are less than 5% by weight.
In view of the above technical deficiencies, the present disclosure addresses these membrane deficiencies and complements the references on the possibility of high solids and high solids crosslinked membrane preparation during membrane polymerization. The membrane preparation process of the present disclosure and the unique membrane compositions derived therefrom begin with the dissolution of azole monomers in polyphosphoric acid. When the azole monomer is dissolved, a quantity of the reinforced ceramic particles is mixed into the azole polyphosphoric acid solution. The mixture was stirred until a homogeneous dispersion was obtained.
The addition of the reinforced ceramic particles enables the high-temperature proton exchange membrane provided by the present disclosure to have better mechanical properties. Meanwhile, the high-solid-content high-temperature proton exchange membrane prepared by the preparation method provided by the disclosure has excellent electrochemical performance, and the creep resistance of the membrane is obviously improved compared with the prior art due to the high solid content, so that the durability of the membrane electrode of the fuel cell is improved.
According to example embodiments of the present disclosure, the acid electrolyte includes polyphosphoric acid. It may be a polyphosphoric acid solution with a mass fraction of 50% to 100%.
According to an exemplary embodiment of the present disclosure, a polyazole polymer includes: a polymer obtained by polymerizing an aromatic tetraamino monomer and a diaminocarboxylic acid monomer, a polymer obtained by polymerizing an aromatic dicarboxylic acid monomer, or a polymer obtained by polymerizing an aromatic tricarboxylic acid and a tetracarboxylic acid monomer.
According to an exemplary embodiment of the present disclosure, a polyazole polymer includes: polymers polymerized from one or more aromatic tetraamino monomers and diamino carboxylic acid monomers. Aromatic tetraamino monomers include: 3,3',4,4' -tetraaminobiphenyl; 1,2,4, 5-tetraaminobenzene; 3,3',4,4' -tetraaminodiphenyl sulfone; 3,3',4,4' -tetraaminobenzophenone; 3,3',4,4' -tetraaminodiphenyl ether; 2,3,5, 6-tetraaminopyridine and/or acid salts thereof. The diamino carboxylic acid monomers include: 3, 4-diaminobenzoic acid; 6, 7-diamino-2-naphthoic acid; 3, 4-diamino-4' -carboxybiphenyl; 3, 4-diamino-4' -carboxydiphenyl sulfide; 3, 4-diamino-4' -carboxydiphenyl sulfoxide; 3, 4-diamino-4' -carboxydiphenyl sulfone; 3, 4-diamino-4' -carboxydiphenyl ether; 3, 4-diamino-4' -carboxybenzophenone.
According to an example embodiment of the present disclosure, the polyazole polymer further includes: polymers formed by the polymerization of one or more aromatic dicarboxylic acid monomers. The aromatic dicarboxylic acid monomers include: terephthalic acid; isophthalic acid; naphthalene-1, 4-dicarboxylic acid; naphthalene-1, 3-dicarboxylic acid; naphthalene-1, 5-dicarboxylic acid; naphthalene-2, 6-dicarboxylic acid; 4,4' -dicarboxybiphenyl; 3,3' -dicarboxybiphenyl; 3,4' -dicarboxybiphenyl; 4,4' -dicarboxydiphenylsulfone; 3,3' -dicarboxydiphenylsulfone; 3,4' -dicarboxydiphenylsulfone; pyridine-2, 5-dicarboxylic acid; pyridine-2, 4-dicarboxylic acid; pyridine-2, 6-dicarboxylic acid; pyridine-3, 5-dicarboxylic acid.
The polyazole polymer further comprises: a crosslinked polymer formed by polymerizing one or more aromatic tricarboxylic acid and tetracarboxylic acid monomers. Aromatic tricarboxylic and tetracarboxylic monomers include: trimer acid (1,3, 5-tricarboxybenzene), 1,3, 5-tris (4-carboxyphenyl) benzene, 3,5,4 '-tricarboxybiphenyl, 3,5,3',5 '-tetracarboxylbiphenyl, 3,5,4' -tricarboxybiphenyl, 3,5,3 '-tricarboxybiphenyl, 3,5,5' -tetracarboxylbiphenyl, 3,5,4 '-tricarboxybiphenyl sulfone, 3,5,3',5 '-tetracarboxylbiphenyl sulfone, 3,5,4' -tricarboxybenzophenone, 3,5,3',5' -tetracarboxylbenzophenone, naphthalene-1, 4, 5-tricarboxylic acid, naphthalene-1, 4, 6-tricarboxylic acid, naphthalene-1, 4, 7-tricarboxylic acid, naphthalene-1, 3, 5-tricarboxylic acid, naphthalene-1, 3, 6-tricarboxylic acid, naphthalene-1, 3, 7-tricarboxylic acid, naphthalene-1, 3,5, 7-tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, piperidine-2, 4, 6-tricarboxylic acid and 1,3, 5-triazine-2, 4, 6-tricarboxylic acid.
