JP2000001701A - Production of nickel series/zirconia series compound powder - Google Patents
Production of nickel series/zirconia series compound powderInfo
- Publication number
- JP2000001701A JP2000001701A JP10185675A JP18567598A JP2000001701A JP 2000001701 A JP2000001701 A JP 2000001701A JP 10185675 A JP10185675 A JP 10185675A JP 18567598 A JP18567598 A JP 18567598A JP 2000001701 A JP2000001701 A JP 2000001701A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- powder
- calcium
- zirconia
- strontium
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000843 powder Substances 0.000 title claims abstract description 59
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- -1 zirconia series compound Chemical class 0.000 title abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000975 co-precipitation Methods 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 18
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 239000007784 solid electrolyte Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 239000011230 binding agent Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- 101000650817 Homo sapiens Semaphorin-4D Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 102100027744 Semaphorin-4D Human genes 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、固体電解質型燃料
電池（以下ＳＯＦＣとも言う）の燃料極等として好適な
ニッケル系／ジルコニウム系複合粉末の製造方法に関す
る。特には、ＳＯＦＣ用燃料極材料として導電性の向上
に寄与し得る、ニッケル系／ジルコニウム系複合粉末の
製造方法に関する。The present invention relates to a method for producing a nickel-based / zirconium-based composite powder suitable as a fuel electrode of a solid oxide fuel cell (hereinafter also referred to as SOFC). In particular, the present invention relates to a method for producing a nickel-based / zirconium-based composite powder that can contribute to improvement in conductivity as a fuel electrode material for an SOFC.
【０００２】[0002]
【従来の技術】ＳＯＦＣの燃料極用材料としては、Ｎｉ
ＯとＹ2Ｏ3安定化ＺｒＯ2（ＹＳＺ）とを混合複合化し
た複合粉末の焼成層が主に用いられている（特開昭６１
−１５３２８０、特開昭６１−１９８５７０等）。な
お、焼成層中のＮｉＯは、ＳＯＦＣの運転中に還元され
てＮｉとなり、該層はＮｉ／ＹＳＺサーメット膜とな
る。2. Description of the Related Art As a fuel electrode material for SOFC, Ni
A baked layer of a composite powder in which O and Y 2 O 3 stabilized ZrO 2 (YSZ) are mixed and compounded is mainly used (Japanese Patent Application Laid-Open No. S61 / 1986).
153280, JP-A-61-198570). Note that NiO in the fired layer is reduced to Ni during operation of the SOFC, and the layer becomes a Ni / YSZ cermet film.
【０００３】このようなＮｉ／ＹＳＺサーメット用の原
料粉末の製造方法としては、一般的に、ＮｉＯ粉末とＹ
ＳＺ粉末を両者とも固体の状態で混合し、その後昇温
（仮焼）して若干焼結することにより複合化する方法
（固体混合法）が採られている。混合方法としては、ボ
ールミルを用いるものや、メカノケミカル的機械混合に
よるものが知られている。また、Ｎｉ，Ｚｒ，Ｙをイオ
ン状態で混合し、これを熱分解する方法も提案されてい
る（特開平７−２９５７５）。[0003] As a method for producing such a raw material powder for Ni / YSZ cermet, generally, NiO powder and Y
A method in which both SZ powders are mixed in a solid state and then heated (calcined) and slightly sintered to form a composite (solid mixing method) is employed. As a mixing method, a method using a ball mill and a method using mechanochemical mechanical mixing are known. A method has also been proposed in which Ni, Zr, and Y are mixed in an ionic state and thermally decomposed (Japanese Patent Laid-Open No. 7-29575).
