CN106083044A - Monoclinic phase VO2the fast preparation method of metal insulator Phase transformation ceramics material - Google Patents

Monoclinic phase VO2the fast preparation method of metal insulator Phase transformation ceramics material Download PDF

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CN106083044A
CN106083044A CN201610435825.5A CN201610435825A CN106083044A CN 106083044 A CN106083044 A CN 106083044A CN 201610435825 A CN201610435825 A CN 201610435825A CN 106083044 A CN106083044 A CN 106083044A
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monoclinic phase
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insulator
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CN106083044B (en
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袁松柳
张润
尹重阳
黄帅
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Huazhong University of Science and Technology
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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Abstract

The present invention relates to VO2Monoclinic phase VO2The fast preparation method of metal insulator Phase transformation ceramics material.The method uses hydro-thermal method to reduce V with citric acid2O5, obtain orthorhombic phase VO through eccentric cleaning2Nano-powder, then obtain monoclinic phase VO through high-temperature heat treatment2Powder body, after obtain monoclinic phase VO through tabletting sintering2Metal insulator Phase transformation ceramics.Present invention process is simple, and preparation efficiency is high, and sintering temperature is low, and energy consumption is little, low cost, and environment-protecting asepsis is pollution-free, and the ceramic phase transition performance made is good, and Stability Analysis of Structures is uniform.

Description

Monoclinic phase VO2The fast preparation method of metal-insulator phase transition ceramic material
Technical field
The present invention relates to Phase transformation ceramics field of material technology, be specifically related to a kind of monoclinic phase VO2Metal-insulator phase transition is made pottery Porcelain fast preparation method.
Background technology
Conductor is different from idioelectric band structure, and the conductance of conductor depends mainly on the situation near Fermi surface, if Band structure or fermi level can be had influence on by changing external condition, the most just can cause between metallic conductor and insulator Change, the phase co-conversion between this metal-insulator has following several theoretical model: Anderson to change, Mott changes, Wilson changes and Peierls changes.Vanadium, as the Typical Representative of 3d group 4 transition metal element, can be formed multiple with oxygen combination Oxide, is followed successively by VO, V from low to high by the valence state of vanadium2O3、VO2、V2O5And VnO2n-1(3≤n≤9)、VnO2n+1(3≤n≤ 6) two mesophases.Currently it turned out in 13 kinds of oxides of vanadium, at least 8 kinds of vanadium oxides have MIT characteristic, the most such as VO、V2O3、VO2、V2O5, its transformation is respectively occurring near-153 DEG C ,-118 DEG C, 68 DEG C and 260 DEG C of temperature.Oxygen at these vanadium In compound, VO2Gain a special interest, this is because its crystal structure changes near room temperature (68 DEG C), its photoelectric properties Have a very large change therewith so that vanadium dioxide become a kind of have wide application prospects photoelectric conversion material, optical storage, Laser radiation and smart window material, be respectively provided with the highest value in theoretical research and application.At present, monoclinic phase VO2Powder body material The preparation method of material and the selection of raw material are had nothing in common with each other, but its synthetic method is the most loaded down with trivial details or ingredient requirement is the harshest, system Standby excessive cycle.The most also many methods are had can efficiently to prepare monoclinic phase VO2Pottery, but there are still relatively costly or thing The defect that reason performance is not enough.
Summary of the invention
The technical problem to be solved is to provide a kind of monoclinic phase VO2Metal-insulator phase transition pottery quickly system Preparation Method, its technical process is few, and materials are simple, and energy consumption is low, and the Ceramic Material Physics Performance of preparation is superior.
