Patent CNB - 一种二氧化钒薄膜及其制备方法 Vanadium dioxide film and preparation method - Google PatentsCN BGrantCN May 24, 2017May 15, 2015May 15, 2015.5, CN
B, CN B, CN , CN-B-, CN B, CNB, CN, CN.5, , , ,
一种二氧化钒薄膜及其制备方法 Vanadium dioxide film and preparation method translated from CN
B 本发明公开一种二氧化钒薄膜及其制备方法，其包括步骤：制备二氧化钒溶液；称取一定量的聚乙烯醇加入至去离子水中，然后在80-90℃条件下加热溶解，得到聚乙烯醇水溶液，所述聚乙烯醇水溶液中聚乙烯醇的质量浓度为2~30%；将制备的二氧化钒溶液与聚乙烯醇水溶液按质量比为1:1~10混合，得到静电纺丝液；将上述静电纺丝液盛装在静电纺丝装置中进行静电纺丝，制得二氧化钒薄膜。 Discloses a vanadium dioxide thin film of the present invention and its preparation method, comprising the steps of: preparing a solution o weighed amount of polyvinyl alcohol was added to the deionized water, and then dissolved by heating at 80-90 deg.] C, to give polyvinyl alcohol aqueous solution, the concentration of polyvinyl alcohol in the polyvinyl alcohol aqueous solution is 2 to 30%; vanadium dioxide prepared aqueous solution of polyvinyl alcohol in a mass ratio of 1: 1 to 10 were mixed to obtain electrosp the electrostatic spinning solution containing an electrostatic spinning in electrostatic spinning apparatus, a thin film made of vanadium dioxide. 采用本发明静电纺丝法获得的二氧化钒薄膜具有高比表面积，均匀密实，结构可控，且获得的薄膜为纳米纤维状薄膜。 VO2 thin films obtained using an electrostatic spinning method of the present invention having a high specific surface area, dense uniform, controllable structures, thin films and nano-fibrillar film is obtained. 另外，本发明方法具有工艺简单，污染少，节约能源，生产成本低和可大规模制膜等优点。 Further, the method of the present invention has simple process, low pollution, energy conservation, low production cost and large-scale film manufactured advantages.
1.一种二氧化钒薄膜的制备方法，其特征在于，包括步骤： A、 制备二氧化钒溶液； B、 称取一定量的聚乙烯醇加入至去离子水中，然后在80-90°C条件下加热溶解，得到聚乙烯醇水溶液，所述聚乙烯醇水溶液中聚乙烯醇的质量浓度为5?15%; C、 将制备的二氧化钒溶液与聚乙烯醇水溶液按质量比1:1?1〇混合，得到静电纺丝液； D、 将上述静电纺丝液盛装在静电纺丝装置中进行静电纺丝，制得二氧化银薄膜； 所述步骤A具体包括： ' A1、将V2〇5粉末与浓盐酸按物质的量比1:5?7进行混合，然后在so—go。 A method for producing a vanadium dioxide film, comprising the steps of: A, Preparation of vanad B, said certain amount of polyvinyl alcohol was added to the deionized water at 80-90 ° C and then dissolving under heating to obtain an aqueous solution of polyvinyl alcohol, a polyvinyl alcohol concentration of the aqueous solution of polyvinyl alcohol is 5~15%; C, the aqueous polyvinyl alcohol solution with a vanadium dioxide prepared in a mass ratio of 1: 1 ~1〇 mixed to obtain an electrostat D, the electrostatic spinning solution containing electrostatic spinning in electrostatic spinning apparatus, the thin film of s said step A comprises: 'A1, the V2 〇5 powder and concentrated hydrochloric acid by the molar ratio 1: 5 ~ 7 were mixed, then the so-go. (：下搅拌反应，得到透明绿色溶液； A2、在所得透明绿色溶液中加入甲醛继续反应，得到透明宝蓝色溶液，所述甲醛与步骤A1中V2〇5粉末的质量比为1:90?110; A3、最后将透明宝蓝色溶液中盐酸蒸出，得到二氧化钒溶液； 所述聚乙炼醇的分子量为1〇〇〇?50000。 (: The reaction was stirred to give a
A2, formaldehyde was added in the resulting clear green solution was continued to give navy blue transparent solution, the mass ratio of the formaldehyde with the powder V2〇5 Step A1 is 1: 90~110 ; A3, navy blue and finally the clear solution of hydrochloric acid was distilled off to obtain a solution molecular weight of the polyvinyl alcohol is 1〇〇〇~50000 refining.
2.根据权利要求1所述二氧化钒薄膜的制备方法，其特征在于，所述步骤D具体包括： D1、将上述静电纺丝液盛装在静电纺丝装置的高压容器中；将铜金属导线作为电极，接收装置为金属网和与金属网相连的硅片，控制电压为8-20kV，接收距离为10-25 D2、开启静电纺丝装置进行静电纺丝，在接收装置的硅片上形成二氧化钒薄膜。 2. The method of claim 1 Preparation of vanadium dioxide thin film as claimed in claim, wherein the step D comprises: D1, the electrostatic spinning solution is contained within a pressure vessel elect copper metal wire as an electrode, a metal mesh and a receiving apparatus silicon and metal mesh connected, the control voltage is 8-20kV, the reception distance is 10-25 D2 of, opening electrospinning electrospinning device, the receiving device on the wafer vanadium dioxide thin film is formed.
3.根据权利要求1所述二氧化钒薄膜的制备方法，其特征在于，所述步骤C中，制备的二氧化钒溶液与聚乙烯醇水溶液按质量比1:4?8混合。 3. The method of claim 1 Preparation of vanadium dioxide film according to claim, wherein the step C, the vanadium dioxide solution and polyvinyl alcohol aqueous solution prepared in a mass ratio of 1: 4 to 8 mixing.
