KR101538106B1 - Solid oxide fuel cell composite sealant and it's fabrication method - Google Patents
Solid oxide fuel cell composite sealant and it's fabrication method Download PDFInfo
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- KR101538106B1 KR101538106B1 KR1020130165159A KR20130165159A KR101538106B1 KR 101538106 B1 KR101538106 B1 KR 101538106B1 KR 1020130165159 A KR1020130165159 A KR 1020130165159A KR 20130165159 A KR20130165159 A KR 20130165159A KR 101538106 B1 KR101538106 B1 KR 101538106B1
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000000446 fuel Substances 0.000 title claims abstract description 36
- 239000007787 solid Substances 0.000 title claims abstract description 28
- 239000000565 sealant Substances 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title description 8
- 239000013078 crystal Substances 0.000 claims abstract description 32
- 239000011521 glass Substances 0.000 claims abstract description 32
- 239000003566 sealing material Substances 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 13
- 229910016066 BaSi Inorganic materials 0.000 claims abstract description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 15
- 229910052712 strontium Inorganic materials 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000005394 sealing glass Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000000020 Nitrocellulose Substances 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 3
- 229940088601 alpha-terpineol Drugs 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920001220 nitrocellulos Polymers 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- 238000005382 thermal cycling Methods 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 32
- 230000007774 longterm Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic 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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0286—Processes for forming seals
-
- 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
- H01M2008/1293—Fuel cells with solid oxide 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
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Abstract
본 발명은 단위전지는 음극, 전해질 및 양극으로 구성되고, 단위전지와 분리판(Interconnect)이 교대로 적층되어 연료전지 스택을 형성하며, 이 연료전지 스택에서 연료인 수소 가스와 공기의 혼합을 방지하고, 가스의 누출을 방지하며 전지 사이를 절연하기 위해 밀봉재를 사용하게 되는 평판형 고체산화물 연료전지에 있어서, 유리에 결정을 복합화한 복합 밀봉재를 제조하는 고체산화물 연료전지용 복합밀봉재 및 이의 제조 방법에 관한 것이다.
본 발명에 따른 고체산화물 연료전지용 복합밀봉재는 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물을 용융하여 제조한 유리 프리트와, 산화규소(SiO2)와 산화바륨(BaO)을 합성하여 제조한 BaSi2O5 결정 필러가 혼합된 것을 특징으로 한다.The unit cell comprises a cathode, an electrolyte, and an anode. The unit cell and the interconnect are alternately stacked to form a fuel cell stack. In the fuel cell stack, a mixture of hydrogen gas and air A composite sealing material for a solid oxide fuel cell in which a composite material in which crystals are mixed in a glass is produced in a planar solid oxide fuel cell in which a sealing material is used to prevent leakage of gas and to insulate the cells, .
The composite sealant for a solid oxide fuel cell according to the present invention is produced by melting a mixture of RO 2 (R = Si, Zr, Ti) -R 2 O 3 (R = Al, La) -RO A glass frit and BaSi 2 O 5 prepared by synthesizing silicon oxide (SiO 2 ) and barium oxide (BaO) And a crystal filler is mixed.
Description
본 발명은 고체산화물 연료전지용 복합 밀봉재 및 이의 제조 방법에 관한 것으로서, 보다 구체적으로는 단위전지는 음극, 전해질 및 양극으로 구성되고, 단위전지와 분리판(Interconnect)이 교대로 적층되어 연료전지 스택을 형성하며, 이 연료전지 스택에서 연료인 수소 가스와 공기의 혼합을 방지하고, 가스의 누출을 방지하며 전지 사이를 절연하기 위해 밀봉재를 사용하게 되는 평판형 고체산화물 연료전지에 있어서, 유리에 결정을 복합화한 복합 밀봉재를 제조하는 고체산화물 연료전지용 복합 밀봉재 및 이의 제조 방법에 관한 것이다.
The present invention relates to a composite sealing material for a solid oxide fuel cell and a method of manufacturing the same. More particularly, the unit cell comprises a cathode, an electrolyte, and an anode. The unit cell and the interconnect are alternately stacked, And a sealing material is used to prevent mixing of hydrogen gas and air as fuel in the fuel cell stack and to prevent leakage of gas and to insulate the spaces between the cells. In the planar solid oxide fuel cell, And more particularly, to a composite sealing material for a solid oxide fuel cell and a method for manufacturing the composite sealing material.
