CN110006980A - Gas sensor element and gas sensor - Google Patents
Gas sensor element and gas sensor Download PDFInfo
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- CN110006980A CN110006980A CN201811510214.8A CN201811510214A CN110006980A CN 110006980 A CN110006980 A CN 110006980A CN 201811510214 A CN201811510214 A CN 201811510214A CN 110006980 A CN110006980 A CN 110006980A
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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
- G01N27/403—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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Abstract
The present invention provides a kind of gas sensor element and gas sensor that gas is capable of detecting when at low ambient temperatures.In gas sensor element, at least one of a pair of electrodes has the construction for being laminated with middle layer and electrode layer.Electrode layer includes perofskite type oxide and the cerium oxide for being added to rare earth, which has Ca-Ti ore type crystal structure and contain La element and Fe element.Middle layer, which has, is laminated with the 1st layer formed by (La-Zr-Ln '-Ce-O) and the 2nd layer of the construction formed by (La-Zr-Ln '-Ce-Fe-O).In gas sensor element, in the case where observing section using the interior len secondary electron detector of scanning electron microscope, the coverage rate of the 2nd layer of the 1st layer of covering is 90% or less.
Description
Technical field
The present invention relates to gas sensor elements and gas sensor with solid electrolytic plastid and a pair of electrodes.
Background technique
As shown in Patent Document 1, it is known that a kind of dense with electrical characteristic and the specific gas ingredient in measured gas
Spend the sensor of correspondingly changed gas sensor element.
For example, disclosing a kind of gas sensor element in patent document 1, solid electrolytic plastid is included, to have
Bottom tube-like, and front end is closed；Medial electrode is formed in the inner surface of the solid electrolytic plastid；And lateral electrode, it is formed
In the front end of the outer surface of solid electrolytic plastid.This gas sensor is used for the exhaust for detecting for example to be discharged from internal combustion engine
The concentration of specific gas contained in gas.
Moreover, disclosing various electroconductive oxides in patent document 2,3.These electroconductive oxides can be used as gas
The electrode material of body sensor element is utilized.If using electroconductive oxide disclosed in patent document 2,3 as gas
The electrode material of sensor element can then obtain the substantially low electrode of resistance value, and thereby, it is possible to improve gas sensor element
Gas detection precision.Moreover, by first as gas sensor using electroconductive oxide disclosed in patent document 2,3
The electrode material of part can obtain cheap gas sensor compared with the case where noble metal is as electrode material is used only
Element.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2009-63330 bulletin
Patent document 2: No. 3417090 bulletins of Japanese Patent No.
Patent document 3: No. 2013/150779 bulletin of International Publication No.
Summary of the invention
Problems to be solved by the invention
But gas sensor is different depending on the application and exists and needs (for example, 300 DEG C or less) progress at low ambient temperatures
The case where gas detection, though using above-mentioned gas sensor element, become inadequate there is also the activation of electrode and can not
The case where detecting gas.
The object of the present invention is to provide one kind to be capable of detecting when the gas sensor of gas at low ambient temperatures
Element and gas sensor.
The solution to the problem
A technical solution of the invention is a kind of gas sensor element, includes solid electrolytic plastid, it includes have
The ZrO of oxygen-ion conductive2；And a pair of electrodes, a pair of electrodes are configured on solid electrolytic plastid.
Also, in gas sensor element of the invention, at least one of a pair of electrodes has from apart from solid electricity
The solution closer side of plastid is at least laminated with the construction of middle layer and electrode layer in order.And electrode layer includes Ca-Ti ore type oxygen
Compound and the cerium oxide for being added to rare earth, the perofskite type oxide have Ca-Ti ore type crystal structure and containing La element with
And Fe element.
Also, in gas sensor element of the invention, middle layer has from apart from solid electrolytic plastid closer one
Side is at least laminated with the 1st layer formed by (La-Zr-Ln '-Ce-O) and in order by (La-Zr-Ln '-Ce-Fe-
O) the 2nd layer of the construction formed.In addition, the rare earth element other than La element and Ce element is set as Ln ' element.
Also, in gas sensor element of the invention, in the interior len secondary electron using scanning electron microscope
In the case where section of the detector observation comprising solid electrolytic plastid, middle layer and electrode layer, the covering of the 2nd layer of the 1st layer of covering
Rate is 90% or less.
The low-temperature working of thus configured gas sensor element of the invention is good, even if as a result, in low temperature environment
Under be also capable of detecting when gas.
Moreover, being also possible to make an addition to the rare earth member for the cerium oxide for being added to rare earth in a technical solution of the invention
Element is Gd element.Gas sensor element of the invention can be realized detection accuracy steady in a long-term as a result,.
Moreover, being also possible to perofskite type oxide in a technical solution of the invention and not including alkaline earth gold substantially
Belong to.Gas sensor element of the invention is able to suppress the alkaline-earth metal and solid electrolytic plastid institute that electrode layer is included as a result,
The ZrO for including2It reacts and forms the conversion zone comprising alkaline-earth metal between electrode layer and solid electrolytic plastid, be able to suppress low
The reduction of warm workability.
Moreover, being also possible to perofskite type oxide is (La-Ni-Fe-O) in a technical solution of the invention
The Perovskite Phase of system.Thus configured gas sensor element of the invention can reduce by containing Ni element and Fe element
Characteristic based on temperature changes.
Another technical solution of the invention is that have the gas sensor element of a technical solution of the invention and keep being somebody's turn to do
The gas sensor of the holding member of gas sensor element.
Thus configured gas sensor of the invention is the gas sensor element with a technical solution of the invention
Gas sensor, effect identical with gas sensor element of the invention can be obtained.
Detailed description of the invention
Fig. 1 is the figure for indicating the state along axial cutting gas sensor.
Fig. 2 is the main view for indicating the appearance of gas sensor element.
Fig. 3 is the cross-sectional view for indicating the structure of gas sensor element.
Fig. 4 is the cross-sectional view for expanding region D1, D2 of Fig. 3.
Fig. 5 is the chart for indicating reflected electron image and Zr distribution, and reflected electron image indicates element body and inside inspection
Survey the section of the near border between electrode portion.
Fig. 6 is using between the interior len secondary electron detector expression element body obtained and inside detecting electrode portion
The secondary electron image of the section of near border.
Fig. 7 is the figure for indicating the linear analysis result of the near border between element body and inside detecting electrode portion.
Fig. 8 is the reflected electron image of embodiment 4 and the secondary electron using the acquirement of interior len secondary electron detector
Image.