4. 根据权利要求2所述二氧化钒薄膜的制备方法，其特征在于，所述步骤D1中，控制电压为10-15kV。 4. The production method 2 of the VO2 thin films according to claim wherein said step D1, the control voltage 10-15kV.
5. 根据权利要求2所述二氧化钒薄膜的制备方法，其特征在于，所述步骤D1中，接收距_为15-20cm。 The production method 2 of the VO2 thin films as claimed in claim wherein said step D1, _ is received from 15-20cm.
6.—种二氧化钒薄膜，其特征在于，应用如权利要求1-5任一所述二氧化钒薄膜的制备方法制备而成。 6.- kinds of vanadium dioxide thin film, characterized in that the application of the claims 1-5 as a production method of vanadium dioxide thin films prepared by the claims.
一种二氧化钒薄膜及其制备方法 Vanadium dioxide film and preparation method
技术领域 FIELD
[0001]本发明涉及功能材料制备领域，尤其涉及一种二氧化钒薄膜及其制备方法。 [0001] The present invention relates to functional materials preparation, particularly to a vanadium dioxide film and preparation method.
背景技术 Background technique
[0002]由于温室气^排放的日益严重，节能减排逐渐成为各国发展的共同目标。 [0002] Since the ^ greenhouse gas emissions growing, energy conservation has become the common goal of national development. “十二五”期间，中国将把大幅度降低能源消耗强度、二氧化碳排放强度和主要污染物的排放总量作为重要的约束性指标。 &Twelve Five& period, China will significantly reduce energy consumption intensity, the intensity of carbon dioxide emissions and emissions of major pollutants as an important binding targets. 建筑耗能尤为突出，而且占建筑总面积I3%的玻璃材料，散热达到了70%，其中普通玻璃对红外和紫外的隔热效果表现不佳。 Building energy consumption is particularly prominent, and accounting for the total construction area I3% of the glass material, the heat reached 70%, of which ordinary glass insulating effect of infrared and ultraviolet poor performance. 二氧化钒(?〇2)在68。 Vanadium dioxide (? 〇2) at 68. (：左右可发生半导体-金属的一级可逆相变，从低温的单斜结构变化到高温的四方结构，升温相变前后其可见光透过率变化不大，但是红外透过率下降可达50%以上。 (: About Semiconductor can occur - a reversible phase transition metals, changed from a low temperature monoclinic to tetragonal high temperature phase change before and after heating the visible light transmittance thereof changed little, but infrared transmittance decreased up to 50 %the above.
[0003]现有制备二氧化钒薄膜的方法多为溶胶凝胶法，化学气相沉积法，磁控溅射法以及真空镀膜法等，但这些方法存在不同的缺点，如:溶胶凝胶法制备二氧化钒薄膜时，在涂膜过程中由于涂膜物质的挥发和收缩经常会出现气泡，裂缝，薄厚不均，甚至脱落等现象。 [0003] The method of preparing vanadium dioxide film prior mostly sol-gel method, chemical vapor deposition, magnetron sputtering method and a vacuum deposition method, etc., but these methods have different drawbacks, such as: Sol - Gel when the vanadium dioxide film, the coating process often bubbles, cracks and shrinkage due to volatilization of the coating material, uneven thickness, or even fall off and so on. 化学气相沉淀法存在设备工艺要求较高，不易于进行大规模工业化生产等缺点。 The presence of chemical vapor deposition method high technology equipment requirements, is not easy to perform large-scale industrial production disadvantages. 磁控溅射法存在对靶材(如纯度，表面光滑度，导电性等)要求较高，设备投入大等缺点。 The presence of the target (e.g., purity, surface smoothness, conductivity, etc.) require a higher magnetron sputtering equipment investment and other shortcomings. 真空蒸镀法则存在制备工艺较为复杂，仪器要求较高，不能进行工业化生产等缺点。 The presence of more complicated manufacturing process, high equipment requirements, and other shortcomings can not be produced industrially vacuum deposition law.
[0004]因此，现有技术还有待于改进和发展。 [0004] Thus, the prior art has yet to be improved and developed.
发明内容 SUMMARY
[0005]鉴于上述现有技术的不足，本发明的目的在于提供一种二氧化钒薄膜及其制备方法，旨在解决现有技术制备的薄膜厚度不均匀，薄膜脱落，工艺复杂及不宜工业化生产的问题。 [0005] In view of the deficiencies of the prior art, an object of the present invention is to provide a method for preparing vanadium dioxide film and, to solve the non-uniformity of the film thickness of the prior art prepared, falling film, industrial production process is complicated and not suitable The problem.
