本文選題：銳鈦礦 + 介孔��； 參考：《天津大學》2015年博士論文

【摘要】：隨著不可再生能源的枯竭和環(huán)境問題的惡化,開發(fā)利用清潔可再生能源迫在眉睫。染料敏化太陽能電池有效的將太陽能轉(zhuǎn)化成電能。鋰離子二次電池有效的儲存電能。介孔TiO_2具有孔體積大、孔徑可調(diào)、比表面積高、成本低廉、結(jié)構(gòu)穩(wěn)定、環(huán)境友好和電子和光學性質(zhì)優(yōu)異等優(yōu)點,用作染料敏化太陽能電池光陽極材料,增加染料的化學吸附量,提高太陽能轉(zhuǎn)化效率;用作鋰離子電池負極材料,增加電極與電解質(zhì)的接觸面積、縮短鋰離子的擴散路徑,而提高儲能能力。本文旨在優(yōu)化和開創(chuàng)介孔TiO_2的制備方法、制備新形貌介孔TiO_2、研究介孔TiO_2的形成機制及探索介孔TiO_2在鋰離子二次電池和染料敏化太陽電池中的應用。本文,以十六烷基胺為結(jié)構(gòu)導向劑,通過溶膠-凝膠和溶劑熱兩步法及空氣下高溫鍛燒,制備出單分散亞微米銳鈦礦型介孔球形TiO_2。系統(tǒng)探索了反應溫度和陳化時間,優(yōu)化了制備方法;介孔球形TiO_2用作鋰離子電池負極材料,1 C(1C=170 mA g-1)下,200次循環(huán)后放電比容量仍有146.4 mA h g-1,容量保持率為85.1%;用作染料敏化太陽能電池光陽極,獲得η=6.25%的光電轉(zhuǎn)化效率。通過對以十六烷基胺為結(jié)構(gòu)導向劑、溶膠-凝膠和溶劑熱兩步法制得的TiO_2,在氬氣中高溫將有機物原位碳化后,制備出單分散亞微米銳鈦礦型介孔球形TiO_2/C。采用多種測試手段表明構(gòu)成介孔球形TiO_2/C的基本顆粒表面包覆了一層約1.5 nm厚的碳膜,碳含量為1.1 wt%。用作鋰離子電池負極材料,1 C和10C下,介孔球形TiO_2/C的放電比容量分別為~180 mA h g-1和110 mA h g-1;而介孔球形TiO_2的放電比容量僅分別為~170 mA h g-1和~97 mA h g-1。開創(chuàng)了一步溶劑熱法,以十六烷基胺為結(jié)構(gòu)導向劑,快速、有效的制備單分散銳鈦礦型介孔球形Ti O_2。用作鋰離子電池負極材料,1 C循環(huán)50次后,單分散介孔球形TiO_2仍有約150 mA h g-1的比容量,高于商品化25 nm TiO_2納米粒子110 mA h g-1的比容量。將方法擴展至制備球/片結(jié)構(gòu)Li_4Ti_5O_(12),20 C(1 C=175 mA g-1)循環(huán)500次,比容量仍在100 mA h g-1以上。不加添加劑的情況下,甲醇和鈦酸丁酯在常溫、常壓下反應得到的中間體TBM作為原位模板在空氣中水解后,通過“原位轉(zhuǎn)化機理”制備出厚度為13-30nm的單顆粒層銳鈦礦型介孔片狀TiO_2。用作鋰離子電池負極材料,在5 C下,經(jīng)過4000次的充放電后,片狀介孔TiO_2仍有~60%的容量保持率。使用溶劑熱方法,在甲醇-鈦酸丁酯體系條件中,首次制備出了新形貌三維銳鈦礦型介孔梭形介晶TiO_2,并提出了一種方向附著生長機理。用作鋰離子電池負極材料,1 C下,1000次的循環(huán)中,其可逆比容量保持在110 mA h g-1。
[Abstract]:With the depletion of non-renewable energy and the deterioration of environmental problems, it is urgent to develop and utilize clean and renewable energy. Dye-sensitized solar cells effectively convert solar energy into electricity. Lithium ion secondary battery can store electric energy effectively. Mesoporous TiO2 has the advantages of large pore volume, adjustable pore size, high specific surface area, low cost, stable structure, environment-friendly and excellent electronic and optical properties. It is used as photoanode material for dye-sensitized solar cells to increase the amount of chemisorption of dyes. It can be used as anode material of lithium ion battery, increase the contact area between electrode and electrolyte, shorten the diffusion path of lithium ion, and improve the energy storage ability. The purpose of this paper is to optimize and create the preparation method of mesoporous TiOs _ 2, to prepare new mesoporous TiO-2, to study the formation mechanism of mesoporous TiO-2 and to explore the application of mesoporous TiO-1 in lithium ion secondary battery and dye sensitized solar cell. In this paper, using hexadecylamine as the structure guide, the monodisperse submicron mesoporous spherical TIO _ 2 was prepared by sol-gel and solvothermal two-step method and high temperature calcination in air. The reaction temperature and aging time were systematically explored and the preparation method was optimized. Mesoporous spherical TiO2 was used as anode material for lithium ion batteries. After 200 cycles, the specific discharge capacity was still 146.4 Ma 路g ~ (-1), and the capacity retention was 85.1%. As a dye sensitized photoanode for solar cells, the photoconversion efficiency of 畏 ~ (6.25%) was obtained. By using hexadecylamine as structure guide, sol-gel and sol-thermal two-step synthesis of TIO _ 2s, the monodisperse submicron mesoporous TIO _ 2 / C was prepared by in-situ carbonization of organic matter at high temperature in argon. The surface of the basic particles of mesoporous tio _ 2 / C is coated with a carbon film about 1.5 nm thick, and the carbon content is 1.1 wt. The discharge specific capacities of mesoporous TiO-2 / C and mesoporous spherical TiO-2 are 180mA hg-1 and 110mA hg-1, respectively, while mesoporous spherical TiO-2 discharge capacity is only 170mA hg-1 and 97mA hg-1, respectively, at 10C and 10C for lithium-ion batteries. A one-step solvothermal method was developed to prepare monodisperse anatase spherical mesoporous TIO _ (2) with hexadecylamine as structure guide. After 50 cycles as anode material for lithium ion battery, the specific capacity of monodisperse mesoporous TiO-2 is still about 150mAhg-1, which is higher than that of commercial 25nm TiO-2 nanoparticles (110mAhg-1). The method was extended to the preparation of Li4Ti5O12 / 20C (1CN175mAg-1) cycle with a specific capacity of more than 100mA / g ~ (-1). The intermediate TBM obtained by reaction of methanol with butyl titanate at room temperature and atmospheric pressure was hydrolyzed in air as an in-situ template without additive. In situ conversion mechanism was used to prepare single granular layer anatase mesoporous tio _ s _ 2s with thickness of 13-30nm. When used as anode material for lithium ion batteries, after 4000 charges and discharges at 5 C, the volume retention of TiO-2 in sheet mesoporous cells is still 60%. A new 3D anatase mesoporous TiO-2 was prepared by solvothermal method in methanol-butyl titanate system for the first time, and a directional adhesion growth mechanism was proposed. The reversible specific capacity of the cathode material for lithium ion battery kept at 110mA h g -1 in 1000 cycles at 1C.
【學位授予單位】：天津大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：TQ134.11
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本文編號：2075493