用于超级电容器柔性高导电纤维素复合纸的制备与性能
发布时间：2018-12-11 23:55
【摘要】：近年来,柔性超级电容器因其储能效率高、循环寿命长、环境友好以及良好的可植入性等优点,越来越受到了国内外研究者的强烈关注和广泛研究。但其储能性能主要受电极材料的影响,而纤维素在自然界中储量非常丰富,它在能源储存设备中的应用前景诱人无比。因此本论文从制备柔性高导电的纤维素复合纸出发,探究其用作柔性超级电容器电极材料时的性能,并初步考察了将其应用于柔性设备的可行性。同时,较系统的研究了不同反应条件对复合纸电化学性能的影响。本论文的研究内容主要包括以下三个部分:(1)、在抽滤制得的PANI/CNF/GNP复合纸体系中,CNF除了能增强CNF/GNP复合纸的力学强度和柔韧性,还可以降低PANI蠕虫状纳米棒的直径,并改善了PANI链原位聚合时的掺杂程度,从而提高了超级电容器的比容量。当CNF占复合基底的负载量为20 wt%时,PANI杂化纸在电流密度为1A/g显示出最大比电容,421.5F/g。并且该复合纸在倍率性能与能量/功率密度平衡性能方面也表现的相当不错。由PANI复合纸组装得到的全固态超级电容器在反复弯折1000次以上以后,仍能表现出优异的电化学性能和比电容保容率。(2)、在喷覆法制得的PANI/GCP复合纸体系中,CP作为骨架基底,为PANI/GCP复合纸提供了很高的力学强度及很好的柔韧性。其次,通过改变喷金处理时间,调控了PANI蠕虫状纳米棒的形成,并证明基底导电性越高,复合纸充放电的倍率性能越佳。再次,通过比较不同酸掺杂,改变了PANI链原位聚合时的微观形貌和掺杂程度,并说明复合膜内阻与倍率性能的反比关系。结果是,喷金处理15min、盐酸掺杂的PANI/GCP复合纸表现出优异的赝电容特性、高的比容量(在1A/g电流密度下比容量为446.25F/g)、良好的倍率性能及循环稳定性(循环充放电1000次后保容率为69.8%)。(3)、在涂覆法制得的MnO_2/M-NCF/GCP复合纸体系中,CP作为骨架基底,为MnO_2/M-NCF/GCP复合纸提供了很高的力学强度及很好的柔韧弯折性。其次,通过改变溶液溶质(硫酸钠和硫酸),调控了MnO_2在M-NCF/GCP复合纸上原位生长的微观形貌与晶型。结果是,硫酸法制得的MnO_2/M-NCF/GCP复合纸显示出了相对更高的比容量(在1A/g电流密度下比容量为667.5F/g),而硫酸钠法制得的MnO_2/M-NCF/GCP复合纸则具有相对更好的倍率性能和循环稳定性(循环充放电500次后保容率高出为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).
【学位授予单位】：东华理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM53;TS761.2
本文编号：2373471
[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).
【学位授予单位】：东华理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM53;TS761.2
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