고체산화물 연료전지는 단위전지의 형상에 따라 평판형(planar design), 원통형(tubular design) 및 평관형(flat-tubular) 등으로 구분할 수 있으며, 평판형 연료전지에서는 구성요소와 분리판의 밀봉이 매우 중요하다.The solid oxide fuel cell can be classified into a planar design, a tubular design, and a flat-tubular type according to the shape of a unit cell. In the case of a planar fuel cell, very important.
평판형 연료전지는 전해질, 음극 및 양극으로 이루어진 단위전지와, 단위전지를 연결하는 연결자와, 연결자와 단위전지를 밀봉하는 밀봉재로 구성되며, 이 평판형 연료전지와 분리판이 교대로 적층된 평판형 연료전지 스택에서, 연료 가스인 수소와 연소 가스인 공기의 혼합을 방지하고, 스택 외부로 가스가 누출되는 것을 방지하며, 단위전지 사이를 절연하기 위해서는 분리판과 단위전지 구성요소 사이를 밀봉해야 한다.The planar fuel cell comprises a unit cell made of an electrolyte, a cathode and an anode, a connector for connecting the unit cell, and a sealer for sealing the connector and the unit cell, and the planar fuel cell and the separator are alternately stacked. In the fuel cell stack, it is necessary to seal the gap between the separator plate and the unit cell components to prevent mixing of hydrogen as the fuel gas and air as the combustion gas, to prevent gas from leaking out of the stack, and to insulate the unit cells .
그러나, 종래의 고체산화물 연료전지용 밀봉재의 경우, 유리(glass), 결정화 유리(glass-ceramics) 및 Ag-CuO등 경화형 밀봉재(rigid seal)는 연결자와 접합 시 구성요소의 열팽창계수가 동일하지 않은 경우 전이온도 아래에서 깨지기 쉬운 거동으로 장기 안정성이 부족하며, 판상의 운모(mica) 및 금속복합체등 압축 밀봉재(compressive-seal)는 작동 중 유리부분이 흘러내려 운모, 섬유 부분과 접합부분에 크랙이 발생하여 가스가 누설되거나 녹은 유리부분이 증발하여 구조적으로 변화를 일으켜 고온 장기열화 성능을 낮게 하는 문제점이 있다.
However, in the case of conventional sealing materials for solid oxide fuel cells, a rigid seal such as glass, glass-ceramics and Ag-CuO has a problem in that when the thermal expansion coefficient of the components is not the same The long-term stability is insufficient due to the fragile behavior at the transition temperature. Compressive-seal such as mica and metal complex in the plate causes the mica, the fiber part and the joint part to crack due to the flowing of the glass part during operation. Thereby causing a problem in that the glass portion that leaks or melts evaporates due to the gas to cause a structural change, thereby deteriorating the high-temperature long-term deterioration performance.
따라서, 본 발명의 목적은 고체산화물 연료전지의 구성요소와 유사한 열팽창계수를 갖게끔 유리와 필러를 혼합하여 복합밀봉한 후, 유리자체에서 운전 작동 시 결정을 생성케 하는 것과 필러 첨가에 따라 강도 및 열팽창계수를 제어하여 장기운전에 따른 안정성을 갖는 고체산화물 연료전지용 복합 밀봉재를 제공하는 것이다.Accordingly, it is an object of the present invention to provide a solid oxide fuel cell in which a glass and a filler are mixed and sealed so as to have a thermal expansion coefficient similar to that of a component of a solid oxide fuel cell, And to provide a composite sealing material for a solid oxide fuel cell having a stability according to long-term operation by controlling a thermal expansion coefficient.
본 발명의 다른 목적은 고체산화물 연료전지 밀봉용 유리가 현재 고온 분위기에서 구조가 파괴되어 열화가 심하고 적층 시 과하중으로 붕괴되거나 크랙이 발생하여 장기 내구성에 문제가 있어 이를 해결코자 유리에 유리와 같은 성분으로 구성된 결정 필러를 혼합한 후 운전 작동시 밀봉 유리로부터 결정이 생성되게끔 하여 강도를 향상시켜 장기운전에 따른 안정성을 갖게끔 복합 밀봉재를 제조하는 고체산화물 연료전지용 복합 밀봉재 제조방법을 제공하는 것이다.
