CN104528826A - Vanadium dioxide powder preparation method and application thereof - Google Patents
Vanadium dioxide powder preparation method and application thereof Download PDFInfo
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- CN104528826A CN104528826A CN201510001234.2A CN201510001234A CN104528826A CN 104528826 A CN104528826 A CN 104528826A CN 201510001234 A CN201510001234 A CN 201510001234A CN 104528826 A CN104528826 A CN 104528826A
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- oxide powder
- preparation
- vanadium dioxide
- hypovanadic oxide
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Abstract
The invention provides a vanadium dioxide powder preparation method. The method comprises the steps that 1, N2H4.2HCl and H2CO4.2H2O are adopted in a hydrochloric acid medium for reducing vanadium pentoxide to obtain a VOCL2 solution; 2, the VOCL2 solution reacts with (NH4)2CO3 to obtain an alkaline-mode vanadyl ammonium carbonate precursor; 3, the obtained precursor is ultrasonically broken in absolute ethyl alcohol to achieve the granularity being smaller than 2 micrometers, the product is placed into a furnace with nitrogen to be heated and decomposed, and then vanadium dioxide powder is obtained, wherein when the product is heated and decomposed in the step 3, the nitrogen flow speed is 15 ml/min, and the temperature increasing speed is 5 DEG C/min.
Description
Technical field
The present invention relates to the synthesis field of metal-powder, especially relate to the hypovanadic oxide powder preparation method that technique is more stable.
Background technology
Vanadium dioxide is a kind of material with phase-change characteristic, thermoinducible reversible SEMICONDUCTOR-METAL phase transformation can occur near 70 DEG C, based on this characteristic, make it in Energy Saving Windows, thermoswitch, lasing safety, and infra-red heat breath imaging side mask has wide practical use.It is low that vanadium dioxide powder material then has cost, the clear superiority that production efficiency is high, but also can, after powdered material preparation technology tends to maturation, develop based on powdered material, prepare the novel process of vanadium dioxide film, the approach of vanadium dioxide widespread use will be realized.And fine-grained vanadium dioxide powder stress when significantly can reduce material phase transformation, and along with the reduction of particle diameter, sudden change of resistivity magnitude and optical transmittance all increase, and thus the research of its synthetic method causes all the more the attention of people.
At present, Study on Preparation about vanadium dioxide mainly concentrates in film preparation, technique in prepared by powder is more rarely seen comparatively speaking, vanadium dioxide film adopts chemical method as chemical baths, crystal pulling method or the method such as reactive sputtering, gaseous phase deposition usually, but these technique ubiquity apparatus expensive, process parameter control is complicated, the limitation such as sedimentation rate is low; The mode of many employings alkaline reagents when synthesizing hypovanadic oxide powder in Chinese patent CN104030355A, CN102115167A.What provide in patent CN1451633A prepares in the method for vanadium dioxide, with the reduction such as oxalic acid, hydrazine Vanadium Pentoxide in FLAKES in hydrochloric acid medium, then thermolysis is carried out after fragmentation, Heating temperature is 350 ~ 700 DEG C, but during due to precursors decompose, each elementary reaction heat absorption and release there are differences, and in present method, Heating temperature can cause that product purity is poor and reaction efficiency is lower.To sum up, existing preparation method is final, technology stability and repeatability poor, be unsuitable for the requirement of producing in batches.
Summary of the invention
The present invention proposes a kind of method preparing Vanadium Pentoxide in FLAKES powder, improve stability and the repeatability of technique, reduce manufacturing cost, provide production efficiency, adapt to batch production requirements, reduce the transformation temperature of vanadium dioxide powder, increase photoelectric properties rangeability before and after phase transformation.
The technical solution used in the present invention is as follows:
The preparation method of hypovanadic oxide powder, step is as follows:
1) N is adopted
2h
42Hcl and H
2cO
42H
2o reduces Vanadium Pentoxide in FLAKES in hydrochloric acid medium, obtained VOCl
2solution;
2) by VOCl
2solution and (NH
4) 2CO
3reaction, obtained alkali formula vanadyl volatile salt precursor;
3) by step 2) prepared by precursor after ultrasonication to granularity is less than 2 μm in dehydrated alcohol, product is inserted thermal degradation in the stove being connected with nitrogen, is heated to 350 ~ 700 DEG C and decomposes and terminate, obtain hypovanadic oxide powder;
Wherein, in described step 3), when product carries out thermal degradation, nitrogen flow rate is 15ml/min, and heat-up rate is 5 DEG C/min.
