KR101578909B1 - Composite of transition materials-substituted vanadium dioxide with inorganic oxides and method for preparing the same - Google Patents
Composite of transition materials-substituted vanadium dioxide with inorganic oxides and method for preparing the same Download PDFInfo
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- KR101578909B1 KR101578909B1 KR1020150122737A KR20150122737A KR101578909B1 KR 101578909 B1 KR101578909 B1 KR 101578909B1 KR 1020150122737 A KR1020150122737 A KR 1020150122737A KR 20150122737 A KR20150122737 A KR 20150122737A KR 101578909 B1 KR101578909 B1 KR 101578909B1
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Abstract
The present invention relates to a transition metal-substituted vanadium dioxide composite coated with an inorganic oxide, and a method for manufacturing a transition metal-substituted vanadium dioxide complex coated with an inorganic oxide through a process of simultaneously coating different kinds of inorganic oxides, Oxide-coated transition metal-substituted vanadium dioxide complex. According to the present invention, by simultaneously coating vanadium dioxide substituted with a transition metal having a transition temperature in a temperature range that can be used in practical use with two kinds of inorganic oxides such as silica and titanium dioxide, the oxidation reaction of vanadium dioxide is suppressed, With this effect, a film having magnetic cleaning property and high visibility can be produced. Due to the above characteristics, the substituted vanadium dioxide composite can selectively block and transmit incident sunlight according to the external temperature to automatically control the internal temperature, thereby increasing the energy efficiency of the indoor air-conditioning and heating , Smart glass, thermoelectric film, and so on.
Description
The present invention relates to a transition metal-substituted vanadium dioxide complex coated with an inorganic oxide and a process for preparing the same, and more particularly, to a process for preparing a vanadium oxide complex by dispersing vanadium dioxide in which a transition metal has been substituted in an alcohol solvent, To a transition metal substituted vanadium dioxide complex in which a heterogeneous inorganic oxide is simultaneously coated.
Vanadium dioxide among the vanadium oxides has a thermochromic characteristic in which the infrared transmittance and electrical resistance change rapidly around 68 캜. The vanadium dioxide exists as a crystal having a monoclinic semiconductor property at a transition temperature or lower and has a high infrared ray transmittance and a low electric conductivity. On the other hand, above the transition temperature, the electrical conductivity increases with the transition from the tetragonal crystal to the metal, reflecting the infrared ray. Due to these characteristics, vanadium dioxide has been studied and utilized as an energy-saving window (smart window) that automatically controls the room temperature by blocking the sunlight transmission according to the electric sensor and the external temperature.
In particular, a method for producing vanadium dioxide film, which is generally used for a smart window, can be divided into two methods: vapor phase and wet phase. Among these methods, chemical vapor deposition, RF magnetron sputtering, and laser pulse deposition are used as a vapor deposition method. However, when the vapor-phase method is applied to the vanadium dioxide coating, a uniformly coated thin film can be obtained. However, it is difficult to control the phase transition temperature and ensure visible light transmission, and it is disadvantageous in application to a large area. There is a drawback to doing so.
On the other hand, the wet method is to synthesize vanadium dioxide particles having thermoelectric properties and to prepare coating liquids and films thereof. In the synthesis of vanadium dioxide particles, it is possible to control the phase transition temperature through the substitution of transition metals, And low-cost coating liquids and films. The vanadium dioxide particles can be prepared by a wet method such as a sol-gel method, a melting method, and a hydrothermal synthesis method, but the process yield is low and the production time is long. Also, when such a wet process is applied, exposure to air and humidity in the air for a long period of time during the process and circulation may oxidize the vanadium dioxide particles and lose their original characteristics, which is problematic in application to smart glass and thermoelectric film Lt; / RTI >
Accordingly, there is a desperate need to develop a thermoelectric material which is excellent in reproducibility and mass productivity, low in economical burden, and capable of remarkably improving the oxidation resistance and phase transition efficiency by a conventional ceramic particle production process.
The present invention relates to a thermoelectric material having a high visible light transmittance, oxidation resistance and self-cleaning ability while reducing the economic burden of the entire process by using a ceramic particle production process such as pyrolysis, excellent in reproducibility and mass productivity, A transition metal-substituted vanadium dioxide complex coated with a different kind of inorganic oxide, and a process for producing the same.
The present invention relates to a core layer of transition metal substituted vanadium dioxide; And a first inorganic oxide and a second single coating layer of crystalline containing an inorganic oxide; made of a, and the first inorganic oxide is silica (SiO 2), the second inorganic oxide is titanium dioxide (TiO 2), zirconia ( ZrO 2 ), and zinc oxide (ZnO). The transition metal-substituted vanadium dioxide complex coated with an inorganic oxide is provided.
The present invention also relates to a process for producing a vanadium compound, comprising the steps of: dispersing a vanadium dioxide substituted with a transition metal in a solvent containing an alcohol;
Wherein the dispersion contains at least one first inorganic oxide precursor selected from the group consisting of tetraethylorthosilicate, tetraethoxysilane, tetramethoxysilane, glycidyloxypropyltrimethoxysilane, and methoxytriethoxysilane, Titanium isopropoxide, titanium tetrabutoxide, titanium tetrachloride, titanium tetraisopropoxide, titanium sulfate, zirconium propoxide, zirconium oxychloride, zirconium tetrachloride, zirconium nitrate, zirconium sulfate, zinc hydroxide, zinc hydroxide, zinc nitrate hexahydrate , And zinc chloride, and performing a hydrolysis process to coat the first and second inorganic oxides with the transition metal-substituted vanadium oxide as a single layer ; And
Sintering the inorganic oxide coated particles to form a single crystalline coating layer;
A transition metal-substituted vanadium dioxide complex coated with the inorganic oxide.
Hereinafter, a transition metal-substituted vanadium dioxide complex coated with an inorganic oxide according to a specific embodiment of the present invention and a method for producing the same will be described in detail. It is to be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
&Quot; Including "or" containing ", unless the context clearly dictates otherwise throughout the specification, refers to any element (or component) including without limitation, excluding the addition of another component . Also, in this specification, the terms " first "and" second "do not represent a separate order, but merely refer to arbitrary reference to distinguish each component.
