CN113340963A - Nitrogen-oxygen electrochemical gas sensor chip - Google Patents
Nitrogen-oxygen electrochemical gas sensor chip Download PDFInfo
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- CN113340963A CN113340963A CN202110669943.3A CN202110669943A CN113340963A CN 113340963 A CN113340963 A CN 113340963A CN 202110669943 A CN202110669943 A CN 202110669943A CN 113340963 A CN113340963 A CN 113340963A
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- 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
- G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
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- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- 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
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- 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
- G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
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- 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
- G01N27/409—Oxygen concentration cells
Abstract
The invention discloses a chip of a nitrogen-oxygen electrochemical gas sensor, which is integrally flaky and comprises a first zirconium oxide solid electrolyte layer, a second zirconium oxide solid electrolyte layer, a third zirconium oxide solid electrolyte layer, a fourth zirconium oxide solid electrolyte layer, a fifth zirconium oxide solid electrolyte layer, a sixth zirconium oxide solid electrolyte layer, a first diffusion barrier, a first outer electrode, a first inner electrode, a first test cavity, a second diffusion barrier, a second inner electrode, a third inner electrode, a second outer electrode, an air reference cavity filled with a porous ceramic I and a heating electrode. The invention solves the problems that the ceramic chip of the common nitrogen-oxygen sensor is mostly provided with four through holes and three diffusion barriers, the structure is very complex, the production and processing difficulty is high, the reject ratio is high, and the chip is cracked due to stress concentration at the excessive parts of the through holes during actual use, thereby saving the cost.
Description
Technical Field
The invention relates to the technical field of a nitrogen oxide electrochemical gas sensor chip, and particularly belongs to a nitrogen oxide electrochemical gas sensor chip.
Background
An automobile engine is a machine that directly converts heat energy released by burning fuel inside the machine into power. At present, people preferably use a lean combustion mixture as fuel in order to save fuel, but harmful pollution gas nitrogen oxide N0x can be generated in the process, and in order to reduce the emission of nitrogen oxide N0x and meet the requirement of up-to-standard emission of engine exhaust gas, a nitrogen-oxygen electrochemical gas sensor chip is required to be used for manufacturing a sensor for detection, regulation and control.
The application publication No. CN 109001284A discloses a nitrogen oxide sensor ceramic chip, wherein a first membrane is provided with an oxygen pump anode with a surface covering protective layer, the oxygen pump anode and the first membrane are provided with a collection cavity, a second membrane is provided with a second through hole, a fourth through hole, a first diffusion barrier is arranged in the second through hole, the second through hole is divided into a first measurement chamber and a buffer cavity by the first diffusion barrier, a main oxygen pump cathode is arranged in the first measurement chamber, a second diffusion barrier is arranged between the second through hole and the third through hole, an auxiliary pump cathode is arranged in the second measurement chamber by the third through hole, a third diffusion barrier is arranged between the third through hole and the fourth through hole, the fourth through hole is a measurement electrode with a surface covering protective layer arranged in the third measurement chamber, a reference channel is arranged on the third membrane, a reference electrode with a surface covering protective layer is arranged in the reference channel, a heating electrode wrapped in a heating electrode insulating layer is arranged between the fourth membrane and the fifth membrane, the heating electrode outer lead penetrates through the fifth layer membrane and is positioned on the lower surface of the fifth layer membrane, and the fifth layer membrane is provided with a stress release hole filled with heating electrode insulating layer slurry. However, the ceramic chip of the oxynitride sensor disclosed in the patent has four through holes and three diffusion barriers, and the structure is very complex, so that the difficulty of production and processing is high, the reject ratio of products is high, and in the actual use process, stress concentration is easily generated at the positions with too many through holes, so that the chip is easy to crack.
In order to solve the problems of the chip products disclosed by the patent in practical use, the invention provides the chip of the nitrogen-oxygen electrochemical gas sensor. The method is suitable for popularization and use in automobile engines and supporting industries during production and manufacturing of the nitrogen-oxygen electrochemical gas sensor.
