二氧化钒的简便制备及其性质研究
摘要
VO2在341K(68℃)发生可逆的一级相变,从低温的半导体相变成高温金属相。伴随着相变的发生,VO2的光学与电学性质也会发生突变。VO2的这种光学和电学的突变性质使VO2成为智能节能领域一种十分有潜力的新型功能材料。VO2的制备已经引起了许多研究者的重视。目前,关于VO2的制备研究还主要集中在薄膜方面,但薄膜的制备工艺复杂,对设备要求高,而且难以实现大面积制膜。对于无法承受高温的表面则无法镀膜。与薄膜相比,VO2粉体材料有其独特的优势,粉体材料不但可以直接通过压片制成温敏开关,也可以通过与有机介质调浆,以简单的涂覆或喷涂工艺在大面积表面或无法承受高温的表面制膜,这无疑将会扩大VO2的应用领域。
本论文发展了两种操作简便的VO2的制备方法：草酸还原法和偏钒酸铵热解法。利用这两种方法获得了具有金红石结构的纯相VO2粉体材料。采用多种分析测试方法对样品进行了表征。采用X射线衍射(XRD)和X射线光电子能谱(XPS)对产物物相纯度和钒的价态进行了分析；通过热分析技术(TG-DSC)、超导量子干涉磁量计(SQUID)、电子自旋共振(ESR)以及电阻-温度关系测试等手段研究了VO2粉体的相变特性。尝试采用交流阻抗谱方法测试了VO2的交流电响,利用等效电路拟合法分析了材料的电性能。实验结果表明：
(1)在草酸还原法中,适当的草酸(H2C2O4，还原剂)含量对控制钒的价态至关重要。最佳制备条件为：H2C2O4与V2O5的摩尔比为1：1,将H2C2O4与V2O5混合物封装于通有N2气的石英管中,然后置于已预热至220℃-300℃的管式炉中,升温至600℃后保温2小时。
(2)在偏钒酸铵热解法中,利用无水CaCl2吸收分解产生的氨气,形成CaCl2·8N3的方法控制反应体系中适当的还原剂量。CaCl2质量为NH4VO3的三倍为最佳。最佳热解温度为600℃,保温时间2小时。热分解需在N2气氛保护下进行。
(3)各种表征方法表明,两种方法制备的样品的热学性能、电学性能及磁学性能都在相变点发生突变,与文献报道相符。
(4)我们还尝试利用交流阻抗谱法表征了VO2的交流电响应性质。利用等效电路拟合法获得了材料的电阻、电容和电感等性能参数。利用材料低温相的电导随温度变化的Arrhenius图,求得了材料的禁带宽度为0.6 eV,这一结果与文献报道中的理论计算值相符。
Vanadium dioxide (VO2) presents a first-order phase transition at 341 K (68℃), from a semi-conducting phase to a metallic phase. During this process abrupt changes of optical and electrical properties can be detected, included that VO2 can be used in the energy-saving techniques as a smart material. A great deal of attention has been paid to the preparation of pure phase VO2, most work on the film preparations. The studies on VO2 powder preparations were minority. In fact, the powder VO2 not only can be prepared to the thermo-sensitive switch directly by mechanical pressing, but also can be further used for film preparation by using coating and spraying methods.
In this work, two methods were developed for the preparations of pure phase VO2 powders: oxalic acid reduction method and NH4VO3 pyrolysis method. The obtained VO2 samples were characterized by XRD, XPS, ESR as well as electric and magnetic measurements. The major results are listed below:
(1) In oxalic acid reduction method, the mixture of V2O5 and suitable amounts of oxalic acid (H2C2O4) were sealed in a quarts tube filled with high-purity N2. The sealed tube was put into a 200℃-300℃preheated tube furnace, and then heated at 600℃for 2 h. For obtaining the pure phase VO2, the optimized molar ratio of V2O5 to H2C2O4 was 1:1.
(2) In ammonium metavanadate pyrolysis method, NH4VO3 sealed in a quarts tube with high-purity N2 was heated at 600℃for 2 h. In the heating process,3 times of CaCl2 in weight was also sealed in the quarts tube.
(3) The characteristics of VO2 powder made by the two methods showed that the samples have abrupt changes in thermal, electrical and magnetic properties near the phase transition temperature, in reasonable agreements with reported data.
