CN112198206A - Electrochemical gas sensor chip - Google Patents

Electrochemical gas sensor chip Download PDF

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Publication number
CN112198206A
CN112198206A CN202010993654.4A CN202010993654A CN112198206A CN 112198206 A CN112198206 A CN 112198206A CN 202010993654 A CN202010993654 A CN 202010993654A CN 112198206 A CN112198206 A CN 112198206A
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solid electrolyte
electrolyte layer
layer
gas
electrode layer
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苗伟峰
张文振
徐斌
李敏
孔德方
王梦寻
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Suzhou Hesu Sensor Science & Technology Co ltd
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Suzhou Hesu Sensor Science & Technology Co ltd
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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
    • G01N27/4072—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure characterized by the diffusion barrier
    • 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
    • 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

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Abstract

The invention discloses an electrochemical gas sensor chip which is a sheet-shaped gas sensor chip as a whole, wherein the right side end part of the gas sensor chip is a trapezoidal inclined interface and comprises a first external electrode layer and a second external electrode layer which are directly exposed in gas, a second diffusion barrier layer, a first internal electrode layer, a second internal electrode layer, a third internal electrode layer, a first measuring gas chamber, a second measuring gas chamber and a resistance heater layer which are positioned in a solid electrolyte layer, a gas inlet positioned on the solid electrolyte layer, a first diffusion barrier layer arranged in the gas inlet and a reference gas channel communicated with the external gas. The invention can measure the oxygen concentration in the gas containing nitrogen oxide and the oxygen concentration in the chip, solves the problem that an oxygen sensor needs to be added when measuring the oxygen concentration in the waste gas flow of the internal combustion engine, saves the cost, and has good use effect and excellent performance.

Description

Electrochemical gas sensor chip
Technical Field
The invention relates to the field of gas sensor chips, in particular to an electrochemical gas sensor chip.
Background
An internal combustion engine is a heat engine that directly converts the heat energy released by burning fuel inside the machine into power. At present, it is preferable to use a lean-burn mixture as a fuel for internal combustion engines in order to save fuel, and in this case, in order to meet the requirement of the internal combustion engine for exhaust gas emission reaching the standard, the internal combustion engine needs to be equipped with a three-way catalyst. But because the three-way catalyst cannot provide a sufficient amount of reducing substance for treating nitrogen oxides NOXFor this purpose, the absorption substances (catalysts) are used to store excess nitrogen oxides NOXSetting the combustion gas to rich combustion for a short period of time until the stored nitrogen oxides NOXCompletely reduced by tail gas such as CO (carbon monoxide) and the like, and then enters a new storage stage. In order to be able to successfully control such a rich/lean alternating gas, two gas sensors are required, one for the nitrogen oxides NOXSensor capable of detecting nitrogen oxides NO at the end of a storage phaseX(iii) an incremental change in; the other is an oxygen sensor which can measure and determine the change in the oxygen concentration, and the oxygen sensor is intended to measure and analyze the change in oxygen in the rich combustion exhaust gas at the end of the regeneration phase when the oxygen content produced from the three-way catalyst is particularly low.
With the changing requirement of domestic standard emission of environmental gases, the research on such gas sensors is gradually increasing. Such as: the sensor of nitrogen oxide described in the patent publication No. CN1186238A includes two chambers for measuring gases, each chamber having a pumping cell at the level of a different layer of a planar oxygen ion-conducting ceramic substrate. Both pump cells comprise two electrodes deposited on a solid electrolyte. The gas to be measured flows through the first diffusion opening into a first measurement gas chamber, where a constant low partial oxygen pressure is set by pumping oxygen in and out of the first pump chamber. The partial pressure of oxygen in the first measurement gas chamber is regulated by the pump voltage of the pump chamber by means of the voltage (electromotive force) of a concentration cell (nernst cell) also located in the first measurement gas chamber; in a second measuring gas chamber, NO in the measuring gas is determinedXConcentration (NO)XMeasuring contents of gasesCan be decomposed on the electrode surface of the second pump cell), the oxygen gas thus generated is extracted together with the oxygen gas still remaining in the measurement gas. The addition of an oxygen sensor to determine the oxygen concentration in the exhaust stream has the disadvantage of requiring two separate gas sensors (one for the nox and one for the oxygen), which increases the overall cost of use. Therefore, the invention provides an electrochemical gas sensor chip, and the sensor manufactured by the chip can use only one sensor, and simultaneously meets the use requirements of two separate gas sensors, thereby ensuring that the whole use cost is not increased.
