CN102504767B - Preparation method of Re-doped vanadium dioxide powder - Google Patents

Preparation method of Re-doped vanadium dioxide powder Download PDF

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CN102504767B
CN102504767B CN201110320919.5A CN201110320919A CN102504767B CN 102504767 B CN102504767 B CN 102504767B CN 201110320919 A CN201110320919 A CN 201110320919A CN 102504767 B CN102504767 B CN 102504767B
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powder
kreo
doping
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purity
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CN102504767A (en
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邹军涛
曹雪茹
王献辉
梁淑华
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Xian University of Technology
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Xian University of Technology
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Abstract

The invention discloses a preparation method of Re-doped vanadium dioxide powder. The method comprises the following steps of: preparing gel powder with V2O5 powder of which purity is more than 99.9% and KReO4 powder of which purity is more than 99.0% as raw materials through a sol-gel process, mixing with C powder, and then injecting N2 to reduce the mixed powder so as to obtain the Re-doped VO2 powder. The phase-transition temperature of the Re<7+>-doped VO2 powder prepared by the method is obviously reduced, the structure is more uniform, the photoelectric properties are better and the powder can be better applied in the novel phase-transition materials of smart materials and energy-saving materials.

Description

A kind of preparation method of vanadium dioxide powder of the rhenium that adulterates
Technical field
The invention belongs to phase change material preparing technical field, relate to the preparation method of the vanadium dioxide powder of a kind of doping rhenium (Re).
Background technology
Single VO 2in 68 ℃ of reversible transformations that low temperature monocline semi-conductor phase-high temperature four directions metallographic phase can occur, the sudden change of simultaneous resistivity, susceptibility, infrared light transmitance and reflectivity.In order to change VO 2transformation temperature, thus the VO that can undergo phase transition at extraordinary temperature is provided 2material is to expand its scope of application, and scientists has been carried out serial research.At present, in research, change VO both at home and abroad 2in the process of transformation temperature, a lot of research is all the method that adopts high volence metal ion doping, comprises doping W + 6, Mo + 6, Ta + 5, Nb + 5etc. method, and the radius of these dopant ions is larger, ectonuclear electron number is more, changes VO 2transformation temperature effect is just more obvious, current doping W + 6change VO 2transformation temperature is the most effective, and every doping molar percentage is centesimal W in theory + 6, VO 2transformation temperature can reduce 23-25 ℃, but than W + 6the Re that radius is larger, valence state is higher 7+doping changes VO 2the research of transformation temperature has no report.
Summary of the invention
The object of the present invention is to provide the preparation method of the vanadium dioxide powder of a kind of doping rhenium (Re), the method is at preparation VO 2re adulterates in the process of powder 7+, make VO 2transformation temperature reduce.
The technical solution adopted in the present invention is, a kind of preparation method of vanadium dioxide powder of the rhenium that adulterates, and the method comprises following operation steps:
Step 1: account for integral molar quantity 1%～5% with mol ratio according to the doping ratio of Re and take V 2o 5powder and KReO 4powder, V 2o 5powder purity is not less than 99.9%, KReO 4powder purity is not less than 99.0%, then by the V taking 2o 5powder and KReO 4powder packs in ball grinder, by V 2o 5powder and KReO 415 times～20 times of powder total mass add abrading-ball, carry out the mixed powder of 4～6 hours;
Step 2: will be contained in clean Al through the mixed powder of step 1 2o 3in crucible, put into chamber type electric resistance furnace, be heated to 700～800 ℃, until it, reach completely after molten state, melt is slowly poured into and in deionized water, made colloid;
Step 3: the colloid that step 2 is obtained is put into chamber type electric resistance furnace is incubated 5～8 hours at the temperature of 100 ℃～200 ℃, takes out after cooling grind into powder;
Step 4: the powder that step 3 is made and C powder are even according to the mixed in molar ratio of 2: 1, and be contained in clean Al 2o 3in porcelain boat, put into two-tube carbon-determining stove, pass into shielding gas, be first heated to 600～700 ℃ of insulation 2～4h, then be warming up to 850～950 ℃ of insulation 3～5h, then with stove, naturally cool to room temperature, make the VO of doping Re 2powder.
Feature of the present invention is also,
Every kilogram of deionized water that powder is joined 10L in step 2.
Shielding gas in step 4 is N 2.
The Re that method of the present invention obtains 7+doping VO 2the transformation temperature of powder obviously reduces, and organizes more evenly, and photoelectric properties are better, can better be for the novel phase-change material of intelligent material and energy-saving material.
Accompanying drawing explanation
Fig. 1 is preparation method's of the present invention process flow sheet;
Fig. 2 is the VO of Re of not adulterating 2the XRD figure spectrum of powder;
Fig. 3 is the VO of doping 1%Re 2the XRD figure spectrum of powder;
Fig. 4 is the VO of doping 3%Re 2the XRD figure spectrum of powder;
Fig. 5 is the VO of doping 5%Re 2the XRD figure spectrum of powder.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The present invention will adopt traditional doping W to reduce VO 2the method of transformation temperature, changes doping Re into and prepares VO to reduce transformation temperature 2powder, recycling sol-gel method, prepares gel, and the method that then adopts hot carbon to reduce restores the VO of doping Re 2powder.As shown in Figure 1, specifically carry out according to the following steps,
