CN115558085A - Preparation method of polymer binder containing basic groups and application of polymer binder in high-temperature fuel cell - Google Patents

Preparation method of polymer binder containing basic groups and application of polymer binder in high-temperature fuel cell Download PDF

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CN115558085A
CN115558085A CN202211340858.3A CN202211340858A CN115558085A CN 115558085 A CN115558085 A CN 115558085A CN 202211340858 A CN202211340858 A CN 202211340858A CN 115558085 A CN115558085 A CN 115558085A
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polymer binder
binder
catalyst
fuel cell
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李南文
晁歌
耿康
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Shanghai Siyi Technology Co ltd
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    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—Binders
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • 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 invention discloses a preparation method of a polymer binder containing an alkaline group and application of the polymer binder in a high-temperature fuel cell. The polymer binder is a high molecular weight copolymer of an aldehyde ketone monomer containing an alkaline group and an aryl monomer, the main chain of the polymer binder is a rigid hydrophobic aryl skeleton without ether bonds, and an alkaline group is hung on a side chain; the polymer binder disclosed by the invention contains alkaline groups, and the adsorption capacity of the binder on electrolyte phosphoric acid can be regulated and controlled by changing the alkaline groups, so that the balance of proton transmission capacity and size swelling is regulated and the utilization rate of a catalyst is improved. The polymer adhesive is applied to an oxyhydrogen fuel cell, and tests show that the maximum power density reaches 821mW/cm under the operating condition of no humidification and pressurization at the temperature of 160 DEG C 2 . Obtained by the inventionThe polymer binder proves excellent conductivity, mass transfer capacity and good dimensional stability, and the performance test result of the polymer binder applied to the high-temperature fuel cell shows that the polymer binder has excellent performance.

Description

Preparation method of polymer binder containing basic groups and application of polymer binder in high-temperature fuel cell
Technical Field
The invention relates to a preparation method of a polymer binder containing an alkaline group and application of the polymer binder in a high-temperature fuel cell, belonging to the technical field of high-temperature fuel cells.
Background
With the rapid development of science and technology, the clean new energy, namely the proton exchange membrane fuel cell, is expected to change the energy structure and replace the traditional fossil energy. The working temperature of the high-temperature proton exchange membrane fuel cell is higher than 100 ℃, so that the selection range and the chemical reaction rate of the catalyst are improved, and the defects of poor CO tolerance, difficult water management, difficult heat management and the like of a low-temperature proton exchange membrane fuel cell represented by Nafion are overcome. The Proton Exchange Membrane (PEM) of polybenzimidazole doped phosphoric acid (PA/PBI) has excellent thermal stability and extremely high proton conductivity, and becomes a hot spot for research on high-temperature proton exchange membranes. In addition to the PEM, the Catalyst Layer (CL) comprises an ionomer (PEI). PEI not only functions as a physical binder in CL, but also conducts reactants (gas), products (water) and H + Ions promote the sufficient contact between CL and PEM, accelerate proton conduction and improve the utilization rate of the catalyst. The quality of the binder directly affects the output performance and the operating life of the fuel cell.
In order to improve the performance of membrane Modules (MEAs) based on PA/PBI membranes, the material of the binder in the catalyst layer is structurally designed and optimized. In recent years, efforts have been made to find highly effective binder materials for HT-PEMFCs. Materials such as fluoropolymers, PBI, phosphino polymers, ion-pair polymers, etc. are widely used as binders for catalyst layers to improve cell performance. Commercial binders often employ hydrophobic perfluoropolymer PTFE materials, which have poor compatibility with the PEM and difficulty in establishing an effective three-phase interface (TPB), leading to poor proton conductivity within the catalyst layer and poor Pt utilization. The PBI-based binder material redistributes the PA distribution, creates good TPB between the electrolyte and the catalyst layer, promotes proton conduction in the catalyst layer, increases the active sites and electrochemically active surface area of the Pt catalyst, but with increasing binder content, the interaction of PBI with PA results in excessive PA in the CL, reducing performance (Journal of Power Sources 2007,170, 275-280). The structure of PEI must be further improved to realize commercialization to meet the future development demand.
