CN103748460A - Sensor element for capturing at least one property of gas in measurement gas space - Google Patents
Sensor element for capturing at least one property of gas in measurement gas space Download PDFInfo
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- CN103748460A CN103748460A CN201280041274.4A CN201280041274A CN103748460A CN 103748460 A CN103748460 A CN 103748460A CN 201280041274 A CN201280041274 A CN 201280041274A CN 103748460 A CN103748460 A CN 103748460A
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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
- G01N27/4067—Means for heating or controlling the temperature of the solid electrolyte
Abstract
Proposed is a sensor element (10) for capturing at least one property of a gas in a gas space, in particular for detecting a gas component in the gas or for capturing a temperature of the gas. The sensor element (10) comprises at least one solid electrolyte (12), at least one electrode (14, 16) arranged on the or in the solid electrolyte (12), and at least one heating element (18) for heating the solid electrolyte (12). The heating element (18) has at least one feed region (24) and one heating region (26), wherein the feed region (24) has a cold resistance which is not greater than 30%, preferably not greater than 25%, and particularly preferably not greater than 16%, of a total cold resistance of the heating element.
Description
Background technology
From prior art, become known for obtaining multiple sensors element and the method for at least one performance of gas measurement gas space.Herein, the performance of gas refers to any physical and/or the chemical property of gas in principle, and wherein one or more gas performances can be acquired.Hereinafter, description of the invention relates in particular to quality and/or the quantity of the gas componant of obtaining gas, is specifically related to obtain the oxygen content in gas.Oxygen content can be for example the form of dividing potential drop and/or the form of percentage composition.But, alternatively or additionally, also can obtain other performances of gas.
For example, this sensor element can be designed to so-called lambda probe, as from Konrad Reif(Hrsg.): Sensoren im kraftfahrzeug, 1.Auflage2010 is S.160-165 known.Utilize wide band lambda probe, particularly utilize planar broad band lambda probe for example can determine the oxygen concentration in the gas in very large region, and then derive air-fuel ratio in firing chamber.Air coefficient represents this air-fuel ratio.
Known from prior art, described sensor element is ceramic sensor element element especially, and the basis of described ceramic sensor element element is to use the known solid of electrolyte performance, the i.e. ion transmission performance of this solid.Especially, these solids refer to solid ceramic electrolyte, for example zirconia (Z
ro
2), especially the stable zirconia (yttriumstabilisiertes Zirkoniumdioxid(YSZ) of yttrium) and/or containing the zirconia (scandiumdotiertes Zirkoniumdioxid (ScSZ)) of scandium, they can contain aluminium oxide (Al
2o
3) and/or silicon dioxide (SiO
2) etc. a small amount of adjuvant.
According to their measuring principle, first lambda probe generally must be heated to its running temperature, because solid electrolyte ability conduct oxygen ions when higher than 350 ℃ of temperature.Described running temperature is usually located in the scope of 600 ℃ to 900 ℃.
DE3538460A1 discloses a kind of automobile oxygen sensor element, and it has sensor unit and heating unit.Because described oxygen sensor element is arranged in automobile, its size is length: 50mm is to 80mm, width: 4mm is to 7mm.Described sensor unit comprises solid electrolyte body and conductor, and described solid electrolyte body has structure reference electrode and potential electrode thereon.Described heating unit is included in the heating region of arranging in ceramic bases, form is stratie, and a pair of stratie conductor below that is positioned at, and the resistance of described conductor is less than the resistance of described stratie.
Motorcycle is applied widely in Asian countries.But these countries have formulated obvious strict waste gas rules in recent years.This causes the demand of sensor element to increase, the especially lambda probe of Chemical Measurement, and these sensor elements are used for the potpourri of the internal combustion engine of adjusting these motorcycles.The requirement of for example, lambda probe to cyclecar (motorcycle) use is obviously different from the requirement of the lambda probe that automobile is used.Especially, also necessary cost is low for the automobile-used sensor element of equipment of small motor, and structure is little.At least almost just the same height of sensor that the temperature holding capacity of different parts (for example solid electrolyte, sensor body or cable outlet) and automobile are used, this is because cyclecar usually uses engine scheme cheaply, this engine combustion is insufficient, thereby causes that work efficiency is not high.Therefore,, in order to make engine reach full load running status in the long running stage, sensor element will be exposed to quite high exhaust gas temperature.
Automobile-use lambda probe has larger heating element, and it has large power consumption, especially automobile of described motor vehicle, or even commerial vehicle.As using low resistance, the high-power well heater applied under this lambda probe situation, too large for cyclecar, and due to fringe cost, for efficient well heater output stage and be in-problem from the heating radiator of controller efficiently radiates heat.
Summary of the invention
Therefore, the invention provides a kind of sensor element, described sensor element is than hitherto known automobile sensor component structure compactness, and is particularly useful for cyclecar, especially two wheeler, for example motorcycle.
Sensor element of the present invention is for obtaining at least one performance of gas space gas, especially the composition of gas or obtain the temperature of gas in probe gas, described sensor element can comprise at least one solid electrolyte, electrode and at least one heating element that at least one on solid electrolyte or is wherein arranged, and wherein said heating element is for heating described solid electrolyte.Described heating element has at least one lead-in wire region and a heating region, the cold-state resistance in wherein said lead-in wire region be not more than described heating element cold conditions all-in resistance 30%, be preferably not more than its 25%, be particularly preferably not more than its 16%.
