本文選題：離子凝膠 + 自修復(fù)��； 參考：《河北大學(xué)》2017年碩士論文

【摘要】：將離子凝膠替代傳統(tǒng)的凝膠聚合物電解質(zhì)應(yīng)用于新型聚合物鋰電池、柔性超級電容器等是目前國內(nèi)外研究的熱點(diǎn)。但是目前聚合物基體局限于含有結(jié)晶性的線形高分子均聚物/共聚物,離子遷移困難,且功能基團(tuán)少,很難吸附更多的離子液體,離子電導(dǎo)率和力學(xué)強(qiáng)度不能滿足在裝配和使用過程中的要求。同時(shí),目前的凝膠聚合物電解質(zhì)在制造和反復(fù)使用中極易出現(xiàn)裂縫等結(jié)構(gòu)缺陷,使用壽命很短。因此,如何實(shí)現(xiàn)離子凝膠同時(shí)具備良好的機(jī)械性能和高離子電導(dǎo)率,以及在制造或使用中受損后如何修復(fù)是目前離子凝膠電解質(zhì)材料研究的關(guān)鍵問題。本文以具有無定型結(jié)構(gòu)且官能團(tuán)豐富的樹枝狀大分子聚酰胺胺(PAMAM)為基體,在離子液體中原位交聯(lián)制備出具有特殊網(wǎng)絡(luò)骨架和離子遷移通道的新型高性能離子凝膠,并對其自修復(fù)機(jī)制、導(dǎo)電性能、力學(xué)性能進(jìn)行了詳細(xì)的研究,揭示離子凝膠高離子電導(dǎo)率的微觀機(jī)理及力學(xué)響應(yīng)機(jī)制,同時(shí)研究了PAMAM/離子液體二元體系的相行為。所得結(jié)果如下:(1)采用希夫堿反應(yīng),以樹枝狀聚合物聚酰胺胺(PAMAM)為聚合物基體,離子液體作為溶劑和電解質(zhì),在離子液體中氨基原位交聯(lián),制備出一種具有動態(tài)共價(jià)鍵聚合物網(wǎng)絡(luò)結(jié)構(gòu)的高效自修復(fù)型離子凝膠。流變結(jié)果表明,離子凝膠的模量隨著PAMAM含量的升高而升高,由于幾何形狀的影響隨著PAMAM代數(shù)的增加有所降低,動態(tài)溫度掃描結(jié)果表明,自修復(fù)型離子凝膠非常穩(wěn)定,并且溫度達(dá)到160 oC時(shí)這種可逆共價(jià)鍵網(wǎng)絡(luò)結(jié)構(gòu)仍然未被破壞。離子凝膠具有優(yōu)異的導(dǎo)電性能,室溫離子電導(dǎo)率能夠達(dá)到10-2 S/cm。重要的是,在大量水的作用下,這種具有動態(tài)共價(jià)鍵聚合物網(wǎng)絡(luò)結(jié)構(gòu)的離子凝膠能夠降解,并且其中的PAMAM和離子液體可回收利用。(2)采用Debus-Radziszewski反應(yīng),離子液體作為溶劑和電解質(zhì),制備出具有咪唑環(huán)交聯(lián)結(jié)構(gòu)的樹枝狀大分子聚酰胺胺(PAMAM)基離子凝膠。其室溫離子電導(dǎo)率達(dá)6.8mS/cm,并且具有可調(diào)彈性模量104-106 Pa,動態(tài)溫度掃描結(jié)果表明,離子凝膠在溫度高達(dá)160 oC時(shí)仍處于穩(wěn)定狀態(tài)。將離子凝膠作為超級電容器中的柔性凝膠電解質(zhì),經(jīng)測試具有較好的循環(huán)性能,比電容經(jīng)5000次充放電后基本維持不變。(3)通過紫外可見分光光度計(jì)和光學(xué)顯微鏡研究了PAMAM/[BMIM][BF_4]體系相行為。結(jié)果表明,半代體系為相容體系,而整代體系發(fā)生了相分離。整代PAMAM/[BMIM][BF_4]體系呈現(xiàn)UCST行為,且臨界共溶溫度Tc隨著PAMAM代數(shù)的增加而增大,對于PAMAM G1.0、PAMAM G3.0和PAMAM G5.0體系,臨界共溶溫度(Tc)分別為92、124和130 oC,臨界濃度(Wc)均為10%。
[Abstract]:The application of ionic gel instead of traditional gel polymer electrolytes in new polymer lithium batteries and flexible supercapacitors is a hot topic at home and abroad. However, at present, the polymer matrix is confined to linear homopolymers / copolymers with crystallization, which makes it difficult to transfer ions, and has fewer functional groups, so it is difficult to adsorb more ionic liquids. Ionic conductivity and mechanical strength can not meet the requirements of assembly and application. At the same time, the current gel polymer electrolytes are prone to crack and other structural defects in manufacture and repeated use, and their service life is very short. Therefore, how to realize the ionic gel with good mechanical properties and high ionic conductivity, and how to repair the ionic gel electrolyte after being damaged in manufacture or use are the key issues in the research of ionic gel electrolyte materials. In this paper, a novel high performance ionic gel with special network skeleton and ion migration channel was prepared by in situ crosslinking of dendrimer polyamide amine (Pamam) with amorphous structure and abundant functional groups in ionic liquids. The mechanism of self-repair, conductivity and mechanical properties were studied in detail. The microscopic mechanism and mechanical response mechanism of ionic gel with high ionic conductivity were revealed. The phase behavior of PAMAM / ionic liquid binary system was also studied. The results are as follows: (1) in the presence of Schiff base reaction, dendrimer polyamide amine (PamAm) was used as polymer matrix, ionic liquid as solvent and electrolyte, and in situ crosslinking of amino groups in ionic liquids. An efficient self-repairable ionic gel with dynamic covalent polymer network structure was prepared. The rheological results show that the modulus of ionic gels increases with the increase of PamAm content, and decreases with the increase of PAMAM algebras due to the effect of geometric shape. The dynamic temperature scanning results show that the self-repairable ionic gels are very stable. And the reversible covalent bond network structure is not destroyed when the temperature reaches 160oC. The ionic gel has excellent conductivity, and the ionic conductivity can reach 10-2 S / cm at room temperature. It is important that the ionic gel with a dynamic covalent polymer network structure can be degraded under the action of a large amount of water, and that the PAMAM and ionic liquids are recyclable. (2) Debus-Radziszewski reaction is used, and ionic liquids are used as solvents and electrolytes. Dendrimer polyamide amine (PamAm) based ionic gel with imidazole ring crosslinking structure was prepared. The ionic conductivity is 6.8 Ms / cm at room temperature and has an adjustable elastic modulus of 104-106 Pa. the dynamic temperature scanning results show that the ionic gel is still stable at 160oC. The ionic gel is used as the flexible gel electrolyte in supercapacitor. (3) the phase behavior of Pamam / [BMIM] [BF4] system was studied by UV-Vis spectrophotometer and optical microscope. The results show that the half-generation system is a compatible system and the whole generation system is separated. The whole generation PAMAM / [BMIM] [BF4] system showed UCST behavior, and the critical co-dissolution temperature (Tc) increased with the increase of PamAM-algebra. For PAMAM G1.0 / PAMAM G3.0 and PamAM-G5.0 systems, the critical co-dissolution temperature (Tc) was 92124 and 130oC, and the critical concentration (WC) was 10oC.
【學(xué)位授予單位】：河北大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O645.1;O648.17

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