KR101451732B1 - Oxygen ion conducting materials - Google Patents

Oxygen ion conducting materials Download PDF

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KR101451732B1
KR101451732B1 KR1020050128191A KR20050128191A KR101451732B1 KR 101451732 B1 KR101451732 B1 KR 101451732B1 KR 1020050128191 A KR1020050128191 A KR 1020050128191A KR 20050128191 A KR20050128191 A KR 20050128191A KR 101451732 B1 KR101451732 B1 KR 101451732B1
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oxygen ion
composition
cazro
ion conductor
additive
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KR20070066728A (en
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황순철
김선욱
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재단법인 포항산업과학연구원
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte 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
    • H01M8/1246—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 the electrolyte consisting of oxides
    • 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

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  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

본 발명의 CaZrO3계 산소 이온 전도체 조성물은 Ca1 - xZr1 - yMyO3 의 조성식으로 구성되며 식 중 첨가제로는 +2가 혹은 +3가의 원소가 치환되고, 식 중의 변수 x가 몰비로 0.01≤x≤0.10 이고, y는 첨가제가 +2가인 경우 몰비로 y=x/2 이고, 첨가제가 +3가인 경우 몰비로 y=x인 것을 특징으로 한다. 이에 따라, 본 발명의 산소 이온 전도체 조성물은 전기 전도도가 크게 향상되고 기계적 안정성이 현저하게 개선되어 연료전지, 산소센서, 산소 투과막 등에 사용되는 산소 이온 전도체 조성물로 실용성이 높은 효과가 있다. The CaZrO 3 -based oxygen ion conductor composition of the present invention is composed of a composition formula of Ca 1 - x Zr 1 - y M y O 3 , wherein +2 or +3 is substituted for the additive in the formula, Y = x / 2 in a molar ratio when the additive is +2, and y = x in a molar ratio when the additive is +3. Accordingly, the oxygen ion conductor composition of the present invention is greatly improved in electrical conductivity and remarkably improved in mechanical stability, and thus has high practicability as an oxygen ion conductor composition used for a fuel cell, an oxygen sensor, an oxygen permeable membrane, and the like.

산소 이온 전도체, 칼슘 지르코네이트, 지르코니아, 전기 전도도 Oxygen ion conductor, calcium zirconate, zirconia, electric conductivity

Description

산소 이온 전도체 조성물{OXYGEN ION CONDUCTING MATERIALS}OXYGEN ION CONDUCTING MATERIALS [0001]

본 발명은 CaZrO3계 산소 이온 전도체 조성물에 관한 것으로, 더 자세하게는 전기 전도도가 향상되고 기계적 안정성이 개선된 CaZrO3계 산소 이온 전도체 조성물에 관한 것이다.The present invention relates to a CaZrO 3 based oxygen ionic conductor composition that, more particularly, electrical conductivity CaZrO 3 based oxygen ionic conductor composition is enhanced and improved mechanical stability of the.

산화물 산소 이온 전도체는 연료전지, 산소 센서, 산소 투과막 등의 용도로 활발한 연구가 이루어지고 있다. 산소 이온 전도체가 갖추어야 할 조건으로는 산소 이온 전도도가 높고 전자 전도도는 낮아야 하며 우수한 열적 및 화학적 안정성 등이 요구된다.Oxide oxygen ion conductors have been actively studied for use in fuel cells, oxygen sensors, and oxygen permeable membranes. The oxygen ion conductors must have high oxygen ion conductivity, low electron conductivity, and excellent thermal and chemical stability.

