JPH0668479B2 - Oxygen concentration detector - Google Patents
Oxygen concentration detectorInfo
- Publication number
- JPH0668479B2 JPH0668479B2 JP61164939A JP16493986A JPH0668479B2 JP H0668479 B2 JPH0668479 B2 JP H0668479B2 JP 61164939 A JP61164939 A JP 61164939A JP 16493986 A JP16493986 A JP 16493986A JP H0668479 B2 JPH0668479 B2 JP H0668479B2
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- electrode layer
- oxygen concentration
- concentration detector
- crystal structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052760 oxygen Inorganic materials 0.000 title claims description 13
- 239000001301 oxygen Substances 0.000 title claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- -1 oxygen ion Chemical class 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000004043 responsiveness Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002148 La0.6Sr0.4MnO3 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は例えば、自動車内燃機関の空燃比制御のために
用いられる酸素濃度検出器に関するものである。The present invention relates to an oxygen concentration detector used for controlling the air-fuel ratio of an automobile internal combustion engine, for example.
従来公知のこの種のものとしては、例えば特開昭53−30
386号公報に記載されているごとく、酸素イオン伝導性
金属酸化物より固体電解質素子の排気ガス側の電極層の
表面にマグネシアアルミナスピネル等の金属酸化物より
成る多孔性保護層を形成し、該保護層により上記電極層
を排気ガスに対し保護する構成の酸素濃度検出器があ
る。Examples of this type known in the art include, for example, JP-A-53-30.
As described in Japanese Patent No. 386, a porous protective layer made of a metal oxide such as magnesia alumina spinel is formed on the surface of the electrode layer on the exhaust gas side of the solid electrolyte element rather than the oxygen ion conductive metal oxide, There is an oxygen concentration detector configured to protect the electrode layer against exhaust gas with a protective layer.
従来のものでは自動車内燃機関に使用した場合、燃料で
あるガソリン中に含まれる鉛、あるいは内燃機関の潤滑
油中に含まれるイオウが排気ガス中に残存しているた
め、該鉛，イオンが上記保護層の多孔部を通って排気ガ
ス側電極層に到達しやすい。In the conventional case, when used in an automobile internal combustion engine, lead contained in gasoline as fuel or sulfur contained in lubricating oil of the internal combustion engine remains in the exhaust gas. It is easy to reach the exhaust gas side electrode layer through the porous portion of the protective layer.
排気ガス側の電極層は白金等の触媒金属で構成されてお
り、上記鉛，イオウがこの電極層と反応して電極層を構
成する白金粒子が凝集し触媒活性が低下するという問題
を有している。The electrode layer on the exhaust gas side is composed of a catalyst metal such as platinum, and there is a problem that the lead and sulfur react with this electrode layer and the platinum particles constituting the electrode layer agglomerate to lower the catalytic activity. ing.
また、排気ガス中の未燃焼炭化水素，一酸化炭素が上記
電極層の触媒作用によりカーボンを生成し、これが電極
層の白金と反応してグラファイト化し電極層の剥離の原
因となるという問題を有している。In addition, there is a problem that unburned hydrocarbons and carbon monoxide in the exhaust gas generate carbon due to the catalytic action of the electrode layer, which reacts with platinum in the electrode layer to graphitize and cause peeling of the electrode layer. is doing.
本発明は上記の諸問題を解決しようとするものであっ
て、燃焼排気ガス側の電極層の表面に、触媒活性を有し
たペロブスカイト型結晶構造の金属酸化物とアルカル土
類炭酸塩を包む多孔性被膜を形成したものである。The present invention is intended to solve the above problems, in which the surface of the electrode layer on the combustion exhaust gas side has a porous structure containing a metal oxide having a perovskite type crystal structure having catalytic activity and an alcal earth carbonate. It is formed with a conductive coating.
本発明によれば、上記多孔性被膜のペロブスカイト型結
晶構造を有した金属酸化物およびアルカル土類炭酸塩が
燃焼排気ガス中の鉛，イオウと反応し、鉛を固溶したペ
ロブスカイト金属酸化物を形成し、また硫酸塩を形成す
る。この結果、鉛，イオウは上記被膜で捕足される。According to the present invention, the metal oxide having a perovskite type crystal structure and the alcal earth carbonate of the above-mentioned porous coating react with lead and sulfur in the combustion exhaust gas to form a perovskite metal oxide in which lead is solid-dissolved. It also forms sulfates. As a result, lead and sulfur are trapped by the film.
