WO2018030691A1 - Procédé de fabrication de poudre composite dans une structure noyau-enveloppe pour pile à combustible à oxyde solide - Google Patents

Procédé de fabrication de poudre composite dans une structure noyau-enveloppe pour pile à combustible à oxyde solide Download PDF

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Publication number
WO2018030691A1
WO2018030691A1 PCT/KR2017/008222 KR2017008222W WO2018030691A1 WO 2018030691 A1 WO2018030691 A1 WO 2018030691A1 KR 2017008222 W KR2017008222 W KR 2017008222W WO 2018030691 A1 WO2018030691 A1 WO 2018030691A1
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WO
WIPO (PCT)
Prior art keywords
core
shell structure
fuel cell
solid oxide
oxide fuel
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PCT/KR2017/008222
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English (en)
Korean (ko)
Inventor
오성민
이영호
윤치호
곽진호
김장한
Original Assignee
대주전자재료 주식회사
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Priority claimed from KR1020160108660A external-priority patent/KR20180018231A/ko
Application filed by 대주전자재료 주식회사 filed Critical 대주전자재료 주식회사
Publication of WO2018030691A1 publication Critical patent/WO2018030691A1/fr

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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
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • 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

Definitions

  • the present invention relates to a composite powder of a core-shell structure for a solid oxide fuel cell (SOFC) and a method of manufacturing the same, and more particularly to nickel, zirconium, and yttrium, which are stably formed in a core shell structure, so that the anode is heated at a high temperature.
  • the present invention relates to a method for producing a composite powder of a core-shell structure for a solid oxide fuel cell (SOFC) having a novel structure that can improve sintering and electrical conductivity while preventing deformation due to coarsening and shrinkage of nickel during operation.
  • Solid Oxide Fuel Cell which converts chemical energy directly into electrical energy, has high energy conversion efficiency, and it is possible to use various fuels by its own internal reforming. As it can be improved, it is attracting attention as a next generation energy source.
  • Solid oxide fuel cell is a structure that uses high oxygen ion conductivity of oxide electrolyte and connects anodes in series, and requires spatial separation of hydrogen and oxygen in order to use electron transfer. It is a battery that uses an electric current generated by chemical bonds to induce electrons to move to another pole.
  • a fuel electrode material nickel oxide (NiO) and stabilized zirconia (YSZ) are generally used as a mixture, and an electrolyte is used.
  • Y2O3 ceria
  • Scandia Sc2O3
  • Gd2O3 gadolinium oxide
  • ZrO2O3 zirconia
  • CeO2O3 ceria
  • Gd2O3 gadolinium oxide
  • SOFC solid oxide fuel cell
  • Yttria-stabilized zirconia which is stabilized by addition of nickel or nickel oxide and yttria, is used as a fuel electrode of a solid oxide fuel cell which is commonly used at present.
  • Nickel is an excellent conductor of electrons in the high-temperature reduction atmosphere and acts as a transport path for electrons.
  • Yttria stabilized zirconia prevents coarsening of the skeleton and nickel particles that maintain the microstructure, and adjusts the thermal expansion coefficient to be similar to other components. It forms an oxygen ion path and serves as an excellent ion conductor.
  • the anode mixed with nickel oxide and stabilized zirconia has a simple mixing method, but since the attraction force between stabilized zirconia and stabilized zirconia, nickel oxide and nickel oxide, or stabilized zirconia and nickel oxide is different from each other, the two powders under the same dispersion conditions At the same time it is not dispersed and aggregation of the powders occurs.
  • homogeneous aggregation of relatively large powders, where there is a difference in size of the powders can lead to microstructure non-uniformity of the anode.
  • about 30% of volume shrinkage occurs during heat treatment in a reducing atmosphere using nickel oxide and stabilized zirconia.
  • volume shrinkage occurs, electrical conductivity decreases due to the decrease in strength of the anode and the occurrence of cracks.
  • nickel (Ni) and stabilized zirconia are used, volume shrinkage does not occur and does not cause deterioration in the reducing atmosphere. It has advantages
  • Non-uniformities such as shape, size, and cohesion of the raw materials constituting the anode may adversely affect the properties of the anode, such as electrical conductivity, fuel permeability, and three-phase interface activity, which may degrade the durability, mechanical properties, and output characteristics of the unit cell. do.
