燃料电池用新型Nafion复合质子交换膜研究
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摘要
质子交换膜燃料电池因其能量转化效率高、环境友好而在近些年备受关注。其中质子交换膜作为以甲醇溶液为燃料的燃料电池的关键材料,其性能的好坏直接影响燃料电池的整体性能与使用寿命,目前基于全氟磺酸膜Nafion的改性是提高膜整体性能的重要途径。
本文着重针对Nafion膜在直接甲醇燃料电池工作条件下,甲醇透过率高的缺点,通过在Nafion树脂溶液中分布添加一定量的多孔纳米二氧化锰颗粒、多孔四氧化三钴颗粒、磺化的聚苯硫醚颗粒、磺化的聚醚砜组分,利用流延成膜法,制备出相应的复合膜材料,并研究了它们在电池中应用的性能。具体内容如下：
1、以多孔纳米MnO2为添加剂与Nafion复合成膜。通过测试,发现随着多孔MnO2添加量的增加,复合膜的质子传导率下降；随着Mn02的添加量的增加,复合膜的甲醇透过率受到明显的抑制；MnO2/Nafion复合膜的质子传导率与甲醇透过率之比均低于Nafion膜。
2、以多孔纳米Co3O4为添加剂与Nafion复合成膜。通过测试,发现随着多孔Co3O4添加量的增加,复合膜的质子传导率下降；随着多孔Co3O4添加量的增加,复合膜的甲醇透过率受到明显的抑制；当Co3O4添加量为1%时,Co3O4/Nafion复合膜的质子传导率与甲醇透过率之比与Nafion膜相当。
3、以磺化的聚苯硫醚颗粒(SPPS)为添加剂与Nafion复合成膜。通过测试,发现随着磺化度的增加,质子传导率呈增加趋势；随着SPPS的添加,复合膜的甲醇透过率受到明显的抑制；当磺化度为50%的SPPS添加量为5%时,复合膜的质子传导率与甲醇透过率之比达到最佳状态,是同比下Nafion膜的1.4倍。
4、以磺化的聚醚砜(SPES)为添加剂与Nafion复合成膜。通过测试,发现随着添加量的增加,质子传导率呈增加趋势；随着SPES的添加,复合膜的甲醇透过率受到明显的抑制；当SPES添加量为1%时,复合膜的质子传导率与甲醇透过率之比优于Nafion膜,是其1.3倍。
Proton exchange membrane fuel cell (PEMFC) has attracted extensive attention in recent years, as its high efficiency in energy conversion and zero emission. As one of key materials in direct methanol fuel cell (DMFC), proton exchange membrane can affect the overall performance and lifetime of DMFC. Currently, modification of Nafion is one of the important ways to improve the property of proton exchange membrane.
In this thesis, to inhibit high methanol permeability of Nafion in DMFC, porous MnO2, Co3O4 nano-particles, sulphonated PPS (SPPS) particles or sulphonated polyether sulphone (SPES) have been prepared and added in Nafion resin solution to make composite membranes by casting method. The basic properties of the Nafion composite membranes were assasyed as well. The detailed contents are given as follows.
1. Porous nano MnO2 particle was synthesized, characterized and doped in Nafion to prepare the corresponding composite membranes. The results indicate that the methanol permeability of the composite membranes could be greatly inhibited with the increase of MnO2 content. However, the proton conductivity of the composite membranes greatly dropped as well, and the ratio between proton conductivity and methanol permeability of MnO2/Nafion composite membrane is lower than that of Nafion membrane.
2. Porous nano Co3O4 particle was synthesized, characterized and doped in Nafion to prepare Co3O4/Nafion composite membranes. The results show that the methanol permeability of the composite membranes could be greatly inhibited with the increase of Co3O4 content. To some extents, the proton conductivity of the composite membranes dropped as well, but the ratio between pronton conductivity and methanol permeability of Co3O4/Nafion composite membrane is similar to that of recasting Nafion membrane when the weight content of Co3O4 is 1%.
3. SPPS resin has been synthesized and been doped in Nafion resin solution to prepare SPPS/Nafion composite membranes. The results show that the methanol permeability of the composite membranes could be greatly inhibited with the increase of SPPS content. The proton conductivity of SPPS/Nafion composite membranes increases with increasing sulphonation degree of SPPS. When 5wt% SPPS (sulphonation degree is 50%) doped in Nafion resin solution, the ratio between proton conductivity and methanol permeability of SPPS/Nafion composite membrane is 40% higher than that of Nafion recasting membranes.
4. SPES has been synthesized and characterized as well, and doped in Nafion solution to prepare SPES/Nafion composite membranes. The results show that the methanol permeability of the composite membranes could be greatly inhibited with the increase of SPES content. The proton conductivity of SPES/Nafion composite membranes increases with increasing content of SPES. When 1wt% SPES doped in Nafion solution, the ratio between proton conductivity and methanol permeability of SPPS/Nafion composite membrane is 30% higher than that of Nafion recasting membranes.
