CN102586796B - Method for preparing vanadium dioxide powder through electrolysis - Google Patents
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- CN102586796B CN102586796B CN201210073258.5A CN201210073258A CN102586796B CN 102586796 B CN102586796 B CN 102586796B CN 201210073258 A CN201210073258 A CN 201210073258A CN 102586796 B CN102586796 B CN 102586796B
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Abstract
The invention provides a method for preparing vanadium dioxide powder under a mild condition. In an alkaline solution containing +5 valence vanadium, direct current is connected to perform electrolytic reaction, the electrolysis temperature is controlled below 100 DEG C, and an electrolysis compound containing vanadium is prepared after electrolysis for more than 2 hours. In the inert atmosphere, the annealing treatment is performed to compound containing vanadium for more than 0.5 hours at the temperature of 200-1100 DEG C to obtain VO2 with high purity. The method for preparing vanadium dioxide powder through electrolysis has the advantages that the process is short, the operation is simple and convenient, the product shape is easily controlled, no reagent is required to be added, harmful gas and sewage are not produced and the like.
Description
Technical field
The present invention relates to field of functional materials, particularly, the present invention relates to a kind of method of preparing vanadium dioxide powder through electrolysis.
Background technology
Vanadium dioxide is a kind of thermochromic material, is black blue powders at normal temperatures.At temperature Tc=68 DEG C, crystal transition occurs, from semi-conductor to Metal Phase Transition, resistivity sudden change reaches 4-5 the order of magnitude.When temperature is lower than 68 DEG C, in monoclinic structure; When temperature is higher than 68 DEG C, in tetragonal crystalline structure.Due to the change of crystal structure, the photoelectric properties of vanadium dioxide change a lot, and these characteristics make vanadium dioxide be widely applied to the field such as modulator of the intelligent temperature control glass of buildings, photoelectric switch material, thermistor material, erasable optical memory material, blinding laser weapons safety guard, photoelectric material, submillimeter wave radiation.Therefore to the research of vanadium dioxide and preparation method thereof, there is very important value.
The preparation method of current vanadium dioxide has thermal decomposition method, chemical precipitation method, hydrothermal method, sol-gel method etc.Deficiency below with regard to following several method and existence separately thereof carries out summarizing and analyzing one by one.
Patent WO9615068 reports a kind of method that vanadium dioxide particles is prepared in thermolysis: by (NH
4)
2v
6o
16be rapidly heated to 400-650 DEG C, keep reaction system constant voltage 66.7Pa, 30-120min, by the VO be obtained by reacting
2under inert atmosphere protection, anneal 1h, can obtain the VO with thermal induced phase transition property
2powder.The main drawback of this technique is that presoma pyrolysis temperature rise rate is at least 200 DEG C/min, and require that process furnace heating power is large, therefore cost is high, and energy consumption is large.
Patent CN 1693212A reports a kind of preparation method of vanadium dioxide powder material, and technique comprises the preparation of presoma and the thermolysis of presoma.The preparation of presoma is with V
2o
5be raw material with oxalic acid, mix by a certain percentage, to add in reactor and the stirring reaction at 40-70 DEG C that adds water, until V
2o
5react completely with oxalic acid.The solution evaporate to dryness reacted can be obtained solid oxalic acid vanadyl presoma; Presoma is heated to 350-500 DEG C under vacuum, insulation 20-40min, afterwards, keeps vacuum, be reduced to room temperature and can obtain vanadium dioxide powder material.The main drawback of the method is that the reductibility of oxalic acid is strong, and product purity is difficult to control, and reaction scheme is longer.
Patent CN 1986125A proposes a kind of method preparing vanadium dioxide powder, the major technique of the method is: be distributed to by vanadium pentoxide powder after in enough organic solvents and join in reactor, be warming up to 140-190 DEG C, 2-24h is kept under the pressure of 0.05-10MPa, Temperature fall discharging, through deionized water and absolute ethanol washing, vacuum-drying, obtains vanadium dioxide powder.The method is reacted under needing condition of high voltage, and condition is harsh, reacts not easy to operate.
Patent CN 101041464A proposes a kind of method that sol-gel method prepares nano vanadium dioxide, the major technique of the method is: Vanadium Pentoxide in FLAKES is heated to 810 DEG C and melts 5-10min, melt is poured in cold water and stir 30min and make pentoxide gel, after pentoxide gel is dried 4h at 105 DEG C, grinding obtains powder.Powder is mixed with the low carbon chain organism (as alcohol, aldehyde etc.) of reductibility, and ultrasonic disperse 30min, be prepared into the dispersion of Vanadium Pentoxide in FLAKES alcohol or aldehyde.Dispersion is moved into 150-250 DEG C of reaction in booster reaction still, dry 4h for products therefrom 60-80 DEG C, namely obtain nano vanadium dioxide product, the main drawback of the method is complex process, and condition is difficult to control, and products therefrom is metastable VO
2(B), phase transition temperature is higher, limits its application.
