| Citation: |
DAI Yu, ZHANG Dongbin, ZENG Zehua, et al. Preparation and properties of PVC-PVP composite high temperature proton exchange membranes reinforced with PTFE for high temperature fuel cells[J]. Acta Materiae Compositae Sinica, 2025, 42(3): 1402-1411. DOI: 10.13801/j.cnki.fhclxb.20240508.004
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Proton exchange membrane fuel cell (PEMFC) operating above 100℃ can overcome the defects of low temperature operation, improve the ability of platinum catalyst to resist CO poisoning, accelerate electrode kinetics, simplify hydrothermal management system and improve heat recycling. In order to achieve both high proton conductivity and excellent mechanical properties of phosphoric acid (PA)-doped high temperature proton exchange membrane (HT-PEM), we prepared a series of polytetrafluoroethylene (PTFE®)-reinforced polyvinylpyrrolidone-polyvinyl chloride (PVP-PVC) composite membranes. By adjusting the ratio of PVP and PVC, the best composite membrane was found, and its physical and chemical properties were tested and characterized. SEM results showed that PVP-PVC was uniformly filled into the pores of PTFE® membrane without bubbles and holes. The results of proton conductivity and mechanical property test show that PTFE® enhanced membrane has good tensile strength and dimensional stability, and the proton conductivity increases with the increase of PVP content in the composite membrane. As a result, the proton conductivity of PA-doped PTFE® reinforced composite membrane, i.e., the mass ratio of PVP to PVC is 4 is as high as 0.161 S·cm−1 at 160℃, and the maximum tensile strength of the membrane at room temperature is 15.6 MPa. At 160℃, the peak power density of the composite membrane is about 359 mW·cm−2. These results indicate that PA-doped PTFE-reinforced composite membranes have the potential to be used as HT-PEM.
Proton exchange membrane fuel cells (PEMFC) are one of the most efficient and sustainable power generation devices and can be used in transportation and portable applications due to their advantages of high power density and low environmental impact. The advantages of PEMFC operating at temperature above 100 ° C are enhanced tolerance of platinum catalyst to CO poisoning, accelerated electrode kinetics, simplified hydrothermal management, and efficient heat recovery and utilization. Proton exchange membrane (PEM), as the electrolyte of high temperature proton exchange membrane fuel cell (HT-PEMFC), should have high proton conductivity under the condition of low relative humidity, and should have high thermal and chemical stability, as well as sufficient mechanical strength and compactness. To satisfy these requirements, researchers have made many efforts to improve the overall performance of PEM in the operating temperature range of 100 ° C to 200 ° C.
Polyvinylpyrrolidone (PVP) was blended with polyvinyl chloride (PVC)，and the content of PVP was optimized to prepare membranes with high proton conductivity. The content of PVP can be used to adjust the adsorption amount of phosphoric acid, PVP is water-soluble which is unable to form a membrane alone, so PVC is blended with PVC which works as a supporting skeleton to form a membrane. In order to achieve both high proton conductivity and excellent mechanical properties of PEM, polytetrafluoroethylene (PTFE) was used as a reinforced membrane to reduce the plasticization caused by PA doping. The porous PTFE membrane is used as a framework, and the PVP-PVC polymer is dissolved and filled into the porous structure of PTFE membrane. After drying, PTFE-reinforced PVP-PVC composite membrane is formed, resulting in a PEM with both high proton conductivity and high mechanical property.
