KR100259212B1 - Method of making the cathode used in mcfc - Google Patents

Method of making the cathode used in mcfc Download PDF

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KR100259212B1
KR100259212B1 KR1019980015240A KR19980015240A KR100259212B1 KR 100259212 B1 KR100259212 B1 KR 100259212B1 KR 1019980015240 A KR1019980015240 A KR 1019980015240A KR 19980015240 A KR19980015240 A KR 19980015240A KR 100259212 B1 KR100259212 B1 KR 100259212B1
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powder
prepare
aluminum oxide
fuel cell
slurry
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KR1019980015240A
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KR19990081359A (en
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윤영기
최영태
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윤영석
한국중공업주식회사
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    • 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
    • H01M4/88—Processes of manufacture
    • 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
    • H01M8/14—Fuel cells with fused electrolytes
    • 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

PURPOSE: A method for preparing fuel electrode of molten carbonate type fuel cell is provided, which improves sintering property and creep resistance and reduces the manufacturing cost. CONSTITUTION: The method comprises steps of: (i) dissolving a mixture of (NO3)26H2O and Al(NO3)3·9H2O in pure water to prepare a nitrate solution; (ii) coprecipitating an alkali solution in the nitrate solution to obtain powder and drying the obtained powder to prepare a mixture powder where 9-15wt.% of aluminum oxide is dispersed in nickel oxide powder particles; (iii) ball-milling the mixture powder of nickel oxide and aluminum oxide with solvent, binder, dispersing agent and antifoaming agent to prepare a slurry; (iv) after deaerating the slurry, tape-casting the slurry by using a doctor blade to prepare a sheet; and (v) sintering the obtained sheet under reduction atmosphere of nitrogen and hydrogen.

Description

용융탄산염형 연료전지의 연료극 제조방법Method for manufacturing anode of molten carbonate fuel cell

본 발명은 차세대 발전장치인 용융탄산염형 연료전지(이하 MCFC로 약칭함)를 구성하여, 반응 가스의 산화 반응을 통해 전자가 발생되게 하는 연료극에 관한 것으로, 특히 내부에서 산화물의 분포가 고르게 이루어져 소결성이 향상되고 크립(creep) 저항성이 낮아지도록 하는데 적합하게 이용될 수 있는 MCFC의 연료극 제조방법에 관한 것이다.The present invention relates to a fuel electrode that is a molten carbonate fuel cell (hereinafter referred to as MCFC), which is a next generation power generation device, and generates electrons through an oxidation reaction of a reaction gas. A method of manufacturing an anode of an MCFC which can be suitably used to improve this and lower creep resistance.

MCFC는 반응물의 산화, 환원에 의한 화학 에너지를 전기 에너지로 바꾸어주는 고효율, 저공해의 차세대 발전장치로 주목받고 있다.MCFC is attracting attention as the next generation of high efficiency and low pollution power generation equipment that converts chemical energy by oxidation and reduction of reactants into electrical energy.

이러한 MCFC는 연료극인 캐소드와 산소극인 애노드 및 그 사이에 전해질 매트릭스가 개재되고, 연료극과 산소극 및 전해질 매트릭스의 기공내에 전해질이 함침되어 있으며, 연료극과 산소극이 각각 전기를 집전하고 반응가스를 전극으로 전달하는 전류 집전체에 인접되어, 반응가스의 유, 출입 및 전기의 흐름을 연결시켜주는 분리판에 의해 지지되는 구조로 이루어진다.In the MCFC, an electrolyte matrix is interposed between a cathode, an anode, and an oxygen electrode, and an electrolyte is impregnated in the pores of the fuel electrode, the oxygen electrode, and the electrolyte matrix. Adjacent to the current collector to be delivered to, and consists of a structure that is supported by a separation plate connecting the flow of oil, in and out of the reaction gas.

이에 따라 MCFC는 연속적으로 공급되는 반응 가스에 의해 연료극에서 반응물의 산화 반응이 일어나 전자가 방출되는 것이며, 산소극에서 환원 반응이 일어나 전자가 받아들여짐으로써 화학 에너지가 전기 에너지로 전환되어 발생되도록 하고 있다.As a result, the MCFC oxidizes the reactants at the fuel electrode and emits electrons by continuously supplying the reaction gas, and the reduction reaction occurs at the oxygen electrode to accept the electrons, thereby converting the chemical energy into electrical energy. .