Therefore, develop a kind of simple to operate, reaction temperature and, the preparation method of lower-cost hypovanadic oxide powder is the difficult problem of this area.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention prepares the method for hypovanadic oxide powder under being to provide a kind of mild conditions, the method, without the need to special preparation, does not produce objectionable impurities, has that temperature of reaction is low, operating procedure is simple, product purity high.
The principle that electrolytic reduction prepares vanadium dioxide is: the vanadium of+5 valencys mainly exists with the form of positive vanadic acid radical ion in the basic solution of pH > 13, negative electrode and anode is put in the alkaline solution having positive vanadic acid radical ion to exist, apply operating voltage, there is the reduction reaction of positive vanadic acid radical ion in negative electrode, generates the vanadium compound of lower valency; There is OH in anode
-oxidizing reaction, produce oxygen.Analytical results shows, product is the amorphous vanadium compound of+4 valencys, and containing a certain amount of Bound moisture.By product under an inert atmosphere anneal can to obtain purity higher, the good VO of crystal formation
2(M).In electro-reduction process, because the reduction potential of vanadium is more negative, and overlap with evolving hydrogen reaction, therefore, have a small amount of hydrogen reducing in electrolytic process and separate out, cause cathode efficiency to reduce.
According to above electrolysis principle, the present invention proposes the technical scheme of the following stated:
Described method comprises: be dissolved with in the electrolytic solution containing vanadium raw materials and alkali, logical direct current carries out electrolytic reaction, and wherein said alkali concn is more than 0.05mol/L; After electrolysis terminates, be separated electrolysate, product carried out anneal in an inert atmosphere, obtains powder vanadium dioxide.
Preferably, described is vanadate containing vanadium raw materials, further preferably, described vanadate can be dissolved in for soluble vanadium hydrochlorate and/or by the oxide compound of vanadium the vanadate solution that strong base solution formed, described strong base solution can only containing a kind of highly basic, also containing one kind or two or more highly basic, such as, the solution etc. of sodium hydroxide and potassium hydroxide can be contained, directly can add vanadate in the electrolytic solution, also can add and be dissolved in by the oxide compound of vanadium the vanadate solution that strong base solution formed, or both combinations, be particularly preferably vanadic acid sodium, potassium vanadate, ammonium meta-vanadate, ammonium poly-vanadate, the combination of in the vanadate solution formed in sodium hydroxide and/or potassium hydroxide and/or ammoniacal liquor a kind or at least 2 kinds is dissolved in by Vanadium Pentoxide in FLAKES, the typical but non-limiting example of described combination has: vanadic acid sodium, the combination of potassium vanadate, vanadic acid sodium, potassium vanadate, the combination of ammonium meta-vanadate, vanadic acid sodium and the combination of sodium hydroxide solution being dissolved with Vanadium Pentoxide in FLAKES, potassium vanadate, ammonium meta-vanadate, ammonium poly-vanadate and the combination etc. of ammoniacal liquor being dissolved with Vanadium Pentoxide in FLAKES.
Preferably, in described electrolytic solution, vanadium concentration is 0.001-10mol/L, such as: 0.002mol/L, 0.003mol/L, 0.005mol/L, 0.01mol/L, 0.015mol/L, 0.02mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 5mol/L, 9mol/L, 9.9mol/L, 9.99mol/L etc., more preferably 0.005-8mol/L, is particularly preferably 0.01-5mol/L.
Preferably, described alkali is highly basic, more preferably inorganic strong alkali, be more preferably strong basicity soluble hydroxide or carbonate, such as: sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium carbonate, salt of wormwood, 1 kind in volatile salt or the combination of at least 2 kinds, described combination typical case but the example of exhaustive have: sodium hydroxide, the combination of potassium hydroxide, potassium hydroxide, ammoniacal liquor, the combination of sodium carbonate, sodium hydroxide, the combination of sodium carbonate, sodium hydroxide, potassium hydroxide, ammoniacal liquor, the combination of sodium carbonate, ammoniacal liquor, sodium carbonate, salt of wormwood, the combination etc. of volatile salt, be particularly preferably sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium carbonate, salt of wormwood, 1 kind in volatile salt or the combination of at least 2 kinds.
