CN1978323A - Method for preparing ITO powder with high sintering activity - Google Patents
Method for preparing ITO powder with high sintering activity Download PDFInfo
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- CN1978323A CN1978323A CN 200510111243 CN200510111243A CN1978323A CN 1978323 A CN1978323 A CN 1978323A CN 200510111243 CN200510111243 CN 200510111243 CN 200510111243 A CN200510111243 A CN 200510111243A CN 1978323 A CN1978323 A CN 1978323A
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Abstract
This invention relates to a preparation method for high sintered active InO powder doped with tin including the following steps: adding an organic complexing agent into a solution composed of Sn source, In source and deionized water, in which, the mol ratio of organic complexing agent and the metal ions is (0.25-5):1, then adding ammonia to adjust the pH value to 4-12, finally, putting it into a reactor for hydrothermal reaction for 3-24 h and the reacted materials are cleaned, dried and heat-processed to get the product, which is advantaged that the size of the produced ITO powder is 6-25 nm, the specific area reaches to 30-80m2/g, the produced ITO powder gets fine sintered activity (reaching to 98.7% relative density at the maximum when being sintered under 1200deg.C and normal pressure).
Description
Technical field
The present invention relates to the preparation method of the active tin-doped indium oxide of a kind of high sintering (ITO) powder.
Background technology
Tin-doped indium oxide (Indium Tin Oxide is called for short ITO), at 5～10% o'clock, conductivity of electrolyte materials can reach 10 at tin content
5Ω
-1Cm
-1More than, only less than the argent of high conductivity, aluminium etc.And ITO is better than the distinguishing feature of metallic conductor is that it has very strong transmitance (can reach more than 80% usually) in the visible region.In addition, ITO also has the ability of reflected infrared.The above-mentioned characteristic of ITO has very widely it and uses in a plurality of fields, become the material that present stage has the middle most critical of transparent conductive oxide material (TCOs, Transparent Conductive Oxides) of ten minutes important application and researching value.
Nicolas etc. (J.Am.Ceram.Soc., 1994,77,834-846) with In
2O
3And SnO
2Be raw material, first solid state reaction obtains the ITO powder, and in 1380 ℃ of sintering, the relative density of ITO block is less than 90% as a result again.Because it is little that nano-powder has particle size, the characteristics that specific surface area is big, thereby when sintering, can reduce sintering temperature significantly, under lower sintering temperature, just can reach very high relative density.Therefore, adopt chemical method to synthesize and obtain the main production that the nano-ITO powder has become the ITO powder.
(Scripta Mater. such as Nam, 2001,44,2047-2050) relative density of the ITO block that obtained in normal pressure-sintered 1 hour of 1500 ℃ of ITO nano-powders that obtains with coprecipitation method is 88.3%, (Mater.Lett. such as Devi, 2002,55, be that raw material is 95%-97% with 1350 ℃ of relative densities that sintering obtains of ITO powder (In is 85: 15 with the ratio of the amount of substance of Sn) that the microemulsion precipitator method prepare with the villaumite 205-210).Though in chemical method synthesis of nano powder, coprecipitation method is because its technology is fairly simple, the parameter ratio is easier to control, and production cost is also lower.But it also exists the particle diameter of the powder that obtains bigger, and the reunion of powder is important disadvantages relatively, and this method is difficult to obtain high-quality nano-powder.Hydrothermal method is because powder has just been realized crystallization under thermal and hydric environment, so the grain-size of powder is smaller, and the reunion degree that its maximum characteristics are exactly powder is low weight, usually can obtain not having reuniting the mono-dispersed nano powder.Therefore, hydrothermal method has progressively been adopted in a lot of now researchs and industrialized powder production.(J.Am.Ceram.Soc., 2001,84 such as Yanagisawa, be that raw material adopts first co-precipitation to obtain the oxyhydroxide presoma of indium, tin with the villaumite 251-253), after carry out repetitive scrubbing and remove chlorion, carry out hydrothermal treatment consists again, heat-treat the ITO powder that has obtained fluorite structure at last.It is 98.5% ITO ceramic block that this powder just obtained relative apparent density in normal pressure-sintered 3 hours at 1450 ℃, has shown the superiority of hydrothermal method aspect synthesis of nano.But this method also has apparent in view defective, show as above-mentioned result of study, the hydro-thermal powder is about the granular size of powder after 700 ℃ of thermal treatment is up to 160nm, the advantage that this result and hydrothermal method can obtain undersized nano-powder not too meets, its reason may with building-up process in to have carried out coprecipitation reaction earlier relevant, hydrothermal treatment consists has worked just to have promoted that the hydration presoma loses moisture content.
