WO2020195346A1 - 固体電解質、ガスセンサ - Google Patents

固体電解質、ガスセンサ Download PDF

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WO2020195346A1
WO2020195346A1 PCT/JP2020/006214 JP2020006214W WO2020195346A1 WO 2020195346 A1 WO2020195346 A1 WO 2020195346A1 JP 2020006214 W JP2020006214 W JP 2020006214W WO 2020195346 A1 WO2020195346 A1 WO 2020195346A1
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solid electrolyte
phase
gas
temperature
gas sensor
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English (en)
French (fr)
Japanese (ja)
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充宏 吉田
聡司 鈴木
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Denso Corp
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Denso Corp
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Priority to DE112020001517.3T priority Critical patent/DE112020001517T5/de
Priority to CN202080023851.1A priority patent/CN113631530B/zh
Publication of WO2020195346A1 publication Critical patent/WO2020195346A1/ja
Priority to US17/448,733 priority patent/US12111282B2/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G01M15/00—Testing of engines
    • G01M15/04—Testing internal-combustion engines
    • G01M15/10—Testing internal-combustion engines by monitoring exhaust gases or combustion flame
    • G01M15/102—Testing internal-combustion engines by monitoring exhaust gases or combustion flame by monitoring exhaust gases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/409—Oxygen concentration cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present disclosure relates to a solid electrolyte composed of stabilized or partially stabilized zirconia, and a gas sensor including the same.
  • Gas sensors are used in the exhaust system of internal combustion engines for the purpose of detecting the oxygen concentration and air-fuel ratio in the exhaust gas.
  • An oxide ion conductive solid electrolyte such as zirconia is used for such a gas sensor.
  • Solid electrolytes are often used in environments with rapid temperature changes. However, since zirconia may have cracks due to a phase transition due to a temperature change, improvement in thermal shock resistance is required.
  • Patent Document 1 discloses a technique for improving thermal shock resistance by forming a monoclinic zirconia layer on the surface of a zirconia oxygen sensor element in which a stabilizer is dissolved by a solid solution.
  • solid electrolytes have tended to be required to be used at a higher load, and further improvement in heat impact resistance is required. Specifically, the solid electrolyte tends to be exposed to a higher temperature environment due to a change in the mounting position of the in-vehicle gas sensor. Further, for example, in a hybrid vehicle or an idle stop vehicle, the solid electrolyte tends to be frequently exposed to the thermal cycle due to the frequent start and stop of the engine and the heater.
  • the present disclosure is intended to provide a solid electrolyte and a gas sensor having excellent thermal shock resistance.
  • One aspect of the present disclosure is a solid electrolyte consisting of stabilized or partially stabilized zirconia.
  • the solid electrolyte has a change rate of at least one crystallite diameter of a cubic phase and a tetragonal phase in the crystal particles constituting the solid electrolyte before and after heating from room temperature to 1200 ° C. of 10% or less.
  • Another aspect of the present disclosure is a gas sensor comprising the solid electrolyte.
  • the rate of change in crystallite diameter of the solid electrolyte is adjusted to a predetermined value or less as described above. Therefore, the decrease in strength with respect to the cold cycle is suppressed, and the occurrence of cracks is suppressed.
  • the solid electrolyte has excellent thermal shock resistance, and can maintain high strength even when exposed to, for example, a high temperature environment or an environment with a high frequency of cold and thermal cycles. The reason is considered to be the reduction of strain by relaxing the internal energy involved in the phase transition of the crystal phase, and the mechanism will be described later.
  • the gas sensor includes the solid electrolyte having excellent thermal shock resistance. Therefore, the gas sensor is highly reliable against the increase in stress in the thermal cycle, and can accurately measure the gas concentration for a long period of time.
  • FIG. 1 is a schematic view showing the microstructure of the solid electrolyte with reduced strain in the first embodiment.
  • FIG. 2 is an explanatory diagram showing the volume change and the coefficient of thermal expansion of the crystal phase in the first embodiment. 3, in the first embodiment, a ZrO 2 -Y 2 O 3 phase diagram,
  • FIG. 4 is an explanatory diagram showing a thermodynamic interpretation of the phase transition of ZrO 2 in the first embodiment.
  • FIG. 5 is an explanatory diagram showing a temperature profile in the case where the cooling heat cycle is performed after the firing step without performing the annealing treatment in the first embodiment.
  • FIG. 6 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in the VI of FIG.
