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WO2012001636A1 - Procédé de production d'oxyde de vanadium alpha dopé ou non dopé - Google Patents

Procédé de production d'oxyde de vanadium alpha dopé ou non dopé Download PDF

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Publication number
WO2012001636A1
WO2012001636A1 PCT/IB2011/052856 IB2011052856W WO2012001636A1 WO 2012001636 A1 WO2012001636 A1 WO 2012001636A1 IB 2011052856 W IB2011052856 W IB 2011052856W WO 2012001636 A1 WO2012001636 A1 WO 2012001636A1
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Prior art keywords
vanadium
reduction
solids
carried out
starting material
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German (de)
English (en)
Inventor
Alexej Michailovski
Matthias Zech
Kirill Bramnik
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BASF China Co Ltd
BASF SE
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BASF China Co Ltd
BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C01P2006/33—Phase transition temperatures

Definitions

  • the present invention relates to a process for the preparation of vanadium oxides of the empirical formula V 1-x M x O 2 -yA y , where M is at least one metal different from vanadium, x is a value from 0 to 0.05, A is a non-oxygen Anion and y is a value from 0 to 0.05.
  • solids containing vanadium oxide of the empirical formula V 1-x M x 0 2 - y A y where M is at least one other than vanadium metal, x is a value of 0 to 0.05, A is an anion other than oxygen and y is a value of 0 to 0.05, and vanadium is 95 to 99.99 mole percent, based on the total amount of vanadium, in the + IV oxidation state, and 0.01 to 5 mole percent, based on the total amount of vanadium, in the + V oxidation state and / or + III as determined by redox titration.
  • Oxides of vanadium are known for their great diversity, both in terms of the oxidation states and the variety of structural modifications.
  • oxides of vanadium in the oxidation state + IV are, inter alia, oxides of vanadium in the oxidation state + IV.
  • Vanadium dioxide exists in various modifications: As alpha-vanadium dioxide, such is referred to as a monoclinically distorted rutile structure. The powder diffractogram of this modification is deposited with the International Center for Diffraction Data under the number PDF 01-076-0456. Alpha-VO 2 is the thermodynamically stable modification at room temperature.
  • Beta vanadium dioxide crystallizes tetragonally in an undistorted rutile structure.
  • phase transition temperature T a phase transition temperature below the phase transition temperature.
  • alpha vanadium dioxide above the beta modification.
  • T a phase transition temperature below the phase transition temperature
  • the phase transition temperature is 68 ° C.
  • suitable doping of the vanadium dioxide it is possible to shift the phase transition temperature up or down.
  • phase transition temperatures can be lowered to 0 ° C.
  • alpha-vanadium dioxide has high transmission for near-infrared radiation (800 to 2000 nm)
  • beta-vanadium dioxide reflects or absorbs infrared rays to a high level.
  • Vanadium dioxide can be prepared by reduction of vanadium compounds in the oxidation state + V.
  • No. 6,358,307 describes a process for preparing doped or undoped vanadium dioxide by pyrolysis of ammonium hexavanadates (NH 4 ) 2 V 6 O 6 at temperatures between 400 and 650 ° C.
  • AT 41 1526 discloses a process for producing doped or undoped vanadium dioxide by pyrolysis of ammonium metavanadate NH 4 V0 3 and tungsten or molybdenum oxide at temperatures between 600 and 700 ° C. In this case, a pyro- lysêts product is obtained, which is then heat treated under inert gas atmosphere.
  • the object of the present invention was to provide a simple process by means of which the initially defined vanadium oxides can be prepared in high purity in the alpha or beta modification.
  • the vanadium oxides thus produced are said to contain only a few impurities of vanadium (V) compounds due to incomplete reduction or of vanadium (III) compounds due to overreduction.
  • the object has been achieved by the above-mentioned process for the preparation of vanadium oxide of the empirical formula V 1-x M x O 2 - y A y , where M is at least one metal different from vanadium, x is a value from 0 to 0.05, A is from Oxygen differs nes anion and y is a value of 0 to 0.05 and wherein the vanadium oxide is present in the distorted or undistorted rutile structure, comprising the reduction of vanadium ⁇ ) containing starting material and the annealing of the reductate under inert gas atmosphere at temperatures of 500 ° C to 1000 ° C.
