JPH04147569A - Manufacture of solid electrolyte fuel cell - Google Patents
Manufacture of solid electrolyte fuel cellInfo
- Publication number
- JPH04147569A JPH04147569A JP2271230A JP27123090A JPH04147569A JP H04147569 A JPH04147569 A JP H04147569A JP 2271230 A JP2271230 A JP 2271230A JP 27123090 A JP27123090 A JP 27123090A JP H04147569 A JPH04147569 A JP H04147569A
- Authority
- JP
- Japan
- Prior art keywords
- powders
- mixture
- granulated
- zirconia
- hours
- 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.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000007784 solid electrolyte Substances 0.000 title description 11
- 239000000843 powder Substances 0.000 claims abstract description 42
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 235000012255 calcium oxide Nutrition 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 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 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 238000000465 moulding Methods 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 5
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 239000004698 Polyethylene Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 abstract 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 abstract 1
- -1 polyethylene Polymers 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 229910052759 nickel Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FVROQKXVYSIMQV-UHFFFAOYSA-N [Sr+2].[La+3].[O-][Mn]([O-])=O Chemical compound [Sr+2].[La+3].[O-][Mn]([O-])=O FVROQKXVYSIMQV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229940088990 ammonium stearate Drugs 0.000 description 2
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011361 granulated particle Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は固体電解質型燃料電池のアノード基板の製造
方法に係り、特に機械的安定性に優れるアノード基板の
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 an anode substrate for a solid oxide fuel cell, and particularly to a method for manufacturing an anode substrate with excellent mechanical stability.
固体電解質型燃料電池はジルコニア等の固体酸化物を電
解質に用い、８００〜１０００℃等の高温で作動するも
ので、電解質の支持や腐食等の問題がないうえ、活性化
分極を減少させる触媒が不要となるなどの特長を有し、
活発に研究開発が進められている。Solid oxide fuel cells use solid oxides such as zirconia as the electrolyte and operate at high temperatures such as 800 to 1000°C.There are no problems such as electrolyte support or corrosion, and there is no catalyst to reduce activation polarization. It has features such as being unnecessary,
Research and development is actively underway.
第２図は従来の固体電解質型燃料電池を示す分解斜視図
である。ニッケルと固体電解質体であるジルコニアから
なる多孔質のアノード基板１の上に、固体電解質体２と
、ストロンチウムがドープされたランタンストロンチウ
ムマンガナイトＬａ （Ｓｒ） −Ｍｎ０３からなるカ
ソード３が形成される。また、同じ＜ Ｌａ（Ｓｒ）Ｍ
ｎ０３からなる多孔質のカソード基板４にカルシウムが
ドープされたＬａ（Ｃａ）Ｃｒｏｗからなるセパレータ
５が積層される。固体電解質体２は通常安定化ジルコニ
アを溶射して形成される。FIG. 2 is an exploded perspective view showing a conventional solid oxide fuel cell. A solid electrolyte body 2 and a cathode 3 made of strontium-doped lanthanum strontium manganite La (Sr) -Mn03 are formed on a porous anode substrate 1 made of nickel and zirconia as a solid electrolyte body. Also, the same < La(Sr)M
A separator 5 made of calcium-doped La(Ca) Crow is laminated on a porous cathode substrate 4 made of n03. The solid electrolyte body 2 is usually formed by thermal spraying stabilized zirconia.
従来、アノード基板１とカソード基板４は、それぞれ酸
化二フケルージルコニアＮ１Ｏ−ＺｒＯｉ粉体と、ラン
タンストロンチウムマンガナイトＬａ（Ｓｒ）ＭｎＯｓ
粉体を造粒し、金型による一軸加圧成型、シート成型、
押し出し成型、或いはＣＩＰ（Ｃｏｌｄ Ｉｓｏｓｔａ
ｔｉｃＰｒｅｓｓｉｎｇ）などの成型を行い、酸化雰囲
気或いは、還元雰囲気中で、焼成して形成される０通常
、アノード基板１は、作動時に燃料ガスを流すことによ
って、電池内部にて還元を行い、Ｎ１Ｏ−ＺｒＯ□の導
電性アノード基板となる。Conventionally, the anode substrate 1 and the cathode substrate 4 are made of difluorozirconia N1O-ZrOi powder and lanthanum strontium manganite La(Sr)MnOs, respectively.
