JPH0737596A - Flat plate type solid electrolyte electrolytic cell - Google Patents
Flat plate type solid electrolyte electrolytic cellInfo
- Publication number
- JPH0737596A JPH0737596A JP5182512A JP18251293A JPH0737596A JP H0737596 A JPH0737596 A JP H0737596A JP 5182512 A JP5182512 A JP 5182512A JP 18251293 A JP18251293 A JP 18251293A JP H0737596 A JPH0737596 A JP H0737596A
- Authority
- JP
- Japan
- Prior art keywords
- interconnector
- solid electrolyte
- ysz
- electrode side
- layer power
- 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.)
- Withdrawn
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 42
- 239000000919 ceramic Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000000446 fuel Substances 0.000 claims abstract description 40
- 239000011521 glass Substances 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims description 47
- 238000010248 power generation Methods 0.000 claims description 37
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 239000002737 fuel gas Substances 0.000 claims description 10
- 229910010293 ceramic material Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 3
- 238000005336 cracking Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 230000001788 irregular Effects 0.000 abstract 1
- 230000002093 peripheral effect Effects 0.000 abstract 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 30
- 239000000470 constituent Substances 0.000 description 24
- 238000012856 packing Methods 0.000 description 8
- 230000008646 thermal stress Effects 0.000 description 8
- 229910018279 LaSrMnO Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229910017563 LaCrO Inorganic materials 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature cells with solid electrolytes
- H01M8/2432—Grouping of unit cells of planar configuration
-
- 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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は平板型固体電解質燃料電
池や平板型高温水蒸気電解装置における平板型固体電解
質電解セルに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plate type solid electrolyte fuel cell and a plate type solid electrolyte electrolytic cell in a plate type high temperature steam electrolyzer.
【０００２】[0002]
【従来の技術】図４および図５に従来の平板型固体電解
質燃料電池の構造例を示す。図４において、三層発電膜
（燃料極、固体電解質、空気極よりなる膜）１０５を燃
料極側支持層１０４および空気極側支持層１０６に挟着
し、更にその外面には夫々燃料極側支持枠１０３および
空気極側支持枠１０７を介してインタコネクタ１０１お
よび１０９が取付けられ、上記夫々の間は強固に接着さ
れている。2. Description of the Related Art FIGS. 4 and 5 show a structural example of a conventional flat plate solid oxide fuel cell. In FIG. 4, a three-layer power generation membrane (a membrane composed of a fuel electrode, a solid electrolyte, and an air electrode) 105 is sandwiched between a fuel electrode side support layer 104 and an air electrode side support layer 106, and the outer surfaces thereof are respectively attached to the fuel electrode side. The interconnectors 101 and 109 are attached via the support frame 103 and the air electrode side support frame 107, and the above-mentioned parts are firmly bonded together.
【０００３】図５においては、その構成部材の相互関係
が明らかになるように各構成部材を分解して示したもの
であり、図４の燃料極側支持枠１０３をパッキン１０２
に、また空気極側支持枠１０７をパッキン１０８に置換
し、インタコネクタ１０１とパッキン１０２間、パッキ
ン１０２と三層発電膜１０５及びインタコネクタ１０９
とパッキン１０８間、パッキン１０８と三層発電膜１０
５間を非接着とし、発電膜１０５とインタコネクタ１０
１，１０９間の熱応力発生を防止したものである。下記
に図４，図５の構成部材の材質の一例を表１として示
す。FIG. 5 is an exploded view of the respective constituent members so that the mutual relationship of the constituent members can be clarified. The fuel electrode side support frame 103 of FIG.
Further, the air electrode side support frame 107 is replaced with a packing 108, and the space between the interconnector 101 and the packing 102, the packing 102, the three-layer power generation film 105, and the interconnector 109.
And the packing 108, the packing 108 and the three-layer power generation film 10
5 is made non-adhesive, and the power generation film 105 and the interconnector 10
This prevents generation of thermal stress between 1 and 109. Table 1 below shows an example of the materials of the constituent members of FIGS. 4 and 5.
【０００４】[0004]
【表１】 [Table 1]
【０００５】図５のパッキンの耐熱シール材としては、
ガラス系繊維又はガラス系粉末；５〜４０ｗｔ％、
無機粉末；３０〜９５ｗｔ％及び結合材；３０ｗｔ％以
下よりなる高温ガスケット、 ガラス系繊維５〜１５
ｗｔ％、セピオライト鉱物５〜３０ｗｔ％、タルク鉱物
５０〜８０ｗｔ％、有機結合材１０ｗｔ％からなり、空
隙率が５０％以下の高温ガスケット及びセラミックス繊
維８〜１２ｗｔ％、セリサイトマイカ鉱物１８〜２２ｗ
ｔ％、タルク鉱物６２〜６６ｗｔ％、有機結合材２〜６
ｗｔ％からなり、空隙率が６０％以下の高温ガスケット
などがあげられる。As a heat-resistant sealing material for the packing shown in FIG.