Wherein, the vanadium dioxide powder that prepared by aforesaid method can be used for preparing vanadium dioxide pottery.
In the above-mentioned methods, can in step 1) VOCl
2solution adds corresponding dopant ion, can prepare doped vanadium dioxide powder.
The present invention is reached by the warming temperature, holding temperature, nitrogen flow rate etc. when regulating thermolysis and accurately controls stoicheiometry object, and then proportioning when controlling whole chemical reaction between reactant, this is obviously different from traditional technology needs atmosphere in accurate controling parameters and deposition process, improves the stability of technique.
The particle diameter of vanadium dioxide powder is less, and before and after its optical medium complex body phase transformation, the rangeability of optical transmittance is larger, and when reaching on nanoscale, before and after complex body phase transformation, optical transmittance rangeability can be suitable with vanadium dioxide film.The covert front and back photoelectric properties rangeability that the application's method prepares vanadium dioxide powder is comparatively large, has outstanding phase transition performance, and reaches or close to the performance of vanadium dioxide film.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 and Fig. 2 is the thermogravimetric analysis of the embodiment of the present invention 1 and the result accompanying drawing of differential thermal analysis;
Fig. 3 and Fig. 4 is the thermogravimetric analysis of comparative example 1 of the present invention and the result accompanying drawing of differential thermal analysis;
Fig. 5 and Fig. 6 is the thermogravimetric analysis of comparative example 2 of the present invention and the result accompanying drawing of differential thermal analysis.
Embodiment
Below in conjunction with the embodiment of the present invention, be clearly and completely described technical scheme of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The preparation method of embodiment 1 hypovanadic oxide powder
First with Vanadium Pentoxide in FLAKES, N
2h
42Hcl, Hcl and NH
4hCO
3for raw material, be prepared into VOCl
2solution, then by prepared solution and (NH
4)
2cO
3reaction, prepares alkali formula vanadyl volatile salt precursor i.e. (NH
4)
5[(VO
6) (CO
3)
4(OH)
9] 10H
2o, the crystal eduction rate of precursor is about 90%; Again by the (NH of synthesis
4)
5[(VO
6) (CO
3)
4(OH)
9] 10H
2o sample is placed in NTG-209 type interlock thermal analyzer, passes into the N that purity is 99.99%
2and carrying out analytic curve mensuration (thermogravimetric analysis TG and differential thermal analysis DTA is as depicted in figs. 1 and 2) simultaneously, gas flow rate is at 15ml/min, and heat-up rate is 5 DEG C/min.During thermolysis, get 5.0g sample is placed in 18mm*130mm silica tube with thin layer, then be positioned in the pipe of diameter 23mm, pass into N with the flow velocity of 2L/min
2, first allow N
2open after replacement air becomes reaction atmosphere extremely completely in injection silica tube and be heated to 350 ~ 700 DEG C of decomposition end, then silica tube pulled out tube furnace and be cooled to room temperature in N2 air-flow, analyzing.
As depicted in figs. 1 and 2, in Fig. 1, B1-B4 is 4 the temperature variation peaks (and left-to-right is arranged successively) occurred in reaction process, is product temperatur running parameter in reacting in reaction process in Fig. 2; Can see before 367 DEG C generate vanadium dioxide, have 4 intermediates and correspond to 4 endotherm(ic)peaks, the exothermic peak of 390 DEG C belongs to the crystallization exothermic effect of vanadium dioxide, and experimental value may be because have the oxygen of trace to exist cause having part vanadium dioxide to become Vanadium Pentoxide in FLAKES a little more than theoretical value analysis in Fig. 1, as seen from Figure 3, the crystallization temperature of vanadium dioxide, than generating temperature high 23 DEG C (being 390 DEG C), can obtain can obtaining unformed hypovanadic oxide powder in embodiment.