According to the disclosed example embodiment, the reinforced ceramic particles may be selected from one or a combination of several of silicon dioxide, aluminum oxide, zirconium oxide, boron nitride, silicon carbide, silicon nitride, mica, talc, and metal nitride. The reinforced ceramic particles are 10% or less of the total film weight. The reinforced ceramic particles are 1 micron or less.
The preparation method of the high-temperature proton exchange membrane provided by the present disclosure is described in detail below.
In this example, polyazole monomer was dissolved in polyphosphoric acid; dissolving a polyazole monomer in polyphosphoric acid; dispersing the reinforced ceramic particles into the polyazole monomer/polyphosphoric acid solution to obtain a dispersion liquid; casting the polyazole monomer/polyphosphoric acid/reinforced ceramic particle dispersion liquid on a plane or an electrode to form a liquid film; placing the liquid film in air or inert gas atmosphere and heating to the temperature of 200-250 ℃ to enable the liquid film to generate polymerization reaction; cooling the liquid film undergoing polymerization; immersing the cooled liquid film into a phosphoric acid solution bath with the concentration of 30-90%. According to some embodiments, the process of dissolving the polyazole monomers in the polyphosphoric acid further comprises a process of adding a cross-linking agent to the polyphosphoric acid. In this example, 1,3, 5-tricarboxylic acid benzene can be used as the crosslinking agent.
In this example, the temperature of the phosphoric acid solution bath was in the range of 0 to 100 ℃.
The final polyazole polymer is present in an amount greater than 10% by weight of the total high temperature proton exchange membrane, and in some preferred embodiments the polyazole polymer is present in an amount greater than 15% by weight. The solids content is clearly superior to the prior art.
The ceramic particle reinforced high-temperature proton exchange membrane prepared by the method has high mechanical property, excellent chemical property and durability. The cost of the high temperature proton exchange membrane provided by the present disclosure is also reduced due to the reduction of manufacturing costs.
According to example embodiments of the present disclosure, the film thickness is generally controlled by the manufacturing method. In the present example, the casting speed, the casting surface size, and the temperature control in the manufacturing method all determine the film thickness.
In order to characterize the excellent properties of the high temperature proton exchange membrane obtained by the above method, the performance of the high temperature proton exchange membrane was tested using the following method.
Composition test method of the membrane:
a circular film having a diameter of 2.5 cm was punched out, and the total weight m of the sample was weighed 0 And placed in a beaker containing 100 ml of water. The acid released by the sample was titrated to the first equivalence point with a 0.1 molar fraction of sodium hydroxide solution using a volume of V. The sample was then removed, excess water wiped off and dried at 160 ℃ for 4 hours. The dry weight m of the sample is then measured 1 . The composition of the film is described by the following formula:
polymer% ═ m 1 /m 0 *100
Phosphoric acid% 0 *100
Water% — 100-polymer% -phosphoric acid%.
In addition, in order to verify that the high-temperature proton exchange membrane generated by the reaction is polymerized and crosslinked (cross link), a "shaking test" is performed on the prepared and punched sample, wherein the test condition is that the sample is placed in concentrated sulfuric acid and shaken at a certain frequency for 24 hours, and if the sample is not dissolved, the high-temperature proton exchange membrane is polymerized and crosslinked.
The anhydrous proton conductivity test method of the membrane comprises the following steps:
the frequency range was scanned by a four-probe through planar measurements using an ac impedance spectrometer from 1Hz (hertz) to 100KHz (kilohertz). A rectangular film sample (3.5 cm. times.7.0 cm) was placed in a glass or polysulfone cell with four platinum wire electrodes. The two outer electrodes were 6.0cm apart, providing current to the cell, while the two inner electrodes measured the voltage drop relative to the membrane at 2.0cm apart. The proton conductivity is calculated as follows:
σ＝D/(L*B*R)
where D is the distance between the two test current electrodes, L is the thickness of the film, B is the width of the film, and R is the measured resistance. At 180 deg.c, the anhydrous proton conductivity of the film is 0.08-0.15S/cm.