また、上記被膜のペロブスカイト型結晶構造の金属酸化
物の触媒活性によって、炭化水素，一酸化炭素の不均化
反応が生じにくいため、カーボンの析出が抑制され、従
ってカーボンと電極層との反応が防止されるのである。In addition, the catalytic activity of the metal oxide having the perovskite type crystal structure of the above-mentioned coating makes it difficult for the disproportionation reaction of hydrocarbons and carbon monoxide to occur, so that the precipitation of carbon is suppressed and therefore the reaction between carbon and the electrode layer is suppressed. It is prevented.
このように、本発明によれば、排気ガス中の成分が電極
層と反応することによる電極層の劣化を防止することが
でき、従って従来に比べて応答性の低下を抑えることが
可能となる。As described above, according to the present invention, it is possible to prevent the deterioration of the electrode layer due to the reaction of the components in the exhaust gas with the electrode layer, and it is possible to suppress the deterioration of the responsiveness as compared with the conventional case. .
以下本発明を具体的実施例により詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to specific examples.
第１図において、１は酸素イオン伝導性金属酸化物から
なる固体電解質素子で、ZrO2,CeO2等の金属酸化物70〜9
7モル％に２価又は３価の金属酸化物を30〜３モル％固
溶させた緻密な焼結体である。この素子１の燃焼排気ガ
スにさらされる側の外周面には多孔性電極層２としてPt
を蒸着、ペースト焼付，無電解メッキ等の方法で付着さ
せてある。また酸素標準ガスにさらされる内周面には、
ペースト焼付，無電解メッキ等の方法で同様にPtを付着
させた多孔性電極層３を設けてある。さらに、電極層２
上には、多孔性保護被膜４が電極保護の目的でAl2O3,Mg
O・Al2O3,ZrO2等の耐熱性金属酸化物をプラズマ溶射法
等により付着させてある。さらに保護被膜４上には本発
明において最も重要なペロブスカイト型結晶構造を有す
る金属酸化物例えはLa0.8Sr0.2C0O3,La0.6Sr0.4MnO3等
をスラリー化し、塗布した多孔性被膜５を付着させてあ
る。保護被膜４は公知の技術であるため説明を省くが、
本発明の被膜５についてより詳細に説明する。In FIG. 1, reference numeral 1 denotes a solid electrolyte element made of an oxygen ion conductive metal oxide, which is a metal oxide 70 to 9 such as ZrO 2 or CeO 2.
It is a dense sintered body in which 30 to 3 mol% of a divalent or trivalent metal oxide is dissolved in 7 mol%. A Pt is formed as a porous electrode layer 2 on the outer peripheral surface of the element 1 exposed to the combustion exhaust gas.
Are deposited by a method such as vapor deposition, paste baking, and electroless plating. Also, on the inner peripheral surface exposed to oxygen standard gas,
Similarly, a porous electrode layer 3 to which Pt is attached is provided by a method such as paste baking or electroless plating. Furthermore, the electrode layer 2
A porous protective film 4 is formed on the upper surface for the purpose of protecting the electrode with Al 2 O 3 and Mg.
A heat resistant metal oxide such as O · Al 2 O 3 and ZrO 2 is attached by a plasma spraying method or the like. Furthermore, a metal oxide having a perovskite type crystal structure, which is the most important in the present invention, such as La 0.8 Sr 0.2 C 0 O 3 or La 0.6 Sr 0.4 MnO 3 is slurried on the protective film 4 and applied as a porous film 5. Is attached. Since the protective film 4 is a known technique, its explanation is omitted.
The coating 5 of the present invention will be described in more detail.
