CN109592711B - Preparation method of graphene modified zirconia powder for oxygen sensor - Google Patents
Preparation method of graphene modified zirconia powder for oxygen sensor Download PDFInfo
- Publication number
- CN109592711B CN109592711B CN201811335825.3A CN201811335825A CN109592711B CN 109592711 B CN109592711 B CN 109592711B CN 201811335825 A CN201811335825 A CN 201811335825A CN 109592711 B CN109592711 B CN 109592711B
- Authority
- CN
- China
- Prior art keywords
- slurry
- zirconia powder
- modified zirconia
- washing
- oxygen sensor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The invention discloses a preparation method of graphene modified zirconia powder for an oxygen sensor, belonging to the technical field of production methods of oxygen sensors, and comprising the following specific steps: preparing an aqueous solution of zirconium oxychloride solution by dissolving Y in water2O3Dissolving in zirconium oxychloride solution, adding PEG dispersant and graphene oxide, adding thiourea, adding ammonia water, and hydrolyzing at 70 deg.C for 12h to obtain slurry; adding a mineralizer into the slurry to perform hydrothermal reaction; filtering, washing and drying the slurry after hydrothermal treatment, grinding the slurry after calcination by vibration to a particle size of below 200 meshes, adding a triethanolamine dispersant, grinding by a sand mill, and spray-drying to obtain the graphene modified zirconia powder. The preparation method has the characteristics of low energy consumption, less agglomeration, small particle size, uniform particle size distribution, high powder activity and the like, and is suitable for industrial batch production. The graphene modified zirconia powder prepared by the method can be used for manufacturing high-end oxygen sensors, and the product has high conductivity and good mechanical properties.
Description
Technical Field
The invention belongs to the technical field of production methods of oxygen sensors, and particularly relates to a preparation method of graphene modified zirconia powder for an oxygen sensor.
Background
The zirconia oxygen sensor has higher oxygen measurement precision and good high-temperature stability, and is widely applied to the fields of oxygen content detection in exhaust emission of internal combustion engines and the like. At present, most of oxygen sensors use 5-8 mol% yttria-stabilized zirconia as a solid electrolyte, but the conductivity of the oxygen sensors is low, and the mechanical properties are general, so that the further development of the oxygen sensors is restricted, therefore, a new electrolyte material with higher conductivity, stronger mechanical properties and good ageing resistance is found, and the method is the key for developing a high-performance oxygen sensor.
Graphene is an ultra-strong two-dimensional carbon material, has very good strength, flexibility, electric conductivity, heat conductivity and optical characteristics, and has wide application prospects in the fields of physics, materials science, electronic information, computers, aerospace and the like. The graphene is added into the nano zirconia powder to modify the zirconia, so that the electric conduction and heat conduction performance of the material can be improved, the reinforcing and toughening effects can be achieved, and the mechanical property of the material can be improved.
At present, the research on zirconia for oxygen sensors at home and abroad mainly focuses on yttria-stabilized zirconia and stabilized zirconia doped with a third phase, but different doping modes and different effects are different. The graphene is adopted for doping modification, so that the process is changed, the cost is slightly increased, a product with more excellent performance can be prepared, and the conductivity is greatly improved.
Disclosure of Invention
The invention aims to provide graphene modified zirconia powder for an oxygen sensor and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the graphene modified zirconia powder for the oxygen sensor comprises the following specific steps: step one, weighing zirconium oxychloride, adding deionized water to prepare a zirconium oxychloride solution aqueous solution with the concentration of 0.5-1.5mol/L, heating the zirconium oxychloride solution aqueous solution to 70 ℃, and adding Y2O3Dissolved in a zirconium oxychloride solution, said Y2O3The content of the graphene oxide is 5-8 mol%, 0.2-0.5 wt.% of PEG dispersant is added, 0.2-2wt.% of graphene oxide is added, and the graphene oxide is industrial graphene oxide and has the thickness of 10 nm;
secondly, slowly adding thiourea which accounts for 5-10 wt% of the total mass of the system under stirring, then slowly adding ammonia water, precipitating into a colloid, continuously adding the ammonia water, adjusting the pH value of the slurry system to 8.5-9.5, and hydrolyzing for 12 hours at 70 ℃ to obtain slurry;
step three, adding the slurry obtained in the step two into a reaction kettle, adding 2-8wt.% of mineralizer, and carrying out hydrothermal reaction for 12-48h at the temperature of 150-;
step four, filtering and washing the slurry after the hydrothermal treatment, washing the slurry by deionized water for circulation washing until the detected conductivity of the washing water is less than 150 mus/cm, finally washing the slurry by ethanol for 2 times, and drying the filter cake at 105 ℃ for 2-12 h;
step five, calcining the dried lump material in the step four at 650-1200 ℃ for 1-6 h;
and step six, crushing the calcined lump materials to the granularity of below 200 meshes by vibration powder, adding 0.1-0.3wt.% of triethanolamine dispersant, carrying out superfine grinding by a sand mill until the median particle size D50 is less than 0.2 mu m, and finally carrying out spray drying to obtain the graphene modified zirconia powder suitable for the sensitive element of the oxygen sensor.
