金屬基原位生長薄膜電極材料的制備及電化學性能研究
發(fā)布時間：2019-01-08 19:00
【摘要】：隨著當代社會的高速發(fā)展，能源材料已經(jīng)越來越重要，學者們將大量的注意力放在可以快速充放電且儲能量超高、性質穩(wěn)定的材料研究上。電化學儲能材料在近些年來研究最為廣泛，從最初的鎳-鎘電池發(fā)展到優(yōu)化儲電性能的鋰離子電池直到如今的充電時間短且使用壽命長的電化學電容器，也稱為超級電容器。這類電容器由三大類材料組成：碳材料、導電聚合物材料以及金屬氧化物/硫化物材料。根據(jù)不同材料所具備的物理化學性質不同，所組成的電極材料的能量密度、循環(huán)壽命等性質也有所不同。目前已有許多超級電容器材料應用在電動汽車、智能設備、電力系統(tǒng)以及太陽能產(chǎn)品等日常生活領域。從儲能機理上可以將超級電容器分為兩種，前一個由活性炭材料、碳纖維、碳納米管等碳材料電極組成的電容器稱為雙電層電容器，而后一由金屬氧化物和聚合物電極材料組成的電容器稱為法拉第贗電容器。 在本論文中我們對兩種類型的電容器都進行了研究，所制備的四種電極材料分別有泡沫鈦基PPy電極材料、泡沫鎳基PPy/Ag復合電極材料、泡沫鎳基C薄膜電極材料以及銅箔基CuS電極材料，我們所制備的四種電極材料特點都是在不添加任何黏合劑的情況下，利用原位生長法在金屬基底上制備出導電的納微米薄膜材料，整個過程不會引入其它雜質。經(jīng)過掃描電子顯微鏡（SEM）、透射電子顯微鏡（TEM）、X射線粉末衍射儀（XRD）、紫外可見光譜儀（UV）以及紅外可見光譜儀（FTIR）這些儀器對電極材料的表面進行形貌的表征和組分的分析，并利用電化學工作站的循環(huán)伏安法（CV）、恒電流充放電法（GCD）以及循環(huán)壽命測試對電極的電化學性質進行表征，文中我們詳細對比了不同時間、不同濃度下制備的電極材料的形貌與電化學性能，通過討論得到性質最優(yōu)的電極材料。比如生長時間為12h的泡沫鈦基PPy電極在電流密度為1A g-1時比電容高達855F g-1；反應時間為7h的泡沫鎳基PPy/Ag電極在1Ag-1時比電容為493Fg-1；利用葡萄糖水熱法原位合成的C修飾泡沫鎳電極的電容性能和循環(huán)壽命較同類型的碳材料要高很多；反應時間為18h的0.1mol L-1CuSO4和Na2S2O3溶液中制備的銅箔基CuS薄膜電極的比電容值高達1093F g-1（1Ag-1）。作為主要的制備手段，，原位生長法是本論文的特點，簡單的操作環(huán)境和方便的制備過程是超級電容器領域新的發(fā)展方向。
[Abstract]:With the rapid development of modern society, energy materials have become more and more important. Scholars have paid a lot of attention to the research of materials which can charge and discharge rapidly and have super high energy storage and stable properties. Electrochemical energy storage materials have been widely studied in recent years, from the initial Ni-CD battery to the lithium ion battery with optimized storage performance to electrochemical capacitors with short charging time and long service life, also known as supercapacitors. These capacitors consist of three main types of materials: carbon materials, conductive polymer materials, and metal oxide / sulfide materials. According to the physical and chemical properties of different materials, the energy density and cycle life of the electrode materials are different. At present, many supercapacitor materials have been used in electric vehicles, smart devices, power systems, solar products and other areas of daily life. In terms of energy storage mechanism, supercapacitors can be divided into two types. The former capacitor composed of activated carbon materials, carbon fibers, carbon nanotubes and other carbon material electrodes is called double layer capacitors. Then a capacitor composed of metal oxide and polymer electrode material is called Faraday pseudo-capacitor. In this thesis, we studied two types of capacitors. The four kinds of electrode materials are titanium foam PPy electrode material, nickel foam PPy/Ag composite electrode material. Foamed nickel based C thin film electrode materials and copper foil based CuS electrode materials, the four kinds of electrode materials we prepared are all characterized by the addition of no binder. In situ growth method was used to fabricate conductive nanometer-thin films on metal substrates without introducing other impurities in the whole process. Scanning electron microscope (SEM), transmission electron microscope (TEM), X ray powder diffractometer (XRD), Ultraviolet visible spectrometer (UV) and infrared visible spectrometer (FTIR) were used to characterize the surface morphology of electrode materials and analyze their components. The electrochemical workstation was used for cyclic voltammetry (CV),). The electrochemical properties of the electrode were characterized by constant current charge-discharge method (GCD) and cyclic life test. In this paper, the morphology and electrochemical properties of the electrode materials prepared at different time and different concentration were compared in detail. The optimal electrode material is obtained by discussion. For example, when the current density is 1A g ~ (-1), the specific capacitance of foamed titanium based PPy electrode is up to 855 F g ~ (-1), and the specific capacitance of foamed nickel based PPy/Ag electrode with 7 h reaction time is 493Fg-1 at 1Ag-1, when the current density is 1A g ~ (-1). The capacitance and cycle life of C-modified nickel foam electrode prepared by in-situ synthesis of glucose hydrothermal method are much higher than those of the same type of carbon materials. The specific capacitance of copper foil based CuS thin film electrode prepared in the solution of 0.1mol L-1CuSO4 and Na2S2O3 for 18 h was 1093 F g ~ (-1) (1Ag-1). As the main preparation method, in situ growth method is the characteristic of this paper. The simple operating environment and convenient preparation process are the new development direction in the field of supercapacitor.
