CN110407578A - ZrO2The preparation method of base oxygen sensing element co-sintering platinum electrode - Google Patents
ZrO2The preparation method of base oxygen sensing element co-sintering platinum electrode Download PDFInfo
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- CN110407578A CN110407578A CN201910806499.8A CN201910806499A CN110407578A CN 110407578 A CN110407578 A CN 110407578A CN 201910806499 A CN201910806499 A CN 201910806499A CN 110407578 A CN110407578 A CN 110407578A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 103
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 62
- 239000001301 oxygen Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 238000005245 sintering Methods 0.000 title claims abstract description 41
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 38
- 239000011267 electrode slurry Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000004615 ingredient Substances 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000006259 organic additive Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000004359 castor oil Substances 0.000 claims description 5
- 229960001777 castor oil Drugs 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 5
- IPZIYGAXCZTOMH-UHFFFAOYSA-N alpha-eudesmol Natural products CC1=CCCC2CCC(CC12)C(C)(C)O IPZIYGAXCZTOMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- WWULHQLTPGKDAM-UHFFFAOYSA-N gamma-eudesmol Natural products CC(C)C1CC(O)C2(C)CCCC(=C2C1)C WWULHQLTPGKDAM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 240000000528 Ricinus communis Species 0.000 claims description 3
- 235000004443 Ricinus communis Nutrition 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000346 nonvolatile oil Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940044949 eucalyptus oil Drugs 0.000 claims description 2
- 239000010642 eucalyptus oil Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 14
- 239000002002 slurry Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- 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
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Abstract
The present invention provides a kind of ZrO2The preparation method of base oxygen sensing element co-sintering platinum electrode, the preparation method is the following steps are included: S1. prepares ZrO2Based solid electrolyte blank；S2. platinum electrode slurry is prepared；And the platinum electrode slurry is coated uniformly on the ZrO by S3.2In the inner wall surface and outer wall surface of based solid electrolyte blank, room temperature dry after to be coated with platinum electrode slurry ZrO2Based solid electrolyte blank is sintered.ZrO according to the present invention2The preparation method of base oxygen sensing element co-sintering platinum electrode passes through addition and ZrO in platinum electrode slurry2The identical component of based solid electrolyte blank material reduces the difference of the ingredient in blank material and slurry, to reduce platinum electrode and ZrO2Thermal expansion coefficient difference between base oxygen sensing element matrix, enhances the adhesion property of platinum electrode, thus extends ZrO2The service life of base oxygen sensing element.
Description
Technical field
The present invention relates to a kind of ZrO2The preparation method of the electrode of base lambda sensor, more particularly, to ZrO2Base oxygen sensing
The preparation method of device oxygen sensing element co-sintering platinum electrode.
Background technique
ZrO2Base lambda sensor is to utilize ZrO2Base oxygen sensing element measures the oxygen voltage under test gas or specific environment,
Oxygen content therein is calculated further according to Nernst equation, this sensor has been widely used in boiler combustion and automobile air-fuel
Than monitoring aspect, play the role of energy saving and protection environment.And the performance and ZrO of this lambda sensor2Base oxygen is sensitive
The preparation method of the platinum electrode of element is closely related.
Currently, ZrO2There are mainly two types of the preparation methods of the platinum electrode of base oxygen sensing element, the first preparation method is, first
ZrO is first prepared at high temperature2Based solid electrolyte matrix, then the electrode coated slurry on matrix, is made electricity through high temperature sintering
Pole.Another preparation method is that electrode slurry is applied directly to ZrO2The surface of based solid electrolyte blank, co-sintering are made
Electrode.
Due to platinum electrode and ZrO2There are larger differences between the thermal expansion coefficient of base oxygen sensing element matrix, therefore, when
When electrode is chronically at corrosive gas, washes away in the environment of serious or high temperature variation, it is easy to appear electrode cracking even
Thus the phenomenon that falling off will lead to lambda sensor failure.
In order to improve platinum electrode in ZrO2The adhesion property of base oxygen sensing element matrix surface, usually adds in electrode slurry
Add glass powder.But when the additive amount of glass powder is excessive, glass powder is melted under high temperature, can block the catalytic activity area of platinum electrode
Domain reduces the catalytic activity of electrode.