[0006] 本发明的技术方案如下： [0006] aspect of the present invention is as follows:
[0007] 一种二氧化钒薄膜的制备方法，其中，包括步骤： [0007] A method for producing a vanadium dioxide thin film, comprising the steps of:
[0008] A、制备二氧化钒溶液； [0008] A, the preparation of vanad
[0009] B、称取一定量的聚乙烯醇加入至去离子水中，然后在80-90°C条件下加热溶解，得到聚乙烯醇水溶液，所述聚乙烯醇水溶液中聚乙烯醇的质量浓度为2?30%; [0009] B, said certain amount of polyvinyl alcohol was added to the deionized water, and then dissolved by heating at 80-90 ° C conditions to give an aqueous solution of polyvinyl alcohol, a polyvinyl alcohol concentration of the aqueous solution of polyvinyl alcohol is 2~30%;
[0010] C、将制备的二氧化钒溶液与聚乙烯醇水溶液按质量比为1:1?1〇混合，得到静电纺丝液； [0010] C, the polyvinyl alcohol aqueous solution with a vanadium dioxide solution prepared in a mass ratio of 1: 1~1〇 mixed to obtain an electrostat
[0011] D、将上述静电纺丝液盛装在静电纺丝装置中进行静电纺丝，制得二氧化钒薄膜。 [0011] D, the electrostatic spinning solution containing an electrostatic spinning in electrostatic spinning apparatus, a thin film made of vanadium dioxide. [0012] 所述二氧化钒薄膜的制备方法，其中，所述步骤A具体包括： [0012] The production method of vanadium dioxide thin film, wherein the step A comprises:
[0013] A1、将V205粉末与浓盐酸按物质的量比1:5?7进行混合，然后在80-90。 [0013] A1, the V205 powder and concentrated hydrochloric acid by molar ratio of 1: 5 ~ 7 were mixed, then 80-90. (：下搅拌反应，得到透明绿色溶液； t〇〇14] A2、在所得透明绿色溶液中加入甲醛继续反应，得到透明宝蓝色溶液，所述甲醛与步骤A1中V205粉末的质量比为1: 9〇?11〇; (: The reaction was stirred to give a
t〇〇14] A2, formaldehyde was added in the resulting clear green solution was continued to give navy blue transparent solution, the powder mass V205 step A1 with formaldehyde ratio of 1: 9〇~11〇;
[0015] A3、最后将透明宝蓝色溶液中盐酸蒸出，得到二氧化钒溶液。 [0015] A3, navy blue and finally the clear solution of hydrochloric acid was distilled off to obtain a solution of vanadium dioxide.
[0016] 所述二氧化钒薄膜的制备方法，其中，所述步骤D具体包括： [0016] The production method of vanadium dioxide thin film, wherein the step D comprises:
[0017] D1、将上述静电纺丝液盛装在静电纺丝装置的高压容器中；铜金属导线作为电极， 接收装置为金属网和与金属网相连的硅片，控制电压为8_2〇kV，接收距离为10-25 [0017] D1, the electrostatic spinning solution is contained within a pressure vessel elect copper wire as an electrode, a metal mesh and a receiving apparatus silicon and metal mesh connected, 8_2〇kV control voltage, receiving distance of 10-25
[0018] D2、开启静电纺丝装置进行静电纺丝，在接收装置的硅片上形成二氧化钒薄膜。 [0018] D2, opening electrospinning electrospinning device, a thin film formed of vanadium dioxide on the wafer receiving device.
[0019] 所述二氧化钒薄膜的制备方法，其中，所述步骤B中，所述聚乙烯醇的分子量为。 The [0019] Preparation of vanadium dioxide thin film, wherein said step B, the molecular weight of the polyvinyl alcohol is .
[0020] 所述二氧化钒薄膜的制备方法，其中，所述步骤B中，所述聚乙烯醇水溶液中聚乙烯醇的质量浓度为5?15%。 The [0020] Preparation of vanadium dioxide thin film, wherein, the step B, the concentration of the polyvinyl alcohol is a polyvinyl alcohol aqueous solution 5~15%.
[0021] 所述二氧化钒薄膜的制备方法，其中，所述步骤C中，制备的二氧化钒溶液与聚乙稀醇水溶液按质量比1:4?8混合。 The [0021] Preparation of vanadium dioxide thin film, wherein said step C, a solution of vanadium dioxide and polyethylene alcohol aqueous solution prepared mass ratio of 1: 4 to 8 mixing.
[0022] 所述二氧化钒薄膜的制备方法，其中，所述步骤D1中，控制电压为10_15kV。 The [0022] Preparation of vanadium dioxide thin film, wherein said step D1, the control voltage 10_15kV.
[0023] 所述二氧化钒薄膜的制备方法，其中，所述步骤D1中，接收距离为15-20cm。 The [0023] Preparation of vanadium dioxide thin film, wherein said step D1, the reception distance is 15-20cm.
[0024] 一种二氧化钒薄膜，其中，应用如上任一所述二氧化钒薄膜的制备方法制备而成。 [0024] A vanadium dioxide thin film, wherein the office applications such as preparation of a vanadium dioxide thin films prepared by.
[0025] 有益效果:本发明通过制备二氧化钒溶液和聚乙烯醇水溶液，然后将制备的二氧化钒溶液和聚乙烯醇水溶液混合制得静电纺丝液，再将配制好的静电纺丝液在静电纺丝装置中进行静电纺丝，形成二氧化钒薄膜。 [0025] Advantageous Effects: The present invention is by preparing an aqueous polyvinyl alcohol solution and the vanadium dioxide, vanadium dioxide solution, and then preparing an aqueous solution of polyvinyl alcohol prepared by electrospinning a mixed solution, then the prepared solution electrospinning electrostatic spinning in electrostatic spinning apparatus to form a vanadium dioxide thin film. 采用本发明静电纺丝法获得的二氧化钒薄膜具有高比表面积，薄膜均匀密实，结构可控，且获得的薄膜为纳米纤维状薄膜。 VO2 thin films obtained using an electrostatic spinning method of the present invention having a high specific surface area, dense film uniformity, controllability structure, and the obtained thin film is nano-fibrillar film.
附图说明 BRIEF DESCRIPTION
[0026] 图1为本发明一种二氧化钒薄膜的制备方法较佳实施例的流程图。 [0026] FIG dioxide A flowchart of a preferred method for preparing a thin film of vanadium embodiment of the present invention.
[0027] 图2为图1所示方法中步骤S100的具体流程图。 [0027] FIG 2 is a flowchart of a method specifically shown in step S100 in FIG.
[0028] 图3为图1所示方法中步骤S400的具体流程图。 [0028] FIG. 3 is a detailed flowchart of the method shown in FIG. 1 in step S400.
