JPS62268063A - Manufacture of solid electrolyte - Google Patents
Manufacture of solid electrolyteInfo
- Publication number
- JPS62268063A JPS62268063A JP61108687A JP10868786A JPS62268063A JP S62268063 A JPS62268063 A JP S62268063A JP 61108687 A JP61108687 A JP 61108687A JP 10868786 A JP10868786 A JP 10868786A JP S62268063 A JPS62268063 A JP S62268063A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- solid electrolyte
- thermal spraying
- electrode
- forming
- 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
Links
- 239000007784 solid electrolyte Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000007751 thermal spraying Methods 0.000 claims abstract description 14
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 6
- 239000010409 thin film Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002254 LaCoO3 Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 3
- 238000001704 evaporation Methods 0.000 abstract 3
- 239000010408 film Substances 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 2
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 20
- 239000011148 porous material Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- -1 etc. Substances 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 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
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 241000219122 Cucurbita Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- FQNGRYARVHJPPC-UHFFFAOYSA-L [La].[Cr](=O)(=O)(O)O Chemical compound [La].[Cr](=O)(=O)(O)O FQNGRYARVHJPPC-UHFFFAOYSA-L 0.000 description 1
- 229910002084 calcia-stabilized zirconia Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 229910052963 cobaltite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- UUGIKJGDAUTOIF-UHFFFAOYSA-L dihydroxy(dioxo)manganese lanthanum Chemical compound [La].[Mn](=O)(=O)(O)O UUGIKJGDAUTOIF-UHFFFAOYSA-L 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高温固体電解質型燃料電池、高温電解装置用
電極として使用される固体電解質の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a solid electrolyte used as an electrode for a high-temperature solid electrolyte fuel cell or a high-temperature electrolyzer.
高温固体電解質型燃料電池の構成方法として第２図に示
すように溶射法による方式がある。As a method of constructing a high-temperature solid oxide fuel cell, there is a method using a thermal spraying method, as shown in FIG.
この場合には、固体電解質を形成する層を２００〜５０
０μｍとしなければガスの漏洩を防止できないし、場合
によっては水柱１０ｍの圧力下でも漏洩があり、燃料と
空気が直接燃・焼をおこして効率が著しく低下するばか
りでなく危険ででもある。また厚み２００〜３００μｍ
と云うのは燃料電池として使用する際にはイオン伝導の
抵抗が大きくさらに薄くすることが望まれる。In this case, the number of layers forming the solid electrolyte is 200 to 50.
Unless the thickness is 0 μm, gas leakage cannot be prevented, and in some cases, leakage may occur even under a pressure of 10 m of water column, causing direct combustion of fuel and air, which not only significantly reduces efficiency but is also dangerous. Also, the thickness is 200 to 300 μm
This is because when used as a fuel cell, the resistance to ion conduction is large and it is desirable to make the material thinner.
一方他の方法として第３図に示すように電気化学的蒸着
方法も提案されていて、この方法は封孔は完全にでき薄
膜化はできるが信頼性ある電池用の固体゛電解質を形成
するにはきわめて時間がか＼す、大量にか＼る固体電解
質材料軍池を生産することは不可能に近い。On the other hand, as another method, an electrochemical vapor deposition method has been proposed as shown in Figure 3. Although this method can completely seal the pores and form a thin film, it is insufficient to form a reliable solid electrolyte for batteries. It is extremely time consuming and nearly impossible to produce solid electrolyte materials in large quantities.
第２図において、０１は例えばアルミナ（Ａ４０３）の
約４箪厚の多孔質基材で、０２はこの通気孔であり全体
に占める割合は２０〜３０％を占める。この表面に燃料
極０３として酸化ニッケル（Ｎ１０ ）が約７０〜１０
０μｍアセチレン溶射で付けられている。この上にプラ
ズマ溶射にて２００．ｕｍ〜３００μｍの厚みに部分安
定化したジルコニア［： （ｚｒｏｚ）ａｔｅ（ｃａｏ
）ａｔ ）が固体電解質０４として付けられている。さ
らにその上層の０６は空気極であって厚み１００〜２０
０μｍのランタンクロム酸（ＬａＣｒ０３） がアセ
チレン溶射法にてつけられたものである。In FIG. 2, 01 is a porous base material made of, for example, alumina (A403) with a thickness of about 4 cm, and 02 is the ventilation hole, which accounts for 20 to 30% of the total. Approximately 70 to 10 nickel oxide (N10) is applied to this surface as the fuel electrode 03.