Disclosure of Invention
The invention provides a chip of a nitrogen-oxygen electrochemical gas sensor, which solves the problems in the background technology by the overall research and development design of a first zirconium oxide solid electrolyte layer, a second zirconium oxide solid electrolyte layer, a third zirconium oxide solid electrolyte layer, a fourth zirconium oxide solid electrolyte layer, a fifth zirconium oxide solid electrolyte layer, a sixth zirconium oxide solid electrolyte layer, a first diffusion barrier, a first outer electrode, a first inner electrode, a first test cavity, a second diffusion barrier, a second inner electrode, a third inner electrode, a second outer electrode, an air reference cavity filled with a porous ceramic I, a heating electrode and a porous ceramic II.
Meanwhile, the invention can measure the content concentration of the nitrogen oxide in the calculated nitrogen-oxygen electrochemical gas in a simpler way, the integral accuracy is high, the sensor chip in the invention integrally comprises two pump units and a Nernst unit, wherein the second pump unit (which is a measuring pump unit) and the Nernst unit can share a common second external electrode and can be arranged to be in direct contact with the ambient air, and an air reference cavity is integrated into the whole sensor chip, thereby simplifying the integral design of the chip, saving the manufacturing cost of the chip and prolonging the service life of the chip nitrogen-oxygen electrochemical gas sensor. The method is suitable for popularization and use in automobile engines and supporting industries during production and manufacturing of the nitrogen-oxygen electrochemical gas sensor.
The technical scheme adopted by the invention for realizing the aim is as follows:
a chip of a nitrogen-oxygen electrochemical gas sensor is characterized in that the chip is integrally flaky and comprises a first zirconium oxide solid electrolyte layer, a second zirconium oxide solid electrolyte layer, a third zirconium oxide solid electrolyte layer, a fourth zirconium oxide solid electrolyte layer, a fifth zirconium oxide solid electrolyte layer and a sixth zirconium oxide solid electrolyte layer, a measuring gas inlet hole is formed in the first zirconium oxide solid electrolyte layer, a first diffusion barrier is filled in the measuring gas inlet hole, a first outer electrode is screened and printed on the outer side of the upper surface of the first diffusion barrier, a first inner electrode is screened and printed on the lower surface of the diffusion barrier, a second zirconium oxide solid electrolyte layer is arranged on the lower portion of the first zirconium oxide solid electrolyte layer, a first testing cavity and a second testing cavity are formed in the second zirconium oxide solid electrolyte layer, the first testing cavity and the second testing cavity are isolated by a second diffusion barrier, a second inner electrode and a third inner electrode are arranged in the second testing cavity, a third zirconia solid electrolyte layer is arranged on the lower portion of the second zirconia solid electrolyte layer, a fourth zirconia solid electrolyte layer is arranged on the lower portion of the third zirconia solid electrolyte layer, an air reference cavity is arranged on the fourth zirconia solid electrolyte layer, a first porous ceramic is filled in the air reference cavity and can enable the air reference cavity to be communicated with the atmosphere, the second inner electrode and the third inner electrode are both screened and printed on the third zirconia solid electrolyte layer, a second outer electrode is screened and printed on a region, corresponding to the second inner electrode, below the third zirconia solid electrolyte layer, a region where the second outer electrode is located in the air reference cavity, a fifth zirconia solid electrolyte layer is arranged on the lower portion of the fourth zirconia solid electrolyte layer, a sixth zirconia solid electrolyte layer is arranged on the lower portion of the fifth zirconia solid electrolyte layer, and a heating electrode is screened and printed on the sixth zirconia solid electrolyte layer, and after the first zirconia solid electrolyte layer, the second zirconia solid electrolyte layer, the third zirconia solid electrolyte layer, the fourth zirconia solid electrolyte layer, the fifth zirconia solid electrolyte layer and the sixth zirconia solid electrolyte layer are pressed together, the materials are sintered and molded at a high temperature according to a common temperature curve.
Further, the first diffusion barrier and the second diffusion barrier are made of a second porous ceramic, the porosity of the first porous ceramic is 70%, and the porosity of the second porous ceramic is 30%.
Furthermore, the first outer electrode and the second outer electrode are platinum electrodes, the first inner electrode is a platinum-gold alloy electrode, the second inner electrode and the third inner electrode are platinum-rhodium alloy electrodes, and the heating electrode is a platinum electrode.
