摻雜聚吡咯及其復合材料的電化學合成與電化學性能研究
發(fā)布時間：2019-03-09 12:13
【摘要】：面對目前越來越嚴峻的能源問題,人們急于尋求一種高效的儲能裝置來實現(xiàn)能量的有效利用。超級電容器的出現(xiàn)改變了二次電池功率密度低和普通電容器能量密度低的限制,成為各領域的研究熱點。電極材料的選擇決定著超級電容器性能的優(yōu)劣。導電高分子聚吡咯(PPy)由于具有成本低、合成方法簡單、氧化電位低和穩(wěn)定性好等特點,因而是超級電容器中研究較為普遍的一種電極材料。本征態(tài)聚吡咯導電性較差,但其處于摻雜態(tài)時導電性提高,電化學活性增強。為了優(yōu)化聚吡咯的電化學性能,本文通過循環(huán)伏安法在酸性體系中合成了摻雜聚吡咯和多壁碳納米管改性的摻雜聚吡咯電極材料,采用傅里葉變換紅外光譜(FT-IR)、X射線衍射(XRD)、場發(fā)射掃描電鏡(SEM)、透射電子顯微鏡(TEM)和X射線光電子能譜(XPS)對其結構和形貌進行表征,并通過循環(huán)伏安(CV)、恒流充放電(GCD)、交流阻抗(EIS)等測試方法對其電化學性能進行了研究。主要內容如下:(1)分別以H_2SO_4和HNO_3作為聚合電解液,通過循環(huán)伏安法在不銹鋼網上合成了質子酸摻雜的聚吡咯(PPy)。研究了其微觀形貌、結構和電化學性能。結果表明,PPy/HNO_3電極材料具有疏松多孔的珊瑚狀結構,而PPy/H_2SO_4呈現(xiàn)出菜花狀結構;電流密度為5 m A cm~(-2)時,在0.5 mol L~(-1)(M)H_2SO_4電解液中,PPy/0.5M HNO_3比電容為596 F g~(-1),循環(huán)1000次后比電容保持了95.9%,在1.0 M HNO_3電解液中,PPy/0.1 M H_2SO_4比電容為442 F g~(-1),循環(huán)1000次后比電容保持了70.6%,相比之下,HNO_3摻雜后的聚吡咯電極材料表現(xiàn)出更優(yōu)異的電化學性能。(2)在硫酸介質中以吡咯為單體,以三種不同過渡金屬離子(Ni~(2+)、Fe~(2+)和Cu~(2+))為摻雜劑,采用循環(huán)伏安法在不銹鋼網上合成了三種過渡金屬離子摻雜的聚吡咯電極材料。研究了其電化學性能,并探討了過渡金屬離子的性質對聚吡咯性能的影響。結果表明,電流密度為5 m A cm~(-2)時,在1.0 M HNO_3電解液中,PPy/0.1M Ni~(2+)、PPy/0.5 M Fe~(2+)和PPy/0.1 M Cu~(2+)電極材料的比電容分別為517、679和764F g~(-1),循環(huán)1000次后比電容分別保持了80.5%、82.7%和83.8%。過渡金屬離子半徑越小,離子勢越大,電極材料的比電容越大。(3)在上述(2)的基礎上,采用混酸處理的多壁碳納米管(MWCNTs)浸漬不銹鋼網,并用循環(huán)伏安法在其上制備了Cu~(2+)摻雜的聚吡咯/多壁碳納米管復合電極材料。系統(tǒng)研究了碳納米管的引入對聚吡咯電化學性能的影響。結果表明,PPy與MWCNTs形成了一種核-殼結構的復合材料,混酸處理MWCNTs回流時間為1h、沉積電解液中多壁碳納米管的加入量為0.8%時,復合材料的比電容為1269 F g~(-1),在掃速為50 m V s~(-1)下經過1000次循環(huán)后的比電容保持率為88.1%。
[Abstract]:In the face of more and more serious energy problems, people are eager to seek an efficient energy storage device to realize the effective utilization of energy. The emergence of supercapacitors has changed the limitations of low power density of secondary batteries and low energy density of ordinary capacitors, and has become a research hotspot in various fields. The selection of electrode material determines the performance of supercapacitor. Conductive polymer polypyrrole (PPy) is a widely used electrode material in supercapacitors due to its low cost, simple synthesis method, low oxidation potential and good stability. The intrinsic state of polypyrrole is poor in conductivity, but in the doped state, the conductivity and electrochemical activity of polypyrrole are enhanced. In order to optimize the electrochemical performance of polypyrrole, doped polypyrrole and multi-walled carbon nanotubes modified polypyrrole electrode materials were synthesized by cyclic voltammetry in acidic system. Fourier transform infrared spectroscopy (FT-IR) was used. X-ray diffraction (XRD), field emission scanning electron microscopy (SEM),) transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure and morphology of the (GCD),. The structure and morphology were characterized