Described heating element has the cold conditions all-in resistance and the preferred cold conditions all-in resistance from 8 ohm to 20 ohm from 6 ohm to 22 ohm.Described heating element is electrical heating elements, and when working voltage is 13V, described electrical heating elements has maximum consumption of power maximal value 5W, preferred maximum 4W and particularly preferably maximal value 3.5W.Described sensor element can have length maximal value 50mm, preferred maximum 45mm and particularly preferably maximal value 35mm, described sensor element has width maximal value 10mm, preferred maximum 8mm and particularly preferably maximal value 4mm, and for example described sensor element has length 35mm and width 4mm.Described heating element comprises heater, described heater in heating region than thering is less thickness and less width at lead-in wire in region, for example thickness of described heater in described heating region be described lead-in wire region thickness at the most 50% and/or the width of described heater in described heating region be described lead-in wire region width at the most 50%.Described heater can have maximum thickness 16 μ m at described heating region, preferred maximum 12 μ m and particularly preferably maximal value 8 μ m, width maximal value 300 μ m, preferred maximum 250 μ m and particularly preferably 200 μ m, for example thickness 8 μ m and width 200 μ m.Described heater is configured to indentation structure in heating region, and comprises at least five indentation turning parts.Described heating element is configured to indentation structure at described heating region, so that form the described conductor segment of described indentation turning part, about median surface mirror image, arrange symmetrically, and the spacing being parallel in the every side of described median surface between this conductor segment of described median surface increases towards described median surface.The turning of described indentation turning part can be by rounding.Described heating element is made with metal-metal pottery or metal alloy-metallic ceramics, and at least one metal in described metal or described metal alloy is selected from the metal of platinum metal family.Described metal alloy-metallic ceramics comprises metal alloy, and described metal alloy comprises aluminium oxide.The manufacturing tolerance that described heating element can be configured to resistance in described heating region and/or lead-in wire region is less than 10%.
Solid electrolyte is interpreted as having object or the material of electrolyte performance within the scope of the invention, also has object or the material of ionic conduction performance.Especially, solid electrolyte refers to solid ceramic electrolyte.It also comprises the starting material of solid electrolyte, thereby is configured to so-called verdigris (Gr ü nling) or Blang green (Braunling), and the starting material of described solid electrolyte only just become solid electrolyte after sintering.Especially, described solid electrolyte is configured to solid electrolyte layer or consists of multiple solid electrolyte layers, and " layer " is interpreted as same substance within the scope of the invention from the plane certain altitude that expands, it is positioned on another element, under or middle.
" electrode " is generally interpreted as a kind of following element in scope of the present invention, and it contacts described solid electrolyte, and electric current can erectly pass described solid electrolyte and electrode.Correspondingly, described electrode comprises following element, and on described element, ion is incorporated in described solid electrolyte and/or from described solid electrolyte and removes.Typically, described electrode comprises noble metal electrode, for example, as metal-ceramic electrode, can be installed on described solid electrolyte or in other mode and be connected with described solid electrolyte.Typical electrode material is platinum-cermet electrodes.But also can use in principle other noble metals, for example gold and/or palladium.Described electrode can be together with solid electrolyte or described electrode can form the measurement battery of sensor element, the measurement battery of for example lambda probe.
" heating element " is generally interpreted as a kind of following element in scope of the present invention, described element for by described solid electrolyte and heated by electrodes to working temperature.Described heating element can have lead-in wire region and heating region.Conventionally at least one arrangement of electrodes on described solid electrolyte or wherein.Described heating element here or by solid electrolyte, the additional insulating material of solid electrolyte layer or electrode separates." heating region of heating element " is interpreted as such region of described heating element, and the described region of described heating element and described electrode are overlapping in the direction towards this layer of structure.Therefore, the heating region of heating element is to use the equitant region of battery with the actual measurement of lambda probe.The side direction teat of heating region, i.e. the teat of broad ways, also belongs to described heating region by a described electrode or multiple electrode.Therefore, at lambda probe, be for example under the situation of planar structure, described in overlap along perpendicular to can be in sight in the direction of planar structure.Described heating region is generally arranged in the end regions of described solid electrolyte here." lead-in wire region " is interpreted as such region of described heating element, for by the Energy Transfer of heat solid electrolyte and electrode to described heating region.
" cold-state resistance " is interpreted as the resistance of actual measurement in the time of 20 ℃ in scope of the present invention.According to this definition, the cold conditions all-in resistance of the resistance of total heating element is interpreted as the summation of the resistance of heating region and the resistance in lead-in wire region.
" manufacturing tolerance " is interpreted as a kind of state of system in scope of the present invention, in this state, by disturbing effect, caused, for example by manufacture determine do not need or do not cause corresponding adjusting or countermeasure with the deviation of normal condition.Especially, in this sense, manufacturing tolerance is the degree that size departs from normal condition or normal size, but the function of system is even not compromised.Therefore, the manufacturing tolerance of resistance is to manufacture the deviation that the resistance causing departs from the ratings arranging during fabrication, and it does not cause obvious and unacceptable Functional change.Thereby the resistance of heating element of the present invention has identical add thermal behavior or have a deviation similar and add thermal behavior within the scope of manufacturing tolerance, when operation, do not cause the Functional change of sensor element to such an extent as to damaged, the unpredictable behavior of sensor element or inefficacy.Described deviation is arranged in restricted section of described heater or region here or even in the planes of molecules of the constituent of heater, for example, in the part xsect inside of described heater.Therefore, " resistance 10% manufacturing tolerance " is interpreted as it and is present in the region or position of heater, its another region from heater or position on this value or under maximum 10%.For example in heating region 8 ohm be set to the ratings of heater, thereby in heating region, exist resistance to be less than 7.9 ohm or be greater than the little position of 8.1 ohm.
