CN110644013B - Indium oxide and preparation method of precursor thereof - Google Patents
Indium oxide and preparation method of precursor thereof Download PDFInfo
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- CN110644013B CN110644013B CN201911049085.1A CN201911049085A CN110644013B CN 110644013 B CN110644013 B CN 110644013B CN 201911049085 A CN201911049085 A CN 201911049085A CN 110644013 B CN110644013 B CN 110644013B
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Abstract
The invention provides a preparation method of indium oxide and a precursor thereof, belonging to the technical field of inorganic materials. According to the invention, metal indium is used as an anode, an inert electrode is used as a cathode, an ammonium salt aqueous solution is used as an electrolyte for electrolysis, and hydrogen peroxide is added during electrolysis to obtain indium hydroxide, so that nitrite or nitrogen oxide generated by nitrate reduction is avoided, and the preparation process is more environment-friendly; the anolyte circularly flows between the anode chamber and the anolyte storage tank, and the catholyte flows from the catholyte storage tank, flows through the cathode chamber and then flows to the anolyte storage tank, NH4 +The cation selective permeation membrane is diffused from the anode chamber to the cathode chamber, so that the stability of the anolyte and the catholyte is ensured, the follow-up stable obtaining of the nano indium oxide powder with uniform granularity is well guaranteed, the zero discharge of waste gas and waste water is easy to realize, meanwhile, the anolyte can still guarantee the normal operation of a system under higher solid content, the process efficiency is improved, the capacity is enlarged, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and relates to a preparation method of indium oxide and a precursor thereof.
Background
Indium oxide (In)2O3) The N-type transparent semiconductor material is a novel n-type transparent semiconductor functional material, and has the advantages of wider forbidden band width, smaller resistivity and higher catalytic activity. An ITO (Indium tin oxide) film formed by sputtering an ITO target material manufactured by using the same has superior optical and electrical properties, and is widely used in Flat Panel Display (FPD) industries, including products such as Liquid Crystal Displays (LCDs), Touch panels (Touch panels), Plasma Display Panels (PDPs), solar cells, functional glass and the like.
Indium oxide is generally prepared by chemical precipitation. The chemical precipitation method generally dissolves indium into an indium salt solution, the indium salt solution is mixed with alkali liquor under certain conditions to produce a precursor of indium oxide, and the precursor is washed, dried and calcined to obtain indium oxide powder.
Patent CN106044849B reports a process for preparing nano metal oxide powder by using arc plasma, but has the disadvantages of large equipment investment and incomplete metal oxidation.
At present, there are also reports of preparing indium oxide by an electrolytic method, for example, patent CN107935026A reports a method and an apparatus for preparing nano indium oxide by an electrolytic method, in which a mixed solution of ammonium nitrate and ammonium polyacrylate is used as an electrolyte to prepare indium hydroxide, an anode is used as high-purity metal indium, a cathode is used as graphite, the anode and the cathode are alternately arranged, the electrolytic process is performed in the presence of ultrasonic waves, and the indium hydroxide obtained by electrolysis is calcined at a high temperature to obtain nano indium oxide; patent TW201529479A reports a method for producing indium hydroxide powder by electrolysis, in which indium hydroxide powder is produced by electrolysis using ammonium nitrate as an electrolyte and using indium metal as an anode and a cathode having a mesh-like main surface portion. In the two methods for preparing indium oxide by electrolysis, the cathode is subjected to nitrate radical reduction reaction, so that waste water and waste gas such as nitrogen oxide, nitrite and the like are generated.
Disclosure of Invention
In order to overcome the above disadvantages and shortcomings of the prior art, the present invention provides a method for preparing indium oxide and a precursor thereof, so as to reduce production cost, improve productivity, protect environment during the process, and obtain indium oxide powder with good characteristics.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect, the invention provides a method for preparing an indium oxide precursor, which comprises the steps of electrolyzing metal indium serving as an anode, an inert electrode serving as a cathode and an ammonium salt aqueous solution serving as an electrolyte, and adding hydrogen peroxide into an electrolytic cell while electrolyzing to obtain the indium oxide precursor, wherein the indium oxide precursor is indium hydroxide. The preparation method of the indium oxide precursor has the following electrolytic reactions:
an anode region: in → In3++3e
In3++2H2O→In(OH)3+3H+；
A cathode region: h2O2+2H++2e→2H2O；
The reduction potential of the hydrogen peroxide is far higher than that of the nitrate radical, so that the hydrogen peroxide preferentially obtains electrons at the cathode to perform reduction reaction, nitrogen oxides and nitrite produced by reduction of the nitrate radical at the cathode are avoided, and the problem of environmental pollution caused by the nitrogen oxides and the nitrite is avoided.