  • FIG. 7 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in FIG. 5VII.
  • FIG. 8 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in FIG. 5VIII.
  • FIG. 9 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in IX of FIG.
  • FIG. 10 is a schematic view showing the microstructure of the solid electrolyte having strain in the first embodiment.
  • FIG. 11 is an explanatory diagram showing a temperature profile in the case where the annealing treatment is performed after the firing step and then the thermal cycle is performed in the first embodiment.
  • FIG. 11 is an explanatory diagram showing a temperature profile in the case where the annealing treatment is performed after the firing step and then the thermal cycle is performed in the first embodiment.
  • FIG. 12 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in XII of FIG.
  • FIG. 13 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in XIII of FIG.
  • FIG. 14 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in XIV of FIG.
  • FIG. 15 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in XV of FIG.
  • FIG. 16 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in the XVI of FIG.
  • FIG. 17 is a schematic view showing the state of the crystal phase constituting the solid electrolyte in XVII of FIG.
  • FIG. 18 is an explanatory diagram showing a change in crystallite diameter due to the annealing treatment in the first embodiment.
  • FIG. 19 is a cross-sectional view of the gas sensor according to the second embodiment.
  • FIG. 20 is a cross-sectional view of the laminated gas sensor element according to the second embodiment.
  • FIG. 21 is a cross-sectional view of the cup-shaped gas sensor element according to the second embodiment.
  • FIG. 22 is an explanatory diagram showing a method for producing a solid electrolyte in Experimental Example 1.
  • FIG. 23 is a diagram showing an example of a peak derived from ⁇ 111 ⁇ of the C phase in the XRD pattern of the solid electrolyte in Experimental Example 1.
  • FIG. 23 is a diagram showing an example of a peak derived from ⁇ 111 ⁇ of the C phase in the XRD pattern of the solid electrolyte in Experimental Example 1.
  • FIG. 24 is a diagram showing the relationship between the rate of change in the crystallite diameter of the C phase and the rate of decrease in strength in Experimental Example 1.
  • FIG. 25 is a diagram showing the relationship between the annealing temperature and the rate of change in the crystallite diameter of the C phase in Experimental Example 1.
  • FIG. 26 is a diagram showing the relationship between the annealing temperature and the strength reduction rate in Experimental Example 1.
  • FIG. 27 is a diagram showing the relationship between the holding time of the annealing temperature and the rate of change in the crystallite diameter of the C phase in Experimental Example 1.
  • the solid electrolyte 1 is composed of a large number of crystal particles 2.
  • the crystal phase of the crystal particle 2 has the forms of C phase 21, M phase 22, and T phase 23.
  • the solid electrolyte 1 is composed of stabilized zirconia or partially stabilized zirconia. Stabilized zirconia and partially stabilized zirconia are so-called sintered bodies, and the stabilizer is dissolved in zirconia.
  • the stabilizer examples include yttria, calcia, magnesia, scandia, and ittervia. Stabilized zirconia and partially stabilized zirconia can contain at least one of these as a stabilizer. From the viewpoint of increasing chemical stability, the stabilizer is preferably yttria. When the stabilizer is yttria, partially stabilized zirconia is formed when the yttria content is 8 mol% or less, and stabilized zirconia is formed when the yttria content exceeds 8 mol%. To.
  • M phase 22, T phase 23, and C phase 21 there are three types of crystal phases constituting the crystal particles 2 of zirconia (ZrO 2 ): M phase 22, T phase 23, and C phase 21.
  • M phase 22, T phase 23, and C phase 21 As the temperature rises, the phase transitions in the order of M phase 22, T phase 23, and C phase 21 and stabilizes.
  • C phase 21 and the T phase 23 are stabilized and metastable even at room temperature.
  • the room temperature is, for example, 25 ° C., and the same applies to the following description.
  • the C phase 21 has the highest ionic conductivity, but the strength is low, and the coefficient of thermal expansion is high as shown in FIG.
  • the solid electrolyte 1 is preferably composed of a mixed phase of C phase 21 and M phase 22.
  • the difference in thermal expansion coefficient between the dissimilar material member such as alumina and spinel (MgAl 2 O 4 ) and the solid electrolyte 1 can be reduced. As a result, it is possible to prevent cracks and peeling due to the difference in thermal expansion at the contact portion between the solid electrolyte 1 and the dissimilar material member.