" platinum metal family " refers to the General Definition according to chemical science within the scope of the invention, 8 to the 10 ethnic elements in 5 cycles, be light platinum ruthenium (Ru), rhodium (Rh), palladium (Pd), and 6 cycles, i.e. heavy platinum osmium (Os), iridium (Ir), platinum (Pt).
In scope of the present invention, diafiltration (Perkolation) illustrates and in the structure causing at random (lattice) occupies situation, forms relevant district's band (bundle).Under a diafiltration situation, lattice-site has definite possibility, exists point self to connect under edge diafiltration situation.Along with the increase of possibility, the field that described lattice occupies forms larger bundle.Occupy possibility and be defined as such numerical value, the size of at least one bundle reaches through whole system and extends, and therefore for example from right to left or from the top down side expands on two lattices.It is believed that: described bundle diafiltration is through described system.This value that occupies possibility is exactly so-called percolation threshold.
The present invention is applicable to various internal combustion engines in principle, it has at least one ceramic sensor element element, for obtaining at least one parameter of engine exhaust gas, especially at least one lambda probe and/or at least one NOx sensor and/or at least one HC sensor, wherein said ceramic sensor element has at least one heating element, for heating described ceramic sensor element.Especially, described internal combustion engine comprises an Otto engine and/or diesel engine.Alternatively or additionally, described internal combustion engine also comprises hybrid drive system, for example there is at least one Otto engine and/or at least one diesel engine and at least one additional motor.
Described ceramic sensor element element can be lambda probe especially, or comprises lambda probe.Described lambda probe can for example be embodied as finger-type probe or plane lambda probe, thereby also may be embodied as and for example have a layer lambda probe for shape structure.For example transition formula probe and/or wide band lambda probe.Alternatively or additionally, described ceramic sensor element element also can comprise the ceramic sensor element of at least one other types, for example NOx sensor.
Described ceramic sensor element can comprise at least one electrochemical cell." electrochemical cell " is interpreted as such element within the scope of the invention, and described element comprises at least two electrodes and at least one solid electrolyte being connected with electrode.The temperature of described ceramic sensor element for example can be determined by the internal resistance of determining electrochemical cell.At ceramic sensor element element, have in the situation of this special battery of energy, the temperature of described ceramic sensor element is for example obtained by the internal resistance of determining described this special battery of energy.This electrochemical cell thereby the measurement battery that can use as described sensor element.
The heating of described ceramic sensor element element and/or the Power supply of described heating element can pass through power supply, and for example the accumulator in motor vehicle provides.
Heating element of the present invention is different from the heating element of automobile-use lambda probe substantially.Heating element of the present invention can be embodied as platinum metal common sintering or additional sintering family structure especially substantially.Especially, described heating element is weak heating element, and for bridge joint cold operation state, for example idle running, have power consumption maximal value 5W, and under automobile-use lambda probe situation, power consumption maximal value is often greater than 7W.Turn-on current is no more than 2A, so that keep the low requirement to sensor element controller.Described probe reaches the behavior of beating of 30 seconds and is applicable to the waste gas probe of trouble-free cyclecar at the most, this because of most amount of pollutant be not here unloading phase produce, but produce in corresponding driving pattern.It is the high-temperature load because of hot waste gas that the structure of described heating element is used the metal of platinum metal family, and when full load is moved, the temperature of hot waste gas can reach about 1000 ℃.Described heating element is especially made with platinum-metallic ceramics, and can be the combination of materials corresponding with prior art, but high temperature hub sections and thin complications and conducting structure are for example designed to total cold-state resistance from 8 ohm to 20 ohm.The design of heating power meets when intrinsic heats in colder environment temperature, and from-20 ℃ to-40 ℃, sensor element temperature reaches 750 ℃ of maximal values.
Especially, the present invention proposes a kind of sensor element, it has maximum length 35m and breadth extreme 4mm, and has integrated heating element, and described heating element has the minimum cold resistance of from 8 to 20 ohm and when working voltage 13V, has the power consumption of 5W in the time of 20 ℃.Described heating element is designed to most of resistance here and is arranged in indentation structure.To this, for example, under the situation of 10.5 ohm of cold-state resistances, it is 8 ohm with the resistance of indentation structure that the resistance of lead-in wire is 1.0 ohm.This obtains the thermal resistance of 34 ohm, and the formation of wherein said thermal resistance is that lead resistance is that the resistance of 2 ohm and indentation structure is 32 ohm.When this is 13V by voltage, Power Limitation is 5W.Thereby the power of introducing is almost complete, reaches 94%, in indentation structure, is converted.High indentation structural resistance realizes by the little bed thickness of maximal value 8 μ m and the small band shape wire widths of 200 μ m.Here, the set-up mode of described ratio is the width for the thickness of indentation structure and indentation structure, and relative thickness fluctuation is equally little, is less than 10%.Thereby scattering for the bed thickness of 1 μ m heating element inside can be minimum bed thickness 10 μ m, the lateral thickness fluctuation of the heating element of side 20 μ m, can be no more than minimum widith 200 μ m.
