WO1999030328A1 - Couches minces d'electrolyte solide et capteurs de gaz fabriques au moyen de ces couches - Google Patents

Couches minces d'electrolyte solide et capteurs de gaz fabriques au moyen de ces couches Download PDF

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Publication number
WO1999030328A1
WO1999030328A1 PCT/JP1998/005475 JP9805475W WO9930328A1 WO 1999030328 A1 WO1999030328 A1 WO 1999030328A1 JP 9805475 W JP9805475 W JP 9805475W WO 9930328 A1 WO9930328 A1 WO 9930328A1
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WO
WIPO (PCT)
Prior art keywords
thin film
solid electrolyte
electrolyte thin
gas sensor
layer
Prior art date
Application number
PCT/JP1998/005475
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English (en)
Japanese (ja)
Inventor
Kiyotaka Shindo
Tomoko Hirai
Original Assignee
Mitsui Chemicals, Inc.
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 Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Publication of WO1999030328A1 publication Critical patent/WO1999030328A1/fr

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    • 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
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides

Definitions

  • the present invention relates to a solid electrolyte thin film having excellent moisture resistance and high density, and a gas sensor using the same. More specifically, the present invention relates to a lithium ion having high moisture resistance and high density.
  • the present invention relates to a solid electrolyte thin film composed of a conductive glassy oxide and a gas sensor using the solid electrolyte thin film with high humidity resistance, high sensitivity, high accuracy, and high speed response.
  • Solid electrolytes are used in all-solid-state electrochemical devices such as gas sensors, solid-state batteries, and electronic mixers, and their use as decomposed materials is being promoted. Among these areas, especially C 0 2, N 0 x, S ⁇ x, can the measurement of NH 3 of which the gas concentration with high accuracy and high sensitivity, high moisture resistance Contact and high-speed response was or There is an urgent need to realize a compact gas sensor that has high conductivity.Solid electrolytes that have been used in the past have been used to conduct Alkalion ions, including Alkaryons such as Li + and Na +. This type is called a solid electrolyte.
  • the internal resistance of the all-solid-state electrochemical device increases in proportion to the thickness of the solid electrolyte.
  • Most of the alkali ion conductors used so far are crystalline ceramics sintered compacts, which are usually used as solid electrolytes in bulk form. . Therefore, when the solid electrolyte is used in a bulk form, the internal resistance is more than 100 to 1000 times larger than when the solid electrolyte is used. Therefore, when a bulk solid electrolyte is used, the solid electrolyte that can be used was originally limited to a solid electrolyte having a high ion conductivity.
  • the oxide composition was further changed (L i 20 )-(S i 0 2 ) -M (M is N b 2 0 3, T a 2 03 s or the W 0 3) or al compositions of Na Ru ternary is that is capable thinned.
  • this composition may also generate electron conduction at the same time, if it is used for a gas sensor, a decrease in sensitivity is expected.
  • the object of the present invention is to have excellent moisture resistance and high denseness.
  • An object of the present invention is to provide a lithium ion conductive glassy solid electrolyte thin film.
  • a second object of the present invention is to provide a solid electrolyte type gas sensor having high moisture resistance, high sensitivity, high accuracy, and high speed response using the lithium ion conductive glass thin film solid electrolyte. It is to be provided.
  • the values of x, y, and z above are 0.1 ⁇ ⁇ ⁇ 0.5, 0.1 ⁇ y ⁇ 0.8, and 0.01 ⁇ z ⁇ 0.5, respectively.
  • the oxide thin film is used, the moisture resistance is further increased and the denseness is also increased. It is more desirable that the thin film be formed by a sputtering method and have a thickness in the range of 0.1 to 10 ⁇ m as a solid electrolyte.
  • the present invention also relates to a gas sensor using the solid electrolyte membrane, and more particularly to a carbon dioxide gas sensor. [Brief description of drawings]
  • FIG. 1 is a cross-sectional structural view of a gas sensor showing one embodiment of the present invention. [Best mode for carrying out the invention]
  • the solid electrolyte membrane according to the present invention is an oxide composition represented by a general formula (L i 20 ) X i (S i 0 z ) y — M z.
  • a 1 2 0 3 is structure of oxygen 4 coordinating glass quality thin film, Chi Sunawa [A 1 0 4] - the Ru with the idea we are ing. This This, together if by crosslinking the non-crosslinked oxygen in the glass REDUCE diffusion of water molecules, [A 1 0 4] - is water to strengthen Lee on-coupling force between the L i + It is thought to suppress the reaction of.
