CN107012476A - A kind of preparation method of composite oxides - Google Patents
A kind of preparation method of composite oxides Download PDFInfo
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- CN107012476A CN107012476A CN201710081201.2A CN201710081201A CN107012476A CN 107012476 A CN107012476 A CN 107012476A CN 201710081201 A CN201710081201 A CN 201710081201A CN 107012476 A CN107012476 A CN 107012476A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/18—Alkaline earth metal compounds or magnesium compounds
Abstract
A kind of preparation method of composite oxides, it is characterized in that step is as follows：Oxide powder or tabletting are combined with metal collector and are used as negative electrode, using graphite as anode, with molten alkali metal halide or alkaline-earth halide, or with the addition of the molten alkali metal halide or alkaline-earth halide of excessive correspondence alkali metal oxide or alkaline earth oxide as electrolyte, in air or protective atmosphere, 400 ~ 900 DEG C of electrolysis temperature, decomposition voltage is 1.4 ~ 3.2V, electrolysis 1 ~ 5 hour, it is cooled to after normal temperature and takes out, then washed in distilled water or organic solvent, alkali metal oxide or alkaline earth oxide are obtained after vacuum drying and hopcalite is reduced；After cleaned and vacuum drying, under air, vacuum or inert atmosphere, 600 ~ 1200 DEG C of calcinations 1 ~ 3 hour obtain composite oxides.The present invention provides a kind of preparation method of composite oxides, and this method realizes that particle size is controllable and ensures lot stability, uniformity.
Description
Technical field
The invention belongs to inorganic material preparation method, more particularly to a kind of preparation method of composite oxides.
Background technology
Composite oxides have good optics, electricity, magnetic performance, are important laser material, pyroelectricity material, pressure
Electric material and strong magnetic material etc., in fields such as information, the energy, electronics, metallurgy, aerospace, chemical industry, biology and medical science using extremely
Extensively.
The method mainly high temperature solid-state method of composite oxides is prepared at present, and high temperature solid-state method is the tradition of composite oxides
Preparation method, this method is simple to operate, and the element system used is very wide, is still widely adopted so far.But, due to solid phase reaction
Belong to it is non-to reaction, it is necessary to repeatedly high-temperature roasting with grinding.Therefore, the phase composition of gained composite oxide powder is uneven.For
Disadvantage mentioned above is overcome, it has been developed that sol-gel process, hydrothermal synthesis method, spray drying process and compound cryosar fuse salt
Method etc. method.These methods respectively have advantage, but are required for the accurate proportioning and height of raw material to be well mixed.However, for
Large-scale production, accurate proportioning and height are well mixed difficult to realize.That is, art methods be difficult avoid it is a variety of
The generation of solid product, so that the stability and uniformity of batch can not be ensured.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of preparation method of composite oxides, and this method realizes particle
Size is controllable and ensures lot stability, uniformity.
The technical scheme is that：Oxide powder or tabletting and metal collector is compound as negative electrode, with graphite
For anode, with molten alkali metal halide or alkaline-earth halide, or with the addition of excessive correspondence alkali metal oxide or alkali
The molten alkali metal halide or alkaline-earth halide of soil metal oxide are electrolyte, in air or protective atmosphere,
400 ~ 900 DEG C of electrolysis temperature, decomposition voltage is 1.4 ~ 3.2V, is electrolysed 1 ~ 5 hour, is cooled to after normal temperature and takes out, then in distillation
Washed in water or organic solvent, alkali metal oxide or alkaline earth oxide and reduced oxygen compound are obtained after vacuum drying
Mixture；After cleaned and vacuum drying, under air, vacuum or inert atmosphere, 600 ~ 1200 DEG C of calcinations 1 ~ 3 hour are obtained
To composite oxides.
The metal collector be fusing point higher than the thread, netted of reaction temperature, the titanium of sheet or foam-like, stainless steel,
Molybdenum, tungsten or nickel.
The mixtures that the alkali halide constitutes for the one or several kinds of Li, Na, K, Rb or Cs halide.
The mixtures that the alkaline-earth halide constitutes for the one or several kinds of Mg, Ca, Sr or Ba halide.
The halide for Cl or F a kind of or both mixture.
The oxide is Al, Si, Ti, V, Co, Zr, Nb, Ta or Ce oxide.
Described tabletting is to suppress oxide powder under 2 ~ 20MPa of pressure, the sintering at 600 ~ 900 DEG C of temperature and
Into.