현재 실용화된 대표적인 산소 이온 전도체로는 YSZ (Yttria-Stabilized Zirconia)가 있다. YSZ는 고온에서 높은 산소 이온 전도도를 나타내므로 고체 산화물 연료전지(SOFC)의 전해질이나, 용융금속 내부의 용존 산소량을 측정하기 위한 산소 센서 등으로 사용되고 있다. 그러나 YSZ는 제강공정의 용강 같은 고온 (>1500℃) 및 낮은 산소 분압 (Po2<10-12atm)의 조건에서는 전자 전도도가 나타나게 되므로 사용이 제한된다. 고온과 낮은 산소 분압(Po2<10-12atm)에서의 사용을 위한 산소 이온 전도체로서 보다 안정적인 재료의 개발이 요구되고 있다.YSZ (Yttria-Stabilized Zirconia) is one of the typical oxygen ion conductors currently practiced. Since YSZ exhibits high oxygen ion conductivity at high temperatures, it is used as an electrolyte of a solid oxide fuel cell (SOFC) or an oxygen sensor for measuring the amount of dissolved oxygen in a molten metal. However, YSZ is limited in its use because it exhibits electronic conductivity under conditions of high temperature (> 1500 ° C) and low oxygen partial pressure (Po 2 <10-12atm) such as steel in the steelmaking process. Development of more stable materials as oxygen ion conductors for use at high temperature and low oxygen partial pressure (Po 2 < 10 -12 atm) is required.

CaZrO3는 이러한 조건에서 YSZ를 대체할 수 있는 전해질 재료중의 하나로 주목 받고 있다. CaZrO3는 높은 융점을 갖고 있으며, 뛰어난 열적, 화학적 안정성과 우수한 열충격 저항성을 나타내기 때문에 구조 재료, 내화물, 고주파 유전체 및 고온 응용분야 등에서 널리 사용되어 왔다. 다만 화학양론비에 따르는 단일상의 형성이 어렵고, 전기전도도가 낮아 산소 이온 전도체로서의 상용화에 한계가 있는 실정이다. CaZrO 3 is one of the electrolyte materials that can replace YSZ under these conditions. CaZrO 3 has been widely used in structural materials, refractories, high frequency dielectrics, and high temperature applications since it has a high melting point and exhibits excellent thermal and chemical stability and excellent thermal shock resistance. However, it is difficult to form a single phase according to the stoichiometric ratio, and since the electric conductivity is low, commercialization as an oxygen ion conductor is limited.

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 전기 전도도가 크게 향상되고 기계적 안정성이 현저하게 개선된 CaZrO3계 산소 이온 전도체 조성물을 제공하는 것이다. DISCLOSURE Technical Problem The present invention has been made to solve the above problems, and it is an object of the present invention to provide a CaZrO 3 -based oxygen ion conductor composition having a remarkably improved electrical conductivity and remarkably improved mechanical stability.

상기한 목적을 달성하기 위하여 본 발명의 CaZrO3계 산소 이온 전도체 조성물은 Ca1 - xZr1 - yMyO3 의 조성식으로 구성되며 식 중 첨가제로는 +2가 혹은 +3가의 원소가 치환되고, 식 중의 변수 x가 몰비로 0.01≤x≤0.10 이고, y는 첨가제가 +2가인 경우 몰비로 y=x/2 이고, 첨가제가 +3가인 경우 몰비로 y=x인 것을 특징으로 하는 CaZrO3계 산소 이온 전도체 조성물을 제공하는 데 그 목적이 있다. In order to achieve the above object, the CaZrO 3 -based oxygen ion conductor composition of the present invention comprises a composition formula of Ca 1 - x Zr 1 - y M y O 3 , wherein +2 or +3 is added as an additive in the formula Wherein x is a mole ratio of the additive, y is x / 2 when the additive is +2, y = x is the mole ratio of the additive is +3, 3 type oxygen ion conductor composition.

이하 본 발명을 더욱 상세하게 설명한다. Hereinafter, the present invention will be described in more detail.

본 발명의 산소 이온 전도체 조성물을 제조하기 위하여 순도가 99.9% 이상인 CaO, ZrO2, 첨가제(M)를 조성에 맞게 혼합하고 분쇄한 후 온도가 약 1200 내지 1400℃인 전기로에서 약 1내지 5시간 동안 하소시켜 본 발명의 단일상 산소 이온 전도체 조성물 분말을 제조한다. In order to prepare the oxygen ion conductor composition of the present invention, CaO, ZrO 2 and additive (M) having a purity of 99.9% or more are mixed and pulverized in accordance with the composition, and the mixture is ground in an electric furnace having a temperature of about 1200 to 1400 ° C for about 1 to 5 hours Followed by calcination to prepare the single-phase oxygen ion conductor composition powder of the present invention.