by cyclic voltammetry (CV), constant current charge-discharge (GCD),. The electrochemical properties were studied by AC impedance (EIS) and other methods. The main contents are as follows: (1) the protonic acid doped polypyrrole (PPy). Was synthesized on stainless steel by cyclic voltammetry using H_2SO_4 and HNO_3 as polymerization electrolyte respectively. The microstructure, structure and electrochemical properties were studied. The results show that the PPy/HNO_3 electrode material has a porous coral-like structure, while PPy/H_2SO_4 has a cauliflower-like structure. When the current density is 5 Ma cm~ (- 2), the specific capacitance of PPy/0.5M HNO_3 in 0.5 mol L ~ (- 1) (M) H_2SO_4 electrolyte is 596 F 路g ~ (- 1), and the specific capacitance is 95.9% after 1000 cycles. In 1.0m HNO_3 electrolyte, the specific capacitance of PPy/0.1 M H_2SO_4 is 442F g ~ (- 1), and the specific capacitance is 70.6% after 1000 cycles. The polypyrrole electrode materials doped with HNO_3 exhibited better electrochemical properties. (2) using pyrrole as monomer in sulfuric acid medium, three different transition metal ions (Ni~ (2), Fe~ (2) and Cu~ (2) were used as dopants. Three transition metal ion doped polypyrrole electrode materials were synthesized by cyclic voltammetry on stainless steel net. The electrochemical properties of polypyrrole were studied and the effects of transition metal ions on polypyrrole were investigated. The results show that when the current density is 5 Ma cm~ (- 2), in 1.0m HNO_3 electrolyte, PPy/0.1M Ni~ (2), The specific capacitance of PPy/0.5 M Fe~ (2) and PPy/0.1 M Cu~ (2) electrode materials is 517679 and 764 F g ~ (- 1), respectively. After 1000 cycles, the specific capacitance remains 80.5%, 82.7% and 83.8% respectively. The smaller the radius of transition metal ions and the larger the neutron potential, the larger the specific capacitance of the electrode material. (3) on the basis of the above (2), multi-walled carbon nanotubes (MWCNTs) impregnated stainless steel mesh with mixed acid treatment. Cu~ (2)-doped polypyrrole / multi-walled carbon nanotubes composite electrode materials were prepared by cyclic voltammetry. The effect of carbon nanotubes on the electrochemical properties of polypyrrole was systematically studied. The results showed that PPy and MWCNTs formed a core-shell structure composite. The refluxing time of MWCNTs treated with mixed acid was 1 h, and the specific capacitance of the composite was 1269 F g ~ (- 1) when the amount of multi-walled carbon nanotubes in the deposition electrolyte was 0.8%, and the specific capacitance of the composite was 1269 F 路g ~ (- 1). The specific capacitance retention rate is 88.1% after 1000 cycles at a sweep rate of 50 MV Ss ~ (- 1).