Preferably, build additional indentation turning part, the total length of described heating element reaches 15mm.Preferably, outer indentation turning part is closely folding, to obtain high indentation structure thermal resistance by heating.
Described indentation structure abrasive pastes can arrange the aluminium oxide hub sections with 25% volume, to concentrate described heating power by higher resistance.Here because of what the local accumulation of described lining caused, with respect to resistance fluctuation, can be no more than 10%.Therefore, use extremely meticulous alumina powder, in described extremely meticulous alumina powder, at least 50% powder particle has the fine particle diameter that is less than 500nm.This extremely meticulous alumina powder preferably ground platinum and obtains before processing grinding cream in dry grinding step, did not reach in addition and made alumina powder cohesion.This causes formation local electrical resistance center, forms hot localised points when heating element turn-on current, and these hot localised points are the output points that make heating element aging.
In addition, by lining content 3% volume, lower than percolation threshold, local electrical resistance fluctuation reduces, and wherein percolation threshold is extremely high to the dependence of lining content.
Preferably, other metal of the palladium of described indentation structure abrasive pastes and 20% volume or platinum metal family forms alloy., by strengthening to grind, alloy is distributed equably here, thereby make local electrical resistance fluctuation be less than 10%.Preferably, to this use still less, the sintering adjuvant of 3% share at the most, sintering adjuvant is for example the ternary alloy three-partalloy of the sintering that phosphorus, silicon, bismuth and/or density are large, as what use in DE19834276A1 for example.Thus especially, cold-state resistance increases, thereby starting power reduces.
Preferably, in common procedure of processing, grind metal and the lining thereof of platinum, platinum metal family.Heater insulation part and lead-in wire can carry out dense sintering, to avoid described palladium to be vaporized and and then described insulating part short circuit.Described lead-in wire also can be set to the resistance higher than 3 ohm, to reduce platinum use amount and the further cost that reduces heating element.Preferably, the turning of described structure can, by rounding, to stop local electrical resistance to reach maximum, make described structure keep colder.Preferably, described heating element is made with 45 ° of methods of baroclining, and to reduce serigraphy parameter and abrasive pastes dependence, and then is reduced in the resistance fluctuation between the horizontal and vertical indentation structure otch existing in structure.
Accompanying drawing explanation
The following explanation of the preferred embodiment schematically showing from figure obtains other details of the present invention and feature, wherein:
The viewgraph of cross-section of Fig. 1 sensor element;
The vertical view of the heating element of the sensor element of Fig. 2 the first embodiment;
The vertical view of the heating element of the sensor element of Fig. 3 the second embodiment;
The vertical view of the heating element of the sensor element of Fig. 4 the 3rd embodiment;
The vertical view of the heating element of the sensor element of Fig. 5 the 4th embodiment;
The schematic plan of the exemplary heating element of Fig. 6;
The Temperature Distribution of the exemplary heating element of Fig. 7;
The view of the voltage difference of Fig. 8 heating element, wherein heating element has the cold-state resistance of 3 ohm at heating region;
The view of the current density of Fig. 9 heating element, wherein heating element has the cold-state resistance of 3 ohm at heating region;
The view of the voltage difference of Figure 10 heating element, wherein heating element has the cold-state resistance of 9 ohm at heating region;
The view of the current density of Figure 11 heating element, wherein heating element has the cold-state resistance of 9 ohm at heating region.
Embodiment
Fig. 1 illustrates the viewgraph of cross-section of the first embodiment of sensor element 10 of the present invention.Sensor element 10 shown in Fig. 1 can be used for physics and/or the chemical property of probe gas, wherein can obtain one or more performances.The present invention relates in particular to quality and/or the quantity of the gas componant of obtaining gas hereinafter, relates in particular to the oxygen content obtaining in gas.Described oxygen content can be the form of for example dividing potential drop and/or the form of percentage composition.But, can obtain in principle dissimilar gas componant, for example nitrogen, hydrocarbon and/or hydrogen.But, alternatively or additionally, also can obtain other performance of gas.The present invention is particularly useful for automotive engineering field, particularly, cyclecar field, for example motorcycle, thereby measurement gas space refers in particular to the off-gas line of the internal combustion engine of motorcycle, gas refers in particular to waste gas.Therefore, the size of sensor element 10 is for example length, along the measured value of Fig. 1 observed ray, maximum 50mm, preferred maximum 45mm and particularly preferably maximum 35mm, and width, in Fig. 1 from right to left or contrary measured value, maximum 10mm, preferred maximum 8mm and particularly preferably maximum 4mm.In the example shown in Fig. 1, the size of sensor element 10 is for example length 35mm and width 4mm.
