CN102246028A - Structured electrode for ceramic sensor elements - Google Patents
Structured electrode for ceramic sensor elements Download PDFInfo
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- CN102246028A CN102246028A CN2009801505528A CN200980150552A CN102246028A CN 102246028 A CN102246028 A CN 102246028A CN 2009801505528 A CN2009801505528 A CN 2009801505528A CN 200980150552 A CN200980150552 A CN 200980150552A CN 102246028 A CN102246028 A CN 102246028A
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- solid electrolyte
- electrolyte layer
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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
- G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
Abstract
The invention relates to a sensor element (110), particularly for capturing a property of a gas in a measuring gas space. The sensor element (110) comprises at least one solid electrolyte layer (116) having at least one ceramic solid electrolyte material (118) and at least one electrode (112) contacting the solid electrolyte layer (116) directly or indirectly. The electrode (112) comprises at least one ceramic material (122) and at least one metal material (120). The electrode (112) has a lateral extension and has structuring (126, 140) extending parallel and/or perpendicular to the lateral extension within the lateral extension. The structuring (126, 140) is designed to enlarge an electrode surface of the electrode (112).
Description
Background technology
The present invention relates to known sensor element, they are based on the electrolysis characteristic of particular solid, the i.e. ability of this solid conduction specific ion.This sensor element uses in the different field of natural science and technology, and wherein, the invention that describes below is not limited to specific application.But this sensor element especially can be used in the waste-gas analysis field, for example is used in motor vehicle, the fixing engine or combustion apparatus.For example this sensor element can be used in the motor vehicle, in order to measure air-fuel-mixed gas composition.This sensor element especially is used in so-called lambda sensor/exhaust gas oxygensensor and not only plays an important role during the objectionable impurities in reducing waste gas in Otto engine but also in the diesel oil technology.Can be with reference to Robert Bosch GmbH as the example that may construct of this sensor element: " Sensoren im Kraftfahrzeug ", June calendar year 2001,112 to 117 pages.But sensor element for the solid electrolyte that comprises described type of other types, promptly for example except jumping type detector and/or wideband detector for the sensor with solid electrolyte of particle sensor or similar type, also can use the present invention.Do not limit may type according to the protection domain of sensor element of the present invention or other and the situation of purposes under, be that example is explained the present invention below with the lambda sensor, but wherein under the inspiration of above explanation, also can make the sensor element of other type.
Usually have at least one electrode based on the ceramic sensor element element that uses solid electrolyte material, by described electrode directly or indirectly, promptly by direct contact or connect one or more middle layers by the centre and connect at least one solid electrolyte layer.Therefore, for example under the situation of lambda sensor (it uses as so-called " finger-type detector ") usually with thin-bed technique, for example by evaporation or spraying plating by platinum produce individual layer, not structurized external electrode (OE) and interior electrode (IE).The electrode of printing, for example the grid of making by tampon printing (Tampondruck) in thin-bed technique is known.For example use metal-ceramic-electrode material (metallic ceramics) as electrode material.For example allow to use noble metal-metallic ceramics, for example platinum-metallic ceramics.An example of this ceramic-metallic ceramic component is yttrium-stabile zirconium dioxide (YSZ).
The also lambda sensor of known other type except that the lambda sensor of finger-type type photodetector, planar type detector (Planarsonden) for example, it is with the ceramic membrane technical construction.Interior electrode and external electrode not structured usually at this, the serigraphy of planar ground pass through platinum-YSZ-metallic ceramics with the thick-layer technical construction.
In addition can be by selecting sintering parameter, protective seam characteristic or for example flooding or the electricity activation influences or regulates the sensor characteristic of electrode by additional technology.
But the electrode structure in the sensor element of known sensor element, for example the above-mentioned type has proposed technical challenge in it is made.Therefore, especially under the background that the noble metal price sharply rises, especially, require by using noble metal amount to produce the electrode of ability to work as few as possible for noble metal platinum for example.At this, the ability to work material conversion of the per unit area maximum possible by electrode activity (being catalytic activity) and electrode (for example external electrode) usually defines.
But the prerequisite that big material is changed on the electrode is that the unit plane-internal volume of electrode has a large amount of as far as possible catalytic active centers and the entire electrode system has good electron and/or ionic conduction ability, for example in this special battery (Nernst-Zelle) of energy.
Summary of the invention
Therefore, the present invention has proposed a kind of sensor element and a kind of method that is used to make sensor element from above-mentioned problem, and they provide the electrode of ability to work under to the still very little situation of the demand of noble metal.
Basic design of the present invention is following cognition: there are directly related property in the ability to work of electrode or efficient with the solid electrolyte material and the three-phase boundary between the gas medium on every side of operational electrode material at the energy conduction electron, energy conducting ion.In addition, between the noble metal (for example platinum) of the responsible decomposition catalysis of the efficient of electrode and main quantity, the solid electrolyte material (for example YSZ) of being responsible for ionic conduction and the electrode of being responsible for the pore that gas enters and oxidation catalysis, there is relation.Pore, solid electrolyte material and electrode metal constitute the activated centre of triple point as electrode or catalyst converter.In sensor element, when reducing noble metal amount, the maximization of electrode efficiency and electrode activity by the pore with meticulous distribution, meticulous distribution noble metal and the big surface of solid electrolyte material by increasing described three-phase boundary and under the situation that good gas enters, realizing by increasing the activated centre.
In addition, electrode system should pass this battery of sensor element or these batteries (for example this special battery of the energy of sensor element) be good conduction and therefore have low interior resistance.If low interior resistance for example at low temperature, reach during especially less than 350 ℃ temperature, then can be considered to use this electrode system in the sensor pottery of non-active heating, for example for the favourable two-wheeled sensor application of cost.
