FFC法中温度对TiO_2阴极的影响研究
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摘要
金属钛是一种性能优越的结构和功能材料。目前制备钛的Kroll法存在工艺复杂,生产周期长,不能连续化生产等问题。自2000年以来,国际上掀起了TiO_2电化学还原制备海绵钛的研究热潮,其中直接电解TiO_2制取钛的FFC工艺被大家认为最具发展前景。
本论文工作以FFC工艺为基础,考察烧结温度对TiO_2阴极物相组成、微观结构、氧空位及电解产物的影响;考察电解温度对电流变化、电解产物的影响,确定了适宜的烧结温度、电解温度;研究了熔盐电解体系中TiO_2阴极的导电性,主要研究工作及内容概况如下:
通过对TiO_2烧结及其电解实验,研究了烧结温度对TiO_2阴极的物相组成、微观结构、氧空位及电解产物的影响。在600～1000℃,随着烧结温度的升高,烧结样品的颗粒尺寸及致密度逐渐增大,开气孔逐渐减少,孔隙、比表面积、平均孔径、孔容及有效反应面积逐渐减小。在相同电解条件下,阴极的导电性和有效反应面积影响电解产物钛含量,随着烧结温度的升高,电解产物含钛量逐渐增加,含氧量逐渐减少;在相同的烧结温度下,随着电解温度的升高,有利于钛的生成。通过实验室研究,得到了熔盐电解二氧化钛制备钛的主要试验参数,确定适宜的烧结温度900℃。这一研究为后续研究奠定了基础。
在电解过程中电流都随时间的增加而减小;电解温度的升高有利于钛的生成,但经在900℃、950℃温度下电解,电解产物的钛含量增加不明显。因此,实验确定电解温度为900℃。
在对烧结TiO_2的XRD、XPS及电导率测定基础上,研究分析了熔盐电解体系中TiO_2电极导电性认为:高温烧结可以改变TiO_2的能带结构,产生导电空位,形成O_2-;TiO_2电极在熔盐中形成双电层,使氧原子离子化,形成TiO_2-X离子结构;熔盐中的离子渗透到TiO_2电极内部,增加了电极内的导电离子数。以上结论说明绝缘TiO_2可在实验条件下可转变为有效电极。
Titanium is a kind of functional material with superior performance. But there are still problems existing in the fabrication titanium process by traditional Kroll method, such as, complicated technology, long production cycle and intermittent operation, etc. Since 2000, sponge titanium prepared by electrochemical reduction of TiO_2 has attracted much attention in the world. Among all kinds of methods, a typical metallurgical process of TiO_2 deoxidation, named FFC, is the best and promising technique considered by scientists.
In this research, based on FFC process, titanium was obtained successfully by a series of electrolysis experiments. The influences of different sintering temperatures on the composition, microstructure, oxygen vacancies and electrolysis products of TiO_2 cathode, and the impacts of different electrolysis temperatures on current changes and electrolysis products of TiO_2 cathode were discussed. Moreover, the appropriate sintering temperature and electrolysis temperature were determined.Conductivity of TiO_2 cathode and the dishydrolysis of CaCl2 molten salt system were explored. The main contents of this disquisition are summarized as following:
After research on TiO_2 sintering and electrolytic process, the result of appropriate sintering temperature and electrolysis temperature was both at 900℃. Sintering temperature affected on the composition and microstructure of TiO_2 cathode and cathodic electrolysis products. In the range of 600～1000℃, with the increasing of the sintering temperature, the grain size and compact extent of the sintering sample gradually increased, while the open holes gradually reduced, the open pore rate,pore surface area,pore average diameter, pore volume and effective reaction area became small gradually. On the same electrolysis condition, the content of titanium was impacted by the conductivity and effective reaction area of the cathode. The titanium content became greater and the oxygen content was lesser with sintering temperature increasing. At the same sintering temperature, higher electrolysis temperature was helpful for the generation of titanium.
The current decreased as the time increasesed in electrolytic process; the increase of the electrolysis temperature is favorable to the generation of the titanium. However, the increase of electrolysis products is not clear under the electrolytic at 900℃、950℃. Therefore, the appropriate electrolysis temperature was 900℃.
Based on the measurement of XRD, XPS and specific conduction of sintered TiO_2, conductivity of TiO_2 electrode was analyzed. It showed that sintering at high temperature may change the energy band structure of TiO_2, forming conductive vacancies, generate O_2-; the form of electric double layer in molten salt of TiO_2 made the oxygen atoms ionized, forming ionic structure of TiO_2-X; The ion in molten salt penetrate internally to the TiO_2 electrode and improved the number of conductive ion in TiO_2 electrode. It can explain reasonable why the TiO_2 cathode could be made effective electrode.
