本文選題：燃料電池　切入點(diǎn)：金屬-空氣電池　出處：《中國科學(xué)技術(shù)大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：人類進(jìn)入21世紀(jì)以來,世界經(jīng)濟(jì)高速發(fā)展,能源的消耗日益增大�，F(xiàn)今的能源結(jié)構(gòu)中,傳統(tǒng)化石燃料依然占據(jù)著很大的比重。然而,化石燃料的不可再生性制約著它不能夠無限制地被開采下去。而且,化石燃料的過度使用所帶來的環(huán)境污染問題也日趨嚴(yán)重。因此,發(fā)展新能源代替?zhèn)鹘y(tǒng)化石能源成了當(dāng)今科學(xué)研究的一個熱門課題。燃料電池、金屬-空氣電池、氫能等都是環(huán)境友好型能源儲存載體,對環(huán)境不會造成任何污染。在燃料電池和金屬-空氣電池的工作中,存在兩個關(guān)鍵的反應(yīng)過程,分別是氧還原和氧析出反應(yīng);電解水制氫同樣有兩個重要的過程,分別是氧析出和氫析出反應(yīng)。然而,這些過程的發(fā)生離不開催化劑的作用,其性能的優(yōu)劣決定了相應(yīng)能源器件的性能。因此,尋找合適的電催化劑去驅(qū)動這些反應(yīng)過程具有重要的科學(xué)研究意義。本論文研究內(nèi)容包括設(shè)計與制備碳基過渡金屬(Fe、Co、Ni)催化劑材料,應(yīng)用于燃料電池、金屬-空氣電池的氧還原(ORR)和氧析出(OER)過程研究,以及電解水過程中的析氫(HER)和析氧(OER)反應(yīng)的研究,系統(tǒng)地揭示了催化劑組成、結(jié)構(gòu)等與ORR/OER/HER電催化性能之間的關(guān)系,主要開展了三部分研究工作。研究內(nèi)容一,利用生物質(zhì)蝦殼為含氮的碳源,與鐵(Fe)的前驅(qū)體進(jìn)行混合后,在惰性氣氛下,通過高溫?zé)峤獾姆绞?制備了碳包覆的鐵基納米催化劑粒子復(fù)合物。XRD物相分析表明,催化劑粒子主要為金屬單質(zhì)Fe和Fe203。對不同溫度下制備的催化劑進(jìn)行性能評價,結(jié)果表明,1000℃下制備催化劑擁有較好的ORR/OER雙功能催化活性。在堿性介質(zhì)中性能測試表明,Fe/Fe2O3@Fe-N-C-1000 ORR反應(yīng)的起始電位和半波電位分別為-0.04和-0.17 V;在固定轉(zhuǎn)速1600 rpm下,極限電流密度為6.5 mA·cm~(-2),其ORR催化性能可與商業(yè)化Pt/C催化劑相媲美;在OER催化過程中,催化劑Fe/Fe2O3@Fe-N-C-1000在10 mA·cm~(-2)時的過電位為460 mV。在酸性介質(zhì)中,催化劑Fe/Fe203@Fe-N-C-1000具有較好的ORR活性,起始電位和1600 rpm轉(zhuǎn)速下的極限電流密度分別為0.52 V和6.0 mA·cm~(-2),經(jīng)過20000秒穩(wěn)定性測試后,其ORR活性依然可以保持在90%以上。進(jìn)一步,Fe/Fe2O3@Fe-N-C-1000作為空氣陰極材料,組裝了簡易金屬鋅-空氣電池。測試結(jié)果表明,電池的開路電壓約1.3 V,放電功率能夠達(dá)到200 mW·cm~(-2)以上,并保持高的電池循環(huán)穩(wěn)定性。研究內(nèi)容二,以空間三維結(jié)構(gòu)金屬有機(jī)骨架材料Ni-BTC作為前驅(qū)體,在氨氣氣氛中,進(jìn)行高溫煅燒,得到了 Ni3N/Ni納米片材料。在堿性介質(zhì)中,對催化劑進(jìn)行OER性能測試。結(jié)果發(fā)現(xiàn),700℃下制備的催化劑材料(Ni3N/Ni-700)具有優(yōu)異的OER性能。在電流密度為10 mA·cm--2時,催化劑Ni3N/Ni-700的過電位為290 mV,與商業(yè)化的RuO2催化劑基本相當(dāng)。經(jīng)過4000次的循環(huán)催化測試之后,其催化活性可以保持在90%以上,表明其具有較高的催化穩(wěn)定性。研究內(nèi)容三,利用活性炭作為載體,在高溫(1000℃)下制備了不同比例的多功能Ni-Co合金催化劑,并進(jìn)行了自供電電解水產(chǎn)氫性能測試。XRD和STEM表征結(jié)果證明了金屬Ni和Co是以合金的形式存在,并且被石墨化的碳緊密包裹,有利于增強(qiáng)其催化活性與應(yīng)用穩(wěn)定性。在堿性條件下對催化劑材料進(jìn)行電化學(xué)測試,結(jié)果表明,所制備的合金催化劑具有ORR/OER/HER三功能催化活性,而且其性能與合金中Ni和Co的比例密切相關(guān)。Ni/Co摩爾比為1:3的催化劑(Ni1Co3@C)具有較好的ORR和OER性能,其ORR的起始電位和1600 rpm下的極限電流密度分別為-0.098 V和5.8 mA·cm~(-2),在OER電流密度為10 mA·cm~(-2)時的過電位為470 mV。Ni/Co摩爾比為3:1的催化劑(Ni3Co1@C)具有較好的HER催化活性,電流密度為10 mA·c,-2時的過電位為280 mV。進(jìn)一步,以NiICo3@C作為空氣電極材料,組裝了簡易金屬鎂-空氣電池。測試發(fā)現(xiàn),電池的開路電壓能達(dá)到1.7 V,放電功率為30 mW·cm~(-2),并可成功點(diǎn)亮LED燈和帶動小功率電風(fēng)扇。以自制的金屬鎂-空氣電池作為電源,NiICo3@C和Ni3Co1@C分別作為氧電極和氫電極,進(jìn)行自供電電解水研究。結(jié)果表明,3 h反應(yīng)可收集8 mL氫氣,分解水產(chǎn)氫效率為0.044 mL·min-1,而且,產(chǎn)氫和產(chǎn)氧的法拉第效率幾乎為100%。