Therefore, need one kind that can enable platinum electrode in the case where ensuring the catalytic activity of platinum electrode in the prior art
It is securely attached to the ZrO of matrix surface2Base oxygen sensing element.
Summary of the invention
At least one of in order to solve the above-mentioned technical problem aspect, the embodiment provides a kind of ZrO2Base oxygen
The preparation method of sensing element co-sintering platinum electrode, the preparation method the following steps are included:
S1. ZrO is prepared2Based solid electrolyte blank；
S2. platinum electrode slurry is prepared；And
S3. the platinum electrode slurry is coated uniformly on the ZrO2The inner wall surface and outer wall of based solid electrolyte blank
On surface, room temperature dry after to be coated with platinum electrode slurry ZrO2Based solid electrolyte blank is sintered.
ZrO according to the present invention2One preferred embodiment of the preparation method of base oxygen sensing element co-sintering platinum electrode,
Step S1 includes using isostatic cool pressing compact technique by 5mol%-8mol%Y2O3The ZrO of doping2Powder pressing is at tubulose, with system
The standby ZrO2Based solid electrolyte blank.
In ZrO according to the present invention2Another of the preparation method of base oxygen sensing element co-sintering platinum electrode is preferred real
It applies in example, step S2 includes: the organic adhesive of (1) by weight additive metal oxide, 2%-10% for 3%-5%
Agent, the organic additive of 5%-10%, the organic solvent of 8%-30% and 60%-75% Ultrafine Platinum Powder proportion carry out ingredient
Prepare；(2) additive metal oxide and Ultrafine Platinum Powder progress is fully dispersed, organic binder, organic addition is then added
Agent and organic solvent, and carry out ultrasonic disperse or grinding.
ZrO according to the present invention2Another of the preparation method of base oxygen sensing element co-sintering platinum electrode is preferably implemented
Example, the additive metal oxide press following weight percent ingredient, the ZrO including 60%-85%2Based solid electrolyte powder
The Al of material and 5%-15%2O3, surplus CaO, MgO and TiO2At least one of.
In ZrO according to the present invention2Another of the preparation method of base oxygen sensing element co-sintering platinum electrode is preferred real
It applies in example, the ZrO2Based solid electrolyte powder and prepare the ZrO2The material of based solid electrolyte blank is identical.
ZrO according to the present invention2Also one of the preparation method of base oxygen sensing element co-sintering platinum electrode is preferred to implement
Example, the organic binder includes at least one of methylcellulose, epoxy resin, polyvinyl alcohol and methacrylate.
In ZrO according to the present invention2Another of the preparation method of base oxygen sensing element co-sintering platinum electrode is preferred real
It applies in example, the organic solvent includes at least one of terpinol, ethyl alcohol, isopropanol and methyl ethyl ketone.
ZrO according to the present invention2Another of the preparation method of base oxygen sensing element co-sintering platinum electrode is preferably implemented
Example, the organic additive includes eucalyptus oil, eudesmol, castor-oil plant fixed oil, Castor Oil Fatty Acid, dimethyl adipate, two
At least one of 2-Butoxyethyl acetate and Span.
In ZrO according to the present invention2Another of the preparation method of base oxygen sensing element co-sintering platinum electrode is preferred real
Apply in example, the particle of the Ultrafine Platinum Powder be it is approximately spherical, particle size range is 0.5 μm -2.0 μm.
ZrO according to the present invention2Also one of the preparation method of base oxygen sensing element co-sintering platinum electrode is preferred to implement
, to the ZrO for being coated with platinum electrode slurry in step S32The step of based solid electrolyte blank is sintered include:
1000 DEG C are heated to the heating rate of 0.5 DEG C/min-2 DEG C/min, and in 1000 DEG C of heat preservation 0.5h-3h；
1450 DEG C -1600 DEG C are heated to the heating rate of 0.5 DEG C/min-2 DEG C/min, and in 1450 DEG C of -1600 DEG C of guarantors
Warm 0.5h-3h；And
1000 DEG C are cooled to the rate of 2 DEG C/min-5 DEG C/min, in 1000 DEG C of heat preservation 1h-3h, is then naturally cooled to
Room temperature.