【０００４】[0004]
【発明が解決しようとする課題】Ｎｉ及び／又はＮｉＯ
とＹＳＺの複合粉末をＳＯＦＣの燃料極として使用する
際には、ＹＳＺ基板上への成膜を行うため、微細粒子で
あると、焼成時に、焼成クラックが生じる。したがっ
て、Ｎｉ及び／又はＮｉＯとＹＳＺの複合粉末を粗大粒
化する必要がある。粗大粒化する方法としては、高温
（８００℃〜１６００℃）での熱処理を行い、一次粒子
自体を粗大粒化する必要がある。上述の従来組成のＮｉ
Ｏ／ＹＳＺ複合粉末では、高温で熱処理して合成した場
合、導電率が低下する。SUMMARY OF THE INVENTION Ni and / or NiO
When a composite powder of YSZ and YSZ is used as a fuel electrode of an SOFC, a film is formed on a YSZ substrate. Therefore, it is necessary to coarsen the composite powder of Ni and / or NiO and YSZ. As a method for coarsening, it is necessary to perform a heat treatment at a high temperature (800 ° C. to 1600 ° C.) to coarsen the primary particles themselves. Ni of the above-mentioned conventional composition
When the O / YSZ composite powder is synthesized by heat treatment at a high temperature, the electrical conductivity decreases.
【０００５】本発明は、このような問題点に鑑みてなさ
れたもので、固体電解質型燃料電池の燃料極としてニッ
ケル系／ジルコニウム系複合粉末にカルシウム、ストロ
ンチウム、マグネシウムを少なくとも１種類以上の添加
元素を加えることにより導電性が向上した、ニッケル系
／ジルコニウム系粉末の製造方法を提供することを目的
とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and at least one of calcium, strontium, and magnesium is added to a nickel-based / zirconium-based composite powder as a fuel electrode of a solid oxide fuel cell. It is an object of the present invention to provide a method for producing a nickel-based / zirconium-based powder in which conductivity is improved by the addition of nickel.
【０００６】[0006]
【課題を解決するための手段およびその作用・効果】上
記目的を達成するために、ニッケル及び／又は酸化ニッ
ケルと、イットリアドープジルコニア（ＹＳＺ）からな
る複合粉末であって、カルシウム、ストロンチウム、マ
グネシウムを少なくとも１種類以上、ジルコニウム元素
に対して５０ｍｏｌ％以下量を、望ましくは３０ｍｏｌ
％以下量を、添加した粉末であって、出発原料が硝酸
塩、硫酸塩、炭酸塩あるいは塩化物等の水溶性の金属塩
であり、共沈法により合成し、 上記粉末を８００℃〜
１６００℃の温度にて熱処理したニッケル系／ジルコニ
ア系複合粉末の製造方法とした。Means for Solving the Problems and Actions and Effects There is provided a composite powder comprising nickel and / or nickel oxide and yttria-doped zirconia (YSZ), comprising calcium, strontium and magnesium. An amount of at least one kind, not more than 50 mol% based on the zirconium element, preferably 30 mol%
% Or less, wherein the starting material is a water-soluble metal salt such as nitrate, sulfate, carbonate or chloride, synthesized by a coprecipitation method,
A method for producing a nickel-based / zirconia-based composite powder heat-treated at a temperature of 1600 ° C. was adopted.
【０００７】本発明の特徴は、燃料極粉末の合成におい
て、ニッケル系／ジルコニア系複合粉末において、カル
シウム、ストロンチウム、マグネシウムの少なくとも１
種類以上の添加元素を加えることにある。カルシウム、
ストロンチウム、マグネシウムの少なくとも１種類以上
の添加元素をニッケル系／ジルコニア系複合粉末中に添
加することにより、複合粉末の焼結性が向上することに
より、導電性を向上させようとするものである。[0007] A feature of the present invention is that in the synthesis of an anode powder, at least one of calcium, strontium and magnesium is contained in a nickel-based / zirconia-based composite powder.
It is to add more than one kind of additional element. calcium,
By adding at least one or more additional elements of strontium and magnesium to the nickel-based / zirconia-based composite powder, the sinterability of the composite powder is improved, thereby improving the conductivity.