  • the phase transition occurs because the internal energy in the crystal particle 2 tends to be lower and more stable.
  • the crystal particles 2 of M phase 22 in a stable state in the room temperature range are in the firing temperature range (specifically, 1400 ° C. or higher). It exists as T-phase 23.
  • T-phase 23 the firing temperature range
  • the temperature is lowered after the completion of firing, a phase transition occurs with expansion from the T phase 23 to the M phase 22. Since the expansion is not released and is accumulated as strain inside the crystal particles 2 near the grain boundaries, the internal energy inside the crystal particles 2 becomes high.
  • the crystal particles 2 of the M phase 22 are in a state where the phase transition to the T phase 23 is likely to occur.
  • the phase transition temperature from the M phase 22 to T phase 23 the temperature defined by the state diagram of FIG. 3, as shown in FIG. 4, decreases by [Delta] T 0 from T 0 to T 0 '.
  • phase transition peculiar to zirconia it is effective to reduce the strain and reduce the internal energy of the crystal particles 2, and the phase transition can be suppressed.
  • annealing treatment is effective for reducing the internal energy. The reason is that the crystal particles 2 are rearranged by thermal vibration due to the thermal energy in the annealing treatment, and the strain is reduced. That is, the reduction in strain lowers the internal energy, resulting in a higher phase transition temperature and suppression of the phase transition. The details will be described below.
  • the transition from the T phase 23 to the M phase 22 accompanied by expansion occurs when the temperature of the firing step is lowered.
  • the solid electrolyte 9 has a strain S at, for example, the grain boundary of the crystal particles 2. And the strain energy becomes the internal energy.
  • FIG. 5 when such a solid electrolyte 9 is subjected to a cold cycle from room temperature to 1200 ° C., as illustrated in FIGS. 6 and 7 during the temperature rise of the cold cycle.
  • the M phase 22 of the crystal particles 2 is transferred to the T phase 23, and volume contraction occurs, for example, about 4%.
  • a phase transition accompanied by expansion from T phase 23 with expansion to M phase 22 occurs as illustrated in FIG. Since the C phase 21 has already expanded as described above, the strain S of the crystal particles 2 becomes larger than that after firing. That is, as illustrated in FIG. 10, the solid electrolyte 9 has a strain at, for example, the grain boundary of the crystal particles 2, and the internal energy of the crystal particles 2 becomes larger than that after firing.
  • the internal energy can be reduced by the following mechanism.
  • the crystal particles 2 of the solid electrolyte 1 have a strain S due to the phase transition from the T phase 23 to the M phase 22 accompanied by expansion.
  • the crystal particles 2 are rearranged by thermal vibration as illustrated in FIG. 13, so that the strain S is reduced.
  • the solid electrolyte 1 is in a state where the internal energy of the crystal particles 2 is low.
  • the phase transition temperature from the M phase 22 to the T phase 23 is high, so that the cold cycle from room temperature to 1200 ° C. is performed with respect to the solid electrolyte 1.
  • the M phase 22 is less likely to undergo a phase transition to the T phase 23 during temperature rise.
  • voids are less likely to occur due to volume shrinkage during the phase transition.
  • the C phase 21 thermally expands as illustrated in FIG. 16, but since there are few voids generated by the volume contraction, the volume of the C phase 21 that fills the voids. Change is unlikely to occur.
  • the influence of the thermal expansion of the C phase 21 is reduced by the amount that the phase transition temperature from the M phase 22 to the T phase 23 is increased.
  • FIG. 11 after cooling in the thermal cycle, for example, at room temperature, a transition from T phase 23 to M phase 22 accompanied by expansion occurs, but the influence of thermal expansion of C phase 21 is small. Therefore (see FIG. 16), the strain S of the crystal particles 2 becomes small. That is, as illustrated in FIGS. 1 and 17, the solid electrolyte 1 has a small internal energy of the crystal particles 2.
  • the annealing temperature is, for example, below the melting point of stabilized zirconia or partially stabilized zirconia, and annealing treatment is a concept different from removing strain S by heating ceramics to near the melting point and softening them.
  • the upper limit of the annealing temperature is 1200 ° C. from the state diagram shown in FIG. Further, as shown in FIG.
  • the phase diagram of FIG. 3 is a theoretical value in the equilibrium state, and in the actual stabilized zirconia and partially stabilized zirconia, yttria has a statistical concentration due to the non-uniformity of the solid solution reaction due to the mixing variation of the raw material powder. Tends to have a distribution. That is, in reality, it is difficult to reach the equilibrium state as shown in the state diagram shown in FIG.