The present invention uses a ceramic particle manufacturing process using a pyrolysis process and a coating process in an aqueous solution, thereby achieving excellent reproducibility and mass productivity, lowering the economic burden, and exhibiting high visible light transmittance, oxidation resistance, A transition metal-substituted vanadium dioxide complex can be effectively produced.
In particular, the transition metal-substituted vanadium dioxide composite prepared by simultaneously coating different kinds of inorganic oxides according to the present invention has a high oxidation resistance and self-cleaning ability in the production of thermoelectric film or smart glass as compared with conventional vanadium dioxide particles, It is possible to remarkably improve the heat transfer characteristic while having visible light transmittance.
In one embodiment of the invention, the present invention provides a transition metal substituted vanadium dioxide complex in which heterogeneous inorganic oxides are simultaneously coated with a single coating layer. The vanadium dioxide composite comprising a core layer of transition metal substituted vanadium dioxide; And a first inorganic oxide and a second single coating layer of crystalline containing an inorganic oxide; made of a, and the first inorganic oxide is silica (SiO 2), the second inorganic oxide is titanium dioxide (TiO 2), zirconia ( ZrO 2 ), and zinc oxide (ZnO).
In the present invention, the composite is centered on vanadium dioxide in which a transition metal having a thermoelectric property is substituted, and two inorganic oxides of different kinds are simultaneously coated on the vanadium dioxide particles to form a single coating layer. In this structure, the different kinds of inorganic oxides forming the coating layer improve the oxidation resistance of vanadium dioxide, thereby suppressing the additional oxidation reaction, thereby having a stable heat transfer effect.
The structure having the above characteristics can provide a composite-function nano material exhibiting two or more characteristics depending on which material is used, respectively, and thus it is utilized in various fields. In particular, in the present invention, when two kinds of inorganic oxides are simultaneously coated with a single coating layer of a transition metal vanadium dioxide, they have thermal and oxidative stability as well as high visible light transmittance and magnetic cleaning ability So that it has a stable thermoelectric effect and a high visibility and magnetic cleaning function.
Particularly, the synthesis of core-shell particles in which vanadium dioxide particles are coated with inorganic oxides such as silica (SiO 2 ) and titanium dioxide (TiO 2 ) has been studied. Of the inorganic oxides studied above, silica is a transparent and chemically stable material. When silica is coated on vanadium dioxide particles, it is possible to produce thermoelectric particles having high oxidation resistance and acid resistance while maintaining the inherent heat transfer characteristics of vanadium dioxide . On the other hand, if titanium dioxide is coated on vanadium dioxide, it is possible to produce thermoelectric particles having self-cleaning ability of titanium dioxide and improved visible light transmittance.
In a specific embodiment of the present invention, the first inorganic oxide such as silica can improve the chemical stability of the core particle in the case of an inorganic oxide that is transparent and chemically stable. In addition, a high refractive index material such as a second inorganic oxide such as titania has an advantage that visibility can be improved when applied to a film due to a difference in refractive index between the core particle and the high refractive index material. Particularly, in order to secure high visible light transmittance, oxidation resistance, and self-cleaning ability while maintaining high phase transition efficiency, it is preferable that the different kinds of inorganic oxides are uniformly coated with a sufficient composition.
According to the present invention, a transition metal-substituted vanadium dioxide composite in which different kinds of inorganic oxides are simultaneously coated has a structure in which vanadium dioxide is in its center in its shape and size, and different kinds of inorganic oxides form a single coating layer on the surface of vanadium dioxide particles And has an average particle size of from 10 nm to 150 nm, preferably from 15 nm to 100 nm, more preferably from 25 nm to 70 nm, in a spherical shape. Further, the crystal structure of the transition metal substituted vanadium dioxide positioned at the center may be monoclinic, and the thickness of a single coating layer of the two kinds of inorganic oxides forming the coating layer is preferably 5 nm to 20 nm, And more preferably from 10 nm to 15 nm. Particularly, in the conventional method, it is possible to prepare a composite having a double coating layer through two coating processes of the first inorganic oxide and the second inorganic oxide on the VO2 particles so as to include the advantages of the two inorganic oxides, May be greater than 20 nm. When the thickness of the coating layer excessively increases, there is a problem that the phase transition property of the core particle VO 2 may be difficult. Also, in the process of coating twice after coating once, it may be difficult to manufacture a uniform size composite by simultaneously coating the aggregated particles.
More specifically, FIG. 2 is a TEM (Transmission Electron Microscope) photograph of a transition metal substituted vanadium dioxide complex coated with an inorganic oxide prepared according to the present invention. As shown in FIG. 2, the vanadium dioxide composite used in the present invention is a composite in which two kinds of inorganic oxides are coated on vanadium dioxide particles. By the coating layer, the vanadium dioxide particles have thermal, oxidative stability and high visible light transmittance, Ability. The composite may be prepared by hydrolysis in an alcohol solvent, and the thickness of the average coating layer is preferably in the range of 5 nm to 20 nm from the viewpoint of the efficient heat transfer property of vanadium dioxide.
The transition metal-substituted vanadium dioxide complex coated with an inorganic oxide of the present invention can be confirmed to have crystallinity by X-ray diffraction (XRD) analysis. In X-ray diffraction analysis, the representative peak of VO 2 (M) Coincident peaks may appear at positions of ° (1 1 0), 37 ° (2 0 0), 42.1 ° (2 10), and 55.4 ° (2 2 0). In addition, the degree to match the strength of the representative peak when XRD measurement of the dioxide vanadium VO 2 (M) strength is not a transition metal is substituted for the representative peak at least 60%, preferably at least 70%, more preferably 80 % ≪ / RTI >
The transition metal-substituted vanadium dioxide complex coated with the inorganic oxide of the present invention may have a phase transition temperature of 25 to 70 캜, preferably 25 to 60 캜, more preferably 25 to 50 캜. In particular, the inorganic oxide-coated vanadium dioxide composite of the present invention exhibits excellent phase transition characteristics not only immediately after synthesis but also after long-term storage under high temperature and high humidity conditions. That is, in the present invention, accelerated weather resistance is tested by applying a severe condition that is more severe than actual conditions, for example, a temperature of 80 ° C and a relative humidity of 80%, in order to enable excellent phase transition characteristics to be exhibited even after long- The phase transition characteristics can be confirmed. The point immediately after the synthesis is before the accelerated weathering test.