Comparative example 1 is that pyrolysis gas prepares hypovanadic oxide powder with hydrogen
First with Vanadium Pentoxide in FLAKES, N
2h
42Hcl, Hcl and NH
4hCO
3for raw material, be prepared into VOCl
2solution, then by prepared solution and (NH
4)
2cO
3reaction, prepares alkali formula vanadyl volatile salt precursor i.e. (NH
4)
5[(VO
6) (CO
3)
4(OH)
9] 10H
2o, the crystal eduction rate of precursor is about 90%; Again by the (NH of synthesis
4)
5[(VO
6) (CO
3)
4(OH)
9] 10H
2o sample is placed in NTG-209 type interlock thermal analyzer, passes into the H that purity is 99.99%
2and carrying out analytic curve mensuration (thermogravimetric analysis TG and differential thermal analysis DTA is as shown in Figure 3 and Figure 4) simultaneously, gas flow rate is at 18ml/min, and heat-up rate is 5 DEG C/min.During thermolysis, get 5.0g sample is placed in 18mm*130mm silica tube with thin layer, then be positioned in the pipe of diameter 23mm, pass into H with the flow velocity of 150ml/min
2, first allow H
2be full of in silica tube and start heating to replacing completely after air becomes reaction atmosphere, at the end of pyrolysis by the time, silica tube pulled out tube furnace and be cooled to room temperature in N2 air-flow, analyzing.
As shown in Figure 3 and Figure 4, wherein A1-A3 is 4 the temperature variation peaks (A1-A3 arranges from left to right successively) occurred in reaction process; Can see before 620 DEG C generate vanadous oxide, there are three intermediates, peak corresponding to 612 DEG C belongs to the exothermic effect that vanadium dioxide is reduced into vanadous oxide, and between 465 DEG C to 612 DEG C, lacked a dehydration peak, explanation is that half hydration vanadium dioxide is reduced into three vanadium oxides, this reaction process before 465 DEG C and fast fierce, and cannot obtain the generation of pure vanadium dioxide.
Comparative example 2 is that pyrolysis gas prepares hypovanadic oxide powder with air
First with Vanadium Pentoxide in FLAKES, N
2h
42Hcl, Hcl and NH
4hCO
3for raw material, be prepared into VOCl
2solution, then by prepared solution and (NH
4)
2cO
3reaction, prepares alkali formula vanadyl volatile salt precursor i.e. (NH
4)
5[(VO
6) (CO
3)
4(OH)
9] 10H
2o, the crystal eduction rate of precursor is about 90%; Again by the (NH of synthesis
4)
5[(VO
6) (CO
3)
4(OH)
9] 10H
2o sample is placed in NTG-209 type interlock thermal analyzer, passes into the N that purity is 99.99%
2and carrying out analytic curve mensuration (thermogravimetric analysis TG and differential thermal analysis DTA is as shown in Figure 5 and Figure 6) simultaneously, gas flow rate is at 20ml/min, and heat-up rate is 5 DEG C/min.During thermolysis, get 5.0g sample is placed in 18mm*130mm silica tube with thin layer, then be positioned in the pipe of diameter 23mm, pass into N with the flow velocity of 150ml/min
2, first allow N
2be full of in silica tube and start heating to replacing completely after air becomes reaction atmosphere, at the end of pyrolysis by the time, silica tube pulled out tube furnace and be cooled to room temperature in N2 air-flow, analyzing.
As shown in Figure 5 and Figure 6, wherein C1-C4 is 4 the temperature variation peaks (C1 to C4 arranges from left to right successively) occurred in reaction process; Can see generating before Vanadium Pentoxide in FLAKES at 354 DEG C have 4 intermediates, and it is similar to hydrogen system, do not observe the endotherm(ic)peak losing crystal water, flood by the exothermic peaks of 354 DEG C, and the theoretical value of No. four intermediates is less than experimental value, show that last dehydration and crystallization carry out at the same time, that is cannot obtain pure vanadium dioxide or Vanadium Pentoxide in FLAKES oxidized lower than having quite a few when 295 DEG C.
Analyze in comparative example 1-2 and embodiment 1, can obtain unformed hypovanadic oxide powder in embodiment 1, comparative example 1-2 cannot obtain pure hypovanadic oxide powder.
Utilize hypovanadic oxide powder prepared by embodiment 1 through compression moulding, sintering can be made into vanadium dioxide pottery, and its transformation temperature is 70 DEG C, and before and after phase transformation, the change in resistance of sample reaches three orders of magnitude.
