CN117819612B - Preparation process of doped cobaltosic oxide - Google Patents
Preparation process of doped cobaltosic oxide Download PDFInfo
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- CN117819612B CN117819612B CN202410023789.6A CN202410023789A CN117819612B CN 117819612 B CN117819612 B CN 117819612B CN 202410023789 A CN202410023789 A CN 202410023789A CN 117819612 B CN117819612 B CN 117819612B
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- deionized water
- cobalt
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000001868 cobalt Chemical class 0.000 claims abstract description 54
- 239000008367 deionised water Substances 0.000 claims abstract description 46
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004094 surface-active agent Substances 0.000 claims abstract description 42
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004202 carbamide Substances 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- 238000003837 high-temperature calcination Methods 0.000 claims description 11
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 10
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 10
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000600 sorbitol Substances 0.000 claims description 10
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 150000001869 cobalt compounds Chemical class 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ADBMTWSCACVHKJ-UHFFFAOYSA-L cobalt(2+);hydrogen carbonate Chemical compound [Co+2].OC([O-])=O.OC([O-])=O ADBMTWSCACVHKJ-UHFFFAOYSA-L 0.000 description 1
- KAGOZRSGIYZEKW-UHFFFAOYSA-N cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Co+3].[Co+3] KAGOZRSGIYZEKW-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Abstract
The invention relates to a preparation process of doped cobaltosic oxide, and belongs to the technical field of doped cobalt compounds. The invention discloses a preparation process of doped cobaltosic oxide, which comprises the following steps: 1. mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved; 2. then adding soluble metal salt for pressurizing reaction, and filtering; 3. and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide. The surfactant improves the dispersibility in the preparation process of the cobaltosic oxide and prevents agglomeration among particles. The pore structure can be increased by adding ammonia water for drying, the specific surface area of the cobaltosic oxide is increased, and more active sites are formed. The invention can prepare the doped cobaltosic oxide with good dispersibility and high activity, and is applied to the fields of lithium ion batteries, super capacitors, gas sensors and the like.
Description
Technical Field
The invention belongs to the technical field of doped cobalt compounds, and relates to a preparation process of doped tricobalt tetraoxide.
Background
Cobalt oxide (Co 3O4) is black or gray black powder at normal temperature, co 3O4 with spinel structure is mixed oxide of cobalt oxide (CoO) and cobalt oxide (Co 2O3), has high oxygen content, has p-type semiconductor property, and has band gap width of 1.5-2.2eV. High spin Co 2+ occupies interstitial sites of tetrahedra, while low spin Co 3+ occupies interstitial sites of closely packed face centered cuboctahedra, the conductivity of which depends on the excess oxygen at Co vacancies or interstitial sites in the lattice. Co 3O4 is used as a potential multifunctional material and is widely applied to the fields of electrochemistry, magnetism, catalysis, energy storage and the like.
Meanwhile, co 3O4 has excellent catalytic activity and multi-valence performance, and also has unique advantages in the aspect of gas sensing. The grain size of the cobaltosic oxide material can directly influence the gas-sensitive performance of the cobaltosic oxide material, and the reduction of the grain size is an effective method for enhancing the gas-sensitive performance. But the agglomeration is easily generated due to the too small crystal size in the preparation process, thereby affecting the performance degradation.
The cobaltosic oxide nano material is usually obtained by a two-step method. Firstly, synthesizing precursor salt of cobaltosic oxide, such as cobalt carbonate, cobalt hydroxide or cobalt bicarbonate, etc. by a hydrothermal method or a precipitation method, and calcining the precursor at a certain temperature to obtain the cobaltosic oxide nano material. The Co 3O4 obtained in this way can keep the complete morphology of the precursor, if the precursor is decomposed to generate gas in the calcining process, the finally decomposed cobaltosic oxide nano material can form a micro-mesoporous structure, and the sensitivity of Yu Qi is improved.
Disclosure of Invention
The invention relates to a preparation process of doped cobaltosic oxide, and belongs to the technical field of doped cobalt compounds. The invention discloses a preparation process of doped cobaltosic oxide, which comprises the following steps: 1. mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved; 2. then adding soluble metal salt for pressurizing reaction, and filtering; 3. and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide. The surfactant improves the dispersibility in the preparation process of the cobaltosic oxide and prevents agglomeration among particles. The pore structure can be increased by adding ammonia water for drying, the specific surface area of the cobaltosic oxide is increased, and more active sites are formed. The invention can prepare the doped cobaltosic oxide with good dispersibility and high activity, and is applied to the fields of lithium ion batteries, super capacitors, gas sensors and the like.