상기 본 발명에서 사용되는 각 성분들의 조성비는 x가 몰비로 0.01≤x≤0.10 이고, y는 첨가제가 +2가인 경우 몰비로 y=x/2 이고, 첨가제가 +3가인 경우 몰비로 y=x 가 되도록 하는 것이 바람직하며, 각 계수의 몰비가 이 범위를 벗어나는 경우에는 본 발명에서 요구하는 물성을 얻을 수 없다.The composition ratio of each component used in the present invention is such that x is a molar ratio of 0.01? X? 0.10, y is a molar ratio of y = x / 2 when the additive is +2, , And when the molar ratio of each coefficient is out of this range, the physical properties required in the present invention can not be obtained.

첨가제로는 +2가 혹은 +3가의 원소가 대부분 사용될 수 있으나 결정구조의 안정성 및 치환의 용이성 측면에서 Zr4 + 원소와 이온 반경이 크게 차이나지 않는 물질이 바람직하다.As the additive, most of the elements of +2 or +3 may be used, but in view of the stability of the crystal structure and ease of substitution, it is preferable to use a substance which does not significantly differ in ionic radius from Zr 4 + element.

상기 본 발명에서 사용되는 첨가제는 Zr4 + 원소와 치환되어 격자내에 산소 공공을 발생시킴으로써 전기 전도도를 향상시키기 위하여 첨가된다. 상기 첨가제의 첨가량은 요구하는 소결체의 조성에 따라 상이할 수 있으나, 본 발명에서 요구하는 효과를 얻기 위해서는 상기 첨가제의 함량 y가 첨가제가 +2가인 경우 몰비로 y=x/2 이고, 첨가제가 +3가인 경우 몰비로 y=x 가 되도록 하는 것이 바람직하다.The additive used in the present invention is added to improve electrical conductivity by replacing the Zr 4 + element with an oxygen vacancy in the lattice. In order to obtain the effect required by the present invention, the content y of the additive is in the range of y = x / 2 when the additive is +2, It is preferable that y = x be a molar ratio.

상기 본 발명의 산소 이온 전도체 조성물을 제조한 후, 조성물의 시편을 제조하여 제조된 세라믹 조성물의 물성을 측정한다. After the oxygen ion conductor composition of the present invention is prepared, the composition of the composition is prepared and the physical properties of the prepared ceramic composition are measured.

다음은 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예들은 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐 본 발명이 하기의 실시예에 한정되는 것은 아니다. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following will describe preferred embodiments in order to facilitate understanding of the present invention. However, it should be understood that the following examples are provided for a better understanding of the present invention, but the present invention is not limited to the following examples.

(실시예 1)(Example 1)

순도 99.9% 이상의 CaO, ZrO2, MgO, In2O3 분말을 하기 표 1에 나타낸 조성이 되도록 칭량하여 혼합한 후, 에탄올 용매 중에서 볼밀을 사용하여 24시간동안 혼합 및 분쇄한 후 건조시키고 온도 약 1350℃에서 4시간 동안 하소시켰다. CaO, ZrO 2 , MgO, and In 2 O 3 powder having a purity of 99.9% or more were weighed and mixed so as to have the composition shown in Table 1, mixed and milled in an ethanol solvent using a ball mill for 24 hours, Lt; RTI ID = 0.0 &gt; 1350 C. &lt; / RTI &gt;

상기 하소된 세라믹 조성물 분말을 24시간 동안 습식 볼밀을 수행하여 평균입도가 0.8내지 1.0㎛이 되도록 하였다. 상기 습식 볼밀된 조성물 분말을 건조시킨 후, 유압프레스를 사용하여 지름 20㎜의 성형몰드로 가압 성형을 수행하고 냉간정수압프레스(cold isostatic press) 등으로 약 2톤/㎠의 압력을 가하여 물성측정을 위한 조성물 시편을 제조하였다.The calcined ceramic composition powder was subjected to wet ball milling for 24 hours to obtain an average particle size of 0.8 to 1.0 탆. After the wet ball milled composition powder was dried, press molding was performed with a molding die having a diameter of 20 mm using a hydraulic press, and a pressure of about 2 ton / cm 2 was applied by a cold isostatic press or the like, Were prepared.