MCFC를 구성하는 요소로서, 반응 가스의 산화 반응을 통해 전자가 발생되게 하는 연료극은 니켈 소결체를 사용하고 있다. 이러한 연료극은 전지의 운전이 고온에서 장시간 이루어지므로, 소결 저항성 부족과 더불어 크립과 구조적 안전성 저하를 나타내고 있으며, 그로 인하여 기공의 구조와 분포의 변화가 일어나고, 전기적 접촉의 상실로 접촉 저항의 증가를 나타내는 문제점이 있다.As an element constituting the MCFC, a nickel sintered compact is used as a fuel electrode for generating electrons through an oxidation reaction of a reaction gas. Since the fuel cell is operated for a long time at a high temperature, the anode exhibits a lack of sintering resistance and a decrease in creep and structural safety, thereby causing changes in the structure and distribution of the pores, and an increase in contact resistance due to loss of electrical contact. There is a problem.

이에 따라 최근에는 니켈-알루미늄 합금을 사용하여 연료극의 크립 문제를 해결하는 방안이 제시되고 있다. 니켈-알루미늄 합금으로 된 연료극은 산화, 환원의 2단계 소결을 거쳐 제조되는 것으로, 소결 후 합금 입자 표면에 니켈 산화물이 포함되고, 그 내부로 알루미늄 산화물 입자들이 분포되어 우수한 크립 저항성과 소결 저항성을 갖추게 된다.Accordingly, a method of solving the creep problem of the anode using a nickel-aluminum alloy has been recently proposed. The anode made of nickel-aluminum alloy is manufactured through two-step sintering of oxidation and reduction, and after the sintering, nickel oxide is included on the surface of the alloy particles, and aluminum oxide particles are distributed therein to provide excellent creep resistance and sinter resistance. do.

그러나 종래의 니켈-알루미늄 합금의 제조방법은 2단계중의 산화 단계에서 전극의 기공 구조가 결정되어 이를 조절하기 어렵고 기공률이 낮은 문제점이 있으며, 알루미늄 분말이 표면으로 확산되어 산화 알루미늄(Al203)층을 형성하므로 소결이 어렵고, 소결 재료인 니켈-알루미늄 합금 분말의 가격이 고가여서 제조 비용이 높은 문제점이 있다.However, the conventional method of manufacturing a nickel-aluminum alloy has a problem in that the pore structure of the electrode is determined in the oxidation step of the second step, making it difficult to control and having low porosity, and aluminum powder is diffused to the surface to form an aluminum oxide (Al203) layer. Since the sintering is difficult to form, the nickel-aluminum alloy powder, which is a sintering material, is expensive, and thus manufacturing costs are high.

앞서 설명된 종래 기술의 문제점을 해소하기 위한 목적에서 안출된 것으로, 본 발명은 니켈과 알루미늄 산화물의 입자가 고르게 분포되도록 하여, 소결성이 향상되고 크립(creep) 저항성이 향상되도록 한 것이며, 낮은 비용으로 제조할 수 있도록 한 MCFC의 연료극 제조방법을 제공함에 그 목적을 두고 있다.In order to solve the problems of the prior art described above, the present invention is to ensure that the particles of nickel and aluminum oxide evenly distributed, to improve the sintering and creep resistance, and at a low cost It is an object of the present invention to provide a method for manufacturing an anode of an MCFC that can be manufactured.

이를 위하여 본 발명은 산화 알루미늄이 분산된 니켈 분말을 질산염으로부터 공침법을 사용하여 낮은 비용으로 제조하고, 이것을 소결하여 니켈 입자에 산화 알루미늄 입자가 분자단위로 미세하게 잘 분포된 연료극을 제조하는 방법을 제안한다.To this end, the present invention provides a method for producing a fuel electrode in which aluminum oxide is dispersed in nickel powder from nitrate using coprecipitation method at low cost, and sintering it to produce finely distributed aluminum oxide particles finely in molecular units. Suggest.