本発明のペロスカイト型金属酸化物は、例えばCo（N
O3）２・6H2O,La（NO3）３・6H2O,Sr（NO3）２を水に溶
かし混合水溶液を準備する。この水溶液に過剰量のNa2C
O3を加えた水溶液を少しずつ滴下させて共沈物を得る。
この時、Co（OH）3,La（OH）3,SrCO3の共沈物が得られ
るため、この共沈物を過しよく洗浄する。次に、この
共沈物を真空凍結乾燥させ、600℃程度の温度で仮焼成
し粉砕後、さらに800〜900℃程度で焼成し、La0.8Sr0.2
C0O3の粉末を得る。この粉末に対して10wt％のアルカリ
土類炭酸塩であるSrCO3を混合し、この混合物をアルミ
ナゾル，硝酸アルミニウム又は硝酸ランタンを添加した
水に溶かし泥漿化し、厚さ10〜30μｍ程度上記の被膜４
の表面に塗布する。その後乾燥し、700〜800℃程度で焼
付けて被膜する。The perovskite-type metal oxide of the present invention is, for example, Co (N
O 3) 2 · 6H 2 O , La (NO 3) 3 · 6H 2 O, Sr a (NO 3) 2 to prepare a mixed aqueous solution dissolved in water. Excess Na 2 C in this aqueous solution
A coprecipitate is obtained by gradually dropping an aqueous solution containing O 3 .
At this time, since a coprecipitate of Co (OH) 3 , La (OH) 3 and SrCO 3 is obtained, the coprecipitate is washed excessively. Next, this coprecipitate is freeze-dried in a vacuum, calcinated at a temperature of about 600 ° C., crushed, and further calcined at about 800 to 900 ° C. to obtain La 0.8 Sr 0.2.
A powder of C 0 O 3 is obtained. This powder was mixed with 10 wt% of an alkaline earth carbonate, SrCO 3, and the mixture was dissolved in water containing alumina sol, aluminum nitrate or lanthanum nitrate to form a sludge, and the thickness of the coating film was about 10 to 30 μm.
Apply to the surface of. After that, it is dried and baked at about 700 to 800 ° C to form a film.
なお、アルカリ土類金属炭酸塩は0.1ないし20wt％、好
ましくは1.0〜10wt％含まれるのが好ましい。0.1wt％以
下ではＳのトラップ効果が低下し、20wt％以上になると
ペロブスカイト型金属酸化物の触媒活性が低下する。The alkaline earth metal carbonate is contained in an amount of 0.1 to 20 wt%, preferably 1.0 to 10 wt%. If it is 0.1 wt% or less, the trapping effect of S is lowered, and if it is 20 wt% or more, the catalytic activity of the perovskite type metal oxide is lowered.
次に、耐久実験結果について説明をする。Next, the results of the durability test will be described.
６気筒2.8のエンジンを用いて、これを4300r.p.m.で
運転し、検出器温度750℃，空燃比（Ａ／Ｆ）12,ガソリ
ン中のPb量100mg／U.S.Gの劣化加速条件にて400時間ま
で実施した。この耐久条件後、６気筒2.8のエンジン
を用い1500r.p.m.で運転し、検出器温度400℃、空燃比
をλ0.9→1.1に変化させた際の応答時間を第２図に、ま
た内部抵抗を第３図に示す。なお、第２図中、従来例は
本発明の被膜５を備えないものである。第２図からわか
るように、本発明は応答性が極めて安定しており、初期
値を400H後も維持している。ここで従来の200時間まで
の応答性向上は、Pbもしくはエンジンオイル中のS,排気
ガス中のPb、HCもしくはＣがPt電極層と反応し凝集が進
行することによる一見ガス応答性が速くなることによ
る。しかし電極層の劣化は進んでいるため、内部抵抗が
増加している。しかし、200時間以後はさらに凝集によ
る劣化が進行し、電極層の触媒活性機能が低下するこ
と、不着物（Pb,P,S,Ca,Zn等の化合物）の推積による電
極層の保護被膜の目詰まり等により応答性が遅くなるこ
とをあらわしている。一方、本発明のものは、電極層が
Pb,S,HC,C等と反応するのをペロブスカイト型金属酸化
物により防止される。また、このペロブスカイト型金属
酸化物より成る被膜は前記の保護被膜４より１オーダ大
きい細孔容積を有しているため、この保護被膜４の目詰
りを生じることなく、ガス拡散を阻害することもない。Using a 6-cylinder 2.8 engine, this was operated at 4300 rpm, detector temperature 750 ° C, air-fuel ratio (A / F) 12, Pb amount in gasoline 100mg / USG up to 400 hours under accelerated deterioration conditions Carried out. After this endurance condition, using a 6-cylinder 2.8 engine and operating at 1500 rpm, the response time when the detector temperature was 400 ° C and the air-fuel ratio was changed from λ0.9 to 1.1 is shown in Fig. 2 and the internal resistance was changed. Is shown in FIG. In FIG. 2, the conventional example does not include the coating 5 of the present invention. As can be seen from FIG. 2, the responsiveness of the present invention is extremely stable, and the initial value is maintained even after 400H. Here, the conventional improvement in responsiveness up to 200 hours is that the gas responsiveness is apparently faster because Pb or S in engine oil and Pb, HC or C in the exhaust gas react with the Pt electrode layer to promote aggregation. It depends. However, since the deterioration of the electrode layer is progressing, the internal resistance is increasing. However, after 200 hours, further deterioration due to aggregation progresses, the catalytic activity function of the electrode layer deteriorates, and the protective coating of the electrode layer due to accumulation of non-adherent substances (compounds such as Pb, P, S, Ca, Zn) It indicates that the responsiveness becomes slow due to clogging of. On the other hand, in the present invention, the electrode layer is
Reaction with Pb, S, HC, C, etc. is prevented by the perovskite type metal oxide. Further, since the film made of the perovskite type metal oxide has a pore volume larger than that of the protective film 4 by one order, the protective film 4 is not clogged and gas diffusion may be hindered. Absent.