Step 1: take mol ratio respectively according to the doping of Re than taking purity and be not less than 99.9% V as 1%～5% 2o 5powder and purity are not less than 99.0% KReO 4powder, then packs the powder taking in ball grinder into, by V 2o 5powder and KReO 415 times～20 times of powder total mass add abrading-ball, carry out the mixed powder of 4～6 hours;
Step 2: mixed powder is contained in to clean Al 2o 3in crucible, put into chamber type electric resistance furnace, be heated to 700～800 ℃, until it, reach completely after molten state, melt is slowly poured in deionized water and made colloid, every 1g powder is joined the deionized water of 10ml;
Step 3: the colloid that upper step is obtained is put into chamber type electric resistance furnace is incubated 5～8 hours at the temperature of 100 ℃～200 ℃, takes out after cooling grind into powder;
Step 4: powder prepared by upper step and C powder are even according to the mixed in molar ratio of 2: 1, and be contained in clean Al 2o 3in porcelain boat, put into two-tube carbon-determining stove, pass into shielding gas N 2, be first heated to 600～700 ℃ of insulation 2～4h, then be warming up to 850～950 ℃ of insulation 3～5h, then with stove, naturally cool to room temperature, make the VO of doping Re 2powder.
Through experimental verification, work as W 6+doping is just difficult to be solidly soluted into VO again after being greater than 5% 2in lattice, W 6+doping reached maximum saturation.And Re 7+ionic radius be greater than W 6+, and introduced unnecessary electronics, its maximum saturation is reduced, so we are by Re 7+doping be selected in the scope of 1%-5%.
Embodiment 1
In molar ratio by 99% V 2o 5powder and 1% KReO 4powder weighs up, and puts into ball grinder, in ball grinder, by V 2o 5powder and KReO 415 times of powder total mass add abrading-ball, carry out the mixed powder of 4 hours.
Then, mixed powder is contained in to clean Al 2o 3in crucible, put into chamber type electric resistance furnace, be heated to 750 ℃, until it, reach completely after molten state, melt is slowly poured in preprepared deionized water and made the even colloid of reddish-brown, every 1g powder is joined the deionized water of 10ml.The colloid obtaining is put into chamber type electric resistance furnace, at the temperature of 200 ℃, be incubated 6h, moisture wherein is fully evaporated, take out after cooling grind into powder.
Finally, powder prepared by upper step and C powder are even according to the mixed in molar ratio of 2: 1, are contained in clean Al 2o 3in porcelain boat, put into two-tube carbon-determining stove, pass into shielding gas N 2, be first heated to 600 ℃ insulation 3h, then be warming up to 900 ℃ insulation 5h reduce, then with stove, naturally cool to room temperature, make doping Re VO 2powder.
Embodiment 2
By V 2o 5powder 97% and KReO 4powder 3% weighs up, and puts into ball grinder, in ball grinder, by V 2o 5powder and KReO 420 times of powder total mass add abrading-ball, mix powder 6 hours.
Then, mixed powder is contained in to clean Al 2o 3in crucible, put into chamber type electric resistance furnace, be heated to 700 ℃, until it, reach completely after molten state, melt is slowly poured into and in preprepared deionized water, made the even colloid of reddish-brown, the deionized water that average 1g powder is joined 10ml, the colloid obtaining is put into chamber type electric resistance furnace, at the temperature of 100 ℃, be incubated 5h, moisture wherein is fully evaporated, take out after cooling grind into powder.
Finally, powder prepared by upper step and C powder are even according to the mixed in molar ratio of 2: 1, are contained in clean Al 2o 3in porcelain boat, put into two-tube carbon-determining stove, pass into shielding gas N 2, be first heated to 670 ℃ insulation 2h, then be warming up to 850 ℃ insulation 4h reduce, then with stove, naturally cool to room temperature, make doping Re VO 2powder.
Embodiment 3
By V 2o 5powder 95% and KReO 4powder 5% weighs up, and puts into ball grinder, in ball grinder, by V 2o 5powder and KReO 417 times of powder total mass add abrading-ball, carry out the mixed powder of 5 hours.
Then, mixed powder is contained in to clean Al 2o 3in crucible, put into chamber type electric resistance furnace, be heated to 800 ℃, until it, reach completely after molten state, melt is slowly poured into and in preprepared deionized water, made the even colloid of reddish-brown, the deionized water that average 1g powder is joined 10ml.The colloid obtaining is put into chamber type electric resistance furnace, at the temperature of 170 ℃, be incubated 8h, moisture wherein is fully evaporated, take out after cooling grind into powder.
Finally, powder prepared by upper step and C powder are even according to the mixed in molar ratio of 2: 1, are contained in clean Al 2o 3in porcelain boat, put into two-tube carbon-determining stove, pass into shielding gas N 2, be first heated to 700 ℃ insulation 4h, then be warming up to 950 ℃ insulation 3h reduce, then with stove, naturally cool to room temperature, make doping Re VO 2powder.
Fig. 2-5 are that the doping of Re is by 0%～5% VO 2the XRD figure spectrum of powder, by Fig. 2-5 relatively in can find out, in the scope of its maximum saturation, along with the increase of doping, the powder of preparing changes Tetragonal into by monoclinic phase gradually, and the VO that mixes Re is described 2powder transformation temperature is than single VO 2powder transformation temperature has had obvious improvement, along with mixing the increase of Re amount, VO 2the transformation temperature of powder reduces gradually, organizes more evenly, and photoelectric properties are better, can better be for the novel phase-change material of intelligent material and energy-saving material.