Disclosure of Invention
The purpose of the invention is: aiming at the defects and problems in the prior art, the polymer binder of the aldehyde ketone monomer containing the alkaline group and the aryl monomer is provided, good TPB is established between the electrolyte and the catalyst layer, so that the proton transport capacity of CL and the utilization rate of the catalyst are improved, the adsorption capacity of the binder to electrolyte phosphoric acid is regulated and controlled by changing the alkaline group, the balance of the proton transport capacity and the size swelling is regulated and controlled, and the utilization rate of the catalyst is further improved.
In order to achieve the above object, the present invention provides a polymeric binder containing a basic group, which is a homopolymer comprising the following repeating structural units:
Figure BDA0003916212690000021
wherein Ar represents an organic group containing an aromatic ring, R represents different basic groups, n represents the average polymerization degree, n is more than or equal to 10 and less than or equal to 200, and the weight average molecular weight of the homopolymer is between 5000 and 800000;
ar is the following group:
Figure BDA0003916212690000022
the R is any one of the following groups:
Figure BDA0003916212690000023
the invention also provides a preparation method of the polymer binder containing the basic groups, which comprises the following steps: under the environment of room temperature, firstly adding an organic compound containing Ar into an organic solvent, stirring and dissolving, adding a ketone monomer containing an alkaline group, then dropwise adding trifluoroacetic acid, methane sulfonic acid and trifluoromethanesulfonic acid into the system under the ice bath condition of less than 0 ℃, initiating a polymerization reaction at the temperature of below 0 ℃, then gradually heating to room temperature for reaction, pouring the obtained mixture into ammonia water after the reaction is finished to obtain a fibrous polymer, washing away redundant acid with an alkaline solution, washing with deionized water to be neutral, filtering and drying to obtain the solid polymer binder.
The invention also provides the application of the polymer binder containing the alkaline group in a high-temperature fuel cell.
Preferably, the high temperature fuel cell includes a membrane electrode assembly including a proton exchange membrane, a catalytic layer, and a diffusion layer, the catalytic layer being prepared from a catalyst ink containing a polymer binder.
Preferably, the content of the polymer binder in the catalytic layer is 3 to 30wt%.
Preferably, the catalyst contained in the catalytic layer is a Pt/C catalyst, and the content of Pt in the Pt/C catalyst is 20-60 wt%.
Preferably, the loading amount of the Pt/C catalyst in the catalytic layer is 0.25-1.00 mg-cm -2 。
Preferably, the catalyst ink is obtained by stirring and ultrasonically dispersing a mixture of a binder solution, a Pt/C catalyst and a solvent uniformly; the binder solvent solution is obtained by dissolving a polymer binder in a polar solvent, wherein the polar solvent is at least one of NMP, DMF, DMAc and DMSO, and the concentration of the binder solution is 2-5 wt%.
