CN1803718A - Method for synthesizing composite oxide powder by non-hydrolytic sol-gel process with alcohol as oxygen donor - Google Patents
Method for synthesizing composite oxide powder by non-hydrolytic sol-gel process with alcohol as oxygen donor Download PDFInfo
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Abstract
The disclosed non-hydrolysis sol-gel synthesis method with alcohol as oxygen donor for composite oxide powder comprises: using anhydrous metal chloride or bromide and anhydrous low-carbon alcohol as main material; converting the sol into gel at 80-160Deg with non-hydrolysis polymerization; cleaning, drying, grinding, and calcining at low temperature to obtain the final product. Compared with prior art, this invention can also react at low temperature with low cost for industrial production.
Description
The invention relates to a method for synthesizing composite oxide powder, in particular to a method for synthesizing composite oxide powder at low temperature by a non-hydrolytic sol-gel method.
Background art the sol-gel method is one of the commonly used methods for synthesizing composite oxide powders. In the traditional hydrolysis sol-gel method, metal alkoxide is mostly used as a precursor raw material, hydrolysis and polycondensation reactions are generated in an organic medium, so that alkoxide solution is converted into gel from sol, and the gel is dried and calcined to obtain composite oxide powder. In the hydrolysis and polycondensation reaction processes, due to different hydrolysis rates of different metal alkoxides, the polycondensation products are difficult to achieve random and uniform distribution of M-O-M and M ' -O-M ' bonding, and M-O-M ' bonding is difficult to form in large quantities, so that the components in the gel are difficult to realize atomic-scale uniform mixing, and the synthesis temperature of the oxide is increased. In addition, the time required for the gelation process is long, and reaction by-products (alcohol and water) are not easily removed, resulting in a long production cycle.
The non-hydrolytic sol-gel method does not generate hydrolysis reaction, and can directly condense precursors to form a large amount of M-O-M' bonding only by changing the process conditions, so that the components are uniformly mixed at the atomic level in the gelation process, and the synthesis temperature of the composite oxide is greatly reduced. Therefore, the non-hydrolytic sol-gel method has the outstanding advantages of short gel time, easy removal of reaction by-products (alkyl halides), short production period, low synthesis temperature and the like.
According to the reports of the United states of America of Materials Chemistry (Chemistry of Materials)1997, volume 9, period 11, pages 2292 to 2299, and volume 13, volume 2001, period 2, pages 247 to 249, the existing methods for synthesizing composite oxide powder by non-hydrolytic sol-gel method can be mainly divided into two types:
(1) the metal alkoxide is used as an oxygen donor to synthesize the composite oxide powder, and the reaction equation is as follows:
wherein mx + nz ═ my + nt;
(2) various ethers are used as oxygen donors to synthesize the composite oxide powder, and the reaction equation is as follows:
in the method (1), because the expensive metal alkoxide is adopted as the oxygen donor, the cost of the raw materials is high, and the raw materials are not easy to obtain, so that the industrial mass production is difficult; the method (2) adopts various ethers as oxygen donors, has the defects of easy volatilization, easy combustion, easy explosion and the like, has certain toxicity and high requirement on production conditions, and leads to high industrial production cost.
The present invention aims at providing a non-hydrolytic sol-gel method for synthesizing composite oxide powder by using alcohol as oxygen donor. The method has the advantages of easily available raw materials and low cost, and solves the problems of high cost in the method (1) and the problems of easy combustion, easy explosion, certain toxicity, high requirement on production conditions and the like in the method (2).
In order to achieve the object of the present invention, the present invention provides a non-hydrolytic sol-gel method for synthesizing composite oxide powder by using alcohol as oxygen donor, which is characterized in that: the preparation method comprises the steps of taking anhydrous metal chloride or bromide as a precursor, taking anhydrous low-carbon alcohol as an oxygen donor, carrying out mixed reaction according to a stoichiometric ratio, converting the prepared sol into gel through non-hydrolytic polymerization reaction at the temperature of 80-160 ℃, carrying out ultrasonic washing and drying, grinding the obtained dry gel, and then carrying out low-temperature calcination to obtain the composite oxide powder.
The reaction equation is as follows:
the anhydrous low-carbon alcohol comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, tert-amyl alcohol, ethylene glycol and glycerol.
The best ultrasonic washing effect is carried out in absolute ethyl alcohol or absolute isopropanol;
the optimal drying temperature is 60-100 ℃;
the calcination is carried out by the following ideal calcination system: the heating rate is 3-5 ℃/min before 400 ℃, then the temperature is raised to the required synthesis temperature at 8-10 ℃/min, and the temperature is kept for 0.5-lh.