  • the actual phase transition temperature is higher than 600 ° C.
  • the annealing temperature can be higher than 600 ° C.
  • the annealing temperature is preferably 1150 ° C. or lower, more preferably 1100 ° C. or lower, and even more preferably 1000 ° C. or lower.
  • the strain S in the cold cycle is an alternative index of internal energy.
  • the strain S may be evaluated by applying a cold cycle of the solid electrolyte 1 from room temperature to 1200 ° C., more specifically, room temperature ⁇ 1200 ° C. ⁇ room temperature to the solid electrolyte 1.
  • the strain S can be regarded as the interatomic distance in the crystal. Therefore, the strain S can be evaluated by measuring and calculating the crystallite diameter by X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • any of the crystal phases of the C phase 21, the M phase 22, and the T phase 23 may be evaluated.
  • the generation of microcracks causes a decrease in the strength of the solid electrolyte 1, and the microcracks due to the strain S are inside the crystal particles 2 of the C phase 21 or in the vicinity of the C phase 21, which are smaller in strength than the M phase 22 and the T phase 23. Occurs at grain boundaries. Therefore, it is preferable to evaluate the crystallite diameter of the C phase 21.
  • the C-phase 21 has a large lattice symmetry, so that crystals are easily cleaved, and the solid solution of Y 2 O 3 increases the reactivity, and the particle size becomes large at the time of sintering. Become.
  • the crystal structures of C-phase 21 and T-phase 23 are similar, and in the XRD evaluation, they can be distinguished by the Miller index on the high angle side, but the peak intensity is weak and the measurement accuracy is lowered. Therefore, from the viewpoint of easily measuring and calculating the crystallite diameter by XRD, it is more preferable to evaluate the rate of change of the crystallite diameter of at least one of the C phase 21 and the T phase 23.
  • the crystallite diameter can be measured and calculated based on the peaks derived from the ⁇ 111 ⁇ plane of the C phase 21 and the ⁇ 101 ⁇ plane of the T phase 23, which have the maximum peak intensity.
  • the rate of change in the crystallite diameter of at least one of the C phase and the T phase in the crystal particles constituting the solid electrolyte 1 when the solid electrolyte 1 is heated from room temperature to 1200 ° C. is 10. % Or less. If the rate of change in crystallite diameter exceeds 10%, the strain energy is large and the thermal shock resistance becomes insufficient. From the viewpoint of further enhancing the thermal shock resistance, the rate of change in crystallite diameter is preferably 6% or less, and more preferably 2% or less.
  • the annealing treatment stabilizes the crystal of the solid electrolyte 1 and increases the crystallite diameter. Then, as compared with the case where the annealing treatment is not performed, the rate of change in the crystallite diameter after the thermal history due to the cooling / heating cycle of the solid electrolyte 1 becomes smaller.
  • the solid electrolyte 1 in which the internal energy is reduced by the annealing treatment and the rate of change in the crystallite diameter is reduced is described, but the rate of change in the crystallite diameter is also described by a method other than the annealing treatment. When is 10% or less, the solid electrolyte 1 exhibits excellent thermal shock strength.
  • the solid electrolyte 1 is suitable for, for example, a gas sensor that detects the exhaust gas of a vehicle.
  • the reason for this is as follows.
  • the exhaust gas temperature is expected to rise in the future due to the further increase in the engine start / stop cycle and the improvement in the thermal efficiency of the engine. That is, the load on the engine becomes high and the exhaust gas temperature rises.
  • the phase transition temperature from the M phase 22 to the T phase 23 is reached as described above, and when cooling, the T phase 23 undergoes a phase transition to the M phase 22 again.
  • the strain S generated by the contraction / expansion at that time may cause microcracks to grow and reduce the strength.
  • the solid electrolyte 1 having a change rate of the crystallite diameter of 10% or less under the above-mentioned predetermined conditions is M. Since the phase transition temperature of the phase 22 can be raised by, for example, 60 ° C. at the maximum, the strength is unlikely to decrease even when the exhaust gas temperature rises in the future.
  • the solid electrolyte 1 is composed of partially stabilized zirconia, and the yttria content of the partially stabilized zirconia is preferably 2 to 8 mol%.
