KR100318207B1 - A method for impregnating a electrolyte for molten carbonate fuel cell - Google Patents
A method for impregnating a electrolyte for molten carbonate fuel cell Download PDFInfo
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- KR100318207B1 KR100318207B1 KR1019990034894A KR19990034894A KR100318207B1 KR 100318207 B1 KR100318207 B1 KR 100318207B1 KR 1019990034894 A KR1019990034894 A KR 1019990034894A KR 19990034894 A KR19990034894 A KR 19990034894A KR 100318207 B1 KR100318207 B1 KR 100318207B1
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- electrolyte
- matrix
- fuel cell
- electrode
- molten carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- 239000000446 fuel Substances 0.000 title claims abstract description 48
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000010294 electrolyte impregnation Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000155 melt Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002737 fuel gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Classifications
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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
- H01M8/14—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
본 발명은 용융탄산염 연료전지의 전해질 함침방법에 관한 것으로, 단위셀의 제조과정에서 산소극(102) 및 매트릭스(108)의 기공 속에 전해질을 미리 함침시켜 제작함으로써, 이에 따른 연료전지는 전해질판이 없는 구조이므로 스택 적층 시에 전해질판의 수축에 의한 높이 감소를 감안할 필요가 없어 그 작업이 매우 용이하며, 전해질판이 녹을 때에 발생되던 접촉 저항의 증가현상은 완전히 방지되고, 전해질판이 수축될 때에 열충격에 의해 매트릭스가 깨질 우려도 말끔히 해소되는 이점이 있다.The present invention relates to an electrolyte impregnation method of a molten carbonate fuel cell, and is prepared by impregnating electrolyte in the pores of the oxygen electrode 102 and the matrix 108 in the manufacturing process of the unit cell, and thus the fuel cell has no electrolyte plate. Because of the structure, it is not necessary to take into consideration the height reduction due to shrinkage of the electrolyte plate during stack stacking, and the work is very easy, and the increase of contact resistance generated when the electrolyte plate is melted is completely prevented, and the thermal shock when the electrolyte plate shrinks. There is an advantage that the matrix can be broken easily.
Description
본 발명은 용융탄산염 연료전지의 전해질 함침방법에 관한 것으로, 더욱 상세하게는 단위셀의 제조과정에서 산소극 및 매트릭스의 기공 속에 전해질을 미리 함침시켜 제작함으로써 스택 적층 작업의 용이성이 향상되고 전극과 매트릭스와의 접촉 저항이 감소되도록 한 용융탄산염 연료전지의 전해질 함침방법에 관한 것이다.The present invention relates to an electrolyte impregnation method of a molten carbonate fuel cell, and more particularly, by fabricating the electrolyte in the pores of the oxygen electrode and the matrix in the manufacturing process of the unit cell in advance, the ease of stack stacking operation is improved and the electrode and matrix The present invention relates to an electrolyte impregnation method of a molten carbonate fuel cell such that the contact resistance with is reduced.
주지와 같이, 연료전지는 전기화학 반응에 의해 반응물(수소와 산소)의 화학에너지를 직접 전기에너지로 변환시키는 발전장치로서 환경 조화성이 우수하고 높은 발전효율이 기대되고 있다.As is well known, a fuel cell is a power generation device that converts chemical energy of reactants (hydrogen and oxygen) directly into electrical energy by an electrochemical reaction, and is expected to have excellent environmental harmony and high power generation efficiency.
연료전지 중에서 용융탄산염 연료전지는 탄산염의 용융물을 전해질로 사용하여 작동온도가 650℃로 높기 때문에 전기화학 반응의 속도가 빨라 저온형 연료전지와는 달리 백금 등의 귀금속 촉매가 필요하지 않으며, 전기와 고온의 배열을 함께 이용할 경우 80% 이상의 열효율을 기대할 수 있어 석탄 가스화에 의한 복합 열병합 발전이 가능하다.Among the fuel cells, molten carbonate fuel cells use a melt of carbonate as an electrolyte and have a high operating temperature of 650 ° C., so the electrochemical reaction is fast, and unlike low-temperature fuel cells, no noble metal catalyst such as platinum is required. When combined with high-temperature arrays, thermal efficiency of 80% or more can be expected, allowing for combined cogeneration with coal gasification.
연료전지에 사용되는 연료가스로서는 천연가스(메탄)나 개질된 혼합수소를 사용하며, 산화제가스로서 공기와 이산화탄소를 사용한다.As fuel gas used in the fuel cell, natural gas (methane) or reformed mixed hydrogen is used, and air and carbon dioxide are used as oxidant gas.
용융탄산염 연료전지는 650℃ 부근의 온도에서 운전되므로 이 온도에서 탄산염이 용융되어 물과 유사한 점성을 지닌 액체로 되어 탄산이온(CO3 2-)의 전도성을 보이게 된다.The molten carbonate fuel cell is operated at a temperature near 650 ° C, so that the carbonate melts at this temperature to become a liquid having a viscosity similar to that of water, thereby exhibiting the conductivity of carbonate (CO 3 2- ).