The aim of the invention can be achieved by the following technical scheme:
a process for preparing doped tricobalt tetraoxide, comprising the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
A3: and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide.
Further, in the step A1, the cobalt salt is composed of cobalt sulfate heptahydrate and cobalt chloride hexahydrate in a mass ratio of 1:1, the mass ratio of the cobalt salt, urea, a surfactant and deionized water is 1-1.5:3-4:0.01-0.05:5-8, and the surfactant is composed of sorbitol and cetyltrimethylammonium bromide in a mass ratio of 1:1.
Further, the power and the temperature of the ultrasound in the step A1 are respectively 300-400W and 30-40 ℃.
Further, the soluble metal salt in the step A2 is at least one chloride or nitrate in K, li, al, cu, mg, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.005-0.015.
Further, the temperature and time of the reaction in the step A2 are 120-130 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
Further, the washing times in the step A3 are 4-6 times, the volume ratio of the ammonia water to the sediment is 1-1.5:3-5, and the concentration of the ammonia water is 25%.
Further, the heating in the step A3 means heating to 50-70 ℃, the drying time is 2-3h, and the high-temperature calcination temperature and time are respectively 250-350 ℃ and 2-2.5h.
The doped cobaltosic oxide is obtained by adopting the preparation process.
Further, the doped cobaltosic oxide is applied to the fields of lithium ion batteries, super capacitors and gas sensors.
The invention has the beneficial effects that:
1. The surfactants sorbitol and cetyl trimethyl ammonium bromide can form a more stable hydrophilic dispersion system, so that the dispersibility of the cobaltosic oxide in the preparation process is improved, and agglomeration among particles is prevented. The pore structure can be increased by adding ammonia water for drying, the specific surface area of the material can be increased by the pore structure, the active sites on the surface are increased, and meanwhile, a channel is provided for the transportation of gas, so that the response value and the response recovery speed of the material are improved. The invention can prepare the doped cobaltosic oxide with good dispersibility and high activity, and is applied to the fields of lithium ion batteries, super capacitors, gas sensors and the like.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific embodiments, structures, features and effects according to the present invention in conjunction with examples.
Example 1
A process for preparing doped tricobalt tetraoxide, comprising the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
A3: and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide.
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate in a mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1:3:0.01:5, and the surface activity consists of sorbitol and cetyltrimethylammonium bromide in a mass ratio of 1:1.
The power and the temperature of the ultrasonic wave in the step A1 are respectively 300W and 30 ℃.
The soluble metal salt in the step A2 is lithium nitrate, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.005.
The temperature and time of the reaction in the step A2 are 120 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
The washing times in the step A3 are 4 times, the volume ratio of the ammonia water to the sediment is 1:3, and the concentration of the ammonia water is 25%.
The heating in the step A3 is to heat to 50 ℃, the drying time is 2 hours, and the high-temperature calcination temperature and time are respectively 250 ℃ and 2 hours.
The doped cobaltosic oxide is obtained by adopting the preparation process.
The doped cobaltosic oxide is applied to a gas sensor.
Example 2
A process for preparing doped tricobalt tetraoxide, comprising the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
A3: and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide.
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate in a mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1:3:0.01:5, and the surface activity consists of sorbitol and cetyltrimethylammonium bromide in a mass ratio of 1:1.
The power and the temperature of the ultrasonic wave in the step A1 are respectively 350W and 35 ℃.
The soluble metal salt in the step A2 is potassium nitrate, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.01.
The temperature and time of the reaction in the step A2 are 125 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
The washing times in the step A3 are 4 times, the volume ratio of the ammonia water to the sediment is 1:4, and the concentration of the ammonia water is 25%.
The heating in the step A3 is to heat to 60 ℃, the drying time is 2.5h, and the high-temperature calcination temperature and time are 300 ℃ and 2h respectively.
The doped cobaltosic oxide is obtained by adopting the preparation process.
The doped cobaltosic oxide is applied to a gas sensor.
Example 3
A process for preparing doped tricobalt tetraoxide, comprising the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
A3: and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide.