  • V0 2 has the empirical formula V0 2 .
  • the lattice is doped with other metal ions M, this has no effect on the stoichiometry if M is in the + IV oxidation state. In all other cases, the total composition is dictated by the crystal lattice.
  • the charge balance can take place by incorrect occupancy of some cation lattice sites, or it can, for example, vanadium ions in other oxidation tion levels are incorporated into the lattice ,
  • x is a value of 0.001 to 0.05 or 0.002 to 0.02. In some embodiments, x is from 0.01 to 0.02, in other embodiments from 0.002 to 0.015, again in others from 0.25 to 0.45.
  • the doping with metal ions M can influence the phase transition temperature T from the alpha to the beta modification of vanadium dioxide.
  • the phase transition temperature can be both increased and decreased.
  • Suitable metal ions to lower the phase transition temperature are, for example, molybdenum, tungsten, tantalum, niobium, ruthenium, rhenium and titanium.
  • Suitable metal ions M for increasing the phase transition temperature include, for example, iron, tin, chromium, gallium, aluminum, germanium. Preference is given to iron or tin.
  • the phase transition temperature T can also be influenced by doping with anions A different from oxygen.
  • a suitable anion A which lowers the phase transition temperature, is in particular fluoride.
  • vanadium oxides which can be prepared by the process according to the invention are not doped with anions A.
  • Y preferably assumes values of 0.001 to 0.05 or of 0.002 to 0.02. In some embodiments, y takes values from 0.01 to 0.02, in other embodiments from 0.002 to 0.015, again in others from 0.25 to 0.45.
  • Suitable starting materials for the production of vanadium dioxides by the process according to the invention are all compounds which contain vanadium in the oxidation state + V.
  • Preferred starting materials are, for example, vanadium pentoxide V 2 0 5 , metavananadata such as ammonium metavanadate NH 4 V0 3 , monovanadates such as ammonium monovanadate (NH 4 ) 3 V0 4 , divanadates such as ammonium dodanadate (NH 4 ) 4 V 2 0 7, hexavanadates such as ammonium hexavanadate (NH 4 ) 2 V 6 0i 6 , decavanadates such as ammonium decavanadate (NH 4 ) 6V 10 O 28, vanadium (V) halides such as vanadium pentafluoride VF 5 , vanadium (V) - oxyhalides such as VOF 3 , VOCl 3 , VOBr 3 , and their mixed halides, V0 2 F, V0 2 Cl, V0 2 Br.
  • metavananadata such as ammonium metavanadate NH 4 V
  • vanadium compounds which are not volatile.
  • those are preferred which are not completely or partially gaseous under reaction conditions.
  • Particularly preferred starting materials are vanadium pentoxide V 2 0 5 or ammonium salts of the above-mentioned vanadates.
  • Alkali or alkaline earth metal salts of the vanadates are generally less preferred. Less preferred is the use of vanadium peroxo compounds.
  • vanadium oxyhalides are possible but also less preferred since they are volatile and may be partially gaseous under the reaction conditions.
  • All vanadium compounds can be used both anhydrous and as hydrates. However, they preferably contain as little or no water of crystallization as possible, that is to say they are preferably essentially anhydrous. Preferably, they are used dry.
  • vanadium (V) containing compounds or the mixture of vanadium (V) containing compounds are generally employed directly for the reduction described below.
  • vanadium dioxide is to be produced which is doped with other metal ions M or with anions A
  • the doping can be achieved in various ways. For the method according to the invention, it is irrelevant on which path the doping is set.
  • the metal ions M or anions A can already be incorporated in the starting material in the crystal lattice. It is also possible that vanadium (V) -containing starting materials are present in the finely divided mixture with the doping material.
  • Suitable compounds for doping the vanadium (V) -containing material by the method described above are any compounds which dissolve in a solvent in which the vanadium (V) -containing material is not soluble.
