本文關(guān)鍵詞： 鋰-聚苯胺電池 摻雜 正極材料 鋰鹽 比容量　出處：《哈爾濱工業(yè)大學(xué)》2014年碩士論文　論文類型：學(xué)位論文

【摘要】：PANi作為一種導(dǎo)電聚合物，以穩(wěn)定的電化學(xué)性、易合成、低價(jià)格和環(huán)境友好的特性，在電池領(lǐng)域廣受關(guān)注。本文分別以質(zhì)子酸和鋰鹽作為摻雜劑，制備摻雜態(tài)聚苯胺并對其結(jié)構(gòu)表征，確定了PANi中發(fā)生摻雜反應(yīng)的活性點(diǎn)位置；根據(jù)電池充放電測試的反饋研究了摻雜陰離子種類、摻雜陰離子數(shù)量、隔膜種類、壓力強(qiáng)度、正極片厚度、浸泡時(shí)間等因素對電池性能的影響，并對PANi的放大合成可行性進(jìn)行初步探討。 對PANi進(jìn)行質(zhì)子酸摻雜，通過電導(dǎo)率測試發(fā)現(xiàn)，近似絕緣的PANi經(jīng)質(zhì)子酸摻雜后，其導(dǎo)電性提升8個數(shù)量級，導(dǎo)電能力提高顯著；摻雜鹽酸PANi的XRD結(jié)果顯示，摻雜質(zhì)子酸后的PANi衍射峰形更加尖銳，其結(jié)晶度由摻雜前的8.20%增加到24.82%；在紅外光譜中，C=N鍵的吸收峰由本征態(tài)中的1140cm-1移動到摻雜態(tài)的1109cm-1處，移動幅度最大且是譜圖中的最強(qiáng)吸收峰，表明了發(fā)生在PANi醌式結(jié)構(gòu)中的C=N上。同時(shí)，XRD、SEM結(jié)果顯示在有機(jī)體系進(jìn)行鋰鹽摻雜也可獲得較高結(jié)晶度的PANi。此外XPS測試結(jié)果表明，摻雜鋰鹽后，，醌式結(jié)構(gòu)中N原子的N1S峰強(qiáng)度明顯下降，而陽離子自由基結(jié)構(gòu)中N原子的N1S峰強(qiáng)度迅速增加，說明了鋰鹽摻雜反應(yīng)發(fā)生在醌式結(jié)構(gòu)中的N原子上。 通過觀察PANi片在電解液中開裂溶脹現(xiàn)象，確定了EA和DMC作為電解液添加劑，對摻雜不同陰離子PANi性能的研究發(fā)現(xiàn)，摻雜ClO4-具有更良好的循環(huán)性能，預(yù)摻雜態(tài)PANi容量可達(dá)75mAh/g。通過設(shè)計(jì)四因素三水平正交試驗(yàn)，確定了反應(yīng)時(shí)間6h，溫度25℃，酸度1.5mol/L的最佳陰離子摻雜工藝。根據(jù)電池性能結(jié)果，確定了使用AGM和聚丙烯復(fù)合隔膜、浸泡48h、正極片厚度0.7-1.0mm、壓力強(qiáng)度4MPa的最佳工藝條件。對PANi的放大合成和電池組裝及測試進(jìn)行了研究。利用SEM進(jìn)行形貌觀測發(fā)現(xiàn)，放大合成的PANi具有較好的結(jié)晶度，組裝成的電池容量可達(dá)80mAh/g，組裝成的電池充放過程超過80000min，容量在前40個循環(huán)內(nèi)幾乎不衰減。最后分析了目前二次電池的市場構(gòu)成并計(jì)算了Li-PANi電池成本，以實(shí)驗(yàn)室合成PANi成本計(jì)算，每千克PANi成本在20元，價(jià)格優(yōu)勢明顯。
[Abstract]:PANi as a conductive polymer, with electrochemical stability, easy synthesis, low price and environmental friendly characteristics, wide attention in the field of battery. In this paper, the proton acid and lithium salt as dopant, preparation of doped polyaniline and its structure characterization, determine the location of activity occurs in PANi doping reaction the battery charge and discharge test; according to the feedback of different dopants and doping amount of anion, diaphragm type, pressure strength, positive plate thickness, effect of soaking time and other factors on the performance of the battery and the PANi amplification can be explored for synthesis.
Proton acid doping on PANi by conductivity test found that the approximation of PANi insulation by protonic acid doping, the conductivity increased by 8 orders of magnitude, the conductivity increased significantly; doped PANi HCl XRD results showed that the PANi diffraction peaks of protonic acid after more sharp, the crystallinity by doping before 8.20% increased to 24.82%; in the infrared spectrum, C=N bond absorption peak at 1109cm-1 from the mobile 1140cm-1 eigenstates in the doped state to the biggest and strongest mobile spectrum figure of the absorption peak that occurred in the PANi quinoid structure of C=N. At the same time, the results show that the XRD, SEM lithium salt doping in organic system can obtain high crystallinity of PANi. and XPS test results show that the doped lithium salt, N1S peak intensity of N atom quinoid structure decreased significantly, while the N1S peak intensity of N atom radical cation in the structure increased rapidly, explained The doping reaction of lithium salt occurs on the N atom in the quinone structure.
Through the observation of PANi cracking swelling in the electrolyte, the EA and DMC as electrolyte additives on the properties of PANi doped with different anions found that doped ClO4- has better cycle performance, pre doped PANi capacity is 75mAh/g. through the design of four factors and three levels orthogonal test, to determine the reaction time 6h, temperature 25 the best anion doping process, acidity 1.5mol/L. According to the battery performance results, determine the use of AGM and polypropylene composite diaphragm for 48h, the positive plate thickness is 0.7-1.0mm, the optimum conditions of pressure strength of 4MPa. The PANi amplification of synthesis and assembly and test battery were studied. The morphology of observations by SEM amplification of PANi synthesis good crystallinity, battery capacity is 80mAh/g assembly, the assembly process of the battery charge and discharge capacity of more than 80000min, almost no decline in the first 40 cycles Finally, the market composition of the two battery is analyzed, and the cost of Li-PANi battery is calculated. The cost of PANi is 20 yuan per kilogram, and the price advantage is obvious. The cost is 20 yuan per kilogram.

【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2014
【分類號】：TM912

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