Attached by 0μm acetylene spraying. 200mm by plasma spraying on top of this. Partially stabilized zirconia [: (zroz)ate(cao) with a thickness of um~300μm
) at ) is attached as the solid electrolyte 04. Furthermore, the upper layer 06 is an air electrode with a thickness of 100 to 20
0 μm of lanthanum chromic acid (LaCr03) was applied by acetylene spraying.
次に第３図においては、厚さ２−のカルシア系部分安定
化ジルコニア［（ＺｒＯｔ）ａ、（ＣａＯ）ａｔ）を多
孔質基材０１ａとして、その上層には［１，７−の空気
極０６ａがあり、ランタンマンガン酸（Ｌ ａ ＭＴＩ
０２ ） をスラリーとして塗布後焼結している。Next, in FIG. 3, a 2-thick calcia-based partially stabilized zirconia [(ZrOt)a, (CaO)at) is used as a porous base material 01a, and the upper layer is a [1,7-] air electrode. 06a, lanthanum manganic acid (L a MTI
02) was applied as a slurry and then sintered.
その上、）Δてイツトリア系部分安定化ジルコニア ［
：（ＺｒＯｚ）ａｓｓ（ＹｔＯｉ）ａｔｅ）を電気化学
的に蒸着して固体電解質層０５ａ ４０〜５０μｍを
形成しさらにその上部には燃料極０５ａとして５０μｍ
のニツケルサーメツ） （Ｎｉ／Ｎ１ｐ）をコーティン
グし焼結して形成している。Moreover, ) Δtetriate partially stabilized zirconia [
:(ZrOz)ass(YtOi)ate) is electrochemically deposited to form a solid electrolyte layer 05a of 40 to 50 μm, and a fuel electrode 05a of 50 μm is formed on top of the solid electrolyte layer 05a.
It is formed by coating and sintering Ni (Ni/N1p).
燃料電池として固体電解質を応用する上にはできるだけ
薄い固体電解質の形成が必要である。In order to apply solid electrolytes to fuel cells, it is necessary to form solid electrolytes as thin as possible.
しかも固体電解の両側には多孔質の電極を介して燃料と
空気のガスが存在するので、お互いに通気（漏洩）する
ことがあってはならない。従来の溶射法では前述したよ
うにこの要求を満たすことはできない。Furthermore, since fuel and air gas exist on both sides of the solid electrolyte via porous electrodes, there must be no ventilation (leakage) between them. Conventional thermal spraying methods cannot meet this requirement as described above.
多数の電池を組み合わして大出力を得ようとするうえに
は数ｋｇ ／ ｅ、”の背圧に耐える必要すらある。し
かし一方多数の電池を徂み合わして使用する大出力の燃
料電池を構成するには大量生産方式が確立されることが
必要で従来の電気化学的蒸着方法では薄膜形成速度のき
わめておそい方式で必要厚みを得るには高価なものとな
り薄膜形成速度のスピードアップが必要とされている。In order to obtain high output by combining a large number of batteries, it is necessary to withstand back pressure of several kg/e. It is necessary to establish a mass production method to construct the structure, and conventional electrochemical deposition methods are extremely slow in forming thin films, and are expensive to obtain the required thickness, so it is necessary to speed up the thin film forming speed. has been done.
本発明は上記従来法における欠点を解消しうる固体電解
質の製造方法を提供しようとするものである。The present invention aims to provide a method for producing a solid electrolyte that can overcome the drawbacks of the above-mentioned conventional methods.