  • the values of X, y, and z are preferably 0.1 ⁇ ⁇ ⁇ 0.5, 0.1 ⁇ y ⁇ 0.8, and 0.0 1 ⁇ z ⁇ , respectively. 0.5. More preferably, 0.15 ⁇ X ⁇ 0.40, 0.2 ⁇ y ⁇ 0.75, and 0.02 ⁇ z ⁇ 0.45.
  • glass quality oxide composition of the present invention in addition to the oxides of, S n 0 2 to the al, C r 2 03 T a 2 0 have N b 2 0 had M n O have L a 2 0 have P b O, M g O, this one least for the well of the B a O or et ing group, which Ru coexist in the ra purpose is not such impaired scope of the present invention I can do it.
  • the oxide composition can be measured by an inductively coupled plasma (ICP) emission spectrometry.
  • ICP inductively coupled plasma
  • the fact that the film is glassy is determined by analyzing the X-ray diffraction method as showing that no beak appears in the diffraction intensity curve and that the film becomes a blade. It can also be judged by observing the cross section of the thin film with a scanning electron microscope (SEM) and by not finding any crystal grain boundaries.
  • SEM scanning electron microscope
  • the thickness of the lithium ion conductive glassy thin film is preferably from 0.1 to: L0 / m, more preferably from 0.2 to 5 m. When the thickness of the thin film is within this range, it is preferable because the internal resistance is small when used for a sensor, and thus high sensitivity can be obtained.
  • a method for producing a solid electrolyte thin film from such a glassy oxide composition is to first sufficiently mix the oxide composition, form a sintered body, and then use the sintered body. It is recommended to use a film forming method such as the snorting method, the ion plating method, the ion beam evaporation method, the CVD method, the vacuum evaporation method, and the sol-gel method. I can do it.
  • the oxide composition does not shift and the formed thin film is rapidly cooled. Since a glassy and dense thin film can be obtained, the sputtering ring method is the most preferable thin film forming method.
  • Spa jitter is not particularly limited Li in g conditions, for example, A r / 0 2 (volume ratio) of 1:.. 1, scan Roh Tsu evening Li in g pressure 0 133 ⁇ 1 33 (P a)
  • the input power can be set in the range of 1.5 to 5.5 (W / cm 2 ).
  • the thin film obtained by the sputtering method is dense and, unlike the film of a conventional ceramics sintered body, can suppress gas permeation. Therefore, the fluctuation of the sensor output can be minimized.
  • the gas sensor according to the present invention uses a solid electrolyte thin film formed from the above-mentioned glassy oxide composition, and includes a carbon dioxide gas sensor, a sulfur oxide gas sensor, and a nitrogen oxide gas sensor. It can be used for gas sensors such as ammonia gas sensor.
  • the preferred structure of the gas sensor is the laminate structure described below. That is, one side of the oxygen ion conductive substrate A detection electrode layer composed of the solid electrolyte thin film, the detection substance layer, and the first metal electrode layer is stacked in this order on the surface of the substrate, and is opposite to the oxygen-ion conductive substrate. The second metal electrode layer and the first metal layer are similarly laminated on the surface in this order, and the laminated body has a structure integrated as a whole.
  • the sensing electrode layer composed of the sensing substance layer and the first metal electrode layer may be stacked in the reverse order, that is, in the order of the first metal electrode layer and the sensing substance layer. .
  • the sensing electrode layer side is arranged so as to be in contact with the measurement atmosphere, and the heater side is so arranged as to be in contact with a reference atmosphere such as the atmosphere.
  • oxygen-ion conductive substrate for example, it is possible to use a stabilized zirconium or the like, and a solid electrolyte thin film is formed on one surface thereof.
  • the sensing substance layer is formed by a metal carbonate that dissociates with carbon dioxide gas.
  • the metal carbonate may be at least one of lithium carbonate, sodium carbonate, potassium carbonate, barium carbonate, strontium carbonate, and calcium carbonate. The use of lithium carbonate is particularly preferred.
  • This layer is formed into a thin film, and its thickness is generally in the range of 0.01 to 3 mm.
  • It may be formed of lithium amide (LiNH 2 ) or the like.
  • the first electrode is a gas detection electrode for measuring an electromotive force depending on the gas concentration
  • the second electrode functions as a reference electrode.
  • Each electrode is usually formed by a method such as sputtering using a noble metal such as platinum, gold, or silver.
  • a conductive adhesive such as gold paste is used for the second electrode, and the aluminum adhesive substrate and the oxygen ion conductive substrate are adhered by the conductive adhesive. You may combine them.