[0029] 图4为实施例1中所制备产物的电导率与温度变化的关系图。 [0029] FIG. 4 is a graph of the conductivity and temperature of the product prepared in Example 1 of the embodiment variations.
[0030] 图5为实施例1所制备产物的XRD图。 [0030] FIG. 5 is a XRD pattern of the product of Preparation Example 1 embodiment.
[0031] 图6为实施例1所制备产物的SEM图。 [0031] FIG. 6 is a SEM image of the product prepared in Example 1 embodiment.
[0032] 图7为实施例2所制备产物的SEM图。 [0032] Example 2 FIG. 7 is a SEM of the product of Preparation embodiment of FIG.
[0033] 图8为实施例3所制备产物的SEM图。 [0033] FIG. 8 is the product of Preparation Example 3 in the embodiment of FIG SEM.
[0034] 图9为实施例4所制备产物的SEM图。 [0034] FIG. 9 is the product of Preparation Example 4 SEM embodiment of FIG.
具体实施方式 detailed description
[0035]本发明提供一种二氧化钒薄膜及其制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。 [0035] The present invention provides a method for preparing vanadium dioxide film and, for the purposes of the present invention, technical solutions and advantages clearer, explicit, the following detailed description of the present invention further. 应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。 It should be understood that the specific embodiments described herein are only intended to illustrate the present invention and are not intended to limit the present invention.
[0036]请参阅图1，图1为本发明一种二氧化钒薄膜的制备方法较佳实施例的流程图，如图所示，其包括步骤： [0036] Referring to FIG. 1, FIG. 1 is a flowchart of the embodiment of a method for preparing a preferred embodiment of the vanadium dioxide film, as shown in FIG present invention comprising the steps of:
[0037] S100、制备二氧化钒溶液； [0037] S100, vanadium
[0038] S200、称取一定量的聚乙烯醇加入至去离子水中，然后在8〇-9(TC条件下加热溶解，得到聚乙烯醇水溶液，所述聚乙烯醇水溶液中聚乙烯醇的质量浓度为2?30%; [0038] S200, weighed amount of polyvinyl alcohol was added to the deionized water, and then dissolved by heating under (TC-9 8〇 conditions, to give an aqueous solution of polyvinyl alcohol, the polyvinyl mass aqueous solution of polyvinyl alcohol a concentration of 2~30%;
[0039] S300、将制备的二氧化钒溶液与聚乙烯醇水溶液按质量比为1:1?1〇混合，得到静电纺丝液； [0039] S300, the aqueous polyvinyl alcohol solution with a vanadium dioxide prepared in a mass ratio of 1: 1~1〇 mixed to obtain an electrostat
[0040] S400、将上述静电纺丝液盛装在静电纺丝装置中进行静电纺丝，制得二氧化钒薄膜。 [0040] S400, the electrostatic spinning solution containing an electrostatic spinning in electrostatic spinning apparatus, a thin film made of vanadium dioxide.
[0041] 本发明预先制备二氧化钒溶液和聚乙烯醇水溶液，然后将制备的二氧化钒溶液和聚乙烯醇水溶液混合制得静电纺丝液，再将配制好的静电纺丝液在静电纺丝装置中进行静电纺丝，形成静电纺丝二氧化钒薄膜。 [0041] The present invention is previously prepared solution of vanadium dioxide and aqueous polyvinyl alcohol solution, and then the electrostatic spinning solution prepared by mixing a solution prepared vanadium dioxide and an aqueous solution of polyvinyl alcohol, and then the prepared solution in electrospinning Electrospinning wire means for electrostatic spinning, electrostatic spinning vanadium dioxide film is formed. 与现有溶胶凝胶法，化学气相沉积法，磁控派射法或真空镀膜法等制备二氧化钒薄膜相比，采用本发明静电纺丝法获得的二氧化钒薄膜具有高比表面积，薄膜均匀密实，结构可控，且获得的薄膜为纳米纤维状薄膜。 The conventional sol-gel method, the preparation of vanadium dioxide thin film chemical vapor deposition method, a magnetron sputtering method or vacuum deposition send method compared, obtained using vanadium dioxide thin film of the present invention, electrospinning having a high specific surface area, the film dense uniform, controllable structures, and the obtained thin film is a nano-fibrillar. 另外，本发明方法具有工艺简单，污染少，节约能源，生产成本低和可大规模制膜等优点。 Further, the method of the present invention has simple process, low pollution, energy conservation, low production cost and large-scale film manufactured advantages.
[0042] 具体地，如图2所示，所述步骤S100具体包括： [0042] Specifically, as shown in FIG. 2, step S100 comprises:
[0043] S101、将V2〇5粉末与浓盐酸按物质的量比1: 5?7进行混合，然后在80-90°C下搅拌反应，得到透明绿色溶液； [0043] S101, the V2〇5 powder and concentrated hydrochloric acid by molar ratio of 1: 5 ~ 7 were mixed, and then the reaction was stirred at 80-90 ° C, to give a
[0044] 所述步骤S101中，所述浓盐酸的质量浓度为37.5%，所述浓盐酸作为还原剂将V2〇5 粉末进行还原。 [0044] In the step S101, the mass concentration of 37.5% concentrated hydrochloric acid, concentrated hydrochloric acid as the reducing agent V2〇5 powder reduction. 具体地，反应时控制反应温度在80-90°C范围内，利于V2〇5粉末被还原为V02。 Specifically, when the control of the reaction temperature is in the range of 80-90 ° C, the powder is reduced to facilitate V2〇5 V02. 这是因为，反应温度过高，还原得到的V02很容易被氧化，而反应温度过低时，V2〇5粉末又不易被还原。 This is because the reaction temperature is too high, the resulting reduction V02 is easily oxidized, while the reaction temperature is too low, the powder V2〇5 not easily reduced. 优选地，在85°C下进行反应，获得的V02溶液产率更高。 Preferably, the reaction is carried out at 85 ° C, a higher yield of the obtained solution V02.