Powder is granulated, uniaxial pressure molding with a mold, sheet molding,
Extrusion molding or CIP (Cold Isosta)
Normally, the anode substrate 1 is formed by molding such as ticPressing) and firing in an oxidizing atmosphere or a reducing atmosphere. Normally, the anode substrate 1 is reduced inside the cell by flowing fuel gas during operation, and N1O- This becomes a conductive anode substrate of ZrO□.
〔発明が解決しようとする課題〕
しかしながらＮ１Ｏ−ＺｒＯ□アノード基板は還元時に
体積収縮を起こし割れを住しるという問題があった。こ
の剖れの問題は還元時に電子伝導性を確保できる限度で
あるニッケル含有量３０体積％の場合においても起こる
。アノード基板の割れとともに固体電解質体２の割れも
起こる。またＮｉ０−Ｚｒ賄テアノード基板還元後に生
したニッケルが再焼結を起こして体積が収縮するという
問題もあり、アノード基板を一層割れやすいものにして
いた。[Problems to be Solved by the Invention] However, the N1O-ZrO□ anode substrate has a problem in that volume shrinks during reduction and cracks occur. This problem of deterioration occurs even when the nickel content is 30% by volume, which is the limit that can ensure electron conductivity during reduction. Along with cracking of the anode substrate, cracking of the solid electrolyte body 2 also occurs. There is also the problem that the nickel produced after reduction of the Ni0-Zr anode substrate causes re-sintering and shrinks in volume, making the anode substrate even more susceptible to cracking.
この発明は上述の点に鑑みてなされ、その目的はアノー
ド基板に大きな体積変化が起こらないようにしてアノー
ド基板に割れや反りがなく借問性に優れる固体電解質型
燃料電池の製造方法を提供することにある。This invention has been made in view of the above-mentioned points, and its purpose is to provide a method for manufacturing a solid oxide fuel cell in which large volume changes do not occur in the anode substrate, the anode substrate is free from cracks and warpage, and has excellent stability. It is in.
上述の目的はこの発明によれば第一工程と、第二工程と
、第三工程とを有し、
第一工程は、酸化ニッケルとジルコニアの各粉体を混合
し、造粒したのち酸化ふん囲気中で熱処理して第一の造
粒粉を調製し、
第二工程は、前記第一〇造粒粉を還元ふん囲気中で熱処
理して第二〇造粒粉を調製し、第三工程は、第二の造粒
粉を成型し、かつ還元ふん囲気中で焼成する、とするこ
とにより達成される。According to the present invention, the above-mentioned object has a first step, a second step, and a third step. A first granulated powder is prepared by heat treatment in an ambient atmosphere, a second step is a heat treatment of the 10th granulated powder in a reducing atmosphere to prepare a 20th granulated powder, and a third step is This is achieved by molding the second granulated powder and firing it in a reducing atmosphere.
第一工程は酸化ニッケルとジルコニアを反応させて強固
に結合させる。The first step is to react nickel oxide and zirconia to form a strong bond.
第二工程は酸化ニッケルを還元するとともに得られたニ
ッケルをよく焼結させる。In the second step, the nickel oxide is reduced and the resulting nickel is thoroughly sintered.
第三工程はアノード基板を形成させる。The third step is to form an anode substrate.
このようにして得られたアノード基板は還元ふん囲気中
で還元による体積収縮やニッケルの再焼結を起こすこと
がないので、割れや反りがなくなる。The anode substrate obtained in this way does not undergo volumetric shrinkage due to reduction or re-sintering of nickel in a reducing atmosphere, and therefore is free from cracking and warping.
次にこの発明の実施例を地面に基いて説明する。 Next, an embodiment of the present invention will be explained based on the ground.
アノード基板ｌは次のようにして調製される６（実施例
１）
アノード材としては、酸化ニッケルＮ１０（特級。The anode substrate 1 is prepared as follows6 (Example 1) The anode material is nickel oxide N10 (special grade).
