CN112259771A - Proton exchange membrane with wide operating temperature, and preparation method and application thereof - Google Patents
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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Abstract
The invention discloses a proton exchange membrane with wide operating temperature and a preparation method and application thereof, wherein the method comprises the following steps: dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to prepare a mixed solution; paving the mixed solution on a glass plate and carrying out heat treatment to obtain an initial film layer; and soaking the initial film layer in a phosphoric acid aqueous solution to obtain the proton exchange membrane. According to the invention, the polyacrylamide hydrogel is introduced into the polybenzimidazole, and the high-low temperature conductivity of the membrane is enhanced by means of the water absorption and phosphoric acid absorption of the polyacrylamide hydrogel, so that the membrane can run in a wide temperature range in a proton exchange membrane fuel cell.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a proton exchange membrane with wide operating temperature and a preparation method and application thereof.
Background
High temperature proton exchange membrane fuel cells (HT-PEMFCs) have many advantages over low temperature proton exchange membrane fuel cells (LT-PEMFCs), such as higher carbon monoxide tolerance, simplified thermal management systems, higher reactivity, etc. The commercialization of clean and efficient fuel cell electric vehicles has been started, but new requirements have been made for fuel cell electric vehicles, such as cost reduction and wider applicability.
Nafion membranes used in LT-PEMFCs have been used in commercial pem fuel cell vehicles, but such membranes can only be used in low temperature and high humidity environments of less than 80 ℃, requiring complex hydrothermal management systems, large radiators and humidifiers. Instead, these problems are solved by HT-PEMFCs, among which are the phosphoric acid doped polybenzimidazole (OPBI) proton exchange membranes that can be operated at high temperature of 120-. However, such membranes cannot be operated at low temperatures because of the very rapid loss of phosphoric acid and the low proton conductivity at low temperatures.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a proton exchange membrane with a wide operating temperature, a preparation method thereof and an application thereof, and aims to solve the problem that the existing proton exchange membrane cannot be applied to a wide operating temperature.
The technical scheme of the invention is as follows:
a preparation method of a proton exchange membrane with wide operating temperature comprises the following steps:
dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to prepare a mixed solution;
paving the mixed solution on a glass plate and carrying out heat treatment to obtain an initial film layer;
and soaking the initial film layer in a phosphoric acid aqueous solution to obtain the proton exchange membrane.
The preparation method of the proton exchange membrane with the wide operating temperature comprises the step of paving the mixed solution on a glass plate and carrying out heat treatment, wherein the temperature of the heat treatment is 60-100 ℃, and the time of the heat treatment is 10-15 h.
The preparation method of the proton exchange membrane with wide operating temperature comprises the following steps of:
and (3) putting the initial film layer into a vacuum oven, and carrying out vacuum drying treatment for 10-24h at the temperature of 110-150 ℃.
The preparation method of the proton exchange membrane with wide operating temperature comprises the following steps before the initial membrane layer is soaked in phosphoric acid aqueous solution:
and after the initial film layer is subjected to water soaking treatment, drying treatment is carried out at the temperature of 100-150 ℃.
The preparation method of the proton exchange membrane with wide operating temperature is characterized in that the concentration of the phosphoric acid aqueous solution is 70-90%.
The preparation method of the proton exchange membrane with the wide operating temperature comprises the step of soaking the initial membrane layer in phosphoric acid aqueous solution at the temperature of 70-90 ℃ for 15-24 hours to obtain the proton exchange membrane.
The preparation method of the proton exchange membrane with wide operating temperature is characterized in that the mass of the added acrylamide monomer is 0.5-2 times of that of the polybenzimidazole.
The preparation method of the proton exchange membrane with wide operating temperature is characterized in that the mass of the added acrylamide monomer is 0.8 times of that of the polybenzimidazole.
The invention relates to a proton exchange membrane with wide operating temperature, which is prepared by the preparation method of the proton exchange membrane with wide operating temperature.
The invention relates to the use of a proton exchange membrane with a wide operating temperature range, wherein the proton exchange membrane according to the invention is used in a fuel cell.
Has the advantages that: the invention provides a preparation method of a proton exchange membrane with wide operating temperature, which comprises the steps of dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to prepare a mixed solution; paving the mixed solution on a glass plate and carrying out heat treatment to obtain an initial film layer; and soaking the initial film layer in a phosphoric acid aqueous solution to obtain the proton exchange membrane. According to the invention, the polyacrylamide hydrogel is introduced into the polybenzimidazole, and the high-low temperature conductivity of the membrane is enhanced by means of the water absorption and phosphoric acid absorption of the polyacrylamide hydrogel, so that the membrane can run in a wide temperature range in a proton exchange membrane fuel cell.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of a method for preparing a proton exchange membrane with a wide operating temperature range according to the present invention.