The present invention principle be：By above-mentioned oxide, in metal halide molten electrolyte carry out electrochemical reduction or
Person's partial reduction.The oxygen of oxide reduction removing is combined with alkali metal or alkaline-earth metal ions, and in oxide particle periphery
Precipitation, hinders to prevent the reunion between oxide particle from sintering to grow up so as to form physics between oxide particle.Therefore, exist
While controlling product particle size, alkali metal or alkaline-earth metal ions are realized quantitative and uniformly adhered to by electrochemical method
After oxide molecule or metallic atom surface, preliminary mixture is obtained.After products therefrom is cleaned, in inert atmosphere or
Calcination is aoxidized under oxidizing atmosphere and obtains target composite oxides.
From before by way of direct mixed oxide it is different, oxygen can be accurately controlled by the way of electrochemical reduction
The stoichiometric proportion of compound, thus be conducive to the stability and uniformity of product batches,.Meanwhile, alkali metal or alkaline-earth metal
Ion retains in the cathode in the form of the oxonium ion with oxide removal is combined, it is possible to achieve the molecule rank of metal oxide
Mixing, can also realize that the compound for the low oxide for being difficult to prepare at present is directly synthesized.
Brief description of the drawings
Fig. 1 is the MgTi of the embodiment of the present invention 12O4XRD spectrum；
Fig. 2 is the MgTi of the embodiment of the present invention 12O4SEM spectrum.
Specific implementation method
The present invention is further described with reference to the accompanying drawings and examples.These descriptions are intended merely to that the present invention is better described,
Rather than limitation of the present invention.
Embodiment 1
By commercially available 0.1 ~ 0.2 μm of TiO2Powder takes 2g, and diameter 20mm, thickness 3mm test piece, in air are pressed under 8MPa
In 600 DEG C sinter 3 hours, obtained TiO2Test piece.By test piece with after molybdenum net tight, then it is wound on molybdenum filament with thin molybdenum filament
As negative electrode, using graphite rod as anode, to melt mol ratio 2:1 MgCl2With NaCl and the mixture of excessive addition magnesia
For electrolyte, in argon gas atmosphere, temperature is 600 DEG C, and voltage is 1.4 V, is electrolysed 5 hours, proposes negative electrode after the completion of electrolysis
Fused salt liquid level is simultaneously cooled to after normal temperature and takes out product in a cell, is cleaned through distilled water, and in after 60 DEG C of vacuum dryings, true
The lower 1200 DEG C of calcinations of Altitude 2 hours, obtain composite oxides MgTi2O4.Fig. 1 is XRD spectrum；Fig. 2 is SEM photograph.By Fig. 1
As can be seen that MgTi2O4In single-phase.
Embodiment 2
By commercially available 0.1 ~ 0.2 μm of Ta2O5Powder takes 5g, is wound in not after foam nickel sheet tight, then with stainless steel wire
Become rusty on steel wire as negative electrode, using graphite rod as anode, to melt KCl mixture as electrolyte, in argon gas atmosphere, temperature is
800 DEG C, voltage is 2.4V, is electrolysed 4 hours, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis and normal temperature is cooled in a cell
After take out product, cleaned through distilled water, and in after 60 DEG C of vacuum dryings, 600 DEG C of calcinations 3 hours, obtain KTaO in atmosphere3。
Embodiment 3
By commercially available 0.1 ~ 0.2 μm of Ce2O3Powder takes 5g, is pressed into diameter 20mm under 5MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in atmosphere.By test piece with after stainless (steel) wire tight, then with stainless steel wire it is wound in stainless steel
As negative electrode on silk, using graphite rod as anode, to melt mol ratio 1:1:1 SrCl2, LiCl, KCl mixture for electrolysis
Matter, in argon gas atmosphere, temperature is 600 DEG C, and voltage is 2.8V, is electrolysed 3 hours, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis
And be cooled to after normal temperature take out product in a cell, through washes of absolute alcohol, and in after 60 DEG C of vacuum dryings, in argon gas atmosphere
In 1000 DEG C of calcinations 3 hours, obtain Sr2CeO4。
Embodiment 4
By commercially available 0.1 ~ 0.2 μm of Al2O3Powder takes 5g, is pressed into diameter 20mm under 5MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in atmosphere.By test piece with titanium silk tight after, then be wound in titanium silk on as negative electrode, with stone
Inker is anode, to melt mol ratio 1:1 NaCl, KCl mixture are electrolyte, and in argon gas atmosphere, temperature is 600
DEG C, voltage is 3.0V, is electrolysed 2 hours, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis and is cooled in a cell after normal temperature