  • the solvent used is water.
  • V vanadium
  • doping material in the solid state without the addition of solvents.
  • Homogeneity can be achieved, for example, by homogenization using suitable apparatus.
  • vanadium (V) -containing material and doping material can be homogenized by means of mixers known to those skilled in the art for highly viscous systems, for example extruders or kneaders.
  • mixers known to those skilled in the art for highly viscous systems, for example extruders or kneaders.
  • Another possibility is the homogenization in shakers, possibly supported by ceramic balls such as steatite balls, which are shaken with the powder to be mixed.
  • Suitable compounds for doping with tungsten as tungsten oxide, tungstates such as ammonium metatungstate (N ⁇ W- ⁇ O ⁇ o, ammonium para-tungstate such as (NH4) 10 H2W 12 O42 or hydrates thereof.
  • Suitable compounds for doping with molybdenum are, for example, molybdenum oxides, molybdate such as ammonium metamolybdates such as ( ⁇ 4 ) 6 ⁇ 2 ⁇ ⁇ 2 ⁇ 4 ⁇ , ammonium paramolybdate such as ( ⁇ 4 ) 6 ⁇ 7 ⁇ 24 or their hydrates.
  • Suitable compounds for doping with iron are preferably soluble iron salts.
  • FeS0 4 , Fe 2 (S0 4 ) 3 , FeCl 2 , FeCl 3 , Fe (OAc) 2 , Fe (OAc) 3 or other readily soluble iron salts are suitable.
  • Suitable compounds for doping with fluoride are inorganic or organic fluorine compounds. For example, ammonium fluoride NH 4 F, ammonium bifluoride NH 4 HF 2, hydrogen fluoride or organic fluorine compounds are preferred.
  • ammonium salts are generally preferred, while alkali or alkaline earth metal salts are in principle possible but not preferred.
  • Another suitable method for doping with fluoride is the addition of gaseous vanadium fluorides such as V0 2 F or VOF 3 to gaseous reducing agent. In this case, the doping does not take place at the stage of the starting materials but during the reduction.
  • gaseous vanadium fluorides such as V0 2 F or VOF 3
  • Another method of doping the starting material is, for example, the co-grinding of vanadium (V) -containing material with doping material.
  • doped starting material may also be obtained by coprecipitation of vanadium (V) -containing material and doping material from a solution.
  • Suitable vanadium (V) -containing material has, for example, particle sizes of 5 to 10 ⁇ m.
  • the drying of the material is usually done at temperatures that allow a rapid drying of the paste, but do not induce changes in the composition of the material. Typical drying temperatures are for example at 80 to 120 ° C. If lower drying temperatures are used, drying is usually assisted by applying a vacuum. The exact drying process is not critical to the practice of the process of this invention.
  • the starting material for the reduction typically has average particle sizes of 1 to 100 ⁇ m (weight average determined by sieving method), preferably 5 to 20 ⁇ m, and a BET surface area (determined according to DIN ISO 9277) of 0.1 to 10 n of Yg.
  • the reduction of the starting material is carried out so that vanadium (V) is completely reduced to vanadium (IV), but further reduction to vanadium (III) or lower oxidation states occurs only to a minor extent.
  • Vanadium dioxide obtained by the process of this invention is typically greater than 95 mole percent, based on the total amount of vanadium, in the + IV oxidation state, more than 97 mole percent in particular embodiments. It is also possible to produce vanadium oxides present in excess of 99 or 99.9 mole percent in the + IV oxidation state.
  • the homogeneity of the vanadium with respect to the oxidation state can be determined up to a value of about 95 mol% by means of powder diffractometry. For higher purities and more accurate values, the determination is usually done by redox titration.
  • the reduction is carried out under a reducing atmosphere containing one or more inert gases and one or more gaseous reducing agents under the reaction conditions.
  • Suitable reducing agents are in principle all substances which can bring about the reduction of vanadium ⁇ ) to vanadium (IV).