[0045] S102、在所得透明绿色溶液中加入甲醛继续反应，得到透明宝蓝色溶液，所述甲醛与步骤S101中V2〇5粉末的质量比为1: 90?110;本发明加入甲醛至步骤S101中所得的透明绿色溶液中继续反应，目的在于进一步将V2〇5粉末还原为V〇2。 [0045] S102, the formaldehyde was added in the resulting clear green solution was continued to give navy blue transparent solution, the mass ratio of formaldehyde to step S101 V2〇5 powder was 1: 90~110; the present invention is the addition of formaldehyde to step S101 the clear green solution obtained in the reaction continued further object of restore V〇2 V2〇5 powder.
[0046] S103、最后将透明宝蓝色溶液中盐酸蒸出，得到二氧化钒溶液。 [0046] S103, navy blue and finally the clear solution of hydrochloric acid was distilled off to obtain a solution of vanadium dioxide.
[0047]所述步骤S200中，称取一定量的聚乙烯醇加入至去离子水中，然后在8〇-9(TC条件下缓慢加热并不断搅拌将其溶解，得到聚乙烯醇水溶液。本发明中采用缓慢加热并不断搅拌有利于聚乙烯醇的溶解，从而得到分散性较好，均匀透明的聚乙烯醇水溶液。另外，所述聚乙烯醇水溶液中聚乙烯醇的质量浓度为2?30%，优选地，所述聚乙烯醇水溶液中聚乙烯醇的质量浓度为5?15%，以确保聚乙烯醇水溶液的粘度适中，而聚乙烯醇的质量浓度过大时， 聚乙烯醇水溶液的粘度会过大，并易发生团聚，从而不利于后续二氧化钒薄膜的制备。本发明中所述聚乙烯醇的分子量为,聚乙醇水溶液的粘度和聚乙烯醇的分子量同样有着直接的关系，聚乙烯醇的分子量越大时，聚乙烯醇水溶液的粘度也会越高，且聚乙烯醇分子量过大时，易导致溶液分散不均匀。优选地， [0047] The step S200, the weighed amount of polyvinyl alcohol was added to the deionized water, and then slowly heating (TC-9 8〇 conditions and constantly stirred and dissolved, to give an aqueous solution of polyvinyl alcohol present invention used was slowly heated with constant stirring to dissolve the polyvinyl alcohol is beneficial to obtain good dispersibility, uniform transparent polyvinyl alcohol solution. in addition, the mass concentration of the aqueous solution of polyvinyl alcohol is a polyvinyl alcohol 2~30% preferably, the concentration of polyvinyl alcohol in the polyvinyl alcohol aqueous solution is 5~15% polyvinyl alcohol aqueous solution to ensure that the viscosity is moderate, while the concentration of polyvinyl alcohol is too large, the viscosity of the aqueous solution of polyvinyl alcohol will be too large and prone to agglomeration, to prepare the subsequent VO2 thin is not conducive to molecular weight of the polyvinyl alcohol in the present invention is 1,000 to 100,000, a molecular weight and viscosity of the aqueous solution of polyvinyl alcohol polyglycol also has a direct relationship, when the higher the molecular weight of the polyvinyl alcohol, the viscosity of the aqueous polyvinyl alcohol solution will be higher, and the polyvinyl alcohol molecular weight is too easily lead to non-uniform dispersion solution. preferably, 本发明所述聚乙烯醇的分子量为,以获得粘度适中，分散性较好的聚乙烯醇水溶液。 The present invention is the molecular weight of the polyvinyl alcohol is , to obtain a moderate viscosity, better dispersion aqueous polyvinyl alcohol solution.
[0048]聚乙烯醇水溶液具有一定的粘度，当聚乙烯醇水溶液加入至二氧化钒溶液中时， 聚乙烯醇水溶液与二氧化钒溶液能较好的粘接在一起，从而有利于二氧化钒薄膜的形成。 [0048] The aqueous solution of polyvinyl alcohol having a certain viscosity, when the polyvinyl alcohol aqueous solution was added to the vanadium dioxide, vanadium dioxide with the aqueous solution of polyvinyl alcohol can be preferably adhered together, thus facilitating vanadium dioxide forming a thin film. 本发明二氧化钒薄膜的性能可通过聚乙烯醇水溶液的用量来调节。 Properties of vanadium dioxide film of the present invention can be adjusted by the amount of the aqueous solution of polyvinyl alcohol. 优选地，所述步骤S3〇〇中，制备的二氧化钒溶液与聚乙烯醇水溶液按质量比丨：4?8混合，以获得硬度适中，连续密实的薄膜。 Preferably, in the step S3〇〇, vanadium dioxide solution and polyvinyl alcohol aqueous solution was prepared by Shu mass ratio: 4 to 8 were mixed to obtain a moderate hardness, continuous dense film.
[0049] 具体地，如图3所示，所述步骤S4〇〇具体包括： [0049] Specifically, as shown in FIG. 3, step S4〇〇 comprises:
[0050] S401、将上述静电纺丝液盛装在静电纺丝装置的高压容器中；铜金属导线作为电极，接收装置为金属网和与金属网相连的桂片，控制电压为8-20kV，接收距离为10-25 [0050] S401, the electrostatic spinning solution is contained within a pressure vessel elect copper wire as an electrode, the receiving means is a metal mesh sheet and a metal mesh Gui connected, the control voltage is 8-20kV, receiving distance of 10-25
[0051] 以〇2、开启静电纺丝装置进行静电纺丝，在接收装置的硅片上形成二氧化钒薄膜。 [0051] In 〇2 open electrospinning electrospinning device, a thin film formed of vanadium dioxide on the wafer receiving device.