Disclosure of Invention
The present invention provides an electrochemical gas sensor chip that solves the problems noted in the background art described above by developing and designing the entirety of a sheet-like gas sensor chip and the entirety of a first external electrode layer, a solid electrolyte layer, a first diffusion barrier layer, a second diffusion barrier layer, a first internal electrode layer, a second internal electrode layer, a third internal electrode layer, a second external electrode layer, a resistive heater layer, a gas inlet, a first measurement gas chamber, a second measurement gas chamber, and a reference gas channel therein. Meanwhile, the invention can measure the oxygen concentration in the gas containing nitrogen oxide, can also measure the oxygen concentration in the chip, solves the problem that an oxygen sensor needs to be added when measuring the oxygen concentration in the waste gas flow of the internal combustion engine, can simultaneously meet the use requirements of two independent gas sensors by only using one sensor manufactured by the chip, saves the cost, has good use effect and excellent performance, and is suitable for popularization and use when producing and manufacturing chemical gas sensors.
The technical scheme adopted by the invention for realizing the aim is as follows:
an electrochemical gas sensor chip is a sheet-shaped gas sensor chip in whole, the right side end part of the gas sensor chip is a trapezoidal inclined interface and comprises a first external electrode layer, a solid electrolyte layer, a first diffusion barrier layer, a second diffusion barrier layer, a first internal electrode layer, a second internal electrode layer, a third internal electrode layer, a second external electrode layer, a resistance heater layer, a gas inlet, a first measuring gas chamber, a second measuring gas chamber and a reference gas channel, the first external electrode layer and the second external electrode layer can be directly exposed in gas, the second diffusion barrier layer, the first internal electrode layer, the second internal electrode layer, the third internal electrode layer, the first measuring gas chamber, the second measuring gas chamber and the resistance heater layer are all positioned in the solid electrolyte layer, the gas inlet is positioned on the upper surface of the outermost solid electrolyte layer, the first diffusion barrier layer is arranged on the upper part of the inner side of the gas inlet, the reference gas channel is positioned in the solid electrolyte layer where the second external electrode layer is positioned and in a space between the solid electrolyte layer and the solid electrolyte layer, wherein the resistance heater layer is embedded inside the solid electrolyte layer, and the reference gas channel is directly communicated with external gas.
Preferably, the solid electrolyte layer comprises a first solid electrolyte layer, a second solid electrolyte layer, a third solid electrolyte layer, a fourth solid electrolyte layer, a fifth solid electrolyte layer, a sixth solid electrolyte layer, a seventh solid electrolyte layer and an eighth solid electrolyte layer in sequence from top to bottom, and the solid electrolyte layer is made of yttrium-containing stabilized zirconia nano powder;
the solid electrolyte layer I, the solid electrolyte layer II, the solid electrolyte layer III, the solid electrolyte layer IV, the solid electrolyte layer V, the solid electrolyte layer VI, the solid electrolyte layer VII and the solid electrolyte layer VIII are all prepared by mixing Shenggobain 5Y-ZrO2 powder, PVB binder and solvent butanone, ball milling for 96 hours, defoaming and tape casting to prepare a green solid electrolyte layer I, a solid electrolyte layer II, a solid electrolyte layer III, a solid electrolyte layer IV, a solid electrolyte layer V, a solid electrolyte layer VI, a solid electrolyte layer VII and a solid electrolyte layer VIII, the solid electrolyte layer I, the solid electrolyte layer II, the solid electrolyte layer III, the solid electrolyte layer IV, the solid electrolyte layer VI, the solid electrolyte layer VII and the solid electrolyte layer VIII through sequential lamination and bonding from top to bottom and sintering, the sintering temperature is 1500 ℃.