  • the difference in thermal expansion coefficient between the dissimilar material member such as alumina and spinel (MgAl 2 O 4 ) and the solid electrolyte 1 can be reduced.
  • the solid electrolyte 1 is suitable for joining with dissimilar material members. Examples of such applications include sensor elements of gas sensors.
  • the yttria content of partially stabilized zirconia is more preferably 4.5-8 mol%. In this case, the coefficients of thermal expansion of the dissimilar material member and the solid electrolyte 1 are more consistent with each other, and the occurrence of cracks can be further prevented.
  • the solid electrolyte 1 is produced by performing a mixing step, a firing step, and an annealing step. In the mixing step, zirconia and the stabilizer are mixed. This gives a mixture. The mixture can be molded into a desired shape into a molded body.
  • the mixture or its molded product is fired to obtain a fired product.
  • the fired body comprises stabilized zirconia or partially stabilized zirconia.
  • the fired body is heated.
  • the annealing temperature is, for example, 800 to 1150 ° C. If the annealing temperature is less than 800 ° C., the internal energy of the crystal particles 2 cannot be sufficiently reduced. On the other hand, if the temperature exceeds 1150 ° C., a phase transition from the M phase 22 to the T phase 23 occurs during the annealing treatment, and the effect of lowering the internal energy cannot be obtained. From the viewpoint of sufficiently obtaining the effect of lowering the internal energy by the annealing treatment, the annealing temperature is preferably 900 to 1100 ° C., and the annealing temperature is more preferably 950 to 1000 ° C. Specific examples of the method for producing the solid electrolyte 1 will be described with reference to Experimental Examples.
  • the gas sensor 5 of this embodiment includes a sensor element 6.
  • the sensor element 6 of this embodiment is a gas sensor element that detects gas.
  • the sensor element 6 has a solid electrolyte 1, a detection electrode 62, a reference electrode 63, and a diffusion resistance layer 66. That is, the gas sensor 5 includes the solid electrolyte 1 in the sensor element 6.
  • the detection electrode 62 and the reference electrode 63 are formed on both surfaces 601A and 602A of the solid electrolyte 1, respectively.
  • the detection electrode 62 and the reference electrode 63 form a pair of electrodes formed at positions facing each other.
  • the diffusion resistance layer 66 limits the flow rate of the measurement gas such as the exhaust gas G reaching the detection electrode 62.
  • the gas sensor 5 detects the oxygen concentration (that is, the air-fuel ratio) of the exhaust gas G by the magnitude of the critical current generated between the pair of electrodes 62 and 63 when a voltage is applied between the pair of electrodes 62 and 63. It is a limit current type.
  • the gas sensor 5 of this embodiment will be described in detail below.
  • the side exposed to the measurement gas such as the exhaust gas G in the axial direction X of the gas sensor 5 and the tip side X1 are referred to, and the opposite side is referred to as the proximal end side X2.
  • the gas sensor 5 is arranged and used in the exhaust pipe of an internal combustion engine such as a vehicle.
  • the limit current type gas sensor 5 as in this embodiment is used as an air-fuel ratio sensor that quantitatively detects the air-fuel ratio of the exhaust gas G flowing through the exhaust pipe. With this gas sensor 5, the air-fuel ratio can be quantitatively obtained regardless of whether the air-fuel ratio of the exhaust gas G is on the rich side or the lean side.
  • the air-fuel ratio of exhaust gas G means the mixing ratio of fuel and air when burned in an internal combustion engine.
  • the rich side means that the air-fuel ratio of the exhaust gas G is on the side with more fuel than the theoretical air-fuel ratio when the fuel and air are completely combusted.
  • the lean side means that the air-fuel ratio of the exhaust gas G is on the side where the fuel is less than the stoichiometric air-fuel ratio.
  • the air-fuel ratio of the exhaust gas is detected by detecting the oxygen concentration of the exhaust gas.
  • the gas sensor 5 as an air-fuel ratio sensor substantially detects the oxygen concentration of the exhaust gas G on the lean side, while it detects the unburned gas concentration of the exhaust gas G on the rich side.
  • the gas sensor 5 has a housing 71, a front end side cover 72, a base end side cover 73, and the like, in addition to the sensor element 6.
  • the housing 71 is attached to the exhaust pipe and holds the sensor element 6 via the insulating insulator 74.
  • the tip side cover 72 is attached to the tip side X1 of the housing 71 and covers the sensor element 6.
  • the front end side cover 72 has a double structure, and includes an inner cover 721 and an outer cover 722.