Fig. 9 is the figure for indicating the luminance distribution of the pixel on boundary line.
Figure 10 is the relationship for indicating to be added between the adding rate and internal resistance value and coverage rate of the cerium oxide of rare earth
Chart.
Figure 11 is the perspective view of template gas sensor element.
Figure 12 is the schematical exploded perspective view of template gas sensor element.
Figure 13 is the enlarged partial sectional view of the front end side of template gas sensor element.
Figure 14 is that the part in the region in the reference electrode portion of reference electrode formed in template gas sensor element is put
Big cross-sectional view.
Description of symbols
1 ... gas sensor, 3 ... gas sensor elements, 21 ... element bodies, 27 ... lateral electrodes, 30 ... insides electricity
Pole, 31 ... middle layers, the 1st layer of 31a ..., the 2nd layer of 31b ..., 32 ... electrode layers, 100 ... template gas sensor elements, 104 ...
Reference electrode, 104b ... middle layer, 104c ... electrode layer, 105 ... solid electrolytic plastids, 106 ... measuring electrodes, 151 ... the 1st
Layer, 152 ... the 2nd layers.
Specific embodiment
(the 1st embodiment)
Below based on Detailed description of the invention the 1st embodiment of the invention.
The gas sensor 1 of present embodiment is installed on the exhaust pipe of the vehicle such as automobile and motorcycle, for examining
Survey the oxygen concentration contained by the exhaust gas in exhaust pipe.
As shown in Figure 1, gas sensor 1 has gas sensor element 3, spacer 5, obstruction component 7, terminal metal-back
Body 9 and conducting wire 11.In addition, gas sensor 1 has base metal shell 13, guard member 15, outer cylinder 16.Base metal shell
13, guard member 15 and outer cylinder 16 are matched in the mode around blanketing gas sensor element 3, spacer 5 and obstruction component 7
It sets.In addition, outer cylinder 16 has inside outer cylinder 17 and outside outer cylinder 19.
Gas sensor 1 does not have the heater for Heating Semiconductor Gas Sensor element 3.That is, gas sensor 1 utilizes row
The heat of gas gas makes the activation of gas sensor element 3 to detect oxygen concentration.
Gas sensor element 3 is formed using the solid electrolyte body with oxygen-ion conductive.As shown in Fig. 2, gas
Sensor element 3 has bottomless drum shape shape in what front end 25 occluded, and gas sensor element 3 has along the side of axes O shown in FIG. 1
The cylindric element body 21 extended to (the following are axial directions).It is formed with circumferentially in the periphery of the element body 21 to radial direction
Outside member flanges portion 23 outstanding.
In addition, constituting the solid electrolytic plastid use of element body 21 to zirconium oxide (ZrO2) oxygen of the addition as stabilizer
Change yttrium (Y2O3) made of partial stabilisation zirconia sintered body constitute.
In the front end of gas sensor element 3 25, lateral electrode 27 is formed in the outer peripheral surface of element body 21.Outside
Electrode 27 is component made of forming Pt or Pt alloy in Porous.
The cricoid annular conductive by formation such as Pt is formed in the front end side (that is, lower section of Fig. 2) in member flanges portion 23
Portion 28.
Between the lateral electrode 27 in the outer peripheral surface of element body 21 and annular conductive portion 28, with the side axially extended
Formula is formed with the vertical conductive part 29 by formation such as Pt.Lateral electrode 27 and annular conductive portion 28 are electrically connected by vertical conductive part 29.
Moreover, as shown in Figure 1, the inner peripheral surface in gas sensor element 3 is formed with medial electrode 30.Narration inside below
The detailed construction of electrode 30.In the front end of gas sensor element 3 25, by making lateral electrode 27 be exposed to exhaust gas,
Medial electrode 30 is set to be exposed to reference gas, to generate electromotive force corresponding with the oxygen concentration in exhaust gas, Jin Erjian
Measure the oxygen concentration in exhaust gas.In the present embodiment, reference gas is atmosphere.
Spacer 5 is the component of the cylindrical shape formed by the material (such as aluminium oxide) with electrical insulating property.Spacer 5
The through-hole 35 being inserted into for conducting wire 11 is formed in its axis center.Spacer 5 is in itself and the inside outer cylinder 17 for covering its peripheral side
Between be formed with the mode in gap 18 and configure.
Obstruction component 7 is the sealing structure of the cylindrical shape formed by the material (such as fluorine element rubber) with electrical insulating property
Part.Obstruction component 7 has in its back-end to radial outside protruding portion 36 outstanding.Obstruction component 7 has in its axis center for leading
The wire insertion hole 37 that line 11 is inserted into.The front end face 95 of obstruction component 7 fits closely the rear end face 97 in spacer 5, occludes structure
Side outer peripheral surface 98 of the ratio protruding portion 36 by front end side in part 7 is fitted closely in the inner surface of inside outer cylinder 17.That is, occlusion structure
Part 7 occludes the rear end side of outer cylinder 16.
The face 99 and outside outer cylinder 19 towards rear end of obstruction component 7 reducing diameter part 19g the face 19a towards front end it
Between sandwich in the state of the flange part 89b of wire-protecting component 89, support wire-protecting component 89.
Wherein, reducing diameter part 19g is extending at rear end side to radially inner side than obstruction component 7, before the direction of reducing diameter part 19g
The face 19a at end is formed towards the face of the front end side of gas sensor 1.It is formed in the middle section of reducing diameter part 19g for inserting
Enter the conducting wire insertion section 19c of conducting wire 11 and wire-protecting component 89.
Wire-protecting component 89 is the cylindrical member with the internal diameter that can store conducting wire 11, by have it is flexible,
The material (for example, glass tube and pitch tube etc.) of heat resistance and insulating properties is constituted.Wire-protecting component 89 is to protect
Conducting wire 11 is not installed by being influenced from external flying object (for example, stone, water etc.).
Wire-protecting component 89 has the convex of the outside plate outstanding of vertical direction in the axial direction in front end side end 89a
Edge 89b.Flange part 89b is not partially formed in the circumferential direction of wire-protecting component 89, is formed within the scope of complete cycle.
The flange part 89b of wire-protecting component 89 is sandwiched in the face 19a towards front end of the reducing diameter part 19g of outside outer cylinder 19
Between the face 99 towards rear end of obstruction component 7.
