Preparation and properties of PVC-PVP composite high temperature proton exchange membranes reinforced with PTFE for high temperature fuel cells
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摘要: 在100℃以上工作的质子交换膜燃料电池(PEMFC)可以克服低温工作时的缺陷，提高铂催化剂抗CO中毒的能力、加速电极动力学、简化水热管理系统以及提高热的循环利用等。为了实现磷酸(PA)掺杂的高温质子交换膜(HT-PEM)同时具有高质子电导率和优异的力学性能，制备了一系列聚四氟乙烯(PTFE®)增强的聚乙烯吡咯烷酮-聚氯乙烯(PVP-PVC)复合膜。通过调整PVP和PVC的配比来寻找综合性能最佳的复合膜，并对其物理化学性能进行测试和表征。SEM结果表明，PVP-PVC均匀的填充到PTFE®膜的孔隙中，没有气泡以及孔洞。通过质子电导率以及机械性能测试结果表明，PTFE增强技术使复合膜具有良好的拉伸强度和尺寸稳定性。其中，PA掺杂的PVP与PVC质量比为4的PTFE®增强复合膜在160℃时的质子电导率高达0.161 S·cm−1，并且该膜在室温下最大的拉伸强度为15.6 MPa。在160℃时，该复合膜的峰值功率密度约为359 mW·cm−2。这些结果表明，PA掺杂的PTFE增强的复合膜具有作为HT-PEM的应用潜质。Abstract: 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.
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图 1 PTFE®增强的PVP-PVC复合膜的制备流程图
Figure 1. Schematic of the fabrication procedure and structure for PTFE reinforced PVP-PVC composite membrane.
图 2 (a) PTFE®膜、(b) PVP-PVC-1复合膜和(c) PTFE/PVP-PVC-1复合膜的实物照片
Figure 2. Photos of (a) PTFE® membrane, (b) PVP-PVC-1 composite membrane and (c) PTFE/PVP-PVC-1 composite membrane.
图 3 PTFE®膜(a : ×30000)、PVP-PVC-1膜(b : ×5000)和PTFE/PVP-PVC-1膜(c : ×5000)表面的SEM图像；PTFE/PVP-PVC-1膜(d : ×1000)膜的截面的SEM图像
Figure 3. SEM images of the surface of the PTFE® membrane (a : ×30000), PVP-PVC-1 membrane (b : ×5000) and PTFE/PVP-PVC-1 (c : ×5000); SEM images of cross-section of PTFE/ PVP-PVC-1 (d : ×1000).
图 4 (a) PVP-PVC-4复合膜和(b) PTFE/PVP-PVC-4复合膜的表面AFM图像
Figure 4. The AFM images of (a) PVP-PVC-4 membrane and (b) PTFE/PVP-PVC-4 membrane.
图 5 PVP-PVC-2和PTFE/PVP-PVC-2复合膜的TGA曲线
Figure 5. TGA curves of PVP-PVC-2 and PTFE/PVP-PVC-2 composite membranes.
图 6 不同比例的PVP-PVC和PTFE增强的复合膜的磷酸掺杂量(复合膜在85 wt%磷酸中浸泡12 h，浸泡温度为45℃)
Figure 6. The acid doping content of the PVP-PVC membranes and PTFE reinforced composite membranes.
图 7 磷酸掺杂的PVP-PVC和PTFE增强的复合膜的溶胀性(复合膜在85 wt%磷酸中浸泡12 h，浸泡温度为45℃)
Figure 7. The swelling ratio of PA doped PVP-PVC membranes and PTFE reinforced composite membranes.
图 8 (a)不同比例的PVP-PVC复合膜和(b) PTFE增强的复合膜的电导率
Figure 8. Conductivity of the PVP-PVC composite membranes (a) and PTFE reinforced composite membranes (b).
图 10 PTFE增强的PVP-PVC复合膜在常温下的机械性能(a)拉伸方向为x(b)拉伸方向为y
Figure 10. Mechanical properties of PTFE reinforced PVP-PVC composite membranes at room temperature (a) the stretching direction is x (b) the stretching direction is y.
图 11 磷酸掺杂的(a) PVP-PVC复合膜、(b) PTFE增强的PVP-PVC复合膜(x方向)在机械性能和(c) PTFE增强的PVP-PVC复合膜(y方向)在常温下的机械性能
Figure 11. Mechanical properties of (a) PA doped PVP-PVC composite membranes, (b) PTFE/PVP-PVC composite membranes (streching dirrection of x) and (c) PTFE/PVP-PVC composite membranes (streching dirrection of y) at room temperature.
图 12 PTFE/PVP-PVC-4复合膜的极化曲线和功率密度图
Figure 12. Polarization and power density curves of the fuel cell based on PTFE/PVP-PVC-4 membrane fueling with anhydrous H2/O2 under atmospheric pressure, the Pt loading of the electrodes is 0.6 mg·cm2.
表 1 不同比例聚乙烯吡咯烷酮-聚氯乙烯(PVP-PVC)共混膜的原料配比
Table 1. Raw material ratio of different proportions of polyvinylpyrrolidone-polyvinyl chloride (PVP-PVC) composite membranes.
membrane PVP-PVC-4 PVP-PVC-3 PVP-PVC-2 PVP-PVC-1 PVP∶PVC
(w∶w)4∶1 3∶1 2∶1 1∶1 
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表 2 聚四氟乙烯(PTFE®)膜的基本参数
Table 2. Basic parameters of polytetrafluoroethylene (PTFE®) membrane.
Membrane Poriness/% Mean Aperture
Diameter/ΜmThickness/
ΜmPTFE® 80 0.15 10
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表 3 不同比例的PVP-PVC浸渍液的配料比
Table 3. Raw material of different proportions of PVP-PVC DMF solution.
Membrane PVP∶PVC
(w∶w)PVP/g PVC/g DMF/
mLConcentration/
(g·mL−1)PTFE/PVP-
PVC-44∶1 2.40 0.60 25 0.12 PTFE/PVP-
PVC-33∶1 2.25 0.75 25 0.12 PTFE/PVP-
PVC-22∶1 2.00 0.10 25 0.12 PTFE/PVP-
PVC-11∶1 1.50 1.50 25 0.12
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表 4 PVP-PVC 基复合膜的电导率和活化能
Table 4. Conductivity and activation energy of PVP-PVC-based composite membranes.
membrane Proton conductivity@120°C/(S·cm−1) Proton conductivity@160°C/(S·cm−1) Activation energy/(kJ·mol−1) PVP-PVC-4 0.151 ± 0.032 0.218 ± 0.033 13.1 PVP-PVC-3 0.138 ± 0.030 0.198 ± 0.028 14.5 PVP-PVC-2 0.081 ± 0.018 0.115 ± 0.012 15.1 PVP-PVC-1 0.031 ± 0.003 0.054 ± 0.007 20.2 PTFE/PVP-PVC-4 0.121 ± 0.015 0.161 ± 0.017 13.6 PTFE/PVP-PVC-3 0.093 ± 0.010 0.125 ± 0.007 14.6 PTFE/PVP-PVC-2 0.066 ± 0.009 0.094 ± 0.004 15.8 PTFE/PVP-PVC-1 0.031 ± 0.002 0.048 ± 0.003 21.0
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