Preferably, the solid electrolyte layer is a solid electrolyte layer capable of conducting oxygen ions, a first external electrode layer is printed on the outer surface of the upper portion of the first solid electrolyte layer, an air inlet is formed on the upper surface of the first solid electrolyte layer, a second internal electrode layer is printed on the lower portion of the first solid electrolyte layer, a first internal electrode layer is printed on the upper surface of the third solid electrolyte layer, a third internal electrode layer is printed on the lower surface of the third solid electrolyte layer, a third internal electrode layer is printed on the upper surface of the fifth solid electrolyte layer, a second external electrode layer is printed on the lower surface of the fifth solid electrolyte layer, an air inlet is formed on the third solid electrolyte layer, a groove is formed in the fifth solid electrolyte layer, the second diffusion barrier layer is embedded and sintered below the air inlet in the third solid electrolyte layer and in the fourth solid electrolyte layer between the groove and the groove in the fifth solid electrolyte layer, the two diffusion barrier layers are positioned on the inner sides of a third internal electrode layer below the third solid electrolyte layer and a third internal electrode layer above the fifth solid electrolyte layer and are close to the area between an upper air inlet of the third solid electrolyte layer and a groove opening of the fifth solid electrolyte layer, the upper air inlet of the third solid electrolyte layer and the groove opening of the fifth solid electrolyte layer are separated from the third internal electrode layer below the third solid electrolyte layer and the third internal electrode layer above the fifth solid electrolyte layer by the second diffusion barrier layer, and the two diffusion barrier layers are positioned in the areas between the third solid electrolyte layer below the third solid electrolyte layer, the upper surface of the fifth solid electrolyte layer and the fourth solid electrolyte layer;
and a resistance heater layer is embedded between the solid electrolyte layer seven and the solid electrolyte layer eight, the resistance heater layer can be used for heating the sensor chip to enable the sensor chip to reach the required working temperature, the second external electrode layer below the solid electrolyte layer five, the right side of the solid electrolyte layer six and the upper surface of the solid electrolyte layer seven are arranged, and a region between the solid electrolyte layer five and the solid electrolyte layer five is a reference gas channel.
Preferably, the first measuring gas chamber is formed by the spaces below the first solid electrolyte layer, between the second solid electrolyte layer, above and between the third solid electrolyte layer and between the two diffusion barrier layers and above the fifth solid electrolyte layer.
Preferably, the space below the third solid electrolyte layer, the space between the fourth solid electrolyte layer, the outer sides of the two diffusion barrier layers and the space above the fifth solid electrolyte layer together form a second measurement gas chamber.
Preferably, the saint-goban 5Y-ZrO2 powder is produced by saint-goban france, the PVB binder is produced by louyang rich chemical products ltd, and the solvent butanone is produced by jiasong chemical ltd.
Preferably, the air inlet located above the outermost solid electrolyte layer can be located at the position of a right center of the solid electrolyte layer, or the air inlet can be located at the position of an upper surface of the solid electrolyte layer close to one side of the left side, or the air inlet can be located at the position of an upper surface of the solid electrolyte layer close to one side of the right side, the air inlet vertically and longitudinally penetrates through the first solid electrolyte layer, the second solid electrolyte layer, the third solid electrolyte layer and the fourth solid electrolyte layer, and the bottom of the air inlet is located in the area of the notch on the fifth solid electrolyte layer.
Preferably, the first and second internal electrode layers are located in a first measurement gas chamber and the third internal electrode layer is located in a second measurement gas chamber.
Preferably, the first internal electrode layer and the second internal electrode layer are located upstream of the gas flowing into the gas inlet, the first internal electrode layer and the second internal electrode layer have no catalytic activity on nitrogen oxide, the third internal electrode layer can catalyze and decompose nitrogen oxide, and the material for manufacturing the third internal electrode layer can be rhodium or platinum or a rhodium-platinum alloy.