Correspondingly propose a kind of design proposal that is used to make sensor element, in this design proposal,, by structuring level and/or vertical portion, realize the ability to work that improves by minimum electrode material for example by using printing process.Basically describe with reference to platinum-YSZ-metallic ceramics-electrode below in this present invention.But other structural scheme also is fine in principle, for example with other noble metal as metal component and/or with the pottery of other type structural scheme as ceramic composition.For example electrode system allows by noble metal for example palladium (Pd) and/or ruthenium (Ru) and/or iridium (Ir) and/or rhodium (Rh) is made and for example Pt/Pd alloy and/or Pt/Au alloy are made by metal mixture or metal alloy.These structural schemes can be migrated in the kind electrode system without a doubt.
Correspondingly propose a kind of sensor element according to the present invention, it is particularly useful for detecting the characteristic of the gas in the measurement gas chamber.For the possible structural scheme and the purposes of this sensor element, especially can be with reference to above explanation.Therefore, sensor element for example can be configured to lambda sensor, for example be configured to the lambda sensor of monocell type and/or many cell types, in order to for example to determine oxygen concentration and/or the partial pressure of oxygen in the measurement gas chamber in the waste gas of internal combustion engine.But other structural schemes also are fine in principle, for example be used for measurement gas one or more other types gas composition concentration and/or dividing potential drop and/or be used for other parameter of detected gas, for example be used to detect particle contamination or similar parameters.
Sensor element comprises that at least one has the solid electrolyte layer of at least a solid ceramic electrolyte.At this, can use solid electrolyte material and/or solid electrolyte layer geometric configuration arbitrarily arbitrarily in principle.Particularly preferably use solid electrolyte material, the especially yttrium-stabile zirconium dioxide (YSZ) of energy conduct oxygen ions.But also can use other solid ceramic electrolyte in principle.
Sensor element also comprises at least one directly or indirectly electrode of the described solid electrolyte layer of contact.Electrode is an element at this in principle, can make ion infiltrate in the solid electrolyte layer on this element or oozes out from solid electrolyte layer and this element provides corresponding conduction contact.Direct or indirect contact is a structural scheme at this, and wherein electrode directly or connect in the centre under the situation at least one middle layer and contact with solid electrolyte layer.
Electrode comprises at least a stupalith and at least a metal material.Thus, electrode especially can be configured to cermet electrodes., also can use solid electrolyte material basically here, preferably as the solid electrolyte material of solid electrolyte layer, have the solid electrolyte material of the ability of the identical ionic type of conduction for stupalith.For example the stupalith for electrode can use yttrium-stabile zirconium dioxide again.But conversion ground additionally also can use other material as the phase stabilization additives that is used for zirconium dioxide, for example other oxide, especially metal oxide, for example Ce
2O
3, MgO, Sc
2O
3, CaO or described and/or other hopcalite.
Allow to use metal, metal mixture or the metal alloy of any type in principle for metal material.In the following material of preferred especially use one or more: platinum, palladium, rhodium, gold.Described and/or other metal potpourri and described and or other the alloy of metal for example platinum-palldium alloy and/or platinum-billon can be expected.But other configuration scheme also is fine in principle.
Sensor element can comprise one or more in the one or more and described electrode in the described solid electrolyte layer at this.The not isomorphism type scheme of the electrode of sensor element inside can expect that also for example at least one is according to electrode configuration scheme of the present invention and at least one configuration scheme combination according to another electrode of prior art.In principle, for example the sensor element of planar type detector type can be made, the planar type detector of for example simple jumping type detector (Sprungsonden), wideband detector or similar type.By also can be constructed in accordance on the known finger-type detector structure principle of prior art and use.
Described at least one electrode has the horizontal expansion size.The horizontal expansion size is one at this and extends size that it is arranged essentially parallel to the extension size of solid electrolyte layer and extends.For example, this horizontal expansion size can be limited, for example is the form of the electrode geometry of cutting apart, form that is for example rectangle, circle, oval or polygonal electrode geometry.This class electrode geometry can for example produce by structuring painting method, for example printing process.
Propose according to the present invention, electrode is provided with the structuring portion that is parallel to and/or extends perpendicular to the horizontal expansion size in horizontal expansion size inside.Structuring portion is at this a kind of configuration of electrode normally, and wherein at least one physics of electrode and/or chemical characteristic are on described direction, promptly be parallel to and/or perpendicular to the horizontal expansion change in size.This physics and/or chemical characteristic especially can be variation in thickness, transmissibility variation, variable density, porosity variation, geometric configuration changes or the variation of other type of described at least one physics and/or chemical characteristic.
Structuring portion should be set for the electrode surface that increases electrode at this.Electrode surface is at this face normally, and it provides described three-phase boundary, promptly at the metal material that is used to provide conductive capability, be used to provide the stupalith of ionic conduction ability and be used for transition part between the surface that gas enters.In other words, compare the quantity that should increase triple point by the structuring portion that proposes with structurized, not traditional electrode.
Particularly preferably be, structuring portion has transversary portion, promptly is parallel to the structuring portion of the horizontal expansion size of electrode.This transversary portion can especially comprise the variation in thickness of the bed thickness of electrode, and wherein, variation in thickness comprises at least two local maximums of thickness of electrode.For example it can be the order of a plurality of peaks and paddy in the electrode bed thickness.In addition, for example can use the ripple struction that has a plurality of pyramidal pyramid structures, has a plurality of troughs and crest, cutting-edge structure, the combination of perhaps described structure or other structure with a plurality of tips (protuberance that promptly has pointed end).A plurality of local eminences can be provided with regularly or brokenly at this.In addition, conversion ground or additionally, this structuring portion also can comprise one or more in the following structuring portion: the hacking portion in the electrode surface; Line pattern in the electrode surface, especially irregular line pattern, but wherein also can expect regular line pattern; Grid in the electrode surface, especially dot pattern, especially irregular dot pattern; Sectional hole patterns, especially irregular sectional hole patterns, but wherein the sectional hole patterns of rule also is fine.