  • the grain size and pores are non-uniform in size, and densification and coarsening of Ni occur. The coarsening of Ni generated in this way causes volume change by thermal cycle and redox reaction, resulting in damage of electrolyte, Ni, YSZ and Due to the reduction of the three-phase interface consisting of pores, the electrochemical activity is reduced to reduce the output of the unit cell.
  • An object of the present invention is to provide a cathode composite having a new structure of nickel yttria core-cell in order to solve the problem of the anode mixed with nickel oxide and stabilized zirconia.
  • Another object of the present invention is to provide a method for producing a fuel electrode having a novel structure according to the present invention.
  • the present invention to solve the above problems
  • a core portion composed of at least one component of Ni particles or NiO particles
  • SOFC solid oxide fuel cell
  • the average diameter of the core portion is 0.1 to 5.0 ⁇ m, and the average thickness of the shell portion is 10 to 500 nm.
  • the shell portion is characterized in that it contains yttrium and zirconium.
  • the composite powder of the core-shell structure for a solid oxide fuel cell (SOFC) according to the present invention is characterized in that 40 to 80% by weight of nickel, 1 to 10% by weight of yttrium, and 20 to 60% by weight of zirconium.
  • the composite powder of the core-shell structure for a solid oxide fuel cell (SOFC) according to the present invention is characterized by having a specific surface area of 1 to 20 m 2 / g.
  • the composite powder of the core-shell structure for a solid oxide fuel cell (SOFC) according to the present invention is characterized in that the average particle size (D50) is 0.2 to 20um.
  • the present invention also provides
  • the zirconium precursor is zirconium hydroxide (Zr (OH) 4 ), and the yttrium precursor is yttrium nitrate Y (NO 3). ) 3 ⁇ 6H 2 O.
  • the present invention also provides
  • the composite powder of the core-shell structure for a solid oxide fuel cell (SOFC) according to the present invention is stably formed with a core shell structure of nickel, zirconium, and yttrium, which is caused by coarsening and shrinking of nickel when the anode is operated at a high temperature. It can improve sintering and electrical conductivity while preventing deformation.
  • Figure 2 is a graph measuring the electrical conductivity of the particles produced in the embodiment of the present invention by the probe method.
  • Example 1 a micro-sized nickel powder required for preparing a nickel / yttria stabilized zirconia core-shell structure powder was prepared using a liquid phase reduction method.
  • Comparative Example 1 in order to prepare a nickel / yttria stabilized zirconia core-shell structure powder, a micro-sized nickel powder and a nano-sized yttria stabilized zirconia powder were mixed at a speed of at least 4000 rpm for 30 minutes or more using a high speed mixing method.
  • the core-shell composite structure was prepared as shown in FIG.
  • Example 2 in order to synthesize nano-sized yttria stabilized zirconia powder, zirconium chloride (ZrOCl2.8H2O) and yttrium nitrate (Y (NO3) 3.6H2O) were uniformly dissolved in distilled water using a starting material of the shell portion, and then in an aqueous solution state. was prepared.
  • zirconium chloride ZrOCl2.8H2O
  • Y (NO3) 3.6H2O yttrium nitrate
  • Example 4 the powder of the nickel / yttria stabilized zirconia core-shell structure of Examples 1 to 3 according to the present invention was added to a hydrothermal synthesizer, and then distilled water was poured by twice the powder and stirred evenly.
  • the hydrothermal synthesizer was maintained at a temperature of 200 degrees for 8 hours to allow zirconium hydroxide and yttrium hydroxide to grow into zirconium oxide and yttrium oxide nanocrystals, respectively.
  • Example 6 in order to coat the nickel / yttria stabilized zirconia core-shell powder on the anode for the solid oxide fuel cell, carbon black was mixed and paste-processed.
  • the surface state of the core-shell powder prepared by the present invention and the powder prepared in the comparative example 1 was measured by FE-SEM. The results are shown in Figure 1 After.
  • the paste was prepared, and a measurement cell was prepared by coating a fuel electrode and an air electrode of a 200um YSZ electrolyte support.
  • the anode was heat-treated in an air atmosphere at 1200 degrees, and the cathode was made of LSCF and GDC powder.
  • a value of 0.07 mm 2 was shown, and the results are shown in FIGS. 3 and 4.
  • the composite powder of the core-shell structure for a solid oxide fuel cell (SOFC) according to the present invention is stably formed with a core shell structure of nickel, zirconium, and yttrium, which is caused by coarsening and shrinking of nickel when the anode is operated at a high temperature. It can improve sintering and electrical conductivity while preventing deformation.