Fig. 2 illustrates the vertical view of the first embodiment of sensor element 10 of the present invention, especially the vertical view of its heating element 18.In example shown here, the sensor element 10 of lambda probe is for example the sensor 10 of plane lambda probe.As directed, heating element 18 has heater 22, and heating region 26, and heater 22 has lead-in wire region 24, and heater 22 is positioned at the view right side of Fig. 2, and heating region 26 is positioned at the view left side of Fig. 2.Heating element 18 especially can be incorporated in solid electrolyte 12 isolator, guarantees the function of lambda probe when low exhaust gas temperature.As particularly shown, the heating region 26 of heating element 18 is configured to indentation structure, has three indentation turning parts 28.The turning of indentation turning part 28 can be by rounding.
Especially, the arrangement of heating element 18 is 30% of the cold-state resistance in lead-in wire region 24 cold-state resistances of being not more than heating element 18, is preferably not more than 25% and be particularly preferably not more than 16%.For example, lead-in wire region 24 cold-state resistance be not more than heating element 18 cold-state resistance 12%.The cold conditions all-in resistance of the heating element 18 of the first embodiment is for example 9 ohm for the sensor element 10 that is applicable to motorcycle situation.Especially, lead-in wire region 22 has 1 ohm of resistance in this example, and heating region 26 has 8 ohm of resistance.Heating element 18 use alloys are made, and contain at least one platinum metal family.Therefore the alloy that, is applicable to heating element 18 can comprise for example platinum.Because the high thermal load of hot waste gas, for example when full load, exhaust gas temperature reaches approximately 1000 ℃, needs to use the element of the platinum metal family that is applicable to heating element 18.Reduce the use amount of platinum, thereby reduce the manufacturing cost of sensor element, but lead-in wire region 24 has higher cold-state resistance, for example 3 ohm equally.The cold conditions all-in resistance of heating element 18 can be 11 ohm.Can use equally the another kind of element of platinum-metallic ceramics or metallic ceramics and platinum metal family.Therefore, the make of heating element 18 is in order to be connected cold operation state, for example, in when idle running, and under the working voltage situation of 13V, the maximum 5W of the power consumption of heating element 18, preferred maximum 4W and particularly preferably maximum 3.5W.Compare with above said content, under the lambda probe situation that is applicable to automobile, be conventionally greater than 7W.Activate the electric current of heating element 18, so-called turn-on current, is no more than 2A, so that keep very little about the requirement of the not shown controller of the layout of well heater output stage and the derivation of loses heat.Heater 22 can be than having less thickness and less width in heating region 26 in lead-in wire region 24, for example, be the maximum 50% of thickness in lead-in wire region 24 and/or the maximum 50% of the width in lead-in wire region 24.The thickness of heater 22 is for example maximum 16 μ m in heating region 26, preferably maximum 12 μ m and particularly preferably 8 μ m, the width of heater 22 is for example maximum 300 μ m in heating region 26, preferably maximum 250 μ m and particularly preferably maximum 200 μ m, for example heater 22 has thickness 8 μ m and width 200 μ m in heating region 26.
Fig. 3 illustrates according to the vertical view of the second embodiment of sensor element 10 of the present invention, the especially vertical view of his heating element 18.The difference of a description and the first embodiment below, wherein identical parts represent with identical Reference numeral.
Fig. 4 illustrates the vertical view of the 3rd embodiment of sensor element 10 of the present invention, especially the vertical view of its heating element 18.Only describe the difference of the 3rd embodiment and the second embodiment below, wherein identical parts represent with identical Reference numeral.
Compared with the second embodiment of Fig. 3, the outer indentation turning part 28 of the heating element 18 of the 3rd embodiment is closely folding, to obtain higher thermal resistance by heating.That is to say, the conductor segment that indentation turning part 28 forms in heating region 26 with respect to virtual median surface longitudinally mirror image arrange symmetrically, wherein, this conductor segment 30 is parallel to median surface in every side of median surface, and the spacing between them is along increasing in the direction towards median surface.Above median surface, from median surface, the spacing between nearest opposed conductor segment 30 may be maximum.
Fig. 5 illustrates the vertical view of the 4th embodiment of sensor element 10 of the present invention, especially the vertical view of its heating element 18.Only describe the 4th embodiment and second and the difference of the 3rd embodiment below, wherein identical parts represent with identical Reference numeral.
Compared with the second embodiment of Fig. 3, the outer indentation turning part 28 of the heating element 18 of the 4th embodiment is closer folding, to obtain higher thermal resistance by heating.That is to say, the conductor segment that indentation turning part 28 forms in heating region 26 with respect to virtual median surface longitudinally mirror image arrange symmetrically, the spacing being wherein parallel in every side of median surface between this conductor segment 30 of median surface increases in the direction towards median surface.Above median surface, from described median surface, the spacing between nearest opposed conductor segment 30 may be maximum.Compared with the 3rd embodiment, the spacing between every two conductor segment 30 of the 4th embodiment is less, and wherein these two conductor segment 30 have the maximum spacing with respect to median surface in every side of median surface.Compared with the 3rd embodiment, the 4th embodiment above median surface, from median surface, the spacing between nearest opposed conductor segment 30 is larger.