As a preferable embodiment of the method for preparing an indium oxide precursor of the present invention, the method for preparing an indium oxide precursor employs a cation selective permeable membrane to divide the electrolytic cell into an anode chamber and a cathode chamber, the anode chamber is communicated with an anolyte storage tank, and the cathode chamber is communicated with a catholyte storage tank and an anolyte storage tank; during electrolysis, the hydrogen peroxide solution is added into the cathode chamber, the anolyte circularly flows between the anode chamber and the anolyte storage tank, and the catholyte flows through the cathode chamber from the catholyte storage tank and then flows to the anolyte storage tank. The preparation method of the indium oxide precursor adopts the same anolyte and catholyte, and the electrolysis reaction is as follows:
an anode region: in → In3++3e
In3++2H2O→In(OH)3+3H+
NH3·H2O+H+→NH4 ++H2O；
NH4 +→NH4 +(diffusion to the cathode chamber);
a cathode region: h2O2+2H++2e→2H2O
NH4 ++OH-→NH3·H2O；
In the course of electrolysis, NH4+By cation selectivityThe permeation membrane is diffused from the anode chamber to the cathode chamber to generate ammonia water with hydroxyl, and meanwhile, the stability of pH of anolyte and catholyte and the stability of electrolyte are ensured through the circulation flow of the anolyte, the mixing of the catholyte and the anolyte and the continuous supply of the catholyte, so that the good guarantee effect on the subsequent stable obtaining of the nano indium oxide powder with uniform granularity is achieved, the regulation and control of the characteristics of the nano indium oxide powder are easy to realize through multi-parameter regulation, the normal operation of a system can be still ensured under the condition of higher solid content, such as 3-12 wt%, of the anolyte, the process efficiency is improved, and the productivity is enlarged; meanwhile, the anolyte can still be used as anolyte and catholyte after solid-liquid separation, fresh electrolyte does not need to be replaced, the long-term continuous use of the electrolyte is ensured, and the production cost is reduced.
The thickness of the anode is ensured to ensure that the inter-polar distance does not change significantly as the electrolysis is carried out; the size of the anode is determined according to the production scale.
As a preferred embodiment of the method for producing an indium oxide precursor of the present invention, the anode is an indium plate having an effective electrolytic size of 200 × 80 × 15 mm.
As a preferred embodiment of the method for producing an indium oxide precursor of the present invention, the anode is produced by an automatic casting system.
As a preferred embodiment of the method for preparing an indium oxide precursor according to the present invention, the inert electrode is at least one of an aluminum plate, a stainless steel plate, a titanium plate, high-purity graphite, and a noble metal-coated or plated titanium electrode; in a further preferred embodiment of the method for producing an indium oxide precursor according to the present invention, the inert electrode is an aluminum plate.
As a preferred embodiment of the method for preparing an indium oxide precursor according to the present invention, the ammonium salt in the ammonium salt aqueous solution is at least one of ammonium nitrate, ammonium chloride, ammonium sulfate and ammonium acetate; as a further preferable embodiment of the method for producing an indium oxide precursor of the present invention, the ammonium salt in the ammonium salt aqueous solution is ammonium nitrate; in a more preferred embodiment of the method for producing an indium oxide precursor according to the present invention, the ammonium nitrate concentration in the ammonium salt aqueous solution is 0.2 to 2.5 mol/L. When the concentration of ammonium nitrate is lower than 0.2mol/L, the voltage is increased during electrolysis, so that the electrified part generates heat, and the power cost is increased; when the concentration of ammonium nitrate is higher than 2.5mol/L, the salt content of the slurry obtained by electrolysis is high, so that the water consumption for removing impurity salt in indium hydroxide is increased, the economy and environmental protection are not sufficient, and the obtained indium hydroxide powder is thick and uneven in particle size distribution.
