本文關鍵詞： 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》2014年碩士論文　論文類型：學位論文

【摘要】：PANi作為一種導電聚合物，以穩(wěn)定的電化學性、易合成、低價格和環(huán)境友好的特性，在電池領域廣受關注。本文分別以質子酸和鋰鹽作為摻雜劑，制備摻雜態(tài)聚苯胺并對其結構表征，確定了PANi中發(fā)生摻雜反應的活性點位置；根據電池充放電測試的反饋研究了摻雜陰離子種類、摻雜陰離子數量、隔膜種類、壓力強度、正極片厚度、浸泡時間等因素對電池性能的影響，并對PANi的放大合成可行性進行初步探討。 對PANi進行質子酸摻雜，通過電導率測試發(fā)現，近似絕緣的PANi經質子酸摻雜后，其導電性提升8個數量級，導電能力提高顯著；摻雜鹽酸PANi的XRD結果顯示，摻雜質子酸后的PANi衍射峰形更加尖銳，其結晶度由摻雜前的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吸收峰，表明了發(fā)生在PANi醌式結構中的C=N上。同時，XRD、SEM結果顯示在有機體系進行鋰鹽摻雜也可獲得較高結晶度的PANi。此外XPS測試結果表明，摻雜鋰鹽后，，醌式結構中N原子的N1S峰強度明顯下降，而陽離子自由基結構中N原子的N1S峰強度迅速增加，說明了鋰鹽摻雜反應發(fā)生在醌式結構中的N原子上。 通過觀察PANi片在電解液中開裂溶脹現象，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，摻雜ClO4-具有更良好的循環(huán)性能，預摻雜態(tài)PANi容量可達75mAh/g。通過設計四因素三水平正交試驗，確定了反應時間6h，溫度25℃，酸度1.5mol/L的最佳陰離子摻雜工藝。根據電池性能結果，確定了使用AGM和聚丙烯復合隔膜、浸泡48h、正極片厚度0.7-1.0mm、壓力強度4MPa的最佳工藝條件。對PANi的放大合成和電池組裝及測試進行了研究。利用SEM進行形貌觀測發(fā)現，放大合成的PANi具有較好的結晶度，組裝成的電池容量可達80mAh/g，組裝成的電池充放過程超過80000min，容量在前40個循環(huán)內幾乎不衰減。最后分析了目前二次電池的市場構成并計算了Li-PANi電池成本，以實驗室合成PANi成本計算，每千克PANi成本在20元，價格優(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.

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

【參考文獻】

相關期刊論文 前9條

1 林生嶺;龍丹;陶楠楠;儲艷文;郭寅丹;萬勇;;聚苯胺的合成優(yōu)化及其電化學性能研究[J];材料開發(fā)與應用;2010年06期

2 唐勁松,王寶忱,王佛松;聚苯胺的合成、結構、性能及應用[J];高分子材料科學與工程;1987年01期

3 曾幸榮,莫毅,楊衛(wèi),吳振耀,龔克成;碘摻雜聚苯胺的結構與性能[J];高分子材料科學與工程;1997年S1期

4 熊碧云;康海波;;電動車動力鋰離子電池的現狀與發(fā)展趨勢[J];電源技術;2013年05期

5 於黃中,陳明光,黃河;不同類型的酸摻雜對聚苯胺結構和電導率的影響[J];華南理工大學學報(自然科學版);2003年05期

6 馬利;劉昊;王成章;;聚苯胺的電致變色理論及應用[J];裝備環(huán)境工程;2006年06期

7 王佛松;王利祥;景遐斌;;聚苯胺的摻雜反應[J];武漢大學學報(自然科學版);1993年06期

8 白詠梅;邱鵬;文中流;韓紹昌;;LiFePO_4/PANI復合材料的制備及電化學性能[J];中國有色金屬學報;2010年08期

9 墨柯;Christophe Pillot;;全球二次電池及鋰離子電池市場研究分析[J];新材料產業(yè);2014年02期

本文編號：1477259