[0052] 静电纺丝法是一种利用高压电场和静电场力对聚合物溶液或熔体进行拉伸而成纳米级纤维的一种纺丝方法。 [0052] Electrospinning is a high voltage electric field and the electrostatic force of one kind of a polymer solution or melt spinning stretching method using nanofibers. 具体静电纺丝的原理是:首先将聚合物溶液或熔体带上几千至上万伏高压静电，带电的聚合物液滴在电场力的作用下在毛细管的Taylor锥顶点被加速。 Embodying the principles of electro-spinning is: first polymer solution or melt to bring thousands of first kilovolt high voltage electrostatic charged droplets under the action of the polymer is accelerated in the electric field force Taylor cone apex of the capillary. 当电场力足够大时，聚合物液滴克服表面张力形成喷射细流。 When an electric field force is large enough to overcome the surface Zhang Li polymer droplets form a fine jet stream. 细流在喷射过程中溶剂蒸发或固化，最终落在接收装置上，固化形成纤维。 Trickle during the spraying curing or solvent evaporation, finally falls on the receiving device, cures to form fibers.
[0053] 本发明通过将V2〇5粉末用浓盐酸还原制得二氧化钒的溶液，再与聚乙烯醇溶液混合形成带电的聚合物溶液，然后将制备好的静电纺丝液盛装在静电纺丝装置的高压容器中，然后通过施加一定大小的电压，压制一定时间，便可得到平整、均匀、结构可控的二氧化钒薄膜。 [0053] The present invention will V2〇5 powder prepared by reducing vanadium dioxide solution with concentrated hydrochloric acid, and then mixed with a polyvinyl alcohol solution to form a polymer solution is charged, and then the prepared spinning solution containing an electrostatic spinning in electrostatic pressure vessel wire device, and then by applying a voltage of a certain size, a certain pressing time, you can obtain a smooth, uniform, controllable structures vanadium dioxide thin film. 具体压制时间根据所需的二氧化钒薄膜的厚度而定，压制时间越长，所得到的二氧化钒薄膜厚度越厚。 DETAILED pressing time depending on the thickness required may be vanadium dioxide thin film, the longer the press time, the thicker the film thickness obtained vanadium dioxide. 该静电纺丝法使用的设备简单，成本低廉，所产生的污染少，并且适合大面积制膜，易于实现工业化生产，利于材料的进一步应用。 This device uses an electrostatic spinning method is simple, low cost, less pollution produced, and suitable for large area film, industrial production easy, conducive to the further application of the material.
[0054] 在静电纺丝过程中，可通过调节静电纺丝的电压和接收距离，以获得最佳工作参数，从而获得最佳静电纺丝工作状态和最佳质量的二氧化钒薄膜。 [0054] In the electrospinning process, and by adjusting the voltage received from the electrostatic spinning, the optimal operating parameters to obtain optimum vanadium dioxide film and best quality operating state of the electrostatic spinning. 具体地，控制电压为8-20kV，这是因为在该电压作用下，聚合物静电纺丝液有着较大的静电斥力，同时，聚合物静电纺丝液能获得较大的加速度，从而引起聚合物静电纺丝液的射流有较大的拉伸应力，利于制得更加密实的二氧化钒薄膜，且在该电压下静电纺丝过程稳定，静电纺丝速度快。 Specifically, the control voltage is 8-20kV, because at this voltage is applied, the polymeric electrostatic spinning solution has a greater electrostatic repulsion, at the same time, the polymer solution electrospinning large acceleration can be obtained, thereby causing polymerization electrostatic spinning solution was jet have a greater tensile stress, facilitate made more dense film of vanadium dioxide, and the voltage at the electrostatic spinning process stability, fast speed electrospinning. 优选地，控制电压为10-15 kV，以进一步提高二氧化钒薄膜的质量，确保静电纺丝较高的速度。 Preferably, the control voltage of 10-15 kV, in order to further improve the quality of the vanadium dioxide film to ensure higher electrostatic spinning speeds. 另外，控制接收距离为10-25cm，即是控制毛细管口与接收装置之间的距离为10-25cm。 Further, controlling the reception distance is 10-25cm, that is, control the distance between the capillary opening and the receiving device is 10-25cm. 聚合物静电纺丝液经毛细管口喷出后，在空气中伴随着溶剂挥发，聚合物浓缩固化成纤维，最后在接收装置的硅片上形成二氧化钒薄膜。 After electrostatic spinning of polymer solution discharge port of the capillary, along with solvent evaporation in air, curing the polymer concentrate into fibers, and finally a thin film formed on a silicon wafer vanadium dioxide reception device. 随着毛细管口与接收装置之间的距离增大，制得的二氧化钒薄膜直径变小，因此，本发明采取控制接收距离为10-25cm，从而有效控制了制得的二氧化钒薄膜的直径在较佳的尺寸范围内，确保二氧化钒薄膜的质量。 As the distance between the capillary opening and the receiving device is increased, the diameter of vanadium dioxide film obtained becomes small, and therefore, the reception distance is 10-25cm take control of the present invention, in order to effectively control the vanadium dioxide film is prepared diameter in the preferred size range to ensure the quality of the vanadium dioxide film. 优选地，控制接收距离为15-20011，以使获得的二氧化钒薄膜的直径在最佳的尺寸范围内，进一步提高二氧化钒薄膜的质量。 Preferably, the control receives 15-20011 distance, so that the diameter of vanadium dioxide thin film obtained in the optimal size range, to improve the quality of the vanadium dioxide film.