In addition, in the prior art, all adopt the muriate of muriate, nitrate and the tin of indium when synthesizing ITO, just all contain a large amount of chlorions in the raw material.Although the muriate raw material becomes more readily available, must see that muriate is cumbersome to the synthetic inconvenience that brings.As, it is then very difficult to wash the chlorion impurity of removing wherein in the precipitation process, often needs to consume a large amount of water sources, electric power, also can cause a large amount of losses of product simultaneously, makes production cost of products increase greatly.In hydro-thermal was synthetic, because chlorion can produce the intensive corrosive nature to the stainless steel lined of autoclave, it was very high to the requirement of reactor to add reaction under high pressure, so synthetic in fact being difficult to of hydro-thermal realized.The chlorion of small amount of residual also can produce very serious agglomeration to powder, reduces the dispersing property of powder.A spot of residual chlorine ion also can produce serious corrosive nature to environment for use in the application process, reduces the work-ing life of parts.
Summary of the invention
The object of the invention is, provide a kind of and have that grain-size is little, surface-area is high, good dispersity and normal pressure-sintered active advantages of higher, and preparation condition controlled easily, cost low and the preparation method of the ITO powder that preparation cycle is short.
The preparation method of the present invention's active tin-doped indium oxide of said high sintering (ITO) powder, it is characterized in that, said preparation method's key step is: at first add organic complexing agent in the solution of being made up of Xi Yuan, indium source and deionized water, the mol ratio of organic complexing agent and metal ion (tin ion and indium ion sum) is (0.25～5): 1; And then adding ammoniacal liquor adjusting pH value is 4～12; Be placed at last in the reactor in 130～260 ℃ and carried out hydro-thermal reaction 3～24 hours, the hydro-thermal reaction product after washing, drying and thermal treatment target compound;
Wherein: in the said solution of being made up of Xi Yuan, indium source and deionized water, the mol ratio of tin ion and indium ion is (3～12): 100 and chloride ion-containing not; Said organic complexing agent is tartrate, amino acid, ethylene glycol, citric acid, disodium salt, oxysuccinic acid, methyl ethyl diketone, glycerol, quadrol or triethylamine.
In the present invention, used Xi Yuan and indium source are required its not chloride ion-containing, being fit to Xi Yuan of the present invention has the alkoxide of (but being not limited to) tin, stannous sulfate, tin sulphate, tin sulfide, Tin tetraiodide, nitric acid tin, the inferior tin of nitric acid, stannous oxalate, stannous acetate, Tin tetrabromide or citric acid tin, is fit to alkoxide, indium bromide, tartrate indium, indium nitrate, indium acetate, oxalic acid indium, citric acid indium or the indium sulfide that there be (but being not limited to) indium sulfate, indium in indium of the present invention source; Be recommended in the solution that 0～90 ℃ of preparation is made up of Xi Yuan, indium source and deionized water; Preferred indium ion concentration is 0.1～3mol/L in the solution of being made up of Xi Yuan, indium source and deionized water.
