CN116216769B - Method for preparing high-purity gallium oxide by metal gallium hydrolysis method - Google Patents
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 50
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 26
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 19
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 230000009467 reduction Effects 0.000 claims abstract description 27
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000006260 foam Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000010924 continuous production Methods 0.000 abstract description 3
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- 238000006722 reduction reaction Methods 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 12
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 9
- 239000000413 hydrolysate Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 6
- -1 alkyl alcohol gallium salt Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000002258 gallium Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- VYNJXUWQBOFNDH-UHFFFAOYSA-K gallium;azane;hydrogen sulfate;sulfate Chemical compound N.[Ga+3].OS([O-])(=O)=O.[O-]S([O-])(=O)=O VYNJXUWQBOFNDH-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparing high-purity gallium oxide by a metal gallium hydrolysis method, and belongs to the technical field of metal oxide material preparation. Adding a gallium simple substance and a surfactant into electrolytic reduction water, and uniformly stirring to obtain a reaction system; at 70-100 deg.c and 4000-8000 rpm, gallium metal is dispersed into fine particles and reacted with electrolytic reduced water to produce GaOOH. GaOOH is wrapped and clamped on the floating foam generated by the surfactant and is discharged to the upper layer of the liquid, the floating foam is collected, pure water is used for cleaning, and GaOOH crystal is obtained after drying. Heating GaOOH crystal to roasting temperature at constant speed, and roasting for 2-4 h to obtain high-purity Ga 2O3. The invention uses metal gallium simple substance as raw material, which can avoid the problem of gallium ion failure in the traditional process. The purity of the high-purity Ga 2O3 prepared by the method can reach 99.99 percent; raw materials can be continuously added in proportion, so that continuous production of high-purity Ga 2O3 is realized, and the production efficiency is greatly improved.
Description
Technical Field
The invention relates to a method for preparing high-purity gallium oxide (Ga 2O3) by a metal gallium hydrolysis method, belonging to the technical field of metal oxide material preparation.
Background
Ga 2O3 is used as a wide-bandgap semiconductor material, and the forbidden bandwidth is as high as 4.8 eV-4.9 eV; in addition, the high stability of Ga 2O3 in extreme environments makes it an alternative material for fourth generation semiconductors. In addition, ga 2O3 can also be used for preparing power devices, ultraviolet detectors, high-energy ray detectors and the like; meanwhile, the material can also be used as a substrate material of semiconductors such as GaN, znO and the like.
At present, the preparation method of Ga 2O3 comprises the following steps:
Firstly, gallium sulfate is generated by utilizing the reaction of gallium metal and sulfuric acid, then gallium sulfate and ammonium sulfate are polymerized and crystallized in aqueous solution to separate out gallium ammonium sulfate crystals, and finally, ga 2O3 is obtained by roasting. The method has the advantages of low purity requirement on raw materials, low reaction rate of gallium metal and acid and low production efficiency.
The alkyl alcohol gallium method utilizes the reaction of metal gallium and alkyl alcohol to generate alkyl alcohol gallium salt; and hydrolyzing the obtained alkyl alcohol gallium salt in an aqueous solution containing alkyl alcohol to generate GaOOH, and roasting to obtain Ga 2O3. The method has the advantages of environmental protection, but has the disadvantage of complex process.
The sol-gel method is to prepare GaOOH by utilizing the hydrolysis reaction of gallium salt (gallium halide, etc.), and then roasting to obtain Ga 2O3. The method has the advantages of high production efficiency, but has the disadvantages of difficult storage of raw materials (the gallium salt is deliquescent and needs to be stored under vacuum), easy failure and higher cost.
The hydrothermal method is to prepare GaOOH by using gallium ions and alkali under hydrothermal conditions, and then roasting to obtain Ga 2O3. The method has the advantages of high product purity, but has the defects that the hydrothermal method is operated intermittently in batches, continuous production cannot be realized, the production efficiency is low, and in addition, potential safety hazards exist in a high-pressure environment.
Disclosure of Invention
Aiming at the problems of easy failure of raw materials, complex process, low production efficiency and the like in the prior art, the invention provides a method for preparing high-purity gallium oxide Ga 2O3 by a gallium hydrolysis method, namely, utilizing gallium to react with electrolytic reduction water under the condition of high-speed stirring to generate GaOOH; gaOOH floats upwards along with the floating foam of the surfactant to realize the separation of GaOOH from the reaction system. Finally, gaOOH is washed and roasted to obtain the high-purity Ga 2O3.
