本文關(guān)鍵詞：納米結(jié)構(gòu)陽極氧化鈦薄膜在超級電容器方面的應(yīng)用　出處：《南京理工大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： TiO_2納米管 可控制備 納米復(fù)合結(jié)構(gòu) 摻雜改性 超級電容器

【摘要】：超級電容器作為一種新型儲能器件,近年來備受關(guān)注。陽極氧化鈦(TiO_2)納米管應(yīng)用于超級電容器領(lǐng)域,具有比表面積大、便于電子傳輸、電位窗口寬等優(yōu)點。然而,TiO_2納米管作為半導(dǎo)體材料,導(dǎo)電性較差,且在可控制備方面仍有很多缺陷。本文旨在研究陽極氧化條件與納米結(jié)構(gòu)TiO_2薄膜形貌參數(shù)之間的關(guān)系,并通過進一步增大比表面積、摻雜改性等方法來改善TiO_2納米管的電化學(xué)性能。首先,通過在常規(guī)電解液中加入乳酸(LA)、聚乙烯醇(PVA)等添加劑的方法,實現(xiàn)TiO_2納米管的快速制備,生長速率最高可達1.9μmmin-1,并保持納米管完整有序的結(jié)構(gòu);在高水含量電解液中制備出海綿狀TiO_2薄膜,提高了TiO_2電極材料的比表面積;研究氧化電壓(電流密度)、電解液溫度、氧化次數(shù)等工藝參數(shù)對TiO_2薄膜形貌的影響,并通過二次氧化及升高氧化電壓的方法改善了 TiO_2納米管的規(guī)整度。其次,通過水熱固-液法(Hydrothermal Solid-Liquid Route,HSLR)及水蒸氣(Hydrothermal Solid-Gas Method,HSGM)處理的方法,制備出TiO_2納米粒子/納米管復(fù)合結(jié)構(gòu),研究處理溫度、蒸氣壓、處理時間等因素對其形貌的影響。結(jié)果表明,復(fù)合結(jié)構(gòu)的形成過程遵循溶解-重結(jié)晶機制,但HSLR處理會導(dǎo)致氧化膜易從基底上脫離,而HSGM處理可保持氧化膜與基底間的結(jié)合力,并顯著增大TiO_2納米管的比表面積。其中,蒸氣壓是控制復(fù)合納米結(jié)構(gòu)形貌的關(guān)鍵因素,加入水量180 μL進行HSGM處理的納米管(HSGM-180)比表面積高達70.8m2g~(-1),是未處理TiO_2納米管的3.16倍。保持蒸氣壓處于飽和狀態(tài),處理20 min便可獲得理想的復(fù)合納米結(jié)構(gòu)(HSGM-20min)。再次,將TiO_2納米粒子/納米管復(fù)合結(jié)構(gòu)在Ar、NH3氣氛中進行退火改性,進一步提高其電化學(xué)性能。實驗發(fā)現(xiàn),NH3退火雖可大幅提高TiO_2電極材料的比電容,但會導(dǎo)致其電化學(xué)性能不穩(wěn)定,倍率特性、循環(huán)穩(wěn)定性較差;而Ar退火可生成氧空位,降低電極材料的內(nèi)阻,Ar退火的HSGM-20min比電容可達76.12mFcm~(-2),是空氣退火的未處理TiO_2納米管的5.49倍,且循環(huán)2000圈后比電容仍維持在初始值的87.7%。最后,在含有金屬離子的溶液中,通過電化學(xué)恒壓或恒流摻雜的方法對TiO_2納米管進行摻雜改性。結(jié)果表明,在非水溶液中Al~(3+)可嵌入TiO_2的晶格結(jié)構(gòu),克服H摻雜循環(huán)穩(wěn)定性較差的缺點,并生成更多的氧空位,而Fe~(3+)及Cu_(2+)則無法嵌入TiO_2的結(jié)構(gòu)中。-3 mA cm~(-2)下恒流Al~(3+)摻雜TiO_2納米管的比電容為8.41 mF cm~(-2),是未摻雜納米管的3.77倍,循環(huán)2000次后電容維持率仍高達93.4%。
[Abstract]:As a new type of energy storage devices, supercapacitors have attracted much attention in recent years. Anodic titanium oxide TiO-2) nanotubes are used in the field of supercapacitors, which have large specific surface area and are convenient for electronic transmission. However, TiO2 nanotubes, as semiconductor materials, have poor electrical conductivity. And there are still many defects in the controllable preparation. The purpose of this paper is to study the relationship between the anodic oxidation conditions and the morphology parameters of nanostructured TiO_2 films, and to further increase the specific surface area. The electrochemical properties of TiO_2 nanotubes were improved by doping and modifying. Firstly, additives such as lactic acid and polyvinyl alcohol were added into the conventional electrolyte. The rapid preparation of TiO_2 nanotubes was achieved, the growth rate was up to 1.9 渭 m min-1, and the structure of the nanotubes remained intact and ordered. Spongy TiO_2 thin films were prepared in high water content electrolyte, which improved the specific surface area of TiO_2 electrode materials. The effects of oxidation voltage (current density, electrolyte temperature, oxidation times) on the morphology of TiO_2 films were studied. The regularity of TiO_2 nanotubes was improved by secondary oxidation and increasing oxidation voltage. Secondly. Hydrothermal Solid-Liquid Route was obtained by hydrothermal solid-liquid method. HSLR) and water vapor Solid-Gas method (HSLR). The composite structure of TiO_2 nanoparticles / nanotubes was prepared, and the effects of treatment temperature, vapor pressure and treatment time on the morphology of the nanotubes were studied. The formation of the composite structure follows the mechanism of dissolution-recrystallization, but HSLR treatment can easily separate the oxide film from the substrate, while the HSGM treatment can maintain the adhesion between the oxide film and the substrate. The vapor pressure is the key factor to control the morphology of composite nanostructures. The specific surface area of HSGM-180 was 70.8 m ~ (2) g ~ (-1) in HSGM treated with 180 渭 L water. It is 3.16 times as high as that of untreated TiO_2 nanotubes. The ideal composite nanostructures can be obtained after 20 minutes of treatment by keeping the vapor pressure in saturated state. The composite structure of TiO_2 nanoparticles / nanotubes was annealed in ArnNH _ 3 atmosphere to further improve its electrochemical performance. NH3 annealing can increase the specific capacitance of TiO_2 electrode material, but it will lead to the instability of electrochemical performance, the rate characteristics and the poor cycle stability. The oxygen vacancy can be formed by ar annealing, and the HSGM-20min specific capacitance of ar annealing can reach 76.12 mFcm-2). It is 5.49 times that of the untreated TiO_2 nanotubes annealed in air, and the specific capacitance is still 87.7% of the initial value after 2000 cycles. Finally, in the solution containing metal ions. The doping modification of TiO_2 nanotubes was carried out by electrochemical constant voltage or constant current doping. The results show that Al~(3 can be embedded in the lattice structure of TiO_2 in non-aqueous solution. The shortcomings of H doping cycle stability are overcome and more oxygen vacancies are generated. Fe~(3) and Cu_(2) could not be embedded in the structure of TiO_2. The specific capacitance of doped TiO_2 nanotubes is 8.41 MF / cm ~ (-2). It is 3.77 times as high as that of undoped nanotubes, and the capacitance maintenance rate is as high as 93.4after 2000 cycles.
【學(xué)位授予單位】：南京理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB383.2;TM53

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