Another object of the present invention is to solve the problem of long-term durability due to the fact that the glass for sealing the solid oxide fuel cell is destroyed by the structure in the high-temperature atmosphere and is severely deteriorated and collapsed or cracked under overload in the stacking, The present invention also provides a method for manufacturing a composite sealing material for a solid oxide fuel cell in which a crystal is formed from a sealing glass during a driving operation so as to improve the strength of the composite sealing material.
상기와 같은 목적을 달성하기 위한 본 발명에 따른 고체산화물 연료전지용 복합 밀봉재의 일례는 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물을 용융하여 제조한 유리 프리트와 산화규소(SiO2)와 산화바륨(BaO)을 합성하여 제조한 BaSi2O5 결정 필러가 혼합된 것을 특징으로 한다.In order to accomplish the above object, there is provided a composite sealing material for a solid oxide fuel cell according to the present invention, comprising at least one of RO 2 (R = Si, Zr, Ti) -R 2 O 3 BaSi 2 O 5 prepared by synthesizing glass frit, silicon oxide (SiO 2 ) and barium oxide (BaO) And a crystal filler is mixed.
상기 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물은 RO2(R=Si, Zr, Ti) 42~45몰%, R2O3(R=Al, La) 13~16몰%, RO(R=Ba, Ca, Sr) 40~45몰%로 구성되는 것을 특징으로 한다.The RO 2 (R = Si, Zr , Ti) -R 2 O 3 (R = Al, La) -RO (R = Ba, Ca, Sr) mixture is RO 2 (R = Si, Zr , Ti) 42 ~ (R = Ba, Ca, Sr) in an amount of 15 to 45 mol%, R 2 O 3 (R = Al, La) and 13 to 16 mol%.
상기 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물은 산화규소(SiO2)-산화바륨(BaO)-산화칼슘(CaO)-산화스트론튬(SrO)-산화알루미늄(Al2O3)-산화란탄(La2O3)-산화지르코니아(ZrO2) 혼합물인 것을 특징으로 한다.The RO 2 (R = Si, Zr , Ti) -R 2 O 3 (R = Al, La) -RO (R = Ba, Ca, Sr) mixture of silicon oxide (SiO 2) - barium oxide (BaO) - And is a mixture of calcium oxide (CaO) - strontium oxide (SrO) - aluminum oxide (Al 2 O 3 ) - lanthanum oxide (La 2 O 3 ) - zirconia (ZrO 2 ).
상기 유리 프리트와 상기 결정 필러는 95wt% : 5wt% ~ 70wt% : 30wt%로 혼합되는 것을 특징으로 한다.The glass frit and the crystal filler are mixed at 95 wt%: 5 wt% to 70 wt%: 30 wt%.
본 발명에 고체산화물 연료전지용 복합 밀봉재 제조 방법은 A method for manufacturing a composite sealing material for a solid oxide fuel cell according to the present invention comprises:
RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr)를 혼합하여, 1450에서 용융하여, 고체산화물 연료전지용 밀봉유리 시료(유리 프리트)를 제조하는 1 단계와,(R = Ba, Ca, Sr) was mixed with RO 2 (R = Si, Zr, Ti) -R 2 O 3 (Glass frit), and a step
유리와 결정 필러가 혼합된 복합 밀봉재를 제조하기 위해 유리와 동일한 조성계인 산화규소(SiO2)-산화바륨(BaO)을 이용하여 BaSi2O5 결정 필러를 합성하는 2 단계와, A second step of synthesizing a BaSi 2 O 5 crystal filler using silicon oxide (SiO 2 ) -barium oxide (BaO), which is the same composition system as glass, to produce a composite sealing material in which glass and crystal filler are mixed,
1 단계의 유리와 2단계의 결정 필러를 혼합하여 복합 밀봉재를 제조하는 3 단계와, A third step of mixing the glass of the first step and the crystal filler of the second step to produce a composite sealing material,
3 단계에서 제조한 복합밀봉재의 물성변화를 확인하기 위해 산화분위기와 환원분위기에서 각각 0, 100, 300 및 500시간 열싸이클 후 굽힘강도 값의 변화를 체크하는 4 단계와, In order to confirm the change of physical properties of the composite sealant manufactured in
3 단계에서 제조한 복합밀봉재 분말에 바인더가 혼입된 비히클(바인더: 니트로셀룰로스, 유기용제: 알파 테르피네올/부틸카비톨아세테이트)을 30중량% 넣고 30분 동안 고속혼합기를 이용하여 충분히 교반하고, 충분히 교반된 슬러리를 3 롤밀을 사용하여 밀링한 후 진공펌프를 이용하여 탈포하여 페이스트를 제조하고, 제조한 페이스트를 연결재 위에 디스펜싱하여 슬러리 도포형 복합밀봉재를 형성하는 4 단계로 구성되는 것을 특징으로 한다.30 weight% of a vehicle (binder: nitrocellulose, organic solvent: alpha terpineol / butyl carbitol acetate) into which the binder was mixed was added to the composite sealing material powder prepared in
상기 2 단계에서는 SiO2 : BaO = 2 : 1의 비율로 혼합하여 고상반응법으로 1200에서 4시간 동안 열처리함으로써, BaSi2O5 결정 필러를 합성하는 것을 특징으로 한다.
