Zinc antimonate-based conductive powder and preparation method thereof
By using Zn and Sb elements abundant in the Earth's crust as raw materials, and combining co-precipitation method and low-temperature sintering process, high-purity zinc antimonate-based conductive powder was prepared, which solved the problems of high cost, easy oxidation and poor dispersibility of existing conductive powders, and achieved low cost, high purity and good dispersibility.
Patent Information
- Application Number
- CN202511846460.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-09
- Publication Date
- 2026-02-13
AI Technical Summary
Existing metal powders have good conductivity but are expensive, easily oxidized, and have poor dispersibility. Carbon-based powders have good conductivity and stability but are difficult to disperse uniformly. Metal oxides, such as zinc oxide conductive powders, have moderate cost but insufficient high-temperature oxidation resistance.
Using abundant Zn and Sb elements from the Earth's crust as raw materials, high-purity zinc antimonate-based conductive powder was prepared by controlling its band gap and carrier concentration through doping modification, combined with co-precipitation method and low-temperature sintering process.
The preparation of low-cost, high-purity zinc antimonate-based conductive powder has been achieved, which has good conductivity and stability, easy control of doping concentration, and good dispersibility.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of powder materials, specifically relating to zinc antimonate-based conductive powder and its preparation method. Background Technology
[0002] Conductive powders, as functional fillers in materials such as plastics, coatings, fibers, and ceramics, can impart properties such as antistatic properties and electromagnetic shielding. Currently, commonly used conductive powders include metal-based powders, carbon-based powders, and metal oxide conductive powders.
[0003] While metal powders exhibit strong conductivity, they suffer from drawbacks such as high cost, susceptibility to oxidation, and poor corrosion resistance. Furthermore, their high density leads to sedimentation and agglomeration, resulting in poor dispersibility within a matrix. Carbon-based conductive powders, although possessing good conductivity and stability, are difficult to disperse uniformly, exhibit poor high-temperature oxidation resistance, and their dark color often makes them less desirable. Metal semiconductor oxides, such as indium oxide (In₂O₃), tin oxide (SnO₂), and zinc oxide (ZnO) conductive powders, have attracted widespread attention due to their high melting points, strong oxidation resistance, and moderate price. Given the abundant Zn and Sb reserves in the Earth's crust and their relatively low cost, the development of ZnSb₂O₆-based conductive powders holds significant application value. Summary of the Invention
[0004] The purpose of this invention is to provide a variety of low-cost zinc antimonate-based conductive powders and their preparation methods. Using Zn and Sb elements, which are abundant in the Earth's crust, as raw materials, the band gap, carrier concentration and mobility are controlled by doping modification. Combined with the "co-precipitation method + low-temperature sintering" process, high-purity conductive powders are prepared, which have the advantages of simple equipment, low cost and easy control of doping concentration.
[0005] The chemical formula of the zinc antimonate-based conductive powder is Zn. 0.92 In 0.08 Sb₂O₆, Zn 0.92 Ge 0.08 Sb₂O₆, Zn 0.92 Al 0.08 Sb₂O₆ or Zn 0.92 Sn 0.08 Sb2O6.
[0006] The preparation method of the zinc antimonate-based conductive powder includes the following steps:
[0007] (1) Using ZnCl2, InCl3 and SbCl3 as raw materials, weigh them into container A according to the molar ratio of Zn:In:Sb of 0.92:0.08:2, add deionized water and mix and stir until completely dissolved.
[0008] (2) Prepare a saturated solution of NH4HCO3 in container B using deionized water.
[0009] (3) The solution in container A is slowly added drop by drop to container B under strong stirring of the stirrer, and the dropping speed is controlled at about 1 drop / second. Strong stirring is maintained throughout the dropping process to obtain a precipitate with uniform particles.
[0010] (4) After the addition is complete, continue stirring the reaction system for 2 hours to allow the precipitate to age. Then, let the entire system stand in a water bath at 60°C for 12 hours to age.
[0011] (5) After the reaction is complete, perform vacuum filtration; wash the precipitate repeatedly with a large amount of deionized water and a small amount of anhydrous ethanol until no white precipitate is detected in the filtrate when tested with nitric acid-acidified AgNO3 solution.
[0012] (6) The precursor powder obtained after drying the wet filter cake of the precipitate is calcined in a calcining furnace at 800°C. After calcination, Zn can be obtained by pulverizing. 0.92 In 0.08 Sb2O6 conductive powder.
[0013] The second method for preparing the zinc antimonate-based conductive powder includes the following steps:
[0014] (1) Using ZnCl2, GeCl4 and SbCl3 as raw materials, weigh them into container A according to the molar ratio of Zn:Ge:Sb of 0.92:0.08:2, add deionized water and mix and stir until completely dissolved.
