JPH09127051A - Solid electrolyte-type oxygen pump - Google Patents

Solid electrolyte-type oxygen pump

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Publication number
JPH09127051A
JPH09127051A JP7286025A JP28602595A JPH09127051A JP H09127051 A JPH09127051 A JP H09127051A JP 7286025 A JP7286025 A JP 7286025A JP 28602595 A JP28602595 A JP 28602595A JP H09127051 A JPH09127051 A JP H09127051A
Authority
JP
Japan
Prior art keywords
platinum
electrode
solid electrolyte
fired
oxygen pump
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.)
Pending
Application number
JP7286025A
Other languages
Japanese (ja)
Inventor
Akihiro Yamashita
晃弘 山下
Nobuaki Murakami
信明 村上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Heavy Industries Ltd
Original Assignee
Mitsubishi Heavy Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Heavy Industries Ltd filed Critical Mitsubishi Heavy Industries Ltd
Priority to JP7286025A priority Critical patent/JPH09127051A/en
Publication of JPH09127051A publication Critical patent/JPH09127051A/en
Pending legal-status Critical Current

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a solid electrolyte-type oxygen pump in which the material resistance of a noble metal electrode itself and an electrode reaction resistance can be lowered simultaneously by providing a platinum net as an electrode collector on the noble metal electrode. SOLUTION: A platinum electrode 12 is formed on the inside surface of a solid- electrolyte cylindrical body 11, a platinum electrode 13 is formed on the outside surface, and platinum nets 14, 15 are formed respectively on the electrodes 12, 13. Voltage lead wires 16 are connected to the nets 14, 15, and they are connected to an external power supply 17. The cylindrical body 11 is formed in such a way that ZrO2 and Y2 O2 are mixed in a weight ratio of 86:14, that they are fired in the air so as to form a complex oxide, that the complex oxide is crushed by a ball mill, and wet- crushed further, pressurized by a mold, and that a molded body is fired in the air at about 150 deg.C for five hours. In addition, the inside and the outside of the cylindrical body 11 are coated with a platinum paste, the paste is fired at about 900 deg.C for one hour, and the electrodes 12, 13 are formed. The nets 14, 15 set about 80 meshes, they are bonded with a platinum paste, and the paste is fired in the air for about one hour. By this constitution, the material resistance of the electrodes themselves and an electrode reaction resistance can be lowered simultaneously.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】この発明は、固体電解質型酸
素ポンプの改良に関する。TECHNICAL FIELD The present invention relates to an improvement of a solid electrolyte type oxygen pump.

【０００２】[0002]

【従来の技術】図４は、固体電解質型酸素ポンプの作動
原理を示す。つまり、両面に空気側電極１，不活性ガス
側電極２を夫々設けた酸素イオン導電体３を、９００℃
から１０００℃の高温にし、この酸素イオン導電体３を
隔壁として、一方に空気、他方に窒素やアルゴン、ヘリ
ウム等の不活性ガスを導入し、前記空気側電極１を陽
極、不活性ガス側電極２を陰極として電圧を印加する
と、不活性ガス中に含まれる低濃度酸素が陰極で酸素イ
オン化し、酸素イオン導電体３を陽極へ拡散して再び酸
素ガスとなる。2. Description of the Related Art FIG. 4 shows the operating principle of a solid electrolyte type oxygen pump. That is, the oxygen ion conductor 3 provided with the air-side electrode 1 and the inert gas-side electrode 2 on both sides is heated to 900 ° C.
To 1000 ° C., an oxygen ion conductor 3 is used as a partition wall, air is introduced into one side, and an inert gas such as nitrogen, argon, or helium is introduced into the other side, and the air side electrode 1 serves as an anode and an inert gas side electrode When a voltage is applied with 2 as the cathode, the low concentration oxygen contained in the inert gas is oxygen-ionized at the cathode and diffuses the oxygen ion conductor 3 to the anode to become oxygen gas again.

【０００３】このように固体電解質型酸素ポンプは、電
圧印加により不活性ガス中の酸素濃度を制御する装置で
ある。固体電解質型酸素ポンプによる酸素の移動量は、
Ｆａｒａｄａｙの法則に従う。即ち、１クーロンの電気
量により１ｇ等量の酸素が移動する。このため、目的の
濃度に制御するためには、酸素イオン導電体に電圧を印
加した際に流れる電流値を制御する必要がある。As described above, the solid electrolyte type oxygen pump is a device for controlling the oxygen concentration in the inert gas by applying a voltage. The amount of oxygen transferred by the solid electrolyte type oxygen pump is
Follow Faraday's law. That is, 1 g of the equivalent amount of oxygen is transferred by the electric quantity of 1 coulomb. Therefore, in order to control the concentration to a desired value, it is necessary to control the value of current flowing when a voltage is applied to the oxygen ion conductor.