Tensile properties (young's modulus) test method:
the mechanical properties of the films were measured by cutting a dog-bone type pattern (ASTM D683v type) from the films using a shear press. Tensile properties were measured using a tensile tester. All measurements were performed at room temperature.
The membrane electrode assembly manufacturing and performance testing method comprises the following steps:
a membrane electrode assembly consists of a polymer membrane sandwiched between two electrodes. The membrane prepared in the example of the present application was hot-pressed between the anode and the cathode at 150 c and 2000 kg for 90-150 seconds to prepare a membrane electrode. Electrode load 1.0mg/cm 2 A platinum (Pt) catalyst. The fuel cell is manufactured by assembling the following cell components: an end plate; an anode current collector; an anode flow field; a membrane electrode; a cathode flow field; a cathode current collector; and an end plate. Gaskets are used on both sides of the membrane electrode to control compression. After assembly, the cells were uniformly tightened.
The performance of the Fuel Cell was tested at 50cm using a testing station purchased from Fuel Cell Technologies, Inc 2 (effective area 45.15cm 2 ) A single stack of fuel cells. With hydrogen as fuel and different oxidants (air or oxygen), polarization curves were obtained at different temperatures. Prior to measuring the polarization curve, the fuel cell was operated at a temperature of 180 ℃ and 0.2A/cm 2 (amps/cm) for at least 100 hours (break-in period). At a constant flow of hydrogen (1.2 stoichiometry) and air (2.0 stoichiometry) at 0.2A/cm 2 And a long-term stability test is carried out at a temperature of 180 ℃.
Example one:
3, 4-diaminobenzoic acid (15.215 g) and polyphosphoric acid (86.2 g) were added to a 250 ml three-neck flask, stirred and heated to 150 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 220 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 65% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 95 μm.
The composition of the membrane in this example was 49.2 wt% polymer, 18.7 wt% water and 32.1 wt% phosphoric acid. The proton conductivity was 0.08S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 150 MPa (MPa).
The membrane electrode formed from the membrane element in this example had a hydrogen/air stoichiometric ratio of (1.2): (2.0), 180 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.54V (volts) and a maximum power density of 0.35W/cm 2 (watts/square centimeter). A back pressure of 45psi (lb/ft) was used 2 Pounds per square foot) of hydrogen and air at a back pressure of 0psi were further tested against the membrane electrode provided in the present application, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The cell was run continuously for 480 hours with constant operation without any film failure traces.
Example two:
3,3',4,4' -tetraamine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.645 g), silicon carbide particles (2.434 g) and polyphosphoric acid (136.9 g) were added to a 250 ml three-neck flask, stirred and heated to 170 ℃ for 6 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 70% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 90 microns.
The composition of the membrane in this example was 32.3 wt% polymer, 20.4% water and 47.3 wt% phosphoric acid. The proton conductivity was 0.12S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 122 MPa (MPa).
The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm 2 Under constant operation of (2), displayShows the performance of the fuel cell of 0.60V and the maximum power density of 0.4W/cm 2 . The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The cell was operated continuously for 480 hours with constant operation without any film failure traces.
Example three:
3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (0.831 g), isophthalic acid (5.814 g), silicon carbide particles (2.434 g) and polyphosphoric acid (136.9 g) were added to a 250 ml three-necked flask, stirred and heated to 190 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 60% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 97 μm.
The composition of the membrane in this example was 31.8 wt% polymer, 27.5 wt% water and 40.7 wt% phosphoric acid. The proton conductivity was 0.10S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 134 MPa (MPa).
The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 200 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.61V with a maximum power density of 0.46W/cm 2 . The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The cell was run continuously for 480 hours with constant operation without any film failure traces.
Example four:
3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (0.789 g), isophthalic acid (5.524 g), 1,3, 5-tricarboxylic acid benzene (0.280 g), silicon carbide particles (2.434 g) and polyphosphoric acid (136.5 g) were added to a 250 ml three-necked flask, stirred and heated to 190 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a room-temperature 50% phosphoric acid bath and hydrolyzed for 4 hours to obtain a film. The film thickness was 94 μm. The composition of the membrane in this example was 33.8 wt% polymer, 32.4% water and 33.8 wt% phosphoric acid. The proton conductivity was 0.10S/cm (180 ℃ C.). Young's modulus at room temperature was 151 MegaPascals (MPa).