For solving above-mentioned technical problem, the technical scheme is that
A kind of monoclinic phase VO2The fast preparation method of metal-insulator phase transition ceramic material, this preparation method includes following Step:
(1) under room temperature, first, load weighted citric acid is put in beaker, add deionized water, the most molten Solve, form clear solution；Then weigh analytically pure vanadic anhydride and put in beaker, magnetic agitation in the lump, formed the most molten Liquid；Wherein the amount of vanadic anhydride and the material of citric acid is than for 1:1.5～2.5, the citric acid-vanadic anhydride of mixed solution Concentration is 0.025 ± 5%g/mL；
(2) mixed solution stirred is poured in airtight high temperature and high pressure containers, then container is put in baking oven with 170 DEG C～190 DEG C heating, it is ensured that carry out High Temperature High Pressure hydro-thermal reaction inside container；Response time is 5～10h；
(3) after question response terminates, then reactant liquor is carried out solid-liquid separation: be centrifuged precipitation cleaning；Again precipitation is hanged Turbid liquid is poured in beaker, is finally putting in baking oven 80 DEG C～100 DEG C and is dried, obtains orthorhombic phase VO2Powder body.
(4) by orthorhombic phase VO2Powder body 500 DEG C～600 DEG C of heat treatments 1～2h under vacuum conditions, organics removal, and very Empty heat treatment process undergoes phase transition, obtains monoclinic phase VO2Powder body；
(5) by monoclinic phase VO2Powder body grind, tabletting sintering, sintering temperature is 700 DEG C～1000 DEG C, sintering time be 2～ 5h, obtains monoclinic phase VO2Metal-insulator phase transition ceramic material.
The monoclinic phase VO obtained2Phase transformation ceramics has structural mutation, resistivity mutability and magnetic sudden change.
Preferably, described solid-liquid separation uses centrifugation, and centrifugal rotational speed is 5000r/min～6000r/min, time centrifugal Between be 3～5min.
Preferably, described vacuum heat and sintering, all use quartz tube type resistance wire furnace, before heating in vacuum, be passed through general Pure argon 10-20min rinses quartz ampoule, and argon gas flow velocity is 300sccm～400sccm.
Pressure≤0.1Pa preferably, before vacuum heat, in quartz ampoule.
The invention have the advantages that
(1) pottery that the present invention prepares is the multifunctional ceramic material that a class has broad prospect of application, has list Phase structure and abundant physical property change.
(2) due to using citric acid as reducing agent, nontoxic, cost of material is the most relatively low.
(3)V2O5Thorough with the hydro-thermal reaction of citric acid, preparation efficiency is high, is greatly shortened preparation time.
(4) magnetics before and after pottery phase transformation and electric property can be changed by control high temperature sintering temperature.
(5) preparation is repeatable high, it is adaptable to prepare production in a large number.
Accompanying drawing explanation
With detailed description of the invention, technical scheme is further described in detail below in conjunction with the accompanying drawings.
Fig. 1 is monoclinic phase VO under different sintering temperatures in embodiment 1 to embodiment 42Metal-insulator phase transition ceramics sample XRD figure spectrum；
Fig. 2 is monoclinic phase VO under different sintering temperatures in embodiment 1 to embodiment 42Metal-insulator phase transition ceramics sample Magnetic temperature change curve；
Fig. 3 is monoclinic phase VO under different sintering temperatures in embodiment 1 to embodiment 42Metal-insulator phase transition ceramics sample Resistance temperature change curve.