【０００４】酸素濃度制御特性を良好にするためには、
低い印加電圧で電流値が大きいことが必要条件である。
通常、窒素やアルゴン、ヘリウムなどの不活性ガス中の
酸素分圧は１０-4ａｔｍ程度であるが、この酸素分圧を
目的の酸素分圧まで低下させるのに必要な電流値は、不
活性ガスの流通量、即ち不活性ガス中の酸素濃度の絶対
量で決定するが、酸素イオン導電体に印加できる電圧値
は、酸素イオン導電体が電気分解しない範囲であること
から、この電圧範囲内で電流値が制限を受けることにな
る。In order to improve the oxygen concentration control characteristic,
It is a necessary condition that the current value is large at a low applied voltage.
Normally, the oxygen partial pressure in an inert gas such as nitrogen, argon, or helium is about 10 -4 atm, but the current value required to reduce this oxygen partial pressure to the target oxygen partial pressure is inactive. Although it is determined by the flow rate of gas, that is, the absolute amount of oxygen concentration in the inert gas, the voltage value that can be applied to the oxygen ion conductor is within this voltage range because the oxygen ion conductor does not undergo electrolysis. Will limit the current value.

【０００５】ＺｒＯ2 系の酸素イオン導電体の電圧範囲
は、約２Ｖ程度が限界である。従って、この電圧範囲内
での酸素濃度制御特性、即ち電流値制御を良好にするた
めには、固体電解質型酸素ポンプの抵抗値を可能な限り
低下させることが必要である。The voltage range of the ZrO 2 type oxygen ion conductor is limited to about 2V. Therefore, in order to improve the oxygen concentration control characteristic within this voltage range, that is, the current value control, it is necessary to reduce the resistance value of the solid electrolyte type oxygen pump as much as possible.

【０００６】[0006]

【発明が解決しようとする課題】固体電解質型酸素ポン
プの特徴は上述した通りであるが、固体電解質型酸素ポ
ンプの抵抗には、酸素イオン導電体と電極自身の材料抵
抗と電極反応抵抗から構成されるため、固体電解質型酸
素ポンプの抵抗低減には、これら二つの抵抗を減少させ
る必要がある。材料抵抗のうち酸素イオン導電体につい
ては、その膜厚を低下させることで材料抵抗を減少でき
るが、極端な膜厚低下は、固体電解質型酸素ポンプ自体
の強度低下を招く。従って、電極自身の材料抵抗と電極
反応抵抗を可能な限り低下させることが必要である。The characteristics of the solid electrolyte oxygen pump are as described above. The resistance of the solid electrolyte oxygen pump is composed of the oxygen ion conductor, the material resistance of the electrode itself, and the electrode reaction resistance. Therefore, in order to reduce the resistance of the solid electrolyte type oxygen pump, it is necessary to reduce these two resistances. Regarding the oxygen ion conductor of the material resistance, it is possible to reduce the material resistance by reducing the film thickness, but an extreme reduction in the film thickness causes a decrease in strength of the solid electrolyte oxygen pump itself. Therefore, it is necessary to reduce the material resistance of the electrode itself and the electrode reaction resistance as much as possible.

【０００７】この発明はこうした事情を考慮してなされ
たもので、貴金属電極上に電極集電体としての白金ネッ
トを設けることにより、電極自身の材料抵抗と電極反応
抵抗を同時に低下できる固体電解質型酸素ポンプを提供
することを目的とする。The present invention has been made in consideration of such circumstances, and by providing a platinum net as an electrode current collector on a noble metal electrode, it is possible to simultaneously reduce the material resistance of the electrode itself and the electrode reaction resistance. The purpose is to provide an oxygen pump.

【０００８】[0008]

【課題を解決するための手段】この発明は、酸素イオン
導電体を隔壁として、その両面に貴金属電極を設けた固
体電解質型酸素ポンプにおいて、前記貴金属電極上に電
極集電体としての白金ネットを設けたことを特徴とする
固体電解質型酸素ポンプである。The present invention provides a solid electrolyte type oxygen pump in which an oxygen ion conductor is used as a partition wall and noble metal electrodes are provided on both sides thereof, and a platinum net as an electrode current collector is provided on the noble metal electrode. It is a solid electrolyte type oxygen pump characterized by being provided.