[Abstract]:Since entering the twenty-first Century, the world economy rapid development, energy consumption is increasing. The current energy structure, traditional fossil fuels still occupy a large proportion. However, non renewable fossil fuels can not restrict its unrestricted exploitation. Moreover, the problem of environmental pollution caused by the excessive use of fossil fuels are becoming more and more serious. Therefore, the development of new energy to replace the traditional fossil energy has become a hot research area. Fuel cell, metal air batteries, hydrogen are environment friendly energy storage carrier, will not cause any pollution to the environment. In fuel cells and metal air batteries work, there are two key processes are oxygen reduction and oxygen evolution reaction; water electrolysis also has two important processes, namely oxygen precipitation and hydrogen evolution reaction. However, these The process cannot do without catalyst, its performance determines the performance of the corresponding energy devices. Therefore, to find a suitable catalyst to drive the electric reaction process has important scientific research significance. This thesis studies the design and preparation of carbon based transition metal (Fe, Co, Ni) catalyst materials. The application in fuel cell, metal air battery oxygen reduction (ORR) and oxygen precipitation (OER) process research, and in the process of water electrolysis hydrogen (HER) and oxygen evolution reaction (OER) research systematically reveals the relationship between catalyst composition, structure and Electrocatalytic Performance of ORR/OER/HER. The three part mainly carried out the research work. The research content, the use of biomass of shrimp shell containing nitrogen and carbon source, iron (Fe) precursors were mixed, under an inert atmosphere by high temperature pyrolysis method, preparation of Fe nano catalyst particles coated with carbon compound Compound.XRD phase analysis showed that the catalyst particles are mainly metal elements Fe and Fe203. on the catalyst synthesized at different temperature are evaluated. The results show that the prepared catalyst has better catalytic activity of ORR/OER double function under 1000 DEG C in alkaline medium. Performance tests show that the initial potential Fe/Fe2O3@Fe-N-C-1000 ORR reaction and half wave the potential was -0.04 and -0.17 V; at a fixed speed of 1600 rpm, the limiting current density of 6.5 mA - cm~ (-2), the catalytic performance of ORR can be comparable with commercial Pt/C catalyst in the catalytic process; OER, Fe /Fe2O3@Fe-N-C-1000 catalyst in 10 mA - cm~ (-2) have potential for 460 mV. in acidic medium, Fe/Fe203@Fe-N-C-1000 catalyst has good activity of ORR, limiting current density and initial potential 1600 RPM speed was 0.52 V and 6 mA cm~ (-2), after 20000 seconds after the stability test, ORR The activity remains more than 90%. Further, Fe/Fe2O3@Fe-N-C-1000 as air cathode materials, assembling a simple metal zinc