Terminal metal shell 9 be in order to by the output of sensor to external take out the tubular structure that is formed by conductive material
Part.Terminal metal shell 9 is in a manner of being electrically connected to conducting wire 11 and be in electrical contact with the medial electrode 30 of gas sensor element 3
Configuration.End side has the outside to radial (that is, relative to axially vertical direction) outstanding convex to terminal metal shell 9 behind
Edge 77.Flange part 77 equally spaced has the convex of plate at 3 positions of circumferential direction (circumferential direction)
Embolium 75.
Conducting wire 11 has core wire 65 and covers the covering part 67 of the periphery of core wire 65.
Base metal shell 13 is the cylindric component formed by metal material (such as iron or SUS430).In main body
Metal shell 13 is formed in inner peripheral surface towards radially inner side stage portion 39 outstanding.Stage portion 39 is in order to support gas sensor
The member flanges portion 23 of element 3 and formed.
The outer peripheral surface of front end side in base metal shell 13 is formed with for gas sensor 1 to be installed on exhaust
The threaded portion 41 of pipe.The rear end side of threaded portion 41 in base metal shell 13 is formed with hexagonal portion 43, which exists
Installation tool is engaged when gas sensor 1 is loaded and unloaded relative to exhaust pipe.Also, the hexagonal portion in base metal shell 13
43 rear end side is equipped with cylindrical portion 45.
Guard member 15 is formed by metal material (such as SUS310S), is the guarantor of the front end side of blanketing gas sensor element 3
Component is protected, imports measurement object gas to gas sensor element 3 via the gas communication hole of multiple formation.After guard member 15
Ora terminalis is clipped in member flanges portion 23 and the base metal of gas sensor element 3 across the gasket 88 formed by conductive material
Between the stage portion 39 of shell 13, to be fixed.
It is gentle in base metal shell 13 in the rear-end side region in the member flanges portion 23 in gas sensor element 3
Between body sensor element 3, in the range of from front end side to rear end side, configured with the ceramic powders 47 formed by talcum and by
The ceramic chamber lining 49 that aluminium oxide is formed.
Also, it is configured in the inside of the rear end of the cylindrical portion of base metal shell 13 45 51: becket 53, by gold
Belong to material (such as SUS430) to be formed；And the front end 55 of inside outer cylinder 17, by metal material (such as SUS304L) shape
At.The front end 55 of inside outer cylinder 17 is formed as the shape extended to radial outside.That is, the rear end 51 by making cylindrical portion 45
It compresses, the front end 55 of inside outer cylinder 17 is made to be clipped in rear end 51 and the ceramic liner of cylindrical portion 45 across 53 ground of becket as a result,
Between set 49, so that inside outer cylinder 17 be made to be fixed on base metal shell 13.
Moreover, being configured with the filter of the tubular formed by resin material (such as PTFE) in the periphery of inside outer cylinder 17
57, and the outside outer cylinder 19 formed by such as SUS304L is configured in the periphery of filter 57.Filter 57 can ventilate but
It is able to suppress the entrance of moisture.
Also, by compressing the compressed part 19b of outside outer cylinder 19 from the lateral radially inner side in periphery, to make inside outer cylinder
17, filter 57, outside outer cylinder 19 are integrally fixed.Moreover, by making the compressed part 19h of outside outer cylinder 19 from the lateral diameter in periphery
Inside side compression, so that inside outer cylinder 17 and outside outer cylinder 19 be made integrally to fix, the side outer peripheral surface 98 of obstruction component 7 can be tight
The closely connected inner surface together in inside outer cylinder 17.
In addition, inside outer cylinder 17 and outside outer cylinder 19 are respectively provided with venthole 59 and venthole 61.That is, via ventilation
Hole 59,61 and filter 57 are able to carry out the inside and outside ventilation of gas sensor 1.
As shown in figure 3, lateral electrode 27 and medial electrode 30 are to clip member at the front end of gas sensor element 3 25
The mode of part main body 21 configures.Element body 21 and a pair of electrodes (that is, lateral electrode 27 and medial electrode 30) constitute oxygen
Concentration cell generates electromotive force corresponding with the oxygen concentration in exhaust gas.That is, by before gas sensor element 3
In end 25, lateral electrode 27 is exposed in exhaust gas, and medial electrode 30 is exposed in reference gas, thus gas sensor
Element 3 is capable of detecting when the oxygen concentration in exhaust gas.
As described above, lateral electrode 27 is electrically connected to annular conductive portion 28 by vertical conductive part 29.Annular conductive portion 28 every
The gasket 88 that is formed by conductive material and guard member 15 be electrically connected to base metal shell 13.Alternatively, it is also possible to be, with
The mode of covering lateral electrode 27 forms the electrode protecting layer (not shown) for protecting lateral electrode 27.In addition, lateral electrode
27 shape and configuration are an example, also can be using various shape and configuration in addition to this.
Moreover, the inner peripheral surface in the element body 21 of gas sensor element 3 is formed with medial electrode 30.Medial electrode 30
It is component made of being formed comprising being added to the equal material porous matter of cerium oxide, perovskite of rare earth.Medial electrode 30
With inside detecting electrode portion 30a and inner conductive portion 30b.
Inside detecting electrode portion 30a is formed in a manner of the inner surface of the front end of cladding element main body 21 25.It leads inside
Electric portion 30b is connected on the detecting electrode portion 30a of inside, and to cover the side of the upper surface entirety of inside detecting electrode portion 30a
Formula is formed, and inner conductive portion 30b is electrically connected with terminal metal shell 9.Inside detecting electrode portion 30a and inner conductive portion 30b
It is formed in a manner of the integrally whole surface of the inner surface of cladding element main body 21.
That is, the element body 21 of gas sensor element 3 is formed with lateral electrode 27 and inside in front-end side region F1
Detecting electrode portion 30a, in rear-end side region, F2 is formed with inner conductive portion 30b.The front-end side region F1 of element body 21 is suitable
In the front end of element body 21 25.
It is laminated in order as shown in figure 4, inside detecting electrode portion 30a has from the closer side of distancing element main body 21
The construction of middle layer 31, electrode layer 32 and front end conductive layer 33a.
Front end conductive layer 33a and aftermentioned rear end conductive layer 33b are formed together conductive layer 33.That is, before conductive layer 33 has
Hold conductive layer 33a and rear end conductive layer 33b.
The zirconium oxide that middle layer 31 is the lanthanum (La) for being included at least through electrode layer 32 and element body 21 is included
(ZrO2) between reaction and the layer that is formed.In addition, in the present embodiment, middle layer 31 is configured to through lanthanum (La) and oxidation
Zirconium (ZrO2) between reaction and the layer that is formed but it is also possible to be lanthanum (La) and zirconium oxide will be made by gimmicks such as printings
(ZrO2) in advance reaction obtained from ingredient separately press from both sides (stacking) between element body 21 and electrode layer 32.