本発明は
■ 多孔質基材の表面に多孔′（電極材料を塗布まだは
溶射により形成する第１工程、
■ 該電極材料表面に固体電解質材料粉末を溶射して計
画厚さの大部分を占める厚さの固体電解質層を形成する
第２工程
■ 該固体電解質層の表面に固体電解質材料を化学蒸着
させて固体電解質層の厚さを計画厚さとすると同時に該
層を封孔する第３工程、及び
■ 上記封孔処理した固体電解質層の表面に、多孔質＠
極材料を塗布または溶射により形成する第４工程
よりなることを特徴とする固体電解質の製造方法である
。The present invention includes: (1) forming pores (electrode material is coated on the surface of a porous base material by thermal spraying); (2) solid electrolyte material powder is thermally sprayed onto the surface of the electrode material so as to occupy most of the planned thickness; A second step of forming a solid electrolyte layer with a certain thickness ■ A third step of chemically depositing a solid electrolyte material on the surface of the solid electrolyte layer to make the thickness of the solid electrolyte layer the planned thickness, and at the same time sealing the layer. and■ Porous @ on the surface of the solid electrolyte layer sealed above
This is a solid electrolyte manufacturing method characterized by comprising a fourth step of forming an electrode material by coating or thermal spraying.
すなわち１本発明は予じめ多孔質ヲ材の表面に形成した
電極層上に先ず溶射法により固体電解質の８０〜９５％
に相当する５０〜３５μｍを形成しその多孔性を利用し
て化学蒸着を行なわせ、封孔が完了した時期に固体電解
質の形成作業を終了する点を骨子とするものである。That is, in the present invention, 80 to 95% of a solid electrolyte is first sprayed onto an electrode layer formed on the surface of a porous material by a thermal spraying method.
The basic idea is to form a solid electrolyte with a diameter of 50 to 35 .mu.m, which corresponds to 50 to 35 .mu.m, to perform chemical vapor deposition using its porosity, and to complete the solid electrolyte formation operation when the pore sealing is completed.
本発明は従来法の溶射法と化学的蒸着法とを巧みに組合
せて、所望の厚さ及び封孔度をもった固体電解質層を能
率よく製造しうるようにしたものである。The present invention skillfully combines conventional thermal spraying methods and chemical vapor deposition methods to efficiently produce a solid electrolyte layer having a desired thickness and degree of sealing.
本発明において、多孔質基材としてはＡｔ２０ｓｅＣＳ
Ｚ （Ｃａｌｃｉａ ５ｔａｂｉｌｉｚｅｄ Ｚｒｃ
ｏｎｉａ、カルシア安定化ジルコニア）等が、電極材料
としてばＬａＣｏＯ３系、、 ＬａＭｎＯ３系などの空
気極、 Ｎｉ、 Ｎｉ−ＺｒＯ２サーメットなどの燃料
極が、固体電解質としてはＣ３Ｚ、ＹＳＺ（イツトリア
安定化ジルコニア）などが使用される。In the present invention, the porous base material is At20seCS
Z (Calcia 5tabilized Zrc
onia, calcia stabilized zirconia), etc., as electrode materials, air electrodes such as LaCoO3-based, LaMnO3-based, etc., fuel electrodes such as Ni, Ni-ZrO2 cermet, etc., and solid electrolytes such as C3Z, YSZ (yttoria-stabilized zirconia), etc. etc. are used.
〔実施例〕 第１図によって本発明の一実施例を説明する。〔Example〕 An embodiment of the present invention will be explained with reference to FIG.
１は多孔質基材で１瓢厚みのアルミナ（八４０３）板で
気孔率は２０％のものを使用した。必要により長さ４０
〜６（１５８の管又は底つきチューブを使うことができ
るし従来法に示した部分安定化ジルコニア系セラミック
スの多孔質材を基材として使うことが可能である。２は
気孔部分である。No. 1 was a porous base material, which was an alumina (8403) plate with a thickness of one gourd and a porosity of 20%. Length 40 as required
6 (158) or a tube with a bottom can be used, and the porous material of partially stabilized zirconia ceramics shown in the conventional method can be used as the base material. 2 is the pore portion.
