CN1251969C - Stannic oxide powder preparation method - Google Patents
Stannic oxide powder preparation method Download PDFInfo
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- CN1251969C CN1251969C CN 200310108633 CN200310108633A CN1251969C CN 1251969 C CN1251969 C CN 1251969C CN 200310108633 CN200310108633 CN 200310108633 CN 200310108633 A CN200310108633 A CN 200310108633A CN 1251969 C CN1251969 C CN 1251969C
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- tin
- stannic oxide
- oxide powder
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Abstract
The present invention relates to a preparation method of tin oxide powder, which comprises the steps as follows: tin salt of the elements free from chlorine and organic substance with complexing power are adopted as raw materials; the tin salt and the organic substance are dissolved in water to prepare a solution; the solution is heated and concentrated to prepared jelly; the jelly is processed with heat treatment to prepare tin oxide powder with small particle diameter, high specific surface area and uniform dispersion. The gas sensitive elements prepared from the tin oxide powder have good response characteristic to various reducing gases.
Description
Affiliated field
The present invention relates to a kind of preparation method of stannic oxide powder, belong to the oxide powder field.
Technical background
Stannic oxide is a kind of important inorganic functional material.Special duct can be fit to ion and transmits therein in the stannic oxide structure, therefore can be used for the negative material of lithium ion battery.Stannic oxide is a kind of good catalyzer and support of the catalyst, has very strong complete oxidation ability, and organic oxidation is had effect preferably, can catalysis fumaric acid glycosylation reaction, and the oxidation of CO.Stannic oxide has good photoelectronic property, can be used for making transparency electrode, solar energy converting material, electro-conductive material.Some ion of doping can effectively change its color in stannic oxide, can substitute existing chromate pigments fully when being used as pigment.Stannic oxide is most widely used so far gas sensitive, it has low price, and machinery, chemistry, Heat stability is good have response preferably to most of reducing gas and toxic gas, and response speed is fast, can adjust by the different elements that mix the selectivity of gas.
Stannic oxide is as gas sensitive the time, and the product confrontation air-sensitive response characteristic of stannic oxide materials has very big influence.There has been sensitivity that lot of documents shows element to improve rapidly with the increase of the reducing of stannic oxide powder particle diameter, specific surface area, substitute micron-sized stannic oxide with the nano tin dioxide powder, particularly the putty powder physical efficiency of grain-size below 20nm increases substantially the sensitivity of gas sensor, reduce response temperature, shorten the response-recovery time.Therefore it is little to synthesize particle diameter, and the high stannic oxide powder of specific surface area has crucial meaning for the raising of Sn system gas sensitive performance.The preparation method of stannic oxide powder has more bibliographical information.As LiF. etc. (Sens.Actuators B 2002,81:165) propose with solid phase method synthetic; ShekC.H. (Nanostruct.Mater.1999 11:887-893) has proposed with SnCl
4For the Sol-Gel method of raw material is synthesized; (Nanostruct.Mater.1996 7:421-427) has proposed to synthesize with hydrothermal synthesis method Wang Chengyuan etc.; (Journal of Inorganic Materials 1999 14:83-88) has proposed with SnCl Pan Qingyi etc.