In the second step, BaSi 2 O 5 crystal filler is synthesized by mixing SiO 2 : BaO = 2: 1 at a ratio of 2: 1 and performing a heat treatment at 1200 for 4 hours in a solid phase reaction method.
이것에 의해, 본 발명에 따른 고체산화물 연료전지용 복합 밀봉재 및 이의 제조방법은 자체적으로 접합 시 또는 운전 작동 중에 결정생성을 유도하거나 억제할 수 있는 조성물 유리-RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr)계 유리-와 유리와 같은 조성계의 BaSi2O5 결정 필러를 혼합하여 제조함으로써, 기존 유리밀봉재가 가지고 있는 문제점을 구조적으로 안정화 시켰고, 기존 밀봉재 보다 강도가 향상되고, 밀봉효율이 우수하며 장기 신뢰성을 가질 뿐만 아니라, 다른 구성요소인 전해질, 전극 및 연결자의 열팽창계수와 열팽창계수가 유사하고, 접합과 운전온도가 700∼800℃에 적합하고, 자체적으로 접합 시 연화되고 운전 작동 중에 결정이 일부 생성되어 산화·환원 분위기 및 장기 운전에 따른 열화가 적어 내구성에 안정하며, 운전 중에 결정생성으로 인해 높은 강도를 나타내고, 스택에 적용 시 가스 누출이 없고, 전기절연성이 우수한 효과가 있다.
Accordingly, the composite sealing material for a solid oxide fuel cell according to the present invention and the method for producing the same can be applied to a glass composition-RO 2 (R = Si, Zr, Ti) which can induce or inhibit crystal formation during bonding or operation, -R 2 O 3 (R = Al, La) -RO (R = Ba, Ca, Sr) based glass and a glass such as BaSi 2 O 5 The present invention relates to a method for producing a glass sealing material, which comprises the steps of: (a) providing a glass sealing material, , The bonding and operating temperature are suitable for 700 to 800 ° C, softened by themselves during bonding, and a part of the crystals are produced during operation, so that the deterioration due to the oxidizing / reducing atmosphere and the long- , Exhibits high strength due to crystal formation during operation, has no gas leakage when applied to a stack, and has an excellent electrical insulating property.
도 1은 본 발명과 제작한 결정질 필러 합성 후 결정상 및 열팽창계수를 나타낸 그래프이다.
도 2는 본 발명과 제작한 고체산화물 연료전지 복합밀봉재의 산화, 환원분위기에서 유지시간에 따른 강도변화를 나타낸 그래프이다.
도 3은 본 발명에서 제작한 고체산화물 연료전지 복합밀봉재의 누설율 측정 결과를 나타낸 그래프이다.
도 4는 본 발명에서 제작한 연결재 기판위에 슬러리 도포된 복합밀봉재를 나타낸 그림이다.1 is a graph showing a crystal phase and a thermal expansion coefficient after synthesizing a crystalline filler according to the present invention.
FIG. 2 is a graph showing changes in strength of the solid oxide fuel cell composite sealing material produced according to the present invention with respect to the holding time in an oxidizing and reducing atmosphere. FIG.
3 is a graph showing leakage rate measurement results of the solid oxide fuel cell composite sealant produced in the present invention.
4 is a view showing a composite sealant applied with a slurry on a connecting substrate substrate manufactured in the present invention.