Described structuring portion allows to produce in every way.Therefore, for example propose a kind ofly to be used for making sensor element,, wherein when electrode coated, produce structuring portion especially according to one or more the method for sensor element of described form of implementation.Therefore, for example can use the structurized paint-on technique of electrode cream,, for example be coated on the solid electrolyte layer directly or indirectly by the structured electrode coated cream of this paint-on technique.At this especially can be structurized printing technology, for example in order to realize the printing technology of one or more above-mentioned transversary portions.Therefore, allow to use for example tampon printing technology, screen printing technique or similar printing technology.Particularly preferably be mask technique, wherein electrode cream is coated by pattern and/or networkization ground.Conversion ground or additionally also can produce transversary portion in structured techniques subsequently, wherein structuring portion produces after electrode coated cream.Particularly this structuring portion for example can and/or pull out the technology of cutting (Zupftechnik) by the brush technology and produces, and for example can produce one or more in the described structuring portion by them.But also can expect other manufacture of described structuring portion or the combination of manufacture method in principle.
The conversion of the transversary portion of extending as the horizontal expansion size that is parallel to electrode or additional, vertical stratification portion also is fine, promptly perpendicular to the structuring portion of the horizontal expansion size of electrode.Therefore, structuring portion can for example comprise at least one physics of electrode and/or the chemical characteristic gradient perpendicular to the horizontal expansion size.At this especially can be porosity gradient and/or material gradient and/or density gradient.Conversion ground or additionally, structuring portion also can be included in the gradient of metal material concentration aspect, the concentration gradient of one or more in the especially described metal material.
In order to be created in, allow in principle to use to be suitable for producing the whole bag of tricks of this gradient or variation perpendicular to the gradient on the direction of electrode horizontal expansion size.Especially as an example can use electrode cream with frothing agent.This frothing agent is open and comprise the material that for example changes gas phase into when sintering and stay cavity by prior art.The exemplary of frothing agent is: the combination of the frothing agent of vitreous carbon, flame black, wax shape hydrocarbon, polymer globules or described and/or other type.
Therefore, electrode cream can for example be equipped with frothing agent, and this frothing agent has with the encirclement material of electrode cream, the organic principle of for example electrode cream compares different density.Because the density difference between all the other compositions of frothing agent and electrode cream, frothing agent moves in coated electrode cream, makes the concentration gradient of in undried electrode cream layer still generation frothing agent.For example frothing agent can have littler density than the adhesive component of all the other materials of electrode cream or at least a material component, for example electrode cream.Particularly preferably be, frothing agent is constructed in this wise, make its migration away from solid electrolyte layer, thereby the concentration of frothing agent increases on the direction away from solid electrolyte layer.After sintering, in electrode, form gradient stomatal frequency or the porosity owing to the concentration gradient of frothing agent.Can for example on the side of solid electrolyte layer, create the surface that increases in this mode at the finger of electrode.
Another aspect of the present invention is to contact the aspect of solid electrolyte layer by electrode indirectly by one or more middle layers, this conversion ground, aspect or additionally can be used for above-mentioned form of implementation.Can use among one or more in above-mentioned enforcement modification in combination with the said structure portion of electrode on the conception principle in middle layer.But also can expect to conversion in not structurized fully electrode, using.In principle for the possible configuration scheme of this class sensor element, can be for example with reference to the above explanation of possible the configuration scheme of sensor element with structurized electrode, wherein this class sensor element must be by additional aspect at least one middle layer.
The sensor element that this aspect according to the present invention proposes comprises that again at least one solid electrolyte layer with at least a solid electrolyte material contacts the electrode of solid electrolyte layer indirectly with at least one, and described electrode has at least a stupalith and at least a metal material.At this, this contact is indirect, promptly inserts at least one middle layer between electrode and solid electrolyte layer.The middle layer has higher ionic conduction ability and/or higher electronic conduction ability according to the present invention than solid electrolyte layer.
The purpose of this aspect of the present invention is, keeps the all-in resistance of electrode system as far as possible little, and for example this cryogenic property for exhaust gas probe is favourable.For this reason, at least one transition resistance of electrode and solid electrolyte is reduced.At this, for example also allow to use closely knit and solid electrolyte material good conducting ion for the middle layer.The same solid dielectric material that for example also is used for solid electrolyte layer also allows individually or is used in described at least one middle layer in combination with other materials.But also can use other material, for example stupalith in principle.Particularly preferably be, not only solid electrolyte material but also middle layer comprise zirconium dioxide, for example yttrium-stabile zirconium dioxide respectively, wherein, the middle layer than the solid electrolyte material of solid electrolyte layer have higher doping, especially higher yttrium mixes and/or higher Yttrium oxide doping.
Compare with known method with known sensor element, the method that being used to of sensor element that proposes among one or more in above-mentioned form of implementation and proposition made sensor element has many advantages.Available electrode surface in many sensor elements for example, the electrode surface of external electrode (OE) and interior electrode (IE) for example is by the size and the structure gauge of sensor element.Typical operational OE face in plane jump detector for example 0.04 and 0.1cm
2Between the motion.At this, for example can use rectangle or oval face, it can directly be stamped on (for example being the form of ceramic monolith film) solid electrolyte layer by Pt-YSZ-metallic ceramics-electrode cream.The component of electrode cream, for example the content of platinum, YSZ and possible other component, especially organic component such as bonding agent, solvent or the like can require to determine by printing technology for electrode coated at least thereupon.The possible raw material for example minimum available granularity of material powder and the ceramic-metallic fineness that obtains thus can be limited by cost and job security aspect.Therefore, the granularity of employed solid can for example be determined in advance in this wise, make it be not less than definite limit, although this maximization for the quantity in activated centre is helpful.Therefore for example typical Pt-YSZ-metallic ceramics-electrode cream for example has the platinum of 60 to 70 percentage by weights, the YSZ of 10 to 25 percentage by weights and the organic principle of 10 to 20 percentage by weights, and wherein the granularity of metal of Jia Ruing and ceramic powders is d90＞15 micron.
In order to make the quantity maximization of using activated centre under the minimum situation at platinum, can increase electrode surface by structuring portion level (promptly being parallel to the horizontal expansion size) and/or vertical (promptly perpendicular to the horizontal expansion size) according to the present invention according to the above-mentioned first aspect of the structuring portion of electrode.