Product is taken out, is cleaned through acetone, and in after 60 DEG C of vacuum dryings, 900 DEG C of calcinations 3 hours, obtain NaAl in argon gas atmosphere2O4。
Embodiment 5
By commercially available 0.1 ~ 0.2 μm of V2O5Powder takes 5g, is pressed into diameter 20mm under 5MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in atmosphere.By test piece with after leaf tight, then with tungsten filament winding as negative electrode, with stone
Inker is anode, to melt the CaCl that with the addition of excess amount of Ca O2For electrolyte, in argon gas atmosphere, temperature is 900 DEG C, and voltage is
3.2V, is electrolysed 1 hour, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis and is cooled to after normal temperature takes out product in a cell,
Cleaned through distilled water, and in after 60 DEG C of vacuum dryings, 900 DEG C of calcinations 3 hours, obtain CaV in argon gas atmosphere2O6。
Embodiment 6
By commercially available 0.1 ~ 0.2 μm of ZrO2Powder takes 1g, is pressed into diameter 20mm under 15MPa, thickness 2mm test piece,
800 DEG C sinter 1 hour in argon gas atmosphere.Test piece is wrapped up with nickel sheet and then with molybdenum filament winding as negative electrode, using graphite rod as sun
Pole, to melt mol ratio 1:2 BaCl2, NaCl be electrolyte, in argon gas atmosphere, temperature be 750 DEG C, voltage is 2.6V, electricity
Solution 2 hours, proposes fused salt liquid level by negative electrode after the completion of electrolysis and is cooled to after normal temperature takes out product in a cell, through anhydrous second
Alcohol is cleaned, and in after 60 DEG C of vacuum dryings, and 1100 DEG C of calcinations 4 hours, obtain BaZrO3 in atmosphere.
Embodiment 7
By commercially available 0.1 ~ 0.2 μm of Nb2O5Powder takes 5g, is pressed into diameter 20mm under 5MPa, test piece totally two of the thickness in 5mm
Piece, 600 DEG C sinter 2 hours in atmosphere.By test piece with after stainless (steel) wire tight, then with stainless steel wire it is wound in stainless steel
As negative electrode on silk, using graphite rod as anode, to melt LiCl, KF mixture as electrolyte, in argon gas atmosphere, temperature is
600 DEG C, voltage is 2.4V, is electrolysed 4 hours, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis and normal temperature is cooled in a cell
After take out product, cleaned through distilled water, and in after 60 DEG C of vacuum dryings, 900 DEG C of calcinations 3 hours, obtain LiNbO in atmosphere3。
Embodiment 8
By commercially available 0.1 ~ 0.2 μm of SiO2Powder 3g, is pressed into diameter 20mm under 10MPa, test piece totally two of the thickness in 5mm
600 DEG C sinter 2 hours in piece, air.By test piece with after stainless (steel) wire tight, then with stainless steel wire it is wound in stainless steel wire
On as negative electrode, using graphite rod as anode, to melt SrCl2For electrolyte, in argon gas atmosphere, temperature is 900 DEG C, and voltage is
2.6V, is electrolysed 4 hours, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis and is cooled to after normal temperature takes out product in a cell,
Cleaned through distilled water, and in after 60 DEG C of vacuum dryings, 1100 DEG C of calcinations 3 hours, obtain SrSiO in atmosphere3。
Embodiment 9
By commercially available 0.1 ~ 0.2 μm of Co2O3The g of powder 5, is pressed into diameter 20mm under 10MPa, test piece totally two of the thickness in 5mm
600 DEG C sinter 2 hours in piece, air.By test piece with after stainless (steel) wire tight, then with stainless steel wire it is wound in stainless steel wire
On as negative electrode, using graphite rod as anode, to melt LiCl as electrolyte, in argon gas atmosphere, temperature is 750 DEG C, and voltage is
2.6V, is electrolysed 4 hours, and negative electrode is proposed into fused salt liquid level after the completion of electrolysis and is cooled to after normal temperature takes out product in a cell,
Cleaned through distilled water, and in after 60 DEG C of vacuum dryings, 1100 DEG C of calcinations 3 hours, obtain LiCoO in atmosphere2。
Claims (7)
1. a kind of preparation method of composite oxides, it is characterized in that step is as follows：By oxide powder or tabletting and metal afflux
Bluk recombination is as negative electrode, using graphite as anode, with molten alkali metal halide or alkaline-earth halide, or with the addition of excess
The molten alkali metal halide or alkaline-earth halide of correspondence alkali metal oxide or alkaline earth oxide are electrolyte,
In air or protective atmosphere, 400 ~ 900 DEG C of electrolysis temperature, decomposition voltage is 1.4 ~ 3.2V, is electrolysed 1 ~ 5 hour, is cooled to often
Taken out after temperature, then washed in distilled water or organic solvent, alkali metal oxide or alkaline-earth metal oxygen are obtained after vacuum drying
Compound and it is reduced hopcalite；After cleaned and vacuum drying, under air, vacuum or inert atmosphere, 600 ~