次に、前記被膜５にアルカリ土類炭酸塩が含まれている
ことによる効果を説明する。検出器の構成は前述したと
おり、被膜の構成としては化学式のLa0.8Sr0.2C0O3のペ
ロブスカイト型結晶構造の金属酸化物とこれに対し10wt
％のSrCO3とを含むものである。Next, the effect of the coating film 5 containing an alkaline earth carbonate will be described. As described above, the detector is composed of a metal oxide of the chemical formula La 0.8 Sr 0.2 C 0 O 3 with a perovskite crystal structure and 10 wt% thereof.
% SrCO 3 is included.
また、上記のSrCO3を含まない上記化学式ペロブスカイ
ト型結晶構造の金属酸化物で構成した被膜を備えた検出
器を比較例として用意した。耐久条件は次のようであ
る。即ち、2.6６気筒エンジンを1600r.p.m.で理論空
燃比で運転し、検出器温度850℃で50時間まで実施し
た。使用したガソリンは1.2mg／のPbを含むものであ
る。In addition, a detector provided with a film made of the above-mentioned metal oxide having the chemical perovskite type crystal structure containing no SrCO 3 was prepared as a comparative example. The durability conditions are as follows. That is, a 2.66 cylinder engine was operated at a stoichiometric air-fuel ratio at 1600 rpm and the detector temperature was 850 ° C. for up to 50 hours. The gasoline used contained 1.2 mg / Pb.
結果を第１表に示す。The results are shown in Table 1.
第１表から理解されるごとく、アルカリ土類炭酸塩を含
むものではS,Pbの補足効果が大きいことがわかる。 As can be seen from Table 1, those containing alkaline earth carbonate have a large supplemental effect of S and Pb.
なお、本発明は、次のごとき変形が可能である。The present invention can be modified as follows.
（１）触媒活性を有したペロブスカイト型結晶構造の金
属酸化物としては、化学式 La1-xSrxMO3（但し、ｘは0.1ないし0.5であり、ＭはCo,
Ni,Mnより選ばれた少なくとも一種である）と表わされ
るものが用いられる。(1) The metal oxide having a perovskite type crystal structure having catalytic activity has a chemical formula of La 1- xSrxMO 3 (where x is 0.1 to 0.5, M is Co,
At least one selected from Ni and Mn) is used.
（２）アルカリ土類金属炭酸塩としては、SrCO3の他にB
aCO3,CaCO3,MgCO3,BaCO3でもよい。(2) As alkaline earth metal carbonates, in addition to SrCO 3 , B
aCO 3, CaCO 3, may be MgCO 3, BaCO 3.
（３）固体電解質素子は一端が開口し他端が閉じたコッ
プ形状に限らず、円板形状等でもよい。(3) The solid electrolyte element is not limited to the cup shape in which one end is open and the other end is closed, and may be a disk shape or the like.