  • the base end side cover 73 is attached to the base end side X2 of the housing 71 and covers the terminal 75 for electrical wiring of the sensor element 6.
  • the sensor element 6 for example, a laminated sensor element is used. That is, the sensor element 6 can be composed of a laminate in which the reference electrode 63, the plate-shaped solid electrolyte 1 and the detection electrode 62 are sequentially laminated.
  • the sensor element 6 has, for example, a plate-shaped solid electrolyte 1.
  • the solid electrolyte 1 has a measurement gas surface 601A and a reference gas surface 602A.
  • the measurement gas surface 601A is a surface exposed to a measurement gas such as exhaust gas G, and serves as a gas contact portion that comes into contact with the measurement gas.
  • the reference gas surface 602A is a surface exposed to a reference gas such as the atmosphere A.
  • the measurement gas surface 601A and the reference gas surface 602A are opposite surfaces in the solid electrolyte 1.
  • the detection electrode 62 is provided on the measurement gas surface 601A of the solid electrolyte 1.
  • the reference electrode 63 is provided on the reference gas surface 602A.
  • the heating element 641 constituting the heater 64 is laminated on the solid electrolyte 1 via the insulator 642.
  • the insulator 642 is made of, for example, alumina.
  • the detection electrode 62 faces the measurement gas chamber 68.
  • the measurement gas is introduced into the measurement gas chamber 68 via the porous diffusion resistance layer 66.
  • the measurement gas chamber 68 is a space surrounded by the solid electrolyte 1, the measurement gas chamber cambium 681, and the diffusion resistance layer 66.
  • the detection electrode 62 is formed in contact with the solid electrolyte 1, and the measurement gas chamber forming layer 681, which is a structural member of the measurement gas chamber 68, is formed in contact with the solid electrolyte 1. This is a portion where the detection electrode 62 is exposed to a measurement gas such as exhaust gas G and gas is detected together with the reference electrode 63.
  • the detection electrode 62 is electrically connected to the terminal 75 to which the lead wire 76 is connected.
  • the reference electrode 63 faces the reference gas chamber 69.
  • a reference gas such as atmosphere A is introduced into the reference gas chamber 69 from the proximal end side X2 via the passage hole 731 of the proximal end side cover 73.
  • the sensor element 6 a cup-type sensor element described later can be used instead of the stacked sensor element.
  • the detection electrode 62 is exposed to a measurement gas such as exhaust gas G that flows into the tip side cover 42 through the passage holes 723, 724, and 725 provided in the tip side cover 72.
  • the reference electrode 63 is exposed to a reference gas such as air A that flows into the reference gas chamber 69 of the solid electrolyte 1 from the base end side cover 73 through the passage hole 731 provided in the base end side cover 73.
  • the heater 64 generates heat when energized, and heats the solid electrolyte 1 and the electrodes 62 and 63 to the active temperature when the internal combustion engine and the gas sensor 5 are started.
  • the heater 64 includes an insulator 642 made of an alumina sintered body and a heating element 641 formed inside the insulator 642.
  • the alumina sintered body constituting the insulator 642 is in contact with the solid electrolyte.
  • the insulator 642 constituting the heater 64 is also a structural member forming the reference gas chamber 69, and also serves as a reference gas chamber forming layer.
  • a measurement gas chamber forming layer 681 constituting the measurement gas chamber 68 is laminated and formed on the measurement gas surface 601A side.
  • the measurement gas chamber cambium 681 is made of alumina. That is, the solid electrolyte 1 is in contact with the insulator 642 constituting the heater 64 on the reference gas surface 602A side, and is in contact with the measurement gas chamber forming layer 681 on the measurement gas surface 601A side. That is, the solid electrolyte 1 has a measurement gas chamber cambium 681, which is a dissimilar material member, and a contact portion 1A with the insulator 642.
  • the diffusion resistance layer 66 is made of, for example, a porous body of spinel. Further, a shielding layer 60 made of alumina is provided on the surface of the diffusion resistance layer 66. The shielding layer 60 is made of a dense body that does not allow gas to pass through. The exhaust gas G that has flowed into the front end side cover 72 passes through the diffusion resistance layer 66 and reaches the measurement unit 50 of the detection electrode 62. In the configuration of the sensor element 6 illustrated in FIG. 20, the diffusion resistance layer 66 is not in contact with the solid electrolyte 1, but it is also possible to adopt a configuration in which the diffusion resistance layer 66 is in contact with the solid electrolyte 1.