[0015] (2) Prepare a saturated solution of NH4HCO3 in container B using deionized water.
[0016] (3) The solution in container A is slowly added drop by drop to container B under strong stirring of the stirrer, and the dropping speed is controlled at about 1 drop / second. Strong stirring is maintained throughout the dropping process to obtain a precipitate with uniform particles.
[0017] (4) After the addition is complete, continue stirring the reaction system for 2 hours to allow the precipitate to age. Then, let the entire system stand in a water bath at 60°C for 12 hours to age.
[0018] (5) After the reaction is complete, perform vacuum filtration; wash the precipitate repeatedly with a large amount of deionized water and a small amount of anhydrous ethanol until no white precipitate is detected in the filtrate when tested with nitric acid-acidified AgNO3 solution.
[0019] (6) The precursor powder obtained after drying the wet filter cake of the precipitate is calcined in a calcining furnace at 800°C. After calcination, Zn can be obtained by pulverizing. 0.92 Ge 0.08 Sb2O6 conductive powder.
[0020] The preparation method of the zinc antimonate-based conductive powder, method three, includes the following steps:
[0021] (1) Using ZnCl2, AlCl3·6H2O and SbCl3 as raw materials, weigh them into container A according to the molar ratio of Zn:Al:Sb of 0.92:0.08:2, add deionized water and mix and stir until completely dissolved.
[0022] (2) Prepare a saturated solution of NH4HCO3 in container B using deionized water.
[0023] (3) The solution in container A is slowly added drop by drop to container B under strong stirring of the stirrer, and the dropping speed is controlled at about 1 drop / second. Strong stirring is maintained throughout the dropping process to obtain a precipitate with uniform particles.
[0024] (4) After the addition is complete, continue stirring the reaction system for 2 hours to allow the precipitate to age. Then, let the entire system stand in a water bath at 60°C for 12 hours to age.
[0025] (5) After the reaction is complete, perform vacuum filtration; wash the precipitate repeatedly with a large amount of deionized water and a small amount of anhydrous ethanol until no white precipitate is detected in the filtrate when tested with nitric acid-acidified AgNO3 solution.
[0026] (6) The precursor powder obtained after drying the wet filter cake of the precipitate is calcined in a calcining furnace at 800°C. After calcination, Zn can be obtained by pulverizing. 0.92 Al 0.08 Sb2O6 conductive powder.
[0027] The fourth method for preparing the zinc antimonate-based conductive powder includes the following steps:
[0028] (1) Using ZnCl2, SnCl4·5H2O and SbCl3 as raw materials, weigh them into container A according to the molar ratio of Zn:Sn:Sb of 0.92:0.08:2, add deionized water and mix and stir until completely dissolved.
[0029] (2) Prepare a saturated solution of NH4HCO3 in container B using deionized water.
[0030] (3) The solution in container A is slowly added drop by drop to container B under strong stirring of the stirrer, and the dropping speed is controlled at about 1 drop / second. Strong stirring is maintained throughout the dropping process to obtain a precipitate with uniform particles.
[0031] (4) After the addition is complete, continue stirring the reaction system for 2 hours to allow the precipitate to age. Then, let the entire system stand in a water bath at 60°C for 12 hours to age.
[0032] (5) After the reaction is complete, perform vacuum filtration; wash the precipitate repeatedly with a large amount of deionized water and a small amount of anhydrous ethanol until no white precipitate is detected in the filtrate when tested with nitric acid-acidified AgNO3 solution.
[0033] (6) The precursor powder obtained after drying the wet filter cake of the precipitate is calcined in a calcining furnace at 800°C. After calcination, Zn can be obtained by pulverizing. 0.92 Sn 0.08 Sb2O6 conductive powder. Detailed Implementation
[0034] The technical solution of the present invention and its beneficial effects compared with the prior art can be fully understood through the embodiments given below.
