【摘要】：質(zhì)子交換膜廣泛應(yīng)用于電化學(xué)能量轉(zhuǎn)化裝置,包括質(zhì)子交換膜燃料電池(含直接甲醇燃料電池)、SPE水電解及釩氧液流電池中。由于具有良好的質(zhì)子傳導(dǎo)性、強(qiáng)的機(jī)械性能、抗氧化性和熱穩(wěn)定性,Nafion膜成為目前應(yīng)用最廣泛的質(zhì)子交換膜。但是,Nafion膜存在選擇透過(guò)性差的問(wèn)題影響了其在直接甲醇燃料電池和釩氧液流電池中的大規(guī)模應(yīng)用。Nafion膜選擇透過(guò)性差在直接甲醇燃料電池應(yīng)用中將導(dǎo)致嚴(yán)重的甲醇燃料滲透。直接甲醇燃料電池在工作過(guò)程中,由于Nafion膜的阻醇性能不好,甲醇分子很容易從陽(yáng)極穿透膜到達(dá)陰極,不僅造成甲醇燃料的浪費(fèi),同時(shí)嚴(yán)重抑制了陰極的氧還原反應(yīng),從而導(dǎo)致電池工作電壓和電池效率下降。因此,可以說(shuō)高選擇性質(zhì)子交換膜的缺乏是影響直接甲醇燃料電池發(fā)展的絆腳石。而開發(fā)選擇性好,價(jià)格低廉的新型質(zhì)子交換膜是直接甲醇燃料電池發(fā)展的關(guān)鍵。同樣,Nafion膜的選擇性也影響了釩氧液流電池的發(fā)展進(jìn)程。雖然Nafion膜極好的化學(xué)穩(wěn)定性使其成為當(dāng)前釩氧液流電池應(yīng)用中主流膜。然而,Nafion膜存在的高的釩離子滲透性使得由Nafion膜組裝的釩氧液流電池的電壓效率、庫(kù)侖效率和能量效率都較低�？偟膩�(lái)說(shuō),設(shè)計(jì)和開發(fā)高選擇性質(zhì)子交換膜是當(dāng)前直接甲醇燃料電池和釩氧液流電池領(lǐng)域的主要研究課題。高度有序的質(zhì)子傳輸通道是保證質(zhì)子高效傳導(dǎo),提高質(zhì)子交換膜選擇性的重要前提。所以,構(gòu)筑高選擇性質(zhì)子傳輸通道是質(zhì)子交換膜方向的最重要的研究課題。本論文通過(guò)調(diào)節(jié)質(zhì)子傳輸功能聚合物微觀結(jié)構(gòu)實(shí)現(xiàn)質(zhì)子傳輸通道在質(zhì)子交換膜中的自組裝,并通過(guò)優(yōu)化質(zhì)子交換膜中多級(jí)質(zhì)子傳輸通道微觀結(jié)構(gòu)來(lái)實(shí)現(xiàn)質(zhì)子交換膜選擇性的進(jìn)一步提升。具體研究?jī)?nèi)容如下所述:1、研究證實(shí)超支化聚酰胺質(zhì)子交換膜可以有效地降低燃料滲透,同時(shí)提高質(zhì)子傳導(dǎo)性。此質(zhì)子交換膜表現(xiàn)出比Nafion117高出至少15倍的阻醇性。在此基礎(chǔ)上,本論文首次提出了一個(gè)新的概念——多級(jí)質(zhì)子傳輸通道(HPCCs)。在這些HPCCs中,超支化聚酰胺分子內(nèi)部高密度磺酸基團(tuán)組成的質(zhì)子傳輸通道稱為一級(jí)質(zhì)子傳輸通道(FOPCC)。另外,超支化聚酰胺分子封端功能基團(tuán)與活化水分子間形成豐富的氫鍵網(wǎng)絡(luò)被稱為二級(jí)質(zhì)子傳輸通道(SOPCC)。由于一級(jí)與二級(jí)質(zhì)子傳輸通道之間的協(xié)同作用,超支化聚酰胺質(zhì)子交換膜表現(xiàn)出高效的質(zhì)子傳輸性能(0.282S/cm,80 oC)。通過(guò)調(diào)節(jié)合成超支化聚酰胺分子單體的納米結(jié)構(gòu),實(shí)現(xiàn)對(duì)多級(jí)質(zhì)子傳輸通道的優(yōu)化,從而降低了質(zhì)子交換膜的甲醇滲透性,同時(shí)其選擇性提高了1倍多。2、在多級(jí)質(zhì)子傳輸通道概念的基礎(chǔ)上,本論文通過(guò)調(diào)節(jié)一級(jí)質(zhì)子傳輸通道微觀結(jié)構(gòu)來(lái)進(jìn)一步增強(qiáng)膜的阻醇性。首先合成了兩種磺酸根密度不同的都以-COOH封端的聚酰胺大分子,通過(guò)將不同質(zhì)量比例的兩種聚合物用溶液澆鑄法制備了一系列共混膜。由于兩種聚酰胺大分子中的磺酸基團(tuán)-SO3H密度不同,所以通過(guò)調(diào)節(jié)共混膜中兩種分子比例可以實(shí)現(xiàn)質(zhì)子交換膜中一級(jí)質(zhì)子傳輸通道的調(diào)節(jié),從而實(shí)現(xiàn)質(zhì)子交換膜阻醇及選擇性能的優(yōu)化。3、使用類似想法,論文對(duì)多級(jí)質(zhì)子傳輸通道中的二級(jí)質(zhì)子傳輸通道的微觀結(jié)構(gòu)進(jìn)行調(diào)節(jié)優(yōu)化,通過(guò)溫和的方法改變二級(jí)質(zhì)子傳輸通道的氫鍵強(qiáng)度及保水性,以此來(lái)優(yōu)化質(zhì)子交換膜的整體性能。首先,設(shè)計(jì)并合成了以不同功能基團(tuán)(-COOH和-NH2)封端,大小相似的超支化聚酰胺大分子;將這兩種聚合物大分子按照不同的比例制備成復(fù)合膜。通過(guò)調(diào)整兩種聚酰胺大分子的比例來(lái)調(diào)節(jié)共混膜中的二級(jí)質(zhì)子傳輸通道的微觀結(jié)構(gòu),質(zhì)子交換膜的選擇性比Nafion117高出1.7倍。4、基于前期設(shè)計(jì)合成的高選擇性超支化聚酰胺質(zhì)子交換膜,將其應(yīng)用領(lǐng)域從直接甲醇燃料電池拓展至同樣對(duì)選擇性要求極高的釩氧液流電池中。超支化聚酰胺中多級(jí)質(zhì)子傳輸通道形成的致密結(jié)構(gòu)有效阻止了釩離子穿透。與Nafion117膜相比,超支化聚酰胺質(zhì)子交換膜表現(xiàn)出良好的的質(zhì)子/釩離子選擇性,高達(dá)14.4×104S.s/cm3,比Nafion117膜高出3倍。5、由于聚酰亞胺良好的化學(xué)穩(wěn)定性,設(shè)計(jì)并合成了超支化聚酰亞胺用于高選擇性多級(jí)質(zhì)子傳輸通道的構(gòu)筑。聚酰亞胺質(zhì)子交換膜機(jī)械性能比聚酰胺高出25%。透過(guò)該共混膜的甲醇滲透性很低以至于無(wú)法用儀器檢測(cè)到。綜上所述,通過(guò)大分子微觀結(jié)構(gòu)設(shè)計(jì)來(lái)構(gòu)筑高效多級(jí)自組裝質(zhì)子傳輸通道,以此獲得高選擇性的質(zhì)子交換膜,同時(shí)這些質(zhì)子交換膜表現(xiàn)出良好的機(jī)械性能。本論文為應(yīng)用于直接甲醇燃料電池及釩氧液流電池的新型質(zhì)子交換膜的開發(fā)研究提供了一定參考。