FIG. 2 is an infrared characterization of the proton exchange membranes and polybenzimidazole membranes prepared in examples 1-4.
FIG. 3 is a thermogravimetric analysis of the proton exchange membrane prepared in example 2, as well as of a polybenzimidazole membrane and a polyacrylamide hydrogel.
FIG. 4 is a surface topography map of OPBI and OPBI-0.8AM films, wherein a, b are surface topography maps of OPBI at different magnifications, and c, d are surface topography maps of OPBI-0.8AM films at different magnifications.
FIG. 5 is a profile of OPBI and OPBI-0.8AM films, wherein A, B is a profile of OPBI at different magnifications and C, D is a profile of OPBI-0.8AM films at different magnifications.
FIG. 6 is a graph showing conductance test curves of the proton exchange membranes and the polybenzimidazole membranes prepared in examples 1 to 4 at 40 to 100 ℃.
FIG. 7 is a graph of conductance test curves of the proton exchange membranes and the polybenzimidazole membranes prepared in examples 1 to 4 at the temperature of 120-200 ℃.
FIG. 8 is a stress-strain plot of the proton exchange membranes and polybenzimidazole membranes prepared in examples 1-4.
Fig. 9 is a graph showing the soaking time and weight loss of the proton exchange membrane and the polybenzimidazole membrane in fenton reagent, which are prepared in examples 1 to 4.
FIG. 10a is a graph showing open circuit voltage and current density curves of the proton exchange membranes and the polybenzimidazole membranes prepared in examples 1 to 4 when they are used in a fuel cell.
FIG. 10b is a graph of power density versus current density for proton exchange membranes and polybenzimidazole membranes made according to examples 1-4 used in fuel cells.
FIG. 11 shows OPBI-0.8AM film at 200mA cm-2Stability test results plot for operation under constant current conditions.
Detailed Description
The invention provides a proton exchange membrane with wide operating temperature, a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a schematic diagram illustrating a method for preparing a proton exchange membrane with a wide operating temperature according to the present invention, which includes the following steps:
s10, dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to obtain a mixed solution;
s20, spreading the mixed solution on a glass plate and carrying out heat treatment to obtain an initial film layer;
and S30, carrying out phosphoric acid water solution soaking treatment on the initial film layer to obtain the proton exchange membrane.
In this embodiment, the acrylamide monomer may have some intermolecular entanglement with the polybenzimidazole (OPBI) during a radical process, and under the action of a thermal initiator potassium persulfate, the acrylamide monomer in the mixed solution undergoes a polymerization reaction to form a polyacrylamide hydrogel having a porous structure, and the polyacrylamide hydrogel is located at a lower layer of the polybenzimidazole gel, i.e., an initial membrane layer is formed; after the initial film layer is soaked in a phosphoric acid aqueous solution, the polyacrylamide hydrogel with a porous structure can effectively absorb water and phosphoric acid, and the polybenzimidazole can also absorb phosphoric acid, so that the proton exchange membrane is prepared. In the embodiment, the polyacrylamide hydrogel is introduced into the polybenzimidazole, and the high and low temperature conductivity of the membrane is enhanced by means of the water absorption and phosphoric acid absorption of the polyacrylamide hydrogel, so that the membrane can run in a wide temperature range in a proton exchange membrane fuel cell.
In some specific embodiments, polybenzimidazole is dissolved in dimethyl sulfoxide solution, then acrylamide monomer and potassium persulfate are added and mixed to prepare a mixed solution, the mixed solution is paved on a glass plate and is subjected to heat treatment, the mixed solution is treated for 10-15 hours at the temperature of 60-100 ℃, so that the acrylamide monomer is subjected to polymerization reaction to generate polyacrylamide hydrogel with a porous structure, and the polyacrylamide hydrogel is positioned at the lower layer of the polybenzimidazole gel; then, heating to 110-150 ℃, and carrying out vacuum drying treatment for 10-24h to remove the redundant solvent in the film layer, thereby obtaining an initial film layer; further, carrying out water soaking treatment on the initial film layer for two days, changing water every 12 hours during the water soaking treatment so as to fully separate out the organic solvent in the initial film layer, and then carrying out drying treatment at the temperature of 100-150 ℃; and finally, soaking the initial membrane layer in 70-90 ℃ phosphoric acid aqueous solution with the concentration of 70-90% for treatment for 15-24h to prepare the proton exchange membrane.