Glass-based fiber or glass-based powder; 5-40 wt%,
Inorganic powder; high temperature gasket consisting of 30 to 95 wt% and binder; 30 wt% or less, glass fiber 5 to 15
wt%, sepiolite mineral 5-30 wt%, talc mineral 50-80 wt%, organic binder 10 wt%, high-temperature gasket and porosity of 50% or less and ceramic fiber 8-12 wt%, sericite mica mineral 18-22w
t%, talc mineral 62-66 wt%, organic binder 2-6
An example is a high temperature gasket made of wt% and having a porosity of 60% or less.
【０００６】[0006]
【発明が解決しようとする課題】図４に示す燃料電池の
如く、電池構成部材の各部を接着固着した場合、下記表
２に示すとおり、各部の構成部材の熱膨張係数が異って
いるため、電池の昇降温時および発電時に生じる各部の
温度差に基づく熱応力が発生し三層発電膜１０５に割れ
が生じ、電池の性能が大幅に低下するという恐れがあ
る。When the respective parts of the cell constituent members are adhered and fixed as in the fuel cell shown in FIG. 4, the thermal expansion coefficients of the constituent members of the respective parts are different as shown in Table 2 below. However, there is a risk that thermal stress is generated due to the temperature difference between the parts during temperature rise and fall of the battery and during power generation, and the three-layer power generation film 105 is cracked, resulting in a significant decrease in battery performance.
【０００７】また、図５に示す燃料電池では、三層発電
膜１０５の周辺が非接着構造となっているため、上記図
４に示す燃料電池に比較すると三層発電膜１０５に生じ
る熱応力は大幅に緩和されるが、三層発電膜１０５は燃
料極側支持層１０４および空気極側支持層１０６の剛性
に応じた熱応力をインタコネクタ１０１および１０９か
ら受けるため、発電出力密度を上昇したとき、出力密度
の上昇に比例して生じる三層発電膜１０５の不均一温度
分布による三層発電膜１０５の熱応力増大に十分対応で
きなくなる。また、三層発電膜１０５と耐熱性シールパ
ッキン１０２および１０８とインタコネクタ１０１およ
び１０９の間が夫々非接着であるため、燃料ガス、空気
の完全な漏洩防止が困難なため漏洩ガスの燃焼による若
干の昇温と燃料利用率の低下が避けられないという問題
点があった。Further, in the fuel cell shown in FIG. 5, since the periphery of the three-layer power generation membrane 105 has a non-adhesive structure, the thermal stress generated in the three-layer power generation membrane 105 is smaller than that of the fuel cell shown in FIG. Although it is significantly relieved, the three-layer power generation membrane 105 receives thermal stress from the interconnectors 101 and 109 according to the rigidity of the fuel electrode side support layer 104 and the air electrode side support layer 106, so that when the power generation output density is increased. However, it becomes impossible to sufficiently cope with the increase in thermal stress of the three-layer power generation film 105 due to the non-uniform temperature distribution of the three-layer power generation film 105 that occurs in proportion to the increase in the power density. Further, since the three-layer power generation membrane 105, the heat-resistant seal packings 102 and 108, and the interconnectors 101 and 109 are not adhered to each other, it is difficult to completely prevent the leakage of fuel gas and air, and the leakage gas may slightly burn. There is a problem that the temperature rise and the fuel utilization rate are unavoidable.
【０００８】[0008]
【表２】 [Table 2]
【０００９】本発明は上記問題点を解決するためのもの
であって、その目的とするところは、インタコネクタ構
成材と固体電解質膜を同一材料あるいは同一線膨張係数
の材質を選ぶことによって熱応力低減、又インタコネク
タと固体電解質膜とをそれ等と同一の線膨張係数をもつ
ガラスまたはセラミックス質接着にて加圧接着あるいは
単に加圧接合することにより燃料ガス、空気の漏洩が防
止可能な燃料電池を提供するものである。The present invention is intended to solve the above-mentioned problems, and an object of the present invention is to select the same material for the interconnector constituent material and the solid electrolyte membrane or a material having the same coefficient of linear expansion for thermal stress. Fuel that can prevent leakage of fuel gas and air by reducing or interconnecting the interconnector and the solid electrolyte membrane by pressure bonding or simply pressure bonding with glass or ceramic bonding having the same linear expansion coefficient as those of them. A battery is provided.
