Ti和TiN基底上陽極氧化膜的制備、摻雜及電化學(xué)性能研究
發(fā)布時(shí)間：2018-11-29 12:43
【摘要】：金屬鈦的陽極氧化膜分為兩種,TiO_2納米管(多孔膜)和致密膜。TiO_2納米管具有有序的多孔結(jié)構(gòu)、大比表面積,可作為超級電容器的電極材料。盡管TiO_2納米管已研究多年,但因Ti片上制備的TiO_2納米管易剝離、電化學(xué)性能較差等缺點(diǎn)使應(yīng)用受限。因此,本文首先對比了 Ti絲、Ti片兩種基底,在不同陽極氧化條件下,制備的TiO_2納米管形貌和電化學(xué)性能的差異。其次,為了提高TiO_2納米管的比電容,研究了 N摻雜的TiO_2納米管的兩種制備方法(一步法、二步法),并與未摻雜的TiO_2納米管的性能相比較。再次,為了簡化摻雜工藝,直接在沉積有TiN涂層的Ti片(TiN-Ti)基底上進(jìn)行不同條件下的陽極氧化,得到電化學(xué)性能更好的含N的TiO_2納米管,為超級電容器電極材料的制備提供指導(dǎo)。最后,盡管TiO_2致密膜可作為電容器的電介質(zhì)材料,但與TiO_2納米管相比,TiO_2致密膜卻很少有人研究。因此,本文還研究了不同基底上、不同條件下致密膜的制備,并對比了致密膜的漏電流及不同頻率下的比電容和損耗。全文的主要工作如下:首先,由于Ti絲上制備的TiO_2納米管與基底結(jié)合力較好,因此系統(tǒng)研究了不同陽極氧化條件下Ti絲上制備的TiO_2納米管的形貌與電化學(xué)性能,并與Ti片上制備的TiO_2納米管相比較。實(shí)驗(yàn)表明,NH_4F濃度越大、溫度越高,Ti絲上制備出的TiO_2納米管的管長越長、比電容越大。其次,分別使用一步法及二步法在Ti片上制備出N摻雜的納米管。一步法是將Ti片在含尿素的電解液中氧化生成N摻雜的納米管,二步法是將常規(guī)制備出的TiO_2納米管在氨水或尿素溶液中浸漬。兩種方法制備出的N摻雜的TiO_2納米管均獲得更大的比電容,但是浸漬后的納米管與基底的結(jié)合力較差,因此一步法更具有優(yōu)勢。另外,將TiN-Ti在常規(guī)電解液中陽極氧化制備出含N的TiO_2納米管,研究了氧化時(shí)間及溫度對納米管的影響。與相同時(shí)間下Ti片上生長的納米管相比,TiN-Ti上生長的管長較短,單位長度上具有更高的比電容。隨著溫度的升高,TiN-Ti上制備的納米管管長變長,比電容提高。最后,為了探索致密膜的陽極氧化工藝,研究了電解液種類、氧化電壓、溫度對TiN-Ti及Ti片上生長的致密膜性能的影響。四種電解液對比結(jié)果表明,電解液種類對Ti片上致密膜性能影響不大,但TiN-Ti在NH_4B_5O_8與H_3BO_3混合溶液中制備的致密膜性能最好。與Ti片上致密膜相比,在TiN-Ti上生長的致密膜的漏電流和損耗性能更優(yōu)。實(shí)驗(yàn)表明,TiN-Ti生長的致密膜性能與Ti片上的相似,隨著氧化電壓的升高,漏電流增加,比電容下降,損耗減小;而隨著溫度的升高,漏電流增加,比電容下降,損耗增加。
[Abstract]:There are two kinds of anodic oxide films of titanium, TiO_2 nanotubes (porous films) and dense films. TiO_2 nanotubes have ordered porous structure and large specific surface area, so they can be used as electrode materials for supercapacitors. Although TiO_2 nanotubes have been studied for many years, the application of TiO_2 nanotubes prepared on Ti wafers is limited due to their easy peeling and poor electrochemical performance. Therefore, the morphology and electrochemical properties of TiO_2 nanotubes prepared under different anodic oxidation conditions were compared between Ti wire and Ti substrate in this paper. Secondly, in order to improve the specific capacitance of TiO_2 nanotubes, two preparation methods (one-step, two-step) of N-doped TiO_2 nanotubes were studied, and the properties of N-doped TiO_2 nanotubes were compared with those of undoped TiO_2 nanotubes. Thirdly, in order to simplify the doping process, TiO_2 nanotubes with better electrochemical properties were obtained by anodizing directly on the Ti (TiN-Ti) substrate deposited with TiN coating under different conditions. To provide guidance for the preparation of electrode materials for supercapacitors. Finally, although TiO_2 dense films can be used as dielectric materials for capacitors, TiO_2 dense films are rarely studied compared with TiO_2 nanotubes. Therefore, the preparation of dense films on different substrates and different conditions were studied, and the leakage current and specific capacitance and loss at different frequencies were compared. The main work of this paper is as follows: firstly, the morphology and electrochemical properties of TiO_2 nanotubes prepared on Ti wires under different anodic oxidation conditions are studied systematically because of the good adhesion between the TiO_2 nanotubes prepared on Ti wires and the substrate. And compared with TiO_2 nanotubes prepared on Ti wafer. The experimental results show that the larger the concentration of NH_4F, the higher the temperature, the longer the length and the larger the specific capacitance of TiO_2 nanotubes prepared on Ti wires. Secondly, N doped nanotubes were prepared on Ti wafer by one step method and two step method respectively. The one-step method is to oxidize the Ti sheet in the electrolyte containing urea to form N-doped nanotubes. The two-step method is to impregnate the conventional prepared TiO_2 nanotubes in ammonia water or urea solution. Both N-doped TiO_2 nanotubes obtained larger specific capacitance, but the impregnated nanotubes have less adhesion to the substrate, so the one-step method has more advantages. In addition, TiO_2 nanotubes containing N were prepared by anodic oxidation of TiN-Ti in conventional electrolyte. The effects of oxidation time and temperature on the nanotubes were studied. Compared with the nanotubes grown on the Ti wafer at the same time, the length of the grown nanotubes on the TiN-Ti is shorter and the specific capacitance per unit length is higher. With the increase of temperature, the length and specific capacitance of nanotubes prepared on TiN-Ti become longer and higher. Finally, in order to explore the anodizing process of dense films, the effects of electrolyte type, oxidation voltage and temperature on the properties of dense films grown on TiN-Ti and Ti were studied. The results of comparison of four electrolytes show that the type of electrolyte has little effect on the properties of dense films on Ti, but the properties of dense films prepared by TiN-Ti in the mixed solution of NH_4B_5O_8 and H_3BO_3 are the best. Compared with the compact film on Ti, the leakage current and loss performance of the compact film grown on TiN-Ti are better. The experimental results show that the properties of the dense film grown by TiN-Ti are similar to those on Ti. With the increase of oxidation voltage, the leakage current increases, the specific capacitance decreases and the loss decreases, but with the increase of temperature, the leakage current increases, the specific capacitance decreases and the loss increases.