【０００８】[0008]
【発明の実施の形態】本発明のカルシウム、ストロンチ
ウム、マグネシウムを添加したニッケル系／ジルコニア
系複合粉末を固体電解質型燃料電池に適用する場合にお
いては、固体電解質との界面においては、ＮｉＯ及び／
又はＮｉが３０〜５０ｍｏｌ％程度とし、界面の上部の
層においては、ＮｉＯ及び／又はＮｉが５０ｍｏｌ％以
上とする。その理由は、固体電解質との界面において
は、固体電解質材料であるＹＳＺとの密着性が重要であ
り、ＮｉＯ及び／又はＮｉが５０ｍｏｌ％以上となる
と、密着性が低下するからである。また、界面の上部の
層においては、高い導電性を必要とし、ＮｉＯ及び／又
はＮｉが５０ｍｏｌ％より少ないと、導電性が急激に低
下するからである。BEST MODE FOR CARRYING OUT THE INVENTION When the nickel / zirconia-based composite powder to which calcium, strontium and magnesium of the present invention are added is applied to a solid oxide fuel cell, NiO and / or
Alternatively, Ni is about 30 to 50 mol%, and NiO and / or Ni is 50 mol% or more in the upper layer of the interface. The reason is that, at the interface with the solid electrolyte, the adhesion to YSZ, which is a solid electrolyte material, is important, and when NiO and / or Ni is 50 mol% or more, the adhesion is reduced. In addition, the upper layer of the interface requires high conductivity, and if the content of NiO and / or Ni is less than 50 mol%, the conductivity is sharply reduced.
【０００９】本発明におけるニッケル系／ジルコニア系
複合粉末中のＹＳＺのＹ2Ｏ3含有量は、望ましくは３〜
２０ｍｏｌ％であり、より好ましくは８〜１２ｍｏｌ％
である。その理由は、固体電解質に用いるＹＳＺのイオ
ン導電性がこの範囲が優れているため、固体電解質と燃
料極とのマッチングの点からである。The YSZ Y 2 O 3 content in the nickel-based / zirconia-based composite powder in the present invention is desirably 3 to 3.
20 mol%, more preferably 8 to 12 mol%
It is. The reason is that the ion conductivity of YSZ used for the solid electrolyte is excellent in this range, so that the solid electrolyte and the fuel electrode are matched.
【００１０】本発明の複合粉末の製造方法としては共沈
法によることが好ましい。ＮｉＯ／ＹＳＺ複合粉末の共
沈法による製造方法については、本願と同一出願人によ
る出願（特開平９−２２７２１２）に詳述されている。
共沈法によれば、均一な組織・組成の複合粉末が得ら
れ、電極（燃料電極）と固体電解質間の界面導電率を固
体混合法による複合粉末の場合と比較して数段増大でき
る。The method for producing the composite powder of the present invention is preferably a coprecipitation method. The method for producing the NiO / YSZ composite powder by the coprecipitation method is described in detail in an application filed by the same applicant as the present application (Japanese Patent Application Laid-Open No. 9-227212).
According to the coprecipitation method, a composite powder having a uniform structure and composition can be obtained, and the interface conductivity between the electrode (fuel electrode) and the solid electrolyte can be increased by several steps as compared with the composite powder obtained by the solid mixing method.
【００１１】本発明のニッケル系／ジルコニア系複合粉
末において共沈法により合成した粉末においては、８０
０℃〜１６００℃の温度にて熱処理することが望まし
い。８００℃より低いと、カルシウム、ストロンチウ
ム、マグネシウムを添加していないニッケル系／ジルコ
ニア系複合粉末においても、十分な焼結性を有している
ため添加元素の効果は特に、現れない。また、１６００
℃よりも高いと、ニッケル系／ジルコニア系複合粉末中
の特に、ジルコニアの焼結が進行しすぎることにより、
添加元素による焼結性の向上が現れなくなる。The powder synthesized by the coprecipitation method in the nickel / zirconia composite powder of the present invention has
It is desirable to heat-treat at a temperature of 0 ° C to 1600 ° C. If the temperature is lower than 800 ° C., the effect of the added element is not particularly exhibited even in a nickel-based / zirconia-based composite powder to which calcium, strontium, and magnesium are not added, because the powder has sufficient sinterability. Also, 1600
C., the sintering of zirconia in the nickel-based / zirconia-based composite powder in particular proceeds excessively,
No improvement in sinterability due to the added element appears.