[Abstract]:The proton exchange membrane is widely used in electrochemical energy conversion devices, including proton exchange membrane fuel cells (including direct methanol fuel cells), SPE water electrolysis and oxygen-enriched liquid flow cells. The Nafion membrane is the most widely used proton exchange membrane due to its good proton conductivity, strong mechanical properties, oxidation resistance and thermal stability. However, the problem of selective permeability of the Nafion membrane has an influence on the large-scale application of the Nafion membrane in the direct methanol fuel cell and the oxygen-enriched liquid flow cell. the poor selectivity of the nafion membrane will result in severe methanol fuel penetration in the direct methanol fuel cell application. in the process of operation, the methanol molecule can easily penetrate the membrane to the cathode from the anode through the membrane due to the bad alcohol resistance of the Nafion membrane, not only the waste of the methanol fuel is caused, but also the oxygen reduction reaction of the cathode is seriously inhibited, resulting in a decrease in the operating voltage of the battery and the efficiency of the battery. Therefore, it can be said that the lack of a high-selectivity proton exchange membrane is a stumbling block to the development of direct methanol fuel cells. The new type of proton exchange membrane with good selectivity and low price is the key to the development of direct methanol fuel cell. Similarly, the selectivity of the Nafion membrane also affects the development process of the oxygen-enriched liquid flow cell. Although the Nafion membrane has excellent chemical stability, it becomes the main membrane in the application of the present oxygen-enriched liquid-flow battery. However, the high ionic permeability of the Nafion membrane is such that the voltage efficiency, coulombic efficiency and energy efficiency of the oxygen-oxygen flow cell assembled by the Nafion membrane are low. In general, the design and development of a highly selective proton exchange membrane is a major subject in the field of direct methanol fuel cells and oxygen-enriched liquid-flow cells. The highly ordered proton transfer channel is an important prerequisite for ensuring the efficient conduction of protons and improving the selectivity of the proton exchange membrane. Therefore, the construction of the high-selective proton transfer channel is the most important research topic in the direction of the proton exchange membrane. The self-assembly of the proton transfer channel in the proton exchange membrane is realized by adjusting the microstructure of the proton transfer function polymer, and the selectivity of the proton exchange membrane can be further improved by optimizing the microstructure of the multi-stage proton transfer channel in the proton exchange membrane. The specific content of the study is as follows: 1. The research confirms that the hyperbranched polyetheramine proton exchange membrane can effectively reduce the fuel penetration and improve the proton conductivity. the proton exchange membrane exhibits a resistance to alcohol that is at least 15 times higher than nafion 117. On this basis, a new concept _ multi-stage proton transfer channel (HPCCs) is proposed for the first time. In these HPCCs, the proton transfer channel consisting of the high-density sulfonic acid groups inside the hyperbranched polyetheramine molecule is referred to as a primary proton transfer channel (FOPCC). In addition, the formation of a rich hydrogen bond network between the functional groups of the hyperbranched polyylamine molecules and the activated water molecules is referred to as a secondary proton transfer channel (SOPCC). The highly effective proton transfer performance (0.282S/ cm, 80oC) is demonstrated by the synergistic effect of the primary and secondary proton transfer channels. the