Compared with the prior art, the invention has the following beneficial effects:
an electrochemical gas sensor chip is manufactured by the research and development design combination of the whole chip of the sheet-shaped gas sensor and a first external electrode layer, a solid electrolyte layer, a first diffusion barrier layer, a second diffusion barrier layer, a first internal electrode layer, a second internal electrode layer, a third internal electrode layer, a second external electrode layer, a resistance heater layer, a gas inlet, a first measuring gas chamber, a second measuring gas chamber and a reference gas channel. The use requirement of two separate gas sensors can be simultaneously met by only using one sensor made of the chip of the invention, the problem of the internal combustion engine accessory mentioned in the background art is solved, one oxygen sensor is required to be added for determining the oxygen concentration in the exhaust gas flow, and two separate gas sensors (one is an oxynitride gas sensor and the other is an oxygen sensor) are required, so the defect of increasing the whole use cost is overcome.
The invention can measure NO containing nitrogen oxideXThe oxygen concentration in the gas can also be measured, the problem that an oxygen sensor needs to be added when the oxygen concentration in the exhaust gas flow of the internal combustion engine is measured is solved, the cost is saved, the using effect is good, the performance is excellent, and when the internal combustion engine uses thin gas, the oxygen concentration can be used for controlling nitric oxide NOXCan also be used as nitrogen oxide NOXThe sensor chip can also be used as an oxygen sensor chip, and is suitable for popularization and use in the production and manufacturing of chemical gas sensors.
Drawings
FIG. 1 is a schematic view of the overall structure of the present invention;
FIG. 2 is a schematic longitudinal sectional view of an integrated vertical solid electrolyte layer according to the present invention taken along the horizontal plane of an upper gas inlet.
Remarks explanation: 1 is a first solid electrolyte layer; 2 is a solid electrolyte layer II; 3 is a solid electrolyte layer III; 4 is a solid electrolyte layer IV; 5 is a solid electrolyte layer five; 6 is a solid electrolyte layer six; 7 is a solid electrolyte layer seven; 8 is a solid electrolyte layer eight; 9 is an air inlet; d1 is a first internal electrode layer; d2 is a first external electrode layer; d3 is a second internal electrode layer; d5 is a third internal electrode layer; d6 is a second external electrode layer; d7 is a resistive heater layer; c1 is a first measurement gas chamber; c2 is a second measurement gas chamber; c3 is a reference gas channel; k1 is a first diffusion barrier layer; k2 is a second diffusion barrier layer.
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: an electrochemical gas sensor chip, which is a sheet-like gas sensor chip as a whole, the right end of the gas sensor chip being a trapezoidal inclined interface, comprising a first external electrode layer D2, a solid electrolyte layer, a diffusion barrier layer one K1, a diffusion barrier layer two K2, a first internal electrode layer D1, a second internal electrode layer D3, a third internal electrode layer D5, a second external electrode layer D6, a resistive heater layer D7, a gas inlet 9, a first measurement gas chamber C1, a second measurement gas chamber C2 and a reference gas channel C3, the first external electrode layer D2 and the second external electrode layer D6 being directly exposed to gas, the diffusion barrier layer two K2, the first internal electrode layer D1, the second internal electrode layer D3, the third internal electrode layer D5, the first measurement gas chamber C1, the second measurement gas chamber C2 and the resistive heater layer D7 being located inside the solid electrolyte layer, the gas inlet 9 being located above the solid electrolyte layer, the upper part of the inner side of the gas inlet 9 is provided with a diffusion barrier layer K1, the reference gas channel C3 is positioned in the solid electrolyte layer where the second external electrode layer D6 is positioned, and in the space between the solid electrolyte layer internally embedded with the resistance heater layer D7, the reference gas channel C3 is directly communicated with the external gas.