And in aspect another of at least one additional middle layer, on purpose improve transmissibility electricity and/or ion of electrode system.The all-in resistance of electrode system is provided by volume resistance and the transition resistance sum between electrode and solid electrolyte layer or ceramic substrate (Interface) by solid electrolyte layer and two electrode layers (Bulk).For example can design this structure as follows for the lambda sensor that is the finger-type panel detector structure:
Exhaust air chamber
External electrode (OE)
The middle layer
Solid electrolyte layer
The middle layer
Interior electrode (IE)
Reference air
But other layer structure also is fine and considers similarly in principle.For the all-in resistance with electrode system keeps as far as possible for a short time, for example in order to improve above-mentioned cryogenic property, that pass through to be proposed, good conducting ion and closely knit middle layer can reduce transition resistance consumingly.
For example can use the YSZ middle layer, they also can have the metal material share.For example can use in the above-mentioned metal material one or more again, for example platinum.Preferably, in the middle layer concentration of metal material less than the concentration of metal material in the electrode.
In addition, conversion ground or additionally, the porosity in middle layer can keep lowlyer than the porosity of electrode.Therefore, for example the porosity in described at least one middle layer can be between the porosity of the porosity of electrode, for example platinum-metallic ceramics-electrode and solid electrolyte layer.
For example, solid electrolyte layer can have 3 to 7 molar percentages, the YSZ of 5.5 molar percentages for example, and wherein, this mole data are usually directed to the molar content of yttria in the zirconium dioxide.For example, at the ZrO of solid electrolyte
2In may have the Y of 5.5 molar percentages
2O
3, and in the middle layer, for example have the Y of 9.0 molar percentages
2O
3, and the Y that in metallic ceramics, for example has 11.0 molar percentages
2O
3For example can use by tetragonal stable ZrO
2(TPZ) Y that form, that in ZrO2, have 3.0 molar percentages
2O
3The solid electrolyte carrier or by Y partially stabilized, that in ZrO2, have 5.5 molar percentages
2O
3The solid electrolyte carrier.Can use for example Y of 5.5 molar percentage to 8.0 molar percentages for the middle layer
2O
3, especially be cubic system, completely stable shape.Metallic ceramics for electrode can use for example Y of 8.0 molar percentage to 11 molar percentages
2O
3
Being connected and reducing transition resistance between the ceramic substrate of electrode and solid electrolyte layer, for example solid electrolyte layer can be improved in described at least one middle layer.Described at least one middle layer equally can be by structuring, for example according in the said structure method one or more.Therefore, can realize being parallel to electrode the horizontal expansion size structuring portion and/or perpendicular to the structuring portion of the horizontal expansion size of electrode.Thus can be all sidedly with reference to above-mentioned structured techniques.Therefore, for example the structuring portion of the structuring portion in described at least one middle layer and described at least one electrode can exist simultaneously.The middle layer can constitute for example non-porously.For example, the middle layer can be at ZrO
2In have the Y of 5 to 11 molar percentages
2O
3, especially content is at 7 to 10 moles percent Y
2O
3Preferred especially ZrO
2Middle Y
2O
3Content is about 8 molar percentages.
Usually cause described at least one middle layer physical strength littler on the one hand although compare the middle layer doping of increase with solid electrolyte layer than the solid electrolyte material of solid electrolyte layer.But this is sustainable when especially being no more than given thickness in the middle layer, although because along with the raising strength degradation of mixing, the ionic conduction ability improves.Can improve by this way electricity between solid electrolyte layer and the electrode and/or ion be connected and reduce transition resistance thus.
Description of drawings
Shown in the drawings and the elaboration at length in following instructions of embodiments of the invention.Wherein:
Figure 1A and 1B illustrate embodiment according to the sensor element of prior art with different views;
Fig. 2 A and 2B illustrate first embodiment that has the sensor element of the electrode of being with pyramid structure according to of the present invention;
Fig. 3 A and 3B illustrate second embodiment that has the sensor element of the electrode of being with cutting-edge structure according to of the present invention;
Fig. 4 illustrates the 3rd embodiment that has the sensor element in band electrode of ripple struction and middle layer according to of the present invention;
Fig. 5 illustrates the 4th embodiment that has the sensor element in electrode, porosity gradient and the middle layer of being with ripple struction according to of the present invention.
Embodiment
In Figure 1A and 1B, schematically illustrate an example of traditional sensor element 110.At this lead-in wire 114 (only in Figure 1A as seen) that only electrode 112 of sensor element 110 is shown respectively and leads to this electrode 112.With vertical view electrode 112 and sensor element 110 are shown at this Figure 1A, and Figure 1B illustrates the cut-open view of sensor element 110 from the side.
Electrode 112 is coated on the solid electrolyte layer 116, and this solid electrolyte layer comprises solid electrolyte material 118.For example solid electrolyte material can be yttrium-stabile zirconium dioxide (YSZ), wherein, uses the YSZ of 5.5 molar percentages usually.On the solid electrolyte layer 116 that for example can be configured to thin layer electrode coated 112.Electrode 112 for example is configured to platinum-YSZ-metallic ceramics-electrode and has porous structure usually.Typically use electrode cream in order to make kind electrode 112, this electrode cream has metal material 120, the especially platinum that content is 60 to 70 percentage by weights, and content is the stupalith 122 and organic principle, for example binder material and/or the solvent of content between 10 to 20 percentage by weights of 10 to 25 percentage by weights.The granularity of the metal material 120 that is added and the powder of stupalith 122 typically is positioned at d90＞15 micron.Typically, electrode 112 has the horizontal expansion size that is parallel to surface 124 and is parallel to the horizontal expansion size of solid electrolyte layer 116 thus, and it marks with D in Figure 1B and it for example can be arranged in from the scope of ten microns until several millimeters.But other electrode size also is fine in principle.The thickness that in Figure 1B, marks of electrode 112 with d for example can be located at several micron until tens microns or even scope between 100 microns in or above 100 microns.