【００１２】[0012]
【実施例】以下、本発明の実施例を説明する。 実施例１：共沈法による合成 （１） 複合粉末調整：ＹＳＺ原料としての硝酸ジルコ
ニウム・イットリウム水溶液（８ｍｏｌ％Ｙ2Ｏ3含
有）、ＮｉＯ原料として硝酸ニッケル水溶液を用いて、
ＹＳＺとＮｉＯがモル比で４：６となるように調合し、
また、カルシウム、ストロンチウムおよびマグネシウム
源として硝酸カルシウム、硝酸ストロンチウムおよび硝
酸マグネシウムを用いてＹＳＺ中のジルコニウム元素に
対して１ｍｏｌ％から５０ｍｏｌ％添加し、十分撹拌を
行う。Embodiments of the present invention will be described below. Example 1 Synthesis by Coprecipitation Method (1) Preparation of Composite Powder: Using an aqueous solution of zirconium nitrate / yttrium (containing 8 mol% Y 2 O 3 ) as a YSZ raw material and an aqueous solution of nickel nitrate as a NiO raw material,
YSZ and NiO are mixed in a molar ratio of 4: 6,
Further, calcium nitrate, strontium nitrate, and magnesium nitrate are used as calcium, strontium, and magnesium sources, and 1 to 50 mol% is added to the zirconium element in YSZ, followed by sufficient stirring.
【００１３】（２） 共沈溶液調整：本実施例において
は、共沈溶液として蓚酸水溶液を用いた。容器に純水を
取り、約８０℃程度に加熱する。この温水を撹拌しなが
ら蓚酸２水和物結晶を徐々に添加して溶解し、７０℃〜
９０℃に保持した。蓚酸水溶液の量については、共沈工
程において金属イオンが完全に沈殿するように、蓚酸量
を化学量論比よりもわずかに過剰となるようすることが
好ましい。今回の過剰量は約５ｍｏｌ％とした。(2) Preparation of coprecipitation solution: In this embodiment, an oxalic acid aqueous solution was used as the coprecipitation solution. Take pure water in a container and heat to about 80 ° C. While stirring the hot water, oxalic acid dihydrate crystals are gradually added and dissolved,
It was kept at 90 ° C. Regarding the amount of the oxalic acid aqueous solution, it is preferable that the amount of the oxalic acid is slightly larger than the stoichiometric ratio so that the metal ions are completely precipitated in the coprecipitation step. The excess amount this time was about 5 mol%.
【００１４】（３） 共沈反応：７０℃〜９０℃に加温
した原料溶液（ＮｉＯ／ＹＳＺ複合溶液）を蓚酸水溶液
中に、よく撹拌しながら徐々に添加していくことで、蓚
酸共沈法による沈殿生成を行った。(3) Coprecipitation reaction: The raw material solution (NiO / YSZ composite solution) heated to 70 ° C. to 90 ° C. is gradually added to an oxalic acid aqueous solution with good stirring, so that oxalic acid coprecipitation is performed. Precipitation by the method was performed.
【００１５】（４） 乾燥：乾燥機内にポリエチレン製
容器を静置し、１２０℃の熱風を送り沈殿物の水分及び
硝酸を蒸発させた。(4) Drying: A polyethylene container was allowed to stand in a dryer, and hot air at 120 ° C. was sent to evaporate water and nitric acid in the precipitate.
【００１６】（５） 熱分解：乾燥後の試料を５００
℃、５時間の熱処理により、残留の硝酸成分と蓚酸を除
去した。(5) Pyrolysis: 500 samples after drying
The residual nitric acid component and oxalic acid were removed by heat treatment at 5 ° C. for 5 hours.
【００１７】（６） 粉砕：熱分解により粉末化した試
料を粗粉砕機や乳鉢等により粒度調整を行う。本実験に
おいては、アルミナ質乳鉢により、二次粒子径を１８０
μｍ以下とした。(6) Pulverization: The particle size of the sample powdered by thermal decomposition is adjusted using a coarse pulverizer or a mortar. In this experiment, the secondary particle diameter was set to 180 using an alumina mortar.
μm or less.
【００１８】（７） 熱処理：得られた粉末に対して、
６００℃から１８００℃の熱処理を行った。(7) Heat treatment: For the obtained powder,
A heat treatment at 600 ° C. to 1800 ° C. was performed.
