CN102285683A - Synthesis method of stibium-doped stannic oxide electroconductive powder material - Google Patents
Synthesis method of stibium-doped stannic oxide electroconductive powder material Download PDFInfo
- Publication number
- CN102285683A CN102285683A CN2011101624352A CN201110162435A CN102285683A CN 102285683 A CN102285683 A CN 102285683A CN 2011101624352 A CN2011101624352 A CN 2011101624352A CN 201110162435 A CN201110162435 A CN 201110162435A CN 102285683 A CN102285683 A CN 102285683A
- Authority
- CN
- China
- Prior art keywords
- stannic oxide
- stibium
- antimony
- powder
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Conductive Materials (AREA)
Abstract
The invention provides a synthesis method of a stibium-doped stannic oxide electroconductive powder material. The synthesis method comprises the following steps: placing a certain amount of metal tin powder and metal stibium powder in a glass reactor and adding a proper amount of nitric acid, and carrying out magnetic stirring reaction for 20-50 hours at room temperature; after the reaction is finished, standing and precipitating, and pouring an upper-layer solution; washing an oxide precipitate obtained in the reaction with distilled water 4-8 times; drying the precipitate for 1-2 hours at the temperature of 100 DEG C; and carrying out thermal treatment on the dried precipitate for 1-3 hours at the temperature of 200-600 DGE C, and pulverizing so as to obtain the stibium-doped stannic oxide electroconductive powder, wherein the resistivity of the stibium-doped stannic oxide electroconductive powder is not larger than 2 omega cm.
Description
Technical field
The present invention relates to conductive powder material, be specifically related to a kind of synthetic method of stibium doping stannic oxide conductive powder material.
Background technology
Stibium doping stannic oxide (ATO) is a kind of conducting ceramic material, have good conductivity, stable chemical performance, light transmission good (film) and characteristics such as air-sensitive performance preferably, be widely used in electro-conductive material, antistatic with fields such as conductive filler material, transparent conductive glass and gas sensors.
The main method of existing synthetic stibium doping stannic oxide has:
1. mechanical mixing: will contain the Sb compound and contain SnO
2600-1200 ℃ of high-temperature heat treatment obtains antimony-doped tin dioxide powder end (CN101468397A) behind compound and the ball milling.
2. coprecipitation method: the containing the Sb inorganic salt and contain in the water-soluble or organic solution of Sn inorganic salt of metering, the pH value that adds change solution such as ammoniacal liquor then makes Sb, the Sn in the solution obtain the antimony-doped tin dioxide powder end with the form co-precipitation of oxide compound.
3. hydrothermal method: with the SnCl of metering
4And SbCl
3Be dissolved in and obtain preparing solution (Hongyan Miao in the distilled water, Microelectronic Engineering, 2003, Volume 66, P142-146), to prepare solution again and inject hydrothermal reaction kettle, the sealing back obtains the antimony-doped tin dioxide powder end at last 290 ℃ of reactions of 250 – 6 hours.Patent CN200410016326 places hydrothermal reaction kettle 120 ℃ ~ 360 ℃ reactions the metal Sb and the metal Sn of nitric acid, metering, obtains the antimony-doped tin dioxide powder end.
Mechanical mixing is owing to the weisspiessglanz that forms, tindioxide mixture need make weisspiessglanz just can obtain the stibium doping stannic oxide conductive powder after tindioxide fully spreads through 600-1200 ℃ high-temperature heat treatment, and the stibium doping stannic oxide specific conductivity of process high-temperature heat treatment is lower than theoretical value.The better performances at the synthetic antimony-doped tin dioxide powder end of coprecipitation method, but in its preparation process, need repeatedly washing could remove the foreign ion of wherein introducing.Hydrothermal method can be reacted synthetic stibium doping stannic oxide comparatively speaking under lower temperature, but the hydro-thermal reaction of passing through 120-360 ℃ under the solution condition must be arranged, and this needs special withstand voltage, acid-resistant system for using the nitric acid equal solvent.