(4) Characterization by using AC impedance spectroscopy tried to analysis the electrical properties of VO2. Equivalent circuit fitting was used for the data analysis and the resistance, capacitance and inductance of VO2 were obtained. The band gap of VO2 was calculated from Arrhenius plots (1gσ～1/T) of the low temperature semiconductor phase, the value of which is about 0.6 eV, agreeing with the theoretical data previously reported.
本论文发展了两种操作简便的VO2的制备方法：草酸还原法和偏钒酸铵热解法。利用这两种方法获得了具有金红石结构的纯相VO2粉体材料。采用多种分析测试方法对样品进行了表征。采用X射线衍射(XRD)和X射线光电子能谱(XPS)对产物物相纯度和钒的价态进行了分析；通过热分析技术(TG-DSC)、超导量子干涉磁量计(SQUID)、电子自旋共振(ESR)以及电阻-温度关系测试等手段研究了VO2粉体的相变特性。尝试采用交流阻抗谱方法测试了VO2的交流电响,利用等效电路拟合法分析了材料的电性能。实验结果表明：
(1)在草酸还原法中,适当的草酸(H2C2O4，还原剂)含量对控制钒的价态至关重要。最佳制备条件为：H2C2O4与V2O5的摩尔比为1：1,将H2C2O4与V2O5混合物封装于通有N2气的石英管中,然后置于已预热至220℃-300℃的管式炉中,升温至600℃后保温2小时。
(2)在偏钒酸铵热解法中,利用无水CaCl2吸收分解产生的氨气,形成CaCl2·8N3的方法控制反应体系中适当的还原剂量。CaCl2质量为NH4VO3的三倍为最佳。最佳热解温度为600℃,保温时间2小时。热分解需在N2气氛保护下进行。
(3)各种表征方法表明,两种方法制备的样品的热学性能、电学性能及磁学性能都在相变点发生突变,与文献报道相符。
(4)我们还尝试利用交流阻抗谱法表征了VO2的交流电响应性质。利用等效电路拟合法获得了材料的电阻、电容和电感等性能参数。利用材料低温相的电导随温度变化的Arrhenius图,求得了材料的禁带宽度为0.6 eV,这一结果与文献报道中的理论计算值相符。
Vanadium dioxide (VO2) presents a first-order phase transition at 341 K (68℃), from a semi-conducting phase to a metallic phase. During this process abrupt changes of optical and electrical properties can be detected, included that VO2 can be used in the energy-saving techniques as a smart material. A great deal of attention has been paid to the preparation of pure phase VO2, most work on the film preparations. The studies on VO2 powder preparations were minority. In fact, the powder VO2 not only can be prepared to the thermo-sensitive switch directly by mechanical pressing, but also can be further used for film preparation by using coating and spraying methods.
In this work, two methods were developed for the preparations of pure phase VO2 powders: oxalic acid reduction method and NH4VO3 pyrolysis method. The obtained VO2 samples were characterized by XRD, XPS, ESR as well as electric and magnetic measurements. The major results are listed below:
(1) In oxalic acid reduction method, the mixture of V2O5 and suitable amounts of oxalic acid (H2C2O4) were sealed in a quarts tube filled with high-purity N2. The sealed tube was put into a 200℃-300℃preheated tube furnace, and then heated at 600℃for 2 h. For obtaining the pure phase VO2, the optimized molar ratio of V2O5 to H2C2O4 was 1:1.
(2) In ammonium metavanadate pyrolysis method, NH4VO3 sealed in a quarts tube with high-purity N2 was heated at 600℃for 2 h. In the heating process,3 times of CaCl2 in weight was also sealed in the quarts tube.
(3) The characteristics of VO2 powder made by the two methods showed that the samples have abrupt changes in thermal, electrical and magnetic properties near the phase transition temperature, in reasonable agreements with reported data.
(4) Characterization by using AC impedance spectroscopy tried to analysis the electrical properties of VO2. Equivalent circuit fitting was used for the data analysis and the resistance, capacitance and inductance of VO2 were obtained. The band gap of VO2 was calculated from Arrhenius plots (1gσ～1/T) of the low temperature semiconductor phase, the value of which is about 0.6 eV, agreeing with the theoretical data previously reported.
引文
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