【摘要】：質(zhì)子交換膜燃料電池是燃料電池的一種,它的電解質(zhì)材料由質(zhì)子交換膜組成。這類(lèi)電池的電解質(zhì)材料直接決定了電池性能,擁有高導(dǎo)電率和高穩(wěn)定性的質(zhì)子交換膜能夠制備性能優(yōu)異的燃料電池。目前采用的材料體系主要分為聚合物和金屬有機(jī)骨架化合物兩類(lèi),它們各有優(yōu)缺點(diǎn)。聚合物往往擁有很好的柔軟度,化學(xué)穩(wěn)定性以及可加工性,但是卻有制作成本高昂,易水解等缺點(diǎn)。金屬有機(jī)骨架化合物具有良好的結(jié)晶度、規(guī)則排列的空隙、可修飾的孔道等特點(diǎn),但在成膜方面卻是一個(gè)難題。基于以上描述的情況,人們考慮將二者雜化,從而產(chǎn)生能夠融合二者優(yōu)點(diǎn)的新材料,這就是混合基質(zhì)膜。本文中我們首先按照已報(bào)道的CoCa·nH2O化合物的合成方法制備了系列化合物CoMg · nH2O、CoSr · 2H20和CoBa。其中CoMg·nH20導(dǎo)電率最高,被選中作為摻雜的化合物。同時(shí),CoCa·nH20和CoMg · nH20是同構(gòu)的,所以CoCa · nH20也被選取做對(duì)比。CoCa·nH20和CoMg·nH20被摻雜進(jìn)Nafion、PVP、PVA和PEG幾個(gè)高分子中,制備混合基質(zhì)膜并進(jìn)行質(zhì)子導(dǎo)電性質(zhì)的測(cè)量和分析。為了更好的融合樣品,本文采用的化合物為層狀物,雜化的方法采用澆鑄法。具體內(nèi)容如下:采用和CoCa ·nH20類(lèi)似的實(shí)驗(yàn)方法,制備CoMg·nH2O、CoSr·2H2O和CoBa化合物。然后使用壓片模具,將多晶粉末壓制成樣品片,使用金膠和金線(xiàn)將樣品連接到樣品夾具上,采用四電極法測(cè)量阻抗譜。測(cè)試結(jié)果表明,由于Mg2+具有更高的Lewis酸性,與Mg2+離子配位的水分子被很好的活化了,有效提高了材料中質(zhì)子載流子的濃度。并且CoCa · nH20和CoMg · nH2O都擁有很高的活化能,使得ClO4-能夠轉(zhuǎn)動(dòng),促進(jìn)質(zhì)子傳導(dǎo)。將CoCa · nH20和CoMg · nH2O按照一定質(zhì)量比分別加入一定量Nafion中,超聲分散混合,然后用吸管吸取分散溶液滴在基底片上,等待溶液鋪開(kāi)并且溶劑揮發(fā)干,再滴加,如此反復(fù)即成膜。制備的膜按照先前的描述制成測(cè)試樣品進(jìn)行導(dǎo)電測(cè)試。然后,選取PVP和PVA與等量的CoCa·nH2O融合并制備成膜(融合與制備方法同上)測(cè)試質(zhì)子導(dǎo)電性。由于PEG成膜后非常脆,故超聲完畢后選取壓片方式成膜,而不采用澆鑄法,其余步驟一樣。結(jié)果表明,對(duì)于Nafion,配合物組分的比例越低,復(fù)合材料的導(dǎo)電性質(zhì)越接近純Nafion的導(dǎo)電性質(zhì)。當(dāng)配合物組分與Nafion的質(zhì)量比為0.5:1時(shí),CoMg復(fù)合材料的導(dǎo)電性能僅略高于CoMg·nH2O純樣。而CoCa復(fù)合材料的導(dǎo)電性能卻比CoMg·nH2O純樣提升一個(gè)數(shù)量級(jí)。在CoCa·nH2O與不同高分子基質(zhì)復(fù)合的體系中,CoCa@PEG具有最優(yōu)的質(zhì)子導(dǎo)電性能。
[Abstract]:Proton exchange membrane fuel cell is a kind of fuel cell, its electrolyte material is made up of proton exchange membrane. The electrolyte material of this kind of battery directly determines the performance of the battery. Proton exchange membrane with high conductivity and high stability can be used to prepare fuel cell with excellent performance. At present, the material systems are mainly divided into polymer and organometallic skeleton compounds, which have their own advantages and disadvantages. Polymers often have good softness, chemical stability and processability, but they have the disadvantages of high cost and easy hydrolysis. Organometallic skeleton compounds have good crystallinity, regular arrangement of voids and modifiable pores, but they are a difficult problem in film formation. Based on the situation described above, hybrid materials are considered to produce new materials which can integrate the advantages of the two materials, which is called mixed matrix membrane. In this paper, we first prepared a series of CoMg nH2O,CoSr 2H20 and CoBa. compounds according to the reported synthesis method of CoCa nH2O compounds. Among them, CoMg nH20 has the highest conductivity and is chosen as the doped compound. At the same time, CoCa nH20 and CoMg nH20 are isomorphic, so CoCa nH20 is also selected for comparison. CoCa nH20 and CoMg nH20 are doped into Nafion,PVP,PVA and PEG to prepare the mixed matrix membrane and the proton conductivity is measured and analyzed. In order to better fuse the sample, the compound used in this paper is laminar, and the hybrid method is cast. The main contents are as follows: CoMg nH2O,CoSr 2H2O and CoBa compounds were prepared by using the same experimental method as CoCa nH20. Then the polycrystalline powder was pressed into a sample sheet by pressing the die, and the sample was connected to the sample fixture by gold glue and gold wire, and the impedance spectrum was measured by four-electrode method. The results show that because of the higher Lewis acidity of Mg2, the water molecules coordinated with Mg2 ions are well activated, which effectively increases the concentration of proton carriers in the materials. And both CoCa nH20 and CoMg nH2O have high activation energies, enabling ClO4- to rotate and promote proton conduction. The CoCa nH20 and CoMg nH2O were added to a certain amount of Nafion according to certain mass ratio, then the ultrasonic dispersion was mixed, then the dispersed solution was dripped on the substrate with a suction tube, waiting for the solution to spread out and the solvent volatilized dry, then the film was formed again and again. The prepared films were prepared to test the electrical conductivity of the samples as described earlier. Then, the PVP and PVA were selected to fuse with the same amount of CoCa nH2O and the film was prepared (fusion and preparation method was used above) to test the proton conductivity. Because PEG is very brittle after film forming, the pressing method is chosen after ultrasonic forming, and the other steps are the same. The results show that the lower the proportion of Nafion, complex is, the closer the conductive properties of the composites are to those of pure Nafion. When the mass ratio of the complexes to Nafion is 0.5: 1, the electrical conductivity of the CoMg composites is only slightly higher than that of the pure CoMg nH2O samples. The conductivity of CoCa composites is one order of magnitude higher than that of CoMg nH2O. In the system of CoCa nH2O and different polymer matrix, CoCa@PEG has the best proton conductivity.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O627.51;O631.23

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