Electrode layer 32 and conductive layer 33 are configured to, comprising having the Ca-Ti ore type for meeting chemical formula below (1) to crystallize structure
The perofskite type oxide made (hereinafter, also referred to as " Perovskite Phase ").
LaaFebNicOX···(1)
Here, a+b+c=1,1.25≤x≤1.75.Preferably, coefficient a, b, c meet respectively following relationship (2a),
(2b)、(2c)。
0.375≤a≤0.535···(2a)
0.200≤b≤0.475···(2b)
0.025≤c≤0.350···(2c)
With the perofskite type oxide formed indicated by above-mentioned relation formula (2a)~(2c) at room temperature (such as 25 DEG C)
Lower conductivity is 250S/cm or more and B constant is 600K hereinafter, with phase the case where not meeting above-mentioned relation formula (2a)~(2c)
Than the smaller such good characteristic of and B constant higher with conductivity.It is placed in an atmosphere about in addition, Pt electrode is worked as
When in the environment of 600 DEG C, it can aoxidize and the interface resistance between solid electrolytic plastid and electrode is caused to rise.On the other hand, on
The perofskite type oxide stated is difficult to cause such time change.
It is also possible to that coefficient a, b, c meet following relational expressions (3a) respectively, (3b), (3c) replace meeting above-mentioned relation
Formula (2a), (2b), (2c).In this case, conductivity can be made further to get higher, B constant further becomes smaller.
0.459≤a≤0.535···(3a)
0.200≤b≤0.375···(3b)
0.125≤c≤0.300···(3c)
In the case where the oxide with above-mentioned composition is formed by Perovskite Phase, O's in above-mentioned chemical formula (1) is
Number x is theoretically 1.5.But the case where deviateing metering composition there are oxygen, therefore, as typical example, by the model of coefficient x
It encloses and is limited to 1.25≤x≤1.75.
Electrode layer 32 is configured to containing above-mentioned Perovskite Phase and is added to the cerium oxide of rare earth.The oxygen of rare earth will be added to
The content ratio for changing the rare earth elements RE in cerium is converted into the molar fraction { RE/ (Ce+ of cerium and the rare earth elements RE in addition to cerium
RE) }, for example, 5mol% or more can be set as and be 40mol% range below.Such cerium oxide for being added to rare earth exists
It is insulator in low temperature (that is, room temperature), for oxygen-ion conductive in high temperature (that is, use temperature of gas sensor 1)
Solid electrolytic plastid.
Moreover, the Perovskite Phase of electrode layer 32 contains substantially no alkaline-earth metal.Here, " containing substantially no " refers to nothing
The degree that method is detected using power dissipation x-ray optical spectroscopy.
Such electrode layer 32 has ionic conductivity and electronic conduction under high temperature (that is, when using gas sensor 1)
Therefore both properties of property indicate substantially low interface resistance value.
Conductive layer 33 is configured to, using above-mentioned Perovskite Phase as main component and without containing the cerium oxide for being added to rare earth.
Inner conductive portion 30b has the multi-ply construction comprising rear end conductive layer 33b and middle layer 34.Middle layer 34 is configured at
The closer side of distancing element main body 21 is leaned on than rear end conductive layer 33b.
Rear end conductive layer 33b with same group of front end conductive layer 33a of above-mentioned inside detecting electrode portion 30a by being shaped to.
But constitute the content ratio and composition inner conductive of the Perovskite Phase in the front end conductive layer 33a of inside detecting electrode portion 30a
The content ratio of Perovskite Phase in the rear end conductive layer 33b of portion 30b is identical, or can also be than in the conductive layer 33b of rear end
The content ratio of Perovskite Phase is more.
Middle layer 34 is when firing inner conductive portion 30b, by the rear end conductive layer 33b lanthanum (La) for being included and element master
The ZrO that body 21 is included2The layer of reaction and formation.In addition, being directed to the middle layer 34, may be set to be will make lanthanum (La) and oxygen
Change zirconium (ZrO2) in advance reaction obtained by ingredient be separately laminated on element body 21.
Then, illustrate the manufacturing method of gas sensor element 3.
In the 1st process, un-sintered formed body is made.Specifically, firstly, the solid of the material as element body 21
It is electrolysed the powder of plastid, prepares following powder, opposite zirconium oxide (ZrO2) addition 5mol% the yttrium oxide as stabilizer
(Y2O3) made of powder (hereinafter, also referred to as 5YSZ), further add alumina powder made of powder.By element body
When 21 material powder is integrally set as 100 mass %, the amount of 5YSZ is 99.6 mass %, and the amount of alumina powder is
0.4 mass %.After carrying out punch process to the powder, implements machining in a manner of becoming tubular, obtain as a result, not
Sintered shaped body.
Then, in the 2nd process, the paste of electrode layer 32 and the paste of conductive layer 33 are made.
In the production of the paste of electrode layer 32, firstly, passing through after the raw material powder to Perovskite Phase weighs
Wet mixed and drying are carried out, adjusts raw material powder mixture as a result, pre-burning 1 hour~5 hours at 700 DEG C~1300 DEG C
To make preburning powder.Also, the preburning powder is crushed using wet ball mill etc. to be modulated into scheduled particle ruler
It is very little.At this point, the raw material powder as Perovskite Phase, for example, being able to use La (OH)3Or La2O3、Fe2O3And NiO.Then,
After the raw material powder to the cerium oxide for being added to rare earth weighs, by carrying out wet mixed and drying, so as to adjust
Raw material powder mixture, under atmospheric environment, pre-burning 1 hour~5 hours is at 1000 DEG C~1600 DEG C to make pre-burning powder
End.Also, the preburning powder is crushed using wet ball mill etc., is modulated into scheduled particle size.As being added to rare earth
The raw material powder of cerium oxide, in addition to CeO2Except, additionally it is possible to use Gd2O3、Sm2O3、Y2O3Deng.Also, utilize wet ball mill
It is mixed Deng the two kinds of preburning powders that will be modulated into scheduled particle size, by being dissolved in together with the adhesives such as ethyl cellulose
In terpineol, butyl carbitol equal solvent, to make paste.
In the production of the paste of conductive layer 33, for example, passing through after the raw material powder to Perovskite Phase weighs
Wet mixed and drying are carried out, adjusts raw material powder mixture as a result, pre-burning 1 hour~5 hours at 700 DEG C~1300 DEG C
To make preburning powder.Also, the preburning powder is mixed using wet ball mill etc., crushes to be modulated into scheduled
Particle size.At this point, the raw material powder as Perovskite Phase, for example, being able to use La (OH)3Or La2O3、Fe2O3And NiO.
