CN109592711A - A kind of preparation method of the modified oxidized zirconium powder of graphene for lambda sensor - Google Patents

A kind of preparation method of the modified oxidized zirconium powder of graphene for lambda sensor Download PDF

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CN109592711A
CN109592711A CN201811335825.3A CN201811335825A CN109592711A CN 109592711 A CN109592711 A CN 109592711A CN 201811335825 A CN201811335825 A CN 201811335825A CN 109592711 A CN109592711 A CN 109592711A
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added
graphene
lambda sensor
modified oxidized
zirconium powder
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CN109592711B (en
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胡天喜
叶旦旺
初薛基
包晓刚
高鸿魁
刘印阁
李小毅
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SANXIANG ADVANCED MATERIALS CO Ltd
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    • 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 kind of preparation methods of modified oxidized zirconium powder of the graphene for lambda sensor, belong to the production method technical field of lambda sensor, specific steps are as follows: zirconyl chloride solution aqueous solution are prepared, by Y2O3It is dissolved in zirconyl chloride solution, PEG dispersing agent and graphene oxide is added, thiocarbamide is added, ammonium hydroxide is added, 12h is hydrolyzed at 70 DEG C and obtains slurry；Mineralizer is added in slurry, carries out hydro-thermal reaction；Slurries filtration, washing after hydro-thermal, it is dry, 200 mesh of granularity is broken to hereinafter, triethanolamine dispersant is added by vibration milling after calcining, is ground using sand mill, it is spray-dried to obtain the modified oxidized zirconium powder of graphene.Such preparation method has the characteristics that low energy consumption, reunites less, partial size is small and even particle size distribution, powder active are high, is suitble to industrialized mass production.And the modified oxidized zirconium powder of graphene prepared by this method can be used to make high-end lambda sensor, product conductivity is high, mechanical property is good.

Description

A kind of preparation method of the modified oxidized zirconium powder of graphene for lambda sensor
Technical field
The invention belongs to the production method technical field of lambda sensor, in particular to a kind of graphene for lambda sensor The preparation method of modified oxidized zirconium powder.
Background technique
Zirconium oxide oxygen sensor oxygen determination precision with higher and good high-temperature stability, are widely used in internal combustion engine The fields such as oxygen content detection in exhaust emissions.Sensing element (oxygen sensitive element) is the critical component of lambda sensor, currently, absolutely mostly Number lambda sensor is using the zirconium oxide of 5~8mol% stabilized with yttrium oxide as solid electrolyte, however its conductivity is lower, power It is general to learn performance, constrains the further development of lambda sensor, therefore, find that a kind of conductivity is higher, mechanical property is stronger and The good electrolyte new material of anti-aging property, is the key that develop high-performance lambda sensor.
Graphene is a kind of superpower two-dimentional carbon material, and with very good intensity, flexible, conductive, thermally conductive, optics is special Property, it has broad application prospects in fields such as physics, materialogy, electronic information, computer, aerospaces.By graphene It is added in nano oxidized zirconium powder, zirconium oxide is modified, the electrical and thermal conductivity performance of material can be improved, moreover it is possible to play activeness and quietness Effect, improves the mechanical property of material.
Yttria-stabilized zirconia is concentrated mainly on to the research of the zirconium oxide of lambda sensor both at home and abroad and is mixed at present The miscellaneous stable type zirconium oxide of third phase, but doping way different-effect is different.Modification, work are doped using graphene Skill process has some changes, and cost slightly rises, but can prepare the more superior product of performance, and conductivity has by a relatively large margin Raising.
Summary of the invention
The purpose of the present invention is to provide a kind of modified oxidized zirconium powders of the graphene for lambda sensor and preparation method thereof.
To achieve the above object, the invention provides the following technical scheme: a kind of modified oxygen of graphene for lambda sensor Change the preparation method specific steps of zirconium powder are as follows: Step 1: weighing zirconium oxychloride and deionized water is added to be configured to concentration is 0.5- Zirconyl chloride solution aqueous solution is heated to 70 DEG C, by Y by the zirconyl chloride solution aqueous solution of 1.5mol/L2O3It is dissolved in oxychlorination In zirconium solution, the Y2O3Content be 5-8mol%, be added 0.2-0.5 wt.% PEG dispersing agent, be incorporated 0.2-2wt.% oxygen Graphite alkene, and the graphene oxide is technical grade graphene oxide, with a thickness of 10nm；
Step 2: being added slowly with stirring thiocarbamide, thiocarbamide accounts for the 5-10wt.% of total system mass fraction, is then slowly added to Ammonium hydroxide precipitates into jelly, continuously adds ammonium hydroxide, and adjusting slurry system pH value is 8.5-9.5, hydrolyzes 12h at 70 DEG C to obtain the final product To slurry；
Step 3: the resulting slurry of step 2 is added in reaction kettle, 2-8wt.% mineralizer, the hydro-thermal at 150-200 DEG C is added React 12-48h；
Step 4: the slurry after hydro-thermal is filtered, is washed, circulation washing is first washed with deionized and is examined to washing water is excluded It until conductivity is surveyed less than 150 μ s/cm, finally uses ethanol washing 2 times, filter cake is dried into 2-12h at 105 DEG C；
Step 5: block of the step 4 after dry is calcined 1-6h at 650 DEG C -1200 DEG C；
Step 6: calcined block is crushed to 200 mesh of granularity hereinafter, three second of 0.1-0.3wt.% are added by vibromill Alcohol amine dispersant carries out extra-fine grinding to median D50 < 0.2 μm using sand mill, just obtains after finally spray-dried It is suitable for the modified oxidized zirconium powder of graphene of the sensing element of lambda sensor.
Preferably, the mineralizer in the step three is one of sodium hydroxide, potassium hydroxide, sodium carbonate or several Kind mixing.
Compared with prior art, beneficial effects of the present invention are as follows: such preparation method is with low energy consumption, reunites less, grain Diameter is small and even particle size distribution, the features such as powder active is high, is suitble to industrialized mass production.And graphene prepared by this method Modified oxidized zirconium powder can be used to make high-end lambda sensor, and product conductivity is high, mechanical property is good.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction in the embodiment of the present invention, it is clear that institute The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair The range of bright protection.
Embodiment 1
Modified oxidized zirconium powder of a kind of graphene for lambda sensor and preparation method thereof, the specific steps are that:
(1) it weighs zirconium oxychloride addition deionized water and is configured to aqueous solution, concentration 1mol/L is heated to 70 DEG C, by Y2O3It is molten Solution is in zirconyl chloride solution, the Y2O3Content be 5mol%, be added 0.2 wt.% PEG dispersing agent, be incorporated 0.2wt.% Graphene oxide (technical grade, thickness about 10nm)；
(2) it is added slowly with stirring thiocarbamide, the mass fraction that thiocarbamide accounts for total system is 5wt.%, is slowly added to ammonium hydroxide, is precipitated Agglutination object, continuously adds ammonium hydroxide, and adjusting slurry system pH value is 8.5-9.5；12h is hydrolyzed at 70 DEG C；
(3) resulting slurry is added in reaction kettle, is added 3wt.% mineralizer (mineralizer is sodium hydroxide), at 150 DEG C Hydro-thermal reaction is for 24 hours；
(4) slurry after hydro-thermal is filtered, washed, circulation washing is first washed with deionized and is detected to washing water is excluded It until conductivity is less than 150 μ s/cm, finally uses ethanol washing 2 times, filter cake is dried into 7h at 105 DEG C；
(5) block after drying is calcined into 2h at 1050 DEG C；
(6) calcined block is crushed to 200 mesh of granularity by vibromill hereinafter, the triethanolamine that 0.2wt.% is added disperses Agent carries out extra-fine grinding to median D50 < 0.2 μm using sand mill, just obtains being suitable for oxygen after finally spray-dried The modified oxidized zirconium powder of the graphene of the sensing element of sensor.Using the oxygen of the modified oxidized zirconium powder preparation of the present embodiment graphene Sensor sensing element, conductivity at 700 DEG C be 121.4s/m, the response time be less than 10ms, bending strength Kf > 620MPa。
Embodiment 2
Modified oxidized zirconium powder of a kind of graphene for lambda sensor and preparation method thereof, the specific steps are that:
(1) it weighs zirconium oxychloride addition deionized water and is configured to aqueous solution, concentration 1mol/L is heated to 70 DEG C, by Y2O3It is molten Solution is in zirconyl chloride solution, the Y2O3Content be 5mol%, be added 0.2 wt.% PEG dispersing agent, be incorporated 0.5wt.% Graphene oxide (technical grade, thickness about 10nm)；
(2) it is added slowly with stirring thiocarbamide, the mass fraction that thiocarbamide accounts for total system is 5wt.%, is slowly added to ammonium hydroxide, is precipitated Agglutination object, continuously adds ammonium hydroxide, and adjusting slurry system pH value is 8.5-9.5；12h is hydrolyzed at 70 DEG C；
(3) resulting slurry is added in reaction kettle, is added 5wt.% mineralizer (mineralizer is sodium hydroxide), at 160 DEG C Hydro-thermal reaction is for 24 hours；
(4) slurry after hydro-thermal is filtered, washed, circulation washing is first washed with deionized and is detected to washing water is excluded It until conductivity is less than 150 μ s/cm, finally uses ethanol washing 2 times, filter cake is dried into 7h at 105 DEG C；
(5) block after drying is calcined into 2h at 1050 DEG C；
(6) calcined block is crushed to 200 mesh of granularity by vibromill hereinafter, the triethanolamine that 0.2wt.% is added disperses Agent carries out extra-fine grinding to median D50 < 0.2 μm using sand mill, just obtains being suitable for oxygen after finally spray-dried The modified oxidized zirconium powder of the graphene of the sensing element of sensor.Using the oxygen of the modified oxidized zirconium powder preparation of the present embodiment graphene Sensor sensing element, conductivity are 155s/m at 700 DEG C, and the response time is less than 10ms, bending strength Kf > 650MPa.
Embodiment 3
Modified oxidized zirconium powder of a kind of graphene for lambda sensor and preparation method thereof, the specific steps are that:
(1) it weighs zirconium oxychloride addition deionized water and is configured to aqueous solution, concentration 1mol/L is heated to 70 DEG C, by Y2O3It is molten Solution is in zirconyl chloride solution, the Y2O3Content be 8mol%, be added 0.2 wt.% PEG dispersing agent, be incorporated 0.3wt.% Graphene oxide (technical grade, thickness about 10nm)；
(2) it is added slowly with stirring thiocarbamide, the mass fraction that thiocarbamide accounts for total system is 5wt.%, is slowly added to ammonium hydroxide, is precipitated Agglutination object, continuously adds ammonium hydroxide, and adjusting slurry system pH value is 8.5-9.5；12h is hydrolyzed at 70 DEG C；
(3) resulting slurry is added in reaction kettle, is added 5wt.% mineralizer (mineralizer is sodium hydroxide), at 150 DEG C Hydro-thermal reaction 20h；
(4) slurry after hydro-thermal is filtered, washed, circulation washing is first washed with deionized and is detected to washing water is excluded It until conductivity is less than 150 μ s/cm, finally uses ethanol washing 2 times, filter cake is dried into 7h at 105 DEG C；
(5) block after drying is calcined into 2h at 1050 DEG C；
(6) calcined block is crushed to 200 mesh of granularity by vibromill hereinafter, the triethanolamine that 0.2wt.% is added disperses Agent carries out extra-fine grinding to median D50 < 0.2 μm using sand mill, just obtains being suitable for oxygen after finally spray-dried The modified oxidized zirconium powder of the graphene of the sensing element of sensor.Using the oxygen of the modified oxidized zirconium powder preparation of the present embodiment graphene Sensor sensing element, conductivity at 700 DEG C be 153.7s/m, the response time be less than 10ms, bending strength Kf > 630MPa。
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (2)

1. a kind of preparation method of the modified oxidized zirconium powder of graphene for lambda sensor, it is characterised in that: specific steps are as follows: step Rapid one, it weighs zirconium oxychloride and the zirconyl chloride solution aqueous solution that deionized water is configured to concentration as 0.5-1.5mol/L is added, it will Zirconyl chloride solution aqueous solution is heated to 70 DEG C, by Y2O3It is dissolved in zirconyl chloride solution, the Y2O3Content be 5- The PEG dispersing agent of 0.2-0.5 wt.% is added in 8mol%, is incorporated 0.2-2wt.% graphene oxide, and the graphite oxide Alkene is technical grade graphene oxide, with a thickness of 10nm；
Step 2: being added slowly with stirring thiocarbamide, thiocarbamide accounts for the 5-10wt.% of total system mass fraction, is then slowly added to Ammonium hydroxide precipitates into jelly, continuously adds ammonium hydroxide, and adjusting slurry system pH value is 8.5-9.5, hydrolyzes 12h at 70 DEG C to obtain the final product To slurry；
Step 3: the resulting slurry of step 2 is added in reaction kettle, 2-8wt.% mineralizer, the hydro-thermal at 150-200 DEG C is added React 12-48h；
Step 4: the slurry after hydro-thermal is filtered, is washed, circulation washing is first washed with deionized and is examined to washing water is excluded It until conductivity is surveyed less than 150 μ s/cm, finally uses ethanol washing 2 times, filter cake is dried into 2-12h at 105 DEG C；
Step 5: block of the step 4 after dry is calcined 1-6h at 650 DEG C -1200 DEG C；
Step 6: calcined block is crushed to 200 mesh of granularity hereinafter, three second of 0.1-0.3wt.% are added by vibromill Alcohol amine dispersant carries out extra-fine grinding to median D50 < 0.2 μm using sand mill, just obtains after finally spray-dried It is suitable for the modified oxidized zirconium powder of graphene of the sensing element of lambda sensor.
2. a kind of preparation method of the modified oxidized zirconium powder of graphene for lambda sensor according to claim 1, special Sign is: the mineralizer in the step three is the mixing of one or more of sodium hydroxide, potassium hydroxide, sodium carbonate.
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Cited By (1)

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CN112645385A (en) * 2020-10-28 2021-04-13 北京理工大学 YSZ/graphene composite powder for sealing coating and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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