Preferably, the solid electrolyte layer comprises a solid electrolyte layer I1, a solid electrolyte layer II 2, a solid electrolyte layer III 3, a solid electrolyte layer IV 4, a solid electrolyte layer V5, a solid electrolyte layer VI 6, a solid electrolyte layer VII 7 and a solid electrolyte layer VIII 8 in sequence from top to bottom, and the solid electrolyte layer is made of yttrium-containing stabilized zirconia nano powder;
the solid electrolyte layer I1, the solid electrolyte layer II 2, the solid electrolyte layer III 3, the solid electrolyte layer IV 4, the solid electrolyte layer V5, the solid electrolyte layer VI 7, the solid electrolyte layer VII 7 and the solid electrolyte layer VIII 8 are all prepared by mixing Shenggobain 5Y-ZrO2 powder, PVB binder and solvent butanone, ball milling for 96 hours, then defoaming and tape casting to prepare a green solid electrolyte layer I1, a solid electrolyte layer II 2, a solid electrolyte layer III 3, a solid electrolyte layer IV 4, a solid electrolyte layer V5, a solid electrolyte layer VI 6, a solid electrolyte layer VII 7 and a solid electrolyte layer VIII 8, sequentially superposing and bonding the green blanks from top to bottom through the solid electrolyte layer I1, the solid electrolyte layer II 2, the solid electrolyte layer III 3, the solid electrolyte layer IV 4, the solid electrolyte layer V5, the solid electrolyte layer VI 6, the solid electrolyte layer VII and the solid electrolyte layer VIII 8, sintering to obtain the material, wherein the sintering temperature is 1500 ℃.
Preferably, the solid electrolyte layer is a solid electrolyte layer capable of conducting oxygen ions, the upper outer surface of the solid electrolyte layer 1 is printed with a first external electrode layer D2, the upper surface of the solid electrolyte layer 1 is printed with an air inlet 9, the lower portion of the solid electrolyte layer 1 is printed with a second internal electrode layer D3, the upper surface of the solid electrolyte layer three 3 is printed with a first internal electrode layer D1, the lower surface of the solid electrolyte layer three 3 is printed with a third internal electrode layer D5, the upper surface of the solid electrolyte layer five 5 is printed with a third internal electrode layer D5, the lower surface of the solid electrolyte layer five 5 is printed with a second external electrode layer D6, the solid electrolyte layer three 3 is provided with an air inlet 9, the solid electrolyte layer five 5 is provided with a groove, the diffusion barrier layer two K2 is embedded and sintered in the solid electrolyte layer four 4 between the air inlet 9 on the solid electrolyte layer three 3 and the groove on the solid electrolyte layer five 5, the second diffusion barrier layer K2 is located inside the third inner electrode layer D5 below the third solid electrolyte layer 3 and the third inner electrode layer D5 above the fifth solid electrolyte layer 5, in a region between the upper gas inlet 9 of the third solid electrolyte layer 3 and the notch of the fifth solid electrolyte layer 5, the second diffusion barrier layer K2 separates the upper gas inlet 9 of the third solid electrolyte layer 3 and the notch of the fifth solid electrolyte layer 5 from the third inner electrode layer D5 below the third solid electrolyte layer 3 and the third inner electrode layer D5 above the fifth solid electrolyte layer 5, the second diffusion barrier layer K2 is two in total, and is located in a region between the lower side of the third solid electrolyte layer 3, the upper side of the fifth solid electrolyte layer 5 and the fourth solid electrolyte layer 4;
a resistance heater layer D7 is embedded between the solid electrolyte layer seven 7 and the solid electrolyte layer eight 8, the resistance heater layer D7 can be used for heating the sensor chip to a desired operating temperature, the second external electrode layer D6 under the solid electrolyte layer five 5, the right side of the solid electrolyte layer six 6 and the upper surface of the solid electrolyte layer seven 7, and a region between the four is a reference gas channel C3.
Preferably, the spaces below the first solid electrolyte layer 1, between the second solid electrolyte layers 2, above and between the third solid electrolyte layers 3, between the two diffusion barrier layers two K2, and above the fifth solid electrolyte layer 5 collectively constitute a first measurement gas chamber C1.
Preferably, the spaces below the third solid electrolyte layer 3, in the middle of the fourth solid electrolyte layer 4, outside the two diffusion barrier layers two K2, and above the fifth solid electrolyte layer 5 together constitute a second measurement gas chamber C2.
Preferably, the saint-goban 5Y-ZrO2 powder is produced by saint-goban france, the PVB binder is produced by louyang rich chemical products ltd, and the solvent butanone is produced by jiasong chemical ltd.