The invention also provides a catalyst ink for a high-temperature fuel cell, which comprises the following raw materials: a binder solution, a Pt/C catalyst, and a solvent; the binder solvent solution is obtained by dissolving the polymer binder containing the basic groups in claim 1 in a polar solvent, wherein the polar solvent is at least one of NMP, DMF, DMAc and DMSO, and the concentration of the binder solution is 2-5 wt%;
compared with the prior art, the invention has the beneficial effects that:
(1) The polymer binder is a high molecular weight copolymer of an aldehyde ketone monomer containing an alkaline group and an aryl monomer, the main chain of the polymer binder is a rigid hydrophobic aryl skeleton without ether bonds, and an alkaline group is suspended on a side chain of the polymer binder;
(2) The polymer binder prepared by the invention has good solubility, and can be dissolved in various polar solvents such as NMP, DMAc, DMSO and the like at room temperature;
(3) The nitrogen atoms contained in the alkaline groups of the polymer binder have good swelling rate and conductivity by balancing the adsorption of the nitrogen atoms on phosphoric acid, can meet the performance requirement of the high-temperature fuel cell binder, and has excellent power density 2 。
Drawings
FIG. 1 is a graph comparing conductivity data of polymers prepared in examples 1 to 2 with those of comparative examples 1 to 3;
FIG. 2 is a comparison of the polarization curve and power density curve of the alkaline group-containing binders prepared in examples 1-2 and comparative examples 1-4 in a high temperature fuel cell;
fig. 3 is a comparison of polarization curves and power density curves of the high temperature fuel cell under the conditions of 5%, 10% and 15% contents in the catalytic layer when the polymer binder of example 1 is applied to the high temperature fuel cell.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Example 1
A method of preparing a polymeric binder comprising an aldehyde monomer containing a basic group and an aromatic group comprising the steps of:
Figure BDA0003916212690000041
(1) Under the room temperature environment, firstly adding p-terphenyl (2.3g, 10mmol) into a three-necked bottle, adding a solvent dichloromethane (8 mL), stirring uniformly, then adding a 4-imidazole formaldehyde monomer (1.05g, 111mmol) into the solution, and stirring uniformly;
(2) Trifluoromethanesulfonic acid (TFSA) (6.0 mL, 60mmol) and methanesulfonic acid (MFA) (6.0 mL, 78mmol) were added dropwise to the solution of step (1) under ice-bath conditions (reaction temperature below 0 ℃). Initiating polymerization reaction at the temperature below 0 ℃, gradually heating to room temperature, reacting for 0.5h, then increasing the system viscosity, slowly pouring the mixture into ammonia water to obtain a fibrous polymer, removing redundant acid in the solution by using 0.50mol/L sodium bicarbonate solution, washing for multiple times by using deionized water until the system is neutral, and filtering to obtain a fibrous solid polymer, namely the polymer binder containing the alkaline group.
The polymer binder prepared as described above is at high temperature H 2 /O 2 Applications in fuel cells:
(1) Dissolving the prepared ketone monomer containing the alkaline group and the ionic polymer binder containing the aryl in a polar solvent NMP, wherein the concentration of the solution is controlled to be 2-5 wt%, and preparing a polymer solution;
(2) Dispersing a polymer solution (2 wt%) and a Pt/C catalyst (40 wt%) in an NMP solvent, uniformly mixing by magnetic stirring and ultrasonic waves to obtain a catalyst slurry, and spraying the catalyst slurry onto a gas diffusion layer (carbon paper) for both sides of an anode and a cathode. Wherein, the polymer in the high-temperature fuel cell binder accounts for 3-30% of the weight of the catalyst slurry; the loading capacity of the catalyst is 0.25-1.00 mg-cm -2 ；
(3) And (3) clamping the carbon paper containing the catalyst layer prepared in the step (2) at two sides of a high-temperature proton exchange membrane (PBI-PA membrane), loading the carbon paper into a fuel cell test fixture, and connecting the carbon paper into a fuel cell test system for testing. And (3) testing conditions are as follows: in the absence of back pressure and humidification, H 2 And O 2 The flow rate of (2) is 200-1000 sccm, and the performance of the fuel cell is tested at 160 ℃.