[0035] Example 1:
[0036] Weigh out 20g of ZnCl2 (4.20g), InCl3 (0.59g), and SbCl3 (15.28g) with a Zn:In:Sb molar ratio of 0.92:0.08:2. Take beaker A, add approximately 200mL of deionized water, then add the raw materials sequentially. Gently heat (<40℃) and stir magnetically until completely dissolved. Make up to a final volume of 250mL with deionized water and stir thoroughly. Take beaker B, add 200mL of deionized water, and slowly add 15g of NH4HCO3 while continuously stirring until completely dissolved, preparing a nearly saturated precipitant solution. Place beaker A on a magnetic stirrer and stir vigorously. Using a separatory funnel, slowly add the salt solution dropwise to the NH4HCO3 solution in beaker B. Control the dropping rate to approximately 1 drop / second, maintaining vigorous stirring throughout the addition process to ensure that the instantaneous supersaturation does not become too high, thus obtaining a uniformly precipitated particle. As the salt solution was added, a white flocculent precipitate was gradually observed to form. After the salt solution was completely added, the reaction system was stirred for another 2 hours to allow the precipitate to age. The entire system was then allowed to stand in a 60°C water bath for 12 hours. After the reaction was complete, the mixture was filtered. The precipitate was washed 5 times alternately with a large amount of deionized water (approximately 500 mL) and a small amount of anhydrous ethanol (until no white precipitate was detected in the filtrate using nitric acid-acidified AgNO3 solution).
[0037] The obtained wet filter cake was transferred to a petri dish and placed in a forced-air drying oven at 80℃ for 12 hours to obtain a dried precursor powder. 2g of the dried precursor powder was weighed and placed in a tube furnace. The calcination program was set as follows: the temperature was increased to 800℃ at a rate of 3℃ / min and held at this temperature for 3 hours. Oxygen was introduced at 420℃ with a flow rate of 1.5, and the oxygen was turned off when the temperature dropped to 600℃. The furnace was then cooled to room temperature. After calcination, the final product, In-doped zinc antimonate (Zn), was obtained. 0.92 In0.08 Sb2O6) is then dispersed using an air jet mill.
[0038] Example 2:
[0039] Weigh out 20g of ZnCl2 (4.21g), GeCl4 (0.64g), and SbCl3 (15.32g) as raw materials, with a Zn:Ge:Sb molar ratio of 0.92:0.08:2. Take beaker A and add approximately 200mL of deionized water. Add the raw materials sequentially, gently heat (<40℃), and stir magnetically until completely dissolved. Make up to 250mL with deionized water and stir thoroughly. Take beaker B and add 200mL of deionized water. While stirring continuously, slowly add 15g of NH4HCO3 until completely dissolved, preparing a nearly saturated precipitant solution. Place beaker A on a magnetic stirrer and stir vigorously. Using a separatory funnel, slowly add the salt solution dropwise to the NH4HCO3 solution in beaker B. Control the dropping rate to approximately 3 drops / second. Maintain vigorous stirring throughout the entire addition process to ensure that the instantaneous supersaturation does not become too high, thus obtaining a uniformly precipitated particle. As the salt solution was added, a white flocculent precipitate was gradually observed to form. After the salt solution was completely added, the reaction system was stirred for another 2 hours to allow the precipitate to age. The entire system was then allowed to stand in a 60°C water bath for 12 hours. After the reaction was complete, the mixture was filtered. The precipitate was washed five times alternately with a large amount of deionized water (approximately 500 mL) and a small amount of anhydrous ethanol.
[0040] The obtained wet filter cake was transferred to a petri dish and placed in a forced-air drying oven at 80°C for 12 hours to obtain a dried precursor powder. The dried precursor powder was then placed in a muffle furnace. The calcination program was set as follows: the temperature was increased to 800°C at a rate of 3°C / min and held at that temperature for 3 hours, then cooled to room temperature with the furnace. After calcination, the final product, Ge-doped zinc antimonate (Zn), was obtained. 0.92 Ge 0.08 Sb2O6) is then dispersed using an air jet mill.
[0041] Example 3:
[0042] Weigh out 20g of ZnCl2 (4.20g), AlCl3·6H2O (0.65g), and SbCl3 (15.28g) as raw materials, with a Zn:Al:Sb molar ratio of 0.92:0.08:2. Take beaker A, add approximately 200mL of deionized water, and then add the raw materials sequentially. Gently heat (<40℃) and stir magnetically until completely dissolved. Make up to a final volume of 250mL with deionized water and stir well. Next, take beaker B, add 200mL of deionized water, and slowly add 15g of NH4HCO3 while continuously stirring until completely dissolved, preparing a nearly saturated precipitant solution. Place beaker A on a magnetic stirrer and stir vigorously. Using a separatory funnel, slowly add the salt solution dropwise to the NH4HCO3 solution in beaker B, controlling the dropping rate to approximately 1 drop / second. Vigorous stirring was maintained throughout the dropwise addition process to ensure that the instantaneous supersaturation was not too high, thus obtaining a uniformly precipitated particle. As the salt solution was added, a white flocculent precipitate was gradually observed to form. After the salt solution was completely added, the reaction system was stirred for another 2 hours to allow the precipitate to age. The entire system was then allowed to stand in a 60°C water bath for 12 hours to age. After the reaction was complete, the mixture was filtered. The precipitate was washed five times alternately with a large amount of deionized water (approximately 500 mL) and a small amount of anhydrous ethanol (until no white precipitate was detected in the filtrate using nitric acid-acidified AgNO3 solution).