  • the solid electrolyte 1 comprises stabilized zirconia or partially stabilized zirconia. Specifically, the solid electrolyte 1 according to the first embodiment is used.
  • the solid electrolyte 1 is excellent in thermal shock resistance, and can maintain high strength even in a cold cycle exposed to a high temperature region exceeding 1050 ° C., for example. Therefore, for example, even if the gas sensor 5 is used in an environment exceeding 1050 ° C., the gas sensor 5 can detect the measurement gas while maintaining high reliability. Further, the strength of the solid electrolyte is suppressed from being lowered even in an environment where the cooling and heating cycles are frequently repeated. Therefore, even if the gas sensor is used in an environment where heating and cooling are frequent, the gas sensor can detect the measured gas while maintaining high reliability.
  • the material of the detection electrode 62 of this embodiment is not particularly limited as long as it has catalytic activity for oxygen or the like.
  • the detection electrode 62 has a composition of any one of Pt (platinum), Au (gold), Ag (silver), Pd (palladium) and Ag mixture or alloy, and Pt and Au mixture or alloy as a noble metal component.
  • the material of the reference electrode 63 is not particularly limited, and Pt, Au, Ag, Pd and the like can be contained as a noble metal component.
  • a bottomed cylindrical type (specifically, a cup type) sensor element can be used as illustrated in FIG.
  • a cup-type sensor element has a bottomed cylindrical (specifically, cup-shaped) solid electrolyte 1, a detection electrode 62, and a reference electrode 63.
  • the detection electrode 62 is provided on the outer peripheral surface 601A of the solid electrolyte 1.
  • the reference electrode 63 is provided on the inner peripheral surface 602A of the solid electrolyte 1.
  • a rod-shaped heater (not shown) is inserted inside the sensor element 6. The heater heats the sensor element 6 to a desired temperature.
  • the detection electrode 62 is provided on the outer peripheral surface 601A of the solid electrolyte 1. Further, a porous protective layer 625 is formed on the outer peripheral surface 601A of the solid electrolyte.
  • the protective layer 625 is a porous body, for example, made of spinel.
  • the detection electrode 62 exists between the protective layer 625 and the solid electrolyte 1, but the detection electrode 62 is not necessarily formed on the entire outer peripheral surface 601A and is usually not formed. There is a forming part. Therefore, although the configuration is not shown, there is a portion where the protective layer 625 and the solid electrolyte 1 come into contact with each other.
  • the solid electrolyte 1 has a contact portion 1A with a protective layer 625 which is a different material member.
  • the outer peripheral surface 601 of the tip side X1 of the solid electrolyte 1 serves as a contact portion in contact with the measurement gas such as the exhaust gas G.
  • the reference electrode 63 is provided on the inner peripheral surface of the cup-shaped solid electrolyte 1, but the reference electrode 63 may be provided on the entire inner peripheral surface or partially. If it is partially provided, the alumina constituting the heater may come into contact with the solid electrolyte.
  • the strength against the thermal cycle is improved by using the solid electrolyte 1 in the first embodiment. Therefore, even in the gas sensor 5 provided with the cup-type sensor element, the gas sensor 5 can detect the measured gas while maintaining high reliability.
  • Example 1 Multiple solid electrolytes are prepared and their performance is compared and evaluated.
  • the method for producing the solid electrolyte in this example will be described below.
  • the mixing step S1, the firing step S2, and the annealing step S3 are performed as illustrated in FIG. 22, but in this example, the molding step is performed after the mixing step and before the firing step.
  • yttria powder was added to the zirconia powder in a desired ratio, mixed by a dry method, and pulverized. As a result, a mixed powder was obtained.
  • the mixed powder and water were mixed to obtain a mixed powder slurry.
  • the mixed powder slurry was granulated. Granulation is performed, for example, by spray granulation.
  • the mixed powder was molded to obtain a molded product. Molding is performed, for example, by powder molding. Further grinding may be performed. In this example, it was molded into a sample shape used for evaluation described later. In this molding step, it is possible to mold into a desired shape such as the element shape in the second embodiment.
  • the molded product was fired at a temperature of 1400 ° C. In this way, a fired body was obtained.
  • the fired body was annealed.
  • the annealing treatment was performed by heating the fired body at a predetermined annealing temperature. In this way, a solid electrolyte was obtained.