Example 2
Figure BDA0003916212690000051
Under the environment of room temperature, terphenyl (1.84g, 8mmol) is firstly added into a three-necked bottle, a solvent dichloromethane (12 mL) is added, the mixture is stirred to be uniform, then 4-pyrazole formaldehyde monomer (0.8g, 8.3mmol) is added into the solution, trifluoromethanesulfonic acid (TFSA) (5.0mL, 50mmol) and methanesulfonic acid (MFA) (5.0mL, 62mmol) are dropwise added into the solution under the condition of ice bath (the temperature of a reaction system is lower than 0 ℃), and the viscosity of the system is increased after the reaction is carried out for 4.5 hours; and (5) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Example 3
Figure BDA0003916212690000052
Under the room temperature environment, terphenyl (1.15g, 5mmol) is firstly added into a three-necked bottle, a solvent dichloromethane (4 mL) is added, the mixture is stirred to be uniform, then pyrazole-3-formaldehyde (0.52g, 6mmol) is added into the solution, trifluoromethanesulfonic acid (TFSA) (3.0mL, 29mmol) and methanesulfonic acid (MFA) (3.0mL, 39mmol) are added into the solution dropwise under the ice-bath condition (the temperature of the reaction system is lower than 0 ℃), and the viscosity of the system is increased after the reaction is carried out for 11 hours; and (5) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Example 4
Figure BDA0003916212690000061
Under the room temperature environment, firstly adding p-terphenyl (4.60g, 15mmol) into a three-neck flask, adding a solvent dichloromethane (10 mL), stirring until the mixture is uniform, then adding an N-methyl-4-piperidone monomer (1.75g, 116mmol) into the solution, dropwise adding trifluoroacetic acid (TFA) (1.0mL, 13mmol) and trifluoromethanesulfonic acid (TFSA) (14mL, 135mmol) into the solution under the ice bath condition (the temperature of a reaction system is lower than 0 ℃), and reacting for 2 hours to increase the viscosity of the system; and (4) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Example 5
Figure BDA0003916212690000062
Under the room temperature environment, terphenyl (3.6 g, 16mmol) is firstly added into a three-necked bottle, a solvent dichloromethane (15 mL) is added, the mixture is stirred to be uniform, then 1-methylpyrazole-3-formaldehyde monomer (2.3 g, 20mmol) is added into the solution, trifluoromethanesulfonic acid (TFSA) (4mL, 40mmol) and methanesulfonic acid (MFA) (3.0mL, 39mmol) are added into the solution dropwise under the ice-bath condition (the temperature of a reaction system is lower than 0 ℃), and the viscosity of the system is increased after the reaction is carried out for 5 hours; and (5) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Example 6
Figure BDA0003916212690000063
Under the room temperature environment, terphenyl (3.6 g, 16mmol) is firstly added into a three-necked bottle, a solvent dichloromethane (15 mL) is added, the mixture is stirred to be uniform, then 2-methylimidazole-4-formaldehyde monomer (2.3 g, 20mmol) is added into the solution, trifluoromethanesulfonic acid (TFSA) (4mL, 40mmol) and methanesulfonic acid (MFA) (6.0 mL, 78mmol) are added into the solution dropwise under the ice-bath condition (the temperature of a reaction system is lower than 0 ℃), and the viscosity of a system is increased after the reaction is carried out for 3 hours; and (5) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Example 7
Figure BDA0003916212690000071
Under the room temperature environment, terphenyl (2.3 g, 10mmol) is firstly added into a three-necked bottle, a solvent dichloromethane (23 mL) is added, the mixture is stirred to be uniform, then 4-pyridine formaldehyde monomer (0.77mL, 11mmol) is added into the solution, trifluoromethanesulfonic acid (TFSA) (8mL, 75mmol) and trifluoroacetic acid (TFA) (6.0 mL, 78mmol) are added into the solution dropwise under the ice-bath condition (the temperature of a reaction system is lower than 0 ℃), and the viscosity of the system is increased after the reaction is carried out for 48 hours; and (5) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Example 8
Figure BDA0003916212690000072