【０００９】この発明においては、貴金属電極上に電極
集電体としての白金ネットを設けることにより、固体電
解質型酸素ポンプの抵抗値を低下することが可能とな
り、優れた酸素分圧制御特性を有する。In the present invention, by providing the platinum net as the electrode current collector on the noble metal electrode, the resistance value of the solid electrolyte type oxygen pump can be lowered and the oxygen partial pressure control characteristic is excellent. .

【００１０】[0010]

【発明の実施の形態】以下、この発明の一実施例を図１
を参照して説明する。図中の符番11は、組成がＺｒＯ2
−１４ｗｔ％Ｙ2 Ｏ3 である固体電解質円筒体である。
この固体電解質円筒体11の内面には貴金属電極としての
白金電極12が形成され、固体電解質円筒体11の外面には
貴金属電極としての白金電極13が形成されている。前記
白金電極12，13上には、夫々白金ネット14，15が形成さ
れている。なお、図中の符番16は白金ネット14，15に接
続した電圧リード線を、符番17はこの電圧リード線16に
設けられた外部電圧を示す。BRIEF DESCRIPTION OF THE DRAWINGS FIG.
This will be described with reference to FIG. Reference numeral 11 in the figure indicates that the composition is ZrO 2
A solid electrolyte cylinder is -14wt% Y 2 O 3.
A platinum electrode 12 as a noble metal electrode is formed on the inner surface of the solid electrolyte cylinder 11, and a platinum electrode 13 as a noble metal electrode is formed on the outer surface of the solid electrolyte cylinder 11. Platinum nets 14 and 15 are formed on the platinum electrodes 12 and 13, respectively. In the figure, reference numeral 16 indicates a voltage lead wire connected to the platinum nets 14 and 15, and reference numeral 17 indicates an external voltage provided on the voltage lead wire 16.

【００１１】こうした構成の固体電解質型酸素ポンプの
作製は次のように行う。まず、前記固体電解質円筒体11
は次のようにして作製する。つまり、ＺｒＯ2 酸化物と
Ｙ2Ｏ3 酸化物を重量分率にして、８６：１４の割合で
混合し、１５００℃，空気中で１０時間焼成してＺｒＯ
2 −Ｙ2 Ｏ3 複合酸化物を合成した後、ボールミルによ
り平均粒子径が約１μｍの酸化物となるように粉砕す
る。次に、粉砕したＺｒＯ2 −Ｙ2 Ｏ3 複合酸化物８５
重量部に対して、エチルアルコール１０重量部，エチレ
ングリコール５重量部を混合し、更に湿式で２４時間混
合粉砕を行う。つづいて、図２に示すような、金型21に
ＺｒＯ2 −１４ｗｔ％Ｙ2 Ｏ3 複合酸化物22を挿入し、
静水圧加圧装置により１０００Ｋｇｆ／ｃｍ2 の圧力で
１８０秒間加圧を行い成型体を得る。成型体は空気中１
３００℃で５時間焼成することにより、外径２０ｍｍ，
内径約１６ｍｍ、長さ約３００ｍｍの固体電解質円筒体
11を得る。The solid electrolyte type oxygen pump having such a structure is manufactured as follows. First, the solid electrolyte cylindrical body 11
Is manufactured as follows. That is, the ZrO 2 oxide and the Y 2 O 3 oxide are mixed in a weight ratio of 86:14, and the mixture is baked in air at 1500 ° C. for 10 hours to obtain ZrO 2.
After synthesizing the 2- Y 2 O 3 composite oxide, it is pulverized by a ball mill so that the oxide has an average particle diameter of about 1 μm. Next, the crushed ZrO 2 —Y 2 O 3 composite oxide 85
10 parts by weight of ethyl alcohol and 5 parts by weight of ethylene glycol are mixed with parts by weight, and the mixture is wet-mixed for 24 hours. Subsequently, as shown in FIG. 2, ZrO 2 -14 wt% Y 2 O 3 composite oxide 22 was inserted into the mold 21,
A hydrostatic pressure device is used to apply a pressure of 1000 Kgf / cm 2 for 180 seconds to obtain a molded product. Molded body is 1 in the air
By firing at 300 ° C for 5 hours, the outer diameter is 20 mm,
Solid electrolyte cylinder with inner diameter of about 16 mm and length of about 300 mm
Get 11