Then, by will be dissolved together with the adhesives such as powder and ethyl cellulose made of the carbon for adding 30 volume % to the preburning powder
In terpineol, butyl carbitol equal solvent, to make paste.
Then, in the 3rd process, lateral electrode 27, inside detecting electrode portion 30a in un-sintered formed body and interior
The formation part of side conductive part 30b is coated with each paste.
Firstly, in the paste of the noble metals such as the formation part coating Pt paste of outer lateral electrode 27.Then, in electrode layer 32
Formation part coating electrode layer 32 paste.Also, in a manner of the whole surface of the inner surface of cladding element main body 21
The paste of conducting layer coated 33.
In next 4th process, for the un-sintered formed body for being coated with each paste, drying is being carried out
Afterwards, it is fired under scheduled firing temperature.The firing temperature is, for example, 1250 DEG C or more and is 1450 DEG C hereinafter, preferably 1350
±50℃.In the ablating work procedure, centre is formed between the electrode layer 32 and element body 21 of inside detecting electrode portion 30a
Layer 31, is formed with middle layer 34 between the rear end conductive layer 33b and element body 21 of inside conductive part 30b.
By implementing above-mentioned each process, gas sensor element 3 can be manufactured.
Fig. 5 is using scanning electron microscope (hereinafter referred to as SEM) to element body 21 and inside detecting electrode portion 30a
Reflected electron image obtained by the section of near border is shot.SEM is Scanning Electron Microscope
Referred to as.
As shown in figure 5, in the near border of element body 21 and inside detecting electrode portion 30a, from distancing element main body 21
The closer side of solid electrolytic plastid be laminated with middle layer 31, electrode layer 32 and conductive layer 33 in order.Moreover, with certainly
Inside detecting electrode portion 30a is gone towards element body 21, and the concentration of zirconium (Zr) element becomes larger.The side of middle layer 31 and electrode layer 32
Boundary line BL is the position that the concentration of Zr element is 5% relative to the concentration maxima of Zr element.
Fig. 6 is to shoot secondary electron image obtained by section identical with Fig. 5 using SEM.The secondary electron image is to make
Obtained by interior len secondary electron detector shooting with the inside for the object lens for being set to SEM.It is taken using the interior len detector
The secondary electron image obtained represents sensitivity by small form poor (or potential difference) in the surface of electric wire for irradiation
Contrast.
As shown in fig. 6, middle layer 31 is formed as the closer side of solid electrolytic plastid from distancing element main body 21 by suitable
The 1st layer of 31a and the 2nd layer of 31b is laminated in sequence.
1st layer of 31a be by containing the rare earth element other than La element, Zr element, La element and Ce element (hereinafter referred to as
Ln ' element), the layer that is formed of the oxide (hereinafter referred to as (La-Zr-Ln '-Ce-O)) of Ce element.
2nd layer of 31b is by containing the oxide of La element, Zr element, Ln ' element, Ce element, Fe element (hereinafter referred to as
(La-Zr-Ln '-Ce-Fe-O)) formed layer.In addition, the boundary line BL of middle layer 31 and electrode layer 32 in Fig. 6 with
Fig. 5 is similarly the position that the concentration of Zr element is 5% relative to the concentration maxima of Zr element.
The image PG1 of Fig. 7 is cuing open using SEM capturing element main body 21 and the near border of inside detecting electrode portion 30a
Reflected electron image obtained by face.The measurement line ML for being set in image PG1 indicates the measurement position of EDS composition analysis.EDS is
The abbreviation of Energy Dispersive X-ray Spectroscopy.
The image PG2 of Fig. 7 is to rotate to the right the figure after 90 ° behind region around the measurement line ML cut in image PG1
Picture.In addition, the rectangular-shaped region RR for being set in image PG2 is replaced by secondary electron image.In the RR of region, with energy
The mode for enough distinguishing the 1st layer of 31a and the 2nd layer of 31b is shown.
The chart GR1 of Fig. 7 indicates point of the Fe element measured and carrying out EDS composition analysis on measuring line ML
Cloth.The chart GR2 of Fig. 7 indicates the distribution of the Zr element measured and carrying out EDS composition analysis on measuring line ML.
As shown in the instruction circle C1 of chart GR1, Fe element there's almost no in the 1st layer of 31a.Such as the instruction of chart GR1
Shown in circle C2, in the 2nd layer of 31b, there is very more Fe elements compared with the 1st layer of 31a.Alternatively, it is also possible to be, Ni element with
Fe element is such present in the region.
As shown in chart GR2, the boundary line BL of middle layer 31 and electrode layer 32 is the concentration of Zr element relative to Zr element
Concentration maxima be 5% position.
Then, for the test knot for the evaluation test implemented to evaluate the low-temperature working of gas sensor element 3
Fruit is illustrated.
Low-temperature working is the finger for indicating to be capable of detecting when gas (for example, 300 DEG C or less) at low ambient temperatures
Mark.Internal resistance value between lateral electrode and medial electrode is higher, and the low-temperature working of gas sensor element 3 is poorer.It changes
Yan Zhi, the internal resistance value between lateral electrode and medial electrode is lower, and the low-temperature working of gas sensor element 3 is more excellent
It is different.
In this evaluation test, the 2nd layer of 31b is made to cover ratio (hereinafter referred to as coverage rate) variation of the 1st layer of 31a, thus
To evaluate the low-temperature working of gas sensor element.Coverage rate can in the production of the paste of electrode layer 32 by adjusting
The adding rate of the cerium oxide of rare earth is added to be controlled, alternatively, also can be by being coated with the paste as electrode
The value of the firing temperature of the un-sintered formed body as element body under state is controlled.Specifically, being expressed as follows
Tendency, by increasing the adding rate for the cerium oxide for being added to rare earth to making coverage rate reduce, alternatively, by making above-mentioned not burn
Form the value decline of the firing temperature of body to make coverage rate reduce.
In the test of low-temperature working, measure between the lateral electrode 27 of gas sensor element and medial electrode 30
Internal resistance value evaluates the low-temperature working of gas sensor element based on internal resistance value.