Detailed description of the invention
Embodiment 1
1. use citric acid-V2O5Hydro-thermal reaction prepares monoclinic phase VO2Powder body:
(1) measure in the beaker that 0.00375mol citric acid puts into 50mL, add deionized water 20mL, under magnetic stirring Dissolve, form clear solution, then weigh 0.0025molV2O5Pressed powder, adds in above-mentioned citric acid solution, magnetic force in the lump Forming homogeneous yellow solution after stir about 30min, the citric acid of mixed solution-vanadic anhydride concentration is 0.025 ± 5%g/ mL；
(2) above-mentioned yellow solution is poured in 50mL stainless steel water thermal synthesis reactor, and point measure several times 10mL go from Residual medicine in sub-water rinsing step (1), adds in reactor in the lump, and end reaction solution is about 50mL, then by reactor Put in baking oven, be heated to 180 DEG C, sustained response 5h；
(3) after the above-mentioned response time terminates, reactant liquor is carried out solid-liquid separation, sucks upper strata about 35mL settled solution, Form precipitation suspension with Glass rod stirring black precipitate and surplus solution, then with sebific duct, suspension is sucked in centrifuge tube, if Putting centrifugal rotational speed 6000r/min, centrifugation time 3min, Acceleration and deceleration time is respectively 1min；After centrifugal end, suck in centrifuge tube Layer settled solution, then clean centrifuge tube with ethanol or distilled water, accompany by Glass rod stirring and form precipitation suspension, then carry out above-mentioned Centrifugally operated；After solid-liquid separation so at least three times, final precipitation suspension is rinsed and pours in beaker, then beaker is put into 90 DEG C of dry 15h of baking oven；
(4) the orthorhombic phase VO obtained after collecting aforesaid operations2Powder body, puts it in clean quartz boat, places into tubular type In stove；Rinse gaseous environment 10-20min in tubular type hearthstone English pipe with general pure argon 300sccm, aspirate tube furnace with mechanical pump, Until intraductal pressure≤0.1Pa, then carry out diamond heating, it is warming up to 550 DEG C with 5 DEG C/min, cools to the furnace after insulation 2h Room temperature, obtains monoclinic phase VO2Powder body；
2. high temperature sintering prepares monoclinic phase VO2Metal-insulator phase transition pottery:
(1) the monoclinic phase VO that aforesaid operations obtains is collected2Powder body, after being fully ground 2h, weighs the powder body tabletting of about 0.6g；
(2) lamellar VO that aforesaid operations is obtained2Put into clean quartz Noah's ark, place in tube furnace；With general straight argon Gas 300sccm rinses gaseous environment 15min in tubular type hearthstone English pipe, aspirates tube furnace with mechanical pump, until intraductal pressure≤ 0.1Pa, then carry out diamond heating, it is warming up to 700 DEG C with 5 DEG C/min, cools to room temperature with the furnace after insulation 2h, obtain monoclinic phase VO2Monoclinic phase VO2Metal-insulator phase transition pottery；
Utilize the monoclinic phase VO that embodiment 1 prepares2The XRD of metal-insulator phase transition ceramics sample as it is shown in figure 1, It is observed from fig. 1 that all characteristic peaks coincide with standard PDF card, single-phase nothing the second phase diffraction maximum occurs.Fig. 2,3 sets forth VO2Magnetic temperature curve, resistance-temperature curve.Wherein, example 1 is expressed as curve T=700 DEG C in Fig. 1,2,3.
Embodiment 2
1. use citric acid-V2O5Hydro-thermal reaction prepares monoclinic phase VO2Powder body:
(1) measure in the beaker that 0.00625mol citric acid puts into 50mL, add deionized water 20mL, under magnetic stirring Dissolve, form clear solution, then weigh 0.0025molV2O5Pressed powder, adds in above-mentioned citric acid solution, magnetic force in the lump Forming homogeneous yellow solution after stir about 30min, the citric acid of mixed solution-vanadic anhydride concentration is 0.025 ± 5%g/ mL；
(2) above-mentioned yellow solution is poured in 50mL stainless steel water thermal synthesis reactor, and point measure several times 10mL go from Residual medicine in sub-water rinsing step (1), adds in reactor in the lump, and end reaction solution is about 50mL, then by reactor Put in baking oven, be heated to 170 DEG C, sustained response 10h；
(3) after the above-mentioned response time terminates, reactant liquor is carried out solid-liquid separation, sucks upper strata about 35mL settled solution, Form precipitation suspension with Glass rod stirring black precipitate and surplus solution, then with sebific duct, suspension is sucked in centrifuge tube, if Putting centrifugal rotational speed 5000r/min, centrifugation time 4min, Acceleration and deceleration time is respectively 1min；After centrifugal end, suck in centrifuge tube Layer settled solution, then clean centrifuge tube with ethanol or distilled water, accompany by Glass rod stirring and form precipitation suspension, then carry out above-mentioned Centrifugally operated；After solid-liquid separation so at least three times, final precipitation suspension is rinsed and pours in beaker, then beaker is put into 80 DEG C of dry 15h of baking oven；