Pure PTFE membrane is milky white and translucent, PVP-PVC composite membrane is colorless and transparent, and PTFE/PVP-PVC composite membrane is also colorless and transparent. From the SEM test results, it can be seen that the PTFE membrane is fibrous and has a porous structure. The surface of PVP-PVC-1 composite membrane is uniform and compact, and there are no holes. The surface of PTFE/PVP-PVC-1 composite membrane has a similar topography to PVP-PVC-1 composite membrane, the surface and the cross section of PTFE/PVP-PVC-1 composite membrane are uniform and dense. It can be seen from TGA test that all the prepared composite membranes are heat stable within 180℃, and the thermal stability of PTFE/PVP-PVC-2 composite membrane is slightly higher than that of PVP-PVC-2 composite membrane. With the increase of PVC content in the composite membrane, the PA doping content of the composite membranes showed a decreasing trend. In addition, the PA doping amount of PTFE-reinforced PVP-PVC composite membrane is also lower than that of PVP-PVC composite membrane. With the increase of PVC content in the composite membrane, the swelling trend decreased, which was positively correlated with the PA doping amount of the composite membrane. In addition, the area and volume swelling of PTFE/PVP-PVC composite membrane is reduced compared with the corresponding PVP-PVC composite membrane, especially the area swelling decreased significantly. The proton conductivity of all PVP-PVC composite membranes increased with the increase of temperature, and the proton conductivity of different proportions of PVP-PVC composite membranes increased with the increase of PVP content in the composite membranes. The proton conductivity of all PA-doped PTFE enhanced PVP-PVC composite membranes also increases with the increase of temperature. The proton conductivity of PTFE enhanced PVP-PVC composite membrane also increases with the increase of PVP content in the composite membrane, but the proton conductivity of PTFE enhanced PVP-PVC composite membrane is lower than that of corresponding PVP-PVC composite membrane. At the same time, the activation energy of PA-doped PTFE/PVP-PVC composite membranes also decreased with the increase of PVP content, but the activation energy of PA doped PTFE/PVP-PVC composite membranes increased compared with the corresponding PA doped PVP-PVC composite membranes. The mechanical properties of PTFE reinforced PVP-PVC composite membranes are directional and exhibit the same rules as porous PTFE membranes. The tensile strength of PTFE/PVP-PVC composite membranes in x direction increases with the increase of PVC content in the composite membranes. However, the tensile strength of PTFE/PVP-PVC composite membranes is similar in the y direction. The maximum tensile strength of PTFE/PVP-PVC-1 composite membrane (x direction) is about 75 MPa, the tensile strength of PTFE/PVP-PVC-4 composite membrane (x direction) is about 50 MPa, and the maximum tensile strength of PTFE/PVP-PVC-1 composite membrane (y direction) is less than 40 MPa. The tensile strength of PVP-PVC composite membranes doped with PA decreases gradually with the increase of PVP content. The tensile strength of PA-doped PVP-PVC-1, PVP-PVC-2, PVP-PVC-3 and PVP-PVC-4 composite membranes were 10.8 MPa, 6.0 MPa, 4.5 MPa and 2.5 MPa, respectively. The tensile strength of PA-doped PTFE/PVP-PVC composite membrane in direction is larger than that in direction, but the elongation at break of PA doped PTFE/PVP-PVC composite membranes in y direction is larger. At 160 C, the peak power density of PA doped PTFE/PVP-PVC-4 composite membrane is about 359 mW cm.Conclusions: A new PTFE-reinforced PVP-PVC composite membrane with different proportions was successfully prepared by a simple method. First, different proportions of PVP-PVC polymers are simply blended, then filled into the pores inside the porous PTFE membrane and covered on its surface, and finally PA doping is performed on the composite membrane to obtain a series of PA-doped PTFE-reinforced HT-PEM. The best composite membrane was found by adjusting the ratio of PVP and PVC, and its physical and chemical properties were tested and characterized. The SEM test results showed that PVP-PVC polymer electrolyte was successfully impregnated into the pores of PTFE membrane and covered the surface of PTFE membrane, forming a sandwich structure. It was found that PTFE reinforced composite membrane has high proton conductivity, good mechanical properties and dimensional stability. Among them, the proton conductivity of PA-doped PTFE/PVP-PVC-4 composite membrane at 160℃ is as high as 0.161 S cm, and the membrane has good mechanical strength, its maximum tensile strength at room temperature is 15.6 MPa. The fuel cell test results show that the peak power density of PA-doped PTFE/PVP-PVC-4 composite membrane is about 359 mW cm at 160℃. These results indicate that PA-doped PTFE-reinforced composite membranes have potential applications as HT-PEM.
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