The invention adopts the cheap anhydrous metal chloride or bromide as the precursor and the anhydrous low-carbon alcohol as the oxygen donor, and synthesizes the composite oxide powder at low temperature by the non-hydrolytic sol-gel process, compared with the traditional hydrolytic sol-gel method, the method simplifies the production process, realizes the uniform mixing of all components at the atomic level in the gelation process, and greatly reduces the synthesis temperature of the composite oxide; compared with the existing non-hydrolytic sol-gel process which adopts metal alkoxide or ether as an oxygen donor, the method has the characteristics of cheap raw materials, simple operation, low production cost, suitability for industrial mass production and the like.
Drawings
FIG. 1 is an XRD spectrum of the powder obtained in example 1;
FIG. 2 is an XRD spectrum of the powder obtained in example 2;
FIG. 3 is an XRD spectrum of the powder obtained in example 3;
FIG. 4 is an XRD spectrum of the powder obtained in example 4.
FIG. 5 is a process flow diagram of the present invention
Detailed Description
Example 1
0.036mol of anhydrous AlCl3(analytical grade), 0.018mol TiCl4(chemically pure) as precursor, with 0.091mol of anhydrous isopropanol (C)3H7OH, analytically pure) to prepare a light yellow transparent sol A, heating the sol A to 110 ℃, converting the sol A into a gel B in 6h, then carrying out ultrasonic washing for 10min by using 0.2mol of anhydrous isopropanol, then placing the gel A in an oven to be dried at 70 ℃ until a dry gel C is formed, grinding the dry gel, then placing the ground dry gel into a crucible, and calcining in an electric furnace: heating up to a temperature of 4 ℃/min before 400 ℃, then heating up to 750 ℃ at a temperature of 8 ℃/min, and preserving heat for 30min to obtain the aluminum titanate powderVolume (see XRD pattern of fig. 1).
Example 2
With 0.037mol of anhydrous AlBr3(analytically pure) 0.012mol SiCl4(chemical purity) is taken as a precursor, and 0.079mol of absolute ethyl alcohol (C)2H5OH, analytical purity) was prepared, sol a was heated to 110 ℃ and converted to gel B in 8h, which was ultrasonically washed with 0.2mol absolute ethanol for 10min and dried in an oven at 70 ℃ until a xerogel C was formed, which was ground and transferred to a crucible and calcined in an electric furnace: heating at a rate of 5 deg.C/min before 400 deg.C, heating to 900 deg.C at 10 deg.C/min, and maintaining for 60min to obtain mullite powder (shown in XRD pattern of FIG. 2).
Example 3
With 0.018mol of anhydrous ZrCl4(analytical grade), 0.018mol TiCl4(chemical purity) is taken as a precursor, and is mixed with 0.072mol of anhydrous n-butyl alcohol (C)4H9OH, analytically pure) to prepare sol A, heating the sol A to 110 ℃, converting the sol A into gel B in 9h, then carrying out ultrasonic washing for 10min by using 0.2mol of anhydrous isopropanol, then placing the sol A in an oven to be dried at 70 ℃ until dry gel C is formed, grinding the dry gel, then placing the ground dry gel into a crucible, and calcining in an electric furnace: heating up to 400 deg.C at a rate of 4 deg.C/min, heating to 600 deg.C at 8 deg.C/min, and maintaining for 50min to obtain zirconium titanate powder (shown in XRD pattern of FIG. 3).
Example 4
With 0.036mol AlCl3(analytical grade), 0.018mol TiCl4(chemically pure), 0.009mol SiCl4(chemical purity) is taken as a precursor, and 0.108mol of absolute ethyl alcohol (C)2H5OH analytical pure), heating the sol a to 110 ℃, converting the sol a into gel B within 5h, ultrasonically washing the gel B with 0.3mol of absolute ethanol for 10min, drying the gel in an oven at 70 ℃ until dry gel C is formed, grinding the dry gel C, transferring the ground dry gel C into a crucible, and calcining the ground dry gel C in an electric furnace: heating at a rate of 3 deg.C/min before 400 deg.C, heating to 900 deg.C at a rate of 10 deg.C/min, and maintaining the temperature45min, XRD analysis of the obtained powder to obtain Al-Ti-Si ternary oxide-Al4Ti2SiO12(see FIG. 4).
Claims (5)
1. A process for synthesizing the powder of composite oxide by non-hydrolytic sol-gel method using alcohol as oxygen donor features that the anhydrous metal chloride or bromide is used as precursor, the anhydrous lower alcohol is used as oxygen donor, and the reaction equation
The prepared sol is converted into gel through non-hydrolytic polymerization reaction at the temperature of 80-160 ℃, the gel is washed and dried by ultrasonic wave, and the obtained dry gel is ground and then calcined at low temperature to obtain the composite oxide powder.
2. The method of synthesizing composite oxide powder according to claim 1, wherein said anhydrous lower alcohol comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, tert-amyl alcohol, ethylene glycol, and glycerol.