As a preferred embodiment of the method for producing an indium oxide precursor of the present invention, the cation permselective membrane includes at least one of a proton membrane, a perfluorosulfonic acid ion membrane, and a perfluorocarboxylic acid sulfonic acid composite membrane.
In a preferred embodiment of the method for producing an indium oxide precursor according to the present invention, the hydrogen peroxide solution is fed to the cathode chamber at a rate of 0.023 to 0.038mol/(a · h) during the electrolysis. When the adding speed of the hydrogen peroxide is less than 0.023 mol/(A.h), nitrate radicals in a cathode area generate side reaction to generate nitrite and nitrogen oxide; when the adding speed of the hydrogen peroxide is more than 0.038 mol/(A.h), the utilization rate of the hydrogen peroxide is low, and the production cost is overhigh.
In a preferred embodiment of the method for producing an indium oxide precursor of the present invention, the circulation flow rate of the anolyte is 15 to 30L/(a · h). When the circulation flow speed of the anolyte is lower than 15L/(A.h), the diffusion speed of the interface layer solution cannot keep up with the electrolysis speed, the concentration polarization of the electrode surface is caused, the cell voltage is increased, and the power consumption is increased; when the circulation flow rate of the anolyte is higher than 30L/(a · h), unnecessary energy consumption occurs.
In a preferred embodiment of the method for producing an indium oxide precursor of the present invention, the flow rate of the catholyte is 0.02 to 0.06L/(a · h).
As a preferred embodiment of the method for producing an indium oxide precursor of the present invention, when the anolyte has a solid concentration of 3 to 12 wt%, it is subjected to solid-liquid separation, and the separated liquid can be used as an anolyte and a catholyte for the electrolysis. When the solid concentration of the anolyte is less than 3 wt%, the separation efficiency is low; when the solid concentration of the anolyte is higher than 12 wt%, the viscosity of the electrolyte may excessively increase, uniform diffusion in the electrolyte may be adversely affected, and precipitates may be formed in the pipe, adversely affecting the uniformity of the particle size of the product and the circulation of the anolyte.
As a preferable embodiment of the method for producing an indium oxide precursor of the present invention, the indium oxide precursor has a specific surface area of 70 to 90m2(g), the particle size distribution is uniform.
As a preferred embodiment of the method for preparing an indium oxide precursor of the present invention, the purity of the metal indium is not less than 99.99 wt%. In order to ensure that the prepared indium oxide can be used as a raw material of the ITO powder and avoid introducing impurities into indium hydroxide or indium oxide, the purity of the used metal indium cannot be lower than 99.99 wt%.
In a preferred embodiment of the method for producing an indium oxide precursor according to the present invention, the pH of the aqueous ammonium salt solution is 3.5 to 8.0. When the pH value of the ammonium salt aqueous solution is less than 3.5, the settling property of the indium hydroxide generated by electrolysis is poor; when the pH value of the ammonium salt aqueous solution is more than 8.0, the precipitation speed of the indium hydroxide is too high, so that the concentration of the anolyte is not uniform on one hand, and the indium hydroxide is directly precipitated on the other hand, so that the indium hydroxide has a wide particle size range and is not suitable as a raw material of ITO powder.
As a preferred embodiment of the method for producing an indium oxide precursor of the present invention, the electrode distance between the anode and the cathode is 10 to 40 mm. When the electrode distance is more than 40mm, the resistance between the cathode and the anode is increased, and the power consumption is increased; when the electrode pitch is less than 10mm, contact or short circuit between electrodes is likely to occur.
As a preferred embodiment of the method for preparing the indium oxide precursor of the present invention, the current density of the electrolysis is 400-1800A/m2. When the current density is less than 400A/m2In the process, the generation amount of indium hydroxide is reduced, and the productivity is lower; when the current density is more than 1800A/m2In the electrolysis, the cell voltage is significantly increased, the electrified part generates heat, and the energy consumption is increased.
