CN103880080A - Method for preparing vanadium dioxide powder through hydrothermal auxiliary homogeneous precipitation method - Google Patents
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 73
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- 239000000843 powder Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 48
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- 229910052720 vanadium Inorganic materials 0.000 claims description 27
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 27
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
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- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000011858 nanopowder Substances 0.000 abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 2
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Abstract
本发明涉及一种水热辅助均匀沉淀法制备二氧化钒粉体的方法，该方法包括：（1）在含四价钒离子的水溶液中加入均匀沉淀剂并搅拌均匀形成混合液；以及（2）将所得的混合液转入水热釜中，于200～350℃保温1～120小时进行水热反应，经冷却、离心、洗涤、干燥，即制得二氧化钒粉体；其中，所述均匀沉淀剂是能够在步骤（2）的水热反应中缓慢水解产生沉淀离子的物质，所述沉淀离子为氢氧根离子；所述四价钒离子和所述均匀沉淀剂的摩尔比为1:5～2:1。通过采用均匀沉淀剂，一方面可以提高收率，另一方面避免了使用直接沉淀剂（例如氨水、氢氧化钠溶液等）导致的溶液中局部浓度不均匀的现象，从而可以获得单分散、高纯度的纳米粉体。
The invention relates to a method for preparing vanadium dioxide powder by a hydrothermal assisted uniform precipitation method, the method comprising: (1) adding a uniform precipitant to an aqueous solution containing tetravalent vanadium ions and stirring uniformly to form a mixed solution; and (2) ) Transfer the obtained mixed solution into a hydrothermal kettle, heat it at 200-350°C for 1-120 hours to carry out hydrothermal reaction, and after cooling, centrifuging, washing and drying, vanadium dioxide powder is obtained; wherein, the The homogeneous precipitant is a substance that can be slowly hydrolyzed in the hydrothermal reaction of step (2) to produce precipitated ions, the precipitated ions are hydroxide ions; the molar ratio of the tetravalent vanadium ions to the homogeneous precipitant is 1 :5～2:1. By using a uniform precipitant, on the one hand, the yield can be increased, and on the other hand, the phenomenon of uneven local concentration in the solution caused by the use of direct precipitants (such as ammonia water, sodium hydroxide solution, etc.) can be avoided, so that monodisperse, high Pure nano powder.
Description
技术领域technical field
本发明涉及化工领域中的二氧化钒粉体的制备，特别涉及通过水热处理技术、均匀沉淀技术制备二氧化钒粉体，属于节能环保新材料领域。The invention relates to the preparation of vanadium dioxide powder in the field of chemical industry, in particular to the preparation of vanadium dioxide powder by hydrothermal treatment technology and uniform precipitation technology, and belongs to the field of energy-saving and environment-friendly new materials.
背景技术Background technique
由于全球资源的日益枯竭，节能减排已经成为各国当前的首要任务。***环境规划署2009年12月11日发表的一份报告称：全球温室气体排放量中有1/3与建筑物耗能有关。我国是能耗大国，每年损耗的能源相当于15亿吨标准煤，其中30%左右为建筑耗能，而建筑耗能中最严重的是通过玻璃产生的能量损失。一般建筑物的窗墙面积比为30-50%，大型建筑物的窗墙面积比高达50-70%，冬季通过窗户产生的能量损失为58%，夏季高达73%，这使得通过玻璃产生的能量损耗占整个建筑能耗的50%。随着中国城镇化的发展，这一比例将持续增加。因此通过推进建筑物节能，开发节能玻璃，有望大幅度降低温室气体排放和能耗，最终达到节能环保的目的。Due to the increasing depletion of global resources, energy conservation and emission reduction has become the current top priority for all countries. According to a report published by the United Nations Environment Program on December 11, 2009, 1/3 of global greenhouse gas emissions are related to building energy consumption. my country is a country with a large energy consumption. The annual energy consumption is equivalent to 1.5 billion tons of standard coal, of which about 30% is energy consumption in buildings, and the most serious energy consumption in buildings is energy loss through glass. The window-to-wall area ratio of general buildings is 30-50%, and the window-to-wall area ratio of large buildings is as high as 50-70%. The energy loss through windows in winter is 58%, and it is as high as 73% in summer. Energy loss accounts for 50% of the entire building energy consumption. With the development of urbanization in China, this proportion will continue to increase. Therefore, by promoting energy saving in buildings and developing energy-saving glass, it is expected to significantly reduce greenhouse gas emissions and energy consumption, and ultimately achieve the goal of energy conservation and environmental protection.
现有的节能玻璃是以市面上销售的低辐射玻璃（Low-E玻璃）为代表，其具有对可见光高透过及对中远红外高反射的特性，保温隔热性能好，但其价格较高，不能随外界环境温度的变化对太阳光进行实时调控，属于“被动响应”，难以适应我国大多数冬冷夏热的气候环境。其他的“主动响应”的节能玻璃，例如电致变色玻璃、气致变色玻璃，其结构复杂，造价昂贵，短期内很难普及，因此急需开发一种智能温控节能玻璃。The existing energy-saving glass is represented by low-emissivity glass (Low-E glass) sold on the market, which has the characteristics of high transmission of visible light and high reflection of mid- and far-infrared, and has good thermal insulation performance, but its price is relatively high , it cannot adjust the sunlight in real time with the change of the external environment temperature, which belongs to "passive response", and it is difficult to adapt to the climate environment of most cold winters and hot summers in our country. Other "active response" energy-saving glasses, such as electrochromic glass and gas-chromic glass, have complex structures and high costs, and are difficult to popularize in the short term. Therefore, it is urgent to develop an intelligent temperature-controlled energy-saving glass.
二氧化钒晶体在68℃发生由低温单斜相（M相）到高温金红石相（R相）的可逆金属半导体相转变，相变前后其对太阳光中红外部分光的透过率发生剧烈的变化，使其在智能温控玻璃上具有较大的用处。Vanadium dioxide crystal undergoes a reversible metal-semiconductor phase transition from a low-temperature monoclinic phase (M phase) to a high-temperature rutile phase (R phase) at 68 ° C. Before and after the phase transition, its transmittance to the mid-infrared part of sunlight changes dramatically. Changes make it more useful in intelligent temperature-controlled glass.