Summary of the invention
The present invention is directed to the deficiency of the technology of existing synthetic stibium doping stannic oxide, and a kind of simple, comparatively safe, synthetic antimony-doped tin dioxide powder end method efficiently is provided, synthetic stibium doping stannic oxide material conductivity is good.
The technical scheme that realizes above-mentioned purpose is:
A kind of synthetic method of stibium doping stannic oxide conductive powder material comprises the steps:
With metallic antimony and metallic tin respectively as the antimony source of sb oxide and the Xi Yuan of tin oxidationization, get the metal antimony powder and the metallic tin of metering, its mass ratio is 2 ~ 20:100, and add concentration be 30% or concentration greater than 30% aqueous nitric acid as oxygenant;
2. magnetic agitation reaction at room temperature is 20 ~ 50 hours;
3. wash 4 ~ 8 times with the oxide precipitation of distilled water above-mentioned reaction;
4. with above-mentioned throw out oven dry, bake out temperature is 100 ℃, and drying time is 1 ~ 2 hour;
5. with 200 ~ 600 ℃ of thermal treatments of dry sediment 1 ~ 2 hour, obtain the antimony-doped tin dioxide powder powder material after the pulverizing.
This product is after testing: the resistivity of this stibium doping stannic oxide conductive powder is not more than 2 Ω cm.
Principle of the present invention: according to concentrated nitric acid can be transformed into water-fast hydration tindioxide to tin rapidly and concentrated nitric acid can be oxidized to metallic antimony+5 valencys, be insoluble in water and be the tart oxide compound---the weisspiessglanz hydrate, reaction formula is:
Sn+4HNO
3=SnO
2·H
2O↓+4NO
2↑+H
2O
6Sb+10HNO
3+4H
2O?=3Sb
2O
5·9H
2O↓+10NO↑
Use elemental metals tin and elemental metals antimony raw material, as oxygenant, allow its reaction synthesize the mixture of tin dioxide hydrate and antimony peroxide hydrate, obtain stibium doping stannic oxide after this mixture dehydration with nitric acid as synthetics.
The present invention compares with existing stibium doping stannic oxide synthetic method, have following characteristics: the raw material of use is easy to get, and it is cheap, whole synthesis process does not use the reagent that environment is had substantial pollution, need in the autoclave of high temperature resistant, acid corrosion-resistant, not carry out, and the resistivity at the antimony-doped tin dioxide powder end that obtains is lower.The inventive method is safer with respect to prior art, environmental protection, fast, and can relatively large preparation stibium doping stannic oxide conductive powder, has reduced production cost, and can realize industrialization easily.
Description of drawings
Fig. 1 is the process flow sheet of stibium doping stannic oxide conductive powder preparation of the present invention.
Embodiment
The invention will be further elaborated below in conjunction with drawings and Examples, but should be understood that following embodiment only is used for the present invention is illustrated, and be not in order to limit protection scope of the present invention.
Embodiment 1
(1) takes by weighing analytical pure tin particles 5 grams and analytical pure antimony powder 1 gram, be positioned in 250 milliliters of Erlenmeyer flasks, and add 60 milliliters in concentration 30% nitric acid;
(2) magnetic agitation reaction at room temperature is 48 hours, staticly settles after reaction finishes, and topples over upper solution;
(3) again with distilled water with the oxide precipitation of above-mentioned reaction elder generation after scouring 6 times;
(4) with 100 ℃ of oven dry of above-mentioned throw out 1 hour;
(5) again with 200 ℃ of thermal treatments of above-mentioned dry sediment 2 hours, pulverizing obtains the stibium doping stannic oxide conductive powder, the stibium doping stannic oxide conductive powder of getting preparation is in the mould of 1.8 centimetres of diameters, apply 10kPa pressure and keep being shaped in 20 minutes 1.8 centimetres of disks of diameter, use the bridge resistor tester to measure its resistance, and calculate its resistivity, obtaining its resistivity is 2 Ω cm.