(4) the orthorhombic phase VO obtained after collecting aforesaid operations2Powder body, puts it in clean quartz boat, places into tubular type In stove；Rinse gaseous environment 10-20min in tubular type hearthstone English pipe with general pure argon 300sccm, aspirate tube furnace with mechanical pump, Until intraductal pressure≤0.1Pa, then carry out diamond heating, it is warming up to 550 DEG C with 5 DEG C/min, cools to the furnace after insulation 2h Room temperature, obtains monoclinic phase VO2Powder body；
2. high temperature sintering prepares monoclinic phase VO2Metal-insulator phase transition pottery:
(1) the monoclinic phase VO that aforesaid operations obtains is collected2Powder body, after being fully ground 2h, weighs the powder body tabletting of about 0.6g；
(2) lamellar VO that aforesaid operations is obtained2Put into clean quartz Noah's ark, place in tube furnace；With general straight argon Gas 400sccm rinses gaseous environment 10min in tubular type hearthstone English pipe, and mechanical pump aspirates tube furnace, until intraductal pressure≤ 0.1Pa, then carry out diamond heating, it is warming up to 800 DEG C with 5 DEG C/min, cools to room temperature with the furnace after insulation 2h, obtain monoclinic phase VO2Monoclinic phase VO2Metal-insulator phase transition pottery；
Utilize the monoclinic phase VO that embodiment 2 prepares2The XRD of metal-insulator phase transition ceramics sample as it is shown in figure 1, It is observed from fig. 1 that all characteristic peaks coincide with standard PDF card, single-phase nothing the second phase diffraction maximum occurs.Fig. 2,3 sets forth VO2Magnetic temperature curve, resistance-temperature curve.Wherein, example 1 is expressed as curve T=800 DEG C in Fig. 1,2,3.
Embodiment 3
1. use citric acid-V2O5Hydro-thermal reaction prepares monoclinic phase VO2Powder body:
(1) measure in the beaker that 0.00525mol citric acid puts into 50mL, add deionized water 20mL, under magnetic stirring Dissolve, form clear solution, then weigh 0.0025molV2O5Pressed powder, adds in above-mentioned citric acid solution, magnetic force in the lump Forming homogeneous yellow solution after stir about 30min, the citric acid of mixed solution-vanadic anhydride concentration is 0.025 ± 5%g/ mL；
(2) above-mentioned yellow solution is poured in 50mL stainless steel water thermal synthesis reactor, and point measure several times 10mL go from Residual medicine in sub-water rinsing step (1), adds in reactor in the lump, and end reaction solution is about 50mL, then by reactor Put in baking oven, be heated to 190 DEG C, sustained response 8h；
(3) after the above-mentioned response time terminates, reactant liquor is carried out solid-liquid separation, sucks upper strata about 35mL settled solution, Form precipitation suspension with Glass rod stirring black precipitate and surplus solution, then with sebific duct, suspension is sucked in centrifuge tube, if Putting centrifugal rotational speed 5500r/min, centrifugation time 5min, Acceleration and deceleration time is respectively 1min；After centrifugal end, suck in centrifuge tube Layer settled solution, then clean centrifuge tube with ethanol or distilled water, accompany by Glass rod stirring and form precipitation suspension, then carry out above-mentioned Centrifugally operated；After solid-liquid separation so at least three times, final precipitation suspension is rinsed and pours in beaker, then beaker is put into 100 DEG C of dry 15h of baking oven；
(4) the orthorhombic phase VO obtained after collecting aforesaid operations2Powder body, puts it in clean quartz boat, places into tubular type In stove；Rinse gaseous environment 10-20min in tubular type hearthstone English pipe with general pure argon 350sccm, aspirate tube furnace with mechanical pump, Until intraductal pressure≤0.1Pa, then carry out diamond heating, it is warming up to 550 DEG C with 5 DEG C/min, cools to the furnace after insulation 2h Room temperature, obtains monoclinic phase VO2Powder body；
2. high temperature sintering prepares monoclinic phase VO2Metal-insulator phase transition pottery:
(1) the monoclinic phase VO that aforesaid operations obtains is collected2Powder body, after being fully ground 2h, weighs the powder body tabletting of about 0.6g；
(2) lamellar VO that aforesaid operations is obtained2Put into clean quartz Noah's ark, place in tube furnace；With general straight argon Gas 300sccm rinses gaseous environment 15min in tubular type hearthstone English pipe, and mechanical pump aspirates tube furnace, until intraductal pressure≤ 0.1Pa, then carry out diamond heating, it is warming up to 900 DEG C with 5 DEG C/min, cools to room temperature with the furnace after insulation 2h, obtain monoclinic phase VO2Monoclinic phase VO2Metal-insulator phase transition pottery；
Utilize the monoclinic phase VO that embodiment 3 prepares2The XRD of metal-insulator phase transition ceramics sample as it is shown in figure 1, It is observed from fig. 1 that all characteristic peaks coincide with standard PDF card, single-phase nothing the second phase diffraction maximum occurs.Fig. 2,3 sets forth VO2Magnetic temperature curve, resistance-temperature curve.Wherein, example 1 is expressed as curve T=900 DEG C in Fig. 1,2,3.