The inorganic oxide-coated transition metal-substituted vanadium dioxide composite coated with the inorganic oxide of the present invention is allowed to stand for at least 7 days under conditions of a temperature of 80 ° C and a relative humidity of 80% , the intensity of the endothermic peak measured by differential scanning calorimeter analysis is preferably 30% or more of the intensity of the endothermic peak measured through differential scanning calorimetry (DSC) , It may be 40% or more, and more preferably 50% or more. Here, when the intensity of the endothermic peak after being left under the high temperature and high humidity condition is first synthesized, when the content is less than 30% of the endothermic peak of the composite, the phase transition property of vanadium dioxide itself is lost due to the external environment. There is a difficulty in reducing solar heat control ability according to the outside temperature. The temperature of the endothermic peak measured through differential scanning calorimetry (DSC) analysis, that is, the phase transition temperature is 22 to 73 ° C, preferably 22 to 63 ° C, more preferably, Lt; RTI ID = 0.0 > 22 C < / RTI > The temperature of the endothermic peak measured through the differential scanning calorimeter analysis after allowing to stand for at least 7 days under the conditions of a temperature of 80 DEG C and a relative humidity of 80% is preferably set to a temperature of the endothermic peak measured through differential scanning calorimetry 3 < 0 > C, more preferably within 2 < 0 > C. As described above, the vanadium dioxide composite coated with the inorganic oxide of the present invention can be applied to a smart glass and a thermally conductive film without losing the original phase transition property by being stable to air and humidity in the atmosphere.
Further, the vanadium dioxide composite coated with the inorganic oxide of the present invention may have a visible light transmittance of preferably 65% or more, more preferably 70% or more. Particularly, as the transmittance in the visible light wavelength region increases, the transparency becomes more transparent and the visibility becomes higher, and the visibility and the view right for use in a building window or a car window become better. Therefore, in order to obtain high transparency and visibility in a building window or an automobile window, it is preferable that the visible light transmittance is 65% or more.
In another embodiment of the present invention, the present invention provides a method for producing a transition metal-substituted vanadium dioxide complex coated with a different kind of inorganic oxide having excellent oxidation resistance and heat transfer characteristics as described above. The method for producing a transition metal-substituted vanadium dioxide complex coated with an inorganic oxide includes the steps of: dispersing a vanadium dioxide substituted with a transition metal in a solvent containing an alcohol; Wherein the dispersion contains at least one first inorganic oxide precursor selected from the group consisting of tetraethylorthosilicate, tetraethoxysilane, tetramethoxysilane, glycidyloxypropyltrimethoxysilane, and methoxytriethoxysilane, Titanium isopropoxide, titanium tetrabutoxide, titanium tetrachloride, titanium tetraisopropoxide, titanium sulfate, zirconium propoxide, zirconium oxychloride, zirconium tetrachloride, zirconium nitrate, zirconium sulfate, zinc hydroxide, zinc hydroxide, zinc nitrate hexahydrate , And zinc chloride, and performing a hydrolysis process to coat the first and second inorganic oxides with the transition metal-substituted vanadium oxide as a single layer ; And sintering the inorganic oxide-coated particles to form a single crystalline coating layer.
The present invention uses a ceramic particle manufacturing process using a pyrolysis process and a coating process in an aqueous solution, thereby achieving excellent reproducibility and mass productivity, lowering the economic burden, and exhibiting high visible light transmittance, oxidation resistance, A transition metal-substituted vanadium dioxide complex can be effectively produced.
In particular, the transition metal-substituted vanadium dioxide composite prepared by simultaneously coating different kinds of inorganic oxides according to the present invention has a high oxidation resistance and self-cleaning ability in the production of thermoelectric film or smart glass as compared with conventional vanadium dioxide particles, It is possible to remarkably improve the heat transfer characteristic while having visible light transmittance.
In the present invention, a vanadium compound and a transition metal compound are mixed in a solution phase, stirred at 100 to 500 rpm for 0.5 to 5 hours, and then heat-treated at 500 to 1,200 ° C for 1 to 5 hours to produce vanadium dioxide And a second step of performing the second step.
In the present invention, the vanadium compound as the starting material of the transition metal-substituted vanadium dioxide may be vanadium oxide or the vanadyl salt represented by the formula (1). Specifically, the vanadium salt in the present invention are vanadium pentoxide (V 2 O 5, vanadium pentoxide), vanadium sulfate (VOSO 4, vanadyl sulfate), vanadyl chloride (VOCl 2, vanadyl chloride), and vanadyl acetylacetonate ( VO (C 5 H 7 O 2 ) 2 , vanadyl acetylacetonate), and vanadium sulfate is preferred from the viewpoint of economical efficiency in obtaining a high yield relative to the cost. Here, it can also be used in the form of hydrate (xH 2 O).
[Chemical Formula 1]
VOX 2
Wherein X is a sulfate group, a halogen group, or an acetylaceto group.
In the transition metal-substituted vanadium dioxide of the present invention, the transition metal may be one selected from the group consisting of tungsten (W), molybdenum (Mo), niobium (Nb), antimony (Sb), indium (In) Or more. A compound containing such a transition metal can be used as a starting material together with the vanadium compound. For example, the transition metal compound as the starting material is sodium tungstate (Na 2 WO 4 ), sodium molybdate (Na 2 MoO 4 ), potassium niobate (KNbO 3 ), sodium antimonate (NaO 3 Sb) InCl 3 ), sodium chromate (Na 2 CrO 4 ), and the like.
Further, the content ratio of the transition metal in the transition metal-substituted vanadium dioxide of the present invention is 0.01 at% to 15 at%, preferably 0.1 at% to 10 at%, more preferably 0.5 at% based on the total atomic amount of vanadium dioxide % To 5 at%. If the content of transition metal is excessively increased, the crystallinity of the vanadium dioxide may be lowered and transformed into the substituted transition metal oxide form (MO x ). If the content of the transition metal is lower than 0.01 at%, it is impossible to expect an effective phase transition temperature reduction due to the transition metal substitution, and it is important to fix the content of the transition metal.