Claims (3)

1. the adulterate preparation method of vanadium dioxide powder of rhenium, is characterized in that, the method comprises following operation steps:
Step 1: the mol ratio of take takes V according to the doping ratio of Re as 1%～5% 2o 5powder and KReO 4powder, V 2o 5powder purity is not less than 99.9%, KReO 4powder purity is not less than 99.0%, then by the V taking 2o 5powder and KReO 4powder packs in ball grinder, by V 2o 5powder and KReO 415 times～20 times of powder total mass add abrading-ball, carry out the mixed powder of 4～6 hours;
Step 2: will be contained in clean Al through the mixed powder of step 1 2o 3in crucible, put into chamber type electric resistance furnace, be heated to 700～800 ℃, until it, reach completely after molten state, melt is slowly poured into and in deionized water, made colloid;
Step 3: the colloid that step 2 is obtained is put into chamber type electric resistance furnace is incubated 5～8 hours at the temperature of 100 ℃～200 ℃, takes out after cooling grind into powder;
Step 4: the powder that step 3 is made and C powder are even according to the mixed in molar ratio of 2:1, and be contained in clean Al 2o 3in porcelain boat, put into two-tube carbon-determining stove, pass into shielding gas, be first heated to 600～700 ℃ of insulation 2～4h, then be warming up to 850～950 ℃ of insulation 3～5h, then with stove, naturally cool to room temperature, make doping Re 7+vO 2powder.
2. method according to claim 1, is characterized in that, every kilogram of deionized water that powder is joined 10L in step 2.
3. method according to claim 1, is characterized in that, the shielding gas in step 4 is N 2.
CN201110320919.5A 2011-10-20 2011-10-20 Preparation method of Re-doped vanadium dioxide powder Expired - Fee Related CN102504767B (en)

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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN101164900A (en) * 2007-10-09 2008-04-23 上海师范大学 Technique for preparing phase-change temperature controllable tungsten doping nano vanadium dioxide powder

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101164900A (en) * 2007-10-09 2008-04-23 上海师范大学 Technique for preparing phase-change temperature controllable tungsten doping nano vanadium dioxide powder

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