As seen by Figure 1A and 1B, according to the electrode 112 of prior art in its horizontal expansion size inside not by structuring, promptly (ignore the porosity that may exist) at its physics and/or the basic homogeneous of chemical characteristics.Therefore, especially the quantity of pore is evenly distributed on the thickness of electrode 112, and the thickness d of electrode 112 is constant substantially on the horizontal expansion size of electrode 112.
And shown in Fig. 2 A to 5 according to the different embodiment of sensor element 110 configuration schemes of the present invention.Show an electrode 112 of sensor element 110 again for example at this.A plurality of electrodes certainly are set, for example a plurality of mutual opposed electrodes, a plurality of electrode, the sensor arrangement monocell type or many cell types or analogs in the identical layer plane.The geometric configuration on also also nonessential use plane and layer structure, but can for example use finger-like structure with curved surface.
In Fig. 2 A and 2B, with Figure 1A and the similar view of 1B, first embodiment according to sensor element 110 of the present invention is shown.Different with Figure 1A and 1B, electrode 112 is by structuring and the structuring portion 126 with the horizontal expansion size on the surface 124 that is parallel to solid electrolyte layer 116 in according to the embodiment of Fig. 2 A and 2B.If should have crooked shape in surface 124, for example in the finger-type sensor, then this collimation relates to the horizontal expansion size of the part of solid electrolyte layer 116.As seen from the figure, this structuring portion 126 for example constitutes with the form of Pyramid 128 in this case, and wherein the thickness of electrode 112 is at approximate zero and maximum ga(u)ge d
MaxBetween change, wherein meaningful is also can contain a plurality of electrode layers in this electrode 112.The pyramid side of Pyramid 128 can be configured to flat or crooked at this, wherein, and in the configuration scheme of a bending shown in Fig. 2 B.As in Fig. 2 A as seen, structuring portion 126 for example observes line pattern 130 in this embodiment, the tip of pyramid structure 128 or paddy are along the line setting in this line pattern, wherein parallel lines and other parallel lines are with for example approximate right angle or other angle of intersection.
In second embodiment that constitutes similarly with Fig. 2 A and 2B shown in Fig. 3 A and the 3B, pyramid structure 128 replaces by cutting-edge structure 132.This cutting-edge structure 132 is as visible configuration example such as dot pattern 134 in according to the vertical view of Fig. 3 A.At this this electrode 112 at it with the horizontal expansion size of solid electrolyte layer 116, for example have variation on its bed thickness in the 124 parallel extension sizes of surface again, wherein, this bed thickness can be similar to disappearance or can drop at least for example less than maximum bed thickness d in the paddy of this structuring portion 126
Max10% number percent.Cutting-edge structure 132 has the tip of sharp ending on its tip, but radius can be set.The structuring portion of other type also is fine in principle.
Embodiment in Fig. 2 A to 3B only is illustrated in two kinds of transversary portion on the extension size of the horizontal expansion size that is parallel to solid electrolyte layer 116 may shapes.Replace dot pattern or line pattern shown in the figure, they also can be called the honeycomb portion with honeycomb pattern, can expect the transversary portion of a large amount of other types, have wherein used the cycle or the aperiodic variation in thickness of electrode 112 bed thickness.
This horizontal or also the structuring portion of level can for example use in external electrode (OE) and/or interior electrode (IE).As implied above, but other configuration also is fine, and for example wherein not every electrode is all by structurized configuration.Structuring portion 126 can for example pass through space, hole or pattern generating, and they can be presented in the electrode 112.Maximum bed thickness d
MaxCan be for example between 5 microns and 100 microns, for example between 10 microns and 50 microns and especially about 30 microns.
Structuring portion 126 can be presented in the electrode 112 when producing electrode 112 at this.Therefore can for example pass through the printing screen implementation structureization, can for example above-mentioned electrode cream be coated on the solid electrolyte layer 116 by printing screen.Printing screen also can comprise corresponding pattern, for example grid, dot pattern or similar pattern.Under the situation of network, recommend in addition to use irregular particle grid, for example in order to avoid Moire effect.If the grid in life cycle or approximate cycle or pattern, then the cycle can for example be tens microns to the hundreds of micron, for example 30 microns to 50 microns.For grid and grid, can minimizing face according to the present invention overlap and reduce thus the consumption of electrode cream, for example platinum cream.
As the conversion that structuring portion 126 is set when the electrode coated cream or additional, structuring portion also can be provided with subsequently.Therefore the combination of hacking, impression, grinding, brush or described processing and/or other processing that for example structuring portion 126 can be by subsequently realizes.These are for example handled can be after applying cream, for example after impression in green state fractional wettability or realized on the electrode layer of drying.
Conversion ground or additionally, structuring portion also can be for example by using frothing agent or realizing by using the low-down cavity of density to form agent in uppermost printed layers, cavity forms agent and is close to come-up and produces density gradient thus in electrode 112 after applying in electrode cream, and this density gradient may for example only just can be discerned after sintering.Thus, the transversary portion 126 shown in Fig. 2 A to 3B also can with the vertical structuring portion combination perpendicular to the surface 124 of solid electrolyte layer 116.
In order to make transversary portion 126, the same permission used many technology, and these technology also can be used in combination.Therefore, the variation of bed thickness can be for example by the stamping structure realization, and wherein, electrode 112 is by structuring.Conversion ground or additionally, solid electrolyte layer 116 also can be by structuring.For example can produce ripple or pyramid structure in this mode.Conversion ground or additionally, the variation of bed thickness also allows the printing by electrode cream, then by the corresponding structure roller tear and/or roll extrusion produces.
At this electrode cream that for example allow to use unusual important place, constitutes hardy.Also can be directly in undried state apply, for example after the impression owing to its extensibility, be that viscosity is at electrode cream very thick and/or that glue, for example have on the surface of electrode cream of long-chain adhesive system and carry out hacking.Various technology is fine.