Compared with prior art, ZrO of the invention2The preparation method of base oxygen sensing element co-sintering platinum electrode has following
At least one of beneficial effect:
(1) present invention passes through addition and ZrO in platinum electrode slurry2The identical component of based solid electrolyte blank material,
The difference for reducing the ingredient in blank material and slurry, to reduce platinum electrode and ZrO2Between base oxygen sensing element matrix
Thermal expansion coefficient difference achievees the purpose that the adhesion property for enhancing platinum electrode；
(2) present invention in electrode slurry by adding Al2O3And other additive metal oxides, so as into
One step enhances the catalytic activity of platinum electrode, achievees the purpose that improve platinum electrode to the response performance of oxygen；
(3) present invention can make platinum electrode and ZrO by the preparation method of co-sintering2Base oxygen sensing element matrix tool
Have higher bond strength, have better high-temperature stability, so as to avoid platinum electrode under the long-time condition of high temperature with
ZrO2The disengaging of base oxygen sensing element matrix, thus extends ZrO2The service life of base oxygen sensing element.
Detailed description of the invention
By the description made for the present invention of below with reference to attached drawing, other objects and advantages of the present invention will be aobvious and easy
See, and can help that complete understanding of the invention will be obtained.
Fig. 1 is the ZrO according to exemplary embodiment of the present2The preparation method of base oxygen sensing element co-sintering platinum electrode
Flow chart.
It should be noted that attached drawing is not necessarily to scale to draw, but only not influence the schematic of reader's understanding
Mode is shown.
Specific embodiment
To keep the purpose of the present invention, technical scheme and beneficial effects clearer, below in conjunction with the embodiment of the present invention
Technical solution of the present invention is clearly and completely described in attached drawing.Obviously, described embodiment is of the invention one
Embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, those of ordinary skill in the art are being not necessarily to
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Unless otherwise defined, the technical term or scientific term that the present invention uses should be tool in fields of the present invention
The ordinary meaning for thering is the personage of general technical ability to be understood.
ZrO of the invention2The preparation method of base oxygen sensing element co-sintering platinum electrode mainly comprises the steps that
S1. ZrO is prepared2Based solid electrolyte blank；
S2. platinum electrode slurry is prepared；And
S3. platinum electrode slurry is coated uniformly on ZrO2In the inner wall surface and outer wall surface of based solid electrolyte blank,
Room temperature dry after to be coated with platinum electrode slurry ZrO2Based solid electrolyte blank is sintered.
In step sl, ZrO2The preparation of based solid electrolyte blank can use isostatic cool pressing compact technique will
5mol%-8mol%Y2O3The ZrO of doping2Powder pressing is at tubulose, to prepare tubular blank.Wherein, 5mol%-8mol%
Y2O3The ZrO of doping2Powder is referred in ZrO2The Y that molar percentage is 5%-8% is doped in powder2O3The material of powder.
In step s 2, the preparation process of platinum electrode slurry may include following content: (1) being by weight 3%-5%
Additive metal oxide, the organic binder of 2%-10%, the organic additive of 5%-10%, 8%-30% it is organic molten
The Ultrafine Platinum Powder of agent and 60%-75% proportion carry out ingredient preparation；(2) additive metal oxide and Ultrafine Platinum Powder are carried out
It is fully dispersed, organic binder, organic additive and organic solvent is then added, and carry out ultrasonic disperse or grinding.Here, In
During dispersing to additive metal oxide and Ultrafine Platinum Powder, it can use ultrasonic wave and ultrasonic disperse carried out to it,
Make the two at uniformly mixed powdery, and again to mixed after organic binder, organic additive and organic solvent is added
It closes object and carries out ultrasonic wave dispersion or grinding, such as can be -3 hours 1 hour with ultrasonic disperse, or is small using ball mill grinding 10
When -15 hours, to form the uniformly mixed electrode slurry of final component.