本文着重针对Nafion膜在直接甲醇燃料电池工作条件下,甲醇透过率高的缺点,通过在Nafion树脂溶液中分布添加一定量的多孔纳米二氧化锰颗粒、多孔四氧化三钴颗粒、磺化的聚苯硫醚颗粒、磺化的聚醚砜组分,利用流延成膜法,制备出相应的复合膜材料,并研究了它们在电池中应用的性能。具体内容如下：
1、以多孔纳米MnO2为添加剂与Nafion复合成膜。通过测试,发现随着多孔MnO2添加量的增加,复合膜的质子传导率下降；随着Mn02的添加量的增加,复合膜的甲醇透过率受到明显的抑制；MnO2/Nafion复合膜的质子传导率与甲醇透过率之比均低于Nafion膜。
2、以多孔纳米Co3O4为添加剂与Nafion复合成膜。通过测试,发现随着多孔Co3O4添加量的增加,复合膜的质子传导率下降；随着多孔Co3O4添加量的增加,复合膜的甲醇透过率受到明显的抑制；当Co3O4添加量为1%时,Co3O4/Nafion复合膜的质子传导率与甲醇透过率之比与Nafion膜相当。
3、以磺化的聚苯硫醚颗粒(SPPS)为添加剂与Nafion复合成膜。通过测试,发现随着磺化度的增加,质子传导率呈增加趋势；随着SPPS的添加,复合膜的甲醇透过率受到明显的抑制；当磺化度为50%的SPPS添加量为5%时,复合膜的质子传导率与甲醇透过率之比达到最佳状态,是同比下Nafion膜的1.4倍。
4、以磺化的聚醚砜(SPES)为添加剂与Nafion复合成膜。通过测试,发现随着添加量的增加,质子传导率呈增加趋势；随着SPES的添加,复合膜的甲醇透过率受到明显的抑制；当SPES添加量为1%时,复合膜的质子传导率与甲醇透过率之比优于Nafion膜,是其1.3倍。
Proton exchange membrane fuel cell (PEMFC) has attracted extensive attention in recent years, as its high efficiency in energy conversion and zero emission. As one of key materials in direct methanol fuel cell (DMFC), proton exchange membrane can affect the overall performance and lifetime of DMFC. Currently, modification of Nafion is one of the important ways to improve the property of proton exchange membrane.
In this thesis, to inhibit high methanol permeability of Nafion in DMFC, porous MnO2, Co3O4 nano-particles, sulphonated PPS (SPPS) particles or sulphonated polyether sulphone (SPES) have been prepared and added in Nafion resin solution to make composite membranes by casting method. The basic properties of the Nafion composite membranes were assasyed as well. The detailed contents are given as follows.
1. Porous nano MnO2 particle was synthesized, characterized and doped in Nafion to prepare the corresponding composite membranes. The results indicate that the methanol permeability of the composite membranes could be greatly inhibited with the increase of MnO2 content. However, the proton conductivity of the composite membranes greatly dropped as well, and the ratio between proton conductivity and methanol permeability of MnO2/Nafion composite membrane is lower than that of Nafion membrane.
2. Porous nano Co3O4 particle was synthesized, characterized and doped in Nafion to prepare Co3O4/Nafion composite membranes. The results show that the methanol permeability of the composite membranes could be greatly inhibited with the increase of Co3O4 content. To some extents, the proton conductivity of the composite membranes dropped as well, but the ratio between pronton conductivity and methanol permeability of Co3O4/Nafion composite membrane is similar to that of recasting Nafion membrane when the weight content of Co3O4 is 1%.
3. SPPS resin has been synthesized and been doped in Nafion resin solution to prepare SPPS/Nafion composite membranes. The results show that the methanol permeability of the composite membranes could be greatly inhibited with the increase of SPPS content. The proton conductivity of SPPS/Nafion composite membranes increases with increasing sulphonation degree of SPPS. When 5wt% SPPS (sulphonation degree is 50%) doped in Nafion resin solution, the ratio between proton conductivity and methanol permeability of SPPS/Nafion composite membrane is 40% higher than that of Nafion recasting membranes.
4. SPES has been synthesized and characterized as well, and doped in Nafion solution to prepare SPES/Nafion composite membranes. The results show that the methanol permeability of the composite membranes could be greatly inhibited with the increase of SPES content. The proton conductivity of SPES/Nafion composite membranes increases with increasing content of SPES. When 1wt% SPES doped in Nafion solution, the ratio between proton conductivity and methanol permeability of SPPS/Nafion composite membrane is 30% higher than that of Nafion recasting membranes.
引文
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