In addition, the average particle diameter of the vanadium dioxide substituted with the transition metal may be 5 nm to 100 nm, preferably 5 nm to 80 nm, more preferably 5 nm to 50 nm. The particle size of vanadium dioxide substituted with transition metal is an important parameter in the application to smart glass and thermoelectric film. If the particle diameter of vanadium dioxide substituted with transition metal becomes larger, it may cause a decrease in transparency of the film . In addition, if the particles have an excessively small particle diameter, the cohesive force between the particles increases, and the dispersibility in the coating liquid can be lowered.
In the present invention, vanadium dioxide in which the transition metal is substituted is dispersed in a solvent containing an alcohol, and then different kinds of inorganic oxide precursors, that is, the first inorganic oxide precursor and the second inorganic oxide precursor are added to the dispersion, And two kinds of inorganic oxides of different kinds can be coated at the same time. In the coating step, the hydrolysis may be performed under basic conditions of pH 8-14, preferably pH 9-13 by adding ammonia water or the like. Further, the hydrolysis step may be performed by adding an inorganic oxide precursor to a dispersion containing vanadium dioxide in which a transition metal is substituted, stirring the mixture at 500 to 600 rpm for 5 to 20 minutes, and then heating the mixture at 150 to 350 rpm for 2 to 8 hours Followed by further stirring.
In a preferred embodiment of the present invention, the heterogeneous inorganic oxide may be made of silica (SiO 2 ) having thermal and oxidative stability and titanium dioxide (TiO 2 ) having high refractive index and magnetic cleaning ability. Examples of the first inorganic oxide precursor and the second inorganic oxide precursor that form such an inorganic oxide include tetraethylorthosilicate, tetraethoxysilane, tetramethoxysilane, glycidyloxypropyltrimethoxysilane, and methoxytri Titanium tetrabutoxide, titanium tetraisopropoxide, titanium sulfate, zirconium propoxide, zirconium oxychloride, zirconium tetrachloride, zirconium nitrate, and zirconium nitrate. , Zirconium sulfate, zinc hydroxide, zinc nitrate hexahydrate, and zinc chloride.
In the hydrolysis step, the first inorganic oxide precursor may be added in an amount of 5 to 40 parts by weight based on 100 parts by weight of vanadium dioxide. The second inorganic oxide precursor may be added in an amount of 5 to 40 parts by weight based on 100 parts by weight of vanadium dioxide. Here, the first inorganic oxide precursor and the second inorganic oxide precursor may be added in a content ratio of 3: 7 to 7: 3 by weight. Particularly, in view of securing the high visible light transmittance, the oxidation resistance and the self-cleaning ability at the same time while maintaining the thermoelectric conversion property in the finally produced vanadium dioxide composite, the first and second inorganic oxides can be uniformly coated in the single coating layer It is desirable to maintain the content range. If the content ratio of the first inorganic oxide precursor and the second inorganic oxide precursor is out of the range of 3: 7 to 7: 3, the content of the oxide having a ratio of 3 or less is decreased, And the probability that particles not containing an oxide having a ratio of 3 or less are not included in the coating layer is increased.
In addition, the two inorganic oxides coated on the vanadium dioxide by the hydrolysis are subjected to an additional annealing step to form a crystalline single coating layer. The annealing step may be performed at a temperature of 400 ° C to 450 ° C under atmospheric pressure of 40 mtorr to 3 torr. A single coating layer of such a crystal can be confirmed by a TEM image and qualitative analysis such as XRD and EDS. Particularly, according to the present invention, vanadium dioxide substituted with a transition metal is simultaneously coated with a different kind of inorganic oxide, and a single coating layer is formed so that all kinds of inorganic oxide characteristics can be simultaneously expressed. Here, the term "single coating layer" refers to vanadium dioxide as a core particle containing only one coating layer, which can be confirmed by TEM image.
Hereinafter, a specific example of the present invention will be described in detail with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow diagram for a method for producing a transition metal substituted vanadium dioxide complex in which two different kinds of inorganic oxides according to the present invention are simultaneously coated. FIG.
As shown in FIG. 1, a method for preparing a transition metal-substituted vanadium dioxide composite in which two kinds of inorganic oxides according to the present invention are coated simultaneously includes a step (P01) of synthesizing a vanadium dioxide substituted with a transition metal (P01) Dispersing vanadium dioxide in an alcohol solvent (P02), adding different kinds of inorganic oxide precursors to the dispersed vanadium dioxide, i.e., the first inorganic oxide precursor and the second inorganic oxide precursor, (P03) coating the inorganic oxide at the same time, and (P04) forming a single crystalline coating layer by annealing the particles coated with two or more inorganic oxides.
In the step P01 of synthesizing vanadium dioxide substituted with the transition metal, a solution containing vanadium salt (hereinafter referred to as a vanadium salt aqueous solution) is first prepared. Vanadium can have various oxidation numbers, and vanadium salts can be any of oxidation numbers +2, +3, +4, and +5. The oxidation number of such a vanadium salt may be varied depending on processing conditions such as the process execution temperature or the concentration of the vanadium salt or the calcination temperature. The prepared vanadium oxide contains vanadium oxide of the oxidation state in the most stable state, but vanadium oxides of other oxidation states having somewhat low stability can be also produced. The vanadium salt used in the present invention is not particularly limited, but it is required to satisfy the condition that a transition metal compound is to be formed after mixing with the transition metal compound. When the vanadium salt is used as an aqueous solution, the vanadium salt solution may include sulfuric acid. At this time, the vanadium salt solution may be an aqueous solution of vanadium sulfate (VOSO 4 ).
The concentration of the vanadium salt aqueous solution can be optimally used to obtain a high yield. For example, the concentration of the vanadium salt aqueous solution may be 0.01 to 1 M, preferably 0.03 to 0.9 M, and more preferably 0.05 to 0.8 M. If the concentration of the vanadium salt is lower than 0.1 M, the vanadium salt acting as a precursor of the vanadium oxide is too small and the yield of the vanadium dioxide oxide substituted with the transition metal as the final product may be too low. Further, if the concentration of the vanadium salt is more than 1 M, an additional side reaction may be generated or the reaction may not proceed after the reaction with the transition metal compound.