Further, in above-mentioned ZrO2In the preparation method of base oxygen sensing element co-sintering platinum electrode, metal oxide adds
Add agent by weight percentage and include the ZrO of 60%-85%2The Al of based solid electrolyte powder and 5%-15%2O3, surplus is
CaO, MgO and TiO2At least one of.Pass through addition and ZrO in platinum electrode slurry2The material phase of based solid electrolyte blank
Same component can reduce the difference of the ingredient in blank material and electrode slurry, to reduce platinum electrode and ZrO2Base oxygen
Thus thermal expansion coefficient difference between sensing element matrix reaches enhancing platinum electrode in ZrO2Adhesion on basis material
Energy.Furthermore because the thermal expansion coefficient of platinum electrode and matrix is essentially identical, thus it is both combined when bearing high temperature not
Otherness deformation can be generated, so that phenomenon will not be broken or separated, it is possible thereby to greatly prolong ZrO2Base oxygen sensing element
Service life in the high temperature environment.Further, by adding Al in platinum electrode slurry2O3Add with other metal oxides
Add agent, the catalytic activity of platinum electrode can be further enhanced, and improves platinum electrode to the response performance of oxygen.
Further, in above-mentioned ZrO2In the preparation method of base oxygen sensing element co-sintering platinum electrode, organic binder packet
At least one of methylcellulose, epoxy resin, polyvinyl alcohol and methacrylate are included, organic additive includes folium eucalypti
In oil, eudesmol, castor-oil plant fixed oil, Castor Oil Fatty Acid, dimethyl adipate, butyl acetate and Span
At least one, organic solvent include at least one of terpinol, ethyl alcohol, isopropanol and methyl ethyl ketone.It is above-mentioned by adding
Organic binder can enable powder to be bonded together, and make platinum electrode by addition organic additive and organic solvent
Powder closely combines and is formed slurry, so as to ZrO2Based solid electrolyte blank carries out surface coating.
Further, in above-mentioned ZrO2In the preparation method of base oxygen sensing element co-sintering platinum electrode, of Ultrafine Platinum Powder
Grain be it is approximately spherical, particle size range be 0.5 μm -2.0 μm.It can make platinum electrode slurry by the Ultrafine Platinum Powder of above-mentioned particle size range
With it is good can coating, and can preferably be attached to ZrO after the sintering2The surface of based solid electrolyte blank
On.
In step s3, to the ZrO for being coated with platinum electrode slurry2The step of based solid electrolyte blank is sintered packet
It includes: (1) being heated to 1000 DEG C with the heating rate of 0.5 DEG C/min-2 DEG C/min, and in 1000 DEG C of heat preservation 0.5h-3h；(2) with
The heating rate of 0.5 DEG C/min-2 DEG C/min is heated to 1450 DEG C -1600 DEG C, and in 1450 DEG C of -1600 DEG C of heat preservation 0.5h-3h；
And (3) are cooled to 1000 DEG C with the rate of 2 DEG C/min-5 DEG C/min, in 1000 DEG C of heat preservation 1h-3h, then naturally cool to room
Temperature.Here, heating process is defined respectively by step (1), step (2) and step (3), such as in step (1),
Blank is heated with 0.5 DEG C -2 DEG C of heating rate per minute, and carries out heat preservation operation after being heated to 1000 DEG C, is kept the temperature
Continue half an hour to 3 hours durations.By sintering processes as described above, platinum electrode slurry can be made to become solid attached securely
On the surface of solid electrolyte blank, thus formed needed for ZrO2Base oxygen sensing element.
Below by way of specific embodiment to ZrO of the invention2The preparation method of base oxygen sensing element co-sintering platinum electrode
Step is more specifically illustrated.
Experimental example 1:
Firstly, carrying out the preparation of platinum electrode slurry: preparing additive metal oxide first, be respectively by weight percentage
10% Al2O3, 80% ZrO2Based solid electrolyte powder (6mol%Y2O3The ZrO of doping2) and 10% CaO preparing metal
Oxide addition；Then, according to weight percent be respectively 5% additive metal oxide, 10% methylcellulose,
8% eudesmol, 10% terpinol and 67% 1.0 μm of partial sizes approximately spherical Ultrafine Platinum Powder proportion relation carry out
Ingredient prepare, by additive metal oxide and Ultrafine Platinum Powder carry out mixing and it is fully dispersed, then be added methylcellulose, eucalyptus
The pure and mild terpinol of leaf oil, ultrasonic disperse 1.5h, or also can use ball mill grinding 10h, platinum electrode slurry is made.