Embodiment 4
1. use citric acid-V2O5Hydro-thermal reaction prepares monoclinic phase VO2Powder body:
(1) measure in the beaker that 0.00575mol citric acid puts into 50mL, add deionized water 20mL, under magnetic stirring Dissolve, form clear solution, then weigh 0.0025molV2O5Pressed powder, adds in above-mentioned citric acid solution, magnetic force in the lump Forming homogeneous yellow solution after stir about 30min, the citric acid of mixed solution-vanadic anhydride concentration is 0.025 ± 5%g/ mL；
(2) above-mentioned yellow solution is poured in 50mL stainless steel water thermal synthesis reactor, and point measure several times 10mL go from Residual medicine in sub-water rinsing step (1), adds in reactor in the lump, and end reaction solution is about 50mL, then by reactor Put in baking oven, be heated to 180 DEG C, sustained response 9h；
(3) after the above-mentioned response time terminates, reactant liquor is carried out solid-liquid separation, sucks upper strata about 35mL settled solution, Form precipitation suspension with Glass rod stirring black precipitate and surplus solution, then with sebific duct, suspension is sucked in centrifuge tube, if Putting centrifugal rotational speed 6000r/min, centrifugation time 4min, Acceleration and deceleration time is respectively 1min；After centrifugal end, suck in centrifuge tube Layer settled solution, then clean centrifuge tube with ethanol or distilled water, accompany by Glass rod stirring and form precipitation suspension, then carry out above-mentioned Centrifugally operated；After solid-liquid separation so at least three times, final precipitation suspension is rinsed and pours in beaker, then beaker is put into 100 DEG C of baking oven is fully dried；
(4) the orthorhombic phase VO obtained after collecting aforesaid operations2Powder body, puts it in clean quartz boat, places into tubular type In stove；Rinse gaseous environment 10-20min in tubular type hearthstone English pipe with general pure argon 350sccm, aspirate tube furnace with mechanical pump, Until intraductal pressure≤0.1Pa, then carry out diamond heating, it is warming up to 550 DEG C with 5 DEG C/min, cools to the furnace after insulation 2h Room temperature, obtains monoclinic phase VO2Powder body；
2. high temperature sintering prepares monoclinic phase VO2Metal-insulator phase transition pottery:
(1) the monoclinic phase VO that aforesaid operations obtains is collected2Powder body, after being fully ground 2h, weighs the powder body tabletting of about 0.6g；
(2) lamellar VO that aforesaid operations is obtained2Put into clean quartz Noah's ark, place in tube furnace；With general straight argon Gas 400sccm rinses gaseous environment 10-20min in tubular type hearthstone English pipe, and mechanical pump aspirates tube furnace, until intraductal pressure≤ 0.1Pa, then carry out diamond heating, it is warming up to 1000 DEG C with 5 DEG C/min, cools to room temperature with the furnace after insulation 2h, obtain monocline Phase VO2Monoclinic phase VO2Metal-insulator phase transition pottery；
Utilize the monoclinic phase VO that embodiment 4 prepares2The XRD of metal-insulator phase transition ceramics sample as it is shown in figure 1, It is observed from fig. 1 that all characteristic peaks coincide with standard PDF card, single-phase nothing the second phase diffraction maximum occurs.Fig. 2,3 sets forth VO2Magnetic temperature curve, resistance-temperature curve.Wherein, example 1 is expressed as curve T=1000 DEG C in Fig. 1,2,3.