【００１９】（８） 再粉砕：熱処理を行った粉末に対
して、再度、アルミナ質乳鉢により、二次粒子径を１８
０μｍ以下とした。(8) Re-pulverization: The powder subjected to the heat treatment is again subjected to an alumina mortar to reduce the secondary particle diameter to 18%.
The thickness was set to 0 μm or less.
【００２０】（９）プレス体作製：上記、熱処理・再粉
砕を行った粉末にバインダーとして、ＰＶＡを１％添加
した後、５０ｍｍ×５ｍｍ×５ｍｍ程度のプレス体を作
製した。(9) Preparation of pressed body: After adding 1% of PVA as a binder to the heat-treated / reground powder, a pressed body of about 50 mm × 5 mm × 5 mm was prepared.
【００２１】実施例２：固体混合法による合成 （１０）複合粉末調整：１μｍ以下、平均粒径０．５μ
ｍ粒径のＹＳＺ粉末と、５〜５０μｍ、平均粒径１５μ
ｍのＮｉＯ粉末がＹＳＺとＮｉＯがモル比で４：６とな
るように調合し、また、１μｍ以下、平均粒径０．３μ
ｍ粒径のＣａＯ粉末をＹＳＺ中のジルコニウム元素に対
して１ｍｏｌ％から５０ｍｏｌ％添加し、ボールミルに
て５０時間混合を行う。Example 2: Synthesis by solid mixing method (10) Preparation of composite powder: 1 μm or less, average particle size 0.5 μm
YSZ powder with m particle size, 5-50 μm, average particle size 15 μ
m of NiO powder is prepared so that the molar ratio of YSZ to NiO is 4: 6, and 1 μm or less, average particle diameter of 0.3 μm.
CaO powder having m particle size is added in an amount of 1 mol% to 50 mol% with respect to the zirconium element in YSZ, and the mixture is mixed by a ball mill for 50 hours.
【００２２】（１１）プレス体作製：上記、混合粉末に
バインダーとして、ＰＶＡを１ｗｔ％添加した後、５０
ｍｍ×５ｍｍ×５ｍｍ程度のプレス体を作製した。(11) Preparation of pressed body: After adding 1 wt% of PVA as a binder to the mixed powder, 50%
A pressed body of about mm × 5 mm × 5 mm was produced.
【００２３】（１２）焼成：上記（９）及び（１２）で
作製したプレス体を１３５０℃×５時間の条件で焼結体
を得た。(12) Firing: The pressed body produced in the above (9) and (12) was sintered at 1350 ° C. for 5 hours.
【００２４】（１３）還元処理：水素：窒素＝１：２流
量をフローさせた雰囲気において、１０００℃×１０時
間の還元処理を行うことで酸化ニッケルをニッケルに還
元した。(13) Reduction treatment: Nickel oxide was reduced to nickel by performing a reduction treatment at 1000 ° C. for 10 hours in an atmosphere in which a flow rate of hydrogen: nitrogen = 1: 2 was flowed.
【００２５】（１４）導電率測定：上記、還元処理を施
したプレス体について、３％水蒸気加湿―水素雰囲気、
１０００℃条件において、直流四端子法により導電率の
測定を行った。図１、図２、及び図３は、共沈法により
カルシウム元素、ストロンチウム元素及びマグネシウム
元素を添加して合成した粉末において、各熱処理温度に
おける粉末を用いた、プレス体のカルシウム、ストロン
チウム及びマグネシウム添加量と導電率との関係を示す
グラフである。３種類の添加元素全てにおいて、熱処理
温度８００℃〜１６００℃においては、導電率が急激に
増加した。添加元素の添加量としては、調べた範囲であ
る５０ｍｏｌ％以下では、添加していない場合と比べて
導電率の増加があった。特に３０ｍｏｌ％以下の添加量
において導電率が大幅に増加した。図４は、固体混合法
によりカルシウム元素を添加した粉末を用いた、プレス
体のカルシウム添加量と導電率との関係を示す。共沈法
により合成した粉末を用いた場合と同様に、カルシウム
添加を行うことで、導電率が増加した。(14) Conductivity measurement: 3% steam humidified-hydrogen atmosphere,
At 1000 ° C., the conductivity was measured by a DC four-terminal method. FIGS. 1, 2, and 3 show that calcium, strontium, and magnesium were added to a pressed body by using powders at each heat treatment temperature in a powder synthesized by adding calcium, strontium, and magnesium by a coprecipitation method. It is a graph which shows the relationship between quantity and conductivity. In all three types of additive elements, the electrical conductivity sharply increased at a heat treatment temperature of 800 ° C to 1600 ° C. When the amount of the additional element added was 50 mol% or less, which is the range of investigation, the conductivity increased compared to the case where no element was added. In particular, the conductivity increased significantly at an addition amount of 30 mol% or less. FIG. 4 shows the relationship between the amount of calcium added and the electrical conductivity of a pressed body using a powder to which calcium was added by the solid mixing method. As in the case of using the powder synthesized by the coprecipitation method, the conductivity was increased by adding calcium.