Then, ZrO is carried out2The preparation of base oxygen sensing element co-sintering platinum electrode: the platinum electrode slurry prepared is coated
In manufactured tubular type ZrO2In the inner wall surface and outer wall surface of based solid electrolyte blank, after room temperature is dried, with 1.5
DEG C/heating rate of min is heated to 1000 DEG C, and in 1000 DEG C of heat preservation 2h；Then, it is heated to the heating rate of 1 DEG C/min
1450 DEG C, in 1450 DEG C of heat preservation 2h；Then, 1000 DEG C are cooled to the rate of temperature fall of 2 DEG C/min, in 1000 DEG C of heat preservation 1h, most
Cooled to room temperature afterwards.
Finally, being verified by experiment to the performance of the platinum electrode prepared in embodiment 1: the platinum electrode and ZrO2Base is solid
The adhesive force of body electrolyte blank is greater than 12N/mm2, the lead resistance of platinum electrode is 1.0 Ω, response of the platinum electrode to oxygen
Time is not more than 3.0s.The demand in actual production to the performance of platinum electrode is met according to platinum electrode manufactured in the present embodiment.
Experimental example 2:
Firstly, carrying out the preparation of platinum electrode slurry: additive metal oxide is prepared, by weight percentage respectively 13%
Al2O3, 76% ZrO2Based solid electrolyte powder (6mol%Y2O3The ZrO of doping2) and 11% CaO preparing metal oxidation
Object additive；It then, is respectively 4.6% additive metal oxide, 6% epoxy resin, 10% according to weight percent
Castor Oil Fatty Acid, 10% methyl ethyl ketone and the 1.5 of 69.4% μm of partial sizes approximately spherical Ultrafine Platinum Powder proportion
Relationship carry out ingredient preparation, by additive metal oxide and Ultrafine Platinum Powder carry out mixing and it is fully dispersed, epoxy is then added
Resin, Castor Oil Fatty Acid and methyl ethyl ketone, ultrasonic disperse 1.5h, or can use ball mill grinding 10h, platinum electricity is made
Pole slurry.
Then, ZrO is carried out2The preparation of base oxygen sensing element co-sintering platinum electrode: the platinum electrode slurry prepared is coated
In tubular type ZrO2In the inner wall surface and outer wall surface of based solid electrolyte blank；After drying at room temperature, with 2 DEG C/min's
Heating rate is heated to 1000 DEG C, keeps the temperature 2h at 1000 DEG C；Then, 1520 DEG C are heated to the heating rate of 1.5 DEG C/min,
2h is kept the temperature at 1520 DEG C；Then, 1000 DEG C are cooled to the rate of temperature fall of 3 DEG C/min, and keep the temperature 1h at 1000 DEG C；Most
Afterwards, cooled to room temperature state.
Finally, being verified by experiment to the performance of the platinum electrode prepared in embodiment 2: the platinum electrode and ZrO2Base is solid
The adhesive force of body electrolyte blank is greater than 12N/mm2, the lead resistance of platinum electrode is less than 1.0 Ω, and the platinum electrode is to oxygen
Response time be not more than 3.0s.Platinum electrode manufactured in the present embodiment is also met in actual production to the need of the performance of platinum electrode
It asks.
As described above, ZrO according to the present invention2The preparation method of base oxygen sensing element co-sintering platinum electrode passes through in platinum electricity
Addition and ZrO in the slurry of pole2The identical component of based solid electrolyte blank material reduces the ingredient in blank of material and slurry
Difference, to reduce platinum electrode and ZrO2Thermal expansion coefficient difference between base oxygen sensing element matrix, enhances platinum electrode
Adhesion property.By adding Al in electrode slurry2O3And other additive metal oxides, so as to further increase
The catalytic activity of strong platinum electrode, and platinum electrode is improved to the response performance of oxygen.In addition, sintering method through the invention, it can
So that platinum electrode and ZrO2Base oxygen sensing element matrix has higher bond strength, has better high-temperature stability, from
And avoid platinum electrode under the long-time condition of high temperature with ZrO2The disengaging of base oxygen sensing element matrix, thus extends ZrO2Base
The service life of oxygen sensing element.
For the embodiment of the present invention, it is also necessary to explanation, in the absence of conflict, the embodiment of the present invention and reality
Applying the feature in example can be combined with each other to obtain new embodiment.
More than, only a specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, and it is of the invention
Protection scope should be subject to the protection scope in claims.
