微管式质子交换膜燃料电池膜电极的制备
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摘要
质子交换膜燃料电池(PEMFC)是一种直接将储存在燃料和氧化剂中的化学能高效、无污染地转化为电能的发电装置。PEMFC的优点是工作温度低,启动性能好、无腐蚀性、电池堆设计简单、系统坚固耐用,被公认为最有希望成为航天、军事、电动汽车和区域性电站以及便携式设备的首选电源。目前质子交换膜燃料电池主要采用平板式结构,存在体积质量功率比较低、成本较高的问题,由于体积较大,很难应用于小型便携设备。
针对以上问题,本文设计制备了一种以多孔中空碳纤维管为支撑管基体的微管式质子交换膜燃料电池的膜电极,研究了不同方法处理碳纤维管的方法以增大其反应表面积;制备了Pt催化剂和Ru催化剂作为膜电极的阳极催化剂,采用浸渍沉积的方法在阴极担载了E-TEKVulcan XC-72 Pt/C电催化剂,并对其催化剂颗粒的结构、催化性能和担载量进行了测试研究;在经过质子交换膜的涂覆后制备了微管式质子交换膜燃料电池膜电极,并对其单电池性能进行了测试。
通过以上研究工作,我们得到以下结论:
(1)聚丙烯腈(PAN)中空原丝的预处理采用50%DMSO对PAN原丝进行刻蚀的方法,有效地增加了表面孔洞使其获得了更大的比表面积。利用酸后处理的方法可以有效地去除经过预氧化与炭化制备的中空碳纤维管(PAN-CF)管壁上存在的无机盐及碳管碎片等杂质。
(2)研究表明,甲醛方法制备的Pt催化剂在碳纤维管表面和内部分散均匀,Pt的担载量为0.4mg/cm~2,低于一般板式PEMFC的电催化剂的担载量,催化剂粒子尺径为4.4nm,有效电化学面积为41.32m~2g_(Pt)~(-1),Pt的利用率较高,电催化性能表现良好。
(3)通过采用浸渍的方法将Nafion溶液涂覆在碳纤维管的表面,并且形成了连续的质子交换膜层,并且由FTIR的测试结果证明与商品Nafion膜的结构一致,在扫描电镜下观察厚度约为0.5μm。
(4)通过采用氢气为燃料以及甲醇为燃料在室温常压环境下对微管式PEMFC的单电池的电化学性能进行了测试,研究表明,采用氢气作为燃料的单电池性能的最大功率密度为0.23 mW/cm~2,最大电流约为2.1mA/cm~2,开路电压为0.6V,单电池的电化学性能相对较差;而采用3mol/L的甲醇作为燃料测试电池的电化学性能较好,最大功率密度为1.75mW/cm~2,最大电流密度为14mA/cm~2,开路电压为0.82V,相比采用氢气作为燃料显示出了较好的单电池电化学性能。
Proton exchange membrane fuel cell (PEMFC) is a power package which could directly transform the chemical energy stored in the fuel and oxidizer into power by an efficient and pollution-free way. PEMFC is widely recognized as the most promising power supply used in the area of aerospace, military, electric vehicles and regional power stations because of its low working temperature, quick start-up and non-corrosion. More over, the cell stack system is simple and stable. Most PEMFC systems are currently designed as a plate structure, however, this structure has several flaws such as low power density, high cost and bulky volume etc., which made it hard to be used in small portable devices.
In this work, a micro-tubular membrane electrode assembly (MEA) was prepared using porous hollow carbon fiber tube as a support. Different treatments of the PAN hollow fibers used to increase the reaction surface area of porous hollow carbon tube have been studied. Pt and Ru anode catalysts were deposited on the hollow carbon tubes and XC-72 Pt/C were used as the cathode catalysts. The micro-structures and the properties of the MEA have been investigated and the electrochemical properties of a single cell have also been tested.
Based on the above work, we draw the conclusions as follows:
(1) Etching the Polyacrylonitrile (PAN) hollow fibers by 50% DMSO can effectively increase the surface area of the hollow carbon tube products and make the holes in the tube wall internal and external linking. Acid washing method can remove the fractions and inorganic impurities on the hollow carbon tube products.
(2) The result showed the Pt catalyst which was deposited by chemical reduction method on the hollow carbon tube has been well dispersed on both surface and inside holes of the hollow carbon tube. The loading of the Pt catalyst was 0.4 mg/cm~2 . The average size of Pt catalyst particles was 4.4nm and its electrochemical active area was calculated to be about 41.32 m~2g_(Pt)~(-1). Pt anode catalysts showed stable performance in 0.1mol/L H_2SO_4.
(3) The nation was coated on the hollow carbon tube by impregnation method. The FTIR result showed the structure of the coated nafion film was similar to the commercial nafion(?) film. The thickness of the coated nafion film was about 1μm.
(4) The electrochemical performance of a single micro-tubular fuel cell made of the above metioned membrane electrode assembly under passive and air breathing conditions at ambient temperature and pressure has been tested. When hydrogen was used as the fuel and air as the oxidizer, it showed a maximum power density of 0.23mW/cm~2 and a maximum current density of 2.1mA/ cm~2 . The open-circuit potential for hydrogen used as the fuel was 0.82V. However, when methanol was used as the fuel and air as the oxidizer, it exhibited a maximum power density of 1.75mW/cm~2and a maximum current density of 14mA/cm~2 and with the open-circuit potential of 0.82V which was proved to be superior to the one using hydrogen as the fuel.