和光純薬工業）とイツトリア安定化ジルコニアＹＳＺ（
ＴＺ−８Ｙ、東ソー）を２＝１の重量比で秤量し、バイ
ンダとしてポリビニルアルコールＰｖ＾、ポリエチレン
グリコールＰＥＧ等を添加しボールミルにて湿式混合す
る。これらのスラリーをスプレードライヤで乾燥・造粒
する。この造粒粉を緻密なアルミナルツボに加圧しない
うに入れ、酸化ふん囲気中の１３００〜１５００℃の温
度で２時間、仮焼する。仮焼した造粒粉をさらに水素還
元ふん囲気中の８００〜１２００℃の温度で２時間、熱
処理する。還元した造粒粉にステアリン酸アンモニウム
を滑材として添加し、直Ｐｋ１３０ｍの金型で３ｆｉの
厚さに０，３〜１ｔ／−の圧力で成形した。この成形体
を水素還元ふん囲気中、１２００〜１４５０℃の温度で
２時間、焼結し、アノード基板を得た。Wako Pure Chemical Industries) and Ittria stabilized zirconia YSZ (
TZ-8Y, Tosoh) was weighed at a weight ratio of 2=1, polyvinyl alcohol Pv^, polyethylene glycol PEG, etc. were added as a binder, and wet-mixed in a ball mill. These slurries are dried and granulated using a spray dryer. This granulated powder is placed in a dense aluminum crucible without pressure and calcined for 2 hours at a temperature of 1,300 to 1,500°C in an oxidizing atmosphere. The calcined granulated powder is further heat-treated at a temperature of 800 to 1200° C. in a hydrogen reducing atmosphere for 2 hours. Ammonium stearate was added as a lubricant to the reduced granulated powder, and it was molded to a thickness of 3fi with a pressure of 0.3 to 1t/- in a mold with a direct Pk of 130m. This molded body was sintered at a temperature of 1200 to 1450° C. for 2 hours in a hydrogen reducing atmosphere to obtain an anode substrate.
（実施例２）
アノード材としては、酸化ニッケルＮ１ｐ（特級和光純
薬工業）とイツトリア安定化ジルコニアＹＳＺ（τＺ−
ＢＹ、東ソー）を２：ｌの重量比で秤量し、バインダと
してＰＶＡ、 ＰＥＧを添加した水中にてボールミルに
て湿式混合する。これらのスラリーをスプレードライヤ
で乾燥・造粒する。得られた造粒粉を直径５０ｍの金型
に入れてＩｔ／−の圧力にて、成形し、厚さ３０簡のデ
ィスク状とする。ディスク状の成形体をスタンプミルま
たはカンタ−ミルにより粗粉砕し、それらの粉体を目開
き３００ ｎの篩いを遭遇させ、造粒する。得られた造
粒粉を緻密なアルミナルツボに加圧しないように入れ、
酸化ふん囲気中、１３００〜１５００℃の温度で２時間
、仮焼する。仮焼した造粒粉をさらに水素還元ふん囲気
中、８００〜１２００℃の温度で２時間、熱処理する。(Example 2) As anode materials, nickel oxide N1p (special grade Wako Pure Chemical Industries) and ittria stabilized zirconia YSZ (τZ-
BY, Tosoh) at a weight ratio of 2:l, and wet-mixed in a ball mill in water to which PVA and PEG were added as binders. These slurries are dried and granulated using a spray dryer. The obtained granulated powder is put into a mold with a diameter of 50 m and molded at a pressure of It/- to form a disk shape with a thickness of 30 pieces. The disc-shaped compact is coarsely ground using a stamp mill or a canter mill, and the resulting powder is passed through a sieve with a mesh size of 300 nm to be granulated. Place the obtained granulated powder into a dense aluminum crucible without applying pressure.
Calcinate in an oxidizing atmosphere at a temperature of 1300 to 1500°C for 2 hours. The calcined granulated powder is further heat-treated at a temperature of 800 to 1200° C. for 2 hours in a hydrogen reducing atmosphere.
還元した造粒粉にステアリン酸アンモニウムを滑材とし
て添加し、直径１３０ｆｉの金型で３ｆｉの厚さに０．
３〜ｉｔ／−の圧力で成形した。この成形体を水素還元
ふん囲気中、１２００〜１４５０℃の温度で２時間、焼
結し、アノード基板を得た。Ammonium stearate was added as a lubricant to the reduced granulated powder, and it was molded to a thickness of 3fi using a mold with a diameter of 130fi.
Molding was carried out at a pressure of 3 to 1/-. This molded body was sintered at a temperature of 1200 to 1450° C. for 2 hours in a hydrogen reducing atmosphere to obtain an anode substrate.
（実施例３） アノード材としては、酸化ニッケルＮ１ｐ（特級。(Example 3) The anode material is nickel oxide N1p (special grade).
