CN114540826B - Method for preparing high-activity indium oxide by electrolytic method and method for preparing ITO target - Google Patents
Method for preparing high-activity indium oxide by electrolytic method and method for preparing ITO target Download PDFInfo
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Abstract
The invention provides a method for preparing high-activity indium oxide by an electrolytic method and a method for preparing an ITO target material, wherein the method for preparing the high-activity indium oxide by the electrolytic method comprises the following steps: (1) The metal indium is used as an anode, the conductive matrix is used as a cathode, and the ammonium nitrate aqueous solution is used as electrolyte for electrolysis to obtain indium hydroxide precipitate; the temperature is controlled between 25 ℃ and 45 ℃ and the current density is 15 to 20A/dm 2 The voltage is 0.35-0.45V; (2) Washing the indium hydroxide precipitate with water, press-filtering and drying to obtain indium hydroxide; (3) calcining. The preparation method of the ITO target comprises the following steps: 1) The indium oxide is prepared by adopting the method; 2) Mixing indium oxide and tin oxide uniformly, adding water for ball milling, and carrying out spray drying granulation to obtain powder; 3) Carrying out cold isostatic pressing on the powder; 4) And (5) sintering in an atmosphere. According to the invention, the high-activity indium oxide powder is prepared through an optimized preparation process, and then the high-density ITO target material can be obtained through mixing, ball milling, granulating and forming and atmosphere sintering of the high-activity indium oxide and tin oxide.
Description
Technical Field
The invention belongs to the technical field of ITO targets, and particularly relates to a method for preparing high-activity indium oxide by an electrolytic method and a preparation method of an ITO target.
Background
In 2 O 3 The ITO film is a novel n-type wide-band-gap semiconductor functional material, has a direct band gap in the range of 3.55-3.75 electron volts and an indirect band gap of 2.5 electron volts, has the characteristics of high conductivity, high visible light transmittance and the like, and has a very bright development prospect in the field of new materials. The ITO film has large-scale industrial application in the fields of flat panel display, photovoltaic solar energy, semiconductors, integrated circuits, aerospace and the like. As a means ofBasic link of later material research and development, nanometer In 2 O 3 The preparation of powders is very important.
The indium hydroxide powder produced by the electrolytic method is fine and easy to agglomerate, the particle size distribution amplitude of the agglomerated particles is widened, the particle structure of the powder in the subsequent calcination process is uncontrollable, and the preparation of the high-performance ITO target is limited.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects in the prior art, and provides a method for preparing high-activity indium oxide by an electrolytic method and a method for preparing an ITO target material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing high-activity indium oxide by an electrolytic method, which comprises the following steps:
(1) Carrying out electrolysis by taking metal indium as an anode, a conductive matrix as a cathode and an ammonium nitrate aqueous solution as an electrolyte to obtain indium hydroxide precipitate; in the electrolytic process, the temperature of the electrolyte is controlled between 25 ℃ and 45 ℃, and the current density of the electrolysis is 15-20A/dm 2 The voltage is 0.35-0.45V;
(2) Washing, press-filtering and drying the indium hydroxide precipitate in sequence to obtain indium hydroxide;
(3) And calcining the indium hydroxide to obtain indium oxide.
In the present invention, an anode and a cathode are immersed in an electrolyte to generate a potential difference between the two electrodes and generate a current, thereby dissolving an anode metal; the reactions occurring during electrolysis are as follows:
anode: in-3e=in 3+ ；
And (3) cathode: 3H (3H) 2 O+3e＝3OH - +3/2H 2 ↑
In the electrolytic process, the current and the voltage are controlled within the ranges, and the indium oxide with small and uniform particle size and high activity can be easily prepared by matching with a subsequent proper process. Meanwhile, the temperature of the electrolyte is controlled between 25 and 45 ℃, so that more uniform indium oxide particles can be obtained, and the overall yield is high. If the temperature of the electrolyte is too low, the precipitation speed of the indium hydroxide is slow, and the production efficiency is reduced; the electrolytic temperature is too high, the precipitation speed of indium hydroxide is too high, the ions are quickly aggregated, the obtained indium oxide particles are uneven, and the particle size distribution range is too wide. On the basis, when the indium hydroxide is calcined, the invention has short integral calcination time and low energy consumption.