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate in a mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1.5:4:0.05:8, and the surface activity consists of sorbitol and cetyltrimethylammonium bromide in a mass ratio of 1:1.
The power and the temperature of the ultrasonic wave in the step A1 are 400W and 40 ℃ respectively.
The soluble metal salt in the step A2 is aluminum nitrate, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.015.
The temperature and time of the reaction in the step A2 are 130 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
The washing times in the step A3 are 6 times, the volume ratio of the ammonia water to the sediment is 1.5:5, and the concentration of the ammonia water is 25%.
The heating in the step A3 is to heat to 70 ℃, the drying time is 3 hours, and the high-temperature calcination temperature and time are respectively 350 ℃ and 2.5 hours.
The doped cobaltosic oxide is obtained by adopting the preparation process.
The doped cobaltosic oxide is applied to a gas sensor.
Example 4
A process for preparing doped tricobalt tetraoxide, comprising the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
A3: and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide.
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate in a mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1.2:3.3:0.02:6, and the surface activity consists of sorbitol and cetyltrimethylammonium bromide in a mass ratio of 1:1.
The power and the temperature of the ultrasonic wave in the step A1 are 400W and 40 ℃ respectively.
The soluble metal salt in the step A2 is copper nitrate, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.01.
The temperature and time of the reaction in the step A2 are 120 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
The washing times in the step A3 are 4 times, the volume ratio of the ammonia water to the sediment is 1.4:4, and the concentration of the ammonia water is 25%.
The heating in the step A3 is to heat to 60 ℃, the drying time is 2.5h, and the high-temperature calcination temperature and time are respectively 350 ℃ and 2.5h.
The doped cobaltosic oxide is obtained by adopting the preparation process.
The doped cobaltosic oxide is applied to the fields of lithium ion batteries, supercapacitors and gas sensors.
Example 5
A process for preparing doped tricobalt tetraoxide, comprising the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
A3: and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide.
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate in a mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1.5:3:0.01:5, and the surface activity consists of sorbitol and cetyltrimethylammonium bromide in a mass ratio of 1:1.
The power and the temperature of the ultrasonic wave in the step A1 are 400W and 40 ℃ respectively.
The soluble metal salt in the step A2 is magnesium nitrate, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.008.
The temperature and time of the reaction in the step A2 are 130 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
The washing times in the step A3 are 4 times, the volume ratio of the ammonia water to the sediment is 1.5:3, and the concentration of the ammonia water is 25%.
The heating in the step A3 is to heat to 70 ℃, the drying time is 3 hours, and the high-temperature calcination temperature and time are respectively 350 ℃ and 2.5 hours.
The doped cobaltosic oxide is obtained by adopting the preparation process.
The doped cobaltosic oxide is applied to the fields of lithium ion batteries, super capacitors and gas sensors
Comparative example 1
On the basis of the embodiment 2, a preparation process of doped cobaltosic oxide comprises the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
A3: and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide.
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate with the mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1:3:0.01:5, and the surfactant is sorbitol.
The power and the temperature of the ultrasonic wave in the step A1 are respectively 350W and 35 ℃.
The soluble metal salt in the step A2 is potassium nitrate, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.01.
The temperature and time of the reaction in the step A2 are 125 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
The washing times in the step A3 are 4 times, and the volume ratio of the ammonia water to the sediment is 1:4.
The heating in the step A3 is to heat to 60 ℃, the drying time is 2.5h, and the high-temperature calcination temperature and time are 300 ℃ and 2h respectively.
The doped cobaltosic oxide is obtained by adopting the preparation process.
The doped cobaltosic oxide is applied to a gas sensor.
Comparative example 2
On the basis of the embodiment 2, a preparation process of doped cobaltosic oxide comprises the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
A3: and (3) washing the precipitate alternately by using deionized water and ethanol to remove impurities, then adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain the doped cobaltosic oxide.
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate with the mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1:3:0.01:5, and the surfactant is cetyltrimethylammonium bromide.
The power and the temperature of the ultrasonic wave in the step A1 are respectively 350W and 35 ℃.
The soluble metal salt in the step A2 is potassium nitrate, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.01.
The temperature and time of the reaction in the step A2 are 125 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
The washing times in the step A3 are 4 times, and the volume ratio of the ammonia water to the sediment is 1:4.