  • reducing agents are chosen in which both the reducing agent and its oxidation product are gaseous.
  • Suitable reducing agents are, for example, ammonia, hydrogen, carbon monoxide, aldehydes, alcohols, formic acid, amines, hydrazine, hydrocarbons such as alkanes, alkenes, alkynes, hydrogen sulfide, sulfur dioxide, thiols.
  • Suitable hydrocarbons are, for example, methane, ethane, propane, butane, ethene, propene, butenes, acetylene (ethyne), propyne.
  • Suitable aldehydes are preferably readily volatile and gaseous under the reaction conditions, for example formaldehyde, acetaldehyde, propanal, butanal.
  • Suitable alcohols are preferably readily volatile and gaseous under the reaction conditions, such as, for example, methanol, ethanol, n / iso-propanol
  • Particularly preferred reducing agents are ammonia, hydrogen, carbon monoxide, methane, ethane, aliphatic amines, sulfur dioxide or mixtures thereof
  • ammonia carbon monoxide or hydrogen.
  • Sulfur-containing compounds are less preferred because they can react with the vanadium oxide to form unwanted by-products such as vanadium oxysulfides or sulfonovanadates.
  • reducing agents in situ from the starting material, for example by pyrolysis of the starting material.
  • ammonia can be released from ammonium salts or carbon monoxide from formates, oxalates or oxalic acid.
  • a reducing atmosphere is preferably produced by adding external reducing agent.
  • the reduction is carried out under a gas atmosphere.
  • the gas atmosphere is fluid. This means that constantly fresh reducing agent is passed over the starting material. This has the consequence that the atmosphere is constantly renewed, so that you can keep the reaction conditions, if desired, constant. It also makes it possible to run a reaction program with changing conditions.
  • the targeted addition of reducing agent also makes the reduction well reproducible. Furthermore, this makes it easier to carry out the method according to the invention continuously.
  • the temperature, the flow rate of the gas, the time and thus the amount of reducing agent, with the Starting material has contact be targeted.
  • the flow rate of the gas atmosphere is usually adjusted by controlling a gas volume flow per unit time.
  • the gas volume flow so that the gas volume of the reactor is statistically exchanged one to 100 times per hour.
  • the gas volume of the reactor is exchanged 2 to 50 times, more preferably 5 to 25 times per hour.
  • the gas volume flow is adjusted so that, based on the starting material to be reduced, 1 to 50 redox equivalents of the gaseous reducing agent are fed per hour. Preferably, 2 to 30, more preferably 4 to 10 redox equivalents are fed per hour.
  • the reaction is carried out at atmospheric pressure.
  • the reducing agents generally have a partial pressure of 10 to 500 mbar, preferably 50 to 300 mbar. In one embodiment, the partial pressure is 70 to 150 mbar, in another embodiment 150 to 250 mbar.
  • the remaining atmosphere typically consists of one or more inert gases.
  • Inert gases in the sense of the invention are all those which undergo no chemical reaction with the remaining atmosphere, the starting material or the reductate under the reaction conditions.
  • Typical inert gases are nitrogen or argon.
  • Less preferred inert gases are carbon dioxide, helium, neon, krypton, xenon, sulfur hexafluoride, or perhalogenated hydrocarbons. However, these may be used if desired. It is also possible to use mixtures of different inert gases.
  • the temperature at which the reduction is carried out is typically in the range of from 200 to 600 ° C, preferably from 250 to 450 ° C, more preferably from 350 to 450 ° C.
  • the amount of time the starting material is exposed to the reducing atmosphere depends on the boundary conditions. If the reaction time is too short, vanadium ⁇ ) is not completely reduced. If the time is too long, it may be possible to terreduction to vanadium (III) or (II) occur.
  • the starting material and the reducing atmosphere are heated at a heating rate of 10 to 500 Kelvin per hour, preferably at a heating rate of 50 to 300 K / h. Subsequently, the temperature is kept at the reaction temperature for a certain period of time. This period can be, for example, 15 to 300 minutes.
  • the starting material can be introduced, for example, into the preheated reactor.