Fig. 6 illustrates the schematic plan of sensor element 10 of the present invention, and wherein sensor element 10 has integrated heating element 18, and heating element 18 has lead-in wire region 24 and heating region 26.The diagram of Fig. 6 is used for illustrating advantage of the present invention and effect, but the invention is not restricted to three indentation turning parts 28 shown in the heating region 26 of heating element 18, but is typically also applicable to all previous embodiment.Especially, heating element 18 has two connection contacts 32 can seeing at the right hand edge of figure, and it is to be connected to unshowned electric energy that object is set.Connecting the working voltage that applies 13V on contact 32, with heat solid electrolyte 12 and electrode 14,16.Fig. 6 also illustrate heater 22 lead-in wire region 24 in than constructing widelyr in heating region 26.
Fig. 7 is illustrated under running status, under heated condition, and Temperature Distribution and heating element 18 layout on solid electrolyte 12 of the heating element 18 of Fig. 6 in the region of electrode 14.As figure indication, electrode 14 has two chain contact points 34, at the right hand edge of figure, can see, it is in order to be connected to unshowned electric energy that object is set.As already mentioned, the connection contact 32 of heating element 18 and the connection contact 34 of electrode 14 are not overlapping.Equally, the arrangement of the contact conductor 36 of electrode 14 be while making contact conductor project in the plane of heating element 18 between the conductor segment in lead-in wire region 24.As shown in Figure 7, the temperature of the temperature in heating region 26 and electrode 14 is overlapping, obviously high than the temperature in lead-in wire region 24.At this moment, solid electrolyte 12 is heated more fast or more consumingly in the region of motor 14,16 than in all the other regions, thereby solid electrolyte 12 and electrode 14,16 can be heated to more quickly its running temperature in heating region 26.
Fig. 8 illustrates that with the vertical view of heating element 18 heating element 18 is when moving, the exemplary distribution of voltage difference (mV) between the connection contact 32 of heating element 18.As shown in the figure, connection contact 32 shown in lower area and apply working voltage 13V or 13000mV between the connection contact 32 shown in upper area in the drawings in the drawings, especially, heating element 18 the arrangement is here to make heating element 18 in heating region, have the cold-state resistance of about 2.7 ohm.
Fig. 9 illustrates when heating element 18 moves under the working voltage situation that applies Fig. 8, current density (A/mm between the connection contact 32 of heating element 18
2) exemplary distribution.Determine that the size of current density relates to the xsect of heater 22 here.As known from Fig. 9, it is maximum that current density reaches in indentation turning part shape heating region 26, and acutely reduce for lead-in wire region 24.The value of the current density of this example is here learnt from the scale in Fig. 9 view left side.
Figure 10 illustrates that with the vertical view of heating element 18 heating element 18 is when moving, another exemplary distribution of voltage difference (mV) between the connection contact 32 of heating element 18.As shown in the figure, connection contact 32 shown in lower area and apply working voltage 13V or 13000mV between the connection contact 32 shown in upper area in the drawings in the drawings, especially, heating element 18 the arrangement is here to make heating element 18 in heating region, have the cold-state resistance of about 8 ohm.When heating element 18 moves, the distribution of the distribution of voltage difference and the example of Fig. 8 is identical, thereby by changing resistance, do not change the distribution of voltage difference.
Figure 11 illustrates when heating element 18 moves under the working voltage situation that applies Figure 10, current density (A/mm between the connection contact 32 of heating element 18
2) exemplary distribution.Determine that the size of current density relates to the xsect of heater 22 here.As known from Figure 11, it is maximum that current density reaches in indentation turning part shape heating region 26, and acutely reduce for lead-in wire region 24.The value of the current density of this example is here learnt from the scale in Figure 11 view left side.Compared with the current density of the heating element 18 of Fig. 9, the current density of the example of Figure 11 is obviously less.Therefore, the heating region 26 of the heating element 18 of Figure 11 has carried out obvious heating than the heating element of Fig. 9 18.
In order to manufacture sensor element, for example plane lambda probe, known different manufacture method, for example film, thin layer or thick-layer technology.Therefore, here this is not clearly defined, but the difference between manufacture method used and automobile or the commerial vehicle field conventional manufacture method of lambda probe has here been described, when manufacturing compact sensor element of the present invention, should be noted that these difference, to obtain so-called advantage.Singularity when especially, elucidated hereinafter is in manufacturing heating element or heating element is incorporated into sensor element of the present invention.Need to clearly emphasize, all details described below are applicable to aforementioned all examples, and are applicable to this situation.
In order to make the manufacturing tolerance of resistance in heater not because the local accumulation of aluminium oxide is greater than 10%, especially use very meticulous alumina powder.For very meticulous alumina powder, the diameter that here powder is interpreted as at least 50% particle is less than 500nm.For this reason, alumina powder preferably before processing grinding cream in dry grinding step with other metal grindings of platinum or described platinum metal family, thereby can not reach the sintering of alumina powder.The grinding of other metals of platinum, platinum metal family and lining (for example aluminium oxide) can be carried out in a common treatment step, to improve mixing or distributing of these constituents.Especially, by making in abrasive pastes the content of aluminium oxide be chosen as, be positioned at percolation threshold below 3% volume, the arrangement of heating element 18 is local electrical resistance fluctuations, it is the manufacturing tolerance of resistance, diminish, wherein in percolation threshold situation, extremely large to the dependence of alumina content.
