【摘要】：近年來(lái),柔性超級(jí)電容器因其儲(chǔ)能效率高、循環(huán)壽命長(zhǎng)、環(huán)境友好以及良好的可植入性等優(yōu)點(diǎn),越來(lái)越受到了國(guó)內(nèi)外研究者的強(qiáng)烈關(guān)注和廣泛研究。但其儲(chǔ)能性能主要受電極材料的影響,而纖維素在自然界中儲(chǔ)量非常豐富,它在能源儲(chǔ)存設(shè)備中的應(yīng)用前景誘人無(wú)比。因此本論文從制備柔性高導(dǎo)電的纖維素復(fù)合紙出發(fā),探究其用作柔性超級(jí)電容器電極材料時(shí)的性能,并初步考察了將其應(yīng)用于柔性設(shè)備的可行性。同時(shí),較系統(tǒng)的研究了不同反應(yīng)條件對(duì)復(fù)合紙電化學(xué)性能的影響。本論文的研究?jī)?nèi)容主要包括以下三個(gè)部分:(1)、在抽濾制得的PANI/CNF/GNP復(fù)合紙?bào)w系中,CNF除了能增強(qiáng)CNF/GNP復(fù)合紙的力學(xué)強(qiáng)度和柔韌性,還可以降低PANI蠕蟲(chóng)狀納米棒的直徑,并改善了PANI鏈原位聚合時(shí)的摻雜程度,從而提高了超級(jí)電容器的比容量。當(dāng)CNF占復(fù)合基底的負(fù)載量為20 wt%時(shí),PANI雜化紙?jiān)陔娏髅芏葹?A/g顯示出最大比電容,421.5F/g。并且該復(fù)合紙?jiān)诒堵市阅芘c能量/功率密度平衡性能方面也表現(xiàn)的相當(dāng)不錯(cuò)。由PANI復(fù)合紙組裝得到的全固態(tài)超級(jí)電容器在反復(fù)彎折1000次以上以后,仍能表現(xiàn)出優(yōu)異的電化學(xué)性能和比電容保容率。(2)、在噴覆法制得的PANI/GCP復(fù)合紙?bào)w系中,CP作為骨架基底,為PANI/GCP復(fù)合紙?zhí)峁┝撕芨叩牧W(xué)強(qiáng)度及很好的柔韌性。其次,通過(guò)改變噴金處理時(shí)間,調(diào)控了PANI蠕蟲(chóng)狀納米棒的形成,并證明基底導(dǎo)電性越高,復(fù)合紙充放電的倍率性能越佳。再次,通過(guò)比較不同酸摻雜,改變了PANI鏈原位聚合時(shí)的微觀形貌和摻雜程度,并說(shuō)明復(fù)合膜內(nèi)阻與倍率性能的反比關(guān)系。結(jié)果是,噴金處理15min、鹽酸摻雜的PANI/GCP復(fù)合紙表現(xiàn)出優(yōu)異的贗電容特性、高的比容量(在1A/g電流密度下比容量為446.25F/g)、良好的倍率性能及循環(huán)穩(wěn)定性(循環(huán)充放電1000次后保容率為69.8%)。(3)、在涂覆法制得的MnO_2/M-NCF/GCP復(fù)合紙?bào)w系中,CP作為骨架基底,為MnO_2/M-NCF/GCP復(fù)合紙?zhí)峁┝撕芨叩牧W(xué)強(qiáng)度及很好的柔韌彎折性。其次,通過(guò)改變?nèi)芤喝苜|(zhì)(硫酸鈉和硫酸),調(diào)控了MnO_2在M-NCF/GCP復(fù)合紙上原位生長(zhǎng)的微觀形貌與晶型。結(jié)果是,硫酸法制得的MnO_2/M-NCF/GCP復(fù)合紙顯示出了相對(duì)更高的比容量(在1A/g電流密度下比容量為667.5F/g),而硫酸鈉法制得的MnO_2/M-NCF/GCP復(fù)合紙則具有相對(duì)更好的倍率性能和循環(huán)穩(wěn)定性(循環(huán)充放電500次后保容率高出為10%)。
[Abstract]:In recent years, flexible supercapacitors have attracted more and more attention from researchers at home and abroad because of their high energy storage efficiency, long cycle life, environmental friendliness and good implantability. However, its energy storage performance is mainly affected by the electrode materials, and cellulose is abundant in nature, and its application prospect in energy storage equipment is very attractive. Therefore, in this paper, we study the properties of cellulose composite paper used as electrode material of flexible supercapacitor, and preliminarily investigate the feasibility of its application in flexible equipment based on the preparation of flexible and highly conductive cellulose composite paper. At the same time, the effects of different reaction conditions on the electrochemical properties of composite paper were studied systematically. The main contents of this thesis are as follows: (1) in the PANI/CNF/GNP composite paper system, CNF can not only enhance the mechanical strength and flexibility of CNF/GNP composite paper, but also enhance the mechanical strength and flexibility of CNF/GNP composite paper. The diameter of PANI worm nanorods can be reduced, and the doping degree of PANI chains in situ polymerization can be improved, thus increasing the specific capacity of supercapacitors. When the load of CNF on the composite substrate is 20 wt%, the PANI hybrid paper shows a maximum specific capacitance of 421.5F / g at the current density of 1A/g. Moreover, the performance of the composite paper is very good in the aspect of ratio performance and energy / power density balance. The all-solid supercapacitors assembled from PANI composite paper can still exhibit excellent electrochemical performance and specific capacitance retention rate after repeated bending for more than 1000 times. (2) in the PANI/GCP composite paper system prepared by spray-coating method, As a skeleton substrate, CP provides high mechanical strength and good flexibility for PANI/GCP composite paper. Secondly, the formation of PANI wormlike nanorods was regulated by changing the treatment time, and it was proved that the higher the substrate conductivity was, the better the charging and discharging performance of the composite paper was. Thirdly, the micro-morphology and doping degree of PANI chain in situ polymerization were changed by comparing different acid doping, and the inverse relationship between the internal resistance and the ratio performance of the composite film was also explained. The results show that the hydrochloric acid doped PANI/GCP composite paper exhibits excellent pseudo-capacitance properties and high specific capacity (specific capacity is 446.25F/g at 1A/g current density). Good rate performance and cyclic stability (capacity retention rate of 69.8%). (3 after 1000 cycles of charge and discharge). In the MnO_2/M-NCF/GCP composite paper system prepared by coating, CP is used as the skeleton substrate. It provides high mechanical strength and good flexural strength for MnO_2/M-NCF/GCP composite paper. Secondly, by changing the solution solute (sodium sulfate and sulfuric acid), the micromorphology and crystal form of MnO_2 in situ growth on M-NCF/GCP composite paper were regulated. As a result, the MnO_2/M-NCF/GCP composite paper prepared by sulfuric acid showed a relatively high specific capacity (667.5F/g at 1A/g current density). On the other hand, the MnO_2/M-NCF/GCP composite paper prepared by sodium sulfate method has better rate performance and cycle stability (the retention rate is 10% higher after 500 cycles of charge and discharge).
【學(xué)位授予單位】：東華理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM53;TS761.2

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