【００１０】[0010]
【課題を解決するための手段】本発明は固体電解質と
ほゞ同一線膨張係数をもつ絶縁性セラミックス材に導電
性セラミックス材を埋め込み又は接合により電気導通性
もたせた構造の２つのインタコネクタ、一つの前記構
造のインタコネクタの、後記の三層発電膜の空気極側に
面する側に配置された空気極側導電性セラミックス板、
他の前記構造のインタコネクタの、後記の三層発電膜
の燃料極側に面する側に配置された燃料極側導電性セラ
ミックス板、上記空気極側導電性セラミックス板と燃
料極側導電性セラミックス板との間に挟装され、燃料ガ
スの流れる面に燃料極、空気の流れる面に空気極を焼結
してなる波状又は凹凸状の固体電解質膜よりなる三層発
電膜よりなり、前記２つのインタコネクタによって前
記空気極側導電性セラミックス板、三層発電膜、燃料極
側導電性セラミックス板を圧着させ、かつ２つの前記イ
ンタコネクタと前記三層発電膜の周縁の固体電解質膜の
圧着部をこれら材料とほゞ同じ線膨張係数のガラスまた
はセラミックス質接着剤で加圧接着してなることを特徴
とする平板型固体電解質電解セルである。DISCLOSURE OF THE INVENTION The present invention provides two interconnectors having a structure in which a conductive ceramic material is embedded in or bonded to an insulating ceramic material having substantially the same linear expansion coefficient as that of a solid electrolyte to provide electrical conductivity. One of the interconnectors of the above structure, the air electrode side conductive ceramics plate arranged on the side facing the air electrode side of the three-layer power generation film described later,
A fuel electrode side conductive ceramic plate disposed on the side of the other interconnector having the above structure facing the fuel electrode side of the three-layer power generation membrane described later, the air electrode side conductive ceramic plate and the fuel electrode side conductive ceramics. A three-layer power generation membrane, which is sandwiched between a plate and a corrugated or concavo-convex solid electrolyte membrane formed by sintering a fuel electrode on a fuel gas flowing surface and an air electrode on an air flowing surface, The air electrode side conductive ceramics plate, the three-layer power generation membrane, and the fuel electrode side conductive ceramics plate are pressure-bonded by one interconnector, and the two connectors are crimped to the solid electrolyte membrane at the periphery of the three-layer power generation membrane. Is a plate-type solid electrolyte electrolytic cell characterized by being pressure-bonded with a glass or ceramic adhesive having a linear expansion coefficient substantially the same as those materials.
【００１１】以下、本発明の平板型固体電解質電解セル
の構成部材の材質について説明するが、本発明はこれら
のものに限定されるものではない。 〇 インタコネクタ：ＺｒＯ2 、Ａｌ2 Ｏ3 −ＭｇＯス
ピネル、ＹＳＺ（イットリア安定化ジルコニア）又はＳ
ｉＯ2 〇 空気極側導電性セラミックス板：ＬａＳｒＭｎ
Ｏ3 、ＬａＳｒＣｒＯ3 、ＬａＭｇＣｒＯ3 又はＬａＣ
ａＣｒＯ3 〇 三層発電膜の固体電解質膜：ＹＳＺ 〇 三層発電膜：ＬａＳｒＭｎＯ3 −ＹＳＺ／ＹＳＺ／
ＮｉＯ−ＹＳＺ 〇 燃料極側導電性セラミックス板：ＮｉＯ−ＹＳＺ、
ＬａＳｒＣｒＯ3 ，ＬａＭｇＣｒＯ3 ，ＬａＣａＣｒＯ
3 ，金属Ｎｉ又はハステロイＸ 〇 ガラス又はセラミックス質接着剤：ＳｉＯ2 ＋Ａｌ
2 Ｏ3 系ガラス，ＺｒＯ 2 系セラミックス，ＬａＣｒＯ
3 系セラミックスHereinafter, the flat plate type solid electrolyte electrolytic cell of the present invention
The material of the constituent members of
It is not limited to ones. 〇 Interconnector: ZrO2, Al2O3-MgO
Pinel, YSZ (yttria-stabilized zirconia) or S
iO2 〇 Air electrode side conductive ceramics plate: LaSrMn
O3, LaSrCrO3, LaMgCrO3Or LaC
aCrO3 -Three-layer power generation membrane solid electrolyte membrane: YSZ-Three-layer power generation membrane: LaSrMnO3-YSZ / YSZ /
NiO-YSZ 〇 Fuel electrode side conductive ceramic plate: NiO-YSZ,
LaSrCrO3, LaMgCrO3, LaCaCrO
3, Metal Ni or Hastelloy X ○ Glass or ceramic adhesive: SiO2+ Al
2O3Glass, ZrO 2Series ceramics, LaCrO
3Ceramics
【００１２】[0012]
【作用】本発明の構成から明らかなように、固体電解質
膜はそれとほゞ同一の材質又は線膨張係数をもつ２つの
インタコネクタ構成材と接合されているため、昇温、降
温、運転時の温度差による熱応力の発生は極少となり、
固体電解質膜の破損を完全に防止できる。As is apparent from the structure of the present invention, the solid electrolyte membrane is bonded to two interconnector constituent materials having substantially the same material or linear expansion coefficient, so that the solid electrolyte membrane can be used for temperature rise, temperature decrease, and operation. Generation of thermal stress due to temperature difference is minimal,
It is possible to completely prevent damage to the solid electrolyte membrane.