상기한 질산염은 Ni(NO3)26H2O 와 Al(NO3)3⋅9H2O 를 무게비 1: 0.148∼0.28로 혼합하고, 이 혼합물을 1: 0.5∼2의 무게비로 순수에 용해하여 얻어지는 것이며, 이렇게 형성된 질산염 용액은 공침법을 사용하여 알칼리 용액과 함께 교반되므로, 니켈 분말 입자에 산화 알루미늄이 9∼15중량%로 분산된 혼합 분말로 제조된다. 이어서 니켈과 산화 알루미늄의 혼합 분말은 용매, 바인더, 분산제 및 소포제와 함께 볼밀링되어 슬러리로 제조되고, 탈포 공정을 거친 후, 닥터 블레이드(doctor blade)를 이용하여 테이프 캐스팅되는 것이며, 질소/수소의 환원 분위기에서 소결되므로 본 발명의 목적물인 연료극으로 제조되는 것이다.The nitrates mentioned above Ni (NO 3 ) 2 6H 2 O Wow Al (NO 3 ) 3 ⋅9H 2 O Is obtained by dissolving at a weight ratio of 1: 0.148 to 0.28 and dissolving the mixture in pure water at a weight ratio of 1: 0.5 to 2, and the nitrate solution thus formed is stirred together with the alkaline solution using a coprecipitation method. Aluminum oxide is prepared from a mixed powder of 9 to 15% by weight. The mixed powder of nickel and aluminum oxide is then ball milled with a solvent, a binder, a dispersant, and an antifoaming agent to make a slurry, subjected to a defoaming process, and then tape cast using a doctor blade. Since it is sintered in a reducing atmosphere, it is manufactured from a fuel electrode which is an object of the present invention.

본 발명을 실현하기 위한 바람직한 실시예를 보다 상세하게 설명하면 다음과 같다.Preferred embodiments for realizing the present invention will be described in detail as follows.

먼저 본 발명에서는 니켈-알루미늄 합금 분말과 동일한 작용을 하는 산화 알루미늄이 분산된 니켈 분말을 제조하기 위해, 질산염으로부터 공침법을 사용하여 낮은 제조 비용으로 분말을 제조하고 있다.First, in the present invention, in order to produce a nickel powder in which aluminum oxide is dispersed, which has the same effect as a nickel-aluminum alloy powder, a powder is manufactured at low cost by using a coprecipitation method from nitrate.

상기한 질산염은 Ni(NO3)26H2O 와 Al(NO3)3⋅9H2O 를 무게비 1: 0.148∼0.28로 혼합하고, 이 혼합물을 1: 0.5∼2의 무게비로 80℃의 순수에 용해하여 얻어지는 것이다.The nitrates mentioned above Ni (NO 3 ) 2 6H 2 O Wow Al (NO 3 ) 3 ⋅9H 2 O Is obtained by mixing at a weight ratio of 1: 0.148 to 0.28 and dissolving the mixture in pure water at 80 ° C. at a weight ratio of 1: 0.5 to 2.

이렇게 얻어진 질산염 용액은 공침법을 이용하여 알칼리 용액( KOH )과 함께 섞여 교반되므로, 수산화 니켈과 수산화 알루미늄의 혼합물로 얻어지는 바, 그 반응식은 다음과 같다.The nitrate solution thus obtained was dissolved in an alkaline solution ( KOH ), And the mixture is agitated, resulting in a mixture of nickel hydroxide and aluminum hydroxide. The reaction scheme is as follows.

xNi+2+ yAl+3+ (2x+3y)OH-⇒ xNi(OH)2⋅yAl(OH)3⋅2H2OxNi +2 + yAl +3 + (2x + 3y) OH - ⇒ xNi (OH) 2 ⋅yAl (OH) 3 ⋅2H 2 O

여기서 얻어진 분말은 600∼800℃의 공기중에서 건조되므로, 니켈 분말 입자에 산화 알루미늄이 9∼15중량%로 분산된 NiO⋅(0.29∼0.56)Al 203 의 산화 니켈/산화 알루미늄 혼합 분말로 제조된다.The powder obtained here is dried in air at 600 to 800 ° C., so that 9 to 15% by weight of aluminum oxide is dispersed in the nickel powder particles. NiO⋅ (0.29 ~ 0.56) Al 203 Is prepared from a nickel oxide / aluminum oxide mixed powder.