Embodiment 2
(1) takes by weighing analytical pure tin particles 5 grams and analytical pure antimony powder 1 gram, be positioned in 250 milliliters of Erlenmeyer flasks, and add 60 milliliters in concentration 30% nitric acid;
(2) magnetic agitation reaction at room temperature is 48 hours, staticly settles after reaction finishes, and topples over upper solution;
(3) again with distilled water with the oxide precipitation of above-mentioned reaction elder generation after scouring 6 times;
(4) with 100 ℃ of oven dry of above-mentioned throw out 1 hour;
(5) again with 400 ℃ of thermal treatments of dry sediment 2 hours, pulverizing obtains the stibium doping stannic oxide conductive powder, the stibium doping stannic oxide conductive powder of getting preparation is in the mould of 1.8 centimetres of diameters, apply 10kPa pressure and keep being shaped in 20 minutes 1.8 centimetres of disks of diameter, use the bridge resistor tester to measure its resistance, and calculate its resistivity, obtaining its resistivity is 0.5 Ω cm.
Embodiment 3
(1) takes by weighing analytical pure tin particles 5 grams and analytical pure antimony powder 1 gram, be positioned in 250 milliliters of Erlenmeyer flasks, and add 60 milliliters in concentration 30% nitric acid;
(2) magnetic agitation reaction at room temperature is 48 hours, staticly settles after reaction finishes, and topples over upper solution;
(3) again with distilled water with the oxide precipitation of above-mentioned reaction elder generation after scouring 6 times;
(4) with 100 ℃ of oven dry of above-mentioned throw out 1 hour;
(5) just 600 ℃ of thermal treatments of dry sediment 1 hour again, pulverizing obtains the stibium doping stannic oxide conductive powder, the stibium doping stannic oxide conductive powder of getting preparation is in the mould of 1.8 centimetres of diameters, apply 10kPa pressure and keep being shaped in 20 minutes 1.8 centimetres of disks of diameter, use the bridge resistor tester to measure its resistance, and calculate its resistivity, obtaining its resistivity is 0.4 Ω cm.
Embodiment 4
(1) takes by weighing analytical pure tin particles 5 grams and analytical pure antimony powder 1 gram, be positioned in 250 milliliters of Erlenmeyer flasks, and add 30 milliliters in concentration 66% nitric acid;
(2) magnetic agitation reaction at room temperature is 20 hours, staticly settles after reaction finishes, and topples over upper solution;
(3) again with distilled water with the oxide precipitation of above-mentioned reaction elder generation after scouring 6 times;
(4) with 100 ℃ of oven dry of above-mentioned throw out 1 hour;
(5) just 600 ℃ of thermal treatments of dry sediment 1 hour again, pulverizing obtains the stibium doping stannic oxide conductive powder, the stibium doping stannic oxide conductive powder of getting preparation is in the mould of 1.8 centimetres of diameters, apply 10kPa pressure and keep being shaped in 20 minutes 1.8 centimetres of disks of diameter, use the bridge resistor tester to measure its resistance, and calculate its resistivity, obtaining its resistivity is 0.5 Ω cm.
Embodiment 5
(1) takes by weighing analytical pure tin particles 5 grams and analytical pure antimony powder 0.2 gram, be positioned in 250 milliliters of Erlenmeyer flasks, and add 60 milliliters in concentration 30% nitric acid;
(2) magnetic agitation reaction at room temperature is 48 hours, staticly settles after reaction finishes, and topples over upper solution;
(3) again with distilled water with the oxide precipitation of above-mentioned reaction elder generation after scouring 6 times;
(4) with 100 ℃ of oven dry of above-mentioned throw out 1 hour;
(5) again with 500 ℃ of thermal treatments of above-mentioned dry sediment 2 hours, pulverizing obtains the stibium doping stannic oxide conductive powder, the stibium doping stannic oxide conductive powder of getting preparation is in the mould of 1.8 centimetres of diameters, apply 10kPa pressure and keep being shaped in 20 minutes 1.8 centimetres of disks of diameter, use the bridge resistor tester to measure its resistance, and calculate its resistivity, obtaining its resistivity is 2 Ω cm.