Preferably, the gas inlet 9 is located above the outermost solid electrolyte layer, the gas inlet 9 can be located at the position right in the center of the solid electrolyte layer one 1, or the gas inlet 9 can be located at the position close to one side of the left side of the solid electrolyte layer one 1, or the gas inlet 9 can be located at the position close to one side of the right side of the solid electrolyte layer one 1, the gas inlet 9 vertically penetrates through the solid electrolyte layer one 1, the solid electrolyte layer two 2, the solid electrolyte layer three 3 and the solid electrolyte layer four 4, and the bottom of the gas inlet 9 is located in the notch area of the solid electrolyte layer five 5.
Preferably, the first and second internal electrode layers D1 and D3 are located within the first measuring gas chamber C1, and the third internal electrode layer D5 is located within the second measuring gas chamber C2.
Preferably, the first internal electrode layer D1 and the second internal electrode layer D3 are located upstream of the gas flowing into the gas inlet 9, the first internal electrode layer D1 and the second internal electrode layer D3 have no catalytic activity for nitrogen oxides, the third internal electrode layer D5 can catalytically decompose nitrogen oxides, and the material for manufacturing the third internal electrode layer D5 can be rhodium or platinum or a rhodium-platinum alloy.
The sensor manufactured by the electrochemical gas sensor chip is arranged at the corresponding position of an internal combustion engine fitting, and when in use:
1) a rich/lean alternative combustion gas execution control sensor as an internal combustion engine for controlling the nitrogen oxide NOx adsorption catalyst;
when the internal combustion engine is operated with lean mixture combustion gas, the excessive nitrogen oxides NOx are not completely decomposed on the three-way catalyst, and the nitrogen oxides NOx are temporarily stored by the adsorption catalyst and are first decomposed during rich combustion;
the sensor made of the electrochemical gas sensor chip is arranged at the downstream of a nitrogen oxide NOx absorption catalyst, and can be used as a nitrogen oxide NOx sensor when mixed gas is in lean combustion; with the exhaustion of the storage capacity of the adsorption catalyst of the nitrogen oxide NOx, the sensor can detect the concentration of the nitrogen oxide NOx, and the concentration is obviously increased, so that the stage of recovering the rich combustion is reached; during this phase, the sensor controls the supply of a rich exhaust gas mixture with a lambda (exhaust gas to air ratio) value <1 to the nitrogen oxide NOx adsorber catalyst, from which the reduction reaction can take place in the adsorber catalyst, the exhaust gas leaving the catalytic converter with a lambda value of about 1; after the nitrogen oxides NOx are completely converted in the rich combustion period, the gas sensor can be used as a lambda value test sensor, and when the lambda value is tested to be reduced, a lean combustion period (the working process of the lean combustion period) is started and can be recycled.
2) As a nitrogen oxide NOx gas sensor;
when the sensor is used as a nitrogen oxide NOx sensor, the first outer electrode layer D2 and the first inner electrode layer D1 can be used as pump electrodes of the first pump unit; the second internal electrode layer D3 connected to the additional second external electrode layer D6 can serve as a reference electrode to form a concentration cell; a pump voltage is applied between the first inner electrode layer D1 and the first outer electrode layer D2, through which oxygen in the first measurement gas chamber C1 is pumped in or out; in this case, the pump voltages applied to the first inner electrode layer D1 and the first outer electrode layer D2 can be self-controlled to ensure that a constant voltage value is established between the second inner electrode layer D3 and the second outer electrode layer D6;
setting a constant oxygen partial pressure when measuring the oxynitride NOx gas, the gas entering through the gas inlet 9 on the first solid electrolyte layer 1 reaches the second measurement gas chamber C2 through the second diffusion barrier layer K2; the third inner electrode layer D5, which is now located inside the second measurement gas chamber C2, can be used as a further pump cell together with the second inner electrode layer D3 connected to an additional second outer electrode layer D6 as a reference electrode, the third inner electrode layer D5 then acting as a sensitive electrode for the nitrogen oxide NOx gas;
according to the reaction formula: NOX->1/2N2+x/2O2Carrying out NOx decomposition; the pump current can be used to represent the sum of free oxygen and oxygen emitted by catalytic decomposition of NOx.