In the present invention, the transition metal compound used in the reaction with the vanadium salt aqueous solution is generally used to provide a substitution element to lower the phase transition temperature of 68 캜 of vanadium oxide to room temperature. Here, the transition metal compound used for substituting the transition metal can be used at a concentration of 0.1 to 1.5 M, preferably 0.15 to 1.2 M, more preferably 0.3 to 1.0 M. Further, the transition metal compound was reacted with an aqueous solution of vanadyl salt according to a transition metal content ratio ranging from 0.01 at% to 15 at%, after preparation into the above-mentioned aqueous solution. If the substitutional content of the transition metal is excessively increased, it is important to fix the content because the crystallinity of the vanadium dioxide is lowered and transformed into the substituted metal oxide form (MO x ). The synthesized substituted vanadium dioxide has an average particle diameter of about 5 nm to 100 nm.
In the step (P02) of dispersing the synthesized substituted vanadium dioxide in an alcohol solvent, it further includes applying ultrasonic waves and stirring to the substituted vanadium dioxide dispersed in the alcohol solvent. The alcohol solvent may be ethanol, methanol or the like, and distilled water may be further added in an amount of 0% to 20% based on the volume of the alcohol solvent.
In the step (P03) in which the first inorganic oxide precursor and the inorganic oxide precursor of the second inorganic oxide precursor are added to dispersed vanadium dioxide and simultaneously coating two different kinds of inorganic oxides, the inorganic oxide precursor is hydrolyzed Thereby forming a coating layer of different kinds of inorganic oxide forms around the vanadium dioxide particles, resulting in finally a substituted vanadium dioxide composite. The solution in which the transition metal-substituted vanadium dioxide was dispersed was added with different kinds of inorganic oxide precursors at 0 to 10 ° C, preferably 0 to 5 ° C, and then stirred at 500 to 600 rpm for about 10 minutes. The mixed solution may be further heated at a temperature of 30 to 100 ° C, preferably 40 to 90 ° C, more preferably 40 to 80 ° C. A mixed solution of water and ethanol and ammonia water are simultaneously added can be carried out under basic conditions of pH 8-14, preferably pH 9-13. The water is added to 5 to 20 parts of skin to 100 parts of ethanol, preferably 5 to 15 parts of skin, more preferably 5 to 10 parts of skin. The mixed solution may contain
Also, in the hydrolysis step, a mixed solution of water and ethanol, ammonia water and the like are simultaneously added to the vanadium dioxide dispersing solvent for a certain period of time, so that a coating layer in which two kinds of inorganic oxides are uniformly coated can be produced. When either one of the two solvents is added first or later, only the hydrolysis of one inorganic oxide precursor of the two inorganic oxides is further progressed by the separately added solvent. Thus, in addition to the two uniform coating layers, Thereby forming an oxide coating layer.
The hydrolysis step is carried out by adding two kinds of inorganic oxide precursors to a dispersion containing vanadium dioxide in which a transition metal is substituted and stirring for 5 to 20 minutes at a temperature of 0 to 10 DEG C and 500 to 600 rpm, Lt; 0 > C and 150 to 350 rpm for 2 to 8 hours.
In the coating process, the thickness of the coating layer in the composite structure can be controlled by adjusting the amount of the two kinds of inorganic oxides and the reaction time. As the amount of the inorganic oxide precursor is increased in the hydrolysis process, the amount of the inorganic oxide to be hydrolyzed increases, so that the thickness of the coating layer becomes thicker. Further, if the reaction time is increased in the above process, the time for the inorganic oxide precursor to be hydrolyzed and coated on the vanadium dioxide particles becomes sufficient, so that the thickness of the coating layer becomes thick according to the reaction time. By suitably adjusting the above two conditions, it is possible to produce a composite structure having a coating layer of a desired thickness, preferably a vanadium dioxide vanadium oxide having a thickness in the range of 5 nm to 20 nm, more preferably 10 nm to 15 nm The composite structure is suitable for use as an efficient heat transfer material.
Thereafter, in the step of forming a crystalline coating layer by annealing the particles coated with the two kinds of inorganic oxides (P04), two kinds of inorganic oxide coating layers of different kinds can be crystallized through an additional annealing step have. The sintering step is carried out at a pressure of 3 torr at 40 mtorr, preferably 3 torr at 30 mtorr, more preferably 3 mtorr at 20 mtorr, at a temperature of 300 ° C to 500 ° C, preferably 400 ° C to 450 ° C Lt; / RTI >
The substituted vanadium dioxide composite produced in this step is washed with an alcohol solvent and distilled water, and then dried in a temperature range of 40 ° C to 80 ° C to produce a black powder.
Further, according to a more preferred embodiment of the present invention, a method for preparing a transition metal-substituted vanadium dioxide complex coated with an inorganic oxide of the present invention comprises mixing a vanadium compound and a transition metal compound in a solution phase and heating the vanadium compound and the transition metal compound at 100 to 500 rpm at 0.5 to 5 Followed by heat treatment at 500 to 1,200 ° C for 1 to 5 hours to produce transition metal-substituted vanadium dioxide; Dispersing the vanadium dioxide substituted with the transition metal in a solvent containing an alcohol; The dispersion may further contain at least one first inorganic oxide selected from the group consisting of tetraethylorthosilicate, tetraethoxysilane, tetramethoxysilane, glycidyloxypropyltrimethoxysilane, and methoxytriethoxysilane, The precursor may be at least one selected from the group consisting of titanium tetrabutoxide, titanium isopropoxide, titanium tetrabutoxide, titanium tetrachloride, titanium tetraisopropoxide, titanium sulfate, zirconium propoxide, zirconium oxychloride, zirconium tetrachloride, At least one second inorganic oxide precursor selected from the group consisting of zirconium, zirconium sulfate, zinc hydroxide, zinc nitrate hexahydrate, and zinc chloride is added and heated at a temperature of 0 to 10 DEG C at 500 to 600 rpm for 5 to 20 minutes After stirring, the mixture was heated at 30 DEG C to 100 DEG C at 150 to 350 rpm for 2 hours Further agitating for 6 hours to 6 hours and then performing a hydrolysis process under a basic condition of pH 8 to 14 to simultaneously coat two kinds of inorganic oxides; And a step of sintering the transition metal-substituted vanadium dioxide complex coated with the two kinds of inorganic oxides at a pressure of from 40 mtorr to 3 torr and a temperature of 400 ° C to 450 ° C to form a crystalline coating layer.