In described example, percolation threshold is described diafiltration possibility, utilizes it to be formed in that broad ways or thickness direction extend through heater or the aluminium oxide region or the bundle that connect or form multiple this interconnective aluminium oxide regions or bundle.Because as already mentioned, aluminium oxide electrical isolation, meets or exceeds percolation threshold and will cause resistance to increase extremely tempestuously.When heating element 18 moves, this situation may cause described heating power to distribute unevenly and/or even cause at least part of section crossing heating electrode 14,16 and/or solid electrolyte 12.If do not use this meticulous alumina powder, may cause local electrical resistance center, so-called focus is caused at run duration in local electrical resistance center, i.e. the very high point of temperature, described very high temperature makes the exit point of heating element 18 aging.Prove alternatively clearly or be additional to aluminium oxide, also can use zirconia.
The abrasive pastes that manufacture heating element is used can have the palladium of 20% volume or other metals of platinum metal family.Should be noted that the homogeneity of alloy here, the grinding that for example can strengthen by use obtains.For example the sintering adjuvant of the little content by maximum 3% volume can be realized the cooling resistance of further raising, sintering adjuvant is the ternary alloy three-partalloy of the sintering that for example phosphorus (P), silicon (Si), bismuth (Bi) and/or density are large, the i.e. alloy of three kinds of elements, disclosed as for example DE19834276A1.Can improve thus cold-state resistance, reduce initial power consumption, identical electric power can obtain higher heating power or less electric power can obtain identical heating power.By the dense sintering of heating element insulating material and heater 22 in lead-in wire region 24, arrange and can make palladium gasify in sintering process, thereby avoid insulating material short circuit.
The lead-in wire region of heating element 18 also can be designed to high-resistance, for example 3 ohm, replaces above-mentioned 1 ohm, to reduce platinum use amount and thereby further to reduce the cost of heating element 18.Heating element 18 can for example be made two pressing steps of separating, and these two pressing steps can be carried out continuously or simultaneously, wherein uses two different abrasive pastes of alumina content, to obtain, passes to region 24 and different resistance heating region 26.Heating region separately 26 and lead-in wire region 24 can for example be expressed on solid electrolyte 12 by serigraphy, and wherein, the alumina content of the abrasive pastes of heating region 26 use is higher than the abrasive pastes of lead-in wire region 24 use.Especially, heating element 18 can what is called 45
°the method of baroclining manufacture, to reduce serigraphy parameter and abrasive pastes dependence and thereby the resistance fluctuation on the Width of sensor element 10 and between on the longitudinal direction of the conductor segment of indentation turning part shape heating region 26.By the configuration of heating element 18, at the turning of structure, as indentation turning part 28, during by rounding, the region of heater 22 can be reduced, but the operation of heater 22 maintenance is colder.
In heating region 26, than higher resistance in lead-in wire region 24, allow for example by heater 22, at heating region 26, than less thickness and/or width in lead-in wire region 24, to obtain.This cold conditions all-in resistance that is applicable to the example of for example Fig. 9 increases than the cold conditions all-in resistance of the example of Figure 11.The present invention proposes the thickness of heater 22 in heating region 26 and width and with relative manufacture-manufacturing tolerance or manufacture deviation, is less than 10% mode and constructs.For the maximum 1 μ m of manufacture-manufacturing tolerance of heating element 18 inner through-thickness, thereby can be no more than minimum thickness 10 μ m, and for the maximum 20 μ m of manufacture-manufacturing tolerance of value element 18 inner broad ways, thereby can be no more than minimum widith 200 μ m.The so-called absolute value of manufacture-manufacturing tolerance is understood to maximal value, and this is that the width of heater 22 in heating region 26 is preferably no more than 200 μ m because the thickness of heater 22 in heating region 26 is preferably no more than 10 μ m.
In a word, can understand sensor element 10 of the present invention and have heating element 18, heating element 18 is to form with metallic ceramics, especially platinum-metallic ceramics, and heating element 18 can be sintered together with stationary electrolyte 12 and other functional layers.In order to be applied to little engine, for example motorcycle, the heating element 18 of the known sensor element that sensor element 10 and automobile and commerial vehicle are used is distinguished by least one following details.The cross-sectional area of the heater of heater in heating region and/or lead-in wire region is less.The resistance of heating region is different for the ratio of the all-in resistance of heating element from the resistance in lead-in wire region, because lead-in wire region has taken the part reducing in all-in resistance.More or thinner indentation turning part is set.Aluminium oxide and/or zirconic lining content is at metallic ceramics, and especially platinum-metallic ceramics is higher.Other elements of platinum metal family are arranged in metallic ceramics, especially platinum-metallic ceramics.
Clearly emphasize, in instructions and/or claims independent disclosed feature as separate and mutually not independently because initial disclosed object is same and the restriction of claim is independent of and enumerates in embodiment and/or desired claim.Be interpreted as being clearly interpreted as of all running examples or post there is respectively the freedom of the unit that intermediate value or subgroup form and limit equally of the present invention open, especially as the restriction of region task.
Claims (12)
1. a sensor element (10), for obtaining at least one performance of gas space gas, in particular for the composition of gas in probe gas or for obtaining the temperature of gas, wherein said sensor element (10) comprising:
At least one solid electrolyte (12),
Solid electrolyte described at least one (12) electrode (14,16) upper or that wherein arrange, and
At least one heating element (18), be used for heating described solid electrolyte (12), wherein said heating element (18) has at least one lead-in wire region (24) and heating region (26), the cold-state resistance in wherein said lead-in wire region (24) be not more than described heating element cold conditions all-in resistance 30%, preferably be not more than its 25%, be particularly preferably not more than its 16%.