Preferably, in the step (1), the concentration of the ammonium nitrate aqueous solution is 0.6-1.6 mol/L, and the pH value is 4-5. In the invention, when the concentration of ammonium nitrate is too low, the cell voltage can be increased in the electrolysis process, and the electricity consumption is high; the concentration of ammonium nitrate is too high, the salt content in the slurry is increased, and the water consumption is increased. When the pH value of the ammonium nitrate aqueous solution is lower than 4, the speed of generating indium hydroxide precipitation in the electrolytic process is lower; when the pH value is higher than 5, the production speed of indium hydroxide precipitation is higher, so that indium hydroxide precipitation is produced under the condition of uneven concentration, and the finally produced indium oxide has wider particle size distribution range. Furthermore, too high a pH will lead to immediate dissolution of the precipitate of indium hydroxide.
The conductive substrate is one of a titanium plate, a graphite plate, a platinum plate and a gold-plated plate. Further preferably, the conductive substrate is a titanium plate.
Preferably, the step (2) specifically includes the following steps: washing indium hydroxide precipitate with deionized water, press filtering, constant temperature drying at 100-120 deg.c for 4-8 hr, and vacuum drying at 80-100 deg.c for 3-5 hr. In the process of indium hydroxide precipitation drying, the indium hydroxide is dried under normal pressure and then is dried under vacuum, and the drying temperature of each stage is reasonably set, so that trace moisture in the powder can be effectively removed, the subsequent roasting of the powder is facilitated, and the performance of the obtained indium oxide is improved.
Preferably, in the step (3), the calcination temperature is 750-900 ℃, the heating rate is 8-10 ℃/10min, and the calcination time is 3-4 h. In the present invention, if the calcination temperature is set too low, the indium hydroxide powder cannot be dehydrated entirely to form indium oxide powder; the high calcination temperature can cause the growth and coarsening of the indium oxide fine particles just produced. The temperature rising rate is controlled to be 8-10 ℃/10min, so that the obtained indium oxide is finer under the condition of keeping the indium hydroxide powder completely dehydrated, and the uniformity of the indium oxide particles can be improved by strictly controlling the temperature rising rate in the calcining process.
Preferably, in the step (1), the anode and the cathode are disposed in an electrolytic tank, and a plurality of anodes and a plurality of cathodes are disposed in the electrolytic tank; the cathodes and the anodes are alternately arranged at intervals, and the interval distance between the cathodes and the anodes is 60-100 mm; the electrolyte is maintained in a circulating flow state in the electrolytic tank.
As a general inventive concept, the invention provides a preparation method of an ITO target, comprising the following steps:
1) Indium oxide (high-activity indium oxide) was prepared by the above method;
2) Mixing the indium oxide and the tin oxide uniformly, adding water for mixing and ball milling, and then carrying out spray drying granulation to obtain powder;
3) Performing cold isostatic pressing on the powder to obtain an ITO target biscuit;
4) Sintering the ITO target biscuit in atmosphere to obtain an ITO target; and no binder or dispersing agent is added in the process of preparing the ITO target.
The indium oxide obtained by the electrolysis process of the invention has no any organic binder and dispersant in the granulating and forming process of the ITO powder, and does not need degreasing links.
Preferably, in the step 2), the average particle diameter D50 of the tin oxide is 35 to 40nm; the mass ratio of the indium oxide to the tin oxide is (9-9.5) to (0.5-1). The invention selects tin oxide with proper particle size and has good matching effect with tin oxide.
Preferably, in the step 2), after water is added, the viscosity of the ball abrasive formed by indium oxide, tin oxide and water is 125-150 CPS; the ball milling temperature is 50-80 ℃, and the ball milling time is 6.5-8.5 h; in the ball milling process, parameters such as viscosity, temperature and the like of the ball grinding material are reasonably set, so that the particle size of powder (indium oxide and tin oxide) is further reduced, meanwhile, the particle size range distribution of the powder is narrowed, the ball milling process is more centralized and uniform, the sintering performance is improved, and the relative density of the ITO target is improved.
The spray drying granulation comprises the following specific steps: conveying the ball-milling material into a centrifugal sprayer for atomization, naturally falling in a cooling tower, controlling the granulating temperature to be 30-50 ℃ and controlling the rotating speed of a centrifugal machine to be 10000-12000 r/min. By the spray drying manufacturing process, powder with the average particle size of about 15-35 nm can be obtained, the whole particle size of the powder is uniform, the powder affinity is strong, the fluidity is good, and the subsequent cold isostatic pressing is facilitated.
Preferably, in the step 3), the pressure of the cold isostatic pressing is 180-250 MPa, the pressurizing speed is 6-10 MPa/min, and the holding time is 15-60 min. Further preferably, the dwell time is 30 to 60 minutes. Through the cold isostatic pressing process, the formed ITO target biscuit has higher relative density, and the pressure is uniformly transmitted by combining with proper pressurizing speed, so that the overall density is uniform.