On the other hand, in another embodiment of the present invention, the present invention provides an optical product comprising a transition metal substituted vanadium dioxide complex in which two kinds of inorganic oxides of different kinds are simultaneously coated with a single coating layer as described above. In particular, the optical article may be in the form of an optical hard coat film having infrared absorption and reflection capabilities.
The optical product can be mass-produced in a simple manner in the form of a film containing a transition metal-substituted vanadium dioxide complex, and is easy to adhere to a building or an automobile window. The transition metal substituted vanadium dioxide complex contained in the film may have a transition temperature from 25 ° C to around 70 ° C, preferably 30 to 60 ° C, more preferably 30 to 50 ° C. By implementing this phase transition temperature, the composite can selectively block and transmit light in the infrared region (780 nm to 1 mm) according to the external temperature, and transmit light in the visible light region (380 nm to 780 nm) The temperature inside the room can be adjusted without power.
In preparing the infrared hard coat film, the transition metal-substituted vanadium dioxide composite particles coated with the two kinds of inorganic oxides may be prepared by dispersing up to 40 wt% of the coating agent. The UV coating curing agent may be a benzophenone- Acetone phenone system was used and the binder was made into a film through a bar coater by using Urethane Acrylate. Since the transition metal-substituted vanadium dioxide composite particles coated with the two kinds of inorganic oxides have high visible light transmittance and self-cleaning ability, they can be imparted with high visibility and ability to remove contaminants themselves when applied to a film or glass, And oxidative stability, it is possible to make an efficient manufacturing process by suppressing heat damage or additional oxidation reaction after coating and coating, and when it is applied to a film, it can improve infrared absorption and reflection performance by high heat transfer property The giver plays a role.
In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.
According to the present invention, there is provided a transition metal-substituted vanadium dioxide complex having a high visible light transmittance, an oxidation resistance, a self-cleaning ability, and simultaneously coating different kinds of inorganic oxides having a transition temperature from 30 ° C to around 70 ° C, It can be effectively manufactured so as to be mass-produced in a simple manner.
In addition, the transition metal-substituted vanadium dioxide complex coated with different kinds of inorganic oxides according to the present invention can be applied to a heat transfer film which is easy to adhere to a building or an automobile window, and can selectively apply infrared ray blocking and transmission It is possible to save energy efficiently by reducing cooling and heating costs in summer and winter.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow diagram for a method for producing a transition metal substituted vanadium dioxide complex in which two different kinds of inorganic oxides according to the present invention are simultaneously coated. FIG.
FIG. 2 is a cross-sectional schematic diagram of a vanadium dioxide composite (a) coated with two inorganic oxides simultaneously according to the present invention and a vanadium dioxide composite (b) in which a double coating layer is formed by coating two inorganic oxides in a conventional manner.
FIG. 3 is a transmission electron microscope (TEM) photograph of a transition metal-substituted vanadium dioxide complex coated with an inorganic oxide prepared by a pyrolysis step according to Example 1 of the present invention.
FIG. 4 is a graph showing the relationship between the transition metal-substituted vanadium dioxide and vanadium oxide-coated transition metal-substituted vanadium dioxide complexes prepared according to Example 1 of the present invention and Comparative Examples 1 to 4 using differential scanning calorimetry (DSC) Differential Scanning Calorimeter) analysis result.
FIG. 5 is a graph showing the relationship between the temperature (80 ° C) and the moisture (humidity: 80%) of transition metal-substituted vanadium dioxide and vanadium oxide coated with transition metal, prepared according to Example 1 of the present invention and Comparative Examples 1 to 4, ) Atmosphere for one week, and the result of DSC analysis of differential scanning calorimetry (DSC).
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.
Example 1
Transition metal-substituted vanadium dioxide synthesis
An aqueous solution of vanadium sulfate (VOSO 4 ) of 0.1 M was prepared from a vanadium salt, and an aqueous solution of sodium tungstate hydrate (Na 2 WO 4 .2H 2 O) of 0.5 M was prepared by using a tungsten compound. And the mixture was stirred at 300 rpm for 1 hour at 30 캜 so as to have a content ratio of 1.5 at%.
A solution of 0.2 M ammonium bicarbonate (NH 4 HCO 3 ) in water at a temperature of 20 to 25 ° C was added to a solution of the aqueous solution of sodium tungstate (Na 2 WO 4 ) and an aqueous solution of vanadium sulfate (VOSO 4 ) ((NH 4 ) 5 [(VO) 6 (CO 3 ) 4 (OH) 9 ]] in which tungsten was substituted for 1 hour after the reaction was carried out at a stirring rate of 300 rpm under the condition of gradually decreasing the flow rate of the amorphous vanadium compound 10H 2 O). As the reaction progressed, the vanadium compound was formed into brown particles.
The thus synthesized amorphous vanadium compound substituted with tungsten was washed with distilled water and anhydrous ethanol three times using a microfilter paper to obtain amorphous vanadium compound particles of brownish, filtered and substituted tungsten. The amorphous amorphous vanadium hydrate brown particles prepared here were dried in a vacuum oven at 40 ° C for 4 hours to remove the hydroxyl groups adsorbed on the surface.
Subsequently, the dried amorphous vanadium particles substituted with tungsten were pyrolyzed at 875 ° C for 3 hours in an electric furnace using a quartz tube. The atmosphere of the tubular electric furnace was pyrolyzed in a nitrogen (N 2 ) atmosphere having a purity of 95% or more, which is an environment in which moisture was shielded from outside, and the flow rate of nitrogen was supplied at a rate of 50 mL / min. / min. Here, the hydroxyl group (-OH) bonded to the inside of the particle pores is removed, and monoclinic tungsten-substituted vanadium dioxide is crystallized and stabilized. Through these pyrolysis steps, vanadium dioxide fine particles having a monoclinic crystal structure and having spherical tungsten substitution were prepared.
Inorganic oxide coating of vanadium dioxide substituted with transition metal
The vanadium disubstituted vanadium dioxide particles thus obtained were dispersed with 50 mL of ethanol and 10 mL of distilled water as a solvent, sonicated for 30 minutes, and dispersed by stirring at 250 rpm for 1 hour.