钒的氧化物是多价态、多晶相的复杂体系，其中二氧化钒的晶体结构多达10余种，主要包括A相、B相、C相、M相、R相及水合物等结晶相。其中只有M/R相二氧化钒具有热致变色的特性。相的纯度以及粉体的颗粒大小、分散性均会对其热致变色特性产生影响。Vanadium oxide is a complex system of multivalent states and polycrystalline phases. Among them, there are more than 10 kinds of crystal structures of vanadium dioxide, mainly including A phase, B phase, C phase, M phase, R phase and hydrate crystals. Mutually. Among them, only the M/R phase vanadium dioxide has thermochromic properties. The purity of the phase, the particle size and dispersibility of the powder will all affect its thermochromic properties.
目前二氧化钒的应用研究主要集中在薄膜制备上，常用的制备方法主要有磁控溅射、化学气相沉积、脉冲激光沉积等，但这些方法存在着设备昂贵、工艺参数控制复杂、工艺稳定性差、成膜面积小，不适合工业化批量生产等局限。而将具有智能温控变色性能的二氧化钒粉体制成薄膜，粘贴或涂覆在玻璃上，可以对现有普通玻璃进行节能改造，降低将现有玻璃全部替换成节能玻璃的高成本。在后者制备薄膜的方法中，单分散、高纯度的纳米粉体的制备是成膜的关键。At present, the application research of vanadium dioxide mainly focuses on the preparation of thin films. The commonly used preparation methods mainly include magnetron sputtering, chemical vapor deposition, pulsed laser deposition, etc., but these methods have the disadvantages of expensive equipment, complicated control of process parameters, and poor process stability. , The film-forming area is small, and it is not suitable for limitations such as industrial mass production. The vanadium dioxide powder with intelligent temperature control and discoloration performance is made into a thin film, pasted or coated on the glass, which can carry out energy-saving transformation of existing ordinary glass and reduce the high cost of replacing all existing glass with energy-saving glass. In the latter method of preparing thin films, the preparation of monodisperse, high-purity nanopowders is the key to film formation.
已有的M/R相二氧化钒粉体的制备方法有：中国专利CN1837061A公开的一种制备掺杂二氧化钒粉体方法，先利用沉淀法制备出前驱体，然后再对前驱体进行高温热处理得到金红石相二氧化钒粉体；中国专利CN102502824A公开的一种二氧化钒及其掺杂粉体的制备方法，先利用水热法制备出B相二氧化钒粉体，在高温热处理制得M/R相二氧化钒粉体；中国专利CN102120614A公开的利用水热法制备M/R相二氧化钒粉体；以及美国专利US5427763公开的喷雾热解法，美国专利US6682596公开的溶胶凝胶法等制备M/R相二氧化钒粉体的方法。但是这些方法均难以以高收率获得单分散、高纯度的纳米粉体。The existing M/R phase vanadium dioxide powder preparation methods include: a method for preparing doped vanadium dioxide powder disclosed in Chinese patent CN1837061A. First, the precursor is prepared by precipitation method, and then the precursor is subjected to high temperature Heat treatment to obtain rutile phase vanadium dioxide powder; Chinese patent CN102502824A discloses a preparation method of vanadium dioxide and its doped powder. M/R phase vanadium dioxide powder; preparation of M/R phase vanadium dioxide powder by hydrothermal method disclosed in Chinese patent CN102120614A; and spray pyrolysis method disclosed in US patent US5427763, sol-gel method disclosed in US patent US6682596 A method for preparing M/R phase vanadium dioxide powder. However, these methods are difficult to obtain monodisperse, high-purity nanopowders with high yield.
发明内容Contents of the invention
鉴于二氧化钒粉体的广泛应用和工业化生产的需求，需要开发一种工艺简单，成本低廉的制备方法。面对现有技术存在的问题，本发明的目的在于提供一种高收率地制备单分散、高纯度的二氧化钒粉体的方法。In view of the wide application of vanadium dioxide powder and the demand for industrial production, it is necessary to develop a preparation method with simple process and low cost. Facing the problems existing in the prior art, the object of the present invention is to provide a method for preparing monodisperse, high-purity vanadium dioxide powder with high yield.
本发明人在此认为，水热反应前，向体系中加入均匀沉淀剂，可以结合水热法和均匀沉淀法的优势，对可以使水热反应更容易进行是有利的。The inventors of the present invention believe that adding a uniform precipitant to the system before the hydrothermal reaction can combine the advantages of the hydrothermal method and the uniform precipitation method, and it is beneficial to make the hydrothermal reaction easier to proceed.
在此，本发明提供一种水热辅助均匀沉淀法制备二氧化钒粉体的方法，所述方法包括：Here, the present invention provides a method for preparing vanadium dioxide powder by a hydrothermal assisted uniform precipitation method, the method comprising:
（1）在含四价钒离子的水溶液中加入均匀沉淀剂并搅拌均匀形成混合液；以及(1) Add a uniform precipitant to the aqueous solution containing tetravalent vanadium ions and stir to form a mixed solution; and
（2）将所得的混合液转入水热釜中，于200～350℃保温1～120小时进行水热反应，经冷却、离心、洗涤、干燥，即制得二氧化钒粉体；(2) Transfer the obtained mixed solution into a hydrothermal kettle, heat it at 200-350°C for 1-120 hours for hydrothermal reaction, and then prepare vanadium dioxide powder by cooling, centrifuging, washing and drying;
其中，所述均匀沉淀剂是能够在步骤（2）的水热反应中缓慢水解产生沉淀离子的物质，所述沉淀离子为氢氧根离子；Wherein, the uniform precipitant is a substance that can be slowly hydrolyzed in the hydrothermal reaction of step (2) to generate precipitated ions, and the precipitated ions are hydroxide ions;
所述四价钒离子和所述均匀沉淀剂的摩尔比为1:5～2:1。The molar ratio of the tetravalent vanadium ions to the uniform precipitant is 1:5˜2:1.