  • a Pt film serving as a heating source may be formed on the alumina substrate.
  • the material of the heater prevents heat diffusion under high temperature, so the range of choice of the heater material is expanded.
  • the second electrode surface is bonded to the surface of the aluminum substrate opposite to the surface on which the Pt film is formed, so that the second electrode and the heater do not come into direct contact with each other.
  • a pair of gold electrodes was formed from a certain distance by the sputtering ring method. Thereafter, the temperature is changed in a tube furnace, and the frequency between the pair of gold electrodes is changed between 10 Hz and 5 MHz by an impedance analyzer, whereby the complex impedance is changed. Analysis was performed. Then, the conductivity of the lithium ion conductive glass thin film was determined from the total resistance component.
  • a lithium ion conductive glassy thin film was prepared in the same manner as in Example 1 except that the composition of the thin film was changed, and the conductivity was evaluated in the same manner as in Example 1 using the thin film. Table 1 shows the results.
  • composition (molar ratio) of the thin film was as follows.
  • a lithium ion conductive glassy thin film was prepared in the same manner as in Example 1 except that the composition of the thin film was changed, and the conductivity was evaluated in the same manner as in Example 1 using the thin film. Table 1 shows the results.
  • composition of the thin film was as follows.
  • the gas sensor element 10 shown in FIG. 1 was manufactured by the method described below with reference to the drawings.
  • an yttria (3 mol%) stabilized zirconium substrate (YSZ substrate: 3 mm ⁇ 3 mm ⁇ 0.3 mm) was used as the oxygen ion conductive substrate 5.
  • a solid electrolyte thin film 4 was formed on the surface.
  • This film L i 2 0, S i 0 2, and A 1 2 0 3 and the using a predetermined amount mixed sintered body te r g e t preparative oxygen reactive RF Spa jitter Li in g method With a thickness of about 1.5 ⁇ m
  • Et al on the solid electrolyte thin film layer 4 is, by applying a Li Ji U Muaruko key shea de solution, Ri by the heat decomposing this carbonate Li Ji um (L i C 0 3) or al of that thickness of about A metal carbonate layer 3 of 2 zm was formed.
  • a first electrode 2 made of gold was formed thereon by a snow ring method.
  • an aluminum substrate 8 made of platinum was formed on the surface of the aluminum substrate 7 (3 mm ⁇ 3 mm ⁇ 0.3 mt) by a sputtering ring method.
  • the back surface of the alumina substrate 7 on which the heater 8 is formed and the back surface of the oxygen-ion conductive substrate 5 on which the first electrode 2, the metal carbonate layer 3, and the solid electrolyte thin film 4 are formed are connected to the second electrode 6.
  • a gas sensor element 10 was fabricated by bonding together with a gold paste.
  • the sensor sensitivity measurement uses a voltmeter in which air with the carbon dioxide concentration changed from 200 ppm to 1% flows over sensor 10 and is connected to a lead wire. This was done by measuring the change in electromotive force in step 1.
  • sensor element 10 was left in an environment of 60 ° C and 92% RH for a certain period of time. The change in sensitivity was examined. Table 2 shows the measurement results.
  • a carbon dioxide sensor was prepared in the same manner as in Example 9 except that the composition of the solid electrolyte thin film 4 was changed, and then sensor sensitivity was measured. The results are shown in Table 2.
  • composition of the thin film used was as follows.
  • the L i 2 0, S i 0 2 in a composition of the third oxide was added a predetermined amount to such a glass substance, to the this was or thinned Therefore, the obtained solid electrolyte thin film has excellent moisture resistance and high denseness, and is suitable for all gas sensors, solid-state batteries, electoric aperture chromic elements, etc. It can be used for solid-state electrochemical devices.
  • the gas sensor using this solid electrolyte thin film as a lithium ion conductive electrolyte is more glassy than a crystalline ceramics sintered body, so it is denser. High sensitivity and excellent sensitivity and accuracy.
  • the vitreous thin film has excellent moisture resistance
  • the gas sensor provided with the thin film can be used under high temperature and high humidity conditions without taking any particular measures to block moisture. It has a stable output with little change over time, and has a high-speed response. In addition, miniaturization is possible, thereby reducing power consumption and excellent mass productivity.
  • this gas sensor uses a solid electrolyte compared to conventional semiconductor gas sensors, the selectivity of the detection gas is high, and carbon dioxide, nitrogen oxide, sulfur dioxide, ammonia gas, etc. It can be suitably used as a gas sensor for such applications.