Preferably, in the step 4), the sintering temperature of the atmosphere is 1400-1600 ℃, the heating rate is 50-70 ℃/h, the heat preservation time is 4-10 h, and the oxygen pressure is-0.02-0.04 MPa. More preferably, the oxygen pressure is 0 to 0.04MPa. When the ITO target biscuit obtained by cold isostatic pressing is sintered in the atmosphere, the temperature rising rate is 50-70 ℃/h, the densification speed is proper, few holes are generated, micro cracks are almost avoided, and the ITO target obtained by sintering has uniform overall density and high density.
Compared with the prior art, the invention has the beneficial effects that:
1. the high-activity indium oxide prepared by the electrolytic method has high purity and high activity, and the obtained nano indium oxide has uniform particle size, good particle shape and good specific surface area, and the average particle size is 18-30 nm.
2. The ITO target material prepared by the high-activity indium oxide prepared by the method does not need any organic adhesive or dispersing agent in the granulating and forming process of the ITO powder, does not need a degreasing link, and has the advantages of good fluidity and uniformity, good grain boundary stability, high grain boundary strength, high compactness, few pores, high density, high purity, good uniformity, high breaking strength and the like. The preparation method of the product is environment-friendly, reduces equipment investment by 40%, saves 50% of energy, and finally can prepare the high-end ITO target with the relative density of more than 99.95%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing BET test results of indium oxide prepared in example 1;
FIG. 2 is a diagram of the TIO target prepared in example 3 and the gold phase of the TIO target after corrosion experiments; wherein, (a) is a golden phase diagram of the TIO target prepared in example 3; (b) The ITO target is etched by hydrochloric acid and amplified to a gold phase diagram of 750X; (c) The ITO target is etched by hydrochloric acid and amplified to 7500X.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
a method for preparing high-activity indium oxide by an electrolytic method, which comprises the following steps:
1) Putting metal indium as an anode and a titanium plate as cathodes and anodes into an electrolytic tank, wherein the number of the anodes and the cathodes is 6, the cathodes and the anodes are alternately arranged at intervals, and the interval distance between the cathodes and the anodes is 100mm; taking an ammonium nitrate aqueous solution as an electrolyte, wherein the concentration of the ammonium nitrate aqueous solution is 0.8mol/L, and the pH value of the ammonium nitrate aqueous solution is adjusted to be 4; the anode and the cathode are communicated with electrolyte in the electrolytic tank in a contact way, and the electrolyte is kept in a circulating flow state in the electrolytic tank;
2) During electrolysis, the temperature of the electrolyte was maintained at about 28℃and the current density of the electrolyte was set at 18A/dm 2 The cell voltage is controlled at 0.4V;
3) After electrolysis for 24 hours, carrying out solid-liquid separation on the electrolyte and the obtained indium hydroxide precipitate, washing the obtained indium hydroxide precipitate by adopting deionized water, drying at the constant temperature of 120 ℃ for 6 hours after filter pressing, and then placing the obtained indium hydroxide precipitate into a vacuum drying oven for vacuum drying at 100 ℃ for 5 hours to obtain indium hydroxide;
4) Taking out indium hydroxide for calcination, wherein the calcination temperature is set to 850 ℃, the temperature rising rate is set to 10 ℃/10min, the calcination time is set to 3.5h, and the high-activity indium oxide powder is obtained, and has the advantages of 28nm average particle diameter, high activity, low impurity content and 99.99 percent purity.
As can be seen from FIG. 1, the BET specific surface area of the indium oxide prepared in example 1 was about 12.4788m 2 The specific surface area of the indium oxide was found to be good and the particle shape was found to be good.
Example 2:
a method for preparing high-activity indium oxide by an electrolytic method, which comprises the following steps:
1) Putting metal indium as an anode and a titanium plate as cathodes and anodes into an electrolytic tank, wherein the number of the anodes and the cathodes is 8, the cathodes and the anodes are alternately arranged at intervals, and the interval distance between the cathodes and the anodes is 80mm; taking an ammonium nitrate aqueous solution as an electrolyte, wherein the concentration of the ammonium nitrate aqueous solution is 1.5mol/L, and the pH value of the ammonium nitrate aqueous solution is adjusted to be 4.5; the anode and the cathode are communicated with electrolyte in the electrolytic tank in a contact way, and the electrolyte is kept in a circulating flow state in the electrolytic tank;
2) During electrolysis, the temperature of the electrolyte is maintained at about 40 ℃, and the current density of the electrolyte is set to be 18A/dm 2 The cell voltage is controlled at 0.4V;
3) After electrolysis for 24 hours, carrying out solid-liquid separation on the electrolyte and the obtained indium hydroxide precipitate, washing the obtained indium hydroxide precipitate by adopting deionized water, drying at a constant temperature of 100 ℃ for 5.5 hours after filter pressing, and then placing the obtained indium hydroxide precipitate into a vacuum drying oven for vacuum drying at 100 ℃ for 5 hours to obtain indium hydroxide;
4) Taking out indium hydroxide for calcination, wherein the calcination temperature is set to 900 ℃, the temperature rising rate is set to 8 ℃/10min, the calcination time is set to 3.5h, and the high-activity indium oxide powder is obtained, and has the advantages of 18nm average particle diameter, high activity, low impurity content and 99.99 percent purity.