Under the room temperature environment, terphenyl (3.6 g, 16mmol) is firstly added into a three-necked bottle, a solvent dichloromethane (13 mL) is added, the mixture is stirred to be uniform, then 1-methylimidazole-2-formaldehyde monomer (2.3 g, 20mmol) is added into the solution, trifluoromethanesulfonic acid (TFSA) (4 mL, 40mmol) and methanesulfonic acid (MFA) (6.0 mL, 78mmol) are added into the solution dropwise under the ice-bath condition (the temperature of the reaction system is lower than 0 ℃), and the viscosity of the system is increased after the reaction is carried out for 13 hours; and (5) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Example 9
Figure BDA0003916212690000073
Under the room temperature environment, terphenyl (3.0g, 13mmol) is firstly added into a three-neck flask, solvent dichloromethane (5 mL) is added, the mixture is stirred to be uniform, then 3-pyridylaldehyde monomer (1.0mL, 14mmol) is added into the solution, trifluoromethanesulfonic acid (TFSA) (10.4mL, 100mmol) and trifluoroacetic acid (TFA) (1.3mL, 17mmol) are added into the solution dropwise under the ice-bath condition (the temperature of the reaction system is lower than 0 ℃), and the viscosity of the system is increased after the reaction is carried out for 36 hours; and (5) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Comparative example 1
Figure BDA0003916212690000081
Under the room temperature environment, terphenyl (1.15g, 5 mmol) is firstly added into a three-necked bottle, a solvent dichloromethane (19 mL) is added, the mixture is stirred to be uniform, isatin (1.44g, 5 mmol) is then added into the solution, trifluoromethanesulfonic acid (TFSA) (3.2mL, 30mmol) and trifluoroacetic acid (TFA) (11mL, 136mmol) are dropwise added into the solution under the ice bath condition (the temperature of a reaction system is lower than 0 ℃), and the viscosity of a system is increased after 24 hours of reaction; and (5) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Comparative example 2
Figure BDA0003916212690000082
Under the room temperature environment, firstly adding p-terphenyl (2.3g, 10mmol) into a three-necked bottle, adding a solvent dichloromethane (10 mL), stirring until the mixture is uniform, then adding imidazole-2-formaldehyde (1.35g, 13mmol) into the solution, and under the ice-bath condition (the temperature of a reaction system is lower than 0 ℃), dropwise adding trifluoromethanesulfonic acid (TFSA) (8.0mL, 80mmol) into the solution, and reacting for 12 hours to increase the viscosity of the system; and (4) carrying out post-treatment. The remaining experimental procedures and application procedures were the same as in example 1.
Comparative example 3
M-polybenzimidazole (mPBI) was dissolved in NMP, a polar solvent, and the concentration of the solution was controlled to 2% by weight, and the polymer solution prepared was used as a binder. The subsequent experimental procedures and application procedures were the same as in example 1.
Comparative example 4
Commercial PTFE (60%) emulsion was used as the binder, and isopropyl alcohol and water were used as the dispersant. The subsequent experimental procedures and application procedures were the same as in example 1.
And (3) performance test results:
in comparative example 1, a polymer containing nitrogen ketone compound and aromatic hydrocarbon which have the smallest interaction with phosphoric acid was selected as a comparative example. In comparative example 2, the polymer containing nitrogen ketones and aromatic hydrocarbons, which most strongly interact with phosphoric acid, was selected as a comparative example.
As is clear from Table 1, by changing the basic group, the acid absorption ability of the polymer was improved, but the volume swelling of the polymer was increased. The proper acid absorption capacity can enhance the dimensional stability of the binder;
TABLE 1 comparison of acid absorption Capacity and swelling Rate of Polymer Binders of examples 1-2 and comparative examples 1-4
Figure BDA0003916212690000091
The acid absorption ADL in Table 1 represents the number of phosphoric acids adsorbed per structural unit.
As can be seen from FIG. 1, the acid absorption capacity of the polymer is changed by changing the basic groups, so that the conductivity of the polymer at 160 ℃ is changed, and the proton transmission capacity of the adhesive in the use process is ensured;
figure 2 shows that the initial performance of the use of a relatively medium basic group polymer as a binder in a high temperature fuel cell is superior to binders containing relatively weak or strong basic groups.