  • the yttria content, the annealing temperature, and the holding time at the annealing temperature were changed to prepare 13 types of solid electrolytes of Samples 2 to 14.
  • Sample 1 is a solid electrolyte that has not been annealed. Table 1 shows the production conditions of Samples 1 to 14. The rate of change in crystallite diameter, initial strength, strength after durability, and strength reduction rate of the solid electrolytes of Samples 1 to 14 were measured as follows.
  • the crystallite diameter D was calculated from the Scheller's formula of the following formula (I). As illustrated in FIG. 23, the half-value width and the diffraction angle of the smoothed XRD pattern are used to calculate the crystallite diameter.
  • the software "Peak Search" manufactured by Rigaku Co., Ltd. was used for the smoothing process.
  • the processing conditions are processing: smoothing, weighted average: 5 points of smoothing points, peak width threshold value for BG removal: 0.1, and intensity threshold value: 0.01.
  • the "rate of change in crystallite diameter of C phase” in this example actually means “C phase and / or T phase” from the viewpoint of the measurement principle of XRD analysis.
  • the solid electrolytes of Samples 1 to 14 were cut into a width of about 5 mm, a length of 45 mm, and a thickness of 5 mm to prepare a measurement sample.
  • This measurement sample was heated from room temperature to 1100 ° C. at a heating rate of 300 ° C./h, and a cooling cycle of heating the measurement sample to room temperature at a temperature lowering rate of ⁇ 300 ° C./h was repeated 1000 times.
  • a strength evaluation sample was prepared from the measurement sample not subjected to the cold cycle and the measurement sample subjected to 1000 cold cycles according to the 4-point bending test of JIS R 1601: 2008, and the 4-point bending strength was measured.
  • the 4-point bending strength 10 strength evaluation samples were prepared from each sample, and the arithmetic mean result was adopted.
  • the 4-point bending strength of the sample that had not been subjected to the cold heat cycle was defined as the initial strength, and the 4-point bending strength of the sample that had undergone 1000 cold heat cycles was defined as the post-durability strength.
  • the rate of decrease in strength after durability with respect to the initial strength was defined as the rate of decrease in strength.
  • the intensity reduction rate was 50% or more, it was determined as "C”, when it was less than 50% and 40% or more, it was determined as "B”, and when it was less than 40%, it was determined as "A”.
  • the rate of change in crystallite diameter is 10% or less, the rate of decrease in strength is low. That is, it has excellent thermal shock resistance.
  • the rate of change in crystallite diameter is more preferably 6% or less, and further preferably 2% or less.
  • the annealing temperature is preferably 800 to 1150 ° C., from the viewpoint of reducing the rate of change in crystallite diameter and sufficiently increasing the thermal shock resistance. It is more preferably about 1100 ° C., and even more preferably 950 to 1000 ° C.
  • the holding time at the annealing temperature is preferably 0.75 hours or more, and is preferably 1 hour or more, from the viewpoint of sufficiently reducing the rate of change in crystallite diameter. Is more preferable.
  • the holding time at the annealing temperature is preferably 3 hours or less, and more preferably 2 hours or less.
  • the initial strength is preferably 350 MPa or more from the viewpoint of being suitable for the solid electrolyte of the sensor element of the gas sensor.
  • the strength after durability is preferably 200 MPa or more, and from the viewpoint of being suitable for a laminated sensor element and a cup type sensor element, the strength after durability is 250 MPa or more. Is more preferable.
  • the strength reduction rate is preferably less than 50%, more preferably less than 40%, and even more preferably 30% or less.
  • the present disclosure is not limited to each of the above embodiments, and can be applied to various embodiments without departing from the gist thereof.
  • the solid electrolyte in Embodiment 1 can also be used in a solid oxide fuel cell (SOFC) fuel cell.
  • the solid electrolyte has, for example, a contact surface with an anode layer and a cathode layer.
  • the configuration is not shown, the solid electrolyte can be applied to a fuel cell single cell in which an anode layer, an electrolyte layer made of a solid electrolyte, and a cathode layer are sequentially laminated.
  • a stack type fuel cell can be constructed by stacking a plurality of single fuel cell cells via a separator.
  • the gas sensor in addition to the air-fuel ratio sensor, there are an oxygen sensor, a NOx sensor and the like, and a solid electrolyte can be applied to these sensors.

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US20220011259A1 (en) 2022-01-13

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