In a preferred embodiment of the method for producing an indium oxide precursor of the present invention, the temperature of the electrolysis is 20 to 50 ℃. When the electrolysis temperature is lower than 20 ℃, the precipitation speed of the indium hydroxide becomes too slow; when the electrolysis temperature is higher than 50 ℃, the energy consumption is high, the electrolyte is seriously volatilized, the environment is not environment-friendly, and the precipitation speed of the indium hydroxide is too high, so that the particle size distribution is widened.
As a preferable embodiment of the method for producing an indium oxide precursor of the present invention, the indium oxide precursor is obtained by washing and drying a solid separated from the electrolyzed system; as a more preferable embodiment of the production method of an indium oxide precursor of the present invention, the washing is washing the solid with high purity water until the conductivity of the water after washing is < 1000 μ s/cm; as a more preferable embodiment of the method for producing an indium oxide precursor of the present invention, the drying is jacket vacuum drying; as a more preferable embodiment of the method for producing an indium oxide precursor of the present invention, the solid is separated from the electrolyzed system by filtration; as a further preferable embodiment of the method for preparing an indium oxide precursor of the present invention, the filtering, washing, and drying are performed in the same filtering and drying apparatus, so that introduction of impurities during the transferring process is avoided.
The second invention also provides a preparation method of indium oxide, which comprises the following steps: the indium hydroxide is prepared by the preparation method, and then the indium hydroxide is calcined to obtain the indium oxide.
As a preferred embodiment of the preparation method of the indium oxide, the calcination temperature is 600-1200 ℃ and the calcination time is 3-18 h.
In a preferred embodiment of the method for producing indium oxide of the present invention, the indium oxide is nano indium oxide.
As a preferred embodiment of the method for producing indium oxide of the present invention, the indium oxide has a specific surface area of 18 to 30m2/g。
As a preferable embodiment of the method for producing indium oxide of the present invention, the particle size of the indium oxide is 40 to 80 nm.
As a preferred embodiment of the method for producing indium oxide of the present invention, the indium oxide has a uniform particle size distribution.
The anolyte refers to liquid in the anode chamber, and the catholyte refers to liquid in the cathode chamber.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, electrons are preferentially obtained at the cathode by hydrogen peroxide to perform a reduction reaction, thereby avoiding the generation of nitrogen oxides and nitrite caused by the reduction of nitrate at the cathode and avoiding the problem of environmental pollution caused by the nitrogen oxides and the nitrite, and having good environmental protection property.
(2) The method can ensure the stability of the pH of the anolyte and the pH of the catholyte as well as the stability of the electrolyte, has good guarantee effect on stably obtaining the nano indium oxide powder with uniform granularity, is easy to realize the regulation and control of the characteristics of the nano indium oxide powder through the adjustment of multiple parameters, can still ensure the normal operation of a system under higher solid content, such as 3-12 wt%, improves the process efficiency and enlarges the productivity, and in addition, the electrolyte can be continuously used for a long time without changing fresh electrolyte, thereby reducing the production cost.
(3) Compared with the common hydrochloric acid system precipitation method, the nitric acid system precipitation method and the existing electrolysis method, the method has the advantages of low consumption of chemical reagents, no generation of nitrogen oxide gas, low wastewater yield and easy realization of zero discharge of waste gas and wastewater; meanwhile, the process route has high productivity and small equipment investment.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of indium oxide in example 1;
FIG. 2 is an electron micrograph of indium oxide in example 1;
FIG. 3 is an XRD pattern of indium oxide in example 2;
FIG. 4 is an electron micrograph of indium oxide in example 2;
FIG. 5 is an XRD pattern of indium oxide in example 3;
FIG. 6 is an electron micrograph of indium oxide in example 3;
FIG. 7 is an XRD pattern of indium oxide from example 4;
FIG. 8 is an electron micrograph of indium oxide in example 4;
FIG. 9 is an XRD pattern of indium oxide from example 5;
FIG. 10 is an electron micrograph of indium oxide in example 5.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
One embodiment of the method for producing indium oxide of the present invention. The electrolysis device adopted by the preparation method consists of 3 cathode chambers and 2 anode chambers, wherein the cathode chambers and the anode chambers are alternately arranged, proton membranes are arranged between the cathode chambers, the sizes of the anode chambers are 230X 40mm (2.1L), the sizes of the cathode chambers are 230X 20mm (1.05L), the volumes of the anolyte storage tanks are 60L, the volumes of the catholyte storage tanks are 30L, the anode chambers are communicated with the anolyte storage tanks, and the cathode chambers are communicated with the catholyte storage tanks and the anolyte storage tanks; the anode indium plates are all made of 4N elemental indium through an automatic casting system, the effective electrolysis size of the anode plates is 200 × 80 × 15mm, and the anode plates are alternately and parallelly arranged in each anode chamber; the cathode aluminum plates are alternately and parallelly arranged in each cathode chamber, the size of each cathode aluminum plate is 205 × 85 × 5mm, and the electrode spacing between the anode and the cathode is 10-40 mm; adding ammonium nitrate aqueous solution with pH value of 5.0-5.5 and concentration of 0.5mol/L into catholyte storage tank, anode chamber and cathode chamber, respectively, heating the anolyte and catholyte to 30 deg.C, switching on power supply, and setting current density at 400A/m2The anolyte is put between the anode chamber and the anolyte storage tank by 0.30m3The ammonium nitrate aqueous solution is conveyed to a cathode chamber from a catholyte storage tank at the speed of 0.6L/h, hydrogen peroxide is conveyed to the cathode chamber at the speed of 0.023 mol/(A.h), meanwhile, catholyte enters an anolyte storage tank through an overflow port of a cathode chamber, electrolysis is stopped until the solid content of anolyte is about 4 wt%, the anolyte is conveyed to a filtering, washing and drying integrated machine for treatment, wherein the filtered filtrate is returned to the anolyte storage tank and the catholyte storage tank for recycling, the filtered solid is washed firstly until the conductivity of the washed water is less than 1000 mu s/cm, and then is dried by a vacuum jacket to obtain the BET (specific surface area) of 85m2The indium oxide precursor is calcined for 18 hours at the temperature of 600 ℃ to obtain an indium oxide product with the particle size of 50-80nmBET of 18m2The XRD pattern is shown in figure 1, the electron microscope image is shown in figure 2, wherein the upper part of the abscissa in figure 1 is the XRD pattern of the indium oxide obtained in the embodiment, and the lower part of the abscissa is the XRD pattern of the indium oxide standard substance.
Example 2
One embodiment of the method for producing indium oxide of the present invention. The electrolysis device, the cathode and the anode adopted by the preparation method are the same as those in the embodiment 1; adding ammonium nitrate aqueous solution with pH value of 5.0-5.5 and concentration of 1.0mol/L into catholyte storage tank, anode chamber and cathode chamber, respectively, heating the anolyte and catholyte to 40 deg.C, switching on power supply, and setting current density at 800A/m2The anolyte is put between the anode chamber and the anolyte storage tank by 0.75m3The ammonium nitrate aqueous solution is conveyed to a cathode chamber from a cathode electrolyte storage tank at the speed of 1.5L/h, hydrogen peroxide is conveyed to the cathode chamber at the speed of 0.030 mol/(A.h), meanwhile, catholyte enters an anolyte storage tank through an overflow port of the cathode chamber, electrolysis is stopped until the solid content of anolyte is about 5 wt%, the anolyte is conveyed to a filtering, washing and drying integrated machine for treatment, wherein filtered filtrate is returned to the anolyte storage tank and the cathode electrolyte storage tank for recycling, filtered solid is washed firstly until the conductivity of the washed water is less than 1000 mu s/cm, and then a vacuum jacket is used for drying, so that the BET of 90m is obtained2The indium oxide precursor is calcined for 4 hours at 800 ℃ to obtain an indium oxide product, the particle size is 50-80nm, and the BET is 19m2The XRD pattern is shown in FIG. 3, the electron microscopic pattern is shown in FIG. 4, wherein the upper part of the abscissa in FIG. 3 is the XRD pattern of the indium oxide obtained in the present example, and the lower part of the abscissa is the XRD pattern of the indium oxide standard.
Example 3
One embodiment of the method for producing indium oxide of the present invention. The electrolysis device, the cathode and the anode adopted by the preparation method are the same as those in the embodiment 1; adding ammonium nitrate aqueous solution with pH of 4.0-4.5 and concentration of 2.5mol/L into catholyte storage tank, anode chamber and cathode chamber, respectively, heating the anolyte and catholyte to 40 deg.C, switching on power supply, and setting current density to 1800A/m2The anolyte is placed in the anode chamber and anolyte storage tankAt a spacing of 1.7m3The ammonium nitrate aqueous solution is conveyed to a cathode chamber from a cathode electrolyte storage tank at the speed of 3.0L/h, hydrogen peroxide is conveyed to the cathode chamber at the speed of 0.038 mol/(A.h), meanwhile, catholyte enters an anolyte storage tank through an overflow port of the cathode chamber, electrolysis is stopped until the solid content of anolyte is about 5 wt%, the anolyte is conveyed to a filtering, washing and drying integrated machine for treatment, wherein the filtered filtrate is returned to the anolyte storage tank and the cathode electrolyte storage tank for recycling, the filtered solid is washed firstly until the conductivity of the washed water is less than 1000 mu s/cm, and then the solid is dried by a vacuum jacket to obtain the BET of 88m2The indium oxide precursor is calcined for 3 hours at 1200 ℃ to obtain an indium oxide product, the particle size is 40-60nm, and the BET is 27m2The XRD pattern is shown in FIG. 5, the electron microscopic pattern is shown in FIG. 6, wherein the upper part of the abscissa in FIG. 5 is the XRD pattern of the indium oxide obtained in the present example, and the lower part of the abscissa is the XRD pattern of the indium oxide standard.
Example 4
One embodiment of the method for producing indium oxide of the present invention. The electrolysis device, the cathode and the anode adopted by the preparation method are the same as those in the embodiment 1; respectively adding ammonium nitrate aqueous solution with pH value of 3.5-4.0 and concentration of 0.2mol/L into catholyte storage tank, anode chamber and cathode chamber, heating the anolyte and catholyte to 50 deg.C, switching on power supply, and setting current density at 800A/m2The anolyte is put between the anode chamber and the anolyte storage tank by 0.6m3The ammonium nitrate aqueous solution is conveyed to a cathode chamber from a cathode electrolyte storage tank at the speed of 1.5L/h, hydrogen peroxide is conveyed to the cathode chamber at the speed of 0.028 mol/(A.h), meanwhile, catholyte enters an anolyte storage tank through an overflow port of the cathode chamber, electrolysis is stopped until the solid content of anolyte is about 3 wt%, the anolyte is conveyed to a filtering, washing and drying integrated machine for treatment, wherein the filtered filtrate is returned to the anolyte storage tank and the cathode electrolyte storage tank for recycling, the filtered solid is washed firstly until the conductivity of the washed water is less than 1000 mu s/cm, and then the solid is dried by a vacuum jacket to obtain the BET of 70m2Per gram of indium oxide precursor, calcining the indium oxide precursor at 1200 ℃ for 4h,obtaining indium oxide product with particle size of 50-80nm and BET of 18m2The XRD pattern is shown in figure 7, the electron microscope image is shown in figure 8, wherein the upper part of the abscissa in figure 7 is the XRD pattern of the indium oxide obtained in the embodiment, and the lower part of the abscissa is the XRD pattern of the indium oxide standard substance.
Example 5
One embodiment of the method for producing indium oxide of the present invention. The electrolysis device, the cathode and the anode adopted by the preparation method are the same as those in the embodiment 1; adding ammonium nitrate aqueous solution with pH value of 7.5-8.0 and concentration of 1.5mol/L into catholyte storage tank, anode chamber and cathode chamber, respectively, heating the anolyte and catholyte to 40 deg.C, switching on power supply, and setting current density at 800A/m2The anolyte is put between the anode chamber and the anolyte storage tank by 0.7m3The ammonium nitrate aqueous solution is conveyed to a cathode chamber from a cathode electrolyte storage tank at the speed of 0.5L/h, hydrogen peroxide is conveyed to the cathode chamber at the speed of 0.032 mol/(A.h), meanwhile, catholyte enters an anolyte storage tank through an overflow port of the cathode chamber, electrolysis is stopped until the solid content of anolyte is about 12 wt%, the anolyte is conveyed to a filtering, washing and drying integrated machine for treatment, wherein filtered filtrate is returned to the anolyte storage tank and the cathode electrolyte storage tank for recycling, filtered solid is washed firstly until the conductivity of the washed water is less than 100 mu s/cm, and then a vacuum jacket is used for drying, so that the BET of 85m is obtained, wherein the conductivity of the washed water is less than 100 mu s/cm2The indium oxide precursor is calcined for 4 hours at 800 ℃ to obtain an indium oxide product, the particle size is 20-80nm, and the BET is 30m2The XRD pattern is shown in figure 9, the electron microscope image is shown in figure 10, wherein the upper part of the abscissa in figure 9 is the XRD pattern of the indium oxide obtained in the embodiment, and the lower part of the abscissa is the XRD pattern of the indium oxide standard substance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. A preparation method of an indium oxide precursor is characterized in that metal indium is used as an anode, an inert electrode is used as a cathode, an ammonium salt aqueous solution is used as an electrolyte for electrolysis, hydrogen peroxide is added into an electrolytic tank during electrolysis to obtain the indium oxide precursor, and the indium oxide precursor is indium hydroxide; the electrolytic cell is divided into an anode chamber and a cathode chamber by adopting a cation selective permeable membrane, the anode chamber is communicated with an anolyte storage tank, and the cathode chamber is communicated with a catholyte storage tank; in the electrolysis process, the hydrogen peroxide is added into the cathode chamber, the anolyte circularly flows between the anode chamber and the anolyte storage tank, the catholyte flows through the cathode chamber from the catholyte storage tank and then flows into the anolyte storage tank, when the solid mass concentration of the anolyte is 3-12%, the anolyte is subjected to solid-liquid separation, and the separated liquid can be used as the anolyte and the catholyte for electrolysis; wherein the ammonium salt aqueous solution is ammonium nitrate aqueous solution with the pH value of 3.5-8.0 and the ammonium nitrate concentration of 0.2-2.5mol/L, the circulation flow speed of the anolyte is 15-30L/(A.h), the circulation flow speed of the catholyte is 0.02-0.06L/(A.h), the addition speed of the hydrogen peroxide is 0.023-0.038 mol/(A.h), and the current density of the electrolysis is 400-1800A/m2The electrolysis temperature is 20-50 ℃.
2. The method for producing an indium oxide precursor according to claim 1, wherein the inert electrode is at least one of an aluminum plate, a stainless steel plate, a titanium plate, high purity graphite, a noble metal-coated or noble metal-plated titanium electrode; the ammonium salt in the ammonium salt aqueous solution is at least one of ammonium nitrate, ammonium chloride, ammonium sulfate and ammonium acetate; the cation selective permeable membrane comprises at least one of a proton membrane, a perfluorosulfonic acid ion membrane and a perfluorocarboxylic acid sulfonic acid composite membrane.
3. The method for producing an indium oxide precursor according to claim 1, wherein the indium oxide precursor has a specific surface area of 70 to 90m2/g。
4. The method according to claim 1, wherein an electrode pitch between the anode and the cathode is 10 to 40 mm.
5. A preparation method of indium oxide is characterized by comprising the following steps: the indium oxide precursor is prepared by the method according to any one of claims 1 to 4, and then the indium oxide precursor is calcined to prepare the indium oxide.
6. The method for producing indium oxide according to claim 5, wherein the indium oxide has a specific surface area of 18 to 30m2(iv) per gram, particle size 40-80 nm.
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| JPH10204669A (en) * | 1997-01-16 | 1998-08-04 | Mitsubishi Materials Corp | Production of indium oxide powder |
| JP2014074224A (en) * | 2012-09-13 | 2014-04-24 | Sumitomo Metal Mining Co Ltd | Method for producing indium hydroxide powder, method for producing indium oxide powder, and spattering target |
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