상기 제조된 시편을 밀폐된 알루미나 도가니내에 넣고 약 1700℃의 온도에서 약 4시간 동안 유지시켜 시편을 소결시켰다. 상기 소결된 시편을 연마기로 두께가 약 4㎜가 되도록 연마하고 초음파 세척기로 이물질을 제거하고 건조시킨 후, 백금 전극을 시편의 양면에 도포시키고 온도 약 1000℃에서 약 1시간 동안 열처리를 수행하여 시편의 양면에 전극을 형성시켰다. 상기 시편을 사용하여 통상의 방법으로 상대 소결밀도 및 1000℃에서의 전기전도도를 측정하고 그 결과를 하기 표2에 나타내었다. 또한 종래 산소 이온 전도체 조성물과 물성을 비교하기 위하여 CaZrO3 세라믹 조성물에 대한 상대 소결밀도 및 1000℃에서의 전기전도도를 측정하고 그 결과 를 하기 표2에 나타내었다.The prepared specimen was placed in a closed alumina crucible and held at a temperature of about 1700 DEG C for about 4 hours to sinter the specimen. The sintered specimens were polished to a thickness of about 4 mm using a grinder, and then debris was removed using an ultrasonic washing machine. Then, a platinum electrode was coated on both sides of the specimen and heat treatment was performed at a temperature of about 1000 ° C for about 1 hour, Electrodes were formed on both surfaces of the substrate. The relative sintering density and electrical conductivity at 1000 캜 were measured using the above-mentioned specimens by a conventional method, and the results are shown in Table 2 below. In order to compare the physical properties with the conventional oxygen ion conductor composition, the relative sintering density and electric conductivity at 1000 캜 of the CaZrO 3 ceramic composition were measured, and the results are shown in Table 2 below.

(실시예 2, 3 및 4)(Examples 2, 3 and 4)

하기 표 1에서 보는 바와 같이 조성물의 함량을 상이하게 한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 압전 세라믹 조성물을 제조하고 상기 실시예 1과 동일한 방법으로 시편을 제조하고, 제조된 시편의 유전상수 및 유전손실 및 공진주파수의 온도계수를 상기 실시예 1과 동일한 방법으로 측정하고, 그 결과를 하기 표2에 나타내었다. The piezoelectric ceramics composition was prepared in the same manner as in Example 1 except that the compositions were varied in content as shown in Table 1 below, and the specimens were prepared in the same manner as in Example 1, Constant and dielectric loss and temperature coefficient of resonance frequency were measured in the same manner as in Example 1. The results are shown in Table 2 below.

실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 XX 0.010.01 0.010.01 0.100.10 0.100.10 Y
(Mg or In)Y
(Mg or In) 0.005
(Mg)0.005
(Mg) 0.01
(In)0.01
(In) 0.05
(Mg)0.05
(Mg) 0.10
(In)0.10
(In)

실시예Example
종례예
Convention example
1
One
2
2
3
3
4
4 상대소결밀도 (%) Relative sintering density (%)
96
96
96
96
97
97
97
97
92
92 전기전도도 (S/cm)Electrical Conductivity (S / cm)
0.0019
0.0019
0.0027
0.0027
0.0017
0.0017
0.0020
0.0020
0.0008
0.0008

상기 표2에서 보는 바와 같이 실시예 1 내지 4의 경우 상대 소결밀도가 향상됨과 동시에 전기전도도가 약 2~3배 이상 증가되어 산소 이온 전도체 조성물로서 우수한 특성을 나타내었다. As shown in Table 2, in Examples 1 to 4, the relative sintering density was improved and the electric conductivity was increased by about 2 to 3 times, indicating excellent properties as the oxygen ion conductor composition.