和光純薬工巣）とイツトリア安定化ジルコニアＹＳＺ（
ＴＺ−８Ｙ、東ソー）を２：１の重量比で秤量し、バイ
ンダとしてＰＶＢ、ＰＥＧを添加したエタノール中にて
湿式混合する。さらに、ジルコニア粗粒粉として、９モ
ル％のマグネシアＭｇＯで部分安定化したジルコニア）
ＩＳＺ（ＴＺ−９ＭＧ、東ソー）を１６００℃で２時間
仮焼し、目開き３００−の篩いを通過させた平均粒子径
を５０〜１００ ｎの範囲に造粒した粉末を添加し、さ
らに混合して乾燥した。得られた粉末を、実施例２と同
様の方法により、成形、粉砕１ｗＩ造粒し、酸化ふん囲
気中の仮焼と水素還元ふん囲気中での熱処理を行い、直
径１３０ｆｉの金型で３鶴の厚さに０．３〜１ ｔ／−
の圧力で成形した。この成形体を水素還元ふん囲気中、
１２００〜１４５０℃の温度で２時間、焼結し、アノー
ド基板を得た。Wako Pure Chemical Industries) and Ittria stabilized zirconia YSZ (
TZ-8Y, Tosoh) were weighed at a weight ratio of 2:1 and wet-mixed in ethanol to which PVB and PEG were added as binders. Furthermore, zirconia partially stabilized with 9 mol% magnesia MgO as zirconia coarse powder)
ISZ (TZ-9MG, Tosoh) was calcined at 1,600°C for 2 hours, passed through a 300-mesh sieve, and granulated powder with an average particle size in the range of 50 to 100 n was added and further mixed. and dried. The obtained powder was molded, pulverized, and granulated for 1 wI in the same manner as in Example 2, and then calcined in an oxidizing atmosphere and heat treated in a hydrogen reducing atmosphere. 0.3 to 1 t/- to the thickness of
It was molded at a pressure of This molded body was placed in a hydrogen reducing atmosphere.
Sintering was performed at a temperature of 1200 to 1450°C for 2 hours to obtain an anode substrate.
以上の実施例において、ジルコニア粗粒粉は、上述の他
イットリア、カルシアまたは、セリアによって部分安定
化あるいは完全安定化されたジルコニアを用いることが
できる。In the above embodiments, the coarse zirconia powder may be zirconia partially or completely stabilized with yttria, calcia, or ceria.
ジルコニア粗粒粉を加えて造粒するのは、造粒。Granulation is the process of adding coarse zirconia powder to make granules.
仮焼により、大きな原料粒子となり、この造粒粉を成形
、焼結することにより、焼結しした造粒粒子間に開口し
た空隙が生じ、ガス透過の良い多孔質基板を造るために
行う、また仮焼温度は、１３００℃以下では、酸化ニッ
ケルとジルコニアの反応性が低く 、１６００℃をこえ
ると、酸化ニッケルが飛散する。他方、成形体の還元ふ
ん囲気中での焼結温度は、１２００℃より低いと焼結性
が悪く強度のある基板は得られない、 １４５０℃をこ
えると、ニッケルの融点以上となるため、成形体の形状
を保持することができず、かつ、多孔質性が失われる。By calcination, large raw material particles are formed, and by molding and sintering this granulated powder, open voids are created between the sintered granulated particles, and this is done to create a porous substrate with good gas permeation. Further, if the calcination temperature is 1300°C or lower, the reactivity of nickel oxide and zirconia is low, and if it exceeds 1600°C, nickel oxide will scatter. On the other hand, if the sintering temperature of the compact in a reducing atmosphere is lower than 1200°C, the sinterability will be poor and a strong substrate cannot be obtained; if it exceeds 1450°C, the temperature will be higher than the melting point of nickel, so forming The shape of the body cannot be maintained and porosity is lost.
（比較例１）
実施例１における酸化ふん囲気中の１３００〜１５００
℃の温度で２時間、仮焼した造粒粉にバインダとしてＰ
ＶＢ、ＰＥＧの水溶液を添加、混合、乾燥し、その造粒
粉を直径１３０ ｍの金型で３日の厚さに１ｔ／−の圧
力で成形した。この成形体を酸化ふん囲気中、１４００
〜１５５０℃の温度で２時間、焼結後、水素還元ふん囲
気中、８００〜１２００℃の温度で還元し、アノード基
板を得た。(Comparative Example 1) 1300 to 1500 in the oxidizing atmosphere in Example 1
P as a binder is added to the granulated powder calcined at a temperature of ℃ for 2 hours.
