【作者】 赵辉；

【导师】 王伟；

【作者基本信息】 长安大学 ， 化学工程与技术， 2023， 硕士

【摘要】 世界范围内化石能源的短缺、环境问题的恶化以及对便携式电子设备需求的增加,极大地促进了高效储能系统的发展。近年来,开发具有高能量密度和功率密度、长循环寿命以及良好实用性能的电化学储能技术一直是实验室研究和商业开发的重点。超级电容器和电池作为主流的储能设备,已经被广泛应用于军事、航空、电动汽车和光伏发电等领域。将各种可充电电池和超级电容器组成混合装置,即所谓的超级电容电池,同时结合了超级电容器（高功率密度和长循环寿命）和可充电电池（高能量密度）的技术优点使其成为当下储能领域的一个研究热点。导电聚合物电极材料具有优异的氧化还原活性、导电性能和较低的成本使其成为一种十分有潜力的候选材料,然而传统的导电聚合物材料具有较差的循环性能和较低的能量密度,限制了其实际应用。因此,开发一种具有优异能量密度和循环性能的导电聚合物电极材料,进而提升超级电容电池的储能表现已成为储能领域研究的一个重中之重。本论文通过制备的Schiff基导电聚合物材料作为正极组建了超级电容电池混合装置,并测试了其电化学性能。研究内容如下:（1）以邻联甲苯胺和均苯三甲醛为反应单体,通过一种简单的席夫碱反应一步合成了Schiff基导电聚合物（TBOT）,同时在TBOT导电聚合物合成过程中掺杂不同摩尔比的二茂铁,制备了席夫碱-二茂铁复合电极材料（TBOT-Fc _X,X=0,0.1,0.3,0.5,0.7）。使用XRD、FT-IR、SEM、BET、XPS和TG等表征手段分析了所制备电极材料的形貌、结构等。采用CV、GCD、EIS、循环性能测试等技术研究了所制备的复合材料的电化学性能,并详细探讨了电荷储存机制。二茂铁具有优异的氧化还原活性和化学稳定性,在引入到聚合物骨架后削弱了聚合物网络的π-π堆积结构,提供了更多的离子传输位点,提高了电化学性能。结果表明,TBOT-Fc_0.5的电化学性能在0.5 A g^-1电流密度时,比电容达到151.3 m Ah g^-1,在10 m V s^-1扫速下的电流响应拟合表明TBOT-Fc_0.5的电荷储存机制主要为扩散控制的电池型。所构建的超级电容电池混合设备TBOFc_0.5//AC能量密度达到了46.5 Wh kg^-1,在10 A g^-1电流密度下连续循环充放电5000次后仍具有83.4%的初始比容量。（2）以3,3’-二氨基联苯胺和对苯二甲醛为反应单体一步合成了成具有蜂窝结构的聚席夫碱导电聚合物（SPOP）,同时在SPOP导电聚合物合成过程中掺杂不同摩尔比的二茂铁,制备了席夫碱-二茂铁复合电极材料SPOP-Fc _X,（X=0,0.2,0.4,0.6,0.8）。使用XRD、FT-IR、SEM、TEM、BET、XPS和TG等表征手段分析了所制备电极材料的形貌、结构。采用CV、GCD、EIS、循环性能测试等技术研究了所制备电极材料的电化学性能,并详细探讨了电荷储存机制。测试结果依然表明,三电极体系下,在0.5A g^-1电流密度时,SPOP-Fc_0.4比电容达到102.3 m Ah g^-1,10 A g^-1电流密度时仍保留有最大比容量的60.9%,在10 m V s^-1扫速下的电流响应拟合表明SPOP-Fc_0.4的电荷储存机制主要为扩散控制的电池型。所构建的超级电容电池混合设备SPOP-Fc_0.4//AC,在电流密度为0.5 A g^-1时功率密度为265.3 W kg^-1,能量密度达到了36.3 Wh kg^-1,在10 A g^-1电流密度下连续循环充放电5000次后仍具有69.5%的初始比容量。（3）本节研究通过在席夫碱基导电聚合物-二茂铁复合材料合成过程中引入碳纳米管合成并制备了席夫碱-二茂铁/碳纳米管复合纳米材料（SPOP-Fc _X/CNTs-X,X=2,5,8）。使用XRD、FT-IR、SEM、TEM、BET、XPS和TG等表征手段研究了所制备电极材料的形貌、结构等,采用CV、GCD、EIS、循环性能测试等技术研究了所制备电极材料的电化学性能,并详细探讨了电荷储存机理。碳纳米管的引入提高了席夫碱聚合物在纳米级别上的机械强度从而改善循环性能,并提供了更多的离子传输通道以改善电荷储存性能,二茂铁和碳纳米管的协同作用共同提高了席夫碱导电聚合物的电化学性能。测试结果表明,在0.5 A g^-1电流密度时,SPOP-Fc_0.4/CNTs-5样品表现出201.3m Ah g^-1的最大容量。组装的SPOP-Fc_0.4/CNTs-5//AC超级电容电池,在344.8 W kg^-1下的功率密度表现出了65.9 Wh kg^-1的优异能量密度。此外,循环稳定性测试表明,在10A g^-1的高电流密度下,超级电容电池混合装置在5000次GCD循环后,容量保持率为73.6%。更多还原