[0043] The obtained wet filter cake was transferred to a petri dish and placed in a forced-air drying oven at 80°C for 12 hours to obtain a dried precursor powder. 15g of the dried precursor powder was placed in a muffle furnace. The calcination program was set as follows: the temperature was increased to 800°C at a rate of 3°C / min and held at that temperature for 3 hours, then cooled to room temperature with the furnace. After calcination, the final product, Al-doped zinc antimonate (Zn), was obtained. 0.92 Al 0.08 Sb2O6) is then dispersed using an air jet mill.
[0044] Example 4:
[0045] Weigh out 20g of ZnCl2 (4.12g), SnCl4·5H2O (0.92g), and SbCl3 (14.96g) as raw materials, with a Zn:Sn:Sb molar ratio of 0.92:0.08:2. Take beaker A, add approximately 200mL of deionized water, and then add the raw materials sequentially. Gently heat (<40℃) and stir magnetically until completely dissolved. Make up to a final volume of 250mL with deionized water and stir well. Next, take beaker B, add 200mL of deionized water, and slowly add 15g of NH4HCO3 while continuously stirring until completely dissolved, preparing a nearly saturated precipitant solution. Place beaker A on a magnetic stirrer and stir vigorously. Using a separatory funnel, slowly add the salt solution dropwise to the NH4HCO3 solution in beaker B, controlling the dropping rate to approximately 1 drop / second. Vigorous stirring was maintained throughout the dropwise addition process to ensure that the instantaneous supersaturation was not too high, thus obtaining a uniformly precipitated particle. As the salt solution was added, a white flocculent precipitate was gradually observed to form. After the salt solution was completely added, the reaction system was stirred for another 2 hours to allow the precipitate to age. The entire system was then allowed to stand in a 60°C water bath for 12 hours to age. After the reaction was complete, the mixture was filtered. The precipitate was washed five times alternately with a large amount of deionized water (approximately 500 mL) and a small amount of anhydrous ethanol (until no white precipitate was detected in the filtrate using nitric acid-acidified AgNO3 solution).
[0046] The obtained wet filter cake was transferred to a petri dish and placed in a forced-air drying oven at 80°C for 12 hours to obtain a dried precursor powder. 15g of the dried precursor powder was placed in a muffle furnace. The calcination program was set as follows: the temperature was increased to 800°C at a rate of 3°C / min and held at that temperature for 3 hours, then cooled to room temperature with the furnace. After calcination, the final product, Sn-doped zinc antimonate (Zn), was obtained. 0.92 Sn 0.08 Sb2O6) is then dispersed using an air jet mill.
[0047] Sample performance testing:
[0048] The samples obtained in the examples were tested using the four-probe method. 1.5g of sample was weighed into a mold and pressed into a compact using a hydraulic press at 5MPa for 5 minutes. Simultaneously, the surface of the pressed sample was ensured to be flat and clean to avoid poor probe contact, and the probes were kept perpendicular to the sample surface to avoid probe tilting or spacing deviation. The resistivity of the samples after sintering is shown in the table below.
[0049] Example sample Resistivity (Ω·m) 1 <![CDATA[Zn 0.92 In 0.08 Sb2O6]]> 0.35 2 <![CDATA[Zn 0.92 Ge 0.08 Sb2O6]]> 26.54 3 <![CDATA[Zn 0.92 Al 0.08 Sb2O6]]> 8.49 4 <![CDATA[Zn 0.92 Sn 0.08 Sb2O6]]> 17.69
Claims
1. A zinc antimonate-based conductive powder, characterized in that, The chemical formula of the zinc antimonate-based conductive powder is Zn. 0.92 In 0.08 Sb₂O₆, Zn 0.92 Ge 0.08 Sb₂O₆, Zn 0.92 Al 0.08 Sb₂O₆ or Zn 0.92 Sn 0.08 Sb2O6.