Further, when the chip of the nitrogen-oxygen electrochemical gas sensor is actually used, the first outer electrode and the first inner electrode can be used as pump electrodes of the first pump unit, pump currents are generated on the first outer electrode and the first inner electrode, oxygen can be pumped in or pumped out through the pump currents, the oxygen partial pressure in the first test cavity is enabled to be a constant value, and the constant value of the oxygen partial pressure is 200 ppm;
the gas regulated to constant oxygen partial pressure in the first test chamber can enter a second test chamber through a second diffusion barrier, and a second inner electrode and a second outer electrode in the second test chamber can be operated as a second pump unit;
the first pump unit can be used for controlling and adjusting oxygen partial pressure in the first test cavity, the first pump current between the first outer electrode and the first inner electrode is controlled and adjusted, the oxygen partial pressure in the first test cavity is controlled and adjusted, a constant second pump current can appear on the second pump unit, when the used nitrogen-oxygen electrochemical gas is a lean measurement gas (the air-fuel ratio is more than 1), oxygen can be pumped out of the first test cavity through the first pump unit, when the used nitrogen-oxygen electrochemical gas is a rich combustion gas (the air-fuel ratio is less than 1), the oxygen is pumped into the first test cavity, the constant value of the oxygen partial pressure is 200ppm, the electrode material of the first inner electrode is a platinum alloy electrode, and nitrogen-oxygen compounds can be pumped out without catalytic decomposition at the first inner electrode;
the third inner electrode and the second outer electrode can form a Nernst unit, the Nernst unit can be used for measuring the content of free oxygen in the second test cavity, the second pump unit is used for pumping out the free oxygen in the second test cavity at the moment, meanwhile, the second inner electrode can decompose oxygen from the nitrogen-oxygen electrochemical gas and be pumped out by the second pump unit, at the moment, the pump current is converted into the amount of the oxygen, the content of the free oxygen is measured by subtracting the Nernst unit, and the content of nitrogen oxide in the nitrogen-oxygen electrochemical gas can be calculated.
Compared with the prior art, the invention has the following beneficial effects:
through the whole research and development design combination of a first zirconium oxide solid electrolyte layer, a second zirconium oxide solid electrolyte layer, a third zirconium oxide solid electrolyte layer, a fourth zirconium oxide solid electrolyte layer, a fifth zirconium oxide solid electrolyte layer, a sixth zirconium oxide solid electrolyte layer, a first diffusion barrier, a first outer electrode, a first inner electrode, a first test cavity, a second diffusion barrier, a second inner electrode, a third inner electrode, a second outer electrode, an air reference cavity filled with a first porous ceramic, a heating electrode and a second porous ceramic, a nitrogen-oxygen electrochemical gas sensor chip is manufactured, and the nitrogen-oxygen electrochemical gas enters the first test cavity through a gas inlet filled with the first diffusion barrier; the air reference cavity filled with the porous ceramic I can be in direct contact with ambient air to serve as a reference gas cavity, the amount of oxygen converted from the pump current I in the first pump unit is detected, the content of free oxygen measured by the Nernst unit is subtracted, and the content of nitrogen oxide in the nitrogen-oxygen electrochemical gas can be calculated.
The invention can simplify the whole design of the chip, save the manufacturing cost of the chip, prolong the service life of the chip nitrogen-oxygen electrochemical gas sensor and solve the problems that the original common nitrogen-oxygen sensor ceramic chip product has four through holes and three diffusion barriers, has very complex structure, large production and processing difficulty and high reject ratio, and the chip is cracked because stress concentration is easy to occur at the excessive parts of the through holes during actual use.
Drawings
FIG. 1 is a schematic view of the overall structure of the present invention;
FIG. 2 is a schematic longitudinal sectional view of a diffusion barrier of the present invention, taken generally perpendicular to a horizontal plane of a first gas inlet hole in a first solid electrolyte layer of zirconia.
Remarks explanation: 1 is a second inner electrode; 2 is a third inner electrode; 3 is a diffusion barrier I; 4 is a first test chamber; 5 is a diffusion barrier II; 6 is a second test cavity; 7a is a first zirconia solid electrolyte layer; 7b is a second zirconia solid electrolyte layer; 7c is a third zirconia solid electrolyte layer; 7d is a fourth zirconia solid electrolyte layer; 7e is a fifth zirconia solid electrolyte layer; 7f is a sixth zirconia solid electrolyte layer; 8 is a first internal electrode; 9 is a first external electrode; 10 is porous ceramic I; 11 is a second external electrode; and 12 is a heating electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious 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.