이렇게 얻어진 산화 니켈과 산화 알루미늄의 혼합 분말은 볼밀링에 의해 크기를 3∼5㎛로 조절하여 적당한 용매에 무게비 1:1 정도 첨가하고, 다시 적당량의 바인더, 분산제 및 소포제(기포제거제)를 혼합하고 24~48시간 볼밀링하므로 슬러리 로 제조된다. 이어서 슬러리는 기포를 제거하기 위해 10~30분 정도 진공펌프에 의해 탈포되고, 닥터 블레이드를 이용하여 테이프 캐스팅된 후 건조되므로, 0.8㎜ 두께의 그린 쉬트로 제작된다.The mixed powder of nickel oxide and aluminum oxide thus obtained is adjusted to a size of 3 to 5 탆 by ball milling, and added in a weight ratio of about 1: 1 in a suitable solvent, and then an appropriate amount of binder, dispersant and antifoaming agent (foaming agent) are mixed. It is ball milled for 24 to 48 hours, so it is prepared as a slurry. Subsequently, the slurry is degassed by a vacuum pump for about 10 to 30 minutes to remove bubbles, tape-casted using a doctor blade, and then dried, thereby making a green sheet 0.8 mm thick.

여기서 얻어진 그린 쉬트는 질소/수소 환원 분위기의 연속 소결로에서 최고 온도 1,000∼1,300℃로 30분 동안 소결되므로 본 발명의 목적물인 연료극으로 제조되는 것이다. 이때 산화 니켈은 금속상의 니켈 금속으로 환원되어 최종 소결된다.The green sheet obtained here is sintered at a maximum temperature of 1,000 to 1,300 ° C. for 30 minutes in a continuous sintering furnace in a nitrogen / hydrogen reducing atmosphere, so that the green sheet is manufactured as a fuel electrode, which is the object of the present invention. At this time, the nickel oxide is reduced to nickel metal on the metal and finally sintered.

한편, 상기 소결 공정은 배치(batch)형의 로일 경우에도 마찬가지로 최고 온도 1,000∼1,300℃로 30분 동안 행하여진다.On the other hand, the sintering step is carried out for 30 minutes at a maximum temperature of 1,000 to 1,300 ° C. even in the case of a batch furnace.

이상에서 설명된 구성 및 작용을 통하여 알 수 있는 바와 같이, 본 발명에 의한 MCFC의 연료극 제조방법은 종래 기술의 문제점을 실질적으로 해소하고 있다.As can be seen through the configuration and operation described above, the method of manufacturing the anode of the MCFC according to the present invention substantially solves the problems of the prior art.

즉, 본 발명은 니켈-알루미늄 합금 분말과 동일 작용을 하는 산화 알루미늄이 분산된 니켈 분말을 질산염으로부터 공침법으로 침전 및 소성하여 제조하므로, 낮은 비용으로 제조할 수 있다.That is, according to the present invention, nickel powder in which aluminum oxide having the same function as nickel-aluminum alloy powder is dispersed is produced by precipitation and sintering from nitrate by coprecipitation method, and thus can be manufactured at low cost.

상기와 같이 산화 알루미늄이 분산된 니켈 분말은 환원 분위기에서 최종 소결시, 표면이 금속상의 니켈로 환원되고 그 내부에 산화 알루미늄 입자가 고르게 분포되므로 크립 저항성이 향상되는 효과를 얻을 수 있으며, 산화 알루미늄의 고른 분포로 소결성이 향상되고 접촉 저항이 최소화되는 효과를 얻을 수 있는 것이다.As described above, the nickel powder in which aluminum oxide is dispersed may have an effect of improving creep resistance since the surface is reduced to metallic nickel and the aluminum oxide particles are evenly distributed therein at the time of final sintering in a reducing atmosphere. Even distribution improves sinterability and minimizes contact resistance.

따라서 본 발명에 의하면 연료전지의 신뢰도가 향상되며 장기 운전이 가능하게 되는 효과도 아울러 얻을 수 있다.Therefore, according to the present invention, the reliability of the fuel cell is improved and long-term operation can be obtained.