Abstract

La présente invention concerne une poudre composite de structure noyau-enveloppe pour une pile à combustible à oxyde solide (SOFC), et plus spécifiquement, une poudre composite de structure noyau-enveloppe pour une pile à combustible à oxyde solide (SOFC) ayant une structure nouvelle dans laquelle le nickel, le zirconium et l'yttrium sont formés de manière stable dans la structure noyau-enveloppe, empêchant ainsi la déformation due au grossissement et au rétrécissement du nickel lorsqu'une anode est utilisée à une température élevée tout en améliorant les propriétés de frittage et la conductivité électrique.
PCT/KR2017/008222 2016-08-10 2017-07-31 Procédé de fabrication de poudre composite dans une structure noyau-enveloppe pour pile à combustible à oxyde solide WO2018030691A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2016-0101985 2016-08-10
KR20160101985 2016-08-10
KR1020160108660A KR20180018231A (ko) 2016-08-10 2016-08-25 고체산화물 연료전지용 코어-쉘 구조의 복합 분말의 제조 방법
KR10-2016-0108660 2016-08-25

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WO2018030691A1 true WO2018030691A1 (fr) 2018-02-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2591462A (en) * 2020-01-27 2021-08-04 Ceres Ip Co Ltd Interlayer for solid oxide cell

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05255796A (ja) * 1991-06-28 1993-10-05 Eniricerche Spa ニッケルサーメット及びその製法
KR101159139B1 (ko) * 2012-03-30 2012-06-25 삼전순약공업(주) Ｎｉ－ＹＳＺ 복합체 제조 방법 및 연료 전지의 제조 방법
KR20120089939A (ko) * 2010-12-28 2012-08-16 주식회사 포스코 고체산화물 연료전지용 ＮｉＯ/ＹＳＺ 복합체 제조방법
KR20150138482A (ko) * 2014-05-29 2015-12-10 한국세라믹기술원 계면활성제와 초음파 분산을 이용한 고체산화물 연료전지 연료극용 니켈-이트리아 안정화 지르코니아 코어-셀 복합체 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05255796A (ja) * 1991-06-28 1993-10-05 Eniricerche Spa ニッケルサーメット及びその製法
KR20120089939A (ko) * 2010-12-28 2012-08-16 주식회사 포스코 고체산화물 연료전지용 ＮｉＯ/ＹＳＺ 복합체 제조방법
KR101159139B1 (ko) * 2012-03-30 2012-06-25 삼전순약공업(주) Ｎｉ－ＹＳＺ 복합체 제조 방법 및 연료 전지의 제조 방법
KR20150138482A (ko) * 2014-05-29 2015-12-10 한국세라믹기술원 계면활성제와 초음파 분산을 이용한 고체산화물 연료전지 연료극용 니켈-이트리아 안정화 지르코니아 코어-셀 복합체 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG, F.H.: "Preparation and properties of Ni/YSZ anode by coating precipitation method", MATERIALS LETTERS, vol. 58, no. 24, 2004, pages 3079 - 3083, XP004525843, DOI: doi:10.1016/j.matlet.2004.05.047 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2591462A (en) * 2020-01-27 2021-08-04 Ceres Ip Co Ltd Interlayer for solid oxide cell
WO2021151692A1 (fr) * 2020-01-27 2021-08-05 Ceres Intellectual Property Company Limited Couche intermédiaire pour pile à oxyde solide
GB2591462B (en) * 2020-01-27 2022-04-20 Ceres Ip Co Ltd Interlayer for solid oxide cell

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