第１図は本発明の一実施例を示す断面図、第２図および
第３図は本発明の効果の説明に供する特性図である。 １……固体電解質素子,2,3……電極層,4……保護被膜,5
……多孔性被膜。FIG. 1 is a sectional view showing an embodiment of the present invention, and FIGS. 2 and 3 are characteristic diagrams for explaining the effect of the present invention. 1 ... Solid electrolyte element, 2, 3 ... Electrode layer, 4 ... Protective coating, 5
... Porous coating.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 雅寿 愛知県刈谷市昭和町１丁目１番地 日本電 装株式会社内 (72)発明者 颯田 耕三 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (72)発明者 長谷川 英雄 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (72)発明者 木村 希夫 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (56)参考文献 特開 昭59−222754（ＪＰ，Ａ) 特開 昭54−146691（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masatoshi, 1-1, Showa-cho, Kariya city, Aichi Prefecture, Nihon Denso Co., Ltd. Area 1 Toyota Central Research Institute Co., Ltd. (72) Hideo Hasegawa Hideo Hasegawa 41, Nagakute-cho, Aichi-gun Nagakute-cho Ai Prefecture Toyota Central Research Institute Co., Ltd. 1 in 41, Yokomichi, Chozaji, Machizai, Toyota Central Research Institute Co., Ltd. (56) Reference JP-A-59-222754 (JP, A) JP-A-54-146691 (JP, A)
Claims (3)
電解質素子と、該素子の一方の側の酸素標準ガスと接触
する表面に設けた多孔性電極層と、前記素子の他方の側
の燃焼排気ガスと接触する表面に設けた多孔性電極層
と、該排気ガス側の電極層の表面に形成され、触媒活性
を有したペロブスカイト型結晶構造の金属酸化物および
アルカリ土類炭酸塩を含む多孔性被膜を包含したことを
特徴とする酸素濃度検出器。1. A solid electrolyte element composed of an oxygen ion conductive metal oxide, a porous electrode layer provided on a surface of the element in contact with an oxygen standard gas, and combustion on the other side of the element. A porous electrode layer provided on a surface in contact with exhaust gas, and a porous layer formed on the surface of the electrode layer on the exhaust gas side and containing a metal oxide and an alkaline earth carbonate having a catalytically active perovskite crystal structure. An oxygen concentration detector characterized in that the oxygen concentration detector comprises a protective film.
物は、化学式がLa1-xSrxMO3であり、式中ｘは0.1ないし
0.5であって、Ｍは、Co,Ni,Mnより選ばれた少なくとも
一種であり、前記アルカリ土類炭酸塩はSrCO3であるこ
とを特徴とする特許請求の範囲第１項記載の酸素濃度検
出器。2. The metal oxide having a perovskite crystal structure has a chemical formula of La 1- xSrxMO 3 , where x is 0.1 to 0.1.
0.5, M is at least one selected from Co, Ni, Mn, and the alkaline earth carbonate is SrCO 3 , wherein the oxygen concentration detection according to claim 1. vessel.
物は化学式La0.8Sr0.2C0O3であり、前記SrCO3はLa0.8Sr
0.2C0O3に対し0.1〜20wt％添加されていることを特徴と
する特許請求の範囲第２項記載の酸素濃度検出器。3. The metal oxide having a perovskite crystal structure has a chemical formula of La 0.8 Sr 0.2 C 0 O 3 , and the SrCO 3 is La 0.8 Sr.
The oxygen concentration detector according to claim 2, wherein 0.1 to 20 wt% is added to 0.2 C 0 O 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61164939A JPH0668479B2 (en) | 1986-07-14 | 1986-07-14 | Oxygen concentration detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61164939A JPH0668479B2 (en) | 1986-07-14 | 1986-07-14 | Oxygen concentration detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6319549A JPS6319549A (en) | 1988-01-27 |
| JPH0668479B2 true JPH0668479B2 (en) | 1994-08-31 |
Family
ID=15802715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61164939A Expired - Lifetime JPH0668479B2 (en) | 1986-07-14 | 1986-07-14 | Oxygen concentration detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0668479B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4438962A1 (en) * | 1994-10-31 | 1996-05-02 | Hoechst Ag | Molding compound for processing sinterable polymer powder by injection molding |
| DE10260849B4 (en) * | 2002-12-23 | 2017-05-24 | Robert Bosch Gmbh | probe |
| JP2010038600A (en) * | 2008-08-01 | 2010-02-18 | Nippon Soken Inc | Gas sensor element |
| CN103529102A (en) * | 2013-10-25 | 2014-01-22 | 郑龙华 | Multi-layer composite protective layer of oxygen sensor and manufacturing method thereof |
-
1986
- 1986-07-14 JP JP61164939A patent/JPH0668479B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6319549A (en) | 1988-01-27 |
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