【００１３】また、導電性セラミックス埋込材をそれぞ
れの絶縁性セラミックスであるインタコネクタに埋込み
又は接合することによりインタコネクタの厚さ方向の導
電性を確保する。また、三層発電膜の固体電解質膜を波
状又は凹凸状に形成することにより、燃料ガス、空気の
通路が形成される。さらに、インタコネクタ、空気極側
導電性セラミックス板、三層発電膜、燃料極側導電性セ
ラミックス板及びインタコネクタは加圧接合されている
だけであるので、それぞれの線膨張係数がほゞ同じであ
ることゝあいまって三層発電膜の固体電解質の割れが大
幅に緩和される。また、インタコネクタと三層発電膜の
周縁の固体電解質膜の接触部を、これらとほゞ同一の線
膨張係数をもつガラス又はセラミックス質接着剤を用い
て加圧接着することにより、電気抵抗を減らすと共に、
燃料ガス、空気の漏れを防止することができる。Further, the conductivity of the interconnector in the thickness direction is secured by embedding or bonding the conductive ceramics embedding material in the interconnector which is each insulating ceramics. Further, by forming the solid electrolyte membrane of the three-layer power generation membrane in a wavy shape or an uneven shape, passages for fuel gas and air are formed. Furthermore, since the interconnector, the air electrode side conductive ceramics plate, the three-layer power generation membrane, the fuel electrode side conductive ceramics plate and the interconnector are only pressure-bonded, their linear expansion coefficients are almost the same. As a result, the cracking of the solid electrolyte of the three-layer power generation membrane is greatly mitigated. In addition, the contact resistance between the interconnector and the solid electrolyte membrane at the periphery of the three-layer power generation membrane is pressure-bonded by using a glass or ceramic adhesive having a coefficient of linear expansion that is almost the same as those of the three-layer power generation membrane, so that electrical resistance can be improved. Reduce and
Leakage of fuel gas and air can be prevented.
【００１４】[0014]
【実施例】以下本発明を図面に基づいて具体的に説明す
る。図１は本発明に係る積層平板状固体電解質燃料電池
セルの分解組立図、図２は組立て同燃料電池セルの断面
図を示す。図中１，７および８は夫々上部インタコネク
タ構成材、中部インタコネクタ構成材および下部インタ
コネクタ構成材、２は空気極側導電セラミックス板、３
は三層発電膜、４はその固体電解質膜、５は燃料極側導
電セラミックス板、６は導電セラミックス埋込材であ
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to the drawings. FIG. 1 is an exploded view of a laminated flat plate solid electrolyte fuel cell according to the present invention, and FIG. 2 is a sectional view of the assembled fuel cell. In the drawing, 1, 7 and 8 are upper interconnector constituent materials, middle interconnector constituent materials and lower interconnector constituent materials, 2 are air electrode side conductive ceramic plates, and 3 respectively.
Is a three-layer power generation membrane, 4 is its solid electrolyte membrane, 5 is a fuel electrode side conductive ceramics plate, and 6 is a conductive ceramics embedding material.
