本文選題：質(zhì)子導(dǎo)體 + 鈮的氫氧化合物�。� 參考：《東北師范大學(xué)》2017年碩士論文

【摘要】：隨著質(zhì)子交換膜燃料電池研究領(lǐng)域的飛速發(fā)展,簡化制備方法開發(fā)合成新型低成本的質(zhì)子傳導(dǎo)電解質(zhì)材料仍然具有一定的挑戰(zhàn)性。由于材料的電導(dǎo)率受到載體和電荷的數(shù)量影響較大,因此,具有豐富電荷和質(zhì)子載體的材料可被認(rèn)為是一種有效的質(zhì)子導(dǎo)體材料。例如多金屬氧酸鹽是一類典型的過渡金屬氧化物簇,作為質(zhì)子導(dǎo)體,其本身可以提供質(zhì)子,結(jié)構(gòu)中存在的大量水分子可作為質(zhì)子載體,而且多金屬簇表面富含氧原子,也可作為質(zhì)子的跳躍位點(diǎn),從而為質(zhì)子的傳輸提供一條通路。近年來,一種基于過渡金屬氫氧化合物(MOx(OH))的新型非晶態(tài)納米材料因具有獨(dú)特的性能而引起人們廣泛關(guān)注,該結(jié)構(gòu)中含有豐富的羥基基團(tuán),能有效構(gòu)筑氫鍵網(wǎng)絡(luò),因而利于質(zhì)子跳躍。另外,在結(jié)構(gòu)中引入磺酸、磷酸、羧基等一些含氧功能性基團(tuán)也能在一定程度上提高質(zhì)子傳導(dǎo)效率。本論文的研究主要包含以下兩個方面:1.以五氯化鈮為原料,通過簡便的溶膠-凝膠法水解合成了一種基于金屬鈮的氫氧化合物NbOx(OH)-Cl,將其作為一種新型的質(zhì)子導(dǎo)體材料,同時(shí)引入一種富含質(zhì)子載體的多金屬氧酸鹽(磷鎢酸)形成了一種富含羥基且具有三維氫鍵網(wǎng)絡(luò)結(jié)構(gòu)的復(fù)合質(zhì)子導(dǎo)體材料NbHyOx(OH)-PW12。結(jié)果表明,摻入多酸的復(fù)合材料NbHyOx(OH)-PW12比單純的NbOx(OH)-Cl表現(xiàn)出更高的質(zhì)子電導(dǎo)率,數(shù)據(jù)顯示在25℃,97%相對濕度條件下,NbHyOx(OH)-PW12的電導(dǎo)率值可達(dá)到6.52 mS cm-1,比同條件下NbOx(OH)-Cl的性能提升了4個數(shù)量級。最后,我們對摻雜劑比例不同對樣品性能的影響進(jìn)行了分析,對比結(jié)果顯示當(dāng)Nb:{PW12}摩爾比達(dá)到67:1時(shí),材料能夠表現(xiàn)出相對較高的質(zhì)子傳導(dǎo)效率。2.在鈮的氫氧化合物骨架中引入植酸分子(Phytic acid,以下簡寫為PA),通過溶膠-凝膠法原位合成了一種富含羥基和磷酸功能性基團(tuán)的植酸摻雜的鈮的氫氧化合物NbHyOx(OH)-PA,并研究了其作為質(zhì)子導(dǎo)體的性能,實(shí)驗(yàn)結(jié)果表明當(dāng)Nb:PA的摩爾比達(dá)到17:1時(shí),材料在75℃,97%相對濕度條件下可達(dá)到最高的電導(dǎo)率(9.8 mS cm-1)。
[Abstract]:With the rapid development of proton exchange membrane fuel cell (PEMFC) research, it is still challenging to develop and synthesize new proton conductive electrolyte materials by simplified preparation method. Because the conductivity of the material is greatly affected by the number of carriers and charges, the materials with rich charge and proton carrier can be considered as an effective proton conductor material. For example, polyoxometalates are a kind of typical transition metal oxide clusters. As proton conductors, polyoxometalates can provide protons themselves. A large number of water molecules in the structure can be used as proton carriers, and the surface of polymetallic clusters is rich in oxygen atoms. It can also be used as a jumping site for protons, thus providing a pathway for proton transport. In recent years, a novel amorphous nanomaterials based on transition metal hydroxides (MOXO) have attracted much attention because of their unique properties. The structure contains abundant hydroxyl groups and can effectively construct hydrogen bond networks. So it's good for proton jumping. In addition, the introduction of sulfonic acid, phosphoric acid and carboxyl groups into the structure can improve the proton conduction efficiency to some extent. The research of this thesis mainly includes the following two aspects: 1. Using niobium pentachloride as raw material, a niobiobium-based hydrogen compound NbOxOH- Cl-Cl was synthesized by a simple sol-gel method, which was used as a new proton conductor material. At the same time, a proton rich polyoxometalate (phosphotungstic acid) was introduced to form a hydroxyl rich composite proton conductor material NbHyOxOHN-PW12 with a three-dimensional hydrogen bond network structure. The results show that the proton conductivity of polyacid-doped composite NbHyOx(OH)-PW12 is higher than that of pure NbOx(OH)-Cl. The data show that the conductivity of NbHyOxOHM-PW12 can reach 6.52 mScm-1 at 25 鈩，

本文編號：1934386