In this test, in the state that gas sensor element is assembled in gas sensor, by the gas sensor
It is installed on well known combustion measurement device, the internal resistance value of gas sensor element is measured using combustion methodologies.In detail
Ground is said, detects that component temperature is 300 DEG C and air-fuel ratio λ=0.9 in the case where input impedance is 1M Ω and 100K Ω respectively
The sensor of (that is, dense combustion) exports, and the internal resistance value of gas sensor element is calculated based on the output difference.
Also, in this test, the gas sensor element by internal resistance value less than 200K Ω is determined as low-temperature working
Property it is good, by internal resistance value be 200K Ω or more gas sensor element be determined as that low-temperature working is bad.
It the use of coverage rate is numerical value shown in table 1 as Examples 1 to 7 and the gas sensor element of comparative example
Gas sensor element.In addition, in Examples 1 to 7 and comparative example, the Perovskite Phase of electrode layer 32 is
LaFe0.5Ni0.5O3, the cerium oxide for being added to rare earth of electrode layer 32 is Ce0.8Ln’0.2O1.9。
As shown in table 1, by making the adding rate for the cerium oxide for being added to rare earth in the range of 10 volume of volume %~65 %
Interior variation, so that coverage rate be made to change in the range of 0%~100%.Moreover, making an addition to the dilute of the cerium oxide for being added to rare earth
Earth elements (that is, Ln ' element) are gadolinium (Gd) element in comparative example and embodiment 1,2,4~7, are in embodiment 3 samarium (Sm)
Element.In addition, the value difference of the firing temperature when gas sensor element of manufacture Examples 1 to 7 and comparative example is constant.
[table 1]
For comparative example and each Examples 1 to 7, the boundary line BL between shooting middle layer 31 and electrode layer 32 is used
Secondary electron image obtained from nearby measures coverage rate.In this test, the multiplying power of SEM is set as 10,000 times,
The secondary electron image at 5 visual angles is achieved for comparative example and each Examples 1 to 7.
Fig. 8 is to shoot reflection electron map obtained near the middle layer 31 of embodiment 4 and the boundary line BL of electrode layer 32
Picture and the secondary electron image obtained using interior len secondary electron detector.
As shown in the secondary electron image of Fig. 8, on the surface from boundary line BL and the solid electrolytic plastid of element body 21
Between, there are the different parts of contrast.For the different part of contrast, the part of 32 side of electrode layer is the 2nd layer of 31b, member
The part of 21 side of part main body is the 1st layer of 31a.In this test, coverage rate is defined as, indicates the electrode layer 32 on the BL of boundary line
Ratio of the part of side relative to the contrast of the overall length of the boundary line BL of secondary electron image.
The different part of above-mentioned contrast is set by method as shown below.
Firstly, making luminance between the surface from boundary line BL and the solid electrolytic plastid of element body 21
Distribution.Also, as shown in figure 9, detecting the peak value PK1 of the luminance comprising 32 side of electrode layer in luminance distribution and comprising element
The peak value PK2 of the luminance of 21 side of main body.The average value of the brightness value L2 of the brightness value L1 of peak value PK1 and peak value PK2 is set as brightness
Spend decision content JC.Also, for each pixel on the BL of boundary line, in the case where luminance is luminance decision content JC or more, if
It is set to the part for indicating the contrast of 32 side of electrode layer, in the case where luminance is less than luminance decision content JC, is set as indicating member
The part of the contrast of 21 side of part main body.
Also, it is directed to comparative example and each Examples 1 to 7, measures and covers in the secondary electron image using 5 visual angles
After lid rate, the average value of the coverage rate at 5 visual angles measured is calculated, which is set as final coverage rate.
It is 200K Ω or more in internal resistance value as the measurement result of internal resistance as shown in table 1 in this test
In the case where be "×", in the case where internal resistance value is 100K Ω~200K Ω be " △ ", internal resistance value be 50K Ω
It is "○" in the case where~100K Ω, is in the case where internal resistance value is 50K Ω situation below " ◎ ".Moreover, in internal resistance
Value will determine that result is set as " NG " in the case where being 200K Ω or more, will determine in the case where internal resistance value is less than 200K Ω
As a result it is set as " OK ".
As shown in Figure 10, in this test, in the case where coverage rate is 100%, internal resistance value is more than 200K Ω.And
And in the case where coverage rate is 89%, internal resistance value is in the range of 100K Ω~200K Ω.Moreover, being in coverage rate
In the case where 47%~63%, internal resistance value is in the range of 50K Ω~100K Ω.Moreover, being 0%~16% in coverage rate
In the case where, internal resistance value is 50K Ω or less.
Thus configured gas sensor element 3 has: element body 21, it includes with oxygen-ion conductive
ZrO2；And lateral electrode 27 and medial electrode 30, the lateral electrode 27 and medial electrode 30 configure on element body 21.
And in gas sensor element 3, medial electrode 30 has from the closer side of distancing element main body 21 by suitable
Sequence is at least laminated with the construction of middle layer 31 and electrode layer 32.And electrode layer 32 includes perofskite type oxide and is added to dilute
The cerium oxide of soil, the perofskite type oxide have Ca-Ti ore type crystal structure and contain La element and Fe element.
And in gas sensor element 3, middle layer 31 has from the closer side of distancing element main body 21 in order
It is at least laminated with by (La-Zr-Ln '-Ce-O) the 1st layer of 31a formed and by (La-Zr-Ln '-Ce-Fe-O) shape
At the 2nd layer of 31b construction.
And in gas sensor element 3, seen using the interior len secondary electron detector of scanning electron microscope
In the case where examining the section comprising element body 21, middle layer 31 and electrode layer 32, the 2nd layer of 31b covers the covering of the 1st layer of 31a
Rate is 90% or less.In addition, according to above-mentioned test result it is understood that the coverage rate included below of coverage rate 90% in the present invention
0%.
The low-temperature working of thus configured gas sensor element 3 is good, as a result, can at low ambient temperatures
Detect gas.
And in gas sensor element 3, making an addition to and being added to the rare earth element of the cerium oxide of rare earth is Gd element.By
This, gas sensor element 3 can be realized detection accuracy steady in a long-term.
Moreover, the perofskite type oxide of electrode layer 32 contains substantially no alkaline-earth metal.Gas sensor element as a result,
3 are able to suppress the ZrO that the alkaline-earth metal that electrode layer 32 is included and element body 21 are included2Reaction and in electrode layer 32 and member
The conversion zone comprising alkaline-earth metal is formed between part main body 21, is able to suppress the reduction of low-temperature working.
Moreover, the perofskite type oxide of electrode layer 32 is the Perovskite Phase of (La-Ni-Fe-O) system.Thus configured
Gas sensor element 3 can reduce characteristic based on temperature and change by containing Ni element and Fe element.