본 발명에 따른 고체산화물 연료전지용 복합 밀봉재는 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물을 용융하여 제조한 유리 프리트와 산화규소(SiO2)와 산화바륨(BaO)을 합성하여 제조한 BaSi2O5 결정 필러가 혼합된 것이다.The composite sealant for a solid oxide fuel cell according to the present invention is produced by melting a mixture of RO 2 (R = Si, Zr, Ti) -R 2 O 3 (R = Al, La) -RO BaSi 2 O 5 prepared by synthesizing a glass frit, silicon oxide (SiO 2 ) and barium oxide (BaO) The crystal filler is mixed.
상기 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물은 RO2(R=Si, Zr, Ti) 42~45몰%, R2O3(R=Al, La) 13~16몰%, RO(R=Ba, Ca, Sr) 40~45몰%로 구성된다.The RO 2 (R = Si, Zr , Ti) -R 2 O 3 (R = Al, La) -RO (R = Ba, Ca, Sr) mixture is RO 2 (R = Si, Zr , Ti) 42 ~ (R = Ba, Ca, Sr) in an amount of 15 to 45 mol%, R 2 O 3 (R = Al, La) and 13 to 16 mol%.
특히, 상기 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물은 산화규소(SiO2)-산화바륨(BaO)-산화칼슘(CaO)-산화스트론튬(SrO)-산화알루미늄(Al2O3)-산화란탄(La2O3)-산화지르코니아(ZrO2) 혼합물일 수 있으며, 1450℃에서 용융될 수 있다.In particular, the RO 2 (R = Si, Zr , Ti) -R 2 O 3 (R = Al, La) -RO (R = Ba, Ca, Sr) mixture of silicon oxide (SiO 2) - barium (BaO oxide ) - calcium oxide (CaO) - strontium oxide (SrO) - aluminum oxide (Al 2 O 3 ) - lanthanum oxide (La 2 O 3 ) - zirconia (ZrO 2 ) mixture and can be melted at 1450 ° C. .
상기 유리 프리트와 상기 결정 필러는 95wt% : 5wt% ~ 70wt% : 30wt%로 혼합될 수 있다.The glass frit and the crystal filler may be mixed at 95wt%: 5wt% ~ 70wt%: 30wt%.
상기와 같은 본 발명에 따른 고체산화물 연료전지용 복합 밀봉재는 자체적으로 접합 시 또는 운전 작동 중에 결정생성을 유도하거나 억제할 수 있는 조성물 유리-RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr)계 유리-와 유리와 같은 조성계의 BaSi2O5 결정 필러를 혼합하여 제조함으로써, 기존 유리밀봉재가 가지고 있는 문제점을 구조적으로 안정화 시켰고, 기존 밀봉재 보다 강도가 향상되고, 밀봉효율이 우수하며 장기 신뢰성을 가질 뿐만 아니라, 다른 구성요소인 전해질, 전극 및 연결자의 열팽창계수와 열팽창계수가 유사하고, 접합과 운전온도가 700∼800℃에 적합한 특성을 갖는다. The composite sealing material for a solid oxide fuel cell according to the present invention as described above is a composition glass-RO 2 (R = Si, Zr, Ti) -R 2 O 3 which can induce or inhibit crystal formation during bonding or operation. (R = Al, La) -RO (R = Ba, Ca, Sr) based glasses and BaSi 2 O 5 crystal fillers such as glass are mixed and structurally stabilized And the thermal expansion coefficient is similar to that of other components such as electrolyte, electrode and connector, and the bonding and operating temperature are in the range of 700 to 800 ° C. .
특히, 자체적으로 접합 시 연화되고 운전 작동 중에 결정이 일부 생성되어 산화·환원 분위기 및 장기 운전에 따른 열화가 적어 내구성에 안정하며, 운전 중에 결정생성으로 인해 높은 강도를 나타내고, 스택에 적용 시 가스 누출이 없고, 전기절연성이 우수한 효과가 있다.Particularly, it is softened at the time of joining itself, and a part of crystals are generated during operation operation, so that it is stable in durability due to less oxidization / reduction atmosphere and deterioration due to long-term operation, exhibits high strength due to crystal formation during operation, And there is an effect of excellent electrical insulation.
본 발명에 따른 고체산화물 연료전지용 복합 밀봉재의 제조 방법은 다음과 같다.A method for producing a composite sealing material for a solid oxide fuel cell according to the present invention is as follows.