The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.58V and a maximum power density of 0.38W/cm 2 . The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The cell was operated continuously for 480 hours with constant operation without any film failure traces.
Example five:
3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.645 g), silicon carbide particles (2.434 g) and polyphosphoric acid (136.9 g) were added to a 250 ml three-neck flask, stirred and heated to 170 ℃ for 6 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the thickness of the liquid film. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours in a nitrogen atmosphere. Cooled to room temperature, and the glass plate and the film obtained thereon were hydrolyzed by immersing in a room-temperature 70% phosphoric acid bath for 4 hours to obtain a film. The film thickness can be controlled in the 98 micron range.
The composition of the membrane in this example was 32.3 wt% polymer, 6.6 wt% silicon carbide particles, 18.4 wt% water and 42.7 wt% phosphoric acid. The proton conductivity was 0.11S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 152 MPa (MPa).
The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.59V and a maximum power density of 0.38W/cm 2 . The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The cell was run continuously for 480 hours with constant operation without any film failure traces.
Example six:
3,3',4,4' -tetraamine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.313 g), 1,3, 5-tricarboxylic acid benzene (0.280 g), zirconia (1.212 g) and polyphosphoric acid (136.5 g) were added to a 250 ml three-neck flask, stirred and heated to 170 ℃ for 4 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 240 ℃ for 12 hours under a nitrogen atmosphere. Cooled to room temperature, and the glass plate and the film obtained thereon were hydrolyzed in a 65% phosphoric acid bath at room temperature for 4 hours to obtain a film. The film thickness can be controlled in the range of 102 microns.
The composition of the membrane in this example was 33.9 wt% polymer, 3.3 wt% carbon fiber, 22.0 wt% water and 40.8 wt% phosphoric acid. The proton conductivity was 0.11S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 173 MPa (MPa).
The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.59V and a maximum power density of 0.39W/cm 2 . The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The cell was run continuously for 480 hours with constant operation without any film failure traces. The addition of the reinforcing ceramic particles results in an increase in viscosity, which allows good tolerance of the low viscosity monomeric polyphosphoric acid solution, making the preparation process more controllable
Comparative example 1:
3,3',4,4' -tetraamine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.645 g), silicon carbide particles (1.212 g) and polyphosphoric acid (136.9 g) were added to a 250 ml three-neck flask, stirred and heated to 220 ℃ for 5 hours. The solution was highly viscous, unable to stir, and unable to cast into a film, so there was no thickness measurement. Part of the polymer is crosslinked to be solid and gelated.
Comparative example 2:
3,3',4,4' -tetraamine-1, 1 ' -biphenyl (4.268 g), terephthalic acid (3.323 g), silicon carbide particles (1.212 g) and polyphosphoric acid (275 g) were added to a 250 ml three-necked flask, heated to 220 ℃ with stirring for 5 hours. The glass plate and the film obtained thereon were immersed in a 65% phosphoric acid bath at room temperature, and hydrolyzed for four hours to obtain a film. The film thickness was 95 microns.
The membrane composition was 6.0 wt% solids, 38.0 wt% water, and 56.0 wt% phosphoric acid. The proton conductivity was 0.18S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 33 MegaPascals (MPa).
The membrane electrode of the membrane structure produced in comparative example 2 was fabricated at a hydrogen-to-air stoichiometric ratio of (1.2): (2.0), 180 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.65V at a maximum power density of 0.5W/cm 2. The membrane electrode provided herein above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The battery was continuously operated for 2 hours with constant operation, and the membrane member was broken.
Comparative example 3:
3,3',4,4' -tetraamine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.645 g), silicon carbide particles (1.212 g) and polyphosphoric acid (60.9 g) were added to a 250 ml three-neck flask, stirred and heated to 150 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 220 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 65% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 98 μm.
The composition of the membrane in this example was 66.9 wt% polymer, 11.6 wt% water and 21.5 wt% phosphoric acid. The proton conductivity was 0.01S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 161 MPa (MPa).
The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.1V (volts) with a maximum power density of 0.05W/cm 2 (watts/square centimeter). A back pressure of 45psi (lb/ft) was used 2 Pounds per square foot) of hydrogen and air at a back pressure of 0psi were further tested against the membrane electrode provided herein above, thereby applying a pressure differential of 45psi to the membrane. At 0.2A/cm 2 The cell was operated continuously for 480 hours with constant operation without any film failure traces.