In the embodiment described above, element body 21 is equivalent to solid electrolytic plastid, lateral electrode 27 and interior
Lateral electrode 30 is equivalent to a pair of electrodes, and base metal shell 13 is equivalent to holding member.
(the 2nd embodiment)
Below based on Detailed description of the invention the 2nd embodiment of the invention.
As shown in figure 11, the template gas sensor element 100 of present embodiment has element body 101 and porous quality guarantee
Sheath 120.
As shown in figure 12, element body 101 has concentration detecting unit 130, heavy seal coat 111, air introduction hole
Layer 107 and undersurface layer 103.In addition, the diagram of Porous protective layer 120 is omitted in Figure 12.
Concentration detecting unit 130 has reference electrode 104, solid electrolytic plastid 105 and measuring electrode 106.Benchmark
Electrode 104 and measuring electrode 106 are configured in a manner of sandwiching solid electrolytic plastid 105.
Reference electrode 104 has reference electrode portion 104a and benchmark conductive part 104L.As shown in figure 14, reference electrode portion
104a have from apart from the closer side of solid electrolytic plastid 105 be laminated in order middle layer 104b, electrode layer 104c and
The multi-ply construction of conductive layer 104d.
Middle layer 104b is laminated with the 1st layer 151 and the 2nd apart from the closer side of solid electrolytic plastid 105 certainly in order
152 ground of layer are formed.
As shown in figure 12, benchmark conductive part 104L is with the length from reference electrode portion 104a along solid electrolytic plastid 105
The mode that direction extends is formed.
Measuring electrode 106 has measuring electrode portion 106a and detection conductive part 106L.Conductive part 106L is detected with measurement
Electrode portion 106a is formed along the mode that the length direction of solid electrolytic plastid 105 extends.
Heavy seal coat 111 has reinforcement part 112 and electrode protection portion 113a.
Reinforcement part 112 is to sandwich detection conductive part 106L between solid electrolytic plastid 105 at it for protecting admittedly
Body is electrolysed the component of the plate of plastid 105.Reinforcement part 112 is formed by material identical with solid electrolytic plastid 105, reinforcement part
112 have the protection portion configuration space 112a that the thickness direction along plate penetrates through.
Electrode protection portion 113a is formed by porous material, and electrode protection portion 113a is configured at protection portion configuration space
112a.Electrode protection portion 113a is to protect survey in such a way that it sandwiches measuring electrode portion 106a between solid electrolytic plastid 105
Measure electrode portion 106a.
In addition, the gas that the template gas sensor element 100 of present embodiment is so-called oxygen concentration difference electromotive force formula passes
Sensor is able to use the value of the electromotive force generated between the electrode of concentration detecting unit 130 to detect oxygen generation concentration.
Undersurface layer 103 and air introduction aperture layer 107 are to sandwich undersurface layer 103 and air introduction for reference electrode 104
Mode between aperture layer 107 and solid electrolytic plastid 105 is laminated in reference electrode 104.Air introduction aperture layer 107 is opened in rear end side
The substantially letter U shape of mouth.It is surrounded by solid electrolytic plastid 105, air introduction aperture layer 107 and undersurface layer 103
Inner space is air introduction hole 107h.Reference electrode 104 is matched in a manner of being exposed to the atmosphere for importing air introduction hole 107h
It sets.
In this way, element body 101 is to be laminated with undersurface layer 103, air introduction aperture layer 107, reference electrode 104, solid
It is electrolysed the laminated body of plastid 105, measuring electrode 106 and heavy seal coat 111.The plate-like formation of element body 101.
The end of benchmark conductive part 104L by be set to solid electrolytic plastid 105 through-hole 105a formed conductor, with
Detecting element side gasket 121 on solid electrolytic plastid 105 is electrically connected.Heavy seal coat 111 is configured to and solid electrolytic plastid
105 sizes for comparing axial (that is, left and right directions in Figure 12) form shorter, and keep the end for detecting conductive part 106L sudden and violent
Dew.Detecting element side gasket 121 and the end for detecting conductive part 106L are exposed from the rear end of heavy seal coat 111 to outside,
It is electrically connected with the external terminal (not shown) of external circuit connection.
As shown in figure 11, Porous protective layer 120 is set as the complete cycle of the front end side of cladding element main body 101.
As shown in figure 13, Porous protective layer 120 is formed as being included the front end face of element body 101 and along axis
To (that is, left and right directions in Figure 13), end side extends backward.
And Porous protective layer 120 is to include at least reference electrode portion in cladding element main body 101 in the axial direction
The mode in the region of 104a and measuring electrode portion 106a is formed.
The presence of template gas sensor element 100, which is exposed to element silicon and P elements included in exhaust gas etc., to be had
The case where noxious material, or be attached in exhaust gas water droplet the case where.Here, by template gas sensor element
100 outer surface covers Porous protective layer 120, be able to suppress template gas sensor element 100 be stained with noxious material, can
Water droplet is inhibited directly to contact template gas sensor element 100.
Then, it is illustrated for solid electrolytic plastid, measuring electrode and reference electrode etc. at being grouped as.
In the same manner as the element body 21 of the 1st embodiment, solid electrolytic plastid 105 is to zirconium oxide (ZrO2) addition work
For the yttrium oxide (Y of stabilizer2O3) made of partial stabilisation's zirconia sintered body constitute.
Measuring electrode 106 as main component and includes monoclinic zirconia using Pt.Measuring electrode 106 can also contain pottery
Porcelain ingredient.
In addition, " main component " refers to, become the position of object (that is, solid electrolytic plastid 105 and survey relative to composition
Amount electrode 106 etc.) whole components be more than 50 mass % ingredient.
The 1st layer 151 in the reference electrode portion 104a of reference electrode 104 is formed by (La-Zr-Ln '-Ce-O)
Layer.2nd layer 152 is the layer formed by (La-Zr-Ln '-Ce-Fe-O).Also, the gas sensing with the 1st embodiment
Similarly, the 2nd layer 152 the 1st layer 151 of covering of coverage rate is 90% or less (including 0%) to device element 3.
Electrode layer 104c is configured to comprising Perovskite Phase and is added to the cerium oxide of rare earth.With the electricity of the 1st embodiment
Similarly, the Perovskite Phase that electrode layer 104c is included has each condition for meeting above formula (1), (2a), (2b), (2c) to pole layer 32
Perofskite type oxide crystal structure, and the Perovskite Phase that electrode layer 104c is included is the crystalline phase containing La.In this way
Electrode layer 104c under high temperature (that is, when using template gas sensor element 100) have ionic conductivity and electronic conduction
Therefore the property of both property indicates substantially low interface resistance value.