The principle of the method for preparing high-purity Ga 2O3 by using the metal gallium hydrolysis method is as follows:
The reaction of the gallium metal and the water is oxidation-reduction reaction, and the water oxidizes the gallium metal into Ga 3+,Ga3+ to generate GaOOH sediment immediately when encountering OH - in the electrolytic reduction water; simultaneously, gallium metal reduces water into H 2;
The reaction is
Metallic gallium is oxidized to Ga 3+Ga-3e-→Ga3+
Ga 3+ generation GaOOH precipitated Ga 3++2OH-→GaOOH↓+H+
The water is reduced to H 2 2H2O+2e-→H2↑+2OH-
Total reactive 2Ga+4H 2O→2GaOOH+3H2 ≡
A method for preparing high-purity gallium oxide by a metal gallium hydrolysis method comprises the following specific steps:
(1) Adding a metal gallium simple substance and a surfactant into electrolytic reduction water, and uniformly mixing to obtain a reaction system;
(2) Heating the reaction system to boil to generate H 2 bubbles, and generating froth by the surfactant under the H 2 bubbles;
(3) At the temperature of 70-100 ℃ and the rotating speed of 4000-8000 rpm, the gallium metal is dispersed to form particles and is subjected to hydrolysis reaction with electrolytic reduced water to generate hydrolysate GaOOH, and the hydrolysate GaOOH is wrapped in the froth generated by the surfactant and is discharged to the upper layer of the liquid;
(4) Collecting floating foam on the upper layer of the liquid, cleaning with pure water, and drying to obtain GaOOH crystals;
(5) GaOOH the crystal is heated to the roasting temperature at a constant speed and then roasted for 2 to 5 hours to obtain the high-purity Ga 2O3.
The surfactant in the step (1) is PVP or CTAB, the pH value of the electrolytic reduction water is 8.5-11, and the electrolytic reduction water is prepared by a proton exchange membrane electrolyzer. The electrolytic reduced water is a product obtained by electrolyzing ultrapure water in a proton membrane electrolytic tank and then in a cathode tank. The pH requirement for producing electrolytically reduced water is greater than 8.5 because OH - is continuously accumulated at the cathode.
The electrolytic reduction water preparation mechanism is as follows:
under the action of an electric field, water is ionized into H + and OH -; the positively charged H + moves to the cathode through the proton exchange membrane, and then the electrons are changed into H 2 to be discharged. As the water is ionized, H - in the cathode region is consumed, resulting in OH - accumulating in the cathode region, thus obtaining electrolytically reduced water in the cathode region.
The reaction is
And (3) cathode: 2H 2O+2e-＝2OH-+H2 ≡;
Anode: 2H 2O-4e-＝4H++O2 ≡
The prepared electrolytic reduction water has no other cationic impurities and does not influence the final purity of the product.
The purity of the raw material gallium is 99.999%.
The purity of the product high-purity Ga 2O3 can reach 99.99 percent.
The solid-liquid ratio g of the gallium metal, the surfactant and the electrolytic reduction water in the step (1) is 30-50:1:1000-2000.
The uniform temperature rising rate of the step (5) is 2-8 ℃/min, the roasting temperature is 300-1000 ℃ and the roasting time is 2-5 h.
Preferably, the roasting temperature is 300-500 ℃, and the high-purity Ga 2O3 is alpha-Ga 2O3; roasting at 500-1000 ℃ and not including 500 ℃, and the high-purity Ga 2O3 is beta-Ga 2O3.
And (3) decomposing the residual active agent in GaOOH crystals in the step (5) into CO 2 gas in the roasting process, and overflowing the CO 2 gas without affecting the final purity of the product.
The beneficial effects of the invention are as follows:
(1) The raw material used in the invention is metallic gallium simple substance, which is easy to store and has lower cost; can solve the problem that the gallium salt is easy to deliquesce and lose efficacy in the traditional process.
(2) The surfactant plays a role of a dispersing agent and a role of a foaming agent in the reaction; the product GaOOH floats up with the surfactant froth to realize the separation of GaOOH from the reaction system.