Preferably, the mineralizer in the third step is one or a mixture of sodium hydroxide, potassium hydroxide and sodium carbonate.
Compared with the prior art, the invention has the following beneficial effects: the preparation method has the characteristics of low energy consumption, less agglomeration, small particle size, uniform particle size distribution, high powder activity and the like, and is suitable for industrial batch production. The graphene modified zirconia powder prepared by the method can be used for manufacturing high-end oxygen sensors, and the product has high conductivity and good mechanical properties.
Detailed Description
The technical solutions of the present invention will be described clearly and completely in the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A graphene modified zirconia powder for an oxygen sensor and a preparation method thereof, the method comprises the following specific steps:
(1) weighing zirconium oxychlorideAdding deionized water to obtain 1mol/L aqueous solution, heating to 70 deg.C, and adding Y2O3Dissolved in a zirconium oxychloride solution, said Y2O3The content of (2) is 5 mol%, 0.2wt.% of PEG dispersant is added, and 0.2wt.% of graphene oxide (industrial grade, thickness about 10 nm) is added;
(2) slowly adding thiourea into the slurry under stirring, wherein the mass fraction of thiourea in the total system is 5 wt%, slowly adding ammonia water, precipitating into a colloid, continuously adding ammonia water, and adjusting the pH value of the slurry system to 8.5-9.5; hydrolyzing at 70 ℃ for 12 h;
(3) adding the obtained slurry into a reaction kettle, adding 3wt.% of mineralizer (the mineralizer is sodium hydroxide), and carrying out hydrothermal reaction for 24 hours at 150 ℃;
(4) filtering and washing the slurry after hydrothermal treatment, washing with deionized water for circulation washing until the conductivity is less than 150 mus/cm when washing water is removed, finally washing with ethanol for 2 times, and drying the filter cake at 105 ℃ for 7 h;
(5) calcining the dried lump material at 1050 ℃ for 2 h;
(6) and (2) crushing the calcined lump materials to the granularity of below 200 meshes by vibration powder, adding 0.2wt.% of triethanolamine dispersant, carrying out superfine grinding by a sand mill until the median particle size D50 is less than 0.2 mu m, and finally carrying out spray drying to obtain the graphene modified zirconia powder suitable for the sensitive element of the oxygen sensor. The oxygen sensor sensitive element prepared by the graphene modified zirconia powder has the conductivity of 121.4s/m at 700 ℃, the response time of less than 10ms and the bending strength Kf of more than 620 MPa.
Example 2
A graphene modified zirconia powder for an oxygen sensor and a preparation method thereof, the method comprises the following specific steps:
(1) weighing zirconium oxychloride, adding deionized water to prepare an aqueous solution with the concentration of 1mol/L, heating to 70 ℃, and adding Y2O3Dissolved in a zirconium oxychloride solution, said Y2O3The content of (2) is 5 mol%, 0.2wt.% of PEG dispersant is added, and 0.5wt.% of graphene oxide (industrial grade, thickness about 10 nm) is added;
(2) slowly adding thiourea into the slurry under stirring, wherein the mass fraction of thiourea in the total system is 5 wt%, slowly adding ammonia water, precipitating into a colloid, continuously adding ammonia water, and adjusting the pH value of the slurry system to 8.5-9.5; hydrolyzing at 70 ℃ for 12 h;
(3) adding the obtained slurry into a reaction kettle, adding 5wt.% of a mineralizer (the mineralizer is sodium hydroxide), and carrying out hydrothermal reaction for 24 hours at 160 ℃;
(4) filtering and washing the slurry after hydrothermal treatment, washing with deionized water for circulation washing until the conductivity is less than 150 mus/cm when washing water is removed, finally washing with ethanol for 2 times, and drying the filter cake at 105 ℃ for 7 h;
(5) calcining the dried lump material at 1050 ℃ for 2 h;
(6) and (2) crushing the calcined lump materials to the granularity of below 200 meshes by vibration powder, adding 0.2wt.% of triethanolamine dispersant, carrying out superfine grinding by a sand mill until the median particle size D50 is less than 0.2 mu m, and finally carrying out spray drying to obtain the graphene modified zirconia powder suitable for the sensitive element of the oxygen sensor. The oxygen sensor sensitive element prepared by the graphene modified zirconia powder has the conductivity of 155s/m at 700 ℃, the response time of less than 10ms and the bending strength Kf of more than 650 MPa.