3) As an oxygen sensor;
when used as an oxygen sensor, can be used as an air-fuel ratio oxygen sensor for determining the oxygen concentration. In this case, such a sensor is realized by combining a pump unit with a concentration (electric) cell, and specifically includes: a first pump unit of the first inner electrode layer D1 and the first outer electrode layer D2 capable of ensuring oxygen transfer into and out of the first measurement gas chamber C1 through the gas inlet 9 on the solid electrolyte layer one 1 until the concentration (electric) cell reaches a predetermined potential, the second inner electrode layer D3 and the second outer electrode layer D6 constituting the concentration (electric) cell; in order to set the predetermined potential, the change of the oxygen concentration measurement signal was measured by measuring the pump current flowing between the first inner electrode layer D1 and the first outer electrode layer D2.
The use of only one sensor made of the electrochemical gas sensor chip of the invention, which is arranged at a corresponding position of an internal combustion engine accessory, can simultaneously meet the use requirements of two separate gas sensors, solves the problems of the internal combustion engine accessory mentioned in the background art, needs to add one oxygen sensor for determining the oxygen concentration in the exhaust gas flow, needs two separate gas sensors (one is an oxynitride gas sensor, and the other is an oxygen sensor), and thus increases the defect of the whole use cost.
The invention can measure NO containing nitrogen oxideXThe oxygen concentration in the gas can also be measured, the problem that an oxygen sensor needs to be added when the oxygen concentration in the exhaust gas flow of the internal combustion engine is measured is solved, the cost is saved, the using effect is good, the performance is excellent, and when the internal combustion engine uses thin gas, the oxygen concentration can be used for controlling nitric oxide NOXCan also be used as nitrogen oxide NOXThe sensor chip can also be used as an oxygen sensor chip, and is suitable for popularization and use in the production and manufacturing of chemical gas sensors.
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 (9)

1. An electrochemical gas sensor chip is a sheet-shaped gas sensor chip in whole, the right side end part of the gas sensor chip is a trapezoidal inclined interface and comprises a first external electrode layer, a solid electrolyte layer, a first diffusion barrier layer, a second diffusion barrier layer, a first internal electrode layer, a second internal electrode layer, a third internal electrode layer, a second external electrode layer, a resistance heater layer, a gas inlet, a first measuring gas chamber, a second measuring gas chamber and a reference gas channel, the first external electrode layer and the second external electrode layer can be directly exposed in gas, the second diffusion barrier layer, the first internal electrode layer, the second internal electrode layer, the third internal electrode layer, the first measuring gas chamber, the second measuring gas chamber and the resistance heater layer are all positioned in the solid electrolyte layer, the gas inlet is positioned on the upper surface of the outermost solid electrolyte layer, the first diffusion barrier layer is arranged on the upper part of the inner side of the gas inlet, the reference gas channel is positioned in the solid electrolyte layer where the second external electrode layer is positioned and in a space between the solid electrolyte layer and the solid electrolyte layer, wherein the resistance heater layer is embedded inside the solid electrolyte layer, and the reference gas channel is directly communicated with external gas.
2. An electrochemical gas sensor chip according to claim 1, wherein the solid electrolyte layer comprises, from top to bottom, a first solid electrolyte layer, a second solid electrolyte layer, a third solid electrolyte layer, a fourth solid electrolyte layer, a fifth solid electrolyte layer, a sixth solid electrolyte layer, a seventh solid electrolyte layer, and an eighth solid electrolyte layer, the solid electrolyte layer being made of yttrium-containing stabilized zirconia nanopowder;
the solid electrolyte layer I, the solid electrolyte layer II, the solid electrolyte layer III, the solid electrolyte layer IV, the solid electrolyte layer V, the solid electrolyte layer VI, the solid electrolyte layer VII and the solid electrolyte layer VIII are all prepared by mixing Shenggobain 5Y-ZrO2 powder, PVB binder and solvent butanone, ball milling for 96 hours, defoaming and tape casting to prepare a green solid electrolyte layer I, a solid electrolyte layer II, a solid electrolyte layer III, a solid electrolyte layer IV, a solid electrolyte layer V, a solid electrolyte layer VI, a solid electrolyte layer VII and a solid electrolyte layer VIII, the solid electrolyte layer I, the solid electrolyte layer II, the solid electrolyte layer III, the solid electrolyte layer IV, the solid electrolyte layer VI, the solid electrolyte layer VII and the solid electrolyte layer VIII through sequential lamination and bonding from top to bottom and sintering, the sintering temperature is 1500 ℃.