(3) The invention is carried out under normal pressure, and the device is simple; the raw materials can be supplemented at any time in the production process, so that the high-efficiency continuous production of GaOOH is realized, and the GaOOH is roasted to obtain high-purity alpha-Ga 2O3 or beta-Ga 2O3.
(3) In the metal gallium hydrolysis process, electrolytic reduction water is adopted, other cations and other impurities are not introduced, and the purification process is omitted; and the electrolytic reduced water can be self-degraded, and no harmful substances are produced.
Drawings
FIG. 1 is an XRD pattern of product GaOOH from examples 1-3;
FIG. 2 is an SEM image of the product GaOOH of examples 1-3;
FIG. 3 is an XRD pattern of the product α -Ga 2O3 of examples 1-3;
FIG. 4 is an SEM image of the product α -Ga 2O3 of examples 1-3;
FIG. 5 is an XRD pattern of the product β -Ga 2O3 of examples 4-6;
FIG. 6 is an SEM image of the product β -Ga 2O3 of examples 4-6.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: a method for preparing high-purity gallium oxide by a metal gallium hydrolysis method comprises the following specific steps:
(1) Adding gallium metal and a surfactant (PVP) into electrolytic reduction water, and uniformly mixing to obtain a reaction system; wherein the electrolytic reduction water is prepared by a proton exchange membrane electrolytic tank, the pH value of the electrolytic reduction water is 8.5, and the solid-to-liquid ratio g of gallium, surfactant (PVP) and the electrolytic reduction water is 30:1:1000;
(2) Heating the reaction system to boil to generate H 2 bubbles, and generating froth by a surfactant (PVP) under the H 2 bubbles;
(3) At the temperature of 70 ℃ and the rotating speed of 4000rpm, the gallium metal is dispersed to form particles with the diameter of less than 10 mu m and is subjected to hydrolysis reaction with electrolytic reduced water to generate hydrolysate GaOOH, and the hydrolysate GaOOH is wrapped in floating foam generated by a surfactant (PVP) and is discharged to the upper layer of the liquid;
(4) Collecting floating foam on the upper layer of the liquid, cleaning with pure water, and drying to obtain GaOOH crystals;
The XRD pattern of product GaOOH in this example is shown in FIG. 1, and the SEM pattern of product GaOOH is shown in FIG. 2; as can be seen from fig. 1 and 2, product GaOOH was successfully prepared, gaOOH was a monoclinic crystal cluster, and the yield of product GaOOH was about 86.2% by calculation;
(5) GaOOH the crystal is heated to 320 ℃ at a constant speed at a heating rate of 8 ℃/min, and then baked for 2 hours at constant temperature to obtain high-purity Ga 2O3;
XRD detection shows that the high-purity Ga 2O3 is carried out, the high-purity Ga 2O3 is alpha-Ga 2O3,α-Ga2O3, and the high-purity Ga is monoclinic crystal; the XRD pattern of product α -Ga 2O3 in this example is shown in FIG. 3, the SEM pattern of product α -Ga 2O3 is shown in FIG. 4,
The purity of the high purity alpha-Ga 2O3 of this example is 99.991%.
Example 2: a method for preparing high-purity gallium oxide by a metal gallium hydrolysis method comprises the following specific steps:
(1) Adding gallium metal and a surfactant (CTAB) into electrolytic reduction water, and uniformly mixing to obtain a reaction system; wherein the electrolytic reduction water is prepared by a proton exchange membrane electrolytic tank, the pH value of the electrolytic reduction water is 9, and the solid-to-liquid ratio g of gallium metal, a surfactant (CTAB) and the electrolytic reduction water is 40:1:1500;
(2) Heating the reaction system to boil to generate H 2 bubbles, and generating froth by a surfactant (CTAB) under the H 2 bubbles;
(3) At the temperature of 85 ℃ and the rotation speed of 6000rpm, the gallium metal is dispersed into particles with the diameter less than 5 mu m and is subjected to hydrolysis reaction with electrolytic reduced water to generate hydrolysate GaOOH, and hydrolysate GaOOH is wrapped in floating foam generated by a surfactant (CTAB) and is discharged to the upper layer of the liquid;
(4) Collecting floating foam on the upper layer of the liquid, cleaning with pure water, and drying to obtain GaOOH crystals;
the XRD pattern of product GaOOH in this example is shown in FIG. 1, and the SEM pattern of product GaOOH is shown in FIG. 2; as can be seen from fig. 1 and 2, product GaOOH was successfully prepared, gaOOH was a monoclinic crystal cluster, and the yield of product GaOOH was calculated to be about 88.7%;
(5) GaOOH the crystal is heated to the roasting temperature of 400 ℃ at a constant speed at a heating rate of 6 ℃/min, and then is roasted for 4 hours at constant temperature to obtain high-purity Ga 2O3;
XRD detection shows that the high-purity Ga 2O3 is carried out, the high-purity Ga 2O3 is alpha-Ga 2O3,α-Ga2O3, and the high-purity Ga is monoclinic crystal; the XRD pattern of product α -Ga 2O3 in this example is shown in FIG. 3, the SEM pattern of product α -Ga 2O3 is shown in FIG. 4,
The purity of the high purity alpha-Ga 2O3 of this example is 99.992%.