4For the microemulsion method of raw material is synthesized; SuhS. etc. (Thin Solid Films 1999 345:240-249) has proposed to synthesize with the CVD method; Sophie de Monredon etc. (J.Mater.Chem.2002,12:2396-2400) having proposed with organic alkoxide is that the Sol-Gel method of raw material is synthetic; (Vaccum1996 47:1175-1177) has proposed to synthesize with sputtering method Micocci G. etc.; Edson R. etc. has proposed with SnCl
2Polymer complexometry (Adv.Mater.2002,14 (12) 905-908) for raw material.(Chem.Mater.2000,12:3419-3426) by synthetic stanniferous title complex with complex construction, hydrolysis obtains the stannic oxide powder to Gamard etc. again.But these methods all come with some shortcomings.With SnCl
2, SnCl
4Fairly simple for Sol-Gel method, the microemulsion method building-up process of raw material, do not need special equipment, be the synthetic method of main flow so far, but the Cl in the synthetic product
-Ionic is removed but difficult unusually, needs to consume a large amount of deionized waters, environment is damaged, and product can a large amount of loss in the multiple washing process.The Cl of small amount of residual
-Ion can produce considerable influence to the performance of powder, as powder is seriously reunited, and causes the particle diameter of powder bigger, and specific surface area is very little, does not reach the unusual requirement that improves of air-sensitive performance.Remain in the Cl in the powder
-Ion be owing to can change the electronic structure of material, and then air-sensitive performance is had a negative impact; Cl in the high temperature use
-Ion can discharge, and parts are produced serious corrosive nature.Therefore with SnCl
2, SnCl
4For the synthetic method of raw material has been not suitable for preparing high-quality air-sensitive stannic oxide materials.For avoiding Cl
-The side effect that ion produces, organic alkoxide process synthesizing tin oxide powder of employing is arranged, but hydrolytic process is difficult to control in organic alkoxide Sol-Gel method, for reaching better control to hydrolytic process, often need the humidity in the strict control building-up process, very high to the requirement of synthesis device, and the costing an arm and a leg of raw material alkoxide, cause the cost of product very high, be difficult to realize industrialization.The stanniferous title complex of complex construction, to obtain the method synthetic route of stannic oxide powder longer in hydrolysis again, and each step all need strict control, more do not have the prospect of industrialization than alkoxide process.And physical methods such as CVD, sputtering method are big owing to apparatus expensive, investment, are difficult to produce in enormous quantities.Therefore also there is not cost lower so far, the higher synthetic air-sensitive of the quality product synthetic method of stannic oxide materials.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of stannic oxide powder, to overcome the defective of above-mentioned technology, the stannic oxide powder that this external application method provided by the invention obtains has the specific surface area height, particle diameter is little, finely dispersed characteristics, be made into gas sensor with it, have response characteristic preferably, can be used for business-like gas sensor production fully.
The concrete enforcement of the present invention is as follows: with tin compound, organism is that preparation of raw material becomes solution, and heating concentrates this solution, forms the jelly of homogeneous transparent.Jelly is promptly obtained having the stannic oxide powder of nanostructure in certain temperature thermal treatment.Its reaction conditions is:
A. the preparation condition of solution:
Pink salt and organism are dissolved in the deionized water, and the concentration of pink salt is 0.01-5molL
-1Mass ratio between pink salt and the organism is 1: 0.5-1: 6, and the preparation temperature of solution is 20-90 ℃.Pink salt is not chloride element pink salt, as nitric acid tin, tin oxalate, Tin tetrabromide, stannous sulfate, tin acetate, tin sulphate, tin sulfide, Tin tetraiodide, tartrate tin, one or more in the citric acid tin.Organism is for having the complex ability organism, as glycerol, polyoxyethylene glycol, oxalic acid, polyvinyl alcohol, quadrol, one or more in trolamine, Witco 1298 Soft Acid, glycine, Methionin, stearic acid, methyl ethyl diketone, ethylene glycol, tartrate, EDTA, oxysuccinic acid, the citric acid.
B. heating condition:
The heating thickening temperature is 70-250 ℃, till concentrating the transparent jelly of generation.
The c heat-treat condition:
Thermal treatment temp is 350-800 ℃, and the time is 1-4 hour.
Concrete processing step is:
A. under vigorous stirring, pink salt, organism be dissolved into and be mixed with certain density solution in the deionized water.
B. above-mentioned solution is concentrated in 70-250 ℃, up to transparent jelly occurring.
C. transparent jelly is heat-treated in 350-800 ℃, the time is 1-4 hour
The preparation method's of stannic oxide powder provided by the invention characteristics are:
1, the median size of stannic oxide powder has only between the 5.5-25nm, and specific surface area is at 30-180m
2/ g.
2, raw material obtains easily, is easy to suitability for industrialized production.
3, synthesis cycle is very short, does not need washing process essential in the conventional liquid-phase synthesis process.
4, owing to fundamentally eliminated Cl
-Ionic is removed problem, and the quality of gained powder is very high, can not cause in use the corrosion to parts.
5, the synthetic powder that obtains is made into gas sensor, has good response characteristic, is useful for commercialization fully.
Description of drawings
Fig. 1 is for being pink salt with the tin acetate among the embodiment 1, and trolamine is the x-ray diffraction pattern of the synthetic stannic oxide powder that obtains of organic complexing agent.
Fig. 2 is for being pink salt with the Tin tetraiodide among the embodiment 2, and quadrol is the x-ray diffraction pattern of the synthetic stannic oxide powder that obtains of organic complexing agent.
Fig. 3 is for being pink salt with citric acid tin among the embodiment 3, and methyl ethyl diketone is the x-ray diffraction pattern of the synthetic stannic oxide powder that obtains of organic complexing agent.
Fig. 4 is for being pink salt with the tin oxalate among the embodiment 4, and stearic acid is the x-ray diffraction pattern of the synthetic stannic oxide powder that obtains of organic complexing agent.
Fig. 5 is gas sensor test circuit figure.
Embodiment
Embodiment 1
Accurately take by weighing tin acetate 18g, trolamine 5g forms stabilizing solution in 40 ℃ of deionized waters that are dissolved in 300mL, and 150 ℃ concentrate 2 hours and obtain transparent jelly.This jelly in 600 ℃ of thermal treatments 2 hours, is obtained white stannic oxide powder.This powder is made into sintered type heater-type gas sensor, and sintering condition is 600 ℃ * 1h, and aging condition is 300 ℃ * 240h, and test process adopts static distribution method.Element is 18.3 to the sensitivity of liquefied gas, and the time of response is 4 seconds, and be 38 seconds time of recovery; Sensitivity to alcohol is 10, and the time of response is 10 seconds, and be 12 seconds time of recovery; Sensitivity to 90# gasoline is 11, and the time of response is 22 seconds, and be 20 seconds time of recovery.
By the Scherrer formula (110) crystal face being calculated grain-size is 10nm, and the specific surface area that the BET nitrogen adsorption records powder is 60m
2/ g.
Embodiment 2
Accurately taking by weighing Tin tetraiodide 5g is pink salt, and quadrol 30g forms stabilizing solution in 20 ℃ of deionized waters that are dissolved in 600mL, and 70 ℃ concentrate 10 hours and obtain transparent jelly.This jelly in 350 ℃ of thermal treatments 3 hours, is obtained faint yellow stannic oxide powder.This powder is made into sintered type heater-type gas sensor, and sintering condition is 600 ℃ * 1h, and aging condition is 300 ℃ * 240h, and test process adopts static distribution method.Element is 150 to the sensitivity of liquefied gas, and the time of response is 3 seconds, and be 5 seconds time of recovery; Sensitivity to alcohol is 45, and the time of response is 5 seconds, and be 13 seconds time of recovery; Sensitivity to 90# gasoline is 73, and the time of response is 14 seconds, and be 23 seconds time of recovery.
By the Scherrer formula (110) crystal face being calculated grain-size is 5.5nm, and the specific surface area that the BET nitrogen adsorption records powder is 180m
2/ g.
Embodiment 3
Accurately take by weighing citric acid tin 18g, methyl ethyl diketone 3g forms stabilizing solution in 70 ℃ of deionized waters that are dissolved in 60mL, and 250 ℃ concentrate 1 hour and obtain transparent jelly.This jelly in 800 ℃ of thermal treatments 4 hours, is obtained white stannic oxide powder.This powder is made into sintered type heater-type gas sensor, and sintering condition is 600 ℃ * 1h, and aging condition is 300 ℃ * 240h, and test process adopts static distribution method.Element is 23 to the sensitivity of liquefied gas, and the time of response is 9 seconds, and be 21 seconds time of recovery; Sensitivity to alcohol is 13, and the time of response is 10 seconds, and be 12 seconds time of recovery; Sensitivity to 90# gasoline is 17, and the time of response is 8 seconds, and be 6 seconds time of recovery.
By the Scherrer formula (110) crystal face being calculated grain-size is 25nm, and the specific surface area that the BET nitrogen adsorption records powder is 30m
2/ g.