【Abstract】 The worldwide shortage of fossil energy,deteriorating environmental issues and the increased demand for convenient electrical devices have significantly facilitated the evolution of high-efficiency energy storage systems.In recent years,the development of electrochemical energy storage technologies with high energy and power densities,long cycle life and good practical performance has been the focus of laboratory research and commercial development.Supercapacitors and batteries have been widely used as mainstream energy storage devices in the military,aviation,electric vehicles and photovoltaic power generation.The combination of various rechargeable batteries and supercapacitors in a hybrid device,the so-called supercapattery,which combines the technical advantages of both supercapacitors（high power density and long cycle life）and rechargeable batteries（high energy density）makes it a hot topic of research in the field of energy storage nowadays.Conductive polymer electrode materials are a promising candidate due to their excellent redox activity,electrical conductivity and low cost,however,conventional conductive polymer materials have poor cycling performance and low energy density,limiting their practical application.Therefore,the development of conducting polymer electrode materials with excellent energy density and cycling performance to enhance the energy storage performance of supercapattery has been a major research priority in the field of energy storage.In this paper,a supercapattery hybrid device was assembled by using Schiff-based conductive polymer material as the positive electrode,and its electrochemical properties were prepared and tested.The research is as follows.（1）Schiff base conductive polymer（TBOT）was synthesized by a simple Schiff base reaction using o-benzotoluidine and homobenzotriazole as the reaction monomers,while different molar ratios of ferrocene were doped to prepare Schiff base-ferrocene composite electrode materials（TBOT-Fc _X,X=0,0.1,0.3,0.5,0.7）during the synthesis of TBOT conductive polymer.The morphology and structure of the prepared electrode materials have been investigated by using XRD,FT-IR,SEM,TEM,BET,XPS and TG.The electrochemical properties of the prepared composites were investigated using techniques such as CV,GCD,EIS and cyclic performance testing,as well as a detailed discussion of the charge storage mechanism.Ferrocene has excellent redox activity and chemical stability.Its synergistic effect with Schiff bases upon introduction into the polymer backbone weakens theπ-πstacking structure of the polymer network,which provides more ion transport sites and improves electrochemical performance.The results show that the electrochemical performance of TBOT-Fc_0.5,particularly at a specific capacitance of 151.3 m Ah g^-1 at a current density of 0.5 A g^-1.The current response fit at a scan rate of 10 m V s^-1 indicates that the charge storage mechanism of TBOT-Fc_0.5 is predominantly of the diffusion-controlled battery-type.In addition,the constructed supercapattery hybrid device(TBOFc_0.5//AC),delivers an energy density of 46.5Wh kg^-1,which still has an initial specific capacity of 83.4%after 5,000 continuous cycles of charging and discharging at a current density of 10 A g^-1.（2）The Schiff-base ferrocene composite electrode materials（SPOP-Fc _X,X=0,0.2,0.4,0.6,0.8）were prepared by doping different molar ratios of ferrocene in the synthesis of SPOP conductive polymers,based on the one-step synthesis of 3,3’-diaminobenzidine and terephthalaldehyde as the reaction monomers to form a poly Schiff-base conductive polymer（SPOP）with a honeycomb structure.The electrochemical properties of the prepared composites were investigated using techniques such as CV,GCD,EIS and cyclic performance testing,as well as a detailed discussion of the charge storage mechanism.The result of the analysis still indicated that the specific capacitance of SPOP-Fc_0.4 reached 102.3 m Ah g^-1 at a current density of 0.5 A g^-1 for the three-electrode system,while 60.9%of the maximum specific capacity was retained at a current density of 10 A g^-1.The fitting of the current response at a scan rate of 10m V s^-1 suggested that the charge storage mechanism of SPOP-Fc_0.4 was mainly of the diffusion-controlled battery-type.The constructed supercapattery hybrid device(SPOP-Fc_0.4//AC),delivered a power density of 265.3 W kg^-1 and an energy density of 36.3 Wh kg^-1 at a current density of 0.5 A g^-1,which still had an initial specific capacity of 69.5%after 5000 consecutive cycles of charging and discharging at a current density of 10 A g^-1.（3）In this section,Schiff base ferrocene/carbon nanotube composite nanomaterials（SPOP-Fc/CNTs-X,X=2,5,8）were synthesized and prepared by introducing carbon nanotubes into the Schiff base ferrocene synthesis process.The electrochemical properties of the prepared composites were investigated using techniques such as CV,GCD,EIS and cyclic performance testing,as well as a detailed discussion of the charge storage mechanism.The introduction of carbon nanotubes increases the mechanical strength of the Schiff base polymer at the nanoscale which improves cycling performance and provides additional ion transport channels for improved charge storage properties.The synergistic effect of ferrocene and carbon nanotubes together improves the electrochemical properties of Schiff-base conducting polymers.The electrochemical properties studies present that the sample（SPOP-Fc0.4/CNTs-5）possesses the maximal specific capacitance（201.3 m Ah g-1）at 0.5 A g-1 and the excellent specific capacity retention（retaining 84.3% of initial capacitance after 5000 GCD cycles at the current density of 10 A g-1）.To evaluate the practicability of electrode materials,the asymmetric supercapattery devices（ASC）were assembled in a configuration of the SPOP-Fc0.4/CNTs-5//activated carbon（AC）.SPOP-Fc0.4/CNTs-5//AC delivered a superb energy density of 65.9 Wh kg-1 with a power density of 344.8 W kg-1 while remaining almost 73.6% of the specific capacitance even after 5000 continuous GCD cycles.更多还原