3. The method for synthesizing composite oxide powder according to claim 1, wherein said ultrasonic washing is carried out in absolute ethyl alcohol or absolute isopropyl alcohol.
4. The method for synthesizing composite oxide powder according to claim 1, wherein the drying temperature is 60 to 100 ℃.
5. The method for synthesizing a composite oxide powder according to claim 1, wherein said calcination is carried out by a calcination system comprising: the heating rate is 3-5 ℃/min before 400 ℃, then the temperature is raised to the required synthesis temperature at 8-10 ℃/min, and the temperature is kept for 0.5-1 h.
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| CN102432286A (en) * | 2011-09-02 | 2012-05-02 | 景德镇陶瓷学院 | Aluminum titanate powder prepared by taking metal aluminum as aluminum source through non-hydrolytic sol-gel process at low temperature and preparation method thereof |
| CN102476819A (en) * | 2010-11-27 | 2012-05-30 | 中国科学院兰州化学物理研究所 | Preparation method of nano alpha-alumina powder |
| CN102765936A (en) * | 2012-08-17 | 2012-11-07 | 景德镇陶瓷学院 | Stable zirconium oxide superfine power prepared by adopting non-aqueous solvent process and preparation method thereof |
| CN104556216A (en) * | 2014-12-29 | 2015-04-29 | 景德镇陶瓷学院 | Method for preparing barium titanate nanopowder by adopting non-hydrolytic sol-gel process |
| CN105271337A (en) * | 2015-10-21 | 2016-01-27 | 景德镇陶瓷学院 | Method for preparing superfine alumina powder with non-water precipitation process |
| CN108511797A (en) * | 2018-05-09 | 2018-09-07 | 哈尔滨工业大学（威海） | A kind of Li7La3Zr2O12Solid electrolyte preparation method |
| CN109663594A (en) * | 2019-01-23 | 2019-04-23 | 景德镇陶瓷大学 | It is a kind of that MgFe is prepared using non-hydrolytic sol-gel process2O4The method of/C-material and its material obtained |
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| CN1183615C (en) * | 2001-06-04 | 2005-01-05 | 中国科学院成都有机化学研究所 | Method of synthesizing LiCo1-xMxO2 as positive electrode material for lithium ion accmulator |
| CN1618768A (en) * | 2003-11-20 | 2005-05-25 | 华东理工大学 | Improved sol-gel method for preparing nano-powder |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102476819A (en) * | 2010-11-27 | 2012-05-30 | 中国科学院兰州化学物理研究所 | Preparation method of nano alpha-alumina powder |
| CN102432286A (en) * | 2011-09-02 | 2012-05-02 | 景德镇陶瓷学院 | Aluminum titanate powder prepared by taking metal aluminum as aluminum source through non-hydrolytic sol-gel process at low temperature and preparation method thereof |
| CN102432286B (en) * | 2011-09-02 | 2013-07-17 | 景德镇陶瓷学院 | Preparation method of aluminum titanate powder by taking metal aluminum as aluminum source through non-hydrolytic sol-gel process at low temperature |
| CN102765936A (en) * | 2012-08-17 | 2012-11-07 | 景德镇陶瓷学院 | Stable zirconium oxide superfine power prepared by adopting non-aqueous solvent process and preparation method thereof |
| CN102765936B (en) * | 2012-08-17 | 2013-11-06 | 景德镇陶瓷学院 | Stable zirconium oxide superfine power prepared by adopting non-aqueous solvent process and preparation method thereof |
| CN104556216A (en) * | 2014-12-29 | 2015-04-29 | 景德镇陶瓷学院 | Method for preparing barium titanate nanopowder by adopting non-hydrolytic sol-gel process |
| CN104556216B (en) * | 2014-12-29 | 2016-05-04 | 景德镇陶瓷学院 | A kind of method that adopts non-hydrolytic sol-gel process to prepare Barium Titanate nano-powder |
| CN105271337A (en) * | 2015-10-21 | 2016-01-27 | 景德镇陶瓷学院 | Method for preparing superfine alumina powder with non-water precipitation process |
| CN105271337B (en) * | 2015-10-21 | 2017-03-08 | 景德镇陶瓷大学 | A kind of method that alumina ultrafine powder body is prepared using non-aqueous depositing technology |
| CN108511797A (en) * | 2018-05-09 | 2018-09-07 | 哈尔滨工业大学（威海） | A kind of Li7La3Zr2O12Solid electrolyte preparation method |
| CN109663594A (en) * | 2019-01-23 | 2019-04-23 | 景德镇陶瓷大学 | It is a kind of that MgFe is prepared using non-hydrolytic sol-gel process2O4The method of/C-material and its material obtained |
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