To point out in addition, a layer of electrode 112 only is shown in Fig. 2 A to 3B.The electrode of multilayer also can be manufactured, wherein, one, a plurality of or all these the layer can be by structured formation.In addition, electrode 112 also can be provided with the protective seam that does not up to the present illustrate in the drawings, for example porous, ventilative, ceramic protective seam, and it can guard electrode 112 for example be avoided polluting.
As implied above, another design of the present invention is that the function of electrode structure additionally is enhanced by using one or more middle layers.Allow integrally to improve electricity and transmissibility ion of electrode system and the all-in resistance of reduction electrode system in this mode.This middle layer also can be made up with transversary portion.Therefore, Fig. 4 illustrates first embodiment of sensor element 110 with the view of similar Fig. 2 B and 3B, has wherein realized this inventive concept.At this, use electrode 112 at first again with metal material 120 and stupalith 122, this electrode can have the transversary portion 126 on the surface 124 that is parallel to solid electrolyte layer 116 again alternatively.This transversary portion 126 is configured to ripple struction 136 in an illustrated embodiment, wherein, for example ripple struction 136 can have again with according to the similar line pattern 130 of the form of implementation of Fig. 2 A.For the possible manufacture method of electrode 112 and the possible structural scheme of electrode cream, can be to a great extent with reference to above explanation.
But with opposite according to the embodiment of Fig. 2 A to 3B, electrode 112 is coated on the solid electrolyte layer 116 at the embodiment middle ground shown in Fig. 4.In an illustrated embodiment, between real electrode 112 and solid electrolyte layer 116, be provided with middle layer 138.This middle layer 138 also can have transversary portion 126, for example is the form of ripple struction 136 again.But the middle layer that does not have structuring portion 126 138 on plane is fine in principle.In addition, the idea of using middle layer 138 also can be fully used under the situation that does not have horizontal or vertical structuring portion.Optional structuring portion 126 for middle layer 138, the top explanation of reference to a great extent, thus this middle layer 138 for example also is the form of honeycomb, pyramid structure, ripple struction, cutting-edge structure, line pattern, network or analog.Therefore, for example can at first at least one middle layer 138 be applied, for example be impressed on the solid electrolyte layer 116.Structuring can and/or subsequently realize during applying again.Then at least one electrode 112 can be applied, for example is impressed on the middle layer 138, wherein again can be alternatively implementation structureization and/or subsequently during applying for example.
Described at least one middle layer 138 is used for low ohm connection the between solid electrolyte layer 116 and the electrode 112.As mentioned above, allow to reduce consumingly the all-in resistance of electrode system thus.This for example has special benefits for the cryogenic property of the sensor element 110 that uses in exhaust gas probe.Use especially middle layer 138 in this permission, it has high ionic conduction ability and constitutes densely.Especially allow to use stupalith 122 again, it can have the metal material 120 of low content for this reason.
Therefore, for example the solid electrolyte material 118 of solid electrolyte layer 116 can be by the Y of 5.5 molar percentages in a kind of structural scheme
2O
3Stable ZrO
2Make.Y
2O
3Content is typically selected like this at this, makes its guarantee optimization to the phase stability and the physical strength of solid electrolyte material 118.For example allowing to use content is 3.0 to 8.0 molar percentages, especially 5.0 to 6.0 molar percentages, and the Y of preferred especially described 5.5 mole percent level
2O
3Additional middle layer 138 is advantageously by the Y of 8.0 molar percentages
2O
3Stable ZrO
2Form.For example the scope between 7.0 molar percentages and 11.0 molar percentages also is fine.Y in the middle layer 138
2O
3Content is preferably in order to optimize electronic conduction ability and oxygen ion conduction ability (O
2The ionic conduction ability) selected.But other structural scheme also is fine basically.
Another embodiment according to sensor element 110 of the present invention shown in Figure 5 wherein uses middle layer 138 equally.Thus, can be to a great extent for example with reference to the explanation of figure 4.Middle layer 138 for example is provided with transversary portion 126 again.In addition, the design in the horizontal middle layer 138 among Fig. 5 again with the electrode 112 design combinations of the transversaryization shown in front the embodiment.Transversary portion 126 for example constitutes with the form of cutting-edge structure 132 at this.But other structuring portion also is fine in principle.As implied above, however the design proposal of the transversaryization 126 of the design proposal in use middle layer 138 and middle layer 138 and/or electrode 112 also can realize in principle with being independent of each other.
In addition, according to another design proposal of the present invention shown in the embodiment of Fig. 5, it can irrespectively use with above-mentioned design proposal, but in principle also can with shown at least one middle layer 138 of use design proposal and/or use the design proposal of the transversary portion 126 at least one electrode 112 and/or at least one middle layer 138 to realize in combination.This design proposal comprise a vertical or vertical structuring portion 140 (notion of vertical and vertical structuring portion is used with the free burial ground for the destitute in this manual, wherein be given in electrode 112 and/or the electrode complex formed by at least one middle layer 138 and at least one electrode 112 in physics and/or chemical characteristic perpendicular to the variation on the direction of the horizontal expansion size of solid electrolyte layer 116 (for example surperficial 124).Example as this vertical structuring portion 140 can use the concentration gradient of the content of metal material 120, the gradient of for example platinum content.Conversion ground or additionally also can use the gradient of the porosity or stomatal frequency, and wherein the pore among Fig. 5 is symbolically represented with Reference numeral 142.Conversion ground or additionally also can use the variation of other physics and/or chemical parameters for vertical structuring portion 140.
As mentioned above, vertically structuring portion 140 allows to produce in a different manner.Therefore, can be for example vertical variation by using frothing agent to produce pore 142 density, this frothing agent in being still liquid state or moistening at least electrode cream because the density difference stands separation continuous or gradually.For example frothing agent can float in electrode cream after applying, to such an extent as to the density of pore 142 is higher than a side of face solid electrolyte layer 116 in a side that deviates from solid electrolyte layer 116 of electrode 112.Conversion ground or additionally also can coated with multiple layer respectively has the electrode material of the frothing agent of different content, makes the density gradient that also can produce pore 142 by this way.In addition, vertically structuring portion 140 also can be reflected on the content of metal material 120 in the electrode complex 140.Therefore as mentioned above, described at least one electrode 112 for example can contain more metal material 120, for example platinum of high-load than described at least one middle layer 138.