  • the heating rates for the starting material may be significantly higher and, for example, from 300 to 3000 K / h.
  • the reduction of the starting material can be carried out in a variety of apparatus, the nature of which is not crucial for the implementation. Quartz flasks are particularly suitable on a laboratory scale. On an industrial scale, the process according to the invention is usually carried out in continuous operation in a rotary kiln, oscillating kiln, or discontinuously in heatable crucibles.
  • the process is carried out continuously.
  • the reduction is carried out such that the starting material continuously passes through an oven through which a reducing gas stream is passed in countercurrent.
  • Suitable furnaces for this purpose are known to the person skilled in the art.
  • the reductate usually contains most, typically at least 90% by weight, of vanadium oxide, which for the most part, as a rule at least 70% by weight, is present in the gamma modification.
  • the reductate according to the invention is subjected to a heat treatment under an inert gas atmosphere.
  • Suitable inert gases are all gases which can also be used during the reduction as inert gases and mixtures thereof.
  • the heat treatment is usually carried out at a temperature of 500 to 1000 ° C. A temperature of 600 to 900 is preferred. In a particularly preferred embodiment, the temperature is from 650 to 800 ° C.
  • the heating rate to reach the annealing temperature has no significant effect on the product.
  • the temperature of the reduction after heating the inert gas atmosphere is heated at a rate of 1 to 50 K / h, preferably 10 to 30 K / h. If the reductate is introduced into a preheated reactor, the heating rates can be significantly higher and, for example, from 300 to 3000 K / h.
  • the duration of annealing may vary over a wide period of time. For example, it can be from 15 minutes to 300 minutes. In a preferred embodiment, it is from 30 to 150 minutes, more preferably from 45 to 90 minutes.
  • the proportion of vanadium dioxide present in the gamma modification is converted to the beta modification (rutile structure), which prevails at the temperature of the annealing.
  • the product is generally cooled to room temperature under inert gas atmosphere. The cooling is usually also under inert gas.
  • the product may optionally be subjected to further treatments to adjust properties necessary for later use.
  • the product is comminuted by suitable grinding methods to desired particle sizes. This can be done for example by jet milling or wet grinding by means of a suitable mill, for example a mill with ceramic grinding media.
  • suitable mill for example a mill with ceramic grinding media.
  • Common particle sizes for solid powder are, for example, average particle sizes of 30 to 300 nm (d 50 value, determined by laser diffraction).
  • ammonium metatungstate is dissolved in water and stirred with suitable vanadium (V) compounds to give a paste. This is dried. The resulting powder is deagglomerated and exposed at a temperature of 350 to 450 ° C a flowing atmosphere of inert gas and ammonia. It is then annealed at 600 ° C.
  • molybdenum oxide MoO 3 is homogeneously mixed with vanadium pentoxide in the solid state and then deagglomerated. Subsequently, the powder is exposed at about 400 ° C, for example at a temperature of 390 to 410 ° C, a flowing atmosphere of inert gas and ammonia. Finally, the mixture is tempered at a temperature of 600 to 800 ° C. In a further preferred embodiment, ammonium molybdate is dissolved in water and kneaded with vanadium pentoxide. The paste is dried and then deagglomerated.
  • the resulting powder is exposed at about 400 ° C, for example at a temperature of 390 to 410 ° C, a flowing atmosphere of inert gas and ammonia. Finally, the mixture is tempered at a temperature of 600 to 800 ° C.
  • a further subject of the present invention are solids which contain vanadium oxide of the empirical formula V 1-x M x O 2- y A y , where M is at least one metal other than vanadium and x is a value from 0 to 0.05, and A a is an anion other than oxygen, and y is a value of 0 to 0.05, and wherein vanadium is 95 to 99.99 mole percent, based on the total amount of vanadium, in the + IV oxidation state, and 0.01 to 5 mole percent to the total amount of vanadium, in the oxidation state + V and / or + III, determined by redox titration.
  • solids of the invention contain vanadium oxide containing vanadium in the + V oxidation state but no vanadium in the + III oxidation state.