Comparative example 1:
a method for preparing high-activity indium oxide by an electrolytic method is different from example 1 in that the temperature of the electrolyte is controlled to 55 ℃ and the current density of electrolysis is 50A/dm during the electrolytic process 2 The voltage was 1V. The remaining steps are identical to those of example 1.
The finally prepared indium oxide had an average particle diameter of 36nm and a purity of 99.70%, and the impurity content was high compared with example 1.
Comparative example 2:
unlike example 1, the concentration of the ammonium nitrate aqueous solution was 0.8mol/L, and the pH was adjusted to 6.5. The remaining steps are identical to those of example 1.
The finally prepared indium oxide had an average particle diameter of 38nm and a purity of 99.62% and an impurity content higher than that of example 1.
Example 3:
a preparation method of a high-performance ITO target comprises the following steps:
1) Uniformly mixing the indium oxide and tin oxide powder (average particle size is 40 nm) prepared in the example 2 according to a weight ratio of 9:1, adding a small amount of pure water for mixed ball milling, ensuring the viscosity of the mixture to be about 130CPS, controlling the ball milling temperature to be 70 ℃ and the ball milling time to be 7.5 hours;
2) Conveying the ball-milled mixture into a centrifugal sprayer for atomization, naturally falling in a cooling tower, controlling the granulating temperature to be 50 ℃, controlling the rotating speed of a centrifugal machine to be 11000r/min, and obtaining powder which is spherical, has an average particle size of about 20nm, is uniformly distributed and is not agglomerated;
3) Carrying out cold isostatic pressing on the powder to obtain an ITO target biscuit, wherein the pressure of the cold isostatic pressing is 200MPa, the pressurizing speed is 10MPa/min, and the pressure maintaining time is 0.5h; the relative density of the ITO target biscuit is about 76%;
4) And (3) sintering the ITO target biscuit in an atmosphere, wherein the oxygen atmosphere pressure is 0 (1 standard atmosphere), the sintering temperature is controlled at 1600 ℃, the heating rate is 50 ℃/h, and the heat preservation time is 5h, so that the ITO target with the relative density of 99.95% is prepared. And no adhesive or dispersing agent is required to be added in the process of preparing the ITO target.
Example 4:
a preparation method of a high-performance ITO target comprises the following steps:
1) Uniformly mixing the indium oxide and tin oxide powder (with the average particle size of 35 nm) prepared in the example 1 according to the weight ratio of 9.5:0.5, adding a small amount of pure water for mixed ball milling, ensuring the viscosity of the mixture to be about 140CPS, controlling the ball milling temperature to be 60 ℃, and controlling the ball milling time to be 7.5 hours;
2) Conveying the ball-milled mixture into a centrifugal sprayer for atomization, naturally falling in a cooling tower, controlling the granulating temperature to be 45 ℃, controlling the rotating speed of a centrifugal machine to be 12000r/min, and obtaining powder which is spherical, has an average particle size of about 18nm, and is uniformly distributed and not agglomerated;
3) Carrying out cold isostatic pressing on the powder to obtain an ITO target biscuit, wherein the pressure of the cold isostatic pressing is 220MPa, the pressurizing speed is 6MPa/min, and the pressure maintaining time is 1.0h; the relative density of the ITO target biscuit is 78.9%;
4) And sintering the ITO target biscuit in atmosphere, wherein the pressure of oxygen atmosphere is 0.02MPa, the sintering temperature is controlled at 1550 ℃, the heating rate is 70 ℃/h, the heat preservation time is 4.5h, and the relative density of the prepared ITO target is 99.96%. And no adhesive or dispersing agent is required to be added in the process of preparing the ITO target.
Comparative example 3:
a method for preparing a high-performance ITO target, unlike example 4, the indium oxide prepared in example 1 used was replaced with the indium oxide of comparative example 1. The remaining steps are identical to those of example 4.
