【摘要】：全釩液流電池具有充放電效率高、使用壽命長、綠色安全和價(jià)格低廉等優(yōu)點(diǎn),成為儲能系統(tǒng)的最佳選擇。質(zhì)子交換膜是全釩液流電池的核心組件之一,決定了釩電池的能量效率和使用壽命。目前釩電池質(zhì)子交換膜為Nafion系列,但昂貴價(jià)格,高釩離子透過率,低的電流效率制約了釩電池的商業(yè)化。研究開發(fā)一種低成本、化學(xué)穩(wěn)定性好、質(zhì)子傳導(dǎo)率高和釩離子滲透率低的質(zhì)子交換膜是推進(jìn)全釩液流電池應(yīng)用的關(guān)鍵�；腔勖衙淹�(sulfonated poly(ether ether ketone),SPEEK)質(zhì)子交換膜具有低成本、高選擇性、制備簡單等優(yōu)點(diǎn)。作為釩電池膜材料使用時(shí),電池能量效率與其磺化度高低有密切關(guān)系。低磺化度SPEEK的質(zhì)子傳導(dǎo)性低,不適合用于釩電池;高磺化度SPEEK的溶脹度大,增加了釩離子透過率。本論文通過摻雜功能化氧化石墨烯(GO)改性高磺化度的SPEEK膜,探討了復(fù)合膜結(jié)構(gòu)與性能的關(guān)系。以對苯二胺(PPD)為修飾劑,制備了氨基化氧化石墨烯(PPD-GO),與SPEEK共混制備了 SPEEK/PPD-GO復(fù)合膜,對復(fù)合膜的結(jié)構(gòu)和性能、釩電池性能進(jìn)行了表征和測試。研究表明,PPD-GO與SPEEK基體界面處形成的酸堿離子對降低了復(fù)合膜的溶脹率和釩離子滲透率,保持了較高質(zhì)子傳導(dǎo)率。在30 mA·cm-2電流密度下,含1 wt%PPD-GO的SPEEK復(fù)合膜展現(xiàn)了良好的綜合性能,單電池的庫倫效率(96.9%vs 91%)和能量效率(82.8%vs 66.8%)均高于Nafion 117膜。經(jīng)300次充放電循環(huán)測試,SPEEK/PPD-GO-1膜具有良好的耐酸性和化學(xué)穩(wěn)定性。采用4,4-二氨基二苯醚(ODA)和苯胺(AN)對GO進(jìn)行了化學(xué)修飾,制備了含氮量(3.04%)的氨基化石墨烯(ODA-AN-GO),與SPEEK共混制備了SPEEK/ODA-AN-GO復(fù)合膜。研究表明,復(fù)合膜中氨基含量的增加,復(fù)合膜的酸堿離子對作用增強(qiáng),提高了復(fù)合膜的質(zhì)子傳導(dǎo)率。經(jīng)300次單電池循環(huán),電池的庫倫效率和能量效率保持穩(wěn)定,2 wf%ODA-AN-GO含量時(shí)SPEEK復(fù)合膜表現(xiàn)出良好的綜合電池性能。
[Abstract]:The full-flow battery has the advantages of high charging and discharging efficiency, long service life, green safety, low price and the like, and becomes the best choice for the energy storage system. The proton exchange membrane is one of the core components of the full-flow battery, and the energy efficiency and the service life of the battery are determined. At present, the proton exchange membrane of the lithium ion battery is the Nafion series, but the high price, the high ion permeability and the low current efficiency restrict the commercialization of the solar cell. The research and development of a proton exchange membrane with low cost, good chemical stability, high proton conductivity and low ion permeability is the key to the application of the full-flow battery. The sulfonated polyetheretherketone (SPEEK) proton exchange membrane has the advantages of low cost, high selectivity, simple preparation and the like. As the battery membrane material is used, the energy efficiency of the battery is closely related to the degree of sulfonation. The low sulfonation degree of the SPEEK has low proton conductivity and is not suitable for use in the lithium ion battery; the swelling degree of the high sulfonation degree SPEEK is large, and the transmittance of the high sulfonation degree is increased. In this paper, the relationship between the structure and properties of the composite membrane is discussed by doping the functionalized graphene oxide (GO) modified SPEEK film with high degree of sulfonation. An amino-modified graphene (PPD-GO) was prepared by using p-phenylenediamine (PPD) as a modifier, and the SPEEK/ PPD-GO composite film was prepared by blending with SPEEK. The structure and properties of the composite film were characterized and tested. The results show that the acid-base ion formed at the interface of the PPD-GO and the SPEEK matrix reduces the swelling rate and the ionic permeability of the composite membrane, and maintains the higher proton conductivity. At the current density of 30 mA 路 cm-2, the SPEEK composite film with 1 wt% PPD-GO exhibited a good comprehensive performance, and the coulombic efficiency of the single cell (96.9% vs 91%) and the energy efficiency (82.8% vs 66.8%) were higher than that of the Nafion 117 film. After 300 charge and discharge cycles, the SPEEK/ PPD-GO-1 film has good acid resistance and chemical stability. In this paper,4,4-diaminodiphenyl ether (ODA) and aniline (AN) were used to chemically modify the GO. The aminolated graphene (ODA-AN-GO) with nitrogen content (3.04%) was prepared, and the SPEEK/ ODA-AN-GO composite film was prepared by blending with SPEEK. The results show that the content of amino groups in the composite membrane is increased, the acid-base ion of the composite membrane is enhanced, and the proton conductivity of the composite membrane is improved. After 300 single cell cycle, the cell's coulomb efficiency and energy efficiency were stable, and the SPEEK composite film exhibited good composite battery performance when the content of 2wf% ODA-AN-GO was stable.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TM912

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 丁虎標(biāo);崔旭梅;陳孝娥;;添加劑對釩電池V(Ⅲ)/V(Ⅳ)混合電解液的影響[J];電源技術(shù);2013年10期

2 陳偉;孟凡明;李曉兵;馬海波;劉效疆;;SPEEK膜與Nafion膜在釩液流電池中的應(yīng)用研究[J];電源技術(shù);2013年07期

3 費(fèi)國平;趙炯心;;釩流電池的應(yīng)用前景和關(guān)鍵材料[J];能源研究與信息;2008年01期

4 王文紅;薛方勤;王新東;;Ir修飾碳?xì)謱O~(2+)／VO_2~+電對電催化性能的影響[J];材料研究學(xué)報(bào);2007年05期

5 毛凌波;張仁元;陳梟;;全釩液流電池正極電解液的研究進(jìn)展[J];電池工業(yè);2007年05期

6 李曉剛;黃可龍;桑商斌;譚寧;劉素琴;陳立泉;;電化學(xué)氧化改性石墨氈電極對VO~(2+)/VO_2~+電對的催化活性[J];功能材料;2006年07期

7 文越華;張華民;錢鵬;趙平;周漢濤;衣寶廉;;全釩液流電池高濃度下V(IV)/V(V)的電極過程研究[J];物理化學(xué)學(xué)報(bào);2006年04期

8 羅冬梅,許茜,康曉雪,李彥丹,隋智通;改性電極復(fù)合材料的導(dǎo)電性和電化學(xué)性能[J];過程工程學(xué)報(bào);2005年04期

9 羅冬梅,許茜,隋智通;添加劑對釩電池電解液性質(zhì)的影響[J];電源技術(shù);2004年02期

10 李華,常守文,嚴(yán)川偉;全釩氧化還原液流電池中電極材料的研究評述[J];電化學(xué);2002年03期

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