Vertically structuring portion 140 represents by Reference numeral 144 and 146 on Fig. 5 the right.Therefore, Reference numeral 144 is also represented metal material 120, for example platinum and the increase of high-load or the high porosity.Stupalith 122, for example YSZ of opposite Reference numeral 146 expression high-loads.The vertical gradient of metal material concentration, the porosity and YSZ content can little by little, continuously or also can be classified to realize.Different design proposals are fine.
The gradient in one or more physics and/or chemistry amount that symbolically marks in Fig. 5 by vertical structuring portion 140 can be crossed over the electrode complex that comprises electrode 112 and middle layer 138 at this and be extended.In addition, this gradient can also be extended to solid electrolyte layer 116 the insides alternatively.Usually this gradient preferably can comprise one or more in the following amount: the porosity; Tenor and/or ceramic content; The granularity of solid; Matrix (Matrix), for example ZrO
2Dopant, especially doping oxide, especially Y in the matrix
2O
3Molar content.Combination described and/or other gradient also is fine.Gradient at this preferred porosity should change in this wise, make the porosity from solid electrolyte layer 116 towards the middle layer 138 and increase towards electrode 112.The molar content of tenor and/or dopant should preferably increase on this direction equally.And granularity and/or ceramic content should preferably increase in the opposite direction.
Claims (10)
1. sensor element (110), in particular for detecting the characteristic of the gas in the measurement gas chamber, comprise that at least one solid electrolyte layer (116) with at least a solid ceramic electrolyte (118) directly or indirectly contacts the electrode (112) of described solid electrolyte layer (116) with at least one, described electrode has at least a stupalith (122) and at least a metal material (120), wherein, described electrode (112) has the horizontal expansion size, described electrode (112) has a structuring portion (126 that is parallel to and/or extends perpendicular to described horizontal expansion size in described horizontal expansion size inside, 140), described structuring portion (126,140) is set for the electrode surface that increases described electrode (112).
2. according to the described sensor element of preceding paragraph claim (110), wherein, described structuring portion (126,140) has a transversary portion (126), described transversary portion (126) comprises the variation in thickness of the bed thickness of described electrode (112), and described variation in thickness is included at least two local maximums in the described bed thickness.
3. according to the described sensor element of preceding paragraph claim (110), wherein, described bed thickness variation comprises a plurality of local eminences, and described local eminence has at least one in the following shape: pyramid structure; Ripple struction; Cutting-edge structure; Honeycomb.
4. according to each described sensor element (110) in the above claim, wherein, described structuring portion (126,140) comprises at least one in the following structuring portion (126,140): the hacking portion in the electrode surface; Line pattern in the electrode surface, especially irregular line pattern; Grid in the electrode surface, especially dot pattern, especially irregular dot pattern; Sectional hole patterns, especially irregular sectional hole patterns.
5. according to each described sensor element (110) in the above claim, wherein, described structuring portion (126,140) comprise a vertical structuring portion (140) of extending perpendicular to described horizontal expansion size, described vertical structuring portion (140) comprises one or more in the gradient of extending perpendicular to described horizontal expansion size: porosity gradient; Material gradient; Density gradient.
6. according to each described sensor element (110) in the above claim, wherein, described structuring portion (126,140) comprise a vertical structuring portion (140) of extending perpendicular to described horizontal expansion size, described vertical structuring portion (140) comprises one or more the concentration gradient in the concentration gradient of described metal material (120), the especially following metal: platinum; Palladium; Rhodium; Gold; Ruthenium; Iridium; Platinum/palldium alloy; Platinum/billon.
7. sensor element (110), especially according to each described sensor element (110) in the above claim, comprise that at least one has the solid electrolyte layer (116) of at least a solid ceramic electrolyte (118) and the electrode (112) of the described solid electrolyte layer of at least one indirect contact (116), described electrode has at least a stupalith (122) and at least a metal material (120), wherein, between described electrode (112) and described solid electrolyte layer (116), insert at least one middle layer (138), especially has structuring portion (126,140) middle layer, described middle layer (138) have higher ionic conduction ability and/or higher electronic conduction ability than described solid electrolyte layer (116).
8. according to the described sensor element of preceding paragraph claim (110), wherein, described solid electrolyte material (118) and described middle layer (138) comprise the zirconium dioxide that yttrium mixes respectively, especially the zirconium dioxide of Yttrium oxide doping, described middle layer (138) have than described solid electrolyte material (118) that higher yttrium mixes, especially higher Yttrium oxide doping.
9. be used to make sensor element (110), especially according to the method for each described sensor element (110) in the above claim, wherein, at least one electrode (112) directly or indirectly is coated on the solid electrolyte layer (116) with at least a solid ceramic electrolyte (118), described electrode (112) has the horizontal expansion size, in described electrode (112), produce one and be parallel to the transversary portion (126) that described horizontal expansion size is extended, described transversary portion (126) is by at least a generation in the following structured techniques: by the paint-on technique of electrode cream, by the structured coating of this paint-on technique described electrode cream, especially printing technology; By mask technique, by described mask technique with the electrode coated cream in pattern or networkization ground; By structured techniques subsequently, after electrode coated cream, produce described transversary portion (126) by described structured techniques subsequently, especially by the brush technology and/or pull out the technology of cutting.