本发明中，在水热反应前向反应体系中加入均匀沉淀剂，该均匀沉淀剂本身不能使四价钒离子形成沉淀，而在水热反应中随着反应温度的升高，均匀沉淀剂（例如尿素和/或六次甲基四胺）缓慢水解产生NH3，进而水解持续释放氢氧根离子沉淀离子，其与四价钒离子形成均匀的混合，持续缓慢形成钒沉淀，这样，一方面可以提高收率，另一方面避免了使用直接沉淀剂（例如氨水、氢氧化钠溶液等）导致的溶液中局部浓度不均匀的现象，从而可以获得单分散、高纯度的纳米粉体。本发明的方法操作简单可控；产物粒径分布均匀，分散性好，适合规模生产。In the present invention, a uniform precipitant is added to the reaction system before the hydrothermal reaction, and the uniform precipitant itself cannot cause tetravalent vanadium ions to form precipitation, but in the hydrothermal reaction, as the reaction temperature increases, the uniform precipitant ( For example, urea and/or hexamethylenetetramine) are slowly hydrolyzed to produce NH 3 , and then hydrolyzed to continuously release hydroxide ions to precipitate ions, which form a uniform mixture with tetravalent vanadium ions, and continuously and slowly form vanadium precipitates. In this way, on the one hand It can improve the yield, and on the other hand, it avoids the uneven local concentration in the solution caused by the use of direct precipitating agents (such as ammonia water, sodium hydroxide solution, etc.), so that monodisperse, high-purity nanopowders can be obtained. The method of the invention is simple and controllable in operation; the particle size distribution of the product is uniform, the dispersibility is good, and it is suitable for large-scale production.
本发明中，步骤（1）中，将均匀沉淀剂和四价钒离子原料加入至水中搅拌均匀即可制得用于水热反应的的混合液。该方法容易操作和控制，无需特殊设备。In the present invention, in step (1), the uniform precipitant and the tetravalent vanadium ion raw material are added into water and stirred evenly to obtain a mixed solution for hydrothermal reaction. The method is easy to operate and control, and requires no special equipment.
较佳地，所述均匀沉淀剂是尿素和/或六次甲基四胺；优选为尿素。Preferably, the uniform precipitating agent is urea and/or hexamethylenetetramine; preferably urea.
较佳地，步骤（1）中，所述含四价钒离子的水溶液中四价钒离子的摩尔浓度为0.01～0.5mol/L；优选为0.05～0.4mol/L。Preferably, in step (1), the molar concentration of tetravalent vanadium ions in the aqueous solution containing tetravalent vanadium ions is 0.01-0.5 mol/L; preferably 0.05-0.4 mol/L.
较佳地，所述含四价钒离子的水溶液通过以下方法中的任意一种制得：将可溶性四价钒源和/或其水合物溶于水；将五价钒源和/或其水合物还原为四价钒并溶于水；或者将三价钒源和/或其水合物氧化为四价钒并溶于水。Preferably, the aqueous solution containing tetravalent vanadium ions is prepared by any one of the following methods: dissolving a soluble tetravalent vanadium source and/or its hydrate in water; dissolving a pentavalent vanadium source and/or its hydrate The product is reduced to tetravalent vanadium and dissolved in water; or the trivalent vanadium source and/or its hydrate is oxidized to tetravalent vanadium and dissolved in water.
较佳地，所述四价钒源为硫酸氧钒、二氯氧钒、和草酸氧钒中的至少一种；所述五价钒源为五氧化二钒和/或偏钒酸铵。Preferably, the tetravalent vanadium source is at least one of vanadyl sulfate, vanadyl dichloride, and vanadyl oxalate; the pentavalent vanadium source is vanadium pentoxide and/or ammonium metavanadate.
较佳地，步骤（1）中，所述四价钒离子和所述均匀沉淀剂的摩尔比优选为优选为1:4～1:1。Preferably, in step (1), the molar ratio of the tetravalent vanadium ions to the homogeneous precipitant is preferably 1:4˜1:1.
较佳地，步骤（2）中，所述水热反应的温度优选为250～300℃。Preferably, in step (2), the temperature of the hydrothermal reaction is preferably 250-300°C.
较佳地，步骤（2）中，所述水热反应的保温时间优选为4～50小时。Preferably, in step (2), the holding time of the hydrothermal reaction is preferably 4-50 hours.
较佳地，步骤（1）中，所述混合液中还可以含有掺杂剂。这样，可以制得掺杂有掺杂元素的二氧化钒粉体。优选地，所述掺杂剂所提供的掺杂元素能够调控二氧化钒粉体的相变温度。较佳地，所述掺杂剂中的掺杂元素与所述四价钒离子的摩尔比为1:1000～1:10。Preferably, in step (1), the mixed liquid may further contain a dopant. In this way, vanadium dioxide powder doped with doping elements can be prepared. Preferably, the doping element provided by the dopant can regulate the phase transition temperature of the vanadium dioxide powder. Preferably, the molar ratio of the doping element in the dopant to the tetravalent vanadium ions is 1:1000˜1:10.
较佳地，所述掺杂元素优选为钨、铌、钼、钽、钛、锡、镉、锰、铝、铋、氟和镁中的至少一种。Preferably, the doping element is preferably at least one of tungsten, niobium, molybdenum, tantalum, titanium, tin, cadmium, manganese, aluminum, bismuth, fluorine and magnesium.
本发明可以制备出形貌和尺寸可控的二氧化钒粉体，该方法制备的二氧化钒粉体可以为颗粒状和棒状，且颗粒的尺寸可以是在至少一个维度上不大于100nm，优选在三个维度上均不大于70nm；棒状的长度达500nm～1μm，宽度达50～100nm。The present invention can prepare vanadium dioxide powder with controllable shape and size, the vanadium dioxide powder prepared by the method can be granular and rod-shaped, and the particle size can be no more than 100nm in at least one dimension, preferably None of the three dimensions is greater than 70nm; the length of the rod is 500nm-1μm, and the width is 50-100nm.
本发明的制备方法与现有的制备方法相比，具有以下优点：Compared with the existing preparation method, the preparation method of the present invention has the following advantages:
（1）本发明制备二氧化钒粉体的方法操作简便、成本低、控制容易，产物结晶好，在水、分散剂中的分散性好；(1) The method for preparing vanadium dioxide powder in the present invention is simple and convenient to operate, low in cost, easy to control, good in product crystallization, and good in dispersibility in water and dispersants;
（2）该制备方法，反应一步完成，反应充分，收率高；(2) In the preparation method, the reaction is completed in one step, the reaction is sufficient, and the yield is high;
（3）该方法所制得的二氧化钒粉体，颗粒尺寸易控制，粒度均匀。(3) The particle size of the vanadium dioxide powder prepared by this method is easy to control and uniform.
本发明制得的二氧化钒粉体可应用于智能节能玻璃涂层、智能节能薄膜、温控装置、光电开关、热敏电阻、光信息存储等领域。The vanadium dioxide powder prepared by the invention can be applied to the fields of intelligent energy-saving glass coating, intelligent energy-saving film, temperature control device, photoelectric switch, thermistor, optical information storage and the like.