【００１２】次に、白金電極12，13及び白金ネット14，
15は次のようにして作製する。まず、固体電解質円筒体
11の内面，外面に白金ペーストを塗布し９００℃，空気
中で１時間焼成し、白金電極12，13を形成する。つづい
て、８０メッシュの白金ネット14，15を固体電解質円筒
体11の内面，外面に白金ペーストによって接着させ、空
気中で１時間焼成することにより白金電極12，13上に白
金ネット14，15を夫々形成させる。Next, the platinum electrodes 12, 13 and the platinum net 14,
15 is manufactured as follows. First, solid electrolyte cylinder
Platinum paste is applied to the inner and outer surfaces of 11 and fired at 900 ° C. in air for 1 hour to form platinum electrodes 12 and 13. Subsequently, 80 mesh platinum nets 14 and 15 are adhered to the inner and outer surfaces of the solid electrolyte cylindrical body 11 with platinum paste and baked in air for 1 hour to form platinum nets 14 and 15 on the platinum electrodes 12 and 13. Form each.

【００１３】図３は、上記実施例に係る固体電解質型酸
素ポンプの抵抗を、空気中８００℃において、白金ネッ
トを形成しない場合と比較した比抵抗を示す特性図であ
る。図３より白金ペーストのみの場合は比抵抗が１００
０Ω・ｃｍであるのに対し、この発明の場合は比抵抗が
１００Ω・ｃｍと約１／10に低下したことが確認でき
た。FIG. 3 is a characteristic diagram showing the resistance of the solid electrolyte type oxygen pump according to the above-mentioned embodiment at 800 ° C. in air as compared with the case where no platinum net is formed. From Fig. 3, the specific resistance is 100 when only platinum paste is used.
While it was 0 Ω · cm, it was confirmed that in the case of the present invention, the specific resistance was 100 Ω · cm, which was about 1/10.

【００１４】このように、上記実施例に係る固体電解質
型酸素ポンプによれば、固体電解質円筒体11の内面に白
金電極12を介して白金ネット14を設け、かつ固体電解質
円筒体11の外面に白金電極13を介して白金ネット15を設
けた構成になっているため、電極自身の材料抵抗と電極
反応抵抗を同時に低下することができる。As described above, according to the solid electrolyte type oxygen pump of the above embodiment, the platinum net 14 is provided on the inner surface of the solid electrolyte cylindrical body 11 via the platinum electrode 12 and the outer surface of the solid electrolyte cylindrical body 11 is provided. Since the platinum net 15 is provided via the platinum electrode 13, the material resistance of the electrode itself and the electrode reaction resistance can be simultaneously reduced.

【００１５】[0015]

【発明の効果】以上詳述したように本発明によれば、貴
金属電極上に電極集電体としての白金ネットを設けるこ
とにより、電極自身の材料抵抗と電極反応抵抗を同時に
低下できる、優れた酸素分圧制御特性を有する固体電解
質型酸素ポンプを提供できる。また、本発明は、例えば
窒素やアルゴン中の酸素濃度を極低濃度（ＰＯ2 ＝１０
-15 ａｔｍ程度）にすることが可能であるため、半導体
製造工程，合金化，熱処理等の酸素濃度管理を行うこと
ができる、高純度不活性ガス製造装置に応用できる。更
に、本発明は、ポンプ電流制御により所定の酸素濃度に
設定することが可能なため、発酵，微生物培養等の嫌気
性雰囲気の制御を行う酸素付加装置に応用できる。As described in detail above, according to the present invention, by providing a platinum net as an electrode current collector on a noble metal electrode, the material resistance of the electrode itself and the electrode reaction resistance can be simultaneously reduced. A solid electrolyte type oxygen pump having oxygen partial pressure control characteristics can be provided. In the present invention, for example, the oxygen concentration in nitrogen or argon is set to an extremely low concentration (PO 2 = 10).
-15 atm), it can be applied to a high-purity inert gas production apparatus capable of controlling the oxygen concentration in the semiconductor production process, alloying, heat treatment, etc. Further, the present invention can be set to a predetermined oxygen concentration by controlling the pump current, so that it can be applied to an oxygen addition device for controlling an anaerobic atmosphere such as fermentation and microbial culture.

【図面の簡単な説明】[Brief description of the drawings]

【図１】この発明の一実施例に係る固体電解質型酸素ポ
ンプの断面図。FIG. 1 is a sectional view of a solid electrolyte type oxygen pump according to an embodiment of the present invention.