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  • Measuring Oxygen Concentration In Cells (AREA)

Abstract

Couches minces d'électrolyte solide possédant d'excellentes caractéristiques de résistance à l'humidité et de densité élevée et fabriquées à partir de compositions d'oxyde vitreuses représentées par la formule suivante: (Li2O)x-(SiO2)y-Mz (dans laquelle M représente un élément sélectionné dans Al2O3, ZrO2, TiO2, ZnO et CaO; x, y et z sont des rapports molaires répondant à l'équation: x + y + z = 1). Ces couches peuvent conduire des ions lithium et leur intégration dans des capteurs de gaz en tant qu'électrolyte permet de fabriquer des capteurs de gaz de dimensions réduites présentant des caractéristiques excellentes de résistance à l'humidité, de sensibilité, de haute précision et de réactivité rapide.
PCT/JP1998/005475 1997-12-11 1998-12-04 Couches minces d'electrolyte solide et capteurs de gaz fabriques au moyen de ces couches WO1999030328A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP34117997 1997-12-11
JP9/341179 1997-12-11

Publications (1)

Publication Number Publication Date
WO1999030328A1 true WO1999030328A1 (fr) 1999-06-17

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012517840A (ja) * 2009-02-17 2012-08-09 シーメンス アクチエンゲゼルシヤフト 内視鏡カプセル
JP2021039049A (ja) * 2019-09-05 2021-03-11 矢崎エナジーシステム株式会社 アンモニアガスセンサ

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5960814A (ja) * 1982-09-29 1984-04-06 株式会社日立製作所 酸化リチウム系非晶質イオン導電体
JPH06265520A (ja) * 1993-03-15 1994-09-22 Nippon Ceramic Co Ltd Ｃｏ２センサ
WO1995034515A1 (fr) * 1994-06-13 1995-12-21 Mitsui Petrochemical Industries, Ltd. Couche vitreuse electro-conductrice par inclusion d'ions lithium et detecteur de co2 integrant cette couche
JPH08178889A (ja) * 1994-12-21 1996-07-12 Tokuyama Corp 固体電解質型ガスセンサ素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5960814A (ja) * 1982-09-29 1984-04-06 株式会社日立製作所 酸化リチウム系非晶質イオン導電体
JPH06265520A (ja) * 1993-03-15 1994-09-22 Nippon Ceramic Co Ltd Ｃｏ２センサ
WO1995034515A1 (fr) * 1994-06-13 1995-12-21 Mitsui Petrochemical Industries, Ltd. Couche vitreuse electro-conductrice par inclusion d'ions lithium et detecteur de co2 integrant cette couche
JPH08178889A (ja) * 1994-12-21 1996-07-12 Tokuyama Corp 固体電解質型ガスセンサ素子

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012517840A (ja) * 2009-02-17 2012-08-09 シーメンス アクチエンゲゼルシヤフト 内視鏡カプセル
US8918154B2 (en) 2009-02-17 2014-12-23 Siemens Aktiengesellschaft Endoscopic capsule
JP2021039049A (ja) * 2019-09-05 2021-03-11 矢崎エナジーシステム株式会社 アンモニアガスセンサ

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