附图说明Description of drawings
图1为实例3所对应的二氧化钒粉体的X射线衍射图；Fig. 1 is the X-ray diffraction pattern of the corresponding vanadium dioxide powder of example 3;
图2为实例3所对应的二氧化钒粉体的扫描电镜（SEM）图；Fig. 2 is the scanning electron microscope (SEM) picture of the vanadium dioxide powder body corresponding to example 3;
图3为实例3所对应的二氧化钒粉体的透射电镜（TEM）图；Fig. 3 is the transmission electron microscope (TEM) picture of the vanadium dioxide powder body corresponding to example 3;
图4为实例3所对应的二氧化钒粉体的DSC曲线图；Fig. 4 is the DSC curve figure of the corresponding vanadium dioxide powder of example 3;
图5为实例4所对应的二氧化钒粉体的扫描电镜图；Fig. 5 is the scanning electron micrograph of the corresponding vanadium dioxide powder of example 4;
图6为实例5所对应的二氧化钒粉体的扫描电镜图。6 is a scanning electron microscope image of the vanadium dioxide powder corresponding to Example 5.
具体实施方式Detailed ways
以下结合附图和下述实施方式进一步说明本发明，应理解，附图及下述实施方式仅用于说明本发明，而非限制本发明。The present invention will be further described below in conjunction with the drawings and the following embodiments. It should be understood that the drawings and the following embodiments are only used to illustrate the present invention rather than limit the present invention.
本发明提供了一种二氧化钒粉体的制备方法，包括以下步骤：配制四价钒离子水溶液；向所得的水溶液中加入规定质量的均匀沉淀剂，搅拌至均匀；然后将所得的混合液转入水热釜中，升温后保温，经水热反应合成；自然冷却后的产物经离心、洗涤、干燥，得到二氧化钒粉体。更具体地，作为示例，本发明的方法可以包括以下步骤。The invention provides a preparation method of vanadium dioxide powder, comprising the following steps: preparing an aqueous solution of tetravalent vanadium ions; adding a uniform precipitant of specified quality into the obtained aqueous solution, stirring until uniform; and then transferring the obtained mixed solution to Put it into a hydrothermal kettle, heat it up, keep it warm, and synthesize it through hydrothermal reaction; the product after natural cooling is centrifuged, washed, and dried to obtain vanadium dioxide powder. More specifically, as an example, the method of the present invention may include the following steps.
（1）配制含四价钒离子的水溶液(1) Prepare an aqueous solution containing tetravalent vanadium ions
含四价钒离子的水溶液的配制可以采用本领域常用的方法来制备：将四价可溶性钒原料溶于适量水，优选为去离子水，合适的浓度可以为0.01～0.5mol/L，优选为0.05～0.4mol/L。四价可溶性钒盐可以采用廉价易得的常用钒盐，例如硫酸氧钒（VOSO4）和二氯氧钒（VOCl2）。当然也可采用钒盐的水合物，例如草酸氧钒无水合物（VOC2O4.5H2O）。含四价钒离子的水溶液的配制通常在常温下进行，但也可理解，可稍微加热助溶或采用超声等方法助溶。The preparation of the aqueous solution containing tetravalent vanadium ions can be prepared by a method commonly used in this field: dissolving the tetravalent soluble vanadium raw material in an appropriate amount of water, preferably deionized water, the suitable concentration can be 0.01-0.5mol/L, preferably 0.05～0.4mol/L. The tetravalent soluble vanadium salts can be cheap and commonly available vanadium salts, such as vanadyl sulfate (VOSO 4 ) and vanadyl dichloride (VOCl 2 ). Of course, hydrates of vanadium salts such as vanadyl oxalate anhydrate (VOC 2 O 4 .5H 2 O) may also be used. The preparation of the aqueous solution containing tetravalent vanadium ions is usually carried out at room temperature, but it is also understandable that a little heating or ultrasonication can be used to assist the dissolution.
作为用于配制含四价钒离子的水溶液的钒原料还可以包括其他可溶性或不溶性的钒原料，例如可采用在三价或五价可溶性钒盐和/或其水合物作为钒原料，将其溶于水中，经氧化或还原成四价钒。应理解，若氧化还原过程中有不溶物析出时，可以再加适量水使其溶解，也可稍加热使其溶解。还应理解，在三价或五价钒盐和/或其水合物作为钒原料时，也可以先经氧化或还原等预处理形成四价钒盐再溶于水。在一个示例中，所采用的五价钒盐例如可为五氧化二钒和/或偏钒酸铵。用于将五价钒还原为四价钒的还原剂可为草酸，甲醇、葡萄糖，甲醛，甲酸等其中的一种或者几种还原剂。在另一个示例中，所采用的三价钒源为硫酸钒（V2(SO4)3）。The vanadium raw material used to prepare the aqueous solution containing tetravalent vanadium ions can also include other soluble or insoluble vanadium raw materials, for example, trivalent or pentavalent soluble vanadium salts and/or hydrates thereof can be used as vanadium raw materials, and dissolved In water, it can be oxidized or reduced to tetravalent vanadium. It should be understood that if insoluble matter is precipitated during the oxidation-reduction process, an appropriate amount of water can be added to dissolve it, or a little heating can be used to dissolve it. It should also be understood that when trivalent or pentavalent vanadium salts and/or hydrates thereof are used as vanadium raw materials, they can also be pretreated by oxidation or reduction to form tetravalent vanadium salts and then dissolved in water. In one example, the pentavalent vanadium salt used may be, for example, vanadium pentoxide and/or ammonium metavanadate. The reducing agent used to reduce pentavalent vanadium to tetravalent vanadium can be one or several reducing agents among oxalic acid, methanol, glucose, formaldehyde, formic acid and the like. In another example, the source of trivalent vanadium employed is vanadium sulfate (V 2 (SO 4 ) 3 ).
还可采用不可溶性钒原料来制备含四价钒离子的水溶液：不可溶性钒原料，例如金属钒、钒氧化物或其组合经氧化、还原或溶解等预处理使其可溶化，然后再溶于水制得所需的含四价钒离子的水溶液。Insoluble vanadium raw materials can also be used to prepare aqueous solutions containing tetravalent vanadium ions: insoluble vanadium raw materials, such as metal vanadium, vanadium oxides, or combinations thereof, are pretreated to be soluble by oxidation, reduction or dissolution, and then dissolved in Water produces the desired aqueous solution containing tetravalent vanadium ions.