本论文工作以FFC工艺为基础,考察烧结温度对TiO_2阴极物相组成、微观结构、氧空位及电解产物的影响;考察电解温度对电流变化、电解产物的影响,确定了适宜的烧结温度、电解温度;研究了熔盐电解体系中TiO_2阴极的导电性,主要研究工作及内容概况如下:
通过对TiO_2烧结及其电解实验,研究了烧结温度对TiO_2阴极的物相组成、微观结构、氧空位及电解产物的影响。在600～1000℃,随着烧结温度的升高,烧结样品的颗粒尺寸及致密度逐渐增大,开气孔逐渐减少,孔隙、比表面积、平均孔径、孔容及有效反应面积逐渐减小。在相同电解条件下,阴极的导电性和有效反应面积影响电解产物钛含量,随着烧结温度的升高,电解产物含钛量逐渐增加,含氧量逐渐减少;在相同的烧结温度下,随着电解温度的升高,有利于钛的生成。通过实验室研究,得到了熔盐电解二氧化钛制备钛的主要试验参数,确定适宜的烧结温度900℃。这一研究为后续研究奠定了基础。
在电解过程中电流都随时间的增加而减小;电解温度的升高有利于钛的生成,但经在900℃、950℃温度下电解,电解产物的钛含量增加不明显。因此,实验确定电解温度为900℃。
在对烧结TiO_2的XRD、XPS及电导率测定基础上,研究分析了熔盐电解体系中TiO_2电极导电性认为:高温烧结可以改变TiO_2的能带结构,产生导电空位,形成O_2-;TiO_2电极在熔盐中形成双电层,使氧原子离子化,形成TiO_2-X离子结构;熔盐中的离子渗透到TiO_2电极内部,增加了电极内的导电离子数。以上结论说明绝缘TiO_2可在实验条件下可转变为有效电极。
Titanium is a kind of functional material with superior performance. But there are still problems existing in the fabrication titanium process by traditional Kroll method, such as, complicated technology, long production cycle and intermittent operation, etc. Since 2000, sponge titanium prepared by electrochemical reduction of TiO_2 has attracted much attention in the world. Among all kinds of methods, a typical metallurgical process of TiO_2 deoxidation, named FFC, is the best and promising technique considered by scientists.
In this research, based on FFC process, titanium was obtained successfully by a series of electrolysis experiments. The influences of different sintering temperatures on the composition, microstructure, oxygen vacancies and electrolysis products of TiO_2 cathode, and the impacts of different electrolysis temperatures on current changes and electrolysis products of TiO_2 cathode were discussed. Moreover, the appropriate sintering temperature and electrolysis temperature were determined.Conductivity of TiO_2 cathode and the dishydrolysis of CaCl2 molten salt system were explored. The main contents of this disquisition are summarized as following:
After research on TiO_2 sintering and electrolytic process, the result of appropriate sintering temperature and electrolysis temperature was both at 900℃. Sintering temperature affected on the composition and microstructure of TiO_2 cathode and cathodic electrolysis products. In the range of 600～1000℃, with the increasing of the sintering temperature, the grain size and compact extent of the sintering sample gradually increased, while the open holes gradually reduced, the open pore rate,pore surface area,pore average diameter, pore volume and effective reaction area became small gradually. On the same electrolysis condition, the content of titanium was impacted by the conductivity and effective reaction area of the cathode. The titanium content became greater and the oxygen content was lesser with sintering temperature increasing. At the same sintering temperature, higher electrolysis temperature was helpful for the generation of titanium.
The current decreased as the time increasesed in electrolytic process; the increase of the electrolysis temperature is favorable to the generation of the titanium. However, the increase of electrolysis products is not clear under the electrolytic at 900℃、950℃. Therefore, the appropriate electrolysis temperature was 900℃.
Based on the measurement of XRD, XPS and specific conduction of sintered TiO_2, conductivity of TiO_2 electrode was analyzed. It showed that sintering at high temperature may change the energy band structure of TiO_2, forming conductive vacancies, generate O_2-; the form of electric double layer in molten salt of TiO_2 made the oxygen atoms ionized, forming ionic structure of TiO_2-X; The ion in molten salt penetrate internally to the TiO_2 electrode and improved the number of conductive ion in TiO_2 electrode. It can explain reasonable why the TiO_2 cathode could be made effective electrode.
引文
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