Embodiment
The preparation method of the active ITO powder of the said high sintering of the present invention comprises the steps:
(1) at first under 0～90 ℃ and agitation condition, the Xi Yuan of chloride ion-containing not and indium source dissolved in respectively to be mixed with indium ion concentration in the deionized water be 0.1～3mol/L, the mol ratio of tin ion and indium ion is (3～12): 100 solution; Add organic complexing agent then in this solution, the mol ratio of organic complexing agent and metal ion (tin ion and indium ion sum) is (0.25～5): 1; Adding ammoniacal liquor adjusting pH value at last again is 4～12;
(2) the pH value that will be made by step (1) is 4～12, the mixture that contains indium, tin and organic complexing agent places reactor, carried out hydro-thermal reaction 3～24 hours in 130～260 ℃, the hydro-thermal reaction product in 80～130 ℃ of dryings 1～5 hour, promptly got target compound in 2～6 hours in 500～900 ℃ of thermal treatments with after drying hydro-thermal reaction product again behind deionized water, absolute ethanol washing.
The present invention has following characteristics:
The particle diameter of the ITO powder that A. makes is 6～25 nanometers, and specific surface area reaches 30～80m
2/ g, the reunion of powder is few;
B. the ITO powder that makes has good sintering activity, and 1200 ℃ normal pressure-sintered can reach 98.7% relative density;
C. raw material is easy to get, preparation process is easy to control, has fundamentally eliminated the trouble that chlorion causes preparation, has shortened the production cycle significantly, has improved production efficiency and relatively more friendly to environment.
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:
Embodiment 1
Accurately taking by weighing Virahol indium 15g, is to take by weighing nitric acid inferior tin at 10: 100 by the mol ratio of tin and indium, is mixed with 3molL
-1Mixing solutions, the preparation temperature be 0 ℃.Under violent stirring, triethylamine is joined in the above-mentioned solution, the mol ratio of triethylamine and metal ion (tin ion and indium ion sum) is 1: 1, is 12 with the pH value of ammoniacal liquor regulation system.This system is transferred to carries out hydro-thermal reaction in the autoclave, hydrothermal temperature is 160 ℃, and the hydro-thermal time is 7 hours.After the hydro-thermal reaction hydrothermal product is taken out, with deionized water and absolute ethanol washing several, again in 130 ℃ of oven dry, the time is 3 hours.The hydro-thermal powder of drying just obtains product ITO powder in 700 ℃ of thermal treatments 2 hours.By the X-ray diffraction method powder is measured, with the Scherrer formula 31.0 ° of crystal faces of locating in the powder diffraction peak being calculated grain-size is 12nm, and the specific surface area that the BET nitrogen adsorption records powder is 68m
2g
-1
Get the synthetic ITO powder pressure with 15 kilograms in the mould of Φ 18 that obtains of 15g and carry out dry pressing, carry out isostatic cool pressing with 4 tons pressure again.The dry body that obtains is normal pressure-sintered 3 hours in 1200 ℃.The light blue ceramic block that obtains is with the density of Archimedes's method mensuration block, and the relative density that draws this ITO block is 97%.
Embodiment 2
Accurately taking by weighing citric acid indium 10g, is to take by weighing Tin tetraiodide at 3: 100 by the mol ratio of tin and indium, is mixed with 1molL
-1Mixing solutions, the preparation temperature be 40 ℃.Under violent stirring, tartrate is joined in the above-mentioned solution, the mol ratio of tartrate and metal ion (tin ion and indium ion sum) is 0.25: 1, is 6 with the pH value of ammoniacal liquor regulation system.This system is transferred to carries out hydro-thermal reaction in the autoclave, hydrothermal temperature is 260 ℃, and the hydro-thermal time is 3 hours.After the hydro-thermal reaction hydrothermal product is taken out, with deionized water and absolute ethanol washing several, again in 80 ℃ of oven dry, the time is 2 hours.The hydro-thermal powder of drying just obtains product ITO powder in 900 ℃ of thermal treatments 5 hours.By the X-ray diffraction method powder is measured, with the Scherrer formula 31.0 ° of crystal faces of locating in the powder diffraction peak being calculated grain-size is 25nm, and the specific surface area that the BET nitrogen adsorption records powder is 30m
2g
-1
Get the synthetic ITO powder pressure with 15 kilograms in the mould of Φ 18 that obtains of 15g and carry out dry pressing, carry out isostatic cool pressing with 4 tons pressure again.The dry body that obtains is normal pressure-sintered 3 hours in 1200 ℃.The light blue ceramic block that obtains is with the density of Archimedes's method mensuration block, and the relative density that draws this ITO block is 98.7%.