Use monoclinic phase VO prepared by above method2Pottery possesses the single-phase superior metal of structure-insulator conversion characteristic, It it is a kind of functional material with broad prospect of application.It is employed herein X-ray diffractometer (XRD) to its material phase analysis；Use The comprehensive property test system (PPMS) of Quantum Design company to the magnetic warm nature of sample can and resistance warm nature can survey Amount.
Phase temperature T=700 DEG C, 800 DEG C, 900 DEG C, the monocline of 1000 DEG C is sintered into through difference as it is shown in figure 1, give Phase VO2The XRD figure spectrum of ceramics sample, it is observed from fig. 1 that all characteristic peaks all identical with standard PDF card, this demonstrates Through the VO prepared by citric acid-vanadic anhydride hydro-thermal reaction method2, the sample purity obtained after high-temperature heat treatment is high, knot Structure is single without dephasign.
Fig. 2 gives and sinters phase temperature T=700 DEG C, 800 DEG C, 900 DEG C, the monoclinic phase VO of 1000 DEG C into2Metal-insulator Body transformation ceramic material sample is under externally-applied magnetic field H=10kOe intensity, and susceptibility varies with temperature measurement result.Can from Fig. 2 To find out, along with the rising of measurement temperature, the susceptibility of sample occurs uprushing near 340K.It addition, its change magnitude with The rising of sintering temperature and increase.Finding out the rising along with sintering temperature from XRD figure is composed, the characteristic peak of sample is more notable, The degree of crystallinity of sample is the highest.And the degree of crystallinity of sample is the highest, its crystal structure is more for the most single, and this is beneficial at VO simultaneously2In Form the complete antiparallel V of electron spin4+-V4+Dimer pair, thus sample has more superior magnetic property to change.
Fig. 3 gives and sinters phase temperature T=700 DEG C, 800 DEG C, 900 DEG C, the monoclinic phase VO of 1000 DEG C into2Sample is heating up During measurements resistivity, from resistance temperature measure of the change can be seen that along with temperature raise, the bust of resistivity is also Occur, near 340K, showing as insulating properties to metallic transformation；The change magnitude of resistivity is along with sintering carrying of phase temperature into High and significantly increase, when sintering temperature is T=700 DEG C and T=800 DEG C, and the transformation of resistivity is approximately about 2 orders of magnitude；When Sintering temperature is T=900 DEG C and T=1000 DEG C, and the transformation of resistance is close to 3 to 4 orders of magnitude.Test result indicate that, by suitable When improving sintering temperature, the metal-insulator body resistivity that can improve sample changes magnitude.
It should be noted last that, above detailed description of the invention only in order to technical scheme to be described and unrestricted, Although the present invention being described in detail with reference to preferred embodiment, it will be understood by those within the art that, can be right Technical scheme is modified or equivalent, and without deviating from the spirit and scope of technical solution of the present invention, it is equal Should contain in the middle of scope of the presently claimed invention.