【００１５】図１において、ＹＳＺからなる上部インタ
コネクタ構成材１の下面とＹＳＺからなる中間インタコ
ネクタ構成材７の上面の間に、ＬａＭｇＣｒＯ3 からな
る空気側導電セラミックス板２、ＹＳＺからなる固体電
解質膜３の空気１０および燃料ガス９の流れる面に夫々
ＬａＳｒＭｎＯ3 −ＹＳＺからなる空気極材、ＮｉＯ−
ＹＳＺからなる燃料極材を焼結することによって形成さ
れたＬａＳｒＭｎＯ3−ＹＳＺ／ＹＳＺ／ＮｉＯ−ＹＳ
Ｚからなる凹凸状（波板状でもよい）三層発電膜４、Ｎ
ｉＯ−ＹＳＺからなる燃料極側導電セラミックス板５を
挟装する。また、ＹＳＺからなる中間インタコネクタ構
成材７の下面とＹＳＺからなる下部インタコネクタ構成
材８の上面との間にも上記同様の構成部材を挟装する。
ただし、燃料ガス、空気の流路に合せた構成順序とす
る。上記ＹＳＺからなるインタコネクタ構成材１，７お
よび８には燃料ガスおよび空気が流入する開口部ａおよ
びｂが互に直交するように設けてある。In FIG. 1, between the lower surface of the upper interconnector constituent member 1 made of YSZ and the upper surface of the intermediate interconnector constituent member 7 made of YSZ, the air side conductive ceramic plate 2 made of LaMgCrO 3 and the solid electrolyte made of YSZ. An air electrode material made of LaSrMnO 3 —YSZ and NiO— were formed on the surfaces of the membrane 3 where the air 10 and the fuel gas 9 flow, respectively.
LaSrMnO formed by sintering the fuel electrode material consisting of YSZ 3 -YSZ / YSZ / NiO- YS
Concavo-convex (may be corrugated) three-layer power generation film 4, N
A fuel electrode side conductive ceramics plate 5 made of iO-YSZ is sandwiched. Further, the same constituent members as described above are sandwiched between the lower surface of the intermediate interconnector constituent member 7 made of YSZ and the upper surface of the lower interconnector constituent member 8 made of YSZ.
However, the order of construction is set according to the flow paths of fuel gas and air. The interconnector constituent members 1, 7 and 8 made of YSZ are provided with openings a and b through which fuel gas and air flow in so as to be orthogonal to each other.
【００１６】図２に示す如く、ＬａＳｒＭｎＯ3 −ＹＳ
Ｚ／ＹＳＺ／ＮｉＯ−ＹＳＺからなる凹凸状三層発電膜
４の周縁のＹＳＺからなる固体電解質膜３とＹＳＺから
なる上部インタコネクタ構成材１とＹＳＺからなる中間
インタコネクタ構成材７および上記固体電解質膜３と上
記中間インタコネクタ構成材７とＹＳＺからなる下部イ
ンタコネクタ構成材８の間にガラス質又はセラミックス
質接着材１１を塗布して全体を１０００℃〜１３００
℃、１ｋｇ／ｃｍ2 〜１００ｋｇ／ｃｍ2 の高温・高圧
で接合することで本発明の電解セルを構成する。ここ
で、ガラス質またはセラミックス接着材１１は固体電解
質膜３並びに上部インタコネクタ構成材１、中間インタ
コネクタ構成材７および下部インタコネクタ構成材８と
ほゞ同一の線膨張係数の材質を選択する。また、上記凹
凸状（波板状）三層発電膜４と前記空気極側導電セラミ
ックス板２および燃料極側導電セラミックス板５とは圧
着するものとする。また、前記凹凸状（波板状）三層発
電膜４は、まずＹＳＺからなる固体電解質膜３の平板に
凹凸を形成し（上面の凸部は下面から見れば凹部となっ
ている）各々の面にＬａＳｒＭｎＯ3 −ＹＳＺからなる
空気極材、ＮｉＯ−ＹＳＺからなる燃料極材を刷毛塗り
して製作する。As shown in FIG. 2, LaSrMnO 3 --YS
The solid electrolyte membrane 3 made of YSZ at the periphery of the concavo-convex three-layer power generation film 4 made of Z / YSZ / NiO-YSZ, the upper interconnector constituent material 1 made of YSZ, the intermediate interconnector constituent material 7 made of YSZ, and the solid electrolyte. A glass or ceramic adhesive 11 is applied between the film 3, the intermediate interconnector component 7 and the lower interconnector component 8 made of YSZ, and the whole is 1000 ° C. to 1300.
° C., constituting the electrolytic cell of the present invention by bonding at high temperature and high pressure 1kg / cm 2 ~100kg / cm 2 . Here, as the vitreous or ceramics adhesive material 11, a material having substantially the same linear expansion coefficient as that of the solid electrolyte membrane 3, the upper interconnector constituent material 1, the intermediate interconnector constituent material 7 and the lower interconnector constituent material 8 is selected. Further, the uneven (corrugated) three-layer power generation film 4, the air electrode side conductive ceramics plate 2 and the fuel electrode side conductive ceramics plate 5 are pressure bonded. In the uneven (corrugated) three-layer power generation film 4, unevenness is first formed on the flat plate of the solid electrolyte membrane 3 made of YSZ (the convex portion on the upper surface is a concave portion when viewed from the lower surface). An air electrode material made of LaSrMnO 3 —YSZ and a fuel electrode material made of NiO—YSZ are applied by brushing on the surface.