  • solids according to the invention contain vanadium oxide which contains vanadium in the oxidation state + III but no vanadium in the oxidation state + V.
  • solids of the invention contain vanadium dioxide in the alpha (below the phase transition temperature T) or beta modification (above the phase transition temperature T).
  • vanadium dioxide is at least 95 mole percent in the alpha or beta modification.
  • x is from 0.001 to 0.05 or from 0.002 to 0.02.
  • x is from 0.01 to 0.02, in other embodiments from 0.002 to 0.015, again in others from 0.25 to 0.45.
  • Suitable metal ions to lower the phase transition temperature are, for example, molybdenum, tungsten, tantalum, niobium, ruthenium, rhenium or titanium.
  • Suitable metal ions M for increasing the phase transition temperature are, for example, iron, tin, chromium, gallium, aluminum or germanium.
  • Y preferably assumes values of 0.001 to 0.05 or 0.002 to 0.02. In some embodiments, y assumes values of 0.01 to 0.02, in other embodiments, 0.002 to 0.015, again in others of 0.25 to 0.45.
  • Suitable anions A are in particular fluoride or nitride.
  • Inventive solids are characterized by a high proportion of vanadium in the oxidation state + IV.
  • Preferably 95 to 99.99 mole percent of the vanadium contained in the solid according to the invention in the oxidation state + IV are present.
  • the remaining vanadium atoms are in the oxidation state + V and / or + III.
  • the ratio of vanadium (IV) to vanadium (III) or vanadium (V) is determined by redox titration. This process is known per se to the person skilled in the art.
  • the solid according to the invention has an average particle size of 30 to 300 nm (d 50 value, determined by laser diffraction).
  • Vanadium oxides which have been prepared by the process according to the invention and solids according to the invention are distinguished by a high purity with respect to the homogeneity of the oxidation state of the vanadium.
  • articles or coatings can be produced which have very uniform properties with regard to the switchability of the thermochromism.
  • vanadium dioxides which have been prepared by the process according to the invention and solids according to the invention have a very sharp transition between the phases.
  • thermochromic pigments are suitable, inter alia, for use as pigments, in particular as thermochromic pigments.
  • polymeric substances such as paints or plastics such as thermoplastics or thermosetting plastics can be dyed.
  • vanadium oxides which have been prepared by the process according to the invention or solids according to the invention can be incorporated into solid, liquid or pasty pigment preparations.
  • Vanadium oxides which have been produced by the process according to the invention or solids according to the invention are furthermore of interest for use in IR detectors, as optical filters, in particular switchable optical filters or in laser welding. Examples
  • Example 1 Comparative Example 15 g of ammonium metavanadate NH 4 VO 3 (Sigma Aldrich, purity 99%) were heated at 500 ° C. for 20 minutes in a slow stream of nitrogen (10 ml / min). The pyrolysis product was analyzed by powder diffractometry and consisted of V 2 0 5 and V 6 0i 3 .
  • ammonium metavanadate NH 4 V0 3 (Sigma Aldrich, purity 99%) and 135.05 g anhydrous oxalic acid were homogenized with the aid of 100 g steatite balls (diameter 10 mm) for five minutes using a shaking mixer. The mixture was then deagglomerated with a knife mill.
  • the product obtained was analyzed by powder diffractometry and compared with the powder diffractograms of known compounds.
  • the product obtained was a mixture of V 2 0 3 and V 4 0 7 .
  • Example 3 Inventive Example 1 3 g of ammonium metatungstate ( ⁇ 4 ) 10 ⁇ 2 ⁇ 12 ⁇ 42 were dissolved in 10 ml of water and stirred with 30.0 g of ammonium metavanadate NH 4 V0 3 . The paste was applied at room temperature. dried in a vacuum drying oven to constant weight and then deagglomerated with a laboratory mill.
  • the reductate thus obtained was analyzed by powder diffractometry and consisted of alpha-V0 2 with an admixture of W0 3 . Less than 2 mol% tungsten was incorporated into the V0 2 lattice relative to vanadium.