Aqueous solutions of VB and PEG were added, mixed, and dried, and the resulting granulated powder was molded to a thickness of 3 days using a mold with a diameter of 130 m at a pressure of 1 t/-. This molded body was placed in an oxidizing atmosphere for 1400 min.
After sintering at a temperature of ~1550°C for 2 hours, reduction was performed at a temperature of 800~1200°C in a hydrogen reducing atmosphere to obtain an anode substrate.
（比較例２）
実施例２における酸化ふん囲気中の１４００〜１５００
℃の温度で２時間、仮焼した造粒粉に比較例１と同様の
条件、方法により、アノード基板を得た。(Comparative Example 2) 1400 to 1500 in the oxidizing atmosphere in Example 2
An anode substrate was obtained using the granulated powder which had been calcined at a temperature of .degree. C. for 2 hours under the same conditions and method as in Comparative Example 1.
（比較例３）
実施例３における酸化ふん囲気中の１４００〜１５００
℃の温度で２時間、仮焼した造粒粉に比較例１と同様の
条件、方法により、アノード基板を得た。(Comparative Example 3) 1400 to 1500 in the oxidizing atmosphere in Example 3
An anode substrate was obtained using the granulated powder which had been calcined at a temperature of .degree. C. for 2 hours under the same conditions and method as in Comparative Example 1.
第１図は、アノード基板の水素還元ふん囲気中での１０
００℃の再焼結による収縮を示すもので、実施例１およ
び２では、再焼結が小さく、実施例３では、はとんど認
められない、これに対し比較例では収縮率が大きい。Figure 1 shows the hydrogen reduction of the anode substrate at 10
It shows the shrinkage due to resintering at 00°C. In Examples 1 and 2, resintering is small, and in Example 3, it is hardly observed. In contrast, the shrinkage rate is large in the comparative example.
第１表は、アノード基板の曲げ強度を示すもので実施例
１〜３のように、還元処理を行いニッケルージルコニア
とした造粒粉を成形、焼結することにより、比較例１〜
３のような、酸化ニッケルージルコニア焼結体を還元し
て得た基板より２倍以上の強度が得られた。Table 1 shows the bending strength of the anode substrate, and as in Examples 1 to 3, by molding and sintering the granulated powder made into nickel-zirconia through reduction treatment, Comparative Examples 1 to 3
The strength was more than twice that of a substrate obtained by reducing a nickel oxide-zirconia sintered body such as No. 3.
実施ａ ｔ〜３のニッケルージルコニアのアノード基板
に、ＹＳＺを溶射し固体電解質体２を形成し、電池とし
て１０００℃で作動試験したところ、固体電解質体およ
びアノード基板に、反り１割れ、脱落は生じなかった。A solid electrolyte body 2 was formed by thermal spraying YSZ on the nickel-zirconia anode substrate of implementation a t~3, and an operation test was performed as a battery at 1000°C. As a result, the solid electrolyte body and anode substrate did not warp, crack, or fall off. It did not occur.
第
表
〔発明の効果〕
こめ発明によれば第一工程と、第二工程と、第三工程と
を有し、
第一工程は、酸化ニッケルとジルコニアの各粉体を混合
し、造粒したのち酸化ふん囲気中で熱処理して第一〇造
粒粉を調製し、
第二工程は、前記第一の造粒粉を還元ふん囲気中で熱処
理して第二の造粒粉を調製し、第三工程は、第二の造粒
粉を成型し、かつ還元ふん囲気中で焼成するので、ニッ
ケルとジルコニア、ニッケルとニッケルとがよく反応し
、強固なアノード基板が得られる。またアノード基板は
製造の段階で還元収縮、ニッケル焼結収縮を行っている
ので、電池作動時にアノード基板に大きな収縮がおこら
ず、従って固体電解質体やアノード基板に割れや反りが
発生せず、信鯨性に優れる固体電解電型燃料電池が得ら
れる。Table [Effects of the invention] According to the invention, there are a first step, a second step, and a third step. Thereafter, the first granulated powder is prepared by heat treatment in an oxidizing atmosphere, and in the second step, the first granulated powder is heat treated in a reducing atmosphere to prepare a second granulated powder, In the third step, the second granulated powder is molded and fired in a reducing atmosphere, so that nickel and zirconia and nickel and nickel react well, resulting in a strong anode substrate. In addition, the anode substrate undergoes reduction shrinkage and nickel sintering shrinkage during the manufacturing stage, so the anode substrate does not undergo large shrinkage during battery operation. Therefore, the solid electrolyte body and the anode substrate do not crack or warp, making it reliable. A solid electrolyte fuel cell with excellent performance can be obtained.