Fig. 3 shows that when the polymer with medium alkaline groups is used as the binder in a high-temperature fuel cell, a proper amount of the binder is beneficial to achieving higher performance of the cell.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way and substantially, it should be noted that those skilled in the art may make several modifications and additions without departing from the scope of the present invention, which should also be construed as a protection scope of the present invention.

Claims (9)

1. A polymeric binder containing basic groups, characterized in that it is a homopolymer comprising the following repeating structural units:
Figure FDA0003916212680000011
wherein Ar represents an organic group containing an aromatic ring, R represents different basic groups, n represents the average polymerization degree, n is more than or equal to 10 and less than or equal to 200, and the weight average molecular weight of the homopolymer is between 5000 and 800000;
ar is the following group:
Figure FDA0003916212680000012
the R is any one of the following groups:
Figure FDA0003916212680000013
2. the method for preparing a polymer binder containing an alkaline group according to claim 1, comprising: under the room temperature environment, firstly adding an organic compound containing Ar into an organic solvent, stirring and dissolving, adding a ketone monomer containing a basic group, then dropwise adding trifluoroacetic acid, methane sulfonic acid and trifluoromethanesulfonic acid into the system under the ice bath condition of lower than 0 ℃, initiating a polymerization reaction at the temperature of below 0 ℃, then gradually heating to room temperature for reaction, pouring the obtained mixture into ammonia water after the reaction is finished to obtain a fibrous polymer, washing away excessive acid with an alkaline solution, washing with deionized water to be neutral, filtering, and drying to obtain the solid polymer binder.
3. Use of the polymeric binder containing basic groups according to claim 1 in high temperature fuel cells.
4. The use of claim 3, wherein the high temperature fuel cell comprises a membrane electrode assembly comprising a proton exchange membrane, a catalytic layer, and a diffusion layer, the catalytic layer being prepared from a catalyst ink comprising a polymer binder.
5. The use according to claim 4, wherein the catalytic layer comprises from 3 to 30wt% of a polymeric binder.
6. The use according to claim 5, wherein the catalyst contained in the catalytic layer is a Pt/C catalyst, and the content of Pt in the Pt/C catalyst is 20-60 wt%.
7. The method of claim 6Characterized in that the loading amount of the Pt/C catalyst in the catalyst layer is 0.25-1 mg cm -2 。
8. The use according to claim 4, wherein the catalyst ink is obtained by uniformly dispersing a mixture of a binder solution, a Pt/C catalyst and a solvent by stirring and ultrasonic treatment; the binder solvent solution is obtained by dissolving a polymer binder in a polar solvent, wherein the polar solvent is at least one of NMP, DMF, DMAc and DMSO, and the concentration of the binder solution is 2-5 wt%.
9. A catalyst ink for a high temperature fuel cell, wherein preparing a raw material comprises: a binder solution, a Pt/C catalyst, and a solvent; the binder solvent solution is obtained by dissolving the polymer binder containing basic groups according to claim 1 in a polar solvent, wherein the polar solvent is at least one of NMP, DMF, DMAc and DMSO, and the concentration of the binder solution is 2-5 wt%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113527684A (en) * 2020-04-21 2021-10-22 武汉理工大学 Oxygen reduction catalyst layer based on grafted polybenzimidazole as proton conductor and preparation method thereof
CN114276505A (en) * 2021-12-31 2022-04-05 安徽师范大学 Polyarylene piperidine copolymer containing polyethylene glycol flexible hydrophilic side chain, preparation method, anion exchange membrane and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113527684A (en) * 2020-04-21 2021-10-22 武汉理工大学 Oxygen reduction catalyst layer based on grafted polybenzimidazole as proton conductor and preparation method thereof
CN114276505A (en) * 2021-12-31 2022-04-05 安徽师范大学 Polyarylene piperidine copolymer containing polyethylene glycol flexible hydrophilic side chain, preparation method, anion exchange membrane and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HANQING PENG，ETC.: "Alkaline polymer electrolyte fuel cells stably working at 80°C", JOURNAL OF POWER SOURCES, pages 165 *

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