  • phase transition temperature for the transition to beta-V0 2 was 65.2 ° C on heating and 61, 2 ° C on cooling (differential thermal analysis (DSC), heating rate 1 K / min).
  • the determined phase transition temperature suggests that only a small part of the tungsten used is present as doping in the V0 2 lattice.
  • the product obtained was examined by powder diffractometry. It consisted of powdery diffractometrically pure alpha-V0 2 . The product therefore has the empirical formula ⁇ 0 , 98 ⁇ , ⁇ 2 ⁇ 2 - It had a phase transition temperature of 52.9 ° C when heated and 30.6 ° C on cooling (DSC, heating rate 1 K / min).

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Abstract

L'invention concerne un procédé de production d'oxyde de vanadium de formule brute V1-xMxO2-yAy, où M est au moins un métal autre que le vanadium, x vaut de 0 à 0,05, A est un anion autre que l'oxygène, et y vaut de 0 bis 0,05, et où l'oxyde de vanadium présente une structure rutile déformée ou non déformée, comprenant la réduction d'un matériau de départ contenant du vanadium (V) et le traitement thermique du produit de la réduction sous une atmosphère de gaz inerte à des températures se situant dans la plage allant de 500 à 1000°C.
PCT/IB2011/052856 2010-06-29 2011-06-29 Procédé de production d'oxyde de vanadium alpha dopé ou non dopé Ceased WO2012001636A1 (fr)

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EP10167713 2010-06-29

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WO2016100967A1 (fr) * 2014-12-19 2016-06-23 Dimien Llc Compositions d'oxyde de vanadium ainsi que systèmes et procédés de création de celles-ci
CN109502643A (zh) * 2018-11-26 2019-03-22 深圳大学 一种硼镁共掺杂vo2粉体及其制备方法和应用
CN111132933A (zh) * 2017-11-24 2020-05-08 株式会社Lg化学 锂二次电池用正极材料以及其制备方法
CN113921805A (zh) * 2021-10-14 2022-01-11 合肥工业大学 一种用于水系锌离子电池的阴离子掺杂三氧化二钒正极材料的制备方法
CN119240788A (zh) * 2024-11-11 2025-01-03 太原理工大学 一种氮掺杂钒氧化物的微波吸收材料及其制备方法

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CN1693211A (zh) * 2005-04-25 2005-11-09 四川大学 复合掺杂二氧化钒纳米粉体材料及其制备方法
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WO2016100967A1 (fr) * 2014-12-19 2016-06-23 Dimien Llc Compositions d'oxyde de vanadium ainsi que systèmes et procédés de création de celles-ci
US10889505B2 (en) * 2014-12-19 2021-01-12 Dimien, Inc. Vanadium oxide compositions and systems and methods for creating them
CN111132933A (zh) * 2017-11-24 2020-05-08 株式会社Lg化学 锂二次电池用正极材料以及其制备方法
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CN111132933B (zh) * 2017-11-24 2024-04-16 株式会社Lg新能源 锂二次电池用正极材料以及其制备方法
CN109502643A (zh) * 2018-11-26 2019-03-22 深圳大学 一种硼镁共掺杂vo2粉体及其制备方法和应用
CN109502643B (zh) * 2018-11-26 2021-03-16 深圳大学 一种硼镁共掺杂vo2粉体及其制备方法和应用
CN113921805A (zh) * 2021-10-14 2022-01-11 合肥工业大学 一种用于水系锌离子电池的阴离子掺杂三氧化二钒正极材料的制备方法
CN113921805B (zh) * 2021-10-14 2022-12-20 合肥工业大学 一种用于水系锌离子电池的阴离子掺杂三氧化二钒正极材料的制备方法
CN119240788A (zh) * 2024-11-11 2025-01-03 太原理工大学 一种氮掺杂钒氧化物的微波吸收材料及其制备方法
CN119240788B (zh) * 2024-11-11 2025-11-25 太原理工大学 一种氮掺杂钒氧化物的微波吸收材料及其制备方法

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