The present invention will be described in further detail with reference to examples and specific embodiments.
Referring to the drawings: a chip of a nitrogen-oxygen electrochemical gas sensor is characterized in that the whole chip is a sheet and comprises a first zirconia solid electrolyte layer 7a, a second zirconia solid electrolyte layer 7b, a third zirconia solid electrolyte layer 7c, a fourth zirconia solid electrolyte layer 7d, a fifth zirconia solid electrolyte layer 7e and a sixth zirconia solid electrolyte layer 7f, a measuring gas inlet hole is formed in the first zirconia solid electrolyte layer 7a, a diffusion barrier 3 is filled in the measuring gas inlet hole, a first outer electrode 9 is screened and printed on the outer side of the upper surface of the diffusion barrier 3, a first inner electrode 8 is screened and printed on the lower surface of the diffusion barrier 3, a second zirconia solid electrolyte layer 7b is arranged on the lower portion of the first zirconia solid electrolyte layer 7a, a first test cavity 4 and a second test cavity 6 are formed in the second zirconia solid electrolyte layer 7b, the first test cavity 4 and the second test cavity 6 are isolated by a second diffusion barrier 5, the second test cavity 6 is internally provided with a second internal electrode 1 and a third internal electrode 2, the lower part of the second zirconium dioxide solid electrolyte layer 7b is provided with a third zirconium oxide solid electrolyte layer 7c, the lower part of the third zirconium oxide solid electrolyte layer 7c is provided with a fourth zirconium oxide solid electrolyte layer 7d, the fourth zirconium oxide solid electrolyte layer 7d is provided with an air reference cavity, the air reference cavity is filled with a porous ceramic 10, the porous ceramic 10 enables the air reference cavity to be communicated with the atmosphere, the second internal electrode 1 and the third internal electrode 2 are both screened and printed on the third zirconium oxide solid electrolyte layer 7c, the area below the third zirconium oxide solid electrolyte layer 7c corresponding to the second internal electrode 1 is screened and printed with a second external electrode 11, the area where the second external electrode 11 is located in the air reference cavity, the lower part of the fourth zirconium oxide solid electrolyte layer 7d is provided with a fifth zirconium oxide solid electrolyte layer 7e, and a sixth zirconia solid electrolyte layer 7f is arranged on the lower part of the fifth zirconia solid electrolyte layer 7e, a heating electrode 12 is screened and printed on the sixth zirconia solid electrolyte layer 7f, and the first zirconia solid electrolyte layer 7a, the second zirconia solid electrolyte layer 7b, the third zirconia solid electrolyte layer 7c, the fourth zirconia solid electrolyte layer 7d, the fifth zirconia solid electrolyte layer 7e and the sixth zirconia solid electrolyte layer 7f are pressed together and then sintered and molded at high temperature through a common temperature curve.
Further, the first diffusion barrier 3 and the second diffusion barrier 5 are made of a second porous ceramic, the first porous ceramic 10 has a porosity of 70%, and the second porous ceramic has a porosity of 30%.
Further, the first external electrode 9 and the second external electrode 11 are platinum electrodes, the first internal electrode 8 is a platinum-gold alloy electrode, the second internal electrode 1 and the third internal electrode 2 are platinum-rhodium alloy electrodes, and the heating electrode 12 is a platinum electrode.