Prepare the method for doped vanadium dioxide powder, be different from embodiment 1 and be: at VOCl
2corresponding dopant ion is added, as W in solution
6+or Mo
6+, doping later stage transformation temperature obviously lowers, and if preparation VMo transformation temperature is 51 DEG C, VW transformation temperature is 20 DEG C.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. the preparation method of hypovanadic oxide powder, is characterized in that, step is as follows:
1) N is adopted
2h
42Hcl and H
2cO
42H
2o reduces Vanadium Pentoxide in FLAKES in hydrochloric acid medium, obtained VOCl
2solution;
2) by VOCl
2solution and (NH
4) 2CO
3reaction, obtained alkali formula vanadyl volatile salt precursor;
3) by step 2) prepared by precursor after ultrasonication to granularity is less than 2 μm in dehydrated alcohol, product is inserted thermal degradation in the stove being connected with nitrogen, is heated to 350 ~ 700 DEG C and decomposes and terminate, namely obtain hypovanadic oxide powder finished product;
Wherein, in described step 3), when product carries out thermal degradation, nitrogen flow rate is 15ml/min, and heat-up rate is 5 DEG C/min.
2. the preparation method of hypovanadic oxide powder as claimed in claim 1, is characterized in that, with Vanadium Pentoxide in FLAKES, N in described step 1)
2h
42Hcl, Hcl and NH
4hCO
3for raw material.
3. the preparation method of hypovanadic oxide powder as claimed in claim 1 or 2, it is characterized in that, the purity of described nitrogen is 99.99%.
4. the preparation method of hypovanadic oxide powder as claimed in claim 1, it is characterized in that, in described step 3), the end reaction temperature risen to is 500 DEG C.
5. the preparation method of hypovanadic oxide powder as claimed in claim 1, is characterized in that, in described step 3), by product as in silica tube, and silica tube N
2passing into flow velocity is 2L/min.
6. the hypovanadic oxide powder prepared of claim 1-5 any means for the preparation of the purposes of vanadium dioxide pottery.
7. prepare the method for doped vanadium dioxide powder, it is characterized in that, the VOCl2 solution described in the step 1) in method described in claim 1-5 adds corresponding dopant ion, and completes other steps and get final product.
8. prepare the method for doped vanadium dioxide powder as claimed in claim 6, it is characterized in that, described dopant ion is W
6+and/or Mo
6+.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540667A (en) * | 2015-12-30 | 2016-05-04 | 山东海容节能新材料有限公司 | Preparation method of doping modified vanadium dioxide powder with lower phase transition temperature |
| CN110255617A (en) * | 2019-06-28 | 2019-09-20 | 东莞深圳清华大学研究院创新中心 | A kind of preparation method of vanadium dioxide nano powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451633A (en) * | 2002-11-16 | 2003-10-29 | 中山大学 | Method for making vanadium dioxide and its adulterant nanoceramics |
| CN102502824A (en) * | 2011-11-15 | 2012-06-20 | 武汉大学 | Preparation method for vanadium dioxide and doped powder thereof |
| US20130344335A1 (en) * | 2011-01-21 | 2013-12-26 | Shanghai Institute Of Ceramics, Chinese Academy Of Sciences | Application and synthesis of doped vanadium dioxide powder and dispersing agent |
| CN104192904A (en) * | 2014-08-29 | 2014-12-10 | 武汉科技大学 | Superlong vanadium dioxide nanowire film and preparation method thereof |
-
2015
- 2015-01-05 CN CN201510001234.2A patent/CN104528826A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451633A (en) * | 2002-11-16 | 2003-10-29 | 中山大学 | Method for making vanadium dioxide and its adulterant nanoceramics |
| US20130344335A1 (en) * | 2011-01-21 | 2013-12-26 | Shanghai Institute Of Ceramics, Chinese Academy Of Sciences | Application and synthesis of doped vanadium dioxide powder and dispersing agent |
| CN102502824A (en) * | 2011-11-15 | 2012-06-20 | 武汉大学 | Preparation method for vanadium dioxide and doped powder thereof |
| CN104192904A (en) * | 2014-08-29 | 2014-12-10 | 武汉科技大学 | Superlong vanadium dioxide nanowire film and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540667A (en) * | 2015-12-30 | 2016-05-04 | 山东海容节能新材料有限公司 | Preparation method of doping modified vanadium dioxide powder with lower phase transition temperature |
| CN110255617A (en) * | 2019-06-28 | 2019-09-20 | 东莞深圳清华大学研究院创新中心 | A kind of preparation method of vanadium dioxide nano powder |
| CN110255617B (en) * | 2019-06-28 | 2022-06-21 | 东莞深圳清华大学研究院创新中心 | Preparation method of vanadium dioxide nano powder |
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Application publication date: 20150422 |