Claims (10)
1. a kind of ZrO2The preparation method of base oxygen sensing element co-sintering platinum electrode, the described method comprises the following steps:
S1. ZrO is prepared2Based solid electrolyte blank；
S2. platinum electrode slurry is prepared；And
S3. the platinum electrode slurry is coated uniformly on the ZrO2The inner wall surface and outer wall surface of based solid electrolyte blank
On, room temperature dry after to be coated with platinum electrode slurry ZrO2Based solid electrolyte blank is sintered.
2. ZrO according to claim 12The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
Step S1 includes using isostatic cool pressing compact technique by 5mol%-8mol%Y2O3The ZrO of doping2Powder pressing at tubulose,
To prepare the ZrO2Based solid electrolyte blank.
3. ZrO according to claim 12The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
Step S2 includes: by weight for the additive metal oxide of 3%-5%, the organic binder of 2%-10%, 5%-
The Ultrafine Platinum Powder proportion of 10% organic additive, the organic solvent of 8%-30% and 60%-75% carries out ingredient preparation；
Additive metal oxide and Ultrafine Platinum Powder are carried out it is fully dispersed, be then added organic binder, organic additive and
Organic solvent, and carry out ultrasonic disperse or grinding.
4. ZrO according to claim 32The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
The additive metal oxide presses following weight percent ingredient, the ZrO including 60%-85%2Based solid electrolyte powder
The Al of material and 5%-15%2O3, surplus CaO, MgO and TiO2At least one of.
5. ZrO according to claim 42The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
The ZrO2Based solid electrolyte powder and prepare the ZrO2The material of based solid electrolyte blank is identical.
6. ZrO according to claim 32The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
The organic binder includes at least one of methylcellulose, epoxy resin, polyvinyl alcohol and methacrylate.
7. ZrO according to claim 32The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
The organic solvent includes at least one of terpinol, ethyl alcohol, isopropanol and methyl ethyl ketone.
8. ZrO according to claim 32The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
The organic additive includes eucalyptus oil, eudesmol, castor-oil plant fixed oil, Castor Oil Fatty Acid, hexanedioic acid dimethyl ester, two
At least one of 2-Butoxyethyl acetate and Span.
9. ZrO according to claim 32The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
The particle of the Ultrafine Platinum Powder be it is approximately spherical, particle size range be 0.5 μm -2.0 μm.
10. ZrO according to claim 12The preparation method of base oxygen sensing element co-sintering platinum electrode, which is characterized in that
To the ZrO for being coated with platinum electrode slurry2The step of based solid electrolyte blank is sintered include:
1000 DEG C are heated to the heating rate of 0.5 DEG C/min-2 DEG C/min, and in 1000 DEG C of heat preservation 0.5h-3h；
1450 DEG C -1600 DEG C are heated to the heating rate of 0.5 DEG C/min-2 DEG C/min, and in 1450 DEG C of -1600 DEG C of heat preservations
0.5h-3h；And
1000 DEG C are cooled to the rate of 2 DEG C/min-5 DEG C/min, in 1000 DEG C of heat preservation 1h-3h, then cooled to room temperature.
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| CN113053558A (en) * | 2021-03-16 | 2021-06-29 | 黄海琴 | Preparation method and use method of platinum slurry for zirconium dioxide-based sensor pin bonding pad |
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|---|---|---|---|---|
| CN1821771A (en) * | 2006-03-23 | 2006-08-23 | 广州杰赛科技股份有限公司 | Co-burning method for oxygen sensor electrolyte and palatinum electrode |
| CN101655474A (en) * | 2009-06-02 | 2010-02-24 | 中国原子能科学研究院 | Method for preparing and sintering platinum slurry for electrode of oxygen sensor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821771A (en) * | 2006-03-23 | 2006-08-23 | 广州杰赛科技股份有限公司 | Co-burning method for oxygen sensor electrolyte and palatinum electrode |
| CN101655474A (en) * | 2009-06-02 | 2010-02-24 | 中国原子能科学研究院 | Method for preparing and sintering platinum slurry for electrode of oxygen sensor |
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| CN113053558A (en) * | 2021-03-16 | 2021-06-29 | 黄海琴 | Preparation method and use method of platinum slurry for zirconium dioxide-based sensor pin bonding pad |
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