The heating in the step A3 is to heat to 60 ℃, the drying time is 2.5h, and the high-temperature calcination temperature and time are 300 ℃ and 2h respectively.
The doped cobaltosic oxide is obtained by adopting the preparation process.
The doped cobaltosic oxide is applied to a gas sensor.
Comparative example 3
On the basis of the embodiment 2, a preparation process of doped cobaltosic oxide comprises the following steps:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
a3: and washing the precipitate alternately with deionized water and ethanol to remove impurities, and calcining at high temperature to obtain the doped cobaltosic oxide.
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate in a mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1:3:0.01:5, and the surface activity consists of sorbitol and cetyltrimethylammonium bromide in a mass ratio of 1:1.
The power and the temperature of the ultrasonic wave in the step A1 are respectively 350W and 35 ℃.
The soluble metal salt in the step A2 is potassium nitrate, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.01.
The temperature and time of the reaction in the step A2 are 125 ℃ and 12 hours respectively, and the pressurizing pressure is 27.5KPa.
The number of times of washing in the step A3 is 4.
The temperature and time of the high-temperature calcination in the step A3 are respectively 300 ℃ and 2 hours.
The doped cobaltosic oxide is obtained by adopting the preparation process.
The doped cobaltosic oxide is applied to a gas sensor.
1. Performance testing
The doped tricobalt tetraoxide prepared in examples 1 to 3 and comparative examples 1 to 3 was used as a sample, and the sample was observed for the presence or absence of agglomeration using a scanning electron microscope. The sensitivity test is carried out on the sample by using a CGS-MT intelligent gas-sensitive test system, wherein the sensitivity=R1/R0, R1 is the resistance value of the sensor in response gas, and R0 is the resistance value of the sensor in air. The test results are shown in Table 1.
Table 1 test results
As can be seen from Table 1, examples 1 to 5 and comparative example 3 did not show agglomeration, and the dispersion properties of comparative examples 1 to 2 were lowered by adding a single surfactant. Examples 1-5 were much more sensitive than comparative examples 1-3, with comparative example 3 being the worst sensitive, because of the lack of the ammonia drying step in comparative example 3, the prepared doped tricobalt tetroxide lacks a void structure and is relatively poorly active.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. The preparation process of the doped cobaltosic oxide is characterized by comprising the following steps of:
a1: mixing cobalt salt, urea, a surfactant and deionized water, and performing ultrasonic treatment until the cobalt salt, the urea, the surfactant and the deionized water are dissolved;
A2: then adding soluble metal salt for pressurizing reaction, and filtering;
a3: washing the precipitate alternately with deionized water and ethanol to remove impurities, adding ammonia water, heating and drying, and calcining the dried precipitate at high temperature to obtain doped cobaltosic oxide;
In the step A1, cobalt salt consists of cobalt sulfate heptahydrate and cobalt chloride hexahydrate in a mass ratio of 1:1, the mass ratio of the cobalt salt to urea to surfactant to deionized water is 1-1.5:3-4:0.01-0.05:5-8, and the surfactant consists of sorbitol and cetyltrimethylammonium bromide in a mass ratio of 1:1.
2. The process for preparing the doped cobaltosic oxide according to claim 1, wherein the power and the temperature of the ultrasound in the step A1 are respectively 300-400W and 30-40 ℃.
3. The process for preparing the doped tricobalt tetraoxide according to claim 1, wherein the soluble metal salt in the step A2 is at least one chloride or nitrate in K, li, al, cu, mg, and the mass ratio of the cobalt salt to the soluble metal salt is 1:0.005-0.015.
4. The process according to claim 1, wherein the reaction in step A2 is carried out at a temperature and for a time of 120-130 ℃ for 12 hours, and the pressurizing pressure is 27.5KPa.
5. The process for preparing the doped tricobalt tetraoxide according to claim 1, wherein the number of times of washing in the step A3 is 4-6, the volume ratio of the ammonia water to the precipitate is 1-1.5:3-5, and the concentration of the ammonia water is 25%.
6. The process for preparing the doped cobaltosic oxide according to claim 1, wherein the heating in the step A3 is to heat to 50-70 ℃, the drying time is 2-3h, and the high-temperature calcination temperature and the high-temperature calcination time are respectively 250-350 ℃ and 2-2.5h.
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