The relative density of the finally prepared ITO target is 99.68%.
Comparative example 5:
the preparation method of the high-performance ITO target material is different from example 4 in that the ball milling temperature is room temperature and the ball milling time is 5 hours. The remaining steps are identical to those of example 4.
The relative density of the finally prepared ITO target is 99.86%.
Comparative example 6:
the preparation method of the high-performance ITO target material is different from example 4 in that in the atmosphere sintering, the heating rate is 100 ℃/h. The remaining steps are identical to those of example 4.
The relative density of the finally prepared ITO target is 99.75%.
Performance test:
the ITO target material prepared in example 3 was subjected to a corrosion test using hydrochloric acid as a solution. FIG. 2, wherein FIG. a is a gold phase diagram of an ITO target that has not been subjected to a corrosion resistance test; FIG. b is a gold phase diagram of the ITO target material after hydrochloric acid corrosion and amplification to 750X; fig. c is a gold phase diagram of the ITO target after hydrochloric acid etching and enlargement to 7500X. As can be seen from the graph a, the ITO target prepared by the method has good grain boundary stability, high grain boundary strength, high density and few pores from a crystal phase structure, and the ITO target prepared by the method has excellent corrosion resistance as can be seen from the graphs b and c.
Claims (7)
1. The preparation method of the ITO target is characterized by comprising the following steps of:
1) The method for preparing the high-activity indium oxide by an electrolytic method comprises the following steps:
(1) Carrying out electrolysis by taking metal indium as an anode, a conductive matrix as a cathode and an ammonium nitrate aqueous solution as an electrolyte to obtain indium hydroxide precipitate, wherein the concentration of the ammonium nitrate aqueous solution is 0.6-1.6 mol/L, and the pH value is 4-5; in the electrolytic process, the temperature of the electrolyte is controlled between 25 ℃ and 45 ℃, and the current density of the electrolysis is 15-20A/dm 2 The voltage is 0.35-0.45V;
(2) Washing, press-filtering and drying the indium hydroxide precipitate in sequence to obtain indium hydroxide;
(3) Calcining the indium hydroxide to obtain indium oxide;
2) Mixing the indium oxide and the tin oxide uniformly, adding water for mixing and ball milling, and then carrying out spray drying granulation to obtain powder; after water is added, the viscosity of the ball abrasive formed by indium oxide, tin oxide and water is 125-150 CPS; the ball milling temperature is 50-80 ℃, and the ball milling time is 6.5-8.5 h;
the spray drying granulation comprises the following specific steps: conveying the ball-milling material into a centrifugal sprayer for atomization, naturally falling in a cooling tower, controlling the granulating temperature to be 30-50 ℃ and controlling the rotating speed of a centrifugal machine to be 10000-12000 r/min;
3) Performing cold isostatic pressing on the powder to obtain an ITO target biscuit;
4) Sintering the ITO target biscuit in atmosphere to obtain an ITO target; no binder or dispersing agent is added in the process of preparing the ITO target; the atmosphere sintering temperature is 1400-1600 ℃, the heating rate is 50-70 ℃/h, the heat preservation time is 4-10 h, and the oxygen pressure is-0.02-0.04 MPa.
2. The method according to claim 1, wherein in the step (1), the conductive substrate is one of a titanium plate, a graphite plate, a platinum plate, and a gold-plated plate.
3. The preparation method according to claim 1, wherein the step (2) specifically comprises the steps of: washing indium hydroxide precipitate with deionized water, press filtering, constant temperature drying at 100-120 deg.c for 4-8 hr, and vacuum drying at 80-100 deg.c for 3-5 hr.
4. The method according to any one of claims 1 to 3, wherein in the step (3), the calcination temperature is 750 to 900 ℃, the temperature rise rate is 8 to 10 ℃/10min, and the calcination time is 3 to 4 hours.
5. A production method according to any one of claims 1 to 3, wherein in the step (1), an anode and a cathode are provided in an electrolytic cell in which a plurality of anodes and a plurality of cathodes are provided; the cathodes and the anodes are alternately arranged at intervals, and the interval distance between the cathodes and the anodes is 60-100 mm; the electrolyte is maintained in a circulating flow state in the electrolytic tank.
6. The method according to claim 1, wherein in the step 2), the average particle diameter D50 of the tin oxide is 35 to 40nm; the mass ratio of the active indium oxide to the tin oxide is (9-9.5) to (0.5-1).
7. The method according to claim 1 or 6, wherein in the step 3), the cold isostatic pressing is performed at a pressure of 180 to 250MPa, a pressing speed of 6 to 10MPa/min, and a dwell time of 15 to 30min.
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