（2）在所得的含四价钒离子的水溶液中加入均匀沉淀剂并搅拌均匀形成混合液：所述的均匀沉淀剂是指能够在下述的水热反应中缓慢水解产生沉淀离子（氢氧根离子）的物质。例如，所述均匀沉淀剂可以是尿素、六次甲基四胺或其任意组合，优选为尿素。尿素、六次甲基四胺在下述水热反应的条件下，随着反应温度的升高，可以缓慢水解产生氨，氨进一步反应生成沉淀离子（氢氧根离子）可以与四价钒离子反应产生沉淀。例如采用尿素作为沉淀剂：(2) Add a homogeneous precipitant to the resulting aqueous solution containing tetravalent vanadium ions and stir to form a mixed solution: the homogeneous precipitant refers to the ability to slowly hydrolyze in the following hydrothermal reaction to produce precipitated ions (hydroxide radicals) ions) substances. For example, the uniform precipitating agent may be urea, hexamethylenetetramine or any combination thereof, preferably urea. Under the conditions of the following hydrothermal reaction, urea and hexamethylenetetramine can be slowly hydrolyzed to produce ammonia as the reaction temperature rises, and the ammonia can further react to form precipitated ions (hydroxide ions), which can react with tetravalent vanadium ions Precipitation occurs. For example, using urea as a precipitant:
CO(NH2)2+3H2O→2NH4 ++CO2(g)+2OH- (1)CO(NH 2 ) 2 +3H 2 O→2NH 4 + +CO 2 (g)+2OH - (1)
VO2++2OH-→VO(OH)2(s)→VO2(s)+H2O (2)VO 2+ +2OH - →VO(OH) 2 (s)→VO 2 (s)+H 2 O (2)
室温时，混合液不发生反应，当温度高于60℃时，尿素缓慢地发生水解，如反应式（1）所示，产生NH4 +，OH-和CO2，使得溶液的pH缓慢地、均匀地增加，VO2+在OH-的作用下成核长大生成VO(OH)2，高温水热下转变为VO2；At room temperature, the mixture does not react. When the temperature is higher than 60°C, urea slowly hydrolyzes, as shown in reaction formula (1), producing NH 4 + , OH - and CO 2 , making the pH of the solution slowly decrease. , increase evenly, VO 2+ nucleates and grows under the action of OH- to generate VO(OH) 2 , and transforms into VO 2 under high temperature water heat;
这样一方面可以使反应充分，从而提高二氧化钒粉体的收率；另一方面，与直接加入沉淀剂（例如碱）相比，避免了使用直接沉淀剂导致的溶液中局部浓度不均匀的现象，从而可以制得形貌和尺寸分布更集中的粉体。另外，四价钒离子与所加入的均匀沉淀剂的摩尔比可为1:5～2:1，优选为1:4～1:1。该步骤中，将含四价钒离子的水溶液与均匀沉淀剂直接混合搅拌均匀，容易操作和控制，无需特殊设备。In this way, on the one hand, the reaction can be fully achieved, thereby increasing the yield of vanadium dioxide powder; on the other hand, compared with directly adding a precipitating agent (such as alkali), it avoids the uneven local concentration in the solution caused by the use of a direct precipitating agent. phenomenon, so that powders with more concentrated morphology and size distribution can be produced. In addition, the molar ratio of tetravalent vanadium ions to the uniform precipitant added may be 1:5-2:1, preferably 1:4-1:1. In this step, the aqueous solution containing tetravalent vanadium ions is directly mixed and stirred evenly with the uniform precipitant, which is easy to operate and control without special equipment.
本发明的方法可以用于制备未掺杂的二氧化钒粉体，也可以制备掺杂的二氧化钒粉体。在制备掺杂二氧化钒粉体时，为了降低相变温度，还可以在上述含四价钒离子的水溶液中加入掺杂剂，经水热反应可制得所需的掺杂二氧化钒粉体。该掺杂剂所提供的掺杂元素可以是能够调控二氧化钒粉体相变温度的元素，包括但不限于钨、铌、钼、钽、钛、锡、镉、锰、铝、铋、氟和镁中的一种或任意组合。掺杂剂中的掺杂元素与四价钒离子水溶液的摩尔比可以根据掺杂元素的掺杂量来确定。本发明中，所加入的掺杂剂中的掺杂元素与所述四价钒离子的摩尔比可为1:1000～1:10。The method of the invention can be used to prepare undoped vanadium dioxide powder, and can also prepare doped vanadium dioxide powder. When preparing doped vanadium dioxide powder, in order to reduce the phase transition temperature, a dopant can also be added to the above-mentioned aqueous solution containing tetravalent vanadium ions, and the required doped vanadium dioxide powder can be obtained through hydrothermal reaction body. The doping element provided by the dopant can be an element capable of regulating the phase transition temperature of vanadium dioxide powder, including but not limited to tungsten, niobium, molybdenum, tantalum, titanium, tin, cadmium, manganese, aluminum, bismuth, fluorine and one or any combination of magnesium. The molar ratio of the doping element in the dopant to the tetravalent vanadium ion aqueous solution can be determined according to the doping amount of the doping element. In the present invention, the molar ratio of the doping elements in the added dopant to the tetravalent vanadium ions may be 1:1000˜1:10.
（3）将所得的混合液转入水热釜中，经水热反应制备二氧化钒粉体(3) Transfer the obtained mixed solution into a hydrothermal kettle, and prepare vanadium dioxide powder through hydrothermal reaction
水热反应温度可以为200～350℃，优选为250～300℃。在这些温度范围内，温度越高越有利于M相二氧化钒的生成。水热反应时间可以为1～120小时，可以随着反应温度进行调整，优选为4～50小时。在这些时间范围内，随着反应时间的延长，粉体的结晶性可以得到明显的提高。水热反应填充比可以为20～90%，优选为40～80%。反应完毕后，经后处理即可获得二氧化钒粉体。后处理方式例如可以是冷却、离心、洗涤、干燥。经检测，本发明中，可以以高于95%的收率获得二氧化钒粉体，大大高于直接加入沉淀剂时的收率。The hydrothermal reaction temperature may be 200-350°C, preferably 250-300°C. Within these temperature ranges, the higher the temperature, the more favorable the formation of M-phase vanadium dioxide. The hydrothermal reaction time can be 1-120 hours, which can be adjusted according to the reaction temperature, and is preferably 4-50 hours. Within these time ranges, the crystallinity of the powder can be significantly improved with the prolongation of the reaction time. The hydrothermal reaction filling ratio can be 20-90%, preferably 40-80%. After the reaction is completed, the vanadium dioxide powder can be obtained through post-treatment. Post-treatment methods may be, for example, cooling, centrifuging, washing, and drying. It has been tested that in the present invention, vanadium dioxide powder can be obtained with a yield higher than 95%, which is much higher than the yield when the precipitating agent is directly added.