(1 단계)(Stage 1)
아래의 표 1과 같이 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr)를 혼합하여, 1450℃에서 용융하여, 고체산화물 연료전지용 밀봉유리 시료(유리 프리트)를 제조한다.(R = Ba, Ca, Sr) was mixed with RO 2 (R = Si, Zr, Ti) -R 2 O 3 Thereby producing a sealed glass sample (glass frit) for a solid oxide fuel cell.
밀봉유리 시료의 열팽창계수는 구성소재와 비슷한 것과 낮은 것이 대부분이었고, 전이온도와 연화온도는 표 1에 나타낸 바와 같이 각각 637∼662℃ 및 690∼716℃부근으로 통상 실제 접합 시 적합한 점성유동을 고려했을 때 700∼800℃ 접합에 적합하다고 할 수 있다.
The thermal expansion coefficient of the sealing glass samples was similar to that of the constituent materials, and the transition temperatures and softening temperatures were in the range of 637 to 662 ° C and 690 to 716 ° C, respectively, as shown in Table 1, It can be said that it is suitable for 700 ~ 800 ℃ junction.
(2 단계)(Step 2)
유리와 결정 필러가 혼합된 복합 밀봉재를 제조하기 위해 유리와 동일한 조성계인 산화규소(SiO2)-산화바륨(BaO)을 이용하여 BaSi2O5 결정 필러를 합성한다. 이때, SiO2 : BaO = 2 : 1의 비율로 혼합하여 고상반응법으로 1200℃에서 4시간 동안 열처리함으로써, BaSi2O5 결정 필러가 합성되었다. 도 1에 나타낸 바와 같이 합성 결정 필러는 단일상을 나타내었고, 열팽창 계수는 121×10-7/℃를 나타내었다.BaSi 2 O 5 crystal filler is synthesized by using silicon oxide (SiO 2 ) - barium oxide (BaO), which is the same composition system as glass, to produce composite sealant mixed glass and crystal filler. At this time, the BaSi 2 O 5 crystal filler was synthesized by mixing SiO 2 : BaO = 2: 1 at a ratio of 2: 1, followed by heat treatment at 1200 ° C. for 4 hours in the solid phase reaction method. As shown in Fig. 1, the composite crystal filler showed a single phase, and the coefficient of thermal expansion was 121 占 10 -7 / 占 폚.
(3 단계)(Step 3)
(1 단계)의 유리 1-5, 1-7 및 1-11과 (2단계)의 결정 필러를 혼합 하여 복합 밀봉재를 제조한 후 특성을 표 2에 나타내었다. 복합 밀봉재의 경우 결정 필러 함량이 증가함에 따라 열팽창계수는 104∼109×10-7/℃로 증가하여 구성소재와 일치하는 경향을 나타내었고, 전이온도와 연화온도는 감소하는 경향을 나타내었다.And the crystalline fillers of (1-5), (1-5), 1-7 and 1-11 and (2) in Example 1 (Step 1) were mixed to prepare a composite sealant. As the content of crystal filler increased, the coefficient of thermal expansion increased to 104 ~ 109 × 10 - 7 / ℃, and the transition temperature and softening temperature tended to decrease.
(4 단계)(Step 4)
(3 단계)에서 제조한 복합밀봉재의 물성변화를 확인하기 위해 산화분위기와 환원분위기에서 각각 0, 100, 300 및 500시간 열싸이클 후 굽힘강도 값의 변화를 도 2에 나타내었다. 밀봉용 유리에 결정 필러를 복합화 한 경우 유지시간이 증가할수록 결정이 생성되어 산화, 환원 분위기에서 강도 값이 증가하는 경향을 나타내었고, 이는 장기 운전 시 누설이 일어나지 않고 기계적 강도가 증가하여 구성소재와 분리판을 접합하기 위한 밀봉재로 적합함을 알 수 있다.Fig. 2 shows changes in the bending strength values after 0, 100, 300 and 500 hours of thermal cycling in an oxidizing atmosphere and a reducing atmosphere, respectively, in order to confirm the change in physical properties of the composite sealant prepared in the step (step 3). When the crystal filler was mixed with the sealing glass, the crystals were formed as the holding time increased, and the strength value increased in the oxidizing and reducing atmosphere. This showed that the mechanical strength was increased due to no leakage during the long - It can be understood that it is suitable as a sealing material for bonding the separator plate.