【００１７】インタコネクタ構成材の複合化を図３に基
づいて説明する。図３はインタコネクタ構成材料の平面
図である。本発明の例えば上部インタコネクタ構成材１
は固体電解質膜（材質はＹＳＺ）と同一の線膨張係数を
もつ絶縁性セラミックス材１′で構成する。該セラミッ
クス材１′は固体電解質膜と同一の材料（一般的にはＹ
ＳＺ）又はＺｒＯ2 系、Ａｌ2 Ｏ3 系、ＭｇＯ系、Ｓｉ
Ｏ系等の適当な混合物系から線膨張係数が一致するよう
製造され、図３に示すよう、その板厚方向に例えばＬａ
ＭｇＣｒＯ3 からなる導電性セラミックス材を穿設して
導電性セラミックス埋込材６を構成する。穿設された導
電性セラミックス材６はＬａＳｒＣｒＯ 3 、ＬａＣａＣ
ｒＯ3 、ＬａＭｇＣｒＯ3 系の材質としインタコネクタ
構成材の絶縁性セラミックス材１とガラス系、セラミッ
クス系接着材１１にて完全に接着する。Based on FIG. 3, a composite of interconnector constituent materials is shown.
I will explain. Figure 3 is a plan view of interconnector constituent materials
It is a figure. For example, the upper interconnector component 1 of the present invention
Has the same linear expansion coefficient as the solid electrolyte membrane (material is YSZ)
It is made of an insulating ceramic material 1 '. The ceramic
The casting material 1'is the same material as the solid electrolyte membrane (generally Y
SZ) or ZrO2System, Al2O3System, MgO system, Si
Make sure that the coefficient of linear expansion matches that of an appropriate mixture such as O
As shown in FIG. 3, it is manufactured and, for example, La in the plate thickness direction.
MgCrO3A conductive ceramic material consisting of
The conductive ceramics embedding material 6 is configured. Perforated guide
The electroceramic material 6 is LaSrCrO. 3, LaCaC
rO3, LaMgCrO3Interconnector as material of system
Insulating ceramics material 1 and glass type, ceramic
Completely bond with a box-type adhesive 11.
【００１８】また、ＮｉＯ−ＹＳＺからなる燃料極側導
電セラミックス板５とＬａＭｇＣｒＯ3 からなる空気極
側導電セラミックス板２をインタコネクタのＬａＭｇＣ
ｒＯ 3 からなる埋込材６と電気的接合が生じるよう１０
００℃〜１３００℃の高温・高圧で圧着する。ＹＳＺか
らなる中間インタコネクタ構成材７および同じくＹＳＺ
からなる下部インタコネクタ構成材８も同様にて構成す
る。Further, a fuel electrode side guide made of NiO-YSZ
Electroceramics plate 5 and LaMgCrO3Air electrode consisting of
The side conductive ceramics plate 2 is connected to the LaMgC interconnector.
rO 3So as to make electrical connection with the embedding material 6 consisting of 10
Pressure bonding is performed at high temperature and high pressure of 00 ° C to 1300 ° C. YSZ
Intermediate interconnector component 7 and YSZ
The lower interconnector component 8 consisting of
It
【００１９】ＮｉＯ−ＹＳＺからなる燃料極側導電セラ
ミックス板５とＬａＭｇＣｒＯ3 からなる空気極側導電
セラミックス板２はＬａＭｇＣｒＯ3 からなる上記埋込
材６と同一材料又はそれぞれの雰囲気に合致した材料
（例えば燃料側は金属材料、空気側は空気側電極膜材
等）の使用も可能である。[0019] NiO-YSZ cathode-side conductive ceramic plate 2 made of the fuel electrode side conductive ceramic plates 5 and LaMgCrO 3 consisting of the matched to the filler material 6 of the same material or each of the atmosphere consisting of LaMgCrO 3 material (e.g. It is also possible to use a metal material on the fuel side and an air-side electrode film material on the air side).