In some embodiments, the mass of acrylamide monomer added is 0.5 to 2 times the mass of polybenzimidazole. Preferably, the mass of the acrylamide monomer is 0.8 times the mass of the polybenzimidazole.
In some embodiments, a proton exchange membrane with a wide operating temperature is also provided, which is prepared by the preparation method of the proton exchange membrane with a wide operating temperature.
In some embodiments, there is also provided a use of a proton exchange membrane having a wide operating temperature for use in a fuel cell.
The proton exchange membrane with wide operating temperature and the preparation method and performance thereof of the present invention are further explained by the following specific examples:
example 1
Dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to prepare a mixed solution, wherein the mass of the added acrylamide monomer is 0.5 times that of the polybenzimidazole; paving the mixed solution on a glass plate, carrying out heat treatment, and carrying out vacuum drying treatment for 12h at 80 ℃ so that an acrylamide monomer is subjected to polymerization reaction to generate polyacrylamide hydrogel with a porous structure, wherein the polyacrylamide hydrogel is positioned at the lower layer of the polybenzimidazole gel; then, heating to 120 ℃, and carrying out vacuum drying treatment for 24 hours to remove redundant solvent in the film layer, thus obtaining an initial film layer; further, carrying out water soaking treatment on the initial film layer for two days, changing water every 12 hours during the water soaking treatment so as to fully separate out the organic solvent in the initial film layer, and then carrying out drying treatment at 120 ℃; and finally, soaking the initial film layer in a phosphoric acid water solution with the concentration of 85% for treatment for 24 hours at the temperature of 70-90 ℃ to obtain the proton exchange membrane, which is marked as OPBI-0.5 AM.
Example 2
Dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to prepare a mixed solution, wherein the mass of the added acrylamide monomer is 0.8 times that of the polybenzimidazole; paving the mixed solution on a glass plate, carrying out heat treatment, and carrying out vacuum drying treatment for 12h at 90 ℃ so that an acrylamide monomer is subjected to polymerization reaction to generate polyacrylamide hydrogel with a porous structure, wherein the polyacrylamide hydrogel is positioned at the lower layer of the polybenzimidazole gel; then, heating to 130 ℃, and carrying out vacuum drying treatment for 12h to remove redundant solvent in the film layer, thus obtaining an initial film layer; further, carrying out water soaking treatment on the initial film layer for two days, changing water every 12 hours during the water soaking treatment so as to fully separate out the organic solvent in the initial film layer, and then carrying out drying treatment at the temperature of 130 ℃; and finally, soaking the initial film layer in 80% phosphoric acid water solution at 80 ℃ for treatment for 20h to prepare the proton exchange membrane which is marked as OPBI-0.8 AM.
Example 3
Dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to prepare a mixed solution, wherein the mass of the added acrylamide monomer is 1.0 time that of the polybenzimidazole; paving the mixed solution on a glass plate, carrying out heat treatment, and carrying out vacuum drying treatment for 14h at 85 ℃ so that an acrylamide monomer is subjected to polymerization reaction to generate polyacrylamide hydrogel with a porous structure, wherein the polyacrylamide hydrogel is positioned at the lower layer of the polybenzimidazole gel; then, heating to 140 ℃, and carrying out vacuum drying treatment for 15h to remove redundant solvent in the film layer, thus obtaining an initial film layer; further, carrying out water soaking treatment on the initial film layer for two days, changing water every 12 hours during the water soaking treatment so as to fully separate out the organic solvent in the initial film layer, and then carrying out drying treatment at the temperature of 110 ℃; and finally, soaking the initial film layer in 90% phosphoric acid aqueous solution at 85 ℃ for 18h to prepare the proton exchange membrane which is marked as OPBI-1.0 AM.
Example 4
Dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to prepare a mixed solution, wherein the mass of the added acrylamide monomer is 2.0 times that of the polybenzimidazole; paving the mixed solution on a glass plate, carrying out heat treatment, and carrying out vacuum drying treatment for 13h at the temperature of 80 ℃ so that an acrylamide monomer is subjected to polymerization reaction to generate polyacrylamide hydrogel with a porous structure, wherein the polyacrylamide hydrogel is positioned at the lower layer of the polybenzimidazole gel; then, heating to 120 ℃, and carrying out vacuum drying treatment for 18h to remove redundant solvent in the film layer, thus obtaining an initial film layer; further, carrying out water soaking treatment on the initial film layer for two days, changing water every 12 hours during the water soaking treatment so as to fully separate out the organic solvent in the initial film layer, and then carrying out drying treatment at 120 ℃; and finally, soaking the initial film layer in 85 ℃ phosphoric acid aqueous solution with the concentration of 85% for treatment for 20 hours to prepare the proton exchange membrane, which is marked as OPBI-2.0 AM.