【００２６】[0026]
【発明の効果】以上の説明から明らかなように、本発明
によれば、ニッケル系ジルコニア系複合粉末にカルシウ
ム、ストロンチウム及びマグネシウムを添加することに
より、導電率を大幅に増加させることが可能となった。As is apparent from the above description, according to the present invention, it is possible to greatly increase the conductivity by adding calcium, strontium and magnesium to a nickel-based zirconia-based composite powder. Was.
【図面の簡単な説明】[Brief description of the drawings]
【図１】共沈法による合成においてカルシウムを添加し
た場合の添加量と導電率との関係を示す図。FIG. 1 is a graph showing the relationship between the amount of calcium added and the conductivity when calcium is added in synthesis by the coprecipitation method.
【図２】共沈法による合成においてストロンチウムを添
加した場合の添加量と導電率との関係を示す図。FIG. 2 is a graph showing the relationship between the amount of strontium added and the electrical conductivity when strontium is added in the synthesis by the coprecipitation method.
【図３】共沈法による合成においてマグネシウムを添加
した場合の添加量と導電率との関係を示す図。FIG. 3 is a graph showing the relationship between the amount of magnesium and the conductivity when magnesium is added in the synthesis by the coprecipitation method.
【図４】固体混合法による合成においてカルシウムを添
加した場合の添加量と導電率との関係を示す図。FIG. 4 is a graph showing the relationship between the amount of calcium added and the electrical conductivity when calcium is added in the synthesis by the solid mixing method.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０４Ｂ 35/48 Ｈ０１Ｍ 4/88 Ｔ Ｈ０１Ｍ 4/88 Ｃ０４Ｂ 35/48 Ｂ Ｆターム(参考） 4G031 AA03 AA04 AA05 AA08 AA12 AA23 BA03 GA01 GA05 4G048 AA05 AB02 AB05 AC06 AD03 AE05 4K017 AA06 BA03 BA10 BB11 BB18 DA01 EJ02 4K018 BA04 BA20 BC12 CA11 DA14 DA21 FA09 KA38 5H018 AA06 BB01 EE02 EE04 HH05──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C04B 35/48 H01M 4/88 T H01M 4/88 C04B 35/48 B F term (Reference) 4G031 AA03 AA04 AA05 AA08 AA12 AA23 BA03 GA01 GA05 4G048 AA05 AB02 AB05 AC06 AD03 AE05 4K017 AA06 BA03 BA10 BB11 BB18 DA01 EJ02 4K018 BA04 BA20 BC12 CA11 DA14 DA21 FA09 KA38 5H018 AA06 BB01 EE02 EE04 HH05
Claims (5)
ットリアドープジルコニア（ＹＳＺ）からなる複合粉末
であって、カルシウム、ストロンチウム、マグネシウム
を少なくとも１種類以上添加して粉末を合成することを
特徴とするニッケル系／ジルコニア系複合粉末。1. A composite powder comprising nickel and / or nickel oxide and yttria-doped zirconia (YSZ), wherein at least one of calcium, strontium and magnesium is added to synthesize the powder. -Based / zirconia-based composite powder.
ネシウムを少なくとも１種類以上を、ジルコニウム元素
に対して５０ｍｏｌ％以下量を添加して粉末を合成する
ことを特徴とする請求項１記載のニッケル系／ジルコニ
ア系複合粉末。2. The nickel-based / zirconia-based powder according to claim 1, wherein at least one of calcium, strontium and magnesium is added in an amount of 50 mol% or less based on zirconium element. Composite powder.