3. An electrochemical gas sensor chip according to claim 1 or 2, wherein the solid electrolyte layer is a solid electrolyte layer capable of conducting oxygen ions, a first external electrode layer is printed on the outer surface of the upper portion of the first solid electrolyte layer, an air inlet is formed on the upper surface of the first solid electrolyte layer, a second internal electrode layer is printed on the lower portion of the first solid electrolyte layer, a first internal electrode layer is printed on the upper surface of the third solid electrolyte layer, a third internal electrode layer is printed on the lower surface of the third solid electrolyte layer, a third internal electrode layer is printed on the upper surface of the fifth solid electrolyte layer, a second external electrode layer is printed on the lower surface of the fifth solid electrolyte layer, an air inlet is formed on the third solid electrolyte layer, a notch is formed in the fifth solid electrolyte layer, and the second diffusion barrier layer is embedded and sintered on the third solid electrolyte layer below the air inlet, the diffusion barrier layer two is positioned on the inner side of a third internal electrode layer below the solid electrolyte layer three and a third internal electrode layer above the solid electrolyte layer five and is close to the area between an upper air inlet of the solid electrolyte layer three and the solid electrolyte layer five upper groove opening;
and a resistance heater layer is embedded between the solid electrolyte layer seven and the solid electrolyte layer eight, the resistance heater layer can be used for heating the sensor chip to enable the sensor chip to reach the required working temperature, the second external electrode layer below the solid electrolyte layer five, the right side of the solid electrolyte layer six and the upper surface of the solid electrolyte layer seven are arranged, and a region between the solid electrolyte layer five and the solid electrolyte layer five is a reference gas channel.
4. An electrochemical gas sensor chip according to claim 3, wherein the spaces below the first solid electrolyte layer, between the second solid electrolyte layer, above and between the third solid electrolyte layer, between the second two diffusion barrier layers, and above the fifth solid electrolyte layer together form a first measurement gas chamber.
5. An electrochemical gas sensor chip according to claim 3, wherein the spaces under the third solid electrolyte layer, in the middle of the fourth solid electrolyte layer, outside the two diffusion barrier layers and above the fifth solid electrolyte layer together form a second measurement gas chamber.
6. The electrochemical gas sensor chip of claim 2, wherein the saint-goban 5Y-ZrO2 powder is produced by saint-goban france, the PVB binder is produced by louyang rich chemical products ltd, and the solvent butanone is produced by jiasong chemical products ltd.
7. An electrochemical gas sensor chip according to claim 1, wherein the gas inlet is located above the outermost solid electrolyte layer, the gas inlet can be located at a position right in the center of the solid electrolyte layer, or the gas inlet can be located at a position on the upper surface of the solid electrolyte layer near one side of the left side surface, or the gas inlet can be located at a position on the upper surface of the solid electrolyte layer near one side of the right side surface, the gas inlet vertically and longitudinally penetrates through the first solid electrolyte layer, the second solid electrolyte layer, the third solid electrolyte layer and the fourth solid electrolyte layer, and the bottom of the gas inlet is located in the area of the notch on the fifth solid electrolyte layer.
8. An electrochemical gas sensor chip according to claim 1, wherein said first and second internal electrode layers are located in a first measurement gas chamber and a third internal electrode layer is located in a second measurement gas chamber.
9. An electrochemical gas sensor chip according to claim 1, wherein said first and second internal electrode layers are located upstream of the gas flowing into the gas inlet, the first and second internal electrode layers are catalytically inactive towards nitrogen oxides, said third internal electrode layer is capable of catalytically decomposing nitrogen oxides, and the material of the third internal electrode layer is made of rhodium or platinum or a rhodium-platinum alloy.
CN202010993654.4A 2020-09-21 2020-09-21 Electrochemical gas sensor chip Pending CN112198206A (en)

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