Example 5
Infrared characterization was performed on the proton exchange membranes and polybenzimidazole membranes obtained in examples 1-4, and the results are shown in FIG. 2 at 3500--1The broad peaks at the positions are the stretching peak of O-H and the peak of N-H on the imidazole ring. At 1600cm-1，794cm-1The peak above belongs to the telescopic transition peak of C ═ N on the imidazole ring. At 1222cm-1The position is the peak of Ar-O-Ar on OPBI. At 1650cm-1The proton exchange membranes of examples 1-4 demonstrated successful incorporation of acrylamide hydrogels on OPBI due to the expansion peak of C ═ O on polyacrylamide.
Example 6
Thermogravimetric analysis of the proton exchange membrane prepared in example 2, as well as the polybenzimidazole membrane and polyacrylamide hydrogel, showed that the OPBI and OPBI-0.8AM membranes had two weight loss regions, as shown in fig. 3, and that the membrane weight loss was very small below 500 ℃, which was due to the residual water and solvent. At 500 ℃ and 600 ℃, the weight loss of the membrane is large because the OPBI backbone decomposes in this temperature interval. The weight loss of the polyacrylamide hydrogel at 60-200 ℃ was 4.3%, which is due to the weight loss of water in the hydrogel. The weight loss of the OPBI-0.8AM membrane after phosphoric acid doping at 250 ℃ was due to dehydration of phosphoric acid. Therefore, the OPBI-0.8AM film and the polyacrylamide hydrogel have good thermal stability at 200 ℃, and the OPB-AM film can be applied to HT-PEMFCs.
Example 7
The proton exchange membrane and the polybenzimidazole membrane prepared in example 2 were observed for morphology under an electron microscope, and the results are shown in fig. 4 and 5, from which it can be seen that the surface and the cross section of OPBI are dense and uniform. The OPBI layer on the surface of OPBI-0.8AM is compact, the layer formed by polyacrylamide hydrogel is porous, the same layered structure is also seen in the section, and the porous structure of polyacrylamide hydrogel is beneficial to absorption of phosphoric acid and water, so that the membrane has higher conductivity.
Example 8
The proton exchange membranes and polybenzimidazole membranes prepared in examples 1 to 4 were tested for phosphoric acid absorption rate and water absorption rate, and the results are shown in table 1:
TABLE 1
As can be seen from Table 1, the phosphoric acid absorption and water absorption of the OPBI-AM film both increased as the polyacrylamide hydrogel content of the film increased. High phosphoric acid absorption and water absorption mean high and low temperature electrical conductance. The polyacrylamide hydrogel absorbs abundant phosphoric acid and water, contains abundant hydrogen bonds and is beneficial to proton transmission. However, OPBI-1.0AM and OPBI-2.0AM have a large swelling ratio at the same time, which is disadvantageous for the mechanical stability of the membrane.
Example 9
The proton exchange membranes and polybenzimidazole membranes prepared in examples 1 to 4 were subjected to high and low temperature conductivity tests, and the results are shown in fig. 6 and 7, and it can be seen from fig. 6 that at low temperatures (40 to 100 ℃), proton conduction is mainly through a transport and hopping mechanism, and water plays a major role in the proton transport process. As can be seen from Table 1, the water absorption of the film increases from OPBI to OPBI-0.5AM to OPBI-2.0 AM. Thus, the conductance of the film is also increased accordingly. As can be seen from fig. 7, at high temperatures (120-. Protons are predominantly transported through the proton in N-H in phosphoric acid doped polybenzimidazole membranes+···H2PO4 -,H3PO4(H2PO4-. H-O-H and H2PO4 -/HPO4 2-To hop between transmissions. The electrical conductivity is related to the temperature and the acid doping amount, and the proton transfer rate of the OPBI-AM membrane is continuously increased along with the increase of the temperature. The drop at 180 ℃ is due to dehydration of the phosphoric acid. From OPBI to OPBI-0.5AM to OPBI-2.0AM, the amount of phosphoric acid doping is increased, and the conductance of the film is increased in turn.