Further, when the chip of the nitrogen-oxygen electrochemical gas sensor is actually used, the first outer electrode 9 and the first inner electrode 8 can be used as pump electrodes of a first pump unit, pump currents are generated on the first outer electrode 9 and the first inner electrode 8, oxygen can be pumped in or pumped out through the pump currents, so that the oxygen partial pressure in the first test cavity 4 is a constant value, and the constant value of the oxygen partial pressure is 200 ppm;
the gas in the first test chamber 4, which is regulated to a constant oxygen partial pressure, can enter the second test chamber 6 through the second diffusion barrier 5, and the second inner electrode 1 in the second test chamber 6, together with the second outer electrode 11, can operate as a second pump unit;
the first pump unit can be used for controlling and adjusting the oxygen partial pressure in the first test cavity 4, the constant pump current II can be generated on the second pump unit by adjusting and controlling the pump current I between the first outer electrode 9 and the first inner electrode 8, when the used nitrogen-oxygen electrochemical gas is a lean measurement gas (the air-fuel ratio is more than 1), oxygen can be pumped out from the first test cavity 4 through the first pump unit, when the used nitrogen-oxygen electrochemical gas is a rich combustion gas (the air-fuel ratio is less than 1), oxygen is pumped into the first test cavity 4, the oxygen partial pressure is 200ppm, the electrode material of the first inner electrode 8 is a platinum alloy electrode, and nitrogen-oxygen compounds can be pumped out without catalytic decomposition at the first inner electrode 8;
the third inner electrode 2 and the second outer electrode 11 can form a Nernst unit which can be used for measuring the content of free oxygen in the second test cavity 6, the second pump unit is used for pumping out the free oxygen in the second test cavity 6 at the moment, meanwhile, the second inner electrode 1 can decompose the oxynitride electrochemical gas into oxygen and is pumped out by the second pump unit, the first pump current is converted into the amount of the oxygen at the moment, and the content of the oxynitride in the oxynitride electrochemical gas can be calculated by subtracting the content of the free oxygen measured by the Nernst unit.
The invention integrally develops and designs a combination of a first zirconia solid electrolyte layer 7a, a second zirconia solid electrolyte layer 7b, a third zirconia solid electrolyte layer 7c, a fourth zirconia solid electrolyte layer 7d, a fifth zirconia solid electrolyte layer 7e, a sixth zirconia solid electrolyte layer 7f, a first diffusion barrier 3, a first outer electrode 9, a first inner electrode 8, a first test cavity 4, a second test cavity 6, a second diffusion barrier 5, a second inner electrode 1, a third inner electrode 2, a second outer electrode 11, an air reference cavity filled with a porous ceramic I10, a heating electrode 12 and a porous ceramic II, so as to manufacture a nitrogen-oxygen electrochemical gas sensor chip, wherein the nitrogen-oxygen electrochemical gas enters the first test cavity 4 through an air inlet filled with the diffusion barrier I3; the air reference cavity filled with the first porous ceramic 10 can be in direct contact with ambient air to serve as a reference gas cavity, the content of nitrogen oxides in the nitrogen-oxygen electrochemical gas can be calculated by detecting the amount of the pump current I converted into oxygen in the first pump unit and subtracting the content of free oxygen measured by the Nernst unit.
Meanwhile, the invention can measure the content concentration of the nitrogen oxide in the calculated nitrogen oxide electrochemical gas in a simpler way, the integral accuracy is high, the sensor chip in the invention integrally comprises two pump units and one Nernst unit, wherein the second pump unit (which is a measuring pump unit) and the Nernst unit can share one common second external electrode and can be arranged to be in direct contact with ambient air, and an air reference cavity is integrated into the whole sensor chip, thereby solving the problems that the original common nitrogen oxide sensor ceramic chip product has four through holes and three diffusion barriers, the structure is very complex, the production and processing difficulty is high, the reject ratio is high, and the parts with excessive through holes are easy to generate stress concentration during actual use, so that the chip is cracked. The chip simplifies the whole design of the chip, saves the manufacturing cost of the chip and prolongs the service life of the chip nitrogen-oxygen electrochemical gas sensor. The method is suitable for popularization and use in automobile engines and supporting industries during production and manufacturing of the nitrogen-oxygen electrochemical gas sensor.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (4)