10. be used to make sensor element (110), especially according to more than relate to the method for each described sensor element (110) in the claim of sensor element (110), wherein, at least one electrode (112) directly or indirectly is coated on the solid electrolyte layer (116) with at least a solid ceramic electrolyte (118), described electrode (112) has the horizontal expansion size, in described electrode (112), produce a vertical structuring portion (140) perpendicular to described horizontal expansion size extension, wherein, coating has the electrode cream of frothing agent, described frothing agent has with the encirclement material of described electrode cream compares different density, because described density difference forms the concentration gradient of frothing agent in coated electrode cream, because the concentration gradient of described frothing agent forms the stomatal frequency gradient in described electrode (112).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008054617.8 | 2008-12-15 | ||
| DE200810054617 DE102008054617A1 (en) | 2008-12-15 | 2008-12-15 | Structured electrode for ceramic sensor elements |
| PCT/EP2009/064794 WO2010072460A1 (en) | 2008-12-15 | 2009-11-06 | Structured electrode for ceramic sensor elements |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102246028A true CN102246028A (en) | 2011-11-16 |
| CN102246028B CN102246028B (en) | 2014-08-27 |
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ID=41559445
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980150552.8A Active CN102246028B (en) | 2008-12-15 | 2009-11-06 | Structured electrode for ceramic sensor elements |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN102246028B (en) |
| DE (1) | DE102008054617A1 (en) |
| WO (1) | WO2010072460A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104285141A (en) * | 2012-05-09 | 2015-01-14 | 大陆汽车有限责任公司 | Sensor element with a cermet base layer and a platinum cover layer |
| CN104634846A (en) * | 2013-11-14 | 2015-05-20 | 罗伯特·博世有限公司 | Sensor element for detecting at least one characteristic of a measurement gas in a measurement gas space |
| CN105087984A (en) * | 2014-05-13 | 2015-11-25 | 罗伯特·博世有限公司 | Platinum ceramic and manufacturing method thereof |
| CN110140044A (en) * | 2016-12-28 | 2019-08-16 | 罗伯特·博世有限公司 | For sensing the sensor element of at least one characteristic of the measurement gas in measurement gas compartment |
| CN110785657A (en) * | 2017-06-23 | 2020-02-11 | 罗伯特·博世有限公司 | Sensor element for an exhaust gas sensor |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012210725A1 (en) | 2012-06-25 | 2014-01-02 | Robert Bosch Gmbh | Sensor element for detecting at least one property of a sample gas in a sample gas space |
| DE102013210903A1 (en) | 2013-06-11 | 2014-12-11 | Heraeus Sensor Technology Gmbh | Gas sensor for measuring different gases and related manufacturing process |
| DE102014211782A1 (en) | 2014-06-18 | 2015-12-24 | Robert Bosch Gmbh | Sensor element for detecting at least one property of a sample gas in a sample gas space |
| DE102014226718A1 (en) * | 2014-12-19 | 2016-06-23 | Continental Automotive Gmbh | Method for operating an oxygen sensor |
| TWI586961B (en) * | 2015-11-23 | 2017-06-11 | 南開科技大學 | Preparation of High Temperature Acid and Alkali Array Sensor by Thick Film Ceramic Substrate Technology |
| DE102020206666A1 (en) * | 2020-05-28 | 2021-12-02 | Robert Bosch Gesellschaft mit beschränkter Haftung | Sensor element for an exhaust gas sensor |
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| DE2913633C2 (en) * | 1979-04-05 | 1986-01-23 | Robert Bosch Gmbh, 7000 Stuttgart | Electrochemical measuring sensor for the determination of the oxygen content in gases, in particular in exhaust gases from internal combustion engines, as well as a method for producing the same |
| JPS56160653A (en) * | 1980-05-14 | 1981-12-10 | Ngk Spark Plug Co Ltd | Manufacture of oxygen concentration cell |
| DE19541619A1 (en) * | 1995-11-08 | 1997-05-15 | Bosch Gmbh Robert | Electrochemical sensor and method for producing an electrochemical sensor |
| JP3106971B2 (en) * | 1996-08-21 | 2000-11-06 | トヨタ自動車株式会社 | Oxygen sensor |
-
2008
- 2008-12-15 DE DE200810054617 patent/DE102008054617A1/en not_active Withdrawn
-
2009
- 2009-11-06 WO PCT/EP2009/064794 patent/WO2010072460A1/en active Application Filing
- 2009-11-06 CN CN200980150552.8A patent/CN102246028B/en active Active
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| GB2054163A (en) * | 1979-06-26 | 1981-02-11 | Nissan Motor | Flat thin film type oxygen sensor |
| US4851105A (en) * | 1987-02-16 | 1989-07-25 | Ngk Insulators, Ltd. | Oxygen sensing element and method for producing the same |
| CN1226965A (en) * | 1996-07-29 | 1999-08-25 | 加利福尼亚大学董事会 | Solid state oxygen sensor |
| CN1904603A (en) * | 2005-07-25 | 2007-01-31 | 日本特殊陶业株式会社 | Gas sensor element and gas sensor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104285141A (en) * | 2012-05-09 | 2015-01-14 | 大陆汽车有限责任公司 | Sensor element with a cermet base layer and a platinum cover layer |
| CN104634846A (en) * | 2013-11-14 | 2015-05-20 | 罗伯特·博世有限公司 | Sensor element for detecting at least one characteristic of a measurement gas in a measurement gas space |
| CN105087984A (en) * | 2014-05-13 | 2015-11-25 | 罗伯特·博世有限公司 | Platinum ceramic and manufacturing method thereof |
| CN110140044A (en) * | 2016-12-28 | 2019-08-16 | 罗伯特·博世有限公司 | For sensing the sensor element of at least one characteristic of the measurement gas in measurement gas compartment |
| CN110140044B (en) * | 2016-12-28 | 2023-11-28 | 罗伯特·博世有限公司 | Sensor element for sensing at least one property of a measurement gas in a measurement gas chamber |
| CN110785657A (en) * | 2017-06-23 | 2020-02-11 | 罗伯特·博世有限公司 | Sensor element for an exhaust gas sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102008054617A1 (en) | 2010-06-17 |
| WO2010072460A1 (en) | 2010-07-01 |
| CN102246028B (en) | 2014-08-27 |
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