Claims (5)

1. a monoclinic phase VO2The fast preparation method of metal-insulator phase transition ceramic material, it is characterised in that this preparation method Comprise the following steps:
(1) under room temperature, first, load weighted citric acid is put in beaker, adds deionized water, dissolve under magnetic stirring, Form clear solution；Then weigh analytically pure vanadic anhydride and put in beaker, magnetic agitation in the lump, form homogeneous solution； Wherein the amount of vanadic anhydride and the material of citric acid is than for 1:1.5～2.5, and the citric acid-vanadic anhydride of mixed solution is dense Degree is 0.025 ± 5%g/mL；
(2) mixed solution stirred is poured in airtight high temperature and high pressure containers, then container is put in baking oven with 170 DEG C ～190 DEG C of heating, it is ensured that carry out High Temperature High Pressure hydro-thermal reaction inside container；Response time is 5～10h；
(3) after question response terminates, then reactant liquor is carried out solid-liquid separation: be centrifuged precipitation cleaning；Suspension will be precipitated again Pour in beaker, be finally putting in baking oven 80 DEG C～100 DEG C and be dried, obtain orthorhombic phase VO2Powder body；
(4) by orthorhombic phase VO2Powder body under vacuum conditions, cools to room temperature with the furnace after 500 DEG C～600 DEG C insulation 2h, removes organic Thing, and vacuum heat treatment process undergo phase transition, obtains monoclinic phase VO2Powder body；
(5) by monoclinic phase VO2Powder body grinds, tabletting sintering, and sintering temperature is 700 DEG C～1000 DEG C, and sintering time is 2～5h, with After cool to room temperature with the furnace and obtain monoclinic phase VO2Metal-insulator phase transition ceramic material.
Monoclinic phase VO the most according to claim 12The fast preparation method of metal-insulator phase transition ceramic material, its feature It is, the monoclinic phase VO obtained2Phase transformation ceramics has structural mutation, resistivity mutability and magnetic sudden change.
Monoclinic phase VO the most according to claim 12The fast preparation method of metal-insulator phase transition ceramic material, its feature Be, described solid-liquid separation use centrifugation, centrifugal rotational speed is 5000r/min～6000r/min, centrifugation time be 3～ 5min。
Monoclinic phase VO the most according to claim 12The fast preparation method of metal-insulator phase transition ceramic material, its feature It is, described vacuum heat and sintering, all uses quartz tube type resistance wire furnace, before heating in vacuum, be passed through general pure argon 10- 20min rinses quartz ampoule, and argon gas flow velocity is 300sccm～400sccm.
Monoclinic phase VO the most according to claim 12The fast preparation method of metal-insulator phase transition ceramic material, its feature It is, the pressure≤0.1Pa before vacuum heat, in quartz ampoule.
CN201610435825.5A 2016-06-17 2016-06-17 Monoclinic phase VO2The fast preparation method of metal-insulator phase transition ceramic material Expired - Fee Related CN106083044B (en)

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CN110342574A (en) * 2019-07-31 2019-10-18 济南大学 A kind of preparation method of monoclinic phase vanadium dioxide nano-powder
CN113105235A (en) * 2021-04-01 2021-07-13 中国计量大学 VO2Ceramic, high-responsivity infrared weak light detector and regulation and control method thereof
CN114142107A (en) * 2021-11-30 2022-03-04 江苏警官学院 Aqueous lithium ion battery based on monoclinic-phase vanadium dioxide cathode

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Publication number Priority date Publication date Assignee Title
CN107162591A (en) * 2017-03-28 2017-09-15 华中科技大学 Nb5+The monoclinic phase VO of doping2Metal insulator Phase transformation ceramics and preparation method thereof
CN106966432A (en) * 2017-05-17 2017-07-21 吉林大学 There is the Mx ' phases VO of metallic character under normal pressure2The preparation method of nano material
CN106966432B (en) * 2017-05-17 2018-03-09 吉林大学 There is the Mx ' phases VO of metallic character under normal pressure2The preparation method of nano material
CN110342574A (en) * 2019-07-31 2019-10-18 济南大学 A kind of preparation method of monoclinic phase vanadium dioxide nano-powder
CN110342574B (en) * 2019-07-31 2021-10-15 济南大学 Preparation method of monoclinic-phase vanadium dioxide nano powder
CN113105235A (en) * 2021-04-01 2021-07-13 中国计量大学 VO2Ceramic, high-responsivity infrared weak light detector and regulation and control method thereof
CN114142107A (en) * 2021-11-30 2022-03-04 江苏警官学院 Aqueous lithium ion battery based on monoclinic-phase vanadium dioxide cathode
CN114142107B (en) * 2021-11-30 2023-05-09 江苏警官学院 Water system lithium ion battery based on monoclinic phase vanadium dioxide negative electrode

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