【學位授予單位】：吉林大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：O646;TB383.2
本文編號：2405000
[Abstract]:With the rapid development of modern society, energy materials have become more and more important. Scholars have paid a lot of attention to the research of materials which can charge and discharge rapidly and have super high energy storage and stable properties. Electrochemical energy storage materials have been widely studied in recent years, from the initial Ni-CD battery to the lithium ion battery with optimized storage performance to electrochemical capacitors with short charging time and long service life, also known as supercapacitors. These capacitors consist of three main types of materials: carbon materials, conductive polymer materials, and metal oxide / sulfide materials. According to the physical and chemical properties of different materials, the energy density and cycle life of the electrode materials are different. At present, many supercapacitor materials have been used in electric vehicles, smart devices, power systems, solar products and other areas of daily life. In terms of energy storage mechanism, supercapacitors can be divided into two types. The former capacitor composed of activated carbon materials, carbon fibers, carbon nanotubes and other carbon material electrodes is called double layer capacitors. Then a capacitor composed of metal oxide and polymer electrode material is called Faraday pseudo-capacitor. In this thesis, we studied two types of capacitors. The four kinds of electrode materials are titanium foam PPy electrode material, nickel foam PPy/Ag composite electrode material. Foamed nickel based C thin film electrode materials and copper foil based CuS electrode materials, the four kinds of electrode materials we prepared are all characterized by the addition of no binder. In situ growth method was used to fabricate conductive nanometer-thin films on metal substrates without introducing other impurities in the whole process. Scanning electron microscope (SEM), transmission electron microscope (TEM), X ray powder diffractometer (XRD), Ultraviolet visible spectrometer (UV) and infrared visible spectrometer (FTIR) were used to characterize the surface morphology of electrode materials and analyze their components. The electrochemical workstation was used for cyclic voltammetry (CV),). The electrochemical properties of the electrode were characterized by constant current charge-discharge method (GCD) and cyclic life test. In this paper, the morphology and electrochemical properties of the electrode materials prepared at different time and different concentration were compared in detail. The optimal electrode material is obtained by discussion. For example, when the current density is 1A g ~ (-1), the specific capacitance of foamed titanium based PPy electrode is up to 855 F g ~ (-1), and the specific capacitance of foamed nickel based PPy/Ag electrode with 7 h reaction time is 493Fg-1 at 1Ag-1, when the current density is 1A g ~ (-1). The capacitance and cycle life of C-modified nickel foam electrode prepared by in-situ synthesis of glucose hydrothermal method are much higher than those of the same type of carbon materials. The specific capacitance of copper foil based CuS thin film electrode prepared in the solution of 0.1mol L-1CuSO4 and Na2S2O3 for 18 h was 1093 F g ~ (-1) (1Ag-1). As the main preparation method, in situ growth method is the characteristic of this paper. The simple operating environment and convenient preparation process are the new development direction in the field of supercapacitor.
【學位授予單位】：吉林大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：O646;TB383.2
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本文編號：2405000
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