Preferably, in described electrolytic solution, alkali concn is 0.05-25mol/L, such as: 0.051mol/L, 0.052mol/L, 0.055mol/L, 0.06mol/L, 0.09mol/L, 0.099mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.2mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 2mol/L, 10mol/L, 15mol/L, 24mol/L, 24.5mol/L, 24.9mol/L, 24.99mol/L etc., more preferably 0.07-20mol/L, be more preferably 0.09-15mol/L, be particularly preferably 0.1-10mol/L.
Preferably, the anode of described electrolysis is have the electrode of analysing oxygen function, such as metal electrode, manganese dioxide electrode, titanium dioxide electrodes, more preferably metal material electrode, is more preferably the combination of in stainless steel electrode, nickel electrode, lead electrode a kind or at least 2 kinds, is particularly preferably stainless steel electrode.
Preferably, described negative electrode is steady oxide electrode and/or carbonaceous electrodes, such as carbon pole, Graphite Electrodes, self baking electrode, titanium dioxide electrodes etc., be particularly preferably glass-carbon electrode, carbon pole, a kind in self baking electrode, Graphite Electrodes, titanium dioxide electrodes or the combination of at least 2 kinds.
Preferably, described electrolysis temperature is less than 100 DEG C, such as: 99 DEG C, 98 DEG C, 97 DEG C, 95 DEG C, 90 DEG C, 80 DEG C, 50 DEG C, 40 DEG C, 20 DEG C, 19 DEG C, 11 DEG C, 9 DEG C etc., and more preferably 10 ~ 99 DEG C, be more preferably 20 ~ 97 DEG C, be particularly preferably 25 ~ 95 DEG C.
Preferably, described electrolysis time is more than 2h, such as 2.1h, 2.2h, 2.3h, 2.5h, 3h, 5h, 10h, 15h, 20h, 25h, 35h, 38h, 39h, 39.1h, 39.9h, 45h etc., more preferably 3 ~ 40h, be more preferably 4 ~ 30h, be particularly preferably 4 ~ 24h.
Preferably, described electrolytic current density is 20-800A/m
2, more preferably 40-600A/m
2, be particularly preferably 50-500A/m
2.
Preferably, after described electrolysis terminates to be separated electrolysate, washed product, then carries out anneal; Preferably, filtration is separated into described in; Preferably, described washing is for using pure water.
Preferably, described inert atmosphere is inert gas atmosphere, such as: a kind in helium, neon, argon gas, Krypton, xenon, nitrogen or the combination of at least 2 kinds, described combination typical case but the example of exhaustive have: the combination of helium, neon, the combination of helium, nitrogen, the combination of argon gas, Krypton, nitrogen, the combination etc. of helium, neon, argon gas, Krypton, is particularly preferably the combination of in nitrogen, argon gas, helium a kind or at least 2 kinds.
Preferably, described anneal temperature is 200 ~ 1100 DEG C, such as: 201 DEG C, 202 DEG C, 203 DEG C, 205 DEG C, 250 DEG C, 300 DEG C, 500 DEG C, 850 DEG C, 1000 DEG C, 1095 DEG C, 1098 DEG C, 1099 DEG C etc., more preferably 250 ~ 900 DEG C, be particularly preferably 300 ~ 800 DEG C.
Preferably, the described anneal time is more than 0.5h, such as 0.51h, 0.52h, 0.53h, 0.6h, 1h, 3h, 5h, 10h, 15h, 20h, 23h, 23.5h, 23.8h, 23.9h, 23.99h, 30h etc., more preferably 0.8 ~ 24h, be more preferably 0.9 ~ 18h, be particularly preferably 1 ~ 12h.
Compared with prior art, the advantage that the method for the invention has is:
(1) raw material is simple, only needs the vanadate of+5 valencys, as vanadic acid sodium, and potassium vanadate, ammonium meta-vanadate, ammonium poly-vanadate etc., without the need to other special solvents, cost is low;
(2) reaction conditions is gentle, only need operate below 100 DEG C;
(3) operating procedure is simple, and electrolytic reaction normal pressure carries out, and electrolysate high-temperature calcination can obtain VO
2;
(3) processing method environmental protection, the alkaline solution that electrolysis obtains can recycle, does not produce harmful waste gas waste water;
(4) vanadium dioxide powder prepared of the inventive method is having the character of photoelectricity sudden change close to room temperature place, therefore in intelligent temperature control material, optoelectronic switch, ir radiation etc., has potential using value.