本发明可以制备出形貌和尺寸可控、结晶性好的二氧化钒粉体。通过X射线衍射（XRD）（参见图1）确定可以制备出晶型为单一的二氧化钒M相结构。通过扫描电镜（SEM）（参见图2、图5）和透射电镜（TEM）（参见图3、图6）观测本实施方式制得的二氧化钒粉体的形状和粒径，本实施方式制备的二氧化钒粉体为颗粒状和/或棒状。颗粒的尺寸可以是在至少一个维度上不大于100nm，优选在三个维度上均不大于70nm；棒状的长度达500nm～1μm，宽度达50～100nm。而且，本发明制得的二氧化钒粉体的颗粒粒度均匀。The invention can prepare vanadium dioxide powder with controllable shape and size and good crystallinity. It was confirmed by X-ray diffraction (XRD) (see Figure 1 ) that a single vanadium dioxide M phase structure could be prepared. The shape and particle size of the vanadium dioxide powder prepared in this embodiment are observed by scanning electron microscope (SEM) (see Figure 2, Figure 5) and transmission electron microscope (TEM) (see Figure 3, Figure 6). The vanadium dioxide powder is granular and/or rod-like. The particle size can be no more than 100nm in at least one dimension, preferably no more than 70nm in all three dimensions; the length of the rod is 500nm-1μm, and the width is 50-100nm. Moreover, the particle size of the vanadium dioxide powder prepared by the invention is uniform.
本发明的方法结合了水热法和均匀沉淀法的优势，操作简单易行，成本低，产物粒度均匀、结晶好，在水、分散剂中的分散性好；粒子形貌和尺寸容易控制，反应一步完成，反应充分，收率高。The method of the present invention combines the advantages of the hydrothermal method and the uniform precipitation method, the operation is simple and easy, the cost is low, the particle size of the product is uniform, the crystallization is good, and the dispersibility in water and dispersant is good; the particle shape and size are easy to control, The reaction is completed in one step, the reaction is complete, and the yield is high.
此外，本发明通过在反应原料中加入掺杂剂经水热反应即可实现掺杂元素的掺杂。通过以不同的掺杂量掺杂不同的掺杂元素，即可实现二氧化钒粉体相变温度的调控。In addition, the present invention can realize the doping of doping elements by adding a dopant to the reaction raw material and undergoing hydrothermal reaction. By doping different doping elements with different doping amounts, the control of the phase transition temperature of vanadium dioxide powder can be realized.
本发明制得的二氧化钒粉体具有热致变色的特性，在一个示例中（参见图4），制得的二氧化钒粉体的升温相变温度为65.8℃，降温相变温度为49.2℃，热滞后温度差为16.6℃。因此，本发明制得的二氧化钒粉体可应用于智能节能玻璃涂层、智能节能薄膜、温控装置、光电开关、热敏电阻、光信息存储等领域。The vanadium dioxide powder prepared by the present invention has thermochromic properties. In one example (see Figure 4), the phase transition temperature of the prepared vanadium dioxide powder is 65.8 ° C, and the phase transition temperature is 49.2 ° C. °C, the thermal hysteresis temperature difference is 16.6 °C. Therefore, the vanadium dioxide powder prepared in the present invention can be applied to the fields of intelligent energy-saving glass coating, intelligent energy-saving film, temperature control device, photoelectric switch, thermistor, optical information storage and the like.
应理解，本发明详述的上述实施方式，及以下实施例仅用于说明本发明而不用于限制本发明的范围，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的反应温度、时间、投料量等也仅是合适范围中的一个示例，即、本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。采用的原料、试剂可以通过购买市售原料或传统化学转化方式合成制得。下列实施例中未注明具体条件的实验方法，通常按照常规条件，例如是《贝尔斯坦有机化学手册》(化学工业出版社，1996年)中的条件，或按照制造厂商所建议的条件。比例和百分比基于摩尔质量，除非特别说明。除非另有定义或说明，本文中所使用的所有专业与科学用语与本领域技术熟练人员所熟悉的意义相同。此外任何与所记载内容相似或等同的方法及材料皆可应用于本发明方法中。本发明的其他方面由于本文的公开内容，对本领域的技术人员而言是容易理解的。It should be understood that the above-mentioned embodiments described in detail in the present invention and the following examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention, and those skilled in the art may make some non-essential improvements and improvements according to the above-mentioned contents of the present invention All adjustments belong to the protection scope of the present invention. The specific reaction temperature, time, feeding amount, etc. of the following examples are only an example of a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific examples exemplified below. value. The raw materials and reagents used can be synthesized by purchasing commercially available raw materials or traditional chemical transformation. The experimental methods in the following examples that do not indicate specific conditions are generally in accordance with conventional conditions, such as the conditions in "Beilstein Organic Chemistry Handbook" (Chemical Industry Press, 1996), or in accordance with the conditions suggested by the manufacturer. Ratios and percentages are based on molar mass unless otherwise stated. Unless otherwise defined or stated, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described can be applied to the method of the present invention. Other aspects of the invention will be readily apparent to those skilled in the art in view of the disclosure herein.
实施例1Example 1
配制0.4mol/L的VOSO4水溶液50ml，加入2.5g尿素并在室温下磁力搅拌直至获得均匀的蓝色溶液，然后将混合液装入100ml的水热釜中，180℃水热反应24小时，自然冷却至室温，离心干燥得到粉体，产物为片状结构，其主要结晶相为B相。Prepare 50ml of 0.4mol/L VOSO 4 aqueous solution, add 2.5g of urea and magnetically stir at room temperature until a uniform blue solution is obtained, then put the mixed solution into a 100ml hydrothermal kettle, and conduct a hydrothermal reaction at 180°C for 24 hours. Natural cooling to room temperature, centrifugal drying to obtain a powder, the product is a sheet structure, and its main crystal phase is B phase.