Example 3: a method for preparing high-purity gallium oxide by a metal gallium hydrolysis method comprises the following specific steps:
(1) Adding gallium metal and a surfactant (PVP) into electrolytic reduction water, and uniformly mixing to obtain a reaction system; wherein the electrolytic reduction water is prepared by a proton exchange membrane electrolytic tank, the pH value of the electrolytic reduction water is 10, and the solid-to-liquid ratio g of gallium, surfactant (PVP) and the electrolytic reduction water is 50:1:2000;
(2) Heating the reaction system to boil to generate H 2 bubbles, and generating froth by a surfactant (PVP) under the H 2 bubbles;
(3) At 98 ℃ and 8000rpm, metallic gallium disperses to form particles with the diameter less than 1 mu m and generates hydrolysis reaction with electrolytic reduced water to generate hydrolysate GaOOH, and hydrolysate GaOOH is wrapped in floating foam generated by surfactant (PVP) and is discharged to the upper layer of liquid;
(4) Collecting floating foam on the upper layer of the liquid, cleaning with pure water, and drying to obtain GaOOH crystals;
The XRD pattern of product GaOOH in this example is shown in FIG. 1, and the SEM pattern of product GaOOH is shown in FIG. 2; as can be seen from fig. 1 and 2, product GaOOH was successfully prepared, gaOOH was a monoclinic crystal cluster, and the yield of product GaOOH was about 92.5% by calculation;
(5) GaOOH the crystal is heated to the roasting temperature of 500 ℃ at a constant speed at a heating rate of 2 ℃/min, and then is roasted for 6 hours at constant temperature to obtain high-purity Ga 2O3;
XRD detection shows that the high-purity Ga 2O3 is carried out, the high-purity Ga 2O3 is alpha-Ga 2O3,α-Ga2O3, and the high-purity Ga is monoclinic crystal; the XRD pattern of product α -Ga 2O3 in this example is shown in FIG. 3, the SEM pattern of product α -Ga 2O3 is shown in FIG. 4,
The purity of the high purity alpha-Ga 2O3 in this example is 99.995%.
Example 4: a method for preparing high-purity gallium oxide by a metal gallium hydrolysis method comprises the following specific steps:
(1) GaOOH preparation of crystals: the preparation method of the GaOOH crystal of the embodiment is the same as that of the embodiment 1;
(2) GaOOH the crystal is heated to the roasting temperature of 600 ℃ at a constant speed at a heating rate of 8 ℃/min, and then is roasted for 2 hours at constant temperature to obtain high-purity Ga 2O3;
The XRD pattern of the product β -Ga 2O3 in this example is shown in FIG. 5, and the SEM pattern of the product β -Ga 2O3 is shown in FIG. 6. As can be seen from fig. 5 and 6, high purity Ga 2O3 is β -Ga 2O3,β-Ga2O3 is a monoclinic crystal. The surface of the beta-Ga 2O3 crystal has a large number of holes, the analysis holes are water vapor channels generated by GaOOH decomposition in the roasting process, and the reaction formula is: 2GaOOH →H 2O↑+Ga2O3.
The purity of the high purity beta-Ga 2O3 of this example is 99.992%.