복합밀봉재의 장기 운전 시 누설을 확인하기 위해 누설률을 측정한 결과를 도 3에 나타내었다. 750시간 유지 후 밀봉재의 누설률은 0.016 sccm/cm로 누설이 거의 발생하지 않음을 알 수 있다.The leakage rate of the composite sealant was measured to confirm leakage during long-term operation, and the result is shown in FIG. The leakage rate of the sealing material after keeping for 750 hours is 0.016 sccm / cm, which means that leakage hardly occurs.
(5 단계)(Step 5)
(3 단계)에서 제조한 복합밀봉재 분말에 바인더가 혼입된 비히클(바인더: 니트로셀룰로스, 유기용제: 알파 테르피네올/부틸카비톨아세테이트)을 30중량% 넣고 30분 동안 고속혼합기를 이용하여 충분히 교반시켰다. 충분히 교반된 슬러리를 3 롤밀을 사용하여 밀링한 후 진공펌프를 이용하여 탈포하여 페이스트를 제조하였다. 제조한 페이스트는 연결재 위에 디스펜싱하여 슬러리 도포형 복합밀봉재를 형성하였고, 이를 도 4에 나타내었다.30% by weight of a vehicle (binder: nitrocellulose, organic solvent: alpha terpineol / butyl carbitol acetate) having a binder mixed therein was added to the composite sealant powder prepared in step (3) . The sufficiently stirred slurry was milled using a 3-roll mill and defoamed using a vacuum pump to prepare a paste. The paste thus prepared was dispensed on the connecting material to form a slurry-applied composite sealant, which is shown in FIG.
Claims (6)
The glass frit and silicon oxide (SiO 2 ) prepared by melting a mixture of RO 2 (R = Si, Zr, Ti) -R 2 O 3 (R = Al, La) BaSi 2 O 5 prepared by synthesizing barium oxide (BaO) And a crystal filler are mixed with each other to form a composite sealing material for a solid oxide fuel cell.
상기 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물은 RO2(R=Si, Zr, Ti) 42~45몰%, R2O3(R=Al, La) 13~16몰%, RO(R=Ba, Ca, Sr) 40~45몰%로 구성되는 것을 특징으로 하는 고체산화물 연료전지용 복합 밀봉재.
The method according to claim 1,
The RO 2 (R = Si, Zr , Ti) -R 2 O 3 (R = Al, La) -RO (R = Ba, Ca, Sr) mixture is RO 2 (R = Si, Zr , Ti) 42 ~ (R = Ba, Ca, Sr) in an amount of 15 to 45 mol%, R 2 O 3 (R = Al, La) in an amount of 13 to 16 mol%, and RO (R = Ba, Ca, Sr) in an amount of 40 to 45 mol%.
상기 RO2(R=Si, Zr, Ti)-R2O3(R=Al, La)-RO(R=Ba, Ca, Sr) 혼합물은 산화규소(SiO2)-산화바륨(BaO)-산화칼슘(CaO)-산화스트론튬(SrO)-산화알루미늄(Al2O3)-산화란탄(La2O3)-산화지르코니아(ZrO2) 혼합물인 것을 특징으로 하는 고체산화물 연료전지용 복합 밀봉재.
The method according to claim 1,
The RO 2 (R = Si, Zr , Ti) -R 2 O 3 (R = Al, La) -RO (R = Ba, Ca, Sr) mixture of silicon oxide (SiO 2) - barium oxide (BaO) - Wherein the mixture is a mixture of calcium oxide (CaO) - strontium oxide (SrO) - aluminum oxide (Al 2 O 3 ) - lanthanum oxide (La 2 O 3 ) - zirconia (ZrO 2 ).
상기 유리 프리트와 상기 결정 필러는 95wt% : 5wt% ~ 70wt% : 30wt%로 혼합되는 것을 특징으로 하는 고체산화물 연료전지용 복합 밀봉재.
The method according to claim 1,
Wherein the glass frit and the crystal filler are mixed at 95 wt%: 5 wt% to 70 wt%: 30 wt%.