2. A method for preparing zinc antimonate-based conductive powder, characterized in that, The method includes the following steps: (1) Using ZnCl2, InCl3 and SbCl3 as raw materials, weigh them into container A according to the molar ratio of Zn:In:Sb of 0.92:0.08:2, add deionized water and mix and stir until completely dissolved; (2) Prepare a saturated solution of NH4HCO3 in container B using deionized water; (3) The solution in container A is slowly added drop by drop to container B under strong stirring of the stirrer, and the dropping speed is controlled at about 1 drop / second. Strong stirring is maintained throughout the dropping process to obtain a precipitate with uniform particles. (4) After the addition is complete, continue to stir the reaction system for 2 hours to allow the precipitate to age. Then, let the entire system stand in a water bath at 60°C for 12 hours to age. (5) After the reaction is complete, perform vacuum filtration; wash the precipitate repeatedly with a large amount of deionized water and a small amount of anhydrous ethanol until no white precipitate is detected in the filtrate when tested with nitric acid-acidified AgNO3 solution. (6) The precursor powder obtained after drying the wet filter cake of the precipitate is calcined in a calcining furnace. After calcination, Zn can be obtained by pulverizing. 0.92 In 0.08 Sb2O6 conductive powder.
3. A method for preparing zinc antimonate-based conductive powder, characterized in that, The method includes the following steps: (1) Using ZnCl2, GeCl4 and SbCl3 as raw materials, weigh them into container A according to the molar ratio of Zn:Ge:Sb of 0.92:0.08:2, add deionized water and mix and stir until completely dissolved; (2) Prepare a saturated solution of NH4HCO3 in container B using deionized water; (3) The solution in container A is slowly added drop by drop to container B under strong stirring of the stirrer, and the dropping speed is controlled at about 1 drop / second. Strong stirring is maintained throughout the dropping process to obtain a precipitate with uniform particles. (4) After the addition is complete, continue to stir the reaction system for 2 hours to allow the precipitate to age. Then, let the entire system stand in a water bath at 60°C for 12 hours to age. (5) After the reaction is complete, perform vacuum filtration; wash the precipitate repeatedly with a large amount of deionized water and a small amount of anhydrous ethanol until no white precipitate is detected in the filtrate when tested with nitric acid-acidified AgNO3 solution. (6) The precursor powder obtained after drying the wet filter cake of the precipitate is calcined in a calcining furnace. After calcination, Zn can be obtained by pulverizing. 0.92 Ge 0.08 Sb2O6 conductive powder.
4. A method for preparing zinc antimonate-based conductive powder, characterized in that, The method includes the following steps: (1) Using ZnCl2, AlCl3·6H2O and SbCl3 as raw materials, weigh them into container A according to the molar ratio of Zn:Al:Sb of 0.92:0.08:2, add deionized water and mix and stir until completely dissolved; (2) Prepare a saturated solution of NH4HCO3 in container B using deionized water; (3) The solution in container A is slowly added drop by drop to container B under strong stirring of the stirrer, and the dropping speed is controlled at about 1 drop / second. Strong stirring is maintained throughout the dropping process to obtain a precipitate with uniform particles. (4) After the addition is complete, continue to stir the reaction system for 2 hours to allow the precipitate to age. Then, let the entire system stand in a water bath at 60°C for 12 hours to age. (5) After the reaction is complete, perform vacuum filtration; wash the precipitate repeatedly with a large amount of deionized water and a small amount of anhydrous ethanol until no white precipitate is detected in the filtrate when tested with nitric acid-acidified AgNO3 solution. (6) The precursor powder obtained after drying the wet filter cake of the precipitate is calcined in a calcining furnace. After calcination, Zn can be obtained by pulverizing. 0.92 Al 0.08 Sb2O6 conductive powder.
5. A method for preparing zinc antimonate-based conductive powder, characterized in that, The method includes the following steps: (1) Using ZnCl2, SnCl4·5H2O and SbCl3 as raw materials, weigh them into container A according to the molar ratio of Zn:Sn:Sb of 0.92:0.08:2, add deionized water and mix and stir until completely dissolved; (2) Prepare a saturated solution of NH4HCO3 in container B using deionized water; (3) The solution in container A is slowly added drop by drop to container B under strong stirring of the stirrer, and the dropping speed is controlled at about 1 drop / second. Strong stirring is maintained throughout the dropping process to obtain a precipitate with uniform particles. (4) After the addition is complete, continue to stir the reaction system for 2 hours to allow the precipitate to age. Then, let the entire system stand in a water bath at 60°C for 12 hours to age. (5) After the reaction is complete, perform vacuum filtration; wash the precipitate repeatedly with a large amount of deionized water and a small amount of anhydrous ethanol until no white precipitate is detected in the filtrate when tested with nitric acid-acidified AgNO3 solution. (6) The precursor powder obtained after drying the wet filter cake of the precipitate is calcined in a calcining furnace. After calcination, Zn can be obtained by pulverizing. 0.92 Sn 0.08 Sb2O6 conductive powder.