The solution in which the tungsten-substituted vanadium dioxide was dispersed was further added with 0.5 g of tetraethoxysilane (TEOS) and 1 mL of titanium tetrabutoxide (TBOT) at a temperature of 5 ° C., Lt; / RTI > The temperature of the mixed solution was raised to 40-40 ° C, 40 mL of a mixed solution of water and ethanol and 30 wt% of ammonia water were simultaneously added to adjust the pH to 8-9, and the mixture was stirred again at 250 rpm for 6 hours Lt; / RTI > At this time, a mixed solution of water and 100 mL of water mixed with 1 L of ethanol was used. As a result, TEOS and TBOT were hydrolyzed by ammonia water and coated on tungsten substituted vanadium dioxide particles to produce tungsten substituted vanadium dioxide particles coated with silica (SiO 2 ) and titanium dioxide (TiO 2 ). Then, by sintering at a temperature of 400 ℃ particles wherein the inorganic oxide coating on the pressure condition of 3 torr for 15 min, silica (SiO 2) and titanium dioxide (TiO 2) a transition metal-substituted dioxide vanadium crystalline coating layer is formed of Complex.
Comparative Example One
A vanadium dioxide nanoparticle substituted with a spherical tungsten was prepared in the same manner as in Example 1, without a separate inorganic oxide coating process.
Comparative Example 2
Vanadium dioxide fine particles substituted with tungsten were prepared in the same manner as in Example 1, and then 50 mL of ethanol and 10 mL of distilled water were dispersed as a solvent, and the mixture was ultrasonicated for 30 minutes and dispersed by stirring for 1 hour. 5 g of 30 wt% aqueous ammonia was added to the solution, and the temperature was raised to 40 ° C. The mixture was stirred at 500 to 600 rpm for 10 minutes, and further stirred at 250 rpm for 6 hours. As a result, TEOS was hydrolyzed by ammonia water and coated on tungsten-substituted vanadium dioxide particles to prepare a silica (SiO 2 ) -coated tungsten-substituted vanadium dioxide composite.
Comparative Example 3
Vanadium dioxide fine particles substituted with tungsten were prepared in the same manner as in Example 1, dispersed with 50 mL of distilled water as a solvent, sonicated for 30 minutes, and dispersed by stirring for 1 hour. The solution was stirred at 500 to 600 rpm for 10 minutes at a temperature of 5 DEG C, and then the temperature was increased to 80 DEG C, and 50 mL of ethanol and 20 mL of distilled water were added. After stirring at 250 rpm for 6 hours, TBOT was hydrolyzed To form tungsten-substituted vanadium dioxide particles coated with titanium dioxide (TiO 2 ) by coating on tungsten-substituted vanadium dioxide particles. Then, by sintering at a temperature of 400 ℃ particles wherein the inorganic oxide coating on the pressure condition of 3 torr for 15 min, silica (SiO 2) and titanium dioxide (TiO 2) a transition metal-substituted dioxide vanadium crystalline coating layer is formed of Complex.
Comparative Example 4
Silica in the same manner as in Comparative Example 2 (SiO 2) coated tungsten substituted dioxide vanadium complexes proceeds to add the same manner as in Comparative Example 3 After preparing a titanium dioxide (TiO 2) is a double-coated tungsten substituted dioxide vanadium complex .
Test Example
Crystallinity and chemical stability related property evaluations were carried out on transition metal-substituted vanadium dioxide complexes coated with vanadium dioxide and inorganic oxide substituted according to Example 1 and Comparative Examples 1 to 4 in the following manner .
a) Crystallinity
X-ray diffraction (XRD) analysis was performed to confirm the crystallinity of the vanadium dioxide and vanadium oxide coated with the transition metal, And the peaks at 27.8 ° (1 10), 37 ° (2 0 0), 42.1 ° (2 10) and 55.4 ° (2 2 0). In addition, the intensity of the representative peak coincided with VO2 (M), indicating that 80% or more is high, 50% or more is normal, and 30% or more is low.
b) Chemical stability (%)
The composite was placed under constant humidity (80%) and temperature (80 ° C) atmosphere to evaluate the chemical stability of the prepared transition metal-substituted vanadium dioxide and inorganic oxide-coated transition metal-substituted vanadium dioxide complexes. As the time passed, a differential scanning calorimeter (DSC) analysis of the composite was performed to observe changes in endothermic peaks over time. The percentage of the endothermic peak intensity of the composite was measured at the endothermic peak intensity after 7 days in the above-mentioned incubation atmosphere so as to confirm whether or not the phase transition property was maintained by stable air and humidity in the atmosphere.
c) visible light transmittance
The transition metal-substituted vanadium dioxide complex coated with vanadium dioxide and inorganic oxide substituted with a transition metal prepared according to Example 1 and Comparative Examples 1 to 4 was coated on a glass substrate through spin coating and then irradiated with a UV ray by a spectroscope (UV / VIS / NIR spectrophotometer) was used to measure visible light transmittance.
Coating layer
Coating layer
Coating layer
Coating layer
FIG. 2 is a cross-sectional view of a vanadium dioxide composite (a) coated with silica and titanium dioxide simultaneously according to the present invention and a vanadium dioxide composite (b) in which silica and titanium dioxide are coated in a conventional manner to form a double coating layer, respectively It is a schematic diagram. In the case of a vanadium dioxide composite in which two inorganic oxides are coated to form a double coating layer, there is a problem in time and economy due to the two processes, and the surface characteristics of the silica forming the inner layer due to the double coating layer There are drawbacks that can be difficult. On the other hand, in the case of the vanadium dioxide composite coated with silica and titanium dioxide according to the present invention, the silica and the titanium dioxide can be simultaneously coated to simplify the coating process, and the structure of the single coating layer can be formed, .
FIG. 3 shows TEM (Transmission Electron Microscopy) analysis of a substituted vanadium dioxide composite having a crystalline coating layer of silica and titanium dioxide prepared through a hydrolysis step according to Example 1. FIG. Figure 3 is a photograph of dispersed vanadium dioxide complexes produced according to the present invention dispersed to produce an organic and water-based coated sol without further ball milling. This TEM analysis confirmed that a complex of transition metal substituted vanadium dioxide having a mean particle size of 100 nm with a coating layer of 12 nm thickness was produced.