Embodiment 3
Accurately taking by weighing indium acetate 20g, is to take by weighing the inferior tin of nitric acid at 12: 100 by the mole of tin and indium, is mixed with 0.1molL
-1Mixing solutions, the preparation temperature be 90 ℃.Under violent stirring, methyl ethyl diketone is joined in the above-mentioned solution, the mol ratio of methyl ethyl diketone and metal ion (tin ion and indium ion sum) is 5: 1, is 4 with the pH value of ammoniacal liquor regulation system.This system is transferred to carries out hydro-thermal reaction in the autoclave, hydrothermal temperature is 130 ℃, and the hydro-thermal time is 24 hours.After the hydro-thermal reaction hydrothermal product is taken out, with deionized water and absolute ethanol washing several, again in 100 ℃ of oven dry, the time is 6 hours.The hydro-thermal powder of drying just obtains product ITO powder in 500 ℃ of thermal treatments 4 hours.By the X-ray diffraction method powder is measured, with the Scherrer formula 31.0 ° of crystal faces of locating in the powder diffraction peak being calculated grain-size is 6nm, and the specific surface area that the BET nitrogen adsorption records powder is 80m
2g
-1
Get the synthetic ITO powder pressure with 15 kilograms in the mould of Φ 18 that obtains of 15g and carry out dry pressing, carry out isostatic cool pressing with 4 tons pressure again.The dry body that obtains is normal pressure-sintered 3 hours in 1200 ℃.The light blue ceramic block that obtains is with the density of Archimedes's method mensuration block, and the relative density that draws this ITO block is 95%.
Embodiment 4
Accurately taking by weighing indium bromide 15g, is to take by weighing stannous sulfate at 8: 100 by the mol ratio of tin and indium, is mixed with 0.5molL
-1Mixing solutions, the preparation temperature be 30 ℃.Under violent stirring, ethylene glycol is joined in the above-mentioned solution, the mol ratio of ethylene glycol and metal ion (tin ion and indium ion sum) is 0.8: 1, is 9 with the pH value of ammoniacal liquor regulation system.This system is transferred to carries out hydro-thermal reaction in the autoclave, hydrothermal temperature is 210 ℃, and the hydro-thermal time is 18 hours.After the hydro-thermal reaction hydrothermal product is taken out, with deionized water and absolute ethanol washing several, again in 110 ℃ of oven dry, the time is 4 hours.The hydro-thermal powder of drying just obtains product ITO powder in 600 ℃ of thermal treatments 3 hours.By the X-ray diffraction method powder is measured, with the Scherrer formula 31.0 ° of crystal faces of locating in the powder diffraction peak being calculated grain-size is 15nm, and the specific surface area that the BET nitrogen adsorption records powder is 55m
2g
-1
Get the synthetic ITO powder pressure with 15 kilograms in the mould of Φ 18 that obtains of 15g and carry out dry pressing, carry out isostatic cool pressing with 4 tons pressure again.The dry body that obtains is normal pressure-sintered 3 hours in 1200 ℃.The light blue ceramic block that obtains is with the density of Archimedes's method mensuration block, and the relative density that draws this ITO block is 97.5%.