この表面に燃料極３として酸化ニッケル（Ｎ１０）をア
セチレン溶射法で約５０μｍにつけ、さらにこの表層へ
プラズマ溶射法にて部分安定化したイツトリヤ系ジルコ
ニアの粉末を溶着させ厚みを平均４０〜４５μｍとした
。粉末は（ＺｒＯｚ）ｕｐ・（ＹｚＯｓ）ｕ＋の混合組
成となるものを平均粒子径１０μｍ以下のものを使用し
た。Nickel oxide (N10) was applied to this surface as a fuel electrode 3 to a thickness of about 50 μm by acetylene spraying, and partially stabilized Ittriya-based zirconia powder was welded to this surface layer by plasma spraying to give an average thickness of 40 to 45 μm. . The powder had a mixed composition of (ZrOz)up/(YzOs)u+ and had an average particle size of 10 μm or less.
この上に化学蒸着層を形成する前に多孔質基材側７に水
素と水を含むガスを流し、溶射層４の表面側８に塩化ジ
ルコニウム及び塩化イツトリウムを約１０対１のモル比
で流し１２００℃に加熱して蒸着反応を行なった。Before forming a chemical vapor deposition layer thereon, a gas containing hydrogen and water is flowed on the porous substrate side 7, and zirconium chloride and yttrium chloride are flowed on the surface side 8 of the thermal sprayed layer 4 at a molar ratio of about 10:1. A vapor deposition reaction was carried out by heating to 1200°C.
Ｚ ｒ Ｃ４＋ ２８２０ →ＺｒＯ２＋４ＨＣ２■２
ＹＣ１３＋３Ｈ２０−Ｉ−Ｙｚ（％ ＋６ＨＣｔ
■この２種の反応が溶射層４の表面でおこυ生成物で
ある酸化物５が蒸着して来てやがて封孔されるに至る。Z r C4+ 2820 →ZrO2+4HC2■2
YC13+3H20-I-Yz(% +6HCt
(2) These two types of reactions occur on the surface of the thermally sprayed layer 4, and the oxide 5, which is a υ product, is deposited and the pores are eventually sealed.
封孔された後に、酸化物５の表面側と基材側に酸素分圧
差が生じて、酸素濃淡電池が形成され、
Ｏ！＋４ｅ →２０− ■の反応で
起るＯｒが移動し酸化物５の表面側でＺ ｒ Ｃ１４＋
４０”−４Ｚ ｒ ０１ ＋ ＣＩ４ ＋ ８ ｅ
■２ＹＣＬｓ ＋ ３０２″″ →Ｙ２０３ ＋
３ Ｃ４＋ ６ ｅ ■の反応が起り成長していく。After the pores are sealed, a difference in oxygen partial pressure occurs between the surface side of the oxide 5 and the base material side, forming an oxygen concentration battery, and O! +4e →20− Or that occurs in the reaction of (2) moves and forms Z r C14+ on the surface side of oxide 5.
40”-4Z r 01 + CI4 + 8 e
■2YCLs + 302″″ →Y203 +
3 C4+ 6 e The following reaction occurs and it grows.
高温かつ酸素分圧が低い時は、酸化物５の層で電子導電
性が現われるため電子の補償はおこなわれている。しか
し酸素イオンの移動方向とは逆方向の電子の移動速度が
遅いため、この反応のみで所定の厚みの酸化物５０層を
得るのは能率が悪い。本発明では耐圧力を満足する時点
で終了するのでこの反応は必要がないか、早々に打ち切
ることが可能である。When the temperature is high and the oxygen partial pressure is low, electron conductivity appears in the layer of oxide 5, so that electron compensation is performed. However, since the moving speed of electrons in the opposite direction to the moving direction of oxygen ions is slow, it is inefficient to obtain 50 layers of oxide with a predetermined thickness only by this reaction. In the present invention, since the reaction ends when the pressure resistance is satisfied, this reaction is not necessary or can be stopped early.