1200 DEG C of calcinations 1 ~ 3 hour, obtain composite oxides.
2. the preparation method of composite oxides according to claim 1, it is characterized in that the metal collector is that fusing point is high
In the titanium of the thread, netted of reaction temperature, sheet or foam-like, stainless steel, molybdenum, tungsten or nickel.
3. the preparation method of composite oxides according to claim 1, it is characterized in that the alkali halide be Li,
The mixture of one or several kinds of compositions of Na, K, Rb or Cs halide.
4. the preparation method of composite oxides according to claim 1, it is characterized in that the alkaline-earth halide be Mg,
The mixture of one or several kinds of compositions of Ca, Sr or Ba halide.
5. the preparation method of the composite oxides according to claim 1,3 or 4, it is characterized in that the halide is Cl or F
A kind of or both mixture.
6. the preparation method of composite oxides according to claim 1, it is characterized in that the oxide be Al, Si, Ti, V,
Co, Zr, Nb, Ta or Ce oxide.
7. the preparation method of composite oxides according to claim 1, it is characterized in that described tabletting is by oxidate powder
End is suppressed under 2 ~ 20MPa, is sintered and is formed at 600 ~ 900 DEG C of temperature.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893751A (en) * | 2018-06-13 | 2018-11-27 | 华中科技大学 | A kind of preparation method and application of titanium-based oxide |
| CN109732187A (en) * | 2019-01-29 | 2019-05-10 | 东北大学 | A kind of method of melten salt electriochemistry assistant metal welding |
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| CN102066620A (en) * | 2008-06-16 | 2011-05-18 | 力拓艾尔坎国际有限公司 | Method of producing aluminium in an electrolysis cell |
| CN102864468A (en) * | 2012-10-17 | 2013-01-09 | 武汉大学 | Method for producing superfine metal powder |
| CN103290426A (en) * | 2013-07-12 | 2013-09-11 | 广州有色金属研究院 | Preparation method of lithium titanate |
| CN103849900A (en) * | 2014-02-25 | 2014-06-11 | 广东省工业技术研究院(广州有色金属研究院) | Method for preparing rare earth alloy |
| CN106906493A (en) * | 2017-02-22 | 2017-06-30 | 广东省稀有金属研究所 | A kind of preparation method of metal and alloy powder |
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- 2017-02-15 CN CN201710081201.2A patent/CN107012476A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040108220A1 (en) * | 2001-01-30 | 2004-06-10 | Hans-Oskar Stephan | Electrochemical production of nanoscale metal (mixed) oxides |
| CN102066620A (en) * | 2008-06-16 | 2011-05-18 | 力拓艾尔坎国际有限公司 | Method of producing aluminium in an electrolysis cell |
| CN102864468A (en) * | 2012-10-17 | 2013-01-09 | 武汉大学 | Method for producing superfine metal powder |
| CN103290426A (en) * | 2013-07-12 | 2013-09-11 | 广州有色金属研究院 | Preparation method of lithium titanate |
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| CN108893751A (en) * | 2018-06-13 | 2018-11-27 | 华中科技大学 | A kind of preparation method and application of titanium-based oxide |
| CN108893751B (en) * | 2018-06-13 | 2020-07-10 | 华中科技大学 | Preparation method and application of titanium-based oxide |
| CN109732187A (en) * | 2019-01-29 | 2019-05-10 | 东北大学 | A kind of method of melten salt electriochemistry assistant metal welding |
| CN109732187B (en) * | 2019-01-29 | 2020-07-21 | 东北大学 | Method for electrochemically assisting metal welding through molten salt |
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