【図２】この発明の一実施例に係る金型の説明図。FIG. 2 is an explanatory view of a mold according to an embodiment of the present invention.

【図３】白金電極のみ、及び白金電極に白金ネットを設
けた固体電解質型酸素ポンプの比抵抗の比較を示す特性
図。FIG. 3 is a characteristic diagram showing a comparison of specific resistances of a solid electrolyte type oxygen pump in which only a platinum electrode is provided and a platinum net is provided on the platinum electrode.

【図４】固体電解質型酸素ポンプの原理図。FIG. 4 is a principle diagram of a solid electrolyte type oxygen pump.

【符号の説明】[Explanation of symbols]

11…固体電解質円筒体、 12，13…白金電極、14，15
…白金ネット、 21…金型、22…ＺｒＯ2
−１４ｗｔ％Ｙ2 Ｏ3 複合酸化物。11 ... Solid electrolyte cylinder, 12,13 ... Platinum electrode, 14,15
… Platinum net, 21… Mold, 22… ZrO 2
-14wt% Y 2 O 3 composite oxide.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 酸素イオン導電体を隔壁として、その両
面に貴金属電極を設けた固体電解質型酸素ポンプにおい
て、前記貴金属電極上に電極集電体としての白金ネット
を設けたことを特徴とする固体電解質型酸素ポンプ。1. A solid electrolyte type oxygen pump having oxygen ion conductors as partition walls and noble metal electrodes provided on both surfaces thereof, wherein a platinum net as an electrode current collector is provided on the noble metal electrodes. Electrolyte-type oxygen pump.
JP7286025A 1995-11-02 1995-11-02 Solid electrolyte-type oxygen pump Pending JPH09127051A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7286025A JPH09127051A (en) 1995-11-02 1995-11-02 Solid electrolyte-type oxygen pump

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7286025A JPH09127051A (en) 1995-11-02 1995-11-02 Solid electrolyte-type oxygen pump

Publications (1)

Publication Number Publication Date
JPH09127051A true JPH09127051A (en) 1997-05-16

Family

ID=17699009

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7286025A Pending JPH09127051A (en) 1995-11-02 1995-11-02 Solid electrolyte-type oxygen pump

Country Status (1)

Country Link
JP (1) JPH09127051A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1333208C (en) * 2003-07-09 2007-08-22 松下电器产业株式会社 Air conditioner
JP2012508103A (en) * 2008-11-10 2012-04-05 プラクスエア・テクノロジー・インコーポレイテッド Oxygen separation assembly and method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5989256U (en) * 1982-12-07 1984-06-16 株式会社フジクラ oxygen sensor
JPH02210254A (en) * 1989-02-10 1990-08-21 Riken Corp Composite electrode and its production
JPH03130657A (en) * 1989-10-17 1991-06-04 Tokuyama Soda Co Ltd Oxygen sensor
JPH04142455A (en) * 1990-10-02 1992-05-15 Osaka Gas Co Ltd Nitrogen oxide sensor and using method thereof
JPH0696780A (en) * 1992-02-28 1994-04-08 Ceramatec Inc Electrochemical solid-state device for transport of ions through ceramic electrolyte and method formanufacture of condensed oxygen by using above device
JPH06123726A (en) * 1992-10-09 1994-05-06 Osaka Gas Co Ltd Nitrogen oxide sensor and its application method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5989256U (en) * 1982-12-07 1984-06-16 株式会社フジクラ oxygen sensor
JPH02210254A (en) * 1989-02-10 1990-08-21 Riken Corp Composite electrode and its production
JPH03130657A (en) * 1989-10-17 1991-06-04 Tokuyama Soda Co Ltd Oxygen sensor
JPH04142455A (en) * 1990-10-02 1992-05-15 Osaka Gas Co Ltd Nitrogen oxide sensor and using method thereof
JPH0696780A (en) * 1992-02-28 1994-04-08 Ceramatec Inc Electrochemical solid-state device for transport of ions through ceramic electrolyte and method formanufacture of condensed oxygen by using above device
JPH06123726A (en) * 1992-10-09 1994-05-06 Osaka Gas Co Ltd Nitrogen oxide sensor and its application method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1333208C (en) * 2003-07-09 2007-08-22 松下电器产业株式会社 Air conditioner
JP2012508103A (en) * 2008-11-10 2012-04-05 プラクスエア・テクノロジー・インコーポレイテッド Oxygen separation assembly and method

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