Claims (4)

Ni(NO3)26H2O 와 Al(NO3)3⋅9H2O 의 혼합물을 순수에 용해하여 질산염 용액을 제조하는 단계와; 상기 질산염 용액에 알칼리 용액을 공침하고, 여기서 얻어진 분말을 건조하여 산화 니켈 분말 입자에 산화 알루미늄이 9∼15중량%로 분산된 혼합 분말을 제조하는 단계와; 산화 니켈과 산화 알루미늄의 혼합 분말을 용매, 바인더, 분산제 및 소포제와 함께 볼밀링하여 슬러리로 제조하고, 탈포 후, 닥터 블레이드를 이용하여 테이프 캐스팅하며, 여기서 얻어진 쉬트를 질소/수소의 환원 분위기에서 소결하는 단계를 포함하여 얻어짐을 특징으로 하는 용융탄산염형 연료전지의 연료극 제조방법. Ni (NO 3 ) 2 6H 2 O Wow Al (NO 3 ) 3 ⋅9H 2 O Dissolving the mixture in pure water to prepare a nitrate solution; Coprecipitating an alkali solution to the nitrate solution, and drying the powder obtained to prepare a mixed powder in which aluminum oxide is dispersed in a nickel oxide powder particle at 9 to 15% by weight; A mixed powder of nickel oxide and aluminum oxide is ball milled together with a solvent, a binder, a dispersant, and an antifoaming agent to prepare a slurry, and after defoaming, tape casting is performed using a doctor blade, and the sheet obtained is sintered in a reducing atmosphere of nitrogen / hydrogen. A method for producing a cathode of a molten carbonate fuel cell, characterized in that it is obtained, including the step of. 제 1 항에 있어서, Ni(NO3)26H2O 와 Al(NO3)3⋅9H2O 는 무게비 1: 0.148∼0.28로 혼합된 것임을 특징으로 하는 용융탄산염형 연료전지의 연료극 제조방법.The method of claim 1, Ni (NO 3 ) 2 6H 2 O Wow Al (NO 3 ) 3 ⋅9H 2 O The fuel cell manufacturing method of the molten carbonate fuel cell, characterized in that the weight ratio 1: 0.148 to 0.28 mixed. 제 1 항에 있어서, 산화 니켈과 산화 알루미늄의 혼합 분말은 볼밀링에 의해 3∼5㎛의 크기로 형성되는 것임을 특징으로 하는 용융탄산염형 연료전지의 연료극 제조방법.The method for manufacturing a fuel electrode of a molten carbonate fuel cell according to claim 1, wherein the mixed powder of nickel oxide and aluminum oxide is formed in a size of 3 to 5 mu m by ball milling. 제 1 항에 있어서, 소결은 1,000∼1,300℃에서 30분 동안 실시되는 것임을 특징으로 하는 용융탄산염형 연료전지의 연료극 제조방법.The method of claim 1, wherein the sintering is performed for 30 minutes at 1,000 ~ 1,300 ℃.
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KR100980205B1 (en) 2008-12-30 2010-09-03 두산중공업 주식회사 A method for manufacturing reinforced green sheet for in-situ sintering anode of molten carbonate fuel cell
KR101311786B1 (en) 2007-12-21 2013-09-25 재단법인 포항산업과학연구원 Fabricating method of anode for molten carbonate fuel cell

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KR100681771B1 (en) * 2005-02-01 2007-02-15 한국과학기술연구원 Ni-Al alloy anode for molten carbonate fuel cell by in-situ sintering the Ni-Al alloy and Method for preparing the same
KR100930206B1 (en) * 2008-05-08 2009-12-07 두산중공업 주식회사 Highly stable nickel-alumina reforming catalyst for internal reforming of molten carbonate fuel cell with strong poisoning resistance of potassium hydroxide and its manufacturing method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101311786B1 (en) 2007-12-21 2013-09-25 재단법인 포항산업과학연구원 Fabricating method of anode for molten carbonate fuel cell
KR100980205B1 (en) 2008-12-30 2010-09-03 두산중공업 주식회사 A method for manufacturing reinforced green sheet for in-situ sintering anode of molten carbonate fuel cell

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