Embodiment 6
(1) takes by weighing analytical pure tin particles 5 grams and analytical pure antimony powder 0.6 gram, be positioned in 250 milliliters of Erlenmeyer flasks, and add 60 milliliters of concentration 30% concentrated nitric acids;
(2) magnetic agitation reaction at room temperature is 48 hours, staticly settles after reaction finishes, and topples over upper solution;
(3) again with distilled water with the oxide precipitation of above-mentioned reaction elder generation after scouring 6 times;
(4) with 100 ℃ of oven dry of above-mentioned throw out 1 hour;
(5) again with 500 ℃ of thermal treatments of above-mentioned dry sediment 2 hours, pulverizing obtains the stibium doping stannic oxide conductive powder, the stibium doping stannic oxide conductive powder of getting preparation is in the mould of 1.8 centimetres of diameters, apply 10kPa pressure and keep being shaped in 20 minutes 1.8 centimetres of disks of diameter, use the bridge resistor tester to measure its resistance, and calculate its resistivity, obtaining its resistivity is 1 Ω cm.
Claims (3)
1. the synthetic method of a stibium doping stannic oxide is characterized in that: comprise the steps:
(1) get a certain amount of metal antimony powder and metallic tin, its mass ratio is 2 ~ 20:100, and add concentration be 30% or concentration greater than 30% aqueous nitric acid as oxygenant;
(2) magnetic agitation reaction at room temperature is 20 ~ 50 hours;
(3) wash 4 ~ 8 times with the oxide precipitation of distilled water above-mentioned reaction;
(4) with above-mentioned throw out oven dry, bake out temperature is 100 ℃, and drying time is 1 ~ 2 hour;
(5) with 200 ~ 600 ℃ of thermal treatments of dry sediment 1 ~ 2 hour, obtain the antimony-doped tin dioxide powder powder material after the pulverizing.
2. according to the synthetic method of the described stibium doping stannic oxide of claim 1, it is characterized in that: with metallic antimony and metallic tin respectively as the antimony source of sb oxide and the Xi Yuan of tin-oxide.
3. according to the synthetic method of the described stibium doping stannic oxide of claim 1, it is characterized in that: with concentration be 30% or concentration greater than 30% aqueous nitric acid as oxygenant oxidation metallic antimony and metallic tin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101624352A CN102285683A (en) | 2011-06-16 | 2011-06-16 | Synthesis method of stibium-doped stannic oxide electroconductive powder material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101624352A CN102285683A (en) | 2011-06-16 | 2011-06-16 | Synthesis method of stibium-doped stannic oxide electroconductive powder material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102285683A true CN102285683A (en) | 2011-12-21 |
Family
ID=45332472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101624352A Pending CN102285683A (en) | 2011-06-16 | 2011-06-16 | Synthesis method of stibium-doped stannic oxide electroconductive powder material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102285683A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108190943A (en) * | 2018-04-02 | 2018-06-22 | 郑州大学 | A kind of method that metallic tin oxidation prepares nano-stannic oxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61205624A (en) * | 1985-03-11 | 1986-09-11 | Fuji Photo Film Co Ltd | Production of electrically conductive fine powder of tin oxide |
| JPS61205622A (en) * | 1985-03-11 | 1986-09-11 | Fuji Photo Film Co Ltd | Production of electrically conductive fine powder of tin oxide |
| JPS61205625A (en) * | 1985-03-11 | 1986-09-11 | Fuji Photo Film Co Ltd | Production of electrically conductive fine powder of tin oxide |
| JPS61205623A (en) * | 1985-03-11 | 1986-09-11 | Fuji Photo Film Co Ltd | Production of electrically conductive fine powder of tin oxide |
| CN1528830A (en) * | 2003-10-21 | 2004-09-15 | 中国科学院上海硅酸盐研究所 | Antimony-doped tin anhydride inorganic nano conductive powder preparing method |
-
2011