Example 3
A graphene modified zirconia powder for an oxygen sensor and a preparation method thereof, the method comprises the following specific steps:
(1) weighing zirconium oxychloride, adding deionized water to prepare an aqueous solution with the concentration of 1mol/L, heating to 70 ℃, and adding Y2O3Dissolved in a zirconium oxychloride solution, said Y2O3The content of (2) is 8 mol%, 0.2wt.% of PEG dispersant is added, and 0.3wt.% of graphene oxide (industrial grade, thickness about 10 nm) is added;
(2) slowly adding thiourea into the slurry under stirring, wherein the mass fraction of thiourea in the total system is 5 wt%, slowly adding ammonia water, precipitating into a colloid, continuously adding ammonia water, and adjusting the pH value of the slurry system to 8.5-9.5; hydrolyzing at 70 ℃ for 12 h;
(3) adding the obtained slurry into a reaction kettle, adding 5wt.% of a mineralizer (the mineralizer is sodium hydroxide), and carrying out hydrothermal reaction for 20 hours at 150 ℃;
(4) filtering and washing the slurry after hydrothermal treatment, washing with deionized water for circulation washing until the conductivity is less than 150 mus/cm when washing water is removed, finally washing with ethanol for 2 times, and drying the filter cake at 105 ℃ for 7 h;
(5) calcining the dried lump material at 1050 ℃ for 2 h;
(6) and (2) crushing the calcined lump materials to the granularity of below 200 meshes by vibration powder, adding 0.2wt.% of triethanolamine dispersant, carrying out superfine grinding by a sand mill until the median particle size D50 is less than 0.2 mu m, and finally carrying out spray drying to obtain the graphene modified zirconia powder suitable for the sensitive element of the oxygen sensor. The oxygen sensor sensitive element prepared by the graphene modified zirconia powder has the conductivity of 153.7s/m at 700 ℃, the response time of less than 10ms and the bending strength Kf of more than 630 MPa.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (2)
1. A preparation method of graphene modified zirconia powder for an oxygen sensor is characterized by comprising the following steps: the method comprises the following specific steps: step one, weighing zirconium oxychloride, adding deionized water to prepare a zirconium oxychloride solution aqueous solution with the concentration of 0.5-1.5mol/L, heating the zirconium oxychloride solution aqueous solution to 70 ℃, and adding Y2O3Dissolved in a zirconium oxychloride solution, said Y2O3The content of the graphene oxide is 5-8 mol%, 0.2-0.5 wt.% of PEG dispersant is added, 0.2-2wt.% of graphene oxide is added, and the graphene oxide is industrial graphene oxide and has the thickness of 10 nm;
secondly, slowly adding thiourea which accounts for 5-10 wt% of the total mass of the system under stirring, then slowly adding ammonia water, precipitating into a colloid, continuously adding the ammonia water, adjusting the pH value of the slurry system to 8.5-9.5, and hydrolyzing for 12 hours at 70 ℃ to obtain slurry;
step three, adding the slurry obtained in the step two into a reaction kettle, adding 2-8wt.% of mineralizer, and carrying out hydrothermal reaction for 12-48h at the temperature of 150-;
step four, filtering and washing the slurry after the hydrothermal treatment, washing the slurry by deionized water for circulation washing until the detected conductivity of the washing water is less than 150 mus/cm, finally washing the slurry by ethanol for 2 times, and drying the filter cake at 105 ℃ for 2-12 h;
step five, calcining the dried lump material in the step four at 650-1200 ℃ for 1-6 h;
and step six, crushing the calcined lump materials to the granularity of below 200 meshes by vibration powder, adding 0.1-0.3wt.% of triethanolamine dispersant, carrying out superfine grinding by a sand mill until the median particle size D50 is less than 0.2 mu m, and finally carrying out spray drying to obtain the graphene modified zirconia powder suitable for the sensitive element of the oxygen sensor.