この酸化物５の層のさらに上層にはランタンコバルタイ
ト（ＬａＣｏ０３）系をアセチレン溶射にて１００μｍ
層積して空気極６を構成している。Further above this layer of oxide 5, lanthanum cobaltite (LaCo03) is applied by spraying with acetylene to a thickness of 100 μm.
The air electrode 6 is formed by stacking layers.
必要によっては燃料極３と空気極６の構成を逆にもでき
る。If necessary, the configurations of the fuel electrode 3 and air electrode 6 can be reversed.
このようにして構成した多孔質基材１の側７に水素或は
−酸化炭素をわずかの水蒸気と共に供給し、空気極６の
側８に空気を供給して１０００℃に全体を保持するとき
、燃料極３と空気極６とを導Ｂｑ ｔ １ｏにて結線す
るとき直流の電気が得られるいわゆる燃料電池が構成さ
れる。When hydrogen or carbon oxide is supplied together with a small amount of water vapor to the side 7 of the porous substrate 1 constructed in this way, and air is supplied to the side 8 of the air electrode 6 to maintain the entire body at 1000°C. When the fuel electrode 3 and the air electrode 6 are connected by a conductor Bq t 1o, a so-called fuel cell is constructed which can obtain direct current electricity.
このとき、空気ｊ６では
０２ ＋ ４ｐ ＃２０− ■の反
応が生じ酸素イオンは固体電解質を構成している第１図
における酸化物５、溶射層４の固体内を、イオン伝導し
て移動し、燃料極３に至る。燃料種３では導線）０，９
を結んで外側を移動して来た電子をもらい式■の逆反応
がおき、さらに、
２Ｈｚ＋０□４ ２Ｈ，０■
２ Ｃｏ ＋ Ｏｚ 、： ２ ＣＯ２■の反応に
よって燃料電池としての反応が終結する。At this time, the reaction 02 + 4p #20- (2) occurs in the air j6, and the oxygen ions move through the solid of the oxide 5 and sprayed layer 4 in Fig. 1, which constitute the solid electrolyte, by ion conduction. It reaches the fuel electrode 3. For fuel type 3, conductor) 0,9
The reverse reaction of the formula ■ occurs when the electrons that have moved on the outside are received, and further, the reaction as a fuel cell is completed by the reaction of 2Hz + 0□4 2H,0■ 2 Co + Oz, : 2 CO2■ .
また、結線９，１０に直流電気を供給するときには上記
■又は０式が逆に行なわれ、酸素イオンが空気極６で酸
素としてとりだせるいわゆる高＠電解装置としても利用
できる。Further, when direct current electricity is supplied to the connections 9 and 10, the above formula (1) or (0) is performed in reverse, and the device can also be used as a so-called high@electrolysis device in which oxygen ions can be taken out as oxygen at the air electrode 6.
１）従来溶射によって構成された方法では到底得られな
い薄膜型の固体電解質が得られる。1) A thin film type solid electrolyte, which could not be obtained by conventional thermal spraying methods, can be obtained.
２）かつ化学蒸着法洸より完全な密閉が可能となり、集
積して使用するとき充分なを圧をかけても洩れがなく安
全となる。2) Furthermore, chemical vapor deposition allows complete sealing, and when used in an integrated manner, there is no leakage and safety even when sufficient pressure is applied.
５）従来の戒気化学的蒸着法のきわめて慇い生産性を著
しく向上できる。5) It is extremely easy to use and the productivity of the conventional chemical vapor deposition method can be significantly improved.
第１図は本発明の固体電解質の構成を示す概略図、第２
図、第５図は従来方法で製造した固体電解質の構成を示
す概略図である。
第１図
８ 空気
第２図
手続補正書
昭和６１年 ９月９日Figure 1 is a schematic diagram showing the structure of the solid electrolyte of the present invention, Figure 2 is a schematic diagram showing the structure of the solid electrolyte of the present invention.