- 2011-06-16 CN CN2011101624352A patent/CN102285683A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61205624A (en) * | 1985-03-11 | 1986-09-11 | Fuji Photo Film Co Ltd | Production of electrically conductive fine powder of tin oxide |
| JPS61205622A (en) * | 1985-03-11 | 1986-09-11 | Fuji Photo Film Co Ltd | Production of electrically conductive fine powder of tin oxide |
| JPS61205625A (en) * | 1985-03-11 | 1986-09-11 | Fuji Photo Film Co Ltd | Production of electrically conductive fine powder of tin oxide |
| JPS61205623A (en) * | 1985-03-11 | 1986-09-11 | Fuji Photo Film Co Ltd | Production of electrically conductive fine powder of tin oxide |
| CN1528830A (en) * | 2003-10-21 | 2004-09-15 | 中国科学院上海硅酸盐研究所 | Antimony-doped tin anhydride inorganic nano conductive powder preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 徐甲强，张海林，李超，樊彦良: "氧化锡的硝酸氧化法制备及其性能研究", 《电池工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108190943A (en) * | 2018-04-02 | 2018-06-22 | 郑州大学 | A kind of method that metallic tin oxidation prepares nano-stannic oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Experimental and first-principles thermodynamic study of the formation and effects of vacancies in layered lithium nickel cobalt oxides | |
| CN104815983B (en) | A kind of carbon cladding nickel oxide/metallic nickel and simple method for synthesizing thereof | |
| CN104261472B (en) | A kind of vanadic anhydride nanobelt and normal temperature synthesis method and application | |
| Ahmad et al. | Hydrothermally grown SnO2 flowers as efficient electrode modifier for simultaneous detection of catechol and hydroquinone | |
| CN102874874B (en) | Application of multistage-structured flower-shaped molybdenum trioxide | |
| CN101597086A (en) | Method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution | |
| CN111056566A (en) | Preparation method of tin dioxide nano material, product and application thereof | |
| CN102702518A (en) | Method for preparing composite material of stannic oxide/polyaniline | |
| CN104201340A (en) | Preparation method of lithium ion battery material lithium vanadate | |
| Li et al. | Novel neuron-network-like Cu–MoO2/C composite derived from bimetallic organic framework for highly efficient detection of hydrogen peroxide | |
| CN101665235B (en) | Method for preparing n-type doped zinc oxide nanometer powder | |
| CN106896151A (en) | A kind of preparation method for detecting the cupric oxide chemically modified electrode of glucose | |
| CN106082306A (en) | A kind of aluminum-doped zinc oxide nanometer powder and microwave-assisted preparation method thereof and application | |
| CN103746108A (en) | Preparation method of lithium ion battery positive electrode material doped with hollow nickel lithium manganate structure | |
| CN113403631B (en) | Granular CuCo-MOF/MoS 2 Catalyst, preparation method and application thereof | |
| CN102285683A (en) | Synthesis method of stibium-doped stannic oxide electroconductive powder material | |
| CN105206816B (en) | A kind of preparation method of nickel sulfide graphene nanocomposite material | |
| CN109371263A (en) | Preparation method of copper-gallium alloy and silver-gallium alloy | |
| CN101708820A (en) | Method for manufacturing nano antimony doped tin oxide | |
| Wang et al. | Growth of Ni5P4/Ni2P/C nanosheet arrays on ITO as dual-function electrochemical sensor for efficient Cu2+ and paracetamol detection | |
| CN111912887B (en) | Preparation method of photoelectrochemical ofloxacin aptamer sensor based on hydrotalcite/graphite-like phase carbon nitride heterojunction | |
| Cao et al. | Triple-Mode Sensor Coupled by Photoelectrochemical, Electrochromic, and Spectral Signals for Sensitive Visualized Detection of Nonylphenol | |
| Wang et al. | Antiperovskite FeNNi2Co and FeNNi3 nanosheets as a non-enzymatic electrochemical sensor for highly sensitive detection of glucose | |
| CN103641157A (en) | Method for preparing low-resistance nanometer powder | |
| CN103242041B (en) | Preparing method for high-thermal expansion coefficient tungstic acid Zr-Na powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111221 |