【００２０】[0020]
（１）インタコネクタを固体電解質と同一の材質又は同
一の線膨張係数を有する材質とすることを可能としたこ
とにより、固体電解質膜に発生する熱応力が全運転温度
範囲でほゞ零となり、固体電解質膜および三層発電膜の
割れを完全に防止できる。 （２）発電膜そのものを凹凸状に形成することで従来の
燃料側、空気側支持層を廃止でき、部品点数が減少する
と共に接触抵抗発生箇所も減少するため電池性能が大巾
に向上する。 （３）インタコネクタと固体電解質膜が完全に接着され
ることにより燃料ガス、空気の洩れが完全に防止可能と
なり、燃料利用率が向上すると共に漏洩ガスの燃焼によ
る電池の焼損が完全に防止できる。(1) Since the interconnector can be made of the same material as the solid electrolyte or a material having the same linear expansion coefficient, the thermal stress generated in the solid electrolyte membrane becomes almost zero in the entire operating temperature range, It is possible to completely prevent cracks in the solid electrolyte membrane and the three-layer power generation membrane. (2) By forming the power generation membrane itself in a concavo-convex shape, the conventional fuel-side and air-side support layers can be eliminated, the number of parts is reduced, and the number of contact resistance generation points is also reduced, so that the cell performance is greatly improved. (3) By completely adhering the interconnector and the solid electrolyte membrane, leakage of fuel gas and air can be completely prevented, the fuel utilization rate is improved, and burning of the battery due to combustion of the leakage gas can be completely prevented. .
【図１】本発明の一実施例の平板状固体電解質燃料電池
セルの分解図。FIG. 1 is an exploded view of a flat solid electrolyte fuel cell unit according to an embodiment of the present invention.
【図２】本発明の一実施例の平板状固体電解質燃料電池
セルの断面図。FIG. 2 is a cross-sectional view of a flat solid electrolyte fuel cell unit according to an embodiment of the present invention.
【図３】本発明のインタコネクタの平面図。FIG. 3 is a plan view of the interconnector of the present invention.
【図４】従来の完全接着型平板状固体電解質燃料電池セ
ルの斜視図。FIG. 4 is a perspective view of a conventional fully-adhesive flat plate solid electrolyte fuel cell.
【図５】従来のパッキン使用による非接着型固体電解質
燃料電池セルの分解図。FIG. 5 is an exploded view of a non-adhesive solid electrolyte fuel cell using a conventional packing.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 内藤 修三 兵庫県神戸市兵庫区和田崎町一丁目１番１ 号 三菱重工業株式会社神戸造船所内 (72)発明者 南條 房幸 兵庫県神戸市兵庫区和田崎町一丁目１番１ 号 三菱重工業株式会社神戸造船所内 (72)発明者 武信 弘一 兵庫県神戸市兵庫区和田崎町一丁目１番１ 号 三菱重工業株式会社神戸造船所内 (72)発明者 舟津 正之 兵庫県神戸市兵庫区和田崎町一丁目１番１ 号 三菱重工業株式会社神戸造船所内 (72)発明者 渡辺 潔 兵庫県神戸市兵庫区和田崎町一丁目１番１ 号 三菱重工業株式会社神戸造船所内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shuzo Naito 1-1-1, Wadasaki-cho, Hyogo-ku, Kobe-shi, Hyogo Mitsubishi Heavy Industries Ltd. Kobe Shipyard (72) Inventor Fusako Nanjo Hyogo-ku, Kobe-shi, Hyogo 1-1-1 Wadazakicho Mitsubishi Heavy Industries, Ltd. Kobe Shipyard (72) Inventor Koichi Takenobu 1-1-1 Wadasakicho, Hyogo-ku, Kobe Hyogo Prefecture Mitsubishi Heavy Industries Ltd. Kobe Shipyard (72) Inventor Masayuki Funatsu 1-1-1, Wadasaki-cho, Hyogo-ku, Kobe-shi, Hyogo Mitsubishi Heavy Industries Ltd. Kobe Shipyard (72) Inventor Kiyoshi Watanabe 1-1-1 Wadasaki-cho, Hyogo-ku, Kobe-shi, Hyogo Mitsubishi Heavy Industries Ltd. Inside the Kobe Shipyard
Claims (1)
つ絶縁性セラミックス材に導電性セラミックス材を埋め
込み又は接合により電気導通性もたせた構造の２つのイ
ンタコネクタ、一つの前記構造のインタコネクタの、
後記の三層発電膜の空気極側に面する側に配置された空
気極側導電性セラミックス板、他の前記構造のインタ
コネクタの、後記の三層発電膜の燃料極側に面する側に
配置された燃料極側導電性セラミックス板、上記空気
極側導電性セラミックス板と燃料極側導電性セラミック
ス板との間に挟装され、燃料ガスの流れる面に燃料極、
空気の流れる面に空気極を焼結してなる波状又は凹凸状
の固体電解質膜よりなる三層発電膜よりなり、前記２
つのインタコネクタによって前記空気極側導電性セラミ
ックス板、三層発電膜、燃料極側導電性セラミックス板
を圧着させ、かつ２つの前記インタコネクタと前記三層
発電膜の周縁の固体電解質膜の圧着部をこれら材料とほ
ゞ同じ線膨張係数のガラスまたはセラミックス質接着剤
で加圧接着してなることを特徴とする平板型固体電解質
電解セル。1. An interconnector having a structure in which an electrically conductive ceramic material is embedded in or bonded to an insulating ceramic material having substantially the same linear expansion coefficient as that of a solid electrolyte to provide electrical conductivity, and one interconnector having the structure described above. ,
An air electrode side conductive ceramics plate disposed on the side facing the air electrode side of the three-layer power generation membrane described later, on the side of the interconnector of the other structure described above that faces the fuel electrode side of the three-layer power generation membrane described below. Fuel electrode side conductive ceramics plate disposed, sandwiched between the air electrode side conductive ceramics plate and the fuel electrode side conductive ceramics plate, the fuel electrode on the surface through which the fuel gas flows,
A three-layer power generation membrane comprising a corrugated or uneven solid electrolyte membrane formed by sintering an air electrode on the surface through which air flows.