Accompanying drawing explanation
Fig. 1 is that in embodiment 1, calcining temperature is 300 DEG C of VO obtained
2the XRD figure of powder;
Fig. 2 is that in embodiment 1, calcining temperature is 300 DEG C of VO obtained
2the SEM Electronic Speculum figure of powder;
Fig. 3 is that in embodiment 1, calcining temperature is 300 DEG C of VO obtained
2the energy spectrogram of powder;
Fig. 4 is that in embodiment 2, calcining temperature is 500 DEG C of VO obtained
2the XRD figure of powder;
Fig. 5 is that in embodiment 3, calcining temperature is 700 DEG C of VO obtained
2the XRD figure of powder;
Fig. 6 is that in embodiment 4, calcining temperature is 750 DEG C of VO obtained
2the XRD figure of powder.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
By 2g Na
3vO
4add in the electrolyzer of 200mL with 25g NaOH, add 100mL pure water stirring and dissolving, controlling electrolysis system temperature is 35 DEG C, take glassy carbon electrode as negative electrode (area 6cm
2), take stainless steel electrode as anode (area 8cm
2), logical direct current carries out electrolytic reaction, and control current density is 50A/m
2.Stop electrolytic reaction after 5h, after being washed by electrolyte filtering, obtain the unbodied vanadium-containing compound of black.Under nitrogen protection atmosphere, by vanadium-containing compound at 300 DEG C of anneal 8h, obtain the VO of crystallization
2(M), as shown in Figure 1, the SEM Electronic Speculum figure of product and energy spectrogram are as shown in Figures 2 and 3 for its XRD figure.
Embodiment 2
By 20g Na
3vO
4add in the electrolyzer of 200mL with 3g NaOH, add 100mL pure water stirring and dissolving, controlling electrolysis system temperature is 80 DEG C, take glassy carbon electrode as negative electrode (area 6cm
2), take lead electrode as anode (area 8cm
2), logical direct current carries out electrolytic reaction, and control current density is 300A/m
2.Stop electrolytic reaction after 5h, after being washed by electrolyte filtering, obtain the unbodied vanadium-containing compound of black.Under nitrogen protection atmosphere, by vanadium-containing compound at 500 DEG C of anneal 5h, obtain the VO of crystallization
2(M), its XRD figure as shown in Figure 4.
Embodiment 3
By 15g Na
3vO
4with 6g Na
2cO
3add in the electrolyzer of 200mL, add 100mL pure water stirring and dissolving, controlling electrolysis system temperature is 40 DEG C, take Graphite Electrodes as negative electrode (area 6cm
2), take stainless steel electrode as anode (area 8cm
2), logical direct current carries out electrolytic reaction, and control current density is 150A/m
2.Stop electrolytic reaction after 5h, after being washed by electrolyte filtering, obtain the unbodied vanadium-containing compound of black.Under nitrogen protection atmosphere, by vanadium-containing compound at 700 DEG C of anneal 2h, obtain the VO of crystallization
2(M), its XRD figure as shown in Figure 5, illustrates at Na
2cO
3equally can Electrowinning VO in solution
2.
Embodiment 4
By 30g K
3vO
4add in the electrolyzer of 200mL with 12g KOH, add 100mL pure water stirring and dissolving, controlling electrolysis system temperature is 90 DEG C, take titanium dioxide electrodes as negative electrode (area 6cm
2), take stainless steel electrode as anode (area 8cm
2), logical direct current carries out electrolytic reaction, and control current density is 350A/m
2.Stop electrolytic reaction after 12h, after being washed by electrolyte filtering, obtain the unbodied vanadium-containing compound of black.Under nitrogen protection atmosphere, by vanadium-containing compound at 750 DEG C of anneal 1h, obtain the VO of crystallization
2(M), its XRD figure as shown in Figure 6, illustrates in the alkaline medium of KOH, to reduce electrolysis, can obtain VO equally
2.
Embodiment 5
By 0.02g Na
3vO
4add in the electrolyzer of 200mL with 0.2g NaOH, add 100mL pure water stirring and dissolving, controlling electrolysis system temperature is 10 DEG C, take Graphite Electrodes as negative electrode (area 6cm
2), take nickel electrode as anode (area 8cm
2), logical direct current carries out electrolytic reaction, and control current density is 20A/m
2.Stop electrolytic reaction after 40h, after being washed by electrolyte filtering, obtain the unbodied vanadium-containing compound of black.Under helium protective atmosphere, by vanadium-containing compound at 200 DEG C of anneal 24h, obtain the VO of crystallization
2(M).