Comparative example 4:
3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.645 g) and polyphosphoric acid (136.9 g) were added to a 250 ml three-necked flask, stirred and heated to 170 ℃ for 6 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the thickness of the liquid film. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 70% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 90 microns.
The composition of the membrane in this example was 32.3 wt% polymer, 20.4% water and 47.3 wt% phosphoric acid. The proton conductivity was 0.12S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 92 MPa (MPa).
The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.60V at a maximum power density of 0.4W/cm 2 . The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The cell was operated continuously for 480 hours with constant operation without any film failure traces.
Comparative example 5:
3,3',4,4' -tetraamine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (0.789 g), isophthalic acid (5.524 g), 1,3, 5-tricarboxylic acid benzene (0.280 g) and polyphosphoric acid (136.5 g) were added to a 250 ml three-neck flask, stirred and heated to 190 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a room-temperature 50% phosphoric acid bath and hydrolyzed for 4 hours to obtain a film. The film thickness was 94 microns. The composition of the membrane in this example was 33.8 wt% polymer, 32.4% water and 33.8 wt% phosphoric acid. The proton conductivity was 0.10S/cm (180 ℃ C.). Young's modulus at room temperature was 130 MegaPascals (MPa).
The membrane electrode formed from the membrane element in this example had a hydrogen/air stoichiometric ratio of (1.2): (2.0), 180 ℃ and 0.2A/cm 2 Shows a fuel cell performance of 0.58V with a maximum power density of 0.38W/cm 2 . The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm 2 The cell was operated continuously for 480 hours with constant operation without any film failure traces.
The above description is only exemplary of the present disclosure and should not be taken as limiting the disclosure, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present disclosure should be included in the scope of protection of the present disclosure.
Claims (9)
1. A high temperature proton exchange membrane for an electrochemical device, comprising:
an acidic electrolyte;
a polyazole polymer accounting for more than 10% of the total weight of the high-temperature proton exchange membrane;
reinforcing ceramic particles;
wherein the acidic electrolyte comprises polyphosphoric acid;
the high-temperature proton exchange membrane is prepared by the following method:
dissolving a polyazole monomer in polyphosphoric acid; dispersing the reinforced ceramic particles into the polyazole monomer/polyphosphoric acid solution to obtain a dispersion liquid; casting the polyazole monomer/polyphosphoric acid/reinforced ceramic particle dispersion liquid on a plane or an electrode to form a liquid film; heating the liquid film to 250 ℃ in the air or inert gas atmosphere to 200 ℃ so that the liquid film is subjected to polymerization reaction; cooling the liquid film undergoing polymerization; immersing the cooled liquid film into a phosphoric acid solution bath with the concentration of 30-90%.
2. A high temperature proton exchange membrane according to claim 1 wherein said polyazole polymer comprises greater than 15% of the total weight of said high temperature proton exchange membrane.
3. A high temperature proton exchange membrane according to claim 1 wherein said polyazole polymer comprises: a polymer obtained by polymerizing an aromatic tetraamino monomer and a diaminocarboxylic acid monomer, a polymer obtained by polymerizing an aromatic dicarboxylic acid monomer, or a polymer obtained by polymerizing an aromatic tricarboxylic acid and a tetracarboxylic acid monomer.
4. A high temperature proton exchange membrane according to claim 1 wherein said high temperature proton exchange membrane comprises 30% to 55% by weight polyazole polymer.
5. A high temperature proton exchange membrane according to claim 1 wherein said reinforced ceramic particles comprise: one or more of silicon dioxide, aluminum oxide, zirconium oxide, boron nitride, silicon carbide, silicon nitride, mica, talc and metal nitride.
6. A high temperature proton exchange membrane according to claim 5 wherein said reinforcing ceramic particles are 10% or less of the total weight of said high temperature proton exchange membrane.
7. A high temperature proton exchange membrane according to claim 5 wherein said reinforced ceramic particles are 1 micron or less.
8. A high temperature proton exchange membrane according to claim 1 wherein said high temperature proton exchange membrane has a thickness of 25-250 μm.
9. A high temperature proton exchange membrane according to claim 1 wherein said high temperature proton exchange membrane has a proton conductivity of 0.07 to 0.15S/cm.
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