Example 10
The proton exchange membranes and polybenzimidazole membranes prepared in examples 1 to 4 were subjected to stress performance tests, and the results are shown in fig. 8, and it can be seen from fig. 8 that the mechanical strength of the membranes after phosphoric acid doping is rapidly reduced and the elongation at break is increased. The OPBI-0.5AM film has the highest tensile strength, which benefits from the hydrogen bonding of OPBI to polyacrylamide hydrogel. The mechanical strength of the OPBI-AM membrane decreases with increasing hydrogel content due to the weak strength of the hydrogel. And the mechanical strength of OPBI-0.5AM and OPBI-0.8AM is not reduced too fast, and the fuel cell can be used.
Example 11
The proton exchange membranes and polybenzimidazole membranes prepared in examples 1 to 4 were subjected to oxidation stability performance test, and the results are shown in fig. 9. as can be seen from fig. 9, OPBI membrane broke after 120h, whereas OPBI-0.5AM broke after 168h and maintained the least weight loss. OPBI-0.8AM and OPBI-1.0AM and OPBI-2.0AM both broke after 192h, but OPBI-2.0AM had greater weight loss due to loss of polyacrylamide hydrogel as the sacrificial phase first during oxidation, thereby protecting the OPBI.
Example 12
The proton exchange membranes and polybenzimidazole membranes prepared in examples 1 to 4 were subjected to cell performance tests, and the results are shown in fig. 10a and 10b, and it can be seen from fig. 10a and 10b that the open circuit voltages of all the membranes are above 0.9V, indicating that the membranes are completely dense. Wherein the OPBI-0.8AM film has a highest power density of 200mW cm at 80 deg.C-2560mW cm at 160 DEG C-2. This is due to the high proton conductivity and moderate mechanical strength. OPBI-0.5AM film. The power densities of OPBI-1.0AM and OPBI-2.0AM are lower than for pure OPBI membranes, probably because the swelling of both membranes is too great, leading to permeation of the fuel. Thus, OPBI-0.8AM membranes have potential for use in proton exchange membrane fuel cells.
Example 13
The stability test of the proton exchange membrane prepared in example 2 was performed under a constant current condition, and the result is shown in FIG. 11, from which it can be seen that the OPBI-0.8AM membrane was operated under a constant current (200mA cm)-2) The stable operation under the condition exceeds 120H, and the low H is proved2Permeability and high efficiencyThe proton transmission can be applied to proton exchange membrane fuel cells.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a proton exchange membrane with wide operating temperature is characterized by comprising the following steps:
dissolving polybenzimidazole in a dimethyl sulfoxide solution, adding an acrylamide monomer and potassium persulfate, and mixing to prepare a mixed solution;
paving the mixed solution on a glass plate and carrying out heat treatment to obtain an initial film layer;
and soaking the initial film layer in a phosphoric acid aqueous solution to obtain the proton exchange membrane.
2. The method for preparing a proton exchange membrane having a wide operating temperature as claimed in claim 1, wherein the step of spreading the mixed solution on a glass plate and performing a heat treatment at a temperature of 60-100 ℃ for a time of 10-15 hours.
3. The method for preparing the proton exchange membrane with the wide operating temperature according to claim 1, wherein the step of spreading the mixed solution on a glass plate and performing heat treatment to obtain an initial membrane layer further comprises the following steps:
and (3) putting the initial film layer into a vacuum oven, and carrying out vacuum drying treatment for 10-24h at the temperature of 110-150 ℃.
4. The method for preparing a proton exchange membrane with a wide operating temperature as claimed in claim 1, wherein the step of soaking the initial membrane layer in phosphoric acid aqueous solution further comprises:
and after the initial film layer is subjected to water soaking treatment, drying treatment is carried out at the temperature of 100-150 ℃.
5. The method of claim 1, wherein the concentration of the phosphoric acid aqueous solution is 70-90%.
6. The method for preparing the proton exchange membrane with the wide operating temperature as claimed in claim 5, wherein the initial membrane layer is soaked in phosphoric acid aqueous solution at 70-90 ℃ for 15-24h to obtain the proton exchange membrane.
7. The method of claim 1, wherein the mass of the acrylamide monomer added is 0.5-2 times of the mass of the polybenzimidazole.
8. The method of claim 1, wherein the mass of the acrylamide monomer added is 0.8 times of the mass of the polybenzimidazole.
9. A proton exchange membrane with a wide operating temperature, which is prepared by the preparation method of the proton exchange membrane with a wide operating temperature as claimed in any one of claims 1 to 8.
10. Use of a proton exchange membrane having a wide operating temperature, wherein the proton exchange membrane of claim 9 is used in a fuel cell.
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