实施例2Example 2
配制0.4mol/L的VOSO4水溶液50ml，加入2.5g尿素并在室温下磁力搅拌直至获得均匀的蓝色溶液，然后将混合液装入100ml的水热釜中，220℃水热反应24小时，自然冷却至室温，离心干燥得到粉体，产物为片状和颗粒状的混合物，其主要结晶相为A相和B相。Prepare 50ml of 0.4mol/L VOSO 4 aqueous solution, add 2.5g of urea and magnetically stir at room temperature until a uniform blue solution is obtained, then put the mixed solution into a 100ml hydrothermal kettle, and conduct a hydrothermal reaction at 220°C for 24 hours. Naturally cool to room temperature, centrifuge and dry to obtain powder, the product is a mixture of flakes and granules, and its main crystal phases are phase A and phase B.
实施例3Example 3
配制0.4mol/L的VOSO4水溶液50ml，加入2.5g尿素并在室温下磁力搅拌直至获得均匀的蓝色溶液，然后将混合液装入100ml的水热釜中，260℃水热反应24小时，自然冷却至室温，离心干燥得到二氧化钒粉体，其化学式为VO2，收率高于95%。如图1XRD图谱所示，其结晶相为纯的M相，如图2SEM照片和图3TEM照片所示，制得的二氧化钒粉体为颗粒状，每个二氧化钒颗粒为单晶颗粒，其颗粒尺寸主要集中在30～50nm之间，长径比集中在1:1～2:1。如图4DSC曲线所示，所制得的粉体的升温相变温度为65.8℃，降温相变温度为49.2℃，热滞后温度差为16.6℃。Prepare 50ml of 0.4mol/L VOSO 4 aqueous solution, add 2.5g of urea and magnetically stir at room temperature until a uniform blue solution is obtained, then put the mixed solution into a 100ml hydrothermal kettle, and conduct a hydrothermal reaction at 260°C for 24 hours. Naturally cool to room temperature, centrifugally dry to obtain vanadium dioxide powder, its chemical formula is VO 2 , and the yield is higher than 95%. As shown in Figure 1 XRD pattern, its crystalline phase is pure M phase, as shown in Figure 2 SEM photo and Figure 3 TEM photo, the prepared vanadium dioxide powder is granular, and each vanadium dioxide particle is a single crystal particle, The particle size is mainly concentrated between 30-50nm, and the aspect ratio is concentrated in 1:1-2:1. As shown in the DSC curve in Figure 4, the phase transition temperature of the prepared powder is 65.8°C when the temperature rises, 49.2°C when the temperature drops, and the thermal hysteresis temperature difference is 16.6°C.
实施例4Example 4
用36小时替换24小时，重复实施例3的实验，最终得到的二氧化钒粉体，其化学式为VO2，其结晶相依然为纯的M相，收率高于95%。随着反应时间的延长，粉体的结晶性得到明显的提高。其颗粒尺寸主要集中在30～100nm之间，长径比集中在1:1～3:1。Replace 24 hours with 36 hours, repeat the experiment of Example 3, the finally obtained vanadium dioxide powder, its chemical formula is VO 2 , its crystalline phase is still pure M phase, and the yield is higher than 95%. With the prolongation of the reaction time, the crystallinity of the powder is obviously improved. The particle size is mainly concentrated between 30-100nm, and the aspect ratio is concentrated in the range of 1:1-3:1.
实施例5Example 5
配置0.2mol/L的VOSO4水溶液50ml，加入1.25g尿素并在室温下磁力搅拌直至获得均匀的蓝色溶液，然后将混合液装入100ml的水热釜中，260℃水热反应24小时，自然冷却至室温，离心干燥得到二氧化钒粉体，其化学式为VO2，收率高于95%。其结晶相为纯的M相，如图5SEM照片所示，制得的二氧化钒粉体为颗粒状和短棒状的混合物，其中每个颗粒状和棒状的二氧化钒均为单晶，颗粒的尺寸主要集中在30～50nm之间，长径比集中在1:1～2:1，短棒长度达100～500nm，宽度达50～100nm。Prepare 50ml of 0.2mol/L VOSO 4 aqueous solution, add 1.25g of urea and magnetically stir at room temperature until a uniform blue solution is obtained, then put the mixed solution into a 100ml hydrothermal kettle, and conduct a hydrothermal reaction at 260°C for 24 hours. Naturally cool to room temperature, centrifugally dry to obtain vanadium dioxide powder, its chemical formula is VO 2 , and the yield is higher than 95%. Its crystalline phase is pure M phase, as shown in the SEM photo of Figure 5, the prepared vanadium dioxide powder is a mixture of granular and short rod-shaped, wherein each granular and rod-shaped vanadium dioxide is a single crystal, the particle The size of the rod is mainly concentrated in the range of 30-50nm, the aspect ratio is concentrated in the range of 1:1-2:1, the length of the short rod is 100-500nm, and the width is 50-100nm.
实施例6Example 6
配置0.05mol/L的VOSO4水溶液50ml，加入0.3g尿素并在室温下磁力搅拌直至获得均匀的蓝色溶液，然后将混合液装入100ml的水热釜中，260℃水热反应24小时，自然冷却至室温，离心干燥得到二氧化钒粉体，其化学式为VO2，其结晶相为纯的M相，并且收率高于95%。如图6SEM照片所示，制得的二氧化钒为棒状，每个棒状的二氧化钒均为单晶，棒状的长度集中在500nm～1μm，宽度集中在50～100nm。Configure 50ml of 0.05mol/L VOSO 4 aqueous solution, add 0.3g of urea and magnetically stir at room temperature until a uniform blue solution is obtained, then put the mixed solution into a 100ml hydrothermal kettle, and conduct a hydrothermal reaction at 260°C for 24 hours. Natural cooling to room temperature, centrifugal drying to obtain vanadium dioxide powder, its chemical formula is VO 2 , its crystal phase is pure M phase, and the yield is higher than 95%. As shown in the SEM photo of Figure 6, the prepared vanadium dioxide is rod-shaped, and each rod-shaped vanadium dioxide is a single crystal. The length of the rods is concentrated in the range of 500 nm to 1 μm, and the width of the rods is concentrated in the range of 50 to 100 nm.