FIG. 5 is a schematic diagram showing the structure of a solid electrolyte manufactured by a conventional method. Figure 1 8 Air Figure 2 Procedural Amendments September 9, 1986
Claims (4)
溶射により形成する第１工程、(1) A first step of forming a porous electrode material on the surface of a porous base material by coating or thermal spraying,
計画厚さの大部分を占める厚さの固体電解質層を形成す
る第２工程(2) A second step of spraying solid electrolyte material powder onto the surface of the electrode material to form a solid electrolyte layer with a thickness that accounts for most of the planned thickness.
着させて固体電解質層の厚さを計画厚さとすると同時に
該層を封孔する第３工程、及び(3) a third step of chemically depositing a solid electrolyte material on the surface of the solid electrolyte layer to bring the thickness of the solid electrolyte layer to the planned thickness and simultaneously sealing the layer;
電極材料を塗布または溶射により形成する第４工程 よりなることを特徴とする固体電解質の製造方法。(4) A method for manufacturing a solid electrolyte, comprising a fourth step of forming a porous electrode material on the surface of the solid electrolyte layer subjected to the sealing treatment by coating or thermal spraying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61108687A JPS62268063A (en) | 1986-05-14 | 1986-05-14 | Manufacture of solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61108687A JPS62268063A (en) | 1986-05-14 | 1986-05-14 | Manufacture of solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62268063A true JPS62268063A (en) | 1987-11-20 |
Family
ID=14491110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61108687A Pending JPS62268063A (en) | 1986-05-14 | 1986-05-14 | Manufacture of solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62268063A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0414270A2 (en) * | 1989-08-24 | 1991-02-27 | Kabushiki Kaisha Meidensha | Fuel cell utilizing solidous electrolyte |
| EP0481679A2 (en) * | 1990-10-15 | 1992-04-22 | Westinghouse Electric Corporation | Solid oxide electrochemical cell fabrication process |
| WO1992010862A1 (en) * | 1990-12-10 | 1992-06-25 | Yuasa Battery Co., Ltd. | Method for manufacturing solid-state electrolytic fuel cell |
| WO1994010717A1 (en) * | 1992-10-28 | 1994-05-11 | Siemens Aktiengesellschaft | Process for sealing high-temperature fuel cells and fuel cells sealed according to this process |
| US5358735A (en) * | 1991-03-28 | 1994-10-25 | Ngk Insulators, Ltd. | Method for manufacturing solid oxide film and method for manufacturing solid oxide fuel cell using the solid oxide film |
| US6093297A (en) * | 1996-04-02 | 2000-07-25 | Nkk Corporation | Method for depositing solid electrolyte layer |
-
1986
- 1986-05-14 JP JP61108687A patent/JPS62268063A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0414270A2 (en) * | 1989-08-24 | 1991-02-27 | Kabushiki Kaisha Meidensha | Fuel cell utilizing solidous electrolyte |
| US5151334A (en) * | 1989-08-24 | 1992-09-29 | Kabushiki Kaisha Meidensha | Fuel cell utilizing solidous electrolyte |
| EP0481679A2 (en) * | 1990-10-15 | 1992-04-22 | Westinghouse Electric Corporation | Solid oxide electrochemical cell fabrication process |
| WO1992010862A1 (en) * | 1990-12-10 | 1992-06-25 | Yuasa Battery Co., Ltd. | Method for manufacturing solid-state electrolytic fuel cell |
| US5290323A (en) * | 1990-12-10 | 1994-03-01 | Yuasa Corporation | Manufacturing method for solid-electrolyte fuel cell |
| US5358735A (en) * | 1991-03-28 | 1994-10-25 | Ngk Insulators, Ltd. | Method for manufacturing solid oxide film and method for manufacturing solid oxide fuel cell using the solid oxide film |
| WO1994010717A1 (en) * | 1992-10-28 | 1994-05-11 | Siemens Aktiengesellschaft | Process for sealing high-temperature fuel cells and fuel cells sealed according to this process |
| US6093297A (en) * | 1996-04-02 | 2000-07-25 | Nkk Corporation | Method for depositing solid electrolyte layer |
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