第１図は、この発明の実施例に係るアノード基板の収縮
率時間依存性を比較例と対比して示す線図、第２図は従
来の固体電解電型燃料電池を示す分解斜視図である。
ｌニアノード基板、２：固体電解質体、３：カソード、
４：カソード基板、５：セパレータ。FIG. 1 is a diagram showing the time dependence of shrinkage rate of an anode substrate according to an example of the present invention in comparison with a comparative example, and FIG. 2 is an exploded perspective view showing a conventional solid electrolyte fuel cell. . l near node substrate, 2: solid electrolyte body, 3: cathode,
4: Cathode substrate, 5: Separator.
Claims (1)
工程は、酸化ニッケルとジルコニアの各粉体を混合し、
造粒したのち酸化ふん囲気中で熱処理して第一の造粒粉
を調製し、第二工程は、前記第一の造粒粉を還元ふん囲
気中で熱処理して第二の造粒粉を調製し、 第三工程は、第二の造粒粉を成型し、かつ還元ふん囲気
中で焼成することを特徴とする固体電解質型燃料電池の
製造方法。 ２）請求項１記載の製造方法において、酸化ニッケルと
ジルコニアの各粉体を混合したのちイットリア、マグネ
シア、カルシアまたはセリアにより部分安定化あるいは
完全安定化されたジルコニア粗粒粉を加えて造粒するこ
とを特徴とする固体電解質型燃料電池の製造方法。 ３）請求項２記載の製造方法において、ジルコニア粗粒
粉の粒度は、その平均粒子径が５０〜１００μｍの範囲
にあることを特徴とする固体電解質型燃料電池の製造方
法。[Claims] 1) It has a first step, a second step, and a third step, and the first step is to mix nickel oxide and zirconia powders,
After granulation, the first granulated powder is prepared by heat treatment in an oxidizing atmosphere, and in the second step, the first granulated powder is heat treated in a reducing atmosphere to prepare a second granulated powder. and the third step is to mold the second granulated powder and sinter it in a reducing atmosphere. 2) In the manufacturing method according to claim 1, after mixing each powder of nickel oxide and zirconia, coarse zirconia powder partially stabilized or completely stabilized with yttria, magnesia, calcia or ceria is added and granulated. A method for manufacturing a solid oxide fuel cell, characterized by: 3) The method of manufacturing a solid oxide fuel cell according to claim 2, wherein the average particle size of the coarse zirconia powder is in the range of 50 to 100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2271230A JP2734768B2 (en) | 1990-10-09 | 1990-10-09 | Method for manufacturing solid oxide fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2271230A JP2734768B2 (en) | 1990-10-09 | 1990-10-09 | Method for manufacturing solid oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04147569A true JPH04147569A (en) | 1992-05-21 |
| JP2734768B2 JP2734768B2 (en) | 1998-04-02 |
Family
ID=17497170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2271230A Expired - Lifetime JP2734768B2 (en) | 1990-10-09 | 1990-10-09 | Method for manufacturing solid oxide fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2734768B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6344426B1 (en) | 1998-05-20 | 2002-02-05 | Nippon Shokubai Co., Ltd. | Porous ceramic sheet, process for producing the same, and setter for use in the process |
| KR100756518B1 (en) * | 2006-03-22 | 2007-09-10 | 고등기술연구원연구조합 | Method of preparing a material for electrolysis |
| JP2012520394A (en) * | 2009-03-12 | 2012-09-06 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Melting cermet products |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101185010B1 (en) * | 2004-12-24 | 2012-09-21 | 재단법인 포항산업과학연구원 | Method for manufacturing cathode of cathode supported solid oxide fuel cell |
-
1990
- 1990-10-09 JP JP2271230A patent/JP2734768B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6344426B1 (en) | 1998-05-20 | 2002-02-05 | Nippon Shokubai Co., Ltd. | Porous ceramic sheet, process for producing the same, and setter for use in the process |
| KR100756518B1 (en) * | 2006-03-22 | 2007-09-10 | 고등기술연구원연구조합 | Method of preparing a material for electrolysis |
| JP2012520394A (en) * | 2009-03-12 | 2012-09-06 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Melting cermet products |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2734768B2 (en) | 1998-04-02 |
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