The air electrode side conductive ceramics plate, the three-layer power generation membrane, and the fuel electrode side conductive ceramics plate are pressure-bonded by one interconnector, and the two connectors are crimped to the solid electrolyte membrane at the periphery of the three-layer power generation membrane. A plate-type solid electrolyte electrolytic cell characterized by being pressure-bonded with a glass or ceramic adhesive having substantially the same linear expansion coefficient as those materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5182512A JPH0737596A (en) | 1993-07-23 | 1993-07-23 | Flat plate type solid electrolyte electrolytic cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5182512A JPH0737596A (en) | 1993-07-23 | 1993-07-23 | Flat plate type solid electrolyte electrolytic cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0737596A true JPH0737596A (en) | 1995-02-07 |
Family
ID=16119600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5182512A Withdrawn JPH0737596A (en) | 1993-07-23 | 1993-07-23 | Flat plate type solid electrolyte electrolytic cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0737596A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10168590A (en) * | 1996-12-12 | 1998-06-23 | Kansai Electric Power Co Inc:The | Cell sealing structure |
| JP2001319665A (en) * | 2000-05-08 | 2001-11-16 | Honda Motor Co Ltd | Fuel cell and method for producing electrolyte thereof |
| JP2002518794A (en) * | 1998-06-12 | 2002-06-25 | エイイーピー・エムテク・エル・エル・シー | Ceramic fuel cell |
| JP2006049195A (en) * | 2004-08-06 | 2006-02-16 | Nissan Motor Co Ltd | Insulating seal structure and fuel cell |
| JP2006255871A (en) * | 2005-03-18 | 2006-09-28 | Nisshin Seisakusho:Kk | Honing wheel and method for manufacturing the same |
| JP2008510288A (en) * | 2004-08-18 | 2008-04-03 | スティヒティング エネルギーオンダーゾーク セントラム ネーデルランド | SOFC stack concept |
| JP2010267618A (en) * | 2009-05-13 | 2010-11-25 | Robert Bosch Gmbh | Electrochemical cell for obtaining electrical energy |
| JP2014194941A (en) * | 2002-12-24 | 2014-10-09 | Versa Power Systems Ltd | Solid oxide fuel cell stack |
| US10971735B2 (en) | 2017-10-31 | 2021-04-06 | Kabushiki Kaisha Toshiba | Electrochemical cell and electrochemical apparatus |
-
1993
- 1993-07-23 JP JP5182512A patent/JPH0737596A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10168590A (en) * | 1996-12-12 | 1998-06-23 | Kansai Electric Power Co Inc:The | Cell sealing structure |
| JP2002518794A (en) * | 1998-06-12 | 2002-06-25 | エイイーピー・エムテク・エル・エル・シー | Ceramic fuel cell |
| JP2001319665A (en) * | 2000-05-08 | 2001-11-16 | Honda Motor Co Ltd | Fuel cell and method for producing electrolyte thereof |
| JP2014194941A (en) * | 2002-12-24 | 2014-10-09 | Versa Power Systems Ltd | Solid oxide fuel cell stack |
| JP2006049195A (en) * | 2004-08-06 | 2006-02-16 | Nissan Motor Co Ltd | Insulating seal structure and fuel cell |
| JP2008510288A (en) * | 2004-08-18 | 2008-04-03 | スティヒティング エネルギーオンダーゾーク セントラム ネーデルランド | SOFC stack concept |
| JP2006255871A (en) * | 2005-03-18 | 2006-09-28 | Nisshin Seisakusho:Kk | Honing wheel and method for manufacturing the same |
| JP2010267618A (en) * | 2009-05-13 | 2010-11-25 | Robert Bosch Gmbh | Electrochemical cell for obtaining electrical energy |
| US10971735B2 (en) | 2017-10-31 | 2021-04-06 | Kabushiki Kaisha Toshiba | Electrochemical cell and electrochemical apparatus |
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