Embodiment 4
Accurately take by weighing tin oxalate 40g, stearic acid 60g forms stabilizing solution in 90 ℃ of deionized waters that are dissolved in 100mL, and 100 ℃ concentrate 5 hours and obtain transparent jelly.This jelly in 500 ℃ of thermal treatments 2 hours, is obtained white stannic oxide powder.This powder is made into sintered type heater-type gas sensor, and sintering condition is 600 ℃ * 1h, and aging condition is 300 ℃ * 240h, and test process adopts static distribution method.Element is 60 to the sensitivity of liquefied gas, and the time of response is 3 seconds, and be 6 seconds time of recovery; Sensitivity to alcohol is 79, and the time of response is 4 seconds, and be 7 seconds time of recovery; Sensitivity to 90# gasoline is 52, and the time of response is 5 seconds, and be 23 seconds time of recovery.
By the Scherrer formula (110) crystal face being calculated grain-size is 7.2nm, and the specific surface area that the BET nitrogen adsorption records powder is 128m
2/ g.
Claims (4)
1, a kind of preparation method of stannic oxide powder, it is characterized in that: adopting the pink salt of chloride element not, the organism with complex ability is raw material, with the deionized water is that solvent is mixed with solution, and heating concentrates this solution and forms jelly, subsequently jelly is heat-treated; The pink salt of described not chloride element is nitric acid tin, tin oxalate, Tin tetrabromide, stannous sulfate, tin acetate, tin sulphate, tin sulfide, Tin tetraiodide, tartrate tin, one or more in the citric acid tin; Described organism with complex ability is one or more in glycerol, polyoxyethylene glycol, oxalic acid, polyvinyl alcohol, quadrol, trolamine, Witco 1298 Soft Acid, glycine, Methionin, stearic acid, methyl ethyl diketone, ethylene glycol, tartrate, EDTA, oxysuccinic acid, the citric acid.
2, by the preparation method of the described a kind of stannic oxide powder of claim 1, it is characterized in that the tin-salt solution concentration that is mixed with is 0.01-5molL
-1, the mass ratio between pink salt and the organism is 1: 0.5-1: 6, and the preparation temperature of solution is 20-90 ℃.
3, by the preparation method of claim 1 or 2 described a kind of stannic oxide powders, it is characterized in that described thermal treatment temp is 70-250 ℃, till concentrating the generation jelly.
4, by the preparation method of claim 1 or 2 described a kind of stannic oxide powders, it is characterized in that described thermal treatment temp is 350-800 ℃, the time is 1-4 hour.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1318306C (en) * | 2004-12-08 | 2007-05-30 | 云南锡业集团有限责任公司研究设计院 | Method for preparing H2SnO3 (tin dioxide) powder |
| CN100482591C (en) * | 2004-12-30 | 2009-04-29 | 广东工业大学 | Method for preparing Nano granules of stannic oxide |
| CN1328208C (en) * | 2005-03-23 | 2007-07-25 | 北京青鸟元芯微***科技有限责任公司 | Semiconductor material of composite metal oxide and its preparation process |
| CN101339959B (en) * | 2008-08-07 | 2012-03-14 | 清华大学 | Thin film transistor and preparation of semiconductor film |
| CN102925880A (en) * | 2012-11-16 | 2013-02-13 | 宁波祈禧电器有限公司 | Preparation method of transparent tin antimony oxide electric heating film |
| CN103332727B (en) * | 2013-06-26 | 2015-04-08 | 宁波今心新材料科技有限公司 | Preparation method of tin oxide nanocrystal |
| CN103332728A (en) * | 2013-06-26 | 2013-10-02 | 宁波今心新材料科技有限公司 | Preparation method of tin oxide ultrafine powder |
| CN104229744B (en) * | 2014-08-26 | 2016-05-11 | 洛阳市方德新材料科技有限公司 | The preparation method of nanometer metal oxide powder |
| CN104211107B (en) * | 2014-08-26 | 2016-03-02 | 洛阳市方德新材料科技有限公司 | The preparation method of nano tin-oxide powder |
| CN109786711B (en) * | 2019-01-23 | 2022-02-08 | 电子科技大学 | Preparation method of porous carbon skeleton-coated tin composite electrode material |
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