Further, for the transition metal-substituted vanadium dioxide composite coated with the substituted vanadium dioxide and the inorganic oxide prepared according to Example 1 and Comparative Examples 1 to 4, a differential scanning calorimetry (DSC) curve The results of the analysis are shown in FIG. Referring to FIG. 4, it can be seen that the thermocompression material having an endothermic peak at about 30 ° C and a phase transition temperature in the temperature range is synthesized. In Comparative Example 4, the intensity of the endothermic peak was found to be weak. This indicates that the phase transition characteristics of the core particles are reduced due to the double coating layer.
FIG. 5 is a graph showing the results of a comparison between a transition metal-substituted vanadium dioxide complex coated with vanadium dioxide and inorganic oxide prepared according to Example 1 and Comparative Examples 1 to 4 under an atmosphere of constant temperature (80 ° C) and moisture (80% The results of the differential scanning calorimetry are shown in Fig. Referring to FIG. 5, in Comparative Example 1 in which no coating layer was formed, all of the endothermic peaks disappeared, and in Comparative Example 3 in which titanium dioxide was coated as a single layer, the endothermic peaks almost disappeared. On the other hand, in Example 1 and Comparative Example 2, although the strength of the endothermic peak was weakened, it was found that the endothermic peak remained and the phase transition characteristics were maintained. Compared with Comparative Example 1 and Comparative Example 2, It can be seen that a more stable thermoelectric material has been synthesized. On the other hand, in the case of Comparative Example 4, the endothermic peak still remains and it is confirmed that the phase transition characteristics are maintained, but the peak intensity is very weak.
As shown in Table 1, Example 1 showed satisfactory results even in the evaluation of visible light transmittance and chemical stability. On the other hand, the visible light transmittance was significantly lower in Comparative Example 1 and Comparative Example 2, and the visible light transmittance was as high as 71% in Comparative Example 3, but the chemical stability was insufficient as compared with Example 1. Comparative Example 4 showed relatively high chemical stability and visible light transmittance, but the crystallinity of the core particle itself was rather low due to the double coating layer coated on the particles, and the coating process was also complicated in comparison with Example 1, There is a problem in that it is economically difficult to do so. In addition, the core-shell structure of Comparative Example 4 has a disadvantage in that the manufacturing process becomes long, so that the manufacturing cost is increased, and the surface properties of silica and titanium dioxide are difficult to manifest due to the double coating layer.
Thus, it can be seen that the substituted vanadium dioxide coated with the inorganic oxide prepared according to the present invention is advantageous in various fields such as a smart glass and a thermoelectric conversion film by being stable both thermally and oxidatively to the external environment.
Claims (9)
A single crystalline coating layer comprising a first inorganic oxide and a second inorganic oxide,
Wherein a first inorganic oxide is silica (SiO 2), the second inorganic oxide is titanium dioxide (TiO 2), zirconia (ZrO 2), and, an inorganic oxide at least one member selected from the group consisting of zinc oxide (ZnO) Coated transition metal substituted vanadium dioxide complexes.
Wherein the coating layer thickness of the inorganic oxide is 5 nm to 20 nm.
Wherein the composite has an average particle size of 10 nm to 150 nm.
A transition metal-substituted vanadium dioxide complex coated with an inorganic oxide having a phase transition temperature of 25 to 70 占 폚.
An inorganic oxide coated transition metal substituted vanadium dioxide complex having a visible light transmittance of 65% or more.
Wherein the dispersion contains at least one first inorganic oxide precursor selected from the group consisting of tetraethylorthosilicate, tetraethoxysilane, tetramethoxysilane, glycidyloxypropyltrimethoxysilane, and methoxytriethoxysilane, Titanium isopropoxide, titanium tetrabutoxide, titanium tetrachloride, titanium tetraisopropoxide, titanium sulfate, zirconium propoxide, zirconium oxychloride, zirconium tetrachloride, zirconium nitrate, zirconium sulfate, zinc hydroxide, zinc hydroxide, zinc nitrate hexahydrate , And zinc chloride, and performing a hydrolysis process to coat the first and second inorganic oxides with the transition metal-substituted vanadium oxide as a single layer ; And
Sintering the inorganic oxide coated particles to form a single crystalline coating layer;
6. The method according to any one of claims 1 to 5, wherein the inorganic oxide-coated transition metal-substituted vanadium dioxide complex is coated on the substrate.
Wherein the transition metal comprises at least one selected from the group consisting of tungsten, molybdenum, niobium, antimony, indium, and chromium.
Wherein the hydrolysis step comprises adding the first inorganic oxide precursor and the second inorganic oxide precursor to the dispersion and stirring for 5 to 20 minutes at a temperature of 0 to 10 DEG C and 500 to 600 rpm, To 350 < RTI ID = 0.0 > rpm < / RTI > for 2 to 8 hours.
Wherein the first and second inorganic oxide precursors are added in an amount of 5 to 40 parts by weight based on 100 parts by weight of vanadium dioxide, respectively.
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| WO2019216152A1 (en) * | 2018-05-11 | 2019-11-14 | 住友金属鉱山株式会社 | Surface-treated infrared-absorbing fine particle dispersion and infrared-absorbing transparent substrate |
| CN116925589A (en) * | 2023-06-06 | 2023-10-24 | 湖州乐通新材料科技有限公司 | Preparation method of thermochromic ink |
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| JP2004346261A (en) | 2003-05-26 | 2004-12-09 | Toagosei Co Ltd | Thermochromic material and thermochromic film or thermochromic glass using the same |
| JP2014505651A (en) | 2011-01-21 | 2014-03-06 | 中国科学院上海硅酸塩研究所 | Doped vanadium dioxide powder, dispersions and their production and application |
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| JP2004346261A (en) | 2003-05-26 | 2004-12-09 | Toagosei Co Ltd | Thermochromic material and thermochromic film or thermochromic glass using the same |
| JP2014505651A (en) | 2011-01-21 | 2014-03-06 | 中国科学院上海硅酸塩研究所 | Doped vanadium dioxide powder, dispersions and their production and application |
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| WO2019216152A1 (en) * | 2018-05-11 | 2019-11-14 | 住友金属鉱山株式会社 | Surface-treated infrared-absorbing fine particle dispersion and infrared-absorbing transparent substrate |
| CN116925589A (en) * | 2023-06-06 | 2023-10-24 | 湖州乐通新材料科技有限公司 | Preparation method of thermochromic ink |
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