air battery. The test results show that the open circuit voltage of the battery is about 1.3 V, the discharge power can reach 200 mW - cm~ (-2), and keep the battery cycle high stability. The research content of two, with metal the three-dimensional structure of organic matrix material Ni-BTC as precursor, ammonia in the atmosphere, high temperature calcination, obtained Ni3N/Ni nanosheets. In alkaline medium, OER test the performance of the catalyst. The results showed that catalyst material prepared under 700 DEG C (Ni3N/Ni-700) OER has excellent performance. At a current density of 10 mA cm--2, the overpotential of Ni3N/Ni-700 catalyst was 290 mV, and RuO2 commercial catalyst is quite basic. After cyclic catalytic test 4000 times, the catalytic activity can be maintained at 90% On the show that the catalytic stability is higher. The research content of three, the use of activated carbon as a carrier, at high temperature (1000 DEG C) multifunctional Ni-Co alloy catalysts were prepared with different proportion, and since the hydrogen water electrolysis capability of the power supply test.XRD and STEM characterization results show that Ni and Co exist in metal alloy the form and graphitized carbon tightly wrapped, is conducive to enhancing the stability of catalytic activity and application. The electrochemical measurements were performed on the catalyst material under alkaline conditions. The results show that the alloy catalyst prepared is ORR/OER/HER three catalytic activity, and Ni and Co and its performance is closely related to the proportion of alloy.Ni/Co molar ratio 1:3 catalyst (Ni1Co3@C) has better ORR and OER performance, the limiting current density ORR and the initial potential of 1600 RPM were -0.098 V and 5.8 mA cm~ (-2), OER in current density 10 mA - cm~ (-2) potential is 470 mV.Ni/Co when the molar ratio of 3:1 (Ni3Co1@C) HER catalyst has good catalytic activity, the current density is 10 mA - C, -2 potential is 280 mV. further, with NiICo3@C as the air electrode material, simple assembly of magnesium metal - air battery. The test found that the open circuit voltage of the battery can reach 1.7 V, the discharge power was 30 mW - cm~ (-2), and can be successfully lit LED lights and drives a small power electric fan. The magnesium - made air battery as power supply, NiICo3@C and Ni3Co1@C were used as the oxygen electrode and the hydrogen electrode for water electrolysis power supply research 3. The results showed that the h reaction can collect 8 mL hydrogen, hydrogen production efficiency was 0.044 mL - min-1, and hydrogen and oxygen production of Faraday efficiency is nearly 100%.

【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;TM911.4
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本文編號：1558444