1. A chip of a nitrogen-oxygen electrochemical gas sensor is characterized in that the chip is integrally flaky and comprises a first zirconium oxide solid electrolyte layer, a second zirconium oxide solid electrolyte layer, a third zirconium oxide solid electrolyte layer, a fourth zirconium oxide solid electrolyte layer, a fifth zirconium oxide solid electrolyte layer and a sixth zirconium oxide solid electrolyte layer, a measuring gas inlet hole is formed in the first zirconium oxide solid electrolyte layer, a first diffusion barrier is filled in the measuring gas inlet hole, a first outer electrode is screened and printed on the outer side of the upper surface of the first diffusion barrier, a first inner electrode is screened and printed on the lower surface of the diffusion barrier, a second zirconium oxide solid electrolyte layer is arranged on the lower portion of the first zirconium oxide solid electrolyte layer, a first testing cavity and a second testing cavity are formed in the second zirconium oxide solid electrolyte layer, the first testing cavity and the second testing cavity are isolated by a second diffusion barrier, a second inner electrode and a third inner electrode are arranged in the second testing cavity, a third zirconia solid electrolyte layer is arranged on the lower portion of the second zirconia solid electrolyte layer, a fourth zirconia solid electrolyte layer is arranged on the lower portion of the third zirconia solid electrolyte layer, an air reference cavity is arranged on the fourth zirconia solid electrolyte layer, a first porous ceramic is filled in the air reference cavity and can enable the air reference cavity to be communicated with the atmosphere, the second inner electrode and the third inner electrode are both screened and printed on the third zirconia solid electrolyte layer, a second outer electrode is screened and printed on a region, corresponding to the second inner electrode, below the third zirconia solid electrolyte layer, a region where the second outer electrode is located in the air reference cavity, a fifth zirconia solid electrolyte layer is arranged on the lower portion of the fourth zirconia solid electrolyte layer, a sixth zirconia solid electrolyte layer is arranged on the lower portion of the fifth zirconia solid electrolyte layer, and a heating electrode is screened and printed on the sixth zirconia solid electrolyte layer, and after the first zirconia solid electrolyte layer, the second zirconia solid electrolyte layer, the third zirconia solid electrolyte layer, the fourth zirconia solid electrolyte layer, the fifth zirconia solid electrolyte layer and the sixth zirconia solid electrolyte layer are pressed together, the materials are sintered and molded at a high temperature according to a common temperature curve.
2. The NI-O electrochemical gas sensor chip of claim 1, wherein said first diffusion barrier and said second diffusion barrier are made of a second porous ceramic, said first porous ceramic having a porosity of 70%, said second porous ceramic having a porosity of 30%.
3. The chip of claim 1, wherein the first and second external electrodes are platinum electrodes, the first internal electrode is a platinum-gold alloy electrode, the second and third internal electrodes are platinum-rhodium alloy electrodes, and the heater electrode is a platinum electrode.
4. The NI electrochemical gas sensor chip according to claims 1 to 3, wherein the first external electrode and the first internal electrode are capable of functioning as pump electrodes of the first pump unit, and a pump current is generated at the first external electrode and the first internal electrode, by which oxygen can be pumped in or out, so that the oxygen partial pressure in the first test chamber is a constant value, and the constant value of the oxygen partial pressure is 200 ppm;
the gas regulated to constant oxygen partial pressure in the first test chamber can enter a second test chamber through a second diffusion barrier, and a second inner electrode and a second outer electrode in the second test chamber can be operated as a second pump unit;
the first pump unit can be used for controlling and adjusting oxygen partial pressure in the first test cavity, the first pump current between the first outer electrode and the first inner electrode is controlled and adjusted, the oxygen partial pressure in the first test cavity is controlled and adjusted, a constant second pump current can appear on the second pump unit, when the used nitrogen-oxygen electrochemical gas is a lean measurement gas (the air-fuel ratio is more than 1), oxygen can be pumped out of the first test cavity through the first pump unit, when the used nitrogen-oxygen electrochemical gas is a rich combustion gas (the air-fuel ratio is less than 1), the oxygen is pumped into the first test cavity, the constant value of the oxygen partial pressure is 200ppm, the electrode material of the first inner electrode is a platinum alloy electrode, and nitrogen-oxygen compounds can be pumped out without catalytic decomposition at the first inner electrode;
the third inner electrode and the second outer electrode can form a Nernst unit, the Nernst unit can be used for measuring the content of free oxygen in the second test cavity, the second pump unit is used for pumping out the free oxygen in the second test cavity at the moment, meanwhile, the second inner electrode can decompose oxygen from the nitrogen-oxygen electrochemical gas and be pumped out by the second pump unit, at the moment, the pump current is converted into the amount of the oxygen, the content of the free oxygen is measured by subtracting the Nernst unit, and the content of nitrogen oxide in the nitrogen-oxygen electrochemical gas can be calculated.
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