2. sensor element according to claim 1 (10), is characterized in that, described heating element (18) has the cold conditions all-in resistance of from 6 to 22 ohm and the cold conditions all-in resistance of preferred from 8 to 20 ohm.
3. according to sensor element in any one of the preceding claims wherein (10), it is characterized in that, described heating element (18) is electrical heating elements, when working voltage 13V, described electrical heating elements has maximum consumption of power maximal value 5W, preferred maximum 4W and particularly preferably maximal value 3.5W, for example power consumption 5W.
4. according to sensor element in any one of the preceding claims wherein (10), it is characterized in that, described sensor element (10) has length maximal value 50mm, preferred maximum 45mm and particularly preferably maximal value 35mm, described sensor element (10) has width maximal value 10mm, preferred maximum 8mm and particularly preferably maximal value 4mm, for example described sensor element (10) has length 35mm and width 4mm.
5. according to sensor element in any one of the preceding claims wherein (10), it is characterized in that, described heating element (18) comprises heater (22), described heater (22) in heating region (26) than there is less thickness and less width in lead-in wire region (24), for example thickness of described heater in described heating region (26) be described lead-in wire region (24) thickness at the most 50% and/or the width of described heater in described heating region (26) be described lead-in wire region (24) width at the most 50%.
6. according to sensor element in any one of the preceding claims wherein (10), it is characterized in that, described heater (22) has maximum thickness 16 μ m at described heating region (26), preferred maximum 12 μ m and particularly preferably maximal value 8 μ m, width maximal value 300 μ m, preferred maximum 250 μ m and particularly preferably 200 μ m, for example thickness 8 μ m and width 200 μ m.
7. according to the sensor element described in claim 5 or 6 (10), it is characterized in that, described heater (22) is configured to indentation structure in heating region (26), and comprises at least five indentation turning parts (28).
8. according to sensor element in any one of the preceding claims wherein (10), it is characterized in that, described heating element (22) is configured to indentation structure at described heating region (26), so that form the described conductor segment of described indentation turning part (28), about median surface mirror image, arrange symmetrically, and the spacing being parallel in the every side of described median surface between this conductor segment (30) of described median surface increases towards described median surface.
9. according to sensor element in any one of the preceding claims wherein (10), it is characterized in that, above described median surface from described median surface the spacing maximum between nearest opposed conductor segment (30).
10. according to the sensor element described in claim 7 or 8 (10), it is characterized in that, the turning of described indentation turning part (28) by rounding construct.
11. according to sensor element in any one of the preceding claims wherein (10), it is characterized in that, described heating element (18) is made with metal-metal pottery or metal alloy-metallic ceramics, and at least one metal in described metal or described metal alloy is selected from the metal of platinum metal family.
12. according to sensor element in any one of the preceding claims wherein (10), it is characterized in that, described metal alloy-metallic ceramics comprises metal alloy, and described metal alloy comprises aluminium oxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011081629.1 | 2011-08-26 | ||
| DE102011081629 | 2011-08-26 | ||
| PCT/EP2012/061738 WO2013029824A1 (en) | 2011-08-26 | 2012-06-19 | Sensor element for capturing at least one property of a gas in a measurement gas space |
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| CN103748460A true CN103748460A (en) | 2014-04-23 |
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| CN201280041274.4A Pending CN103748460A (en) | 2011-08-26 | 2012-06-19 | Sensor element for capturing at least one property of gas in measurement gas space |
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| Country | Link |
|---|---|
| CN (1) | CN103748460A (en) |
| DE (1) | DE102012214133A1 (en) |
| WO (1) | WO2013029824A1 (en) |
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| CN105911102A (en) * | 2015-02-20 | 2016-08-31 | 罗伯特·博世有限公司 | Microheating apparatus for a sensor and the sensor |
| CN107076570A (en) * | 2014-09-19 | 2017-08-18 | Sc2N公司 | Measurement probe including sensing element |
| CN107949785A (en) * | 2015-07-08 | 2018-04-20 | 株式会社电装 | The pump electrode and reference electrode of gas sensor |
| CN109765263A (en) * | 2018-12-28 | 2019-05-17 | 青岛青缆科技有限责任公司 | It is a kind of for making the heating device of Geothermal electric cable |
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| JP5832479B2 (en) | 2012-08-09 | 2015-12-16 | 日本特殊陶業株式会社 | Gas sensor |
| DE102013211796A1 (en) * | 2013-06-21 | 2014-12-24 | Robert Bosch Gmbh | Sensor element with conductor track and feedthrough |
| DE102013212370A1 (en) * | 2013-06-27 | 2014-12-31 | Robert Bosch Gmbh | Sensor element for detecting at least one property of a sample gas in a sample gas space |
| DE102018215322A1 (en) * | 2018-09-10 | 2020-03-12 | Robert Bosch Gmbh | Procedure for testing the integrity of a printed circuit |
| CN115785462B (en) * | 2022-11-02 | 2023-08-22 | 常州大学 | Zr-PTC luminophor material, electrochemical luminescence sensor, and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE102012214133A1 (en) | 2013-02-28 |
| WO2013029824A1 (en) | 2013-03-07 |
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Application publication date: 20140423 |