[0055] 本发明还提供一种二氧化钒薄膜，本发明所述二氧化钒薄膜应用如上所述二氧化钒薄膜的制备方法制备而成。 [0055] The present invention also provides a vanadium dioxide thin film, the present invention is prepared by application of vanadium dioxide film production method described above, vanadium dioxide thin film. 采用本发明静电纺丝法获得的二氧化钒薄膜具有高比表面积，薄膜均匀密实，结构可控，且获得的薄膜为纳米纤维状薄膜。 VO2 thin films obtained using an electrostatic spinning method of the present invention having a high specific surface area, dense film uniformity, controllability structure, and the obtained thin film is nano-fibrillar film.
[0056]下面以具体实施例对本发明做详细说明： [0056] The following specific embodiments of the present invention is described in detail:
[0057] 实施例1 _] 将2g V2〇5粉末与40mL浓盐酸混合，在温度为85°C下快速搅拌反应，反应体系由混浊的红褐色溶液逐渐变成透明的绿色溶液，然后加入0.02g甲醛继续反应，体系逐渐变为宝石蓝的透明溶液，最后将多余的盐酸蒸出，得到二氧化钒溶液。 [0057]] Example 1 _ 2g mixing the powder with a V2〇5 embodiment 40mL of concentrated hydrochloric acid, the reaction was stirred rapidly at a temperature of 85 ° C, the reaction system by the red-brown turbid solution was gradually became a clear green solution, followed by addition of 0.02 g formaldehyde reaction was continued, Sapphire system gradually became a clear solution, and finally the excess of hydrochloric acid was distilled off to obtain a solution of vanadium dioxide.
[0059] 称取2g聚乙烯醇(Mn=10000)加入到38mL去离子水中，温度控制在85°C左右，缓慢加热使其溶解，得到质量百分比浓度为5%的聚乙烯醇水溶液。 [0059] Weigh 2g of polyvinyl alcohol (Mn = 10000) was added to 38mL of deionized water, temperature controlled at 85 ° C, was slowly heated to dissolve, to obtain an aqueous solution of a polyvinyl alcohol concentration of 5% by mass percentage of.
[0060] 将二氧化钒溶液与聚乙烯醇溶液充分混合得到静电纺丝液，将其装入高压容器， 电极采用铜金属导线，接收装置为金属网和与金属网相连的硅片，电压控制在10kV，接收距离控制在15cm，在硅片上制备二氧化钒薄膜。 [0060] The polyvinyl alcohol solution of vanadium dioxide solution and mixed well to give an electrostatic spinning solution, which was charged with high-pressure container, copper metal electrode wire, a metal mesh and a receiving device wafer connected with the metal mesh, a voltage control in 10kV, received from the control 15cm, vanadium dioxide thin films on silicon wafers. 所制备二氧化钒薄膜的电导率与温度变化的关系见图4所示。 Conductivity and temperature of vanadium dioxide thin films prepared changing relationships shown in Figure 4. 所制备二氧化钒薄膜的XRD图见图5所示。 The XRD pattern of the vanadium dioxide film prepared as shown in Figure 5. 所制备二氧化钒薄膜的形貌见图6所示。 Vanadium dioxide film morphology shown in Figure 6 produced.
[0061] 实施例2 [0061] Example 2
[0062]将lg V2〇5粉末与2〇1^浓盐酸混合，在温度为sor下快速搅拌反应，反应体系由混浊的红褐色逐渐变成透明的绿色，然后加入〇o 0 3/4 甲醛继续反应，体系逐渐变为宝石蓝的透明溶液，最后将多余的盐酸蒸出，得到二氧化钒溶液。 [0062] The powder ^ lg V2〇5 2〇1 mixed with concentrated hydrochloric acid, the reaction was stirred rapidly under sor temperature, the reaction system gradually becomes turbid red-brown transparent green, then formaldehyde was added the reaction was continued o 0 3/4
square, Sapphire system gradually became a clear solution, and finally the excess of hydrochloric acid was distilled off to obtain a solution of vanadium dioxide.
[0063]称取3g聚乙烯醇(Mn=50000)加入到30mL去离子水中，温度控制在85°C左右，缓慢加热使其溶解，得到质量百分比浓度为15%的聚乙稀醇水溶液。 [0063] 3g of polyvinyl alcohol was weighed (Mn = 50000) was added to 30mL of deionized water, temperature controlled at 85 ° C, was slowly heated to dissolve, polyethylene alcohol aqueous solution to obtain the mass concentration of 15%.
[0064^将二氧化钒溶液与聚乙烯醇溶液充分混合得到静电纺丝液，将其装入高压容器， 电极采用铜金属导线，接收装置为金属网和与金属网相连的硅片，电压控制在15kV，接收距离控制在20cm，在硅片上制备二氧化钒薄膜。 [0064 ^ vanadium dioxide solution was thoroughly mixed with polyvinyl alcohol solution to obtain the electrostatic spinning solution, which was charged with high-pressure container, copper metal electrode wire, a metal mesh and a receiving device wafer connected with the metal mesh, a voltage control in 15kV, received from the control 20cm, vanadium dioxide thin films on silicon wafers. 所制备二氧化钒薄膜的形貌见图7所示。 Morphology VO2 thin films prepared as shown in Figure 7.