针对以上问题,本文设计制备了一种以多孔中空碳纤维管为支撑管基体的微管式质子交换膜燃料电池的膜电极,研究了不同方法处理碳纤维管的方法以增大其反应表面积;制备了Pt催化剂和Ru催化剂作为膜电极的阳极催化剂,采用浸渍沉积的方法在阴极担载了E-TEKVulcan XC-72 Pt/C电催化剂,并对其催化剂颗粒的结构、催化性能和担载量进行了测试研究;在经过质子交换膜的涂覆后制备了微管式质子交换膜燃料电池膜电极,并对其单电池性能进行了测试。
通过以上研究工作,我们得到以下结论:
(1)聚丙烯腈(PAN)中空原丝的预处理采用50%DMSO对PAN原丝进行刻蚀的方法,有效地增加了表面孔洞使其获得了更大的比表面积。利用酸后处理的方法可以有效地去除经过预氧化与炭化制备的中空碳纤维管(PAN-CF)管壁上存在的无机盐及碳管碎片等杂质。
(2)研究表明,甲醛方法制备的Pt催化剂在碳纤维管表面和内部分散均匀,Pt的担载量为0.4mg/cm~2,低于一般板式PEMFC的电催化剂的担载量,催化剂粒子尺径为4.4nm,有效电化学面积为41.32m~2g_(Pt)~(-1),Pt的利用率较高,电催化性能表现良好。
(3)通过采用浸渍的方法将Nafion溶液涂覆在碳纤维管的表面,并且形成了连续的质子交换膜层,并且由FTIR的测试结果证明与商品Nafion膜的结构一致,在扫描电镜下观察厚度约为0.5μm。
(4)通过采用氢气为燃料以及甲醇为燃料在室温常压环境下对微管式PEMFC的单电池的电化学性能进行了测试,研究表明,采用氢气作为燃料的单电池性能的最大功率密度为0.23 mW/cm~2,最大电流约为2.1mA/cm~2,开路电压为0.6V,单电池的电化学性能相对较差;而采用3mol/L的甲醇作为燃料测试电池的电化学性能较好,最大功率密度为1.75mW/cm~2,最大电流密度为14mA/cm~2,开路电压为0.82V,相比采用氢气作为燃料显示出了较好的单电池电化学性能。
Proton exchange membrane fuel cell (PEMFC) is a power package which could directly transform the chemical energy stored in the fuel and oxidizer into power by an efficient and pollution-free way. PEMFC is widely recognized as the most promising power supply used in the area of aerospace, military, electric vehicles and regional power stations because of its low working temperature, quick start-up and non-corrosion. More over, the cell stack system is simple and stable. Most PEMFC systems are currently designed as a plate structure, however, this structure has several flaws such as low power density, high cost and bulky volume etc., which made it hard to be used in small portable devices.
In this work, a micro-tubular membrane electrode assembly (MEA) was prepared using porous hollow carbon fiber tube as a support. Different treatments of the PAN hollow fibers used to increase the reaction surface area of porous hollow carbon tube have been studied. Pt and Ru anode catalysts were deposited on the hollow carbon tubes and XC-72 Pt/C were used as the cathode catalysts. The micro-structures and the properties of the MEA have been investigated and the electrochemical properties of a single cell have also been tested.
Based on the above work, we draw the conclusions as follows:
(1) Etching the Polyacrylonitrile (PAN) hollow fibers by 50% DMSO can effectively increase the surface area of the hollow carbon tube products and make the holes in the tube wall internal and external linking. Acid washing method can remove the fractions and inorganic impurities on the hollow carbon tube products.
(2) The result showed the Pt catalyst which was deposited by chemical reduction method on the hollow carbon tube has been well dispersed on both surface and inside holes of the hollow carbon tube. The loading of the Pt catalyst was 0.4 mg/cm~2 . The average size of Pt catalyst particles was 4.4nm and its electrochemical active area was calculated to be about 41.32 m~2g_(Pt)~(-1). Pt anode catalysts showed stable performance in 0.1mol/L H_2SO_4.
(3) The nation was coated on the hollow carbon tube by impregnation method. The FTIR result showed the structure of the coated nafion film was similar to the commercial nafion(?) film. The thickness of the coated nafion film was about 1μm.
(4) The electrochemical performance of a single micro-tubular fuel cell made of the above metioned membrane electrode assembly under passive and air breathing conditions at ambient temperature and pressure has been tested. When hydrogen was used as the fuel and air as the oxidizer, it showed a maximum power density of 0.23mW/cm~2 and a maximum current density of 2.1mA/ cm~2 . The open-circuit potential for hydrogen used as the fuel was 0.82V. However, when methanol was used as the fuel and air as the oxidizer, it exhibited a maximum power density of 1.75mW/cm~2and a maximum current density of 14mA/cm~2 and with the open-circuit potential of 0.82V which was proved to be superior to the one using hydrogen as the fuel.
引文
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