实施例7Example 7
配置0.2mol/L的VOSO4水溶液50ml，加入1.25g尿素并在室温下搅拌直至获得均匀的蓝色溶液。然后在混合液中加入50mg的H2WO4，混合均匀后将混合液装入100ml的水热釜中，260℃水热反应24小时，离心干燥得到掺杂的二氧化钒粉体，其结晶相为纯的M相。所制得的粉体的升温相变温度为52.5℃，降温相变温度为34.5℃，热滞后温度差为18℃，与未掺杂的二氧化钒粉体相比，升温相变温度降低了13.3℃。Prepare 50ml of 0.2mol/L VOSO 4 aqueous solution, add 1.25g of urea and stir at room temperature until a uniform blue solution is obtained. Then add 50 mg of H 2 WO 4 to the mixed solution, mix well, put the mixed solution into a 100ml hydrothermal kettle, conduct a hydrothermal reaction at 260°C for 24 hours, and centrifugally dry to obtain doped vanadium dioxide powder, which crystallizes The phase is pure M phase. The phase transition temperature of the prepared powder is 52.5°C when the temperature rises, 34.5°C when the temperature drops, and the thermal hysteresis temperature difference is 18°C. Compared with the undoped vanadium dioxide powder, the phase transition temperature when the temperature rises is lower 13.3°C.
实施例8Example 8
用200mg H2WO4替换50mg H2WO4，重复实施例7的实验，得到二氧化钒粉体，其化学式为VO2，其结晶相依然为纯的M相，收率高于95%。制得的二氧化钒升温相变温度为33.2℃。Replace 50mg H 2 WO 4 with 200mg H 2 WO 4 , repeat the experiment of Example 7, and obtain vanadium dioxide powder, whose chemical formula is VO 2 , and its crystal phase is still pure M phase, and the yield is higher than 95%. The warming phase transition temperature of the prepared vanadium dioxide is 33.2°C.
实施例9Example 9
配制0.4mol/L的VOSO4水溶液50ml，加入5.0g尿素并在室温下磁力搅拌直至获得均匀的蓝色溶液，然后将混合液装入100ml的水热釜中，260℃水热反应24小时，自然冷却至室温，离心干燥得到粉体，产物为颗粒状，其主要结晶相为M相。Prepare 50ml of 0.4mol/L VOSO 4 aqueous solution, add 5.0g of urea and magnetically stir at room temperature until a uniform blue solution is obtained, then put the mixed solution into a 100ml hydrothermal kettle, and conduct a hydrothermal reaction at 260°C for 24 hours. Natural cooling to room temperature, centrifugal drying to obtain powder, the product is granular, and its main crystal phase is M phase.
产业应用性：本发明的制备二氧化钒粉体的方法，工艺简单、成本低、收率高，适合规模生产。本发明的二氧化钒粉体可以应用于节能涂料、节能油漆、温控装置（例如太阳能温控装置）以及节能涂层；还可以应用于既有建筑、车船等表面的节能改造；又可应用于能源信息设备，包括微型光电开关器件、热敏电阻、电池材料和光信息存储器件等。Industrial applicability: The method for preparing vanadium dioxide powder of the present invention has simple process, low cost and high yield, and is suitable for large-scale production. The vanadium dioxide powder of the present invention can be applied to energy-saving coatings, energy-saving paints, temperature control devices (such as solar temperature control devices) and energy-saving coatings; it can also be applied to energy-saving renovation of the surfaces of existing buildings, vehicles and ships; For energy information equipment, including micro photoelectric switching devices, thermistors, battery materials and optical information storage devices, etc.
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| CN105060242B (en) * | 2015-07-10 | 2017-01-04 | 上海纳米技术及应用国家工程研究中心有限公司 | A preparation method of hierarchical self-assembled SnO2-SnO composite nanomaterials |
| CN105060242A (en) * | 2015-07-10 | 2015-11-18 | 上海纳米技术及应用国家工程研究中心有限公司 | A preparation method of hierarchical self-assembled SnO2-SnO composite nanomaterials |
| CN109496203A (en) * | 2016-07-29 | 2019-03-19 | 柯尼卡美能达株式会社 | The manufacturing method of the particle containing vanadium dioxide and particle containing vanadium dioxide |
| CN110615476A (en) * | 2019-10-24 | 2019-12-27 | 成都先进金属材料产业技术研究院有限公司 | M-phase VO prepared by using failed vanadium battery positive electrolyte2Method (2) |
| CN110734088A (en) * | 2019-10-24 | 2020-01-31 | 成都先进金属材料产业技术研究院有限公司 | M-phase VO prepared by using invalid vanadium battery negative electrolyte2Method (2) |
| CN110808176B (en) * | 2019-11-04 | 2021-09-17 | 辽宁工程技术大学 | VO2/Co(OH)2Nano composite material and preparation method thereof and super capacitor |
| CN110808176A (en) * | 2019-11-04 | 2020-02-18 | 辽宁工程技术大学 | VO2/Co(OH)2Nano composite material and preparation method thereof and super capacitor |
| CN114901596B (en) * | 2020-08-26 | 2024-01-30 | 安比莱特 | VO with charge balance material for electrochromic device X Vanadium oxide of formula |
| CN114901596A (en) * | 2020-08-26 | 2022-08-12 | 安比莱特 | VO used as charge balance material of electrochromic device X Vanadium oxide of the formula |
| CN112209440A (en) * | 2020-10-16 | 2021-01-12 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing M-phase vanadium dioxide nano powder |
| CN112266019A (en) * | 2020-10-16 | 2021-01-26 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization homogeneous precipitation method |
| CN112158883A (en) * | 2020-10-16 | 2021-01-01 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing vanadium dioxide nano powder |
| CN112125337A (en) * | 2020-10-16 | 2020-12-25 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing nano vanadium dioxide by using pentavalent vanadium alkoxide as raw material |
| CN112239229A (en) * | 2020-10-19 | 2021-01-19 | 成都先进金属材料产业技术研究院有限公司 | Preparation of spherical VO by ultrasonic atomization method2Method and device for preparing nano powder |
| CN112239229B (en) * | 2020-10-19 | 2022-03-22 | 成都先进金属材料产业技术研究院股份有限公司 | Method and device for preparing spherical VO2 nano powder by ultrasonic atomization method |
| CN113998736A (en) * | 2021-11-09 | 2022-02-01 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of tungsten-lanthanum co-doped vanadium dioxide powder |
| CN113880139A (en) * | 2021-11-18 | 2022-01-04 | 成都先进金属材料产业技术研究院股份有限公司 | Tin oxide/vanadium dioxide composite nano material and preparation method thereof |
| CN115611310A (en) * | 2022-10-08 | 2023-01-17 | 武汉科技大学 | A method for preparing high-purity vanadium pentoxide with vanadium-containing solution |
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