ネシウムを少なくとも１種類以上を、ジルコニウム元素
に対して３０ｍｏｌ％以下量を添加して粉末を合成する
ことを特徴とする請求項１記載のニッケル系／ジルコニ
ア系複合粉末。3. The nickel-based / zirconia-based powder according to claim 1, wherein at least one of calcium, strontium and magnesium is added in an amount of 30 mol% or less based on zirconium element. Composite powder.
炭酸塩あるいは塩化物等の水溶性の金属塩であり、共沈
法により合成した請求項１〜３記載のニッケル系／ジル
コニア系複合粉末の製造方法。4. The method according to claim 1, wherein the starting material of the powder is nitrate, sulfate,
The method for producing a nickel-based / zirconia-based composite powder according to any one of claims 1 to 3, which is a water-soluble metal salt such as a carbonate or a chloride and is synthesized by a coprecipitation method.
にて熱処理することを特徴とする請求項１〜４記載のニ
ッケル系／ジルコニア系複合粉末の製造方法。5. The method for producing a nickel-based / zirconia-based composite powder according to claim 1, wherein said powder is heat-treated at a temperature of 800 ° C. to 1600 ° C.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10185675A JP2000001701A (en) | 1998-06-16 | 1998-06-16 | Production of nickel series/zirconia series compound powder |
| US09/673,934 US6692855B1 (en) | 1998-04-21 | 1999-04-19 | Solid electrolyte type fuel cell and method of producing the same |
| PCT/JP1999/002048 WO1999054946A1 (en) | 1998-04-21 | 1999-04-19 | Solid electrolyte fuel cell and method of producing the same |
| AU31713/99A AU3171399A (en) | 1998-04-21 | 1999-04-19 | Solid electrolyte fuel cell and method of producing the same |
| EP99913694A EP1081778A4 (en) | 1998-04-21 | 1999-04-19 | Solid electrolyte fuel cell and method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10185675A JP2000001701A (en) | 1998-06-16 | 1998-06-16 | Production of nickel series/zirconia series compound powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000001701A true JP2000001701A (en) | 2000-01-07 |
Family
ID=16174910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10185675A Pending JP2000001701A (en) | 1998-04-21 | 1998-06-16 | Production of nickel series/zirconia series compound powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000001701A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003346820A (en) * | 2002-05-30 | 2003-12-05 | Sulzer Hexis Ag | Ink manufacturing method |
| JP2004327278A (en) * | 2003-04-25 | 2004-11-18 | Nissan Motor Co Ltd | Electrode material for fuel cell, and solid oxide fuel cell using same |
| KR100921218B1 (en) | 2009-03-26 | 2009-10-09 | 재단법인 구미전자정보기술원 | Method for manufacturing an anode for solid oxide fuel cell |
| KR101176795B1 (en) | 2009-04-09 | 2012-08-27 | 연세대학교 산학협력단 | M/Ni-YSZ composite for fuel cell, the method of preparing the same, fuel cell using the same |
-
1998
- 1998-06-16 JP JP10185675A patent/JP2000001701A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003346820A (en) * | 2002-05-30 | 2003-12-05 | Sulzer Hexis Ag | Ink manufacturing method |
| JP4603773B2 (en) * | 2002-05-30 | 2010-12-22 | ヘクシス アクチェンゲゼルシャフト | Ink production method |
| JP2004327278A (en) * | 2003-04-25 | 2004-11-18 | Nissan Motor Co Ltd | Electrode material for fuel cell, and solid oxide fuel cell using same |
| JP4534188B2 (en) * | 2003-04-25 | 2010-09-01 | 日産自動車株式会社 | Fuel cell electrode material and solid oxide fuel cell using the same |
| KR100921218B1 (en) | 2009-03-26 | 2009-10-09 | 재단법인 구미전자정보기술원 | Method for manufacturing an anode for solid oxide fuel cell |
| KR101176795B1 (en) | 2009-04-09 | 2012-08-27 | 연세대학교 산학협력단 | M/Ni-YSZ composite for fuel cell, the method of preparing the same, fuel cell using the same |
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