In the same manner as the conductive layer 33 of the 1st embodiment, conductive layer 104d is configured to containing making as main component to have
Meet the structure of the Perovskite Phase of the perofskite type oxide crystal structure of each condition of above formula (1), (2a), (2b), (2c).Separately
Outside, the conductive layer 104d of present embodiment does not contain the cerium oxide for being added to rare earth.
Benchmark conductive part 104L is formed by material identical with conductive layer 104d.
The position of measuring electrode 106 is at least covered by spinelle (MgAl in Porous protective layer 1202O4) and dioxy
Change titanium (TiO2) formed, and it is supported with noble metal (at least one in Pt, Pd, Rh).The noble metal is used as promoting exhaust
The catalyst of the burning for the unburned gas ingredient that gas is included functions.In addition, at least covering in Porous protective layer 120
The position of lid measuring electrode 106 refers to Chong Die with measuring electrode 106 position on the stacking direction of element body 101.
Thus configured template gas sensor element 100 includes solid electrolytic plastid 105, and it includes with oxonium ion
Conductive ZrO2；And reference electrode 104 and measuring electrode 106, the reference electrode 104 and measuring electrode 106 configure
On solid electrolytic plastid 105.
And in template gas sensor element 100, reference electrode 104 have from apart from solid electrolytic plastid 105 compared with
Close side is at least laminated with the construction of middle layer 104b and electrode layer 104c in order.And electrode layer 104c includes perovskite
Type oxide and the cerium oxide for being added to rare earth, the perofskite type oxide have Ca-Ti ore type crystal structure and containing La members
Element and Fe element.
And in template gas sensor element 100, middle layer 104b has from relatively close apart from solid electrolytic plastid 105
Side be at least laminated with the 1st layer 151 formed by (La-Zr-Ln '-Ce-O) in order and by (La-Zr-Ln '-
Ce-Fe-O) the 2nd layer 152 of the construction formed.
And in template gas sensor element 100, examined using the interior len secondary electron of scanning electron microscope
In the case where surveying section of the device observation comprising solid electrolytic plastid 105, middle layer 104b and electrode layer 104c, the 2nd layer of 152 covering
1st layer 151 of coverage rate is 90% or less.
Thus configured template gas sensor element 100 can obtain the gas sensor element 3 with the 1st embodiment
Same effect.
In the embodiment described above, template gas sensor element 100 is equivalent to gas sensor element, solid
Electrolysis plastid 105 is equivalent to solid electrolytic plastid, and reference electrode 104 and measuring electrode 106 are equivalent to a pair of electrodes.
More than, it is illustrated for one embodiment of the present invention, but the present invention is not limited to the above embodiments, it can
Implemented by various modifications.
It is to be laminated with middle layer, electrode layer and conductive layer for medial electrode such as in the first embodiment described above
The gas sensor element of multi-ply construction is illustrated, and but not limited to this.That is, either lateral electrode is above-mentioned more
The gas sensor element of layer construction, is also possible to medial electrode and lateral electrode is respectively the gas sensing of above-mentioned multi-ply construction
Device element.It similarly, is to be laminated with middle layer, electrode layer and conductive layer for reference electrode in above-mentioned 2nd embodiment
The template gas sensor element of multi-ply construction be illustrated, but not limited to this.That is, either measuring electrode is
The template gas sensor element of above-mentioned multi-ply construction, is also possible to reference electrode and measuring electrode is respectively above-mentioned multi-ply construction
Template gas sensor element.
And in the above-described embodiment, it is added to for using above-mentioned Perovskite Phase as main component and with not containing
The gas sensor element of the conductive layer of the cerium oxide of rare earth is illustrated, and but not limited to this.For example, conductive layer can also
With containing being added to the cerium oxide of rare earth, such conductive layer can be reduced in using gas sensor element lateral electrode with
Internal resistance value between medial electrode.In addition, be illustrated with the situation that conductive layer is covering electrode layer upper surface entirety,
But at least part of electrode layer upper surface can also be covered.
It is also possible to want function sharing possessed by a constituent element in the respective embodiments described above to multiple compositions
Element, or bring function possessed by multiple constituent elements by a constituent element into play.Furthermore, it is also possible to omit above-mentioned each
A part of the structure of embodiment.Furthermore, it is also possible to the other structures of above embodiment are directed to, to the respective embodiments described above
At least part of structure be added or replace.In addition, skill determined by the text according to documented by claim
All modes that art thought is included are embodiments of the present invention.
Claims (6)
1. a kind of gas sensor element includes solid electrolytic plastid, it includes the ZrO with oxygen-ion conductive2；And
A pair of electrodes, which is configured on the solid electrolytic plastid, in the gas sensor element,
At least one of the pair of electrode has from apart from the closer side of solid electrolytic plastid at least layer in order
It is laminated with the construction of middle layer and electrode layer,
The electrode layer includes perofskite type oxide and the cerium oxide for being added to rare earth, which has calcium titanium
Mine type crystal structure and include La element and Fe element,
Using the rare earth element other than La element and Ce element as Ln ' element, the middle layer has from apart from the solid
The electrolysis closer side of plastid is at least laminated with the 1st layer formed by (La-Zr-Ln '-Ce-O) and in order by (La-
Zr-Ln '-Ce-Fe-O) formed the 2nd layer of construction,
In the interior len secondary electron detector observation using scanning electron microscope includes the solid electrolytic plastid, is described
In the case where the section of interbed and the electrode layer, the 2nd layer of covering the 1st layer of the coverage rate is 90% or less.
2. gas sensor element according to claim 1, wherein
The rare earth element for making an addition to the cerium oxide for being added to rare earth is Gd element.
3. gas sensor element according to claim 1 or 2, wherein
The perofskite type oxide does not include alkaline-earth metal substantially.
4. gas sensor element according to claim 1 or 2, wherein
The perofskite type oxide is the perofskite type oxide of (La-Ni-Fe-O) system.
5. gas sensor element according to claim 3, wherein
The perofskite type oxide is the perofskite type oxide of (La-Ni-Fe-O) system.
6. a kind of gas sensor, wherein
The gas sensor includes gas sensor element according to any one of claims 1 to 5；And keep institute
State the holding member of gas sensor element.
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| JP6577408B2 (en) * | 2016-04-20 | 2019-09-18 | 日本特殊陶業株式会社 | Gas sensor element and gas sensor |
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