Claims (4)
1, the preparation method of the active tin-doped indium oxide powder of a kind of high sintering, it is characterized in that, said preparation method's key step is: at first add organic complexing agent in the solution of being made up of Xi Yuan, indium source and deionized water, the mol ratio of organic complexing agent and metal ion is (0.25～5): 1; And then adding ammoniacal liquor adjusting pH value is 4～12; Be placed at last in the reactor in 130～260 ℃ and carried out hydro-thermal reaction 3～24 hours, the hydro-thermal reaction product after washing, drying and thermal treatment target compound;
Wherein: in the said solution of being made up of Xi Yuan, indium source and deionized water, the mol ratio of tin ion and indium ion is (3～12): 100 and chloride ion-containing not; Said organic complexing agent is tartrate, amino acid, ethylene glycol, citric acid, disodium salt, oxysuccinic acid, methyl ethyl diketone, glycerol, quadrol or triethylamine.
As the said preparation method of claim 1, it is characterized in that 2, the preparation temperature of wherein preparing the solution of being made up of Xi Yuan, indium source and deionized water is 0～90 ℃.
As claim 1 or 2 said preparation methods, it is characterized in that 3, wherein indium ion concentration is 0.1～3mol/L in the solution of being made up of Xi Yuan, indium source and deionized water.
4, as the said preparation method of claim 3, it is characterized in that the alkoxide that wherein said Xi Yuan is a tin, stannous sulfate, tin sulphate, tin sulfide, Tin tetraiodide, nitric acid tin, the inferior tin of nitric acid, stannous oxalate, stannous acetate, Tin tetrabromide or citric acid tin; Said indium source is alkoxide, indium bromide, tartrate indium, indium nitrate, indium acetate, oxalic acid indium, citric acid indium or the indium sulfide of indium sulfate, indium.
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| CNB2005101112433A CN100465099C (en) | 2005-12-08 | 2005-12-08 | Method for preparing ITO powder with high sintering activity |
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| CN100465099C CN100465099C (en) | 2009-03-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2062857A1 (en) * | 2007-11-21 | 2009-05-27 | Corning SAS | Thermoelectric materials comprising a matrix of In2O3 with regions of In2Ge2O7 dispersed therein, thermoelectric elements and methods of making the same |
| CN102001698A (en) * | 2010-10-26 | 2011-04-06 | 江苏大学 | Preparation method of indium oxide mesoporous nanospheres |
| CN102176339A (en) * | 2011-02-28 | 2011-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of conductive oxide nanometer powder |
| CN101624173B (en) * | 2009-07-23 | 2011-11-16 | 暨南大学 | Low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder |
| CN102786080A (en) * | 2012-07-18 | 2012-11-21 | 中国科学院福建物质结构研究所 | Indium tin oxide compound, its preparation method and its photocatalytic application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237006C (en) * | 2003-10-10 | 2006-01-18 | 桂林电子工业学院 | In2O3 and ITO monodisperse nano powder hydrothermal preparation method |
| CN1237007C (en) * | 2003-10-15 | 2006-01-18 | 中国科学院上海硅酸盐研究所 | Method for preparing nano tin anhydride powder |
-
2005
- 2005-12-08 CN CNB2005101112433A patent/CN100465099C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2062857A1 (en) * | 2007-11-21 | 2009-05-27 | Corning SAS | Thermoelectric materials comprising a matrix of In2O3 with regions of In2Ge2O7 dispersed therein, thermoelectric elements and methods of making the same |
| CN101624173B (en) * | 2009-07-23 | 2011-11-16 | 暨南大学 | Low-temperature solvent hot preparation method of indium tin oxide monodisperse nano powder |
| CN102001698A (en) * | 2010-10-26 | 2011-04-06 | 江苏大学 | Preparation method of indium oxide mesoporous nanospheres |
| CN102001698B (en) * | 2010-10-26 | 2012-08-15 | 江苏大学 | Preparation method of indium oxide mesoporous nanospheres |
| CN102176339A (en) * | 2011-02-28 | 2011-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of conductive oxide nanometer powder |
| CN102786080A (en) * | 2012-07-18 | 2012-11-21 | 中国科学院福建物质结构研究所 | Indium tin oxide compound, its preparation method and its photocatalytic application |
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| CN100465099C (en) | 2009-03-04 |
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