【學位授予單位】：蘭州理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O633.5;TB332;O646
本文編號：2437439
[Abstract]:In the face of more and more serious energy problems, people are eager to seek an efficient energy storage device to realize the effective utilization of energy. The emergence of supercapacitors has changed the limitations of low power density of secondary batteries and low energy density of ordinary capacitors, and has become a research hotspot in various fields. The selection of electrode material determines the performance of supercapacitor. Conductive polymer polypyrrole (PPy) is a widely used electrode material in supercapacitors due to its low cost, simple synthesis method, low oxidation potential and good stability. The intrinsic state of polypyrrole is poor in conductivity, but in the doped state, the conductivity and electrochemical activity of polypyrrole are enhanced. In order to optimize the electrochemical performance of polypyrrole, doped polypyrrole and multi-walled carbon nanotubes modified polypyrrole electrode materials were synthesized by cyclic voltammetry in acidic system. Fourier transform infrared spectroscopy (FT-IR) was used. X-ray diffraction (XRD), field emission scanning electron microscopy (SEM),) transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure and morphology of the (GCD),. The structure and morphology were characterized by cyclic voltammetry (CV), constant current charge-discharge (GCD),. The electrochemical properties were studied by AC impedance (EIS) and other methods. The main contents are as follows: (1) the protonic acid doped polypyrrole (PPy). Was synthesized on stainless steel by cyclic voltammetry using H_2SO_4 and HNO_3 as polymerization electrolyte respectively. The microstructure, structure and electrochemical properties were studied. The results show that the PPy/HNO_3 electrode material has a porous coral-like structure, while PPy/H_2SO_4 has a cauliflower-like structure. When the current density is 5 Ma cm~ (- 2), the specific capacitance of PPy/0.5M HNO_3 in 0.5 mol L ~ (- 1) (M) H_2SO_4 electrolyte is 596 F 路g ~ (- 1), and the specific capacitance is 95.9% after 1000 cycles. In 1.0m HNO_3 electrolyte, the specific capacitance of PPy/0.1 M H_2SO_4 is 442F g ~ (- 1), and the specific capacitance is 70.6% after 1000 cycles. The polypyrrole electrode materials doped with HNO_3 exhibited better electrochemical properties. (2) using pyrrole as monomer in sulfuric acid medium, three different transition metal ions (Ni~ (2), Fe~ (2) and Cu~ (2) were used as dopants. Three transition metal ion doped polypyrrole electrode materials were synthesized by cyclic voltammetry on stainless steel net. The electrochemical properties of polypyrrole were studied and the effects of transition metal ions on polypyrrole were investigated. The results show that when the current density is 5 Ma cm~ (- 2), in 1.0m HNO_3 electrolyte, PPy/0.1M Ni~ (2), The specific capacitance of PPy/0.5 M Fe~ (2) and PPy/0.1 M Cu~ (2) electrode materials is 517679 and 764 F g ~ (- 1), respectively. After 1000 cycles, the specific capacitance remains 80.5%, 82.7% and 83.8% respectively. The smaller the radius of transition metal ions and the larger the neutron potential, the larger the specific capacitance of the electrode material. (3) on the basis of the above (2), multi-walled carbon nanotubes (MWCNTs) impregnated stainless steel mesh with mixed acid treatment. Cu~ (2)-doped polypyrrole / multi-walled carbon nanotubes composite electrode materials were prepared by cyclic voltammetry. The effect of carbon nanotubes on the electrochemical properties of polypyrrole was systematically studied. The results showed that PPy and MWCNTs formed a core-shell structure composite. The refluxing time of MWCNTs treated with mixed acid was 1 h, and the specific capacitance of the composite was 1269 F g ~ (- 1) when the amount of multi-walled carbon nanotubes in the deposition electrolyte was 0.8%, and the specific capacitance of the composite was 1269 F 路g ~ (- 1). The specific capacitance retention rate is 88.1% after 1000 cycles at a sweep rate of 50 MV Ss ~ (- 1).
【學位授予單位】：蘭州理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O633.5;TB332;O646
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