본 발명의 산소 이온 전도체 조성물은 전기 전도도가 크게 향상되고 기계적 안정성이 현저하게 개선되어 연료전지, 산소센서, 산소 투과막 등에 사용되는 산소 이온 전도체 조성물로 실용성이 높은 효과가 있다.  The oxygen ion conductor composition of the present invention has a remarkably improved electrical conductivity and remarkably improved mechanical stability, and thus has high practicality as an oxygen ion conductor composition used for a fuel cell, an oxygen sensor, an oxygen permeable membrane, and the like.

Claims (4)

CaZrO3계 산소 이온 전도체 조성물로서, 격자 내에 산소공공을 형성하기 위하여 첨가제(M)로서 +2가의 원소를 Zr 원소와 치환시켜 Ca1-xZr1-yMyO3의 조성식으로 구성하고, 상기 조성식 중의 변수 x가 몰비로 0.01≤x≤0.10 이고, y는 몰비로 y=x/2 것을 특징으로 하는 전기전도도가 향상된 CaZrO3계 산소 이온 전도체 조성물.A CaZrO 3 -based oxygen ion conductor composition comprising a composition formula of Ca 1-x Zr 1 -y M y O 3 by replacing a +2 valence element as an additive (M) with a Zr element in order to form an oxygen vacancy in a lattice, and the variable x in the composition formula by molar ratio 0.01≤x≤0.10, y is the enhanced CaZrO electrical conductivity, characterized in that y = x / 2 in a molar ratio 3 based oxygen ionic conductor composition. 제1항에 있어서, 상기 +2가의 첨가제(M)는 MgO를 이용한 것을 특징으로 하는 전기전도도가 향상된 CaZrO3계 산소 이온 전도체 조성물. The method of claim 1, wherein the +2 valent additives (M) the electric conductivity is improved CaZrO 3 based oxygen ionic conductor composition characterized by a MgO. CaZrO3계 산소 이온 전도체 조성물로서, 격자 내에 산소공공을 형성하기 위하여 첨가제(M)로서 +3가의 원소를 Zr 원소와 치환시켜 Ca1-xZr1-yMyO3의 조성식으로 구성하고, 상기 조성식 중의 변수 x가 몰비로 0.01≤x≤0.10 이고, y는 몰비로 y=x인 것을 특징으로 하는 전기전도도가 향상된 CaZrO3계 산소 이온 전도체 조성물. A CaZrO 3 -based oxygen ion conductor composition comprising a composition formula of Ca 1-x Zr 1 -y M y O 3 by replacing a +3 element as an additive (M) with a Zr element in order to form an oxygen vacancy in a lattice, Wherein the variable x in the composition formula is in a molar ratio of 0.01? X? 0.10, and y is a mole ratio of y = x, wherein the electric conductivity is improved in the CaZrO 3 -based oxygen ion conductor composition. 제3항에 있어서, 상기 +3가의 첨가제(M)는 In2O3를 이용한 것을 특징으로 하는 전기전도도가 향상된 CaZrO3계 산소 이온 전도체 조성물. 4. The method of claim 3 wherein the +3 valence additives (M) of In 2 O CaZrO an improved electrical conductivity, characterized in that using the 33-based oxygen ionic conductor composition.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05274912A (en) * 1992-03-27 1993-10-22 Kyocera Corp Dielectric porcelain composite
JP2001122675A (en) * 1999-10-27 2001-05-08 Natl Inst Of Advanced Industrial Science & Technology Meti Calcium zirconate/magnesia-based composite porous body and its manufacturing method
KR100534017B1 (en) * 2004-02-11 2005-12-07 한국화학연구원 Novel Zirconate Phosphor Compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05274912A (en) * 1992-03-27 1993-10-22 Kyocera Corp Dielectric porcelain composite
JP2001122675A (en) * 1999-10-27 2001-05-08 Natl Inst Of Advanced Industrial Science & Technology Meti Calcium zirconate/magnesia-based composite porous body and its manufacturing method
KR100534017B1 (en) * 2004-02-11 2005-12-07 한국화학연구원 Novel Zirconate Phosphor Compositions

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