Embodiment 6
By 183g Na
3vO
4add in the electrolyzer of 200mL with 100g NaOH, add 100mL pure water stirring and dissolving, controlling electrolysis system temperature is 100 DEG C, take Graphite Electrodes as negative electrode (area 6cm
2), take nickel electrode as anode (area 8cm
2), logical direct current carries out electrolytic reaction, and control current density is 800A/m
2.Stop electrolytic reaction after 2h, after being washed by electrolyte filtering, obtain the unbodied vanadium-containing compound of black.Under helium protective atmosphere, by vanadium-containing compound at 1100 DEG C of anneal 0.5h, obtain the VO of crystallization
2(M).
Found by great many of experiments, in technical scheme provided by the invention, electrolytic solution vanadium concentration, alkali concn, electrolysis temperature, electrolysis time, current density, annealing temperature, annealing time are to gained VO
2the productive rate of powdered product all has a certain impact.As vanadium concentration 0.001-10mol/L, more than alkali concn 0.05mol/L, electrolysis temperature is less than 100 DEG C, and electrolysis time is more than 2h, and annealing temperature is 200 ~ 1100 DEG C, and annealing time is more than 0.5h, and the productive rate of products therefrom is higher.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (1)
1. a method for preparing vanadium dioxide powder through electrolysis, comprising: by 2g Na
3vO
4add in the electrolyzer of 200mL with 25g NaOH, add 100mL pure water stirring and dissolving, controlling electrolysis system temperature is 35 DEG C, and be negative electrode with glassy carbon electrode, take stainless steel electrode as anode, logical direct current carries out electrolytic reaction, and control current density is 50A/m
2; Stop electrolytic reaction after 5h, after being washed by electrolyte filtering, obtain the unbodied vanadium-containing compound of black; Under nitrogen protection atmosphere, by vanadium-containing compound at 300 DEG C of anneal 8h, obtain the M phase VO of crystallization
2.
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| CN103556168A (en) * | 2013-10-25 | 2014-02-05 | 上海师范大学 | Vanadium dioxide porous nano-film and preparation method thereof |
| CN104022286B (en) * | 2014-06-24 | 2016-08-24 | 武汉理工大学 | Porous VO2nano wire and its preparation method and application |
| CN113897626B (en) * | 2021-10-14 | 2023-03-21 | 电子科技大学广东电子信息工程研究院 | Au/VO 2 Composite nano catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2606148A (en) * | 1948-11-02 | 1952-08-05 | Natural Products Refining Co | Process for electrolytic preparation of vanadium oxide |
| JPS5357491A (en) * | 1976-11-02 | 1978-05-24 | Hitachi Ltd | Manufacturing process of thermo-sensing filmy resistance element |
| CN101863511A (en) * | 2010-07-05 | 2010-10-20 | 中国科学技术大学 | Method for preparing monoclinic phase vanadium dioxide and doped nano powder thereof |
| CN101880060A (en) * | 2010-07-14 | 2010-11-10 | 中国科学技术大学 | Method for quickly preparing monoclinic phase VO2 |
| CN102120614A (en) * | 2011-01-21 | 2011-07-13 | 中国科学院上海硅酸盐研究所 | Preparation method of vanadium dioxide powder |
-
2012
- 2012-03-19 CN CN201210073258.5A patent/CN102586796B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2606148A (en) * | 1948-11-02 | 1952-08-05 | Natural Products Refining Co | Process for electrolytic preparation of vanadium oxide |
| JPS5357491A (en) * | 1976-11-02 | 1978-05-24 | Hitachi Ltd | Manufacturing process of thermo-sensing filmy resistance element |
| CN101863511A (en) * | 2010-07-05 | 2010-10-20 | 中国科学技术大学 | Method for preparing monoclinic phase vanadium dioxide and doped nano powder thereof |
| CN101880060A (en) * | 2010-07-14 | 2010-11-10 | 中国科学技术大学 | Method for quickly preparing monoclinic phase VO2 |
| CN102120614A (en) * | 2011-01-21 | 2011-07-13 | 中国科学院上海硅酸盐研究所 | Preparation method of vanadium dioxide powder |
Non-Patent Citations (2)
| Title |
|---|
| THE CATHODIC REDUCTION OF VANADIUM (V) AT A MERCURY COVERED ELECTRODE;Mcfall, Inez E.;《A DISSERTATION SUBMITTED TO THE GRADUATE FACULTY》;19581231;第11-12页和第21-28页 * |
| 二氧化钒薄膜制备及其相变机理研究分析;陈长琦等;《真空科学与技术学报》;20011205;第21卷(第06期);第452-456页 * |
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