2. The method for preparing graphene-modified zirconia powder for an oxygen sensor according to claim 1, wherein: the mineralizer in the third step is one or a mixture of sodium hydroxide, potassium hydroxide and sodium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811335825.3A CN109592711B (en) | 2018-11-11 | 2018-11-11 | Preparation method of graphene modified zirconia powder for oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811335825.3A CN109592711B (en) | 2018-11-11 | 2018-11-11 | Preparation method of graphene modified zirconia powder for oxygen sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109592711A CN109592711A (en) | 2019-04-09 |
| CN109592711B true CN109592711B (en) | 2021-06-22 |
Family
ID=65958053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811335825.3A Active CN109592711B (en) | 2018-11-11 | 2018-11-11 | Preparation method of graphene modified zirconia powder for oxygen sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109592711B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645385B (en) * | 2020-10-28 | 2022-04-08 | 北京理工大学 | YSZ/graphene composite powder for sealing coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861559A (en) * | 2014-03-12 | 2014-06-18 | 陕西科技大学 | Zirconia-modified graphene and method for removing fluorine ions in water |
| CN106000297A (en) * | 2016-05-10 | 2016-10-12 | 郑州大学 | Graphene loaded zirconium oxide composite material, preparing method thereof, and application thereof as desulfurizer adsorbent |
| CN108467264A (en) * | 2018-03-06 | 2018-08-31 | 三祥新材股份有限公司 | A kind of combined oxidation zirconium powder for lambda sensor |
-
2018
- 2018-11-11 CN CN201811335825.3A patent/CN109592711B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861559A (en) * | 2014-03-12 | 2014-06-18 | 陕西科技大学 | Zirconia-modified graphene and method for removing fluorine ions in water |
| CN106000297A (en) * | 2016-05-10 | 2016-10-12 | 郑州大学 | Graphene loaded zirconium oxide composite material, preparing method thereof, and application thereof as desulfurizer adsorbent |
| CN108467264A (en) * | 2018-03-06 | 2018-08-31 | 三祥新材股份有限公司 | A kind of combined oxidation zirconium powder for lambda sensor |
Non-Patent Citations (2)
| Title |
|---|
| light induced oxygen sensing using ZnO/GO based gas sensor;Yousef Khosravi et al.;《Materials science in semiconductor processing》;20180530;第85卷;第9-14页 * |
| THE ANALYSIS AND RESEARCH FOR THE PLATE DIFFERENTIAL OXYGEN GAS SENSOR OF AUTO BASED ON THE TEMPERATURE FIELD AND THERMAL STRESS FIELD;Jianjun YANG;《International Journal of Mechatronics and Applied Mechanics》;20171231;第67-74页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109592711A (en) | 2019-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103626492B (en) | For the Zirconium powder of the scandia stabilized in Solid Oxide Fuel Cell | |
| CN104810509B (en) | Ferroso-ferric oxide/graphene three dimensional composite structure and its preparation method and application | |
| CN101891471B (en) | Method for preparing zirconium oxide nanopowder stabilized by yttrium oxide | |
| CN103524128A (en) | Preparation method of yttria-stabilized zirconia tetragonal nano powder with high specific surface area | |
| CN107792887A (en) | A kind of high-specific surface area ZnMn2O4Preparation method | |
| CN101708829A (en) | Method for preparing yttria-stabilized zirconia powder | |
| CN102513083A (en) | Preparation method of diatomite loaded nano-zinc oxide composite powder material | |
| CN108467264A (en) | A kind of combined oxidation zirconium powder for lambda sensor | |
| CN109704759A (en) | A kind of compound rare-earth modified zirconia ceramic powder and preparation method thereof | |
| CN109592711B (en) | Preparation method of graphene modified zirconia powder for oxygen sensor | |
| CN107473737B (en) | Composite zirconia powder for solid oxide fuel cell and preparation method thereof | |
| CN113461051A (en) | Preparation method of nano zirconia powder | |
| CN101948134A (en) | Method for preparing lithium titanate powder | |
| CN101700912B (en) | Preparation method of silky nano-MnO2 | |
| CN103318954A (en) | Method for preparing sodium trititanate nanorods through solid-phase chemical reaction | |
| CN108609652A (en) | A method of preparing Zirconium dioxide nano powder using fused salt | |
| CN110817954B (en) | Solid electrolyte, preparation method thereof and solid oxide fuel cell | |
| CN108083334A (en) | A kind of preparation method of monodisperse spherical nano zirconium dioxide powder body material | |
| CN107364884B (en) | A kind of nano zirconium oxide powder preparation method | |
| CN103101975A (en) | Rodlike bismuth oxide and preparation method thereof | |
| CN105600834A (en) | Low-cost large-scale preparation method of ferroferric oxide micron magnetic particles | |
| CN106006761B (en) | A kind of preparation method of cobaltosic oxide hierarchical organization material | |
| CN101704505B (en) | Method for preparing high-thermostability tin oxide nano-powder on Ca-doped basis | |
| CN102849964B (en) | Preparation method for titanium dioxide nanometer microcrystal interface fusion structural material | |
| CN107445202B (en) | A kind of small size, super-dispersed nano zirconium oxide base coating raw powder's production technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |