CN109632915B - Nitrogen oxide sensor chip and manufacturing method thereof - Google Patents
Nitrogen oxide sensor chip and manufacturing method thereof Download PDFInfo
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- CN109632915B CN109632915B CN201811555112.8A CN201811555112A CN109632915B CN 109632915 B CN109632915 B CN 109632915B CN 201811555112 A CN201811555112 A CN 201811555112A CN 109632915 B CN109632915 B CN 109632915B
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000001301 oxygen Substances 0.000 claims abstract description 97
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 97
- 239000007789 gas Substances 0.000 claims abstract description 76
- 230000003197 catalytic effect Effects 0.000 claims abstract description 55
- 230000004888 barrier function Effects 0.000 claims abstract description 38
- 238000009792 diffusion process Methods 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000001514 detection method Methods 0.000 claims abstract description 24
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000010410 layer Substances 0.000 claims description 217
- 239000000843 powder Substances 0.000 claims description 83
- 238000007639 printing Methods 0.000 claims description 55
- 239000007790 solid phase Substances 0.000 claims description 53
- 239000011368 organic material Substances 0.000 claims description 43
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 42
- 239000002002 slurry Substances 0.000 claims description 41
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 38
- 238000005520 cutting process Methods 0.000 claims description 24
- 239000004014 plasticizer Substances 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000020 Nitrocellulose Substances 0.000 claims description 19
- 229920001220 nitrocellulos Polymers 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 19
- 239000002562 thickening agent Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052596 spinel Inorganic materials 0.000 claims description 14
- 239000011029 spinel Substances 0.000 claims description 14
- 238000007650 screen-printing Methods 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- 210000001161 mammalian embryo Anatomy 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000007769 metal material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000005056 compaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005498 phthalate group Chemical group 0.000 claims 2
- 238000010030 laminating Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000013354 porous framework Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical group [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000010345 tape casting Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229910000579 plumbide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G01N27/41—Oxygen pumping cells
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
The invention relates to a nitrogen oxide sensor chip and a manufacturing method thereof. The nitrogen oxide sensor chip comprises an upper oxygen pump cell layer, a tail gas control layer, a lower oxygen pump cell layer, a porous oxygen reference layer, an upper heating substrate layer and a lower heating substrate layer which are sequentially laminated, wherein an upper oxygen pump electrode layer is printed on one surface of the upper oxygen pump cell layer, a gas detection chamber and a porous gas diffusion barrier layer are arranged between the other surface of the upper oxygen pump cell layer and the lower oxygen pump cell layer, a boss is arranged in the gas detection chamber, and through the design of the boss, the contact area of automobile tail gas and a catalytic electrode is increased, so that more non-nitrogen oxide gas is catalyzed, and the detection precision is improved; by adopting the porous air inlet technology, particles in the tail gas can be filtered, so that the air flow and the supporting structure are better stabilized, and the strength and the yield of chips are improved; the porous ceramic supporting technology is adopted, the reference air cavity is prepared through a porous framework, the mechanical strength of the ceramic chip is improved, and the yield is improved.
Description
Technical Field
The invention relates to the technical field of oxygen sensors, in particular to a nitrogen oxide sensor chip and a manufacturing method thereof.
Background
The motor vehicle brings convenience to the daily life of people, and meanwhile, the tail gas emission of the motor vehicle has bad influence on the natural environment and the human health. For example, harmful gases contained in fuel automobile exhaust, particulate matter (plumbides, soot, oil mist) and the like have been seriously threatened from the fields of air, water and even food. In order to meet increasingly stringent emission regulations, advanced post-treatment monitoring and regulation techniques are imperative.
It is well known that engine harmful emissions mainly consist of: nitrogen oxides (NOx), carbon monoxide (CO), unburned Hydrocarbons (HC), particulates (PM), and the like. The main emissions of the gasoline engine are NOx, CO and HC, and the harmful components in the tail gas of the diesel engine are mainly NOx and PM. In addition to advanced in-cylinder combustion technology and precise engine control strategies, exhaust aftertreatment technology is becoming increasingly indispensable in order to cope with increasingly stringent emission regulations. Gasoline engines operating near stoichiometric ratios can use three-way catalysts to efficiently remove three primary emissions, while for diesel engines using oxy-fuel combustion, there is a relationship between NOx and PM that is difficult to remove simultaneously. In particular, NOx removal has been a major and difficult task in emissions control research. Therefore, the development of a sensor with a precise detection of the oxygen content in the exhaust gas of a diesel engine is a necessary trend of future development.
Disclosure of Invention
In order to solve the problems, the invention provides a nitrogen oxide sensor chip and a manufacturing method thereof, wherein the sensitivity of the chip is improved by improving materials and structures of an exhaust gas stabilization layer and an oxygen reference layer.
The technical scheme adopted by the invention is as follows: the utility model provides a nitrogen oxide sensor chip, includes last oxygen pump cell layer, tail gas control layer, lower oxygen pump cell layer, porous oxygen reference layer, goes up heating substrate layer and heats substrate layer down that stacks gradually, its characterized in that: an upper oxygen pump electrode layer is printed on one surface of the upper oxygen pump cell layer, a gas detection chamber and a porous gas diffusion barrier layer are arranged between the other surface of the upper oxygen pump cell layer and the lower oxygen pump cell layer, a boss is arranged in the gas detection chamber, the boss is printed on the lower oxygen pump cell layer, and a compact gas diffusion barrier layer is arranged between the boss and the upper oxygen pump cell layer; the boss divides the gas detection chamber into a first cavity and a second cavity, a first cavity catalytic electrode layer is arranged in the first cavity, a second cavity catalytic electrode layer and a nitrogen oxide catalytic electrode are arranged in the second cavity, the first cavity catalytic electrode layer and the second cavity catalytic electrode layer are printed on the upper oxygen pump cell layer, and the nitrogen oxide catalytic electrode is printed on the lower oxygen pump cell layer; a reference electrode is arranged between the porous oxygen reference layer and the lower oxygen pump cell layer, and an insulating layer and a built-in heating electrode are sequentially arranged between the upper heating substrate layer and the lower heating substrate layer.
Preferably, the height of the boss is 1/4-1/2 of the height of the gas detection chamber, so that the contact area between the automobile exhaust and the corresponding catalytic electrode is increased, more non-nitrogen oxide gas is catalyzed, and the detection precision is improved.
Preferably, the surface of the upper oxygen pump electrode layer is provided with an alumina protective layer.
Preferably, the porous oxygen reference layer is internally provided with a filler with a porous structure, so that the mechanical strength of the gas-sensitive ceramic sheet can be improved.
The preparation method of the nitrogen oxide sensor chip comprises the following steps:
1) Preparing each dielectric layer: adopting yttrium stabilized zirconia nano-powder as a main material, respectively adding organic material binder polyvinyl butyral, plasticizer dibutyl phthalate and absolute ethyl alcohol, ball-milling and mixing uniformly, adopting a tape casting technology to prepare a diaphragm, adopting an automatic cutting machine to cut into sample slices with uniform length, and enabling the single-layer thickness to be 500-600 mu m; cutting lines and positioning lines are printed on each layer respectively, and each dielectric layer is cut by a laser cutter;
2) Printing a corresponding upper oxygen pump electrode layer, a first cavity catalytic electrode layer, a second cavity catalytic electrode layer, a reference electrode and a built-in heating electrode on the corresponding dielectric layers, wherein the upper oxygen pump electrode layer, the first cavity catalytic electrode layer, the second cavity catalytic electrode layer, the reference electrode and the built-in heating electrode are all platinum electrode layers, drying, then carrying out laser punching, and controlling the aperture to be 0.1-0.5 mm;
3) Printing a nitrogen oxide catalytic electrode on a lower oxygen pump cell layer corresponding to the dielectric layer, wherein an electrode metal material used for the nitrogen oxide catalytic electrode is platinum-rhodium-palladium alloy;
4) Printing a boss on the lower oxygen pump cell layer, wherein the height of the boss is 1/4-1/2 of the height of the first cavity and the second cavity, and the boss is used for increasing the contact area between automobile exhaust and a catalytic electrode, so that more non-nitrogen oxides are catalyzed, and the detection precision is improved;
5) Preparing a porous gas diffusion barrier layer, wherein the solid phase powder in the printing slurry comprises the following components: the sum of the weight percentages of the components of the zirconia powder, the magnesia-alumina spinel powder and the carbon powder is 100 percent; organic materials are added into the printing slurry, and the addition amount of the organic materials is as follows: thickener nitrocellulose, plasticizer phthalate, organic solvent tributyl citrate, solid phase powder all pass through a 300-mesh sieve;
6) Preparing a compact gas diffusion barrier layer, wherein solid phase powder in printing slurry comprises the following components: the sum of the weight percentages of the components of the zirconia powder, the magnesia-alumina spinel powder and the carbon powder is 100 percent; organic materials are added into the printing slurry, and the addition amount of the organic materials is as follows: thickener nitrocellulose, plasticizer phthalate and organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
7) Printing a porous oxygen reference layer on the substrate layer, wherein the screen printing paste is the same as the paste used for the porous gas diffusion barrier layer;
8) Electrode lead holes are formed in each dielectric layer, the embryo sheet layers are sequentially positioned and laminated according to the structure of the oxygen sensor ceramic sheet, and the embryo sheet layers are placed into a pressing table for compaction;
9) Cutting the blank according to the cutting line to obtain an oxygen sensor ceramic chip plain blank;
10 After removing organic matters at 650 ℃, sintering at a high temperature of 1400-1500 ℃ for 5-10 hours, preserving heat for 2 hours at 1150-1250 ℃ when the temperature is reduced by sintering, and then cooling along with a furnace to obtain the nitrogen oxide sensor chip.
Preferably, the boss is made of zirconia ceramics and is prepared by adopting a screen printing mode, and solid phase powder in printing slurry is commercial YSZ; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 2-4wt% of thickener nitrocellulose, 0.5-5wt% of plasticizer phthalate and 30-60% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve.
Preferably, the porous gas diffusion barrier layer and the compact gas diffusion barrier layer are printed by screen printing, and the material ratio of the two diffusion barrier layers is different due to different purposes.
Preferably, the porous gas diffusion barrier layer comprises the following solid phase powder in weight percentage in printing slurry: 10 to 20 weight percent of zirconia powder, 50 to 65 weight percent of magnesia-alumina spinel powder, 20 to 30 weight percent of carbon powder, and the sum of the weight percentages of the components is 100 percent; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 1 to 5 weight percent of thickener nitrocellulose, 0.5 to 5 weight percent of plasticizer phthalate and 30 to 60 percent of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve.
Preferably, the dense gas diffusion barrier layer comprises the following solid phase powder in weight percentage in printing slurry: 10 to 20 weight percent of zirconia powder, 65 to 80 weight percent of magnesia-alumina spinel powder, 5 to 15 weight percent of carbon powder, and the sum of the weight percentages of the components is 100 percent; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 1 to 5 weight percent of thickener nitrocellulose, 0.5 to 5 weight percent of plasticizer phthalate and 30 to 60 percent of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve.
Preferably, the electrode metal material used in the nitrogen oxide catalytic electrode is platinum rhodium palladium alloy, and has the biggest characteristic of catalyzing nitrogen oxide. The electrode comprises the following metals in percentage by weight: 70-80 wt% of platinum, 10-20 wt% of rhodium, 5wt% of palladium and 5% of zirconia, and the alloy powder is sieved by a 300-mesh sieve.
The beneficial effects obtained by the invention are as follows:
(1) Through the boss design, increase automobile exhaust and catalytic electrode area of contact, make more non-nitrogen oxide gas catalyzed, improve detection precision.
(2) By adopting the porous air inlet technology, particles in the tail gas can be filtered, the air flow and the supporting structure are better stabilized, and the strength and the yield of the chip are improved.
(3) The porous ceramic supporting technology is adopted, the reference air cavity is prepared through a porous framework, the mechanical strength of the ceramic chip is improved, and the yield is improved.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
In the figure: the solar cell comprises a 1-upper oxygen pump cell layer, a 2-tail gas control layer, a 3-lower oxygen pump cell layer, a 4-porous oxygen reference layer, a 5-upper heating substrate layer, a 6-lower heating substrate layer, a 7-upper oxygen pump electrode layer, an 8-first cavity catalytic electrode layer, a 9-second cavity catalytic electrode layer, a 10-porous gas diffusion barrier layer, an 11-first cavity, a 12-compact gas diffusion barrier layer, a 13-boss, a 14-second cavity 15-nitrogen oxide catalytic electrode, a 16-reference electrode, a 17-insulating layer and an 18-built-in heating electrode.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples.
As shown in fig. 1, the nitrogen oxide sensor chip of the invention comprises an upper oxygen pump cell layer 1, a tail gas control layer 2, a lower oxygen pump cell layer 3, a porous oxygen reference layer 4, an upper heating substrate layer 5 and a lower heating substrate layer 6 which are laminated in sequence, wherein one surface of the upper oxygen pump cell layer 1 is printed with an upper oxygen pump electrode layer 7, a gas detection chamber and a porous gas diffusion barrier layer 10 are arranged between the other surface of the upper oxygen pump cell layer 1 and the lower oxygen pump cell layer 3, a boss 13 is arranged in the gas detection chamber, the boss 13 is printed on the lower oxygen pump cell layer 3, and a compact gas diffusion barrier layer 12 is arranged between the boss 13 and the upper oxygen pump cell layer 1; the boss 13 divides the gas detection chamber into a first cavity 11 and a second cavity 14, a first cavity catalytic electrode layer 8 is arranged in the first cavity 11, a second cavity catalytic electrode layer 9 and a nitrogen oxide catalytic electrode 15 are arranged in the second cavity 14, the first cavity catalytic electrode layer 8 and the second cavity catalytic electrode layer 9 are printed on the upper oxygen pump cell layer 1, and the nitrogen oxide catalytic electrode 15 is printed on the lower oxygen pump cell layer 3; a reference electrode 16 is arranged between the porous oxygen reference layer 4 and the lower oxygen pump cell layer 3, and an insulating layer 17 and a built-in heating electrode 18 are sequentially arranged between the upper heating substrate layer 5 and the lower heating substrate layer 6.
In this embodiment, the height of the boss 13 is 1/4-1/2 of the height of the gas detection chamber, so as to increase the contact area between the automobile exhaust and the first cavity catalytic electrode layer 8 and the second cavity catalytic electrode layer 9, so that more non-nitrogen oxide gas is catalyzed, and the detection precision is improved.
In this embodiment, the upper oxygen pump electrode layer 7 has an alumina protective layer on its surface.
In this embodiment, the porous oxygen reference layer 4 is different from a common oxygen sensor reference cavity, and has a filler inside, and the filler inside is of a porous structure, so that the mechanical strength of the gas-sensitive ceramic sheet can be improved.
In this embodiment, the electrode metal materials used in the upper oxygen pump electrode layer 7, the first cavity catalytic electrode layer 8, the second cavity catalytic electrode layer 9, the reference electrode 16, and the internal heating electrode 18 are platinum, so that hydrocarbons, carbon oxides, and the like can be catalyzed, but nitrogen oxides cannot be catalyzed. The electrode metal material used in the nitrogen oxide catalytic electrode 15 is platinum-rhodium-palladium alloy, and has the biggest characteristic of catalyzing nitrogen oxide.
Example 1
Oxygen sensor preparation
1) Preparing each dielectric layer: yttrium Stabilized Zirconia (YSZ) nano powder is adopted as a main material, wherein an organic material binder polyvinyl butyral, a plasticizer dibutyl phthalate and absolute ethyl alcohol are respectively added, ball milling and mixing are carried out uniformly, and a tape casting technology is adopted to prepare a membrane; cutting into sample pieces with uniform length by an automatic cutting machine, wherein the single-layer thickness is 500-600 mu m; cutting lines and positioning lines are printed on each layer respectively, and each layer is cut by a laser knife;
2) Printing a platinum electrode layer, namely an upper oxygen pump electrode layer 7, a first cavity catalytic electrode layer 8, a second cavity catalytic electrode layer 9, a reference electrode 16 and a built-in heating electrode 18 on the corresponding dielectric layer; drying, and then carrying out laser punching, wherein the aperture is controlled to be 0.1-0.5 mm;
3) The nitrogen oxide catalytic electrode 15 is printed on the lower oxygen pump cell layer 3, the electrode metal material used is platinum rhodium palladium alloy, and the weight percentages of metals in the electrode composition are respectively as follows: 70wt% of platinum, 20wt% of rhodium, 5wt% of palladium and 5wt% of zirconia, and the preparation of the slurry is performed by a method known to a skilled person;
4) Printing a boss 13 on the lower oxygen pump cell layer 3, wherein the height of the boss is 1/4 of the height of a gas detection chamber (a first cavity 11 or a second cavity 14), the boss is prepared by adopting a screen printing mode, and solid phase powder in printing slurry is commercial YSZ; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 2wt% of thickener nitrocellulose, 5wt% of plasticizer phthalate and 60% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
5) Preparing a porous gas diffusion barrier layer 10, wherein the weight percentage composition of solid phase powder in printing slurry is as follows: 20wt% of zirconia powder, 50wt% of magnesia-alumina spinel powder, 30wt% of carbon powder, and 100% of the sum of the components in percentage by weight; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 5wt% of thickener nitrocellulose, 0.5wt% of plasticizer phthalate and 30% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
6) A dense gas diffusion barrier layer 12 is prepared, wherein the weight percentage composition of solid phase powder in the printing slurry is as follows: 20wt% of zirconia powder, 75wt% of magnesia-alumina spinel powder, 5wt% of carbon powder and 100% of the sum of the components in percentage by weight; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: thickener nitrocellulose 1wt%, plasticizer phthalate 5wt%, organic solvent tributyl citrate 30%; the solid phase powder passes through a 300-mesh sieve;
7) Printing a porous oxygen reference layer 4 on the substrate layer, wherein the paste for screen printing is the same as the paste used for the porous gas diffusion barrier layer 10;
8) Electrode lead holes are formed in each dielectric layer, the embryo sheet layers are sequentially positioned and laminated according to the structure of the oxygen sensor ceramic sheet, and the embryo sheet layers are placed into a pressing table for compaction;
9) Cutting the blank according to the cutting line to obtain an oxygen sensor ceramic chip plain blank;
10 After removing organic matters at 650 ℃, sintering at a high temperature of 1400 ℃ for 10 hours, preserving heat for 2 hours at a temperature of 1250 ℃ when the temperature is reduced by sintering, and then cooling along with a furnace to obtain the oxygen sensor ceramic sheet.
Example 2
Oxygen sensor preparation
1) Preparing each dielectric layer: yttrium Stabilized Zirconia (YSZ) nano powder is adopted as a main material, wherein an organic material binder polyvinyl butyral, a plasticizer dibutyl phthalate and absolute ethyl alcohol are respectively added, ball milling and mixing are carried out uniformly, and a tape casting technology is adopted to prepare a membrane; cutting into sample pieces with uniform length by an automatic cutting machine, wherein the single-layer thickness is 500-600 mu m; cutting lines and positioning lines are printed on each layer respectively, and each layer is cut by a laser knife;
2) Printing a platinum electrode layer, namely an upper oxygen pump electrode layer 7, a first cavity catalytic electrode layer 8, a second cavity catalytic electrode layer 9, a reference electrode 16 and a built-in heating electrode 18 on the corresponding dielectric layer; drying, and then carrying out laser punching, wherein the aperture is controlled to be 0.1-0.5 mm;
3) The nitrogen oxide catalytic electrode 15 is printed on the lower oxygen pump cell layer 3, the electrode metal material used is platinum rhodium palladium alloy, and the weight percentages of metals in the electrode composition are respectively as follows: 75wt% of platinum, 15wt% of rhodium, 5wt% of palladium and 5wt% of zirconia, and the preparation of the slurry is performed by a method known to a skilled person;
4) Printing a boss 13 on the lower oxygen pump cell layer 3, wherein the height of the boss is 1/2 of the height of a gas detection chamber (a first cavity 11 or a second cavity 14), the boss is prepared by adopting a screen printing mode, and solid phase powder in printing slurry is commercial YSZ; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 4wt% of thickener nitrocellulose, 0.5wt% of plasticizer phthalate and 30% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
5) Preparing a porous gas diffusion barrier layer 10, wherein the weight percentage composition of solid phase powder in printing slurry is as follows: 10wt% of zirconia powder, 65wt% of magnesia-alumina spinel powder, 25wt% of carbon powder, and 100% of the sum of the components in percentage by weight; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 2wt% of thickener nitrocellulose, 4wt% of plasticizer phthalate and 40% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
6) A dense gas diffusion barrier layer 12 is prepared, wherein the weight percentage composition of solid phase powder in the printing slurry is as follows: 10wt% of zirconia powder, 80wt% of magnesia-alumina spinel powder, 10wt% of carbon powder, and 100% of the sum of the components in percentage by weight; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 5wt% of thickener nitrocellulose, 0.5wt% of plasticizer phthalate and 40% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
7) Printing a porous oxygen reference layer 4 on the substrate layer, wherein the paste for screen printing is the same as the paste used for the porous gas diffusion barrier layer 10;
8) Electrode lead holes are formed in each dielectric layer, the embryo sheet layers are sequentially positioned and laminated according to the structure of the oxygen sensor ceramic sheet, and the embryo sheet layers are placed into a pressing table for compaction;
9) Cutting the blank according to the cutting line to obtain an oxygen sensor ceramic chip plain blank;
10 After removing organic matters from the ceramic green sheet at 650 ℃, sintering the ceramic green sheet for 5 hours at a high temperature of 1500 ℃, preserving heat for 2 hours at a temperature of 1150 ℃ when the temperature is reduced by sintering, and then cooling the ceramic green sheet along with a furnace to obtain the oxygen sensor ceramic sheet.
Example 3
Oxygen sensor preparation
1) Preparing each dielectric layer: yttrium Stabilized Zirconia (YSZ) nano powder is adopted as a main material, wherein an organic material binder polyvinyl butyral, a plasticizer dibutyl phthalate and absolute ethyl alcohol are respectively added, ball milling and mixing are carried out uniformly, and a tape casting technology is adopted to prepare a membrane; cutting into sample pieces with uniform length by an automatic cutting machine, wherein the single-layer thickness is 500-600 mu m; cutting lines and positioning lines are printed on each layer respectively, and each layer is cut by a laser knife;
2) Printing a platinum electrode layer, namely an upper oxygen pump electrode layer 7, a first cavity catalytic electrode layer 8, a second cavity catalytic electrode layer 9, a reference electrode 16 and a built-in heating electrode 18 on the corresponding dielectric layer; drying, and then carrying out laser punching, wherein the aperture is controlled to be 0.1-0.5 mm;
3) The nitrogen oxide catalytic electrode 15 is printed on the lower oxygen pump cell layer 3, the electrode metal material used is platinum rhodium palladium alloy, and the weight percentages of metals in the electrode composition are respectively as follows: 80wt% of platinum, 10wt% of rhodium, 5wt% of palladium and 5wt% of zirconia, and the preparation of slurry is prepared by a method known to a skilled person;
4) Printing a boss 13 on the lower oxygen pump cell layer 3, wherein the height of the boss is 1/3 of the height of a gas detection chamber (a first cavity 11 or a second cavity 14), the boss is prepared by adopting a screen printing mode, and solid phase powder in printing slurry is commercial YSZ; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 3wt% of thickener nitrocellulose, 3wt% of plasticizer phthalate and 40% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
5) Preparing a porous gas diffusion barrier layer 10, wherein the weight percentage composition of solid phase powder in printing slurry is as follows: 18 weight percent of zirconia powder, 62 weight percent of magnesia-alumina spinel powder, 20 weight percent of carbon powder and 100 weight percent of the sum of the components; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: thickener nitrocellulose 1wt%, plasticizer phthalate 5wt%, organic solvent tributyl citrate 60%; the solid phase powder passes through a 300-mesh sieve;
6) A dense gas diffusion barrier layer 12 is prepared, wherein the weight percentage composition of solid phase powder in the printing slurry is as follows: 20wt% of zirconia powder, 65wt% of magnesia-alumina spinel powder, 15wt% of carbon powder, and 100% of the sum of the components in percentage by weight; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 3wt% of thickener nitrocellulose, 5wt% of plasticizer phthalate and 60% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
7) Printing a porous oxygen reference layer 4 on the substrate layer, wherein the paste for screen printing is the same as the paste used for the porous gas diffusion barrier layer 10;
8) Electrode lead holes are formed in each dielectric layer, the embryo sheet layers are sequentially positioned and laminated according to the structure of the oxygen sensor ceramic sheet, and the embryo sheet layers are placed into a pressing table for compaction;
9) Cutting the blank according to the cutting line to obtain an oxygen sensor ceramic chip plain blank;
10 After removing organic matters at 650 ℃, sintering at a high temperature of 1450 ℃ for 8 hours, preserving heat at a temperature of 1200 ℃ for 2 hours when the temperature is reduced by sintering, and then cooling along with a furnace to obtain the oxygen sensor ceramic sheet.
The foregoing has shown and described the basic principles and main structural features of the present invention. The present invention is not limited to the above examples, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The utility model provides a nitrogen oxide sensor chip, includes last oxygen pump cell layer (1), tail gas control layer (2), lower oxygen pump cell layer (3), porous oxygen reference layer (4), goes up heating substrate layer (5) and lower heating substrate layer (6) of laminating in proper order, its characterized in that: an upper oxygen pump electrode layer (7) is printed on one surface, far away from the tail gas control layer (2), of the upper oxygen pump cell layer (1), a gas detection chamber and a porous gas diffusion barrier layer (10) are arranged between one surface, opposite to the tail gas control layer (2), of the upper oxygen pump cell layer (1) and the lower oxygen pump cell layer (3), the porous gas diffusion barrier layer (10) is arranged on one side, far away from the tail gas control layer (2), of the gas detection chamber, a boss (13) is arranged in the gas detection chamber, the boss (13) is printed on the lower oxygen pump cell layer (3), and a compact gas diffusion barrier layer (12) is arranged between the boss (13) and the upper oxygen pump cell layer (1); the gas detection chamber is divided into a first cavity (11) and a second cavity (14) by the boss (13) and the compact gas diffusion barrier layer (12), a first cavity catalytic electrode layer (8) is arranged in the first cavity (11), a second cavity catalytic electrode layer (9) and a nitrogen oxide catalytic electrode (15) are arranged in the second cavity (14), the first cavity catalytic electrode layer (8) and the second cavity catalytic electrode layer (9) are printed on the upper oxygen pump cell layer (1), one end, close to the porous gas diffusion barrier layer (10), of the boss (13) is opposite to the first cavity catalytic electrode layer (8), one end, far away from the porous gas diffusion barrier layer (10), of the boss (13) is opposite to the second cavity catalytic electrode layer (9), and the nitrogen oxide catalytic electrode (15) is printed on the lower oxygen pump cell layer (3); a reference electrode (16) is arranged between the porous oxygen reference layer (4) and the lower oxygen pump cell layer (3), and an insulating layer (17) and a built-in heating electrode (18) are sequentially arranged between the upper heating substrate layer (5) and the lower heating substrate layer (6);
the boss (13) is made of zirconia ceramics and is prepared by adopting a screen printing mode, and solid phase powder in printing slurry is commercial YSZ; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 2-4wt% of thickener nitrocellulose, 0.5-wt wt% of plasticizer phthalate and 30-60 wt% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve.
2. The nitrogen oxide sensor chip of claim 1, wherein: the height of the boss (13) is 1/4-1/2 of the height of the gas detection chamber.
3. The nitrogen oxide sensor chip of claim 1, wherein: the surface of the upper oxygen pump electrode layer (7) is provided with an alumina protective layer.
4. The nitrogen oxide sensor chip of claim 1, wherein: and a filler with a porous structure is arranged in the porous oxygen reference layer (4).
5. A method of manufacturing a nitrogen oxide sensor chip according to any one of claims 1 to 4, comprising the steps of:
1) Preparing each dielectric layer: the yttrium stabilized zirconia nano-powder is adopted as a main material, and an organic material binder polyvinyl butyral, a plasticizer dibutyl phthalate and absolute ethyl alcohol are respectively added, and uniformly mixed to prepare a membrane; cutting into sample pieces, printing cutting lines and positioning lines on each layer respectively, and cutting into each medium layer;
2) Corresponding upper oxygen pump electrode layers (7), first cavity catalytic electrode layers (8), second cavity catalytic electrode layers (9), reference electrodes (16) and built-in heating electrodes (18) are printed on the corresponding dielectric layers, the upper oxygen pump electrode layers (7), the first cavity catalytic electrode layers (8), the second cavity catalytic electrode layers (9), the reference electrodes (16) and the built-in heating electrodes (18) are all platinum electrode layers, and the holes are punched after drying;
3) Printing a nitrogen oxide catalytic electrode (15) on the lower oxygen pump cell layer (3) corresponding to the dielectric layer, wherein the electrode metal material used by the nitrogen oxide catalytic electrode is platinum-rhodium-palladium alloy;
4) Printing a boss (13) on the corresponding lower oxygen pump cell layer (3);
5) Preparing a porous gas diffusion barrier layer (10), wherein the solid phase powder in the printing slurry comprises the following components: zirconia powder, magnesia-alumina spinel powder and carbon powder, wherein the sum of the weight percentages of the components is 100 percent; adding an organic material into the printing slurry, wherein the organic material comprises the following components: the thickener is nitrocellulose, the plasticizer is phthalate, and the organic solvent is tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
6) Preparing a compact gas diffusion barrier layer (12), wherein the solid phase powder in the printing slurry comprises the following components: zirconia powder, magnesia-alumina spinel powder and carbon powder, wherein the sum of the weight percentages of the components is 100 percent; the printing slurry is added with organic materials, and the organic materials are: the thickener is nitrocellulose, the plasticizer is phthalate, and the organic solvent is tributyl citrate; the solid phase powder passes through a 300-mesh sieve;
7) Printing a porous oxygen reference layer (4) on the substrate layer, wherein the paste used for screen printing is the same as the paste used for the porous gas diffusion barrier layer (10);
8) Electrode lead holes are formed in each dielectric layer, the upper layers of the nitrogen oxide sensor chip are sequentially positioned and laminated according to the structural sequence, and the laminated layers are placed into a pressing table for compaction, so that a nitrogen oxide sensor chip blank is obtained;
9) Cutting the nitrogen oxide sensor chip embryo according to the cutting line to obtain a nitrogen oxide sensor chip element embryo;
10 After removing organic matters, sintering at high temperature, preserving heat when sintering and cooling, and cooling along with a furnace to obtain the nitrogen oxide sensor chip.
6. The method for manufacturing a nitrogen oxide sensor chip according to claim 5, wherein: the porous gas diffusion barrier layer (10) and the compact gas diffusion barrier layer (12) are printed by screen printing, and the material ratio of the two diffusion barrier layers is different due to different purposes.
7. The method for manufacturing a nitrogen oxide sensor chip according to claim 6, wherein: the porous gas diffusion barrier layer (10) comprises the following solid phase powder in weight percentage in printing slurry: 10-20wt% of zirconia powder, 50-65wt% of magnesia-alumina spinel powder, 20-30wt% of carbon powder, wherein the sum of the weight percentages of the components is 100%; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 1-5wt% of thickener nitrocellulose, 0.5-wt% by weight of plasticizer phthalate and 30-60wt% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve.
8. The method for manufacturing a nitrogen oxide sensor chip according to claim 6, wherein: the compact gas diffusion barrier layer (12) comprises the following solid phase powder in weight percentage in printing slurry: 10-20wt% of zirconia powder, 65-80wt% of magnesia-alumina spinel powder, 5-15wt% of carbon powder, and the sum of the weight percentages of the components is 100%; organic materials are added into the printing slurry, and the addition amount of the organic materials is calculated on the basis of the weight of the solid phase powder: 1-5wt% of thickener nitrocellulose, 0.5-wt% by weight of plasticizer phthalate and 30-60wt% of organic solvent tributyl citrate; the solid phase powder passes through a 300-mesh sieve.
9. The method for manufacturing a nitrogen oxide sensor chip according to claim 5, wherein: the nitrogen oxide catalytic electrode (15) comprises the following metals in percentage by weight: 70-80 wt% of platinum, 10-20 wt% of rhodium, 5wt% of palladium and 5wt% of zirconia, and sieving the alloy powder through a 300-mesh sieve.
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| JP2003344350A (en) * | 2002-05-28 | 2003-12-03 | Kyocera Corp | Oxygen sensor element |
| CN104049018A (en) * | 2014-06-30 | 2014-09-17 | 东风电子科技股份有限公司 | Nox sensor chip |
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| CN103822952A (en) * | 2013-12-12 | 2014-05-28 | 苏州工业园区福特斯汽车电子有限公司 | Wide-band oxygen sensor chip and manufacturing method thereof |
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| JP2003344350A (en) * | 2002-05-28 | 2003-12-03 | Kyocera Corp | Oxygen sensor element |
| CN104049018A (en) * | 2014-06-30 | 2014-09-17 | 东风电子科技股份有限公司 | Nox sensor chip |
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