Example 5: a method for preparing high-purity gallium oxide by a metal gallium hydrolysis method comprises the following specific steps:
(1) GaOOH preparation of crystals: the preparation method of the GaOOH crystal of the embodiment is the same as that of the embodiment 2;
(2) GaOOH the crystal is heated to the roasting temperature of 800 ℃ at a constant speed at a heating rate of 6 ℃/min, and then is roasted for 4 hours at constant temperature to obtain high-purity Ga 2O3;
The XRD pattern of the product β -Ga 2O3 in this example is shown in FIG. 5, and the SEM pattern of the product β -Ga 2O3 is shown in FIG. 6. As can be seen from fig. 5 and 6, high purity Ga 2O3 is β -Ga 2O3,β-Ga2O3 is a monoclinic crystal. The surface of the beta-Ga 2O3 crystal has a large number of holes, the analysis holes are water vapor channels generated by GaOOH decomposition in the roasting process, and the reaction formula is: 2GaOOH →H 2O↑+Ga2O3.
The purity of the high-purity beta-Ga 2O3 in the embodiment is 99.993%.
Example 6: a method for preparing high-purity gallium oxide by a metal gallium hydrolysis method comprises the following specific steps:
(1) GaOOH preparation of crystals: the preparation method of the GaOOH crystal of the embodiment is the same as that of the embodiment 2;
(2) GaOOH the crystal is heated to the roasting temperature of 1000 ℃ at a constant speed at a heating rate of 2 ℃/min, and then is roasted for 6 hours at constant temperature to obtain high-purity Ga 2O3;
The XRD pattern of the product β -Ga 2O3 in this example is shown in FIG. 5, and the SEM pattern of the product β -Ga 2O3 is shown in FIG. 6. As can be seen from fig. 5 and 6, high purity Ga 2O3 is β -Ga 2O3,β-Ga2O3 is monoclinic crystal; the surface of the beta-Ga 2O3 crystal has a large number of holes, the analysis holes are water vapor channels generated by GaOOH decomposition in the roasting process, and the reaction formula is: 2GaOOH →H 2O↑+Ga2O3.
The purity of the high purity beta-Ga 2O3 of this example is 99.996%.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (4)
1. A method for preparing high-purity gallium oxide by a metal gallium hydrolysis method is characterized in that a metal gallium simple substance and electrolytic reduction water are subjected to hydrolysis reaction under high-speed stirring to prepare GaOOH, and then roasting treatment is carried out to obtain high-purity Ga 2O3; the method comprises the following specific steps:
(1) Adding gallium metal and a surfactant into electrolytic reduction water, and uniformly stirring to obtain a reaction system; the pH value of the electrolytic reduction water is 8.5-11;
(2) The reaction system is heated to boiling and generates H 2 bubbles, and the surfactant generates froth under the H 2 bubbles;
(3) Dispersing gallium metal into particles at 70-100 ℃ and 4000-8000 rpm, and carrying out hydrolysis reaction with electrolytic reduction water to generate a hydrolysis product GaOOH, wherein the GaOOH is wrapped in the froth and discharged to the upper layer of the liquid;
(4) Collecting floating foam on the upper layer of the liquid, cleaning with pure water, and drying to obtain GaOOH crystals;
(5) Heating GaOOH to a roasting temperature at a constant speed, and roasting for 2-4 hours to obtain high-purity Ga 2O3; the roasting temperature is 300-1000 ℃ and the roasting time is 2-6 h; the roasting temperature is 300-500 ℃, and the high-purity Ga 2O3 is alpha-Ga 2O3; roasting at 500-1000 ℃ and not including 500 ℃, and the high-purity Ga 2O3 is beta-Ga 2O3.
2. The method for preparing high-purity gallium oxide by using a gallium metal hydrolysis method according to claim 1, wherein: the surfactant in the step (1) is PVP or CTAB.
3. The method for preparing high-purity gallium oxide by using a gallium metal hydrolysis method according to claim 1, wherein: the solid-liquid ratio g of the metal gallium simple substance, the surfactant and the electrolytic reduction water in the step (1) is 30-50:1:1000-2000.
4. The method for preparing high-purity gallium oxide by using a gallium metal hydrolysis method according to claim 1, wherein: the uniform temperature rising rate in the step (5) is 2-8 ℃/min.
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| CN110627112A (en) * | 2019-10-12 | 2019-12-31 | 成都中建材光电材料有限公司 | Preparation method and preparation device of high-purity gallium oxide |
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