[0065] 实施例3 [0065] Example 3
[0066] 将lg 乂咖粉末与2〇mL浓盐酸混合，在温度为9(TC下快速搅拌反应，反应体系由混浊的红褐色逐渐变成透明的绿色，然后加入〇. 〇2g甲醛继续反应，体系逐渐变为宝石蓝的透明溶液，最后将多余的盐酸蒸出，得到二氧化钒溶液。 [0066] The coffee powder is mixed with lg qe 2〇mL concentrated hydrochloric acid, at a temperature of 9 (with rapid stirring reaction TC, the turbidity of the reaction system gradually became a clear red-brown, green, square then added. The reaction was continued formaldehyde 〇2g , Sapphire system gradually became a clear solution, and finally the excess of hydrochloric acid was distilled off to obtain a solution of vanadium dioxide.
[0067] 称取5g聚乙烯醇(Mn=80000)加入到20mL去离子水中，温度控制在90°C左右，缓慢加热使其溶解，得到质量百分比浓度为25%的聚乙烯醇水溶液。 [0067] Weigh 5g of polyvinyl alcohol (Mn = 80000) was added to 20mL of deionized water, temperature controlled at 90 ° C, was slowly heated to dissolve, to obtain percentage concentration of 25 mass% polyvinyl alcohol aqueous solution.
[0068]将二氧化钒溶液与聚乙烯醇溶液充分混合得到静电纺丝液，将其装入高压容器， 电极采用铜金属导线，接收装置为金属网和与金属网相连的硅片，电压控制在8kV，接收距离控制在10cm，在硅片上制备二氧化钒薄膜。 [0068] The polyvinyl alcohol solution of vanadium dioxide solution and mixed well to give an electrostatic spinning solution, which was charged with high-pressure container, copper metal electrode wire, a metal mesh and a receiving device wafer connected with the metal mesh, a voltage control in 8kV, received from the control 10cm, vanadium dioxide thin films on silicon wafers. 所制备二氧化钒薄膜的形貌见图8所示。 Morphology VO2 thin films prepared as shown in Figure 8.
[0069] 实施例4 [0069] Example 4
[0070] 将0_5g V2〇5粉末与20mL浓盐酸混合，在温度为88°C下快速搅拌反应，反应体系由混浊的红褐色逐渐变成透明的绿色，然后加入〇.〇2g甲醛继续反应，体系逐渐变为宝石蓝的透明溶液，最后将多余的盐酸蒸出，得到二氧化钒溶液。 [0070] The 0_5g V2〇5 mixed powder and 20mL of concentrated hydrochloric acid, the reaction was stirred rapidly at a temperature of 88 ° C, the reaction system by the red-brown turbid green gradually becomes transparent, and then the formaldehyde was added the reaction was continued 〇.〇2g, Sapphire system gradually became a clear solution, and finally the excess of hydrochloric acid was distilled off to obtain a solution of vanadium dioxide.
[0071] 称取3g聚乙烯醇(Mn=50000)加入到30mL去离子水中，温度控制在84°c左右，缓慢加热使其溶解，得到质量百分比浓度为15%的聚乙烯醇水溶液。 [0071] 3g of polyvinyl alcohol was weighed (Mn = 50000) was added to 30mL of deionized water, temperature controlled at 84 ° c, was slowly heated to dissolve, to obtain percentage concentration of 15 mass% polyvinyl alcohol aqueous solution.
[0072] 将二氧化钒溶液与聚乙烯醇溶液充分混合得到静电纺丝液，将其装入高压容器， 电极采用铜金属导线，接收装置为金属网和与金属网相连的硅片，电压控制在15kV，接收距离控制在15cm，在硅片上制备二氧化钒薄膜。 [0072] The polyvinyl alcohol solution of vanadium dioxide solution and mixed well to give an electrostatic spinning solution, which was charged with high-pressure container, copper metal electrode wire, a metal mesh and a receiving device wafer connected with the metal mesh, a voltage control in 15kV, received from the control 15cm, vanadium dioxide thin films on silicon wafers. 所制备二氧化钒薄膜的形貌见图9所示。 Vanadium dioxide film morphology shown in Figure 9 is prepared.
[0073] 综上所述，本发明通过将V205粉末用浓盐酸还原制得二氧化钒的溶液，再与聚乙烯醇溶液混合形成带电的聚合物溶液，然后将制备好的静电纺丝液盛装在静电纺丝装置的高压容器中，然后通过施加一定大小的电压，压制一定时间，便可得到平整、均匀、结构可控的二氧化钒薄膜。 [0073] In summary, the present invention is by the V205 powder was prepared by reducing vanadium dioxide solution with concentrated hydrochloric acid, and then mixed with a polyvinyl alcohol solution to form a polymer solution is charged, and the electrostatic spinning solution prepared to contain in the high-pressure vessel electrostatic spinning apparatus, and then by applying a voltage of a certain size, a certain pressing time, you can obtain a smooth, uniform, controllable structures vanadium dioxide thin film. 该静电纺丝法使用的设备简单，成本低廉，所产生的污染少，并且适合大面积制膜，易于实现工业化生产，利于材料的进一步应用。 This device uses an electrostatic spinning method is simple, low cost, less pollution produced, and suitable for large area film, industrial production easy, conducive to the further application of the material.
[0074]应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。 [0074] It should be appreciated that the present invention is applied is not limited to the above-described example, those of ordinary skill in the art, can be modified or converted according to the above description, all such modifications and variations shall fall within the appended claims of the invention the scope of protection.
*中国科学院化学研究所Functional polymer nano composite material and preparation method and uses thereof *中国科学院上海硅酸盐研究所Vanadium dioxide precursor liquid and method for preparing thin-film material by using the same *中国科学院上海硅酸盐研究所Vanadium dioxide thin film and preparation method thereof *电子科技大学Method for preparing vanadium oxide thin film by virtue of pulse reaction magnetron sputtering *US Title not availableInternational Classification, , C06PublicationEXSBDecision made by sipo to initiate substantive examinationGR01 Rotate}