유리와 결정 필러가 혼합된 복합 밀봉재를 제조하기 위해 유리와 동일한 조성계인 산화규소(SiO2)-산화바륨(BaO)을 이용하여 BaSi2O5 결정 필러를 합성하는 2 단계와,
1 단계의 유리와 2단계의 결정 필러를 혼합하여 복합 밀봉재를 제조하는 3 단계와,
3 단계에서 제조한 복합밀봉재의 물성변화를 확인하기 위해 산화분위기와 환원분위기에서 각각 0, 100, 300 및 500시간 열싸이클 후 굽힘강도 값의 변화를 체크하는 4 단계와,
3 단계에서 제조한 복합밀봉재 분말에 바인더가 혼입된 비히클(바인더: 니트로셀룰로스, 유기용제: 알파 테르피네올/부틸카비톨아세테이트)을 30중량% 넣고 30분 동안 고속혼합기를 이용하여 충분히 교반하고, 충분히 교반된 슬러리를 3 롤밀을 사용하여 밀링한 후 진공펌프를 이용하여 탈포하여 페이스트를 제조하고, 제조한 페이스트를 연결재 위에 디스펜싱하여 슬러리 도포형 복합밀봉재를 형성하는 4 단계로 구성되는 것을 특징으로 하는 고체산화물 연료전지용 복합 밀봉재 제조 방법.
A mixture of RO 2 (R = Si, Zr , Ti) -R 2 O 3 (R = Al, La) -RO (R = Ba, Ca, Sr), and melted at 1450 ℃, solid oxide fuel cell sealing glass A first step of preparing a sample (glass frit)
A second step of synthesizing a BaSi 2 O 5 crystal filler using silicon oxide (SiO 2 ) -barium oxide (BaO), which is the same composition system as glass, to produce a composite sealing material in which glass and crystal filler are mixed,
A third step of mixing the glass of the first step and the crystal filler of the second step to produce a composite sealing material,
In order to confirm the change of physical properties of the composite sealant manufactured in Step 3, four steps of checking changes in the bending strength values after 0, 100, 300, and 500 hours of thermal cycling in an oxidizing atmosphere and a reducing atmosphere, respectively,
30 weight% of a vehicle (binder: nitrocellulose, organic solvent: alpha terpineol / butyl carbitol acetate) into which the binder was mixed was added to the composite sealing material powder prepared in step 3, and the mixture was sufficiently stirred for 30 minutes using a high- The slurry sufficiently agitated is milled using a three-roll mill, and then defoamed by using a vacuum pump to prepare a paste, and the paste thus prepared is dispensed on the connecting material to form a slurry-applied composite sealant. Wherein the solid oxide fuel cell is a solid oxide fuel cell.
상기 2 단계에서는 SiO2 : BaO = 2 : 1의 비율로 혼합하여 고상반응법으로 1200℃에서 4시간 동안 열처리함으로써, BaSi2O5 결정 필러를 합성하는 것을 특징으로 하는 고체산화물 연료전지용 복합 밀봉재 제조 방법.
6. The method of claim 5,
In the second step, a BaSi 2 O 5 crystal filler is synthesized by mixing in a ratio of SiO 2 : BaO = 2: 1 and performing a heat treatment at 1200 ° C. for 4 hours in a solid-phase reaction method to produce a composite sealing material for a solid oxide fuel cell Way.
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| KR100838731B1 (en) * | 2006-12-20 | 2008-06-16 | 주식회사 포스코 | Manufacturing method of sealing material for solid electrolyte fuel cell |
| KR100905217B1 (en) * | 2007-11-21 | 2009-07-01 | 명지대학교 산학협력단 | High Temperature Sealant Composition Containing Alumina Particle for Solid Oxide Fuel Cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100838731B1 (en) * | 2006-12-20 | 2008-06-16 | 주식회사 포스코 | Manufacturing method of sealing material for solid electrolyte fuel cell |
| KR100905217B1 (en) * | 2007-11-21 | 2009-07-01 | 명지대학교 산학협력단 | High Temperature Sealant Composition Containing Alumina Particle for Solid Oxide Fuel Cell |
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| M.K.Mahapatra, et al., Seal glass for solid oxide fuel cell, Journal of Power Sources, 195 (2010) 7199-7139 * |
| Saswati Ghosh, et al., Development and characterizations of BaO-CaO-Al2O3-SiO2 glass-ceramic sealants for intermediate temperature solid oxide~, Journal of Non-Crystalline Solids 354(2008) 4081-4088 * |
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