invention realizes the optimization of the multi-stage proton transfer channel by adjusting the nano-structure of the synthetic hyperbranched polyetheramine molecular monomer, thereby reducing the methanol permeability of the proton exchange membrane, and simultaneously improving the selectivity of the proton exchange membrane by more than 1. This paper further enhances the resistance of the membrane by adjusting the microstructure of the first-order proton transfer channel. A series of co-mixed membranes were prepared by casting two kinds of polymers with different mass ratios with the solution casting method. because the density of the sulfonic acid groups-SO3H in the two polyetheramine macromolecules is different, the regulation of the primary proton transfer channel in the proton exchange membrane can be realized by adjusting the proportion of the two molecules in the blending membrane, so as to realize the optimization of the proton exchange membrane resistance alcohol and the selection performance. In this paper, the micro-structure of the two-stage proton transfer channel in the multi-stage proton transfer channel is optimized, and the hydrogen bond strength and water-retaining property of the second-stage proton transfer channel are changed by a gentle method, thus the overall performance of the proton exchange membrane is optimized. First, the hyperbranched polyetheramine macromolecules with different functional groups (-COOH and-NH2) and similar in size are designed and synthesized, and the two polymer macromolecules are prepared into the composite membrane according to different proportions. the micro-structure of the two-stage proton transfer channel in the blending film is adjusted by adjusting the proportion of the two polyetheramine macromolecules, the selectivity of the proton exchange membrane is 1 to 7 times higher than that of the Nafion 117, the application field is extended from a direct methanol fuel cell to an oxygen-oxygen flow cell that is also highly selective to a very high selectivity. The dense structure of the multi-stage proton transfer channel in the hyperbranched polyetheramine effectively prevents the penetration of the oxygen ions. Compared with the Nafion 117 membrane, the hyperbranched polyetheramine proton exchange membrane exhibits good proton/ polar ion selectivity, a high of 14. 4-104S. s/ cm3, 3-fold higher than that of the Nafion 117 membrane, and 5, due to the good chemical stability of the polycarbodiimide, In this paper, a hyperbranched polycarbodiimide is designed and synthesized for the construction of high-selectivity multi-stage proton transfer channels. The mechanical properties of the polycarbodiimide proton exchange membrane were 25% higher than that of polyalicyclic amine. the methanol permeability through the blend membrane was so low that the instrument could not be detected with the instrument. To sum up, a high-selectivity proton exchange membrane is obtained by a macromolecular microstructure design to obtain a high-selectivity proton exchange membrane, and at the same time, the proton exchange membranes exhibit good mechanical properties. This paper provides a reference for the development and research of a new type of proton exchange membrane for direct methanol fuel cell and oxygen-oxygen flow cell.
【學(xué)位授予單位】：中國(guó)地質(zhì)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM911.4

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