【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】：TB306
本文編號：2365028
[Abstract]:There are two kinds of anodic oxide films of titanium, TiO_2 nanotubes (porous films) and dense films. TiO_2 nanotubes have ordered porous structure and large specific surface area, so they can be used as electrode materials for supercapacitors. Although TiO_2 nanotubes have been studied for many years, the application of TiO_2 nanotubes prepared on Ti wafers is limited due to their easy peeling and poor electrochemical performance. Therefore, the morphology and electrochemical properties of TiO_2 nanotubes prepared under different anodic oxidation conditions were compared between Ti wire and Ti substrate in this paper. Secondly, in order to improve the specific capacitance of TiO_2 nanotubes, two preparation methods (one-step, two-step) of N-doped TiO_2 nanotubes were studied, and the properties of N-doped TiO_2 nanotubes were compared with those of undoped TiO_2 nanotubes. Thirdly, in order to simplify the doping process, TiO_2 nanotubes with better electrochemical properties were obtained by anodizing directly on the Ti (TiN-Ti) substrate deposited with TiN coating under different conditions. To provide guidance for the preparation of electrode materials for supercapacitors. Finally, although TiO_2 dense films can be used as dielectric materials for capacitors, TiO_2 dense films are rarely studied compared with TiO_2 nanotubes. Therefore, the preparation of dense films on different substrates and different conditions were studied, and the leakage current and specific capacitance and loss at different frequencies were compared. The main work of this paper is as follows: firstly, the morphology and electrochemical properties of TiO_2 nanotubes prepared on Ti wires under different anodic oxidation conditions are studied systematically because of the good adhesion between the TiO_2 nanotubes prepared on Ti wires and the substrate. And compared with TiO_2 nanotubes prepared on Ti wafer. The experimental results show that the larger the concentration of NH_4F, the higher the temperature, the longer the length and the larger the specific capacitance of TiO_2 nanotubes prepared on Ti wires. Secondly, N doped nanotubes were prepared on Ti wafer by one step method and two step method respectively. The one-step method is to oxidize the Ti sheet in the electrolyte containing urea to form N-doped nanotubes. The two-step method is to impregnate the conventional prepared TiO_2 nanotubes in ammonia water or urea solution. Both N-doped TiO_2 nanotubes obtained larger specific capacitance, but the impregnated nanotubes have less adhesion to the substrate, so the one-step method has more advantages. In addition, TiO_2 nanotubes containing N were prepared by anodic oxidation of TiN-Ti in conventional electrolyte. The effects of oxidation time and temperature on the nanotubes were studied. Compared with the nanotubes grown on the Ti wafer at the same time, the length of the grown nanotubes on the TiN-Ti is shorter and the specific capacitance per unit length is higher. With the increase of temperature, the length and specific capacitance of nanotubes prepared on TiN-Ti become longer and higher. Finally, in order to explore the anodizing process of dense films, the effects of electrolyte type, oxidation voltage and temperature on the properties of dense films grown on TiN-Ti and Ti were studied. The results of comparison of four electrolytes show that the type of electrolyte has little effect on the properties of dense films on Ti, but the properties of dense films prepared by TiN-Ti in the mixed solution of NH_4B_5O_8 and H_3BO_3 are the best. Compared with the compact film on Ti, the leakage current and loss performance of the compact film grown on TiN-Ti are better. The experimental results show that the properties of the dense film grown by TiN-Ti are similar to those on Ti. With the increase of oxidation voltage, the leakage current increases, the specific capacitance decreases and the loss decreases, but with the increase of temperature, the leakage current increases, the specific capacitance decreases and the loss increases.
【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】：TB306
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