연료극(anode)으로 연료가스를 공급하고 산소극(cathode)으로는 산화제가스를 공급하면 각각의 전극에서 전기화학반응이 발생하여 직류전력이 얻어진다. 이때 전지전체에서는 수소와 산소가 반응하여 물이 생성되는 반응이다.When the fuel gas is supplied to the anode and the oxidant gas is supplied to the cathode, an electrochemical reaction occurs at each electrode, thereby obtaining DC power. At this time, in the entire battery, hydrogen and oxygen react to produce water.
용융탄산염 연료전지의 단위셀(unit cell) 전압은 정격방전시에 약 0.8V로 낮기 때문에 실제 발전에서는 기본 구성셀인 단위셀을 다수 적층하여 전압을 높이고, 셀 면적을 증가시켜 고출력화를 달성하게 된다. 이때 단위셀을 여러 단 적층한 것을 스택(stack)이라고 부른다.Since the unit cell voltage of molten carbonate fuel cell is low at about 0.8V at the rated discharge, in actual power generation, it is possible to increase the voltage by increasing the number of unit cells which are the basic constituent cells and increase the cell area to achieve high output. do. In this case, a stack of unit cells is called a stack.
도 1은 종래 기술에 따른 용융탄산염 연료전지의 단위셀 단면도이다.1 is a cross-sectional view of a unit cell of a molten carbonate fuel cell according to the prior art.
이에 나타낸 바와 같이 연료전지는, 연료가스의 수소와 탄산이온이 반응하여 물과 탄산가스로 변하면서 전자가 발생되는 연료극(1)과, 산화제가스의 탄산가스와 산소가 전자 2개와 반응하여 탄산이온으로 변하는 산소극(2)과, 연료전지 몸체를 지지하며 연료가스와 산화제가스가 격리되어 연료극(1)과 산소극(2)으로 공급되는 가스의 유로를 형성하는 상분리판(3) 및 하분리판(4)과, 연료극(1)을 지지하며 연료극(1)에서 발생된 전하를 포집하는 연료극집전판(5)과, 산소극(2)을 지지하며 산소극(2)에서 발생된 전하를 포집하는 산소극집전판(6)과, 전해질을 흡수·수용하여 이온의 이동통로를 제공하는 매트릭스(8)로 구성된다.As shown in the drawing, a fuel cell includes a fuel electrode 1 in which electrons are generated while hydrogen and carbonate ions of a fuel gas react to change into water and carbon dioxide gas, and carbon dioxide and carbonate gas and oxygen of an oxidant gas react with two electrons. Phase separation plate 3 and lower separation which support the oxygen electrode 2 which changes to the fuel cell body, and the fuel gas and the oxidant gas are separated to form a flow path of the gas supplied to the fuel electrode 1 and the oxygen electrode 2. The plate 4, the anode collector plate 5 which supports the anode 1 and collects the charges generated at the anode 1, and the charges generated at the oxygen electrode 2 while supporting the oxygen electrode 2. Oxygen collector plate 6 to be collected, and a matrix (8) for absorbing and receiving the electrolyte to provide a passage for the movement of ions.
도면 중 미설명 부호 7은 적층의 편의를 위해 시트의 형태로 제작되어 두 장의 매트릭스(8) 사이에 배치된 전해질판(7)이며, 9는 스택의 접촉저항을 줄이기 위한 일정 압력을 발생하는 공기압실린더이고, 10은 압력을 단위셀의 전면에 골고루 전달하기 위한 스테인리스 스틸 재질의 가압판이다.In the drawing, reference numeral 7 denotes an electrolyte plate 7 formed in a sheet form for convenience of lamination and disposed between two sheets of matrix 8, and 9 denotes an air pressure for generating a constant pressure to reduce contact resistance of the stack. Cylinder 10, 10 is a pressure plate made of stainless steel for evenly transmitting pressure to the front of the unit cell.
연료극(1) 물질로는 니켈-크롬(Ni-Cr)을 사용하며, 산소극(2) 물질로는 산화니켈(NiO)을 사용하고, 연료극집전판(5)은 연료극 분위기에서 부식에 안정한 니켈을 사용하고, 산소극집전판(6)은 스테인리스 스틸 316L을 사용하며, 분리판(3,4)의 재질은 스테인리스 스틸 316L 또는 310S를 이용하는 것이 보통이다.Nickel-chromium (Ni-Cr) is used as the anode 1 material, nickel oxide (NiO) is used as the oxygen anode 2 material, and the anode current collector 5 is nickel that is stable to corrosion in the anode atmosphere. In this case, the oxygen collector plate 6 is made of stainless steel 316L, and the separator plates 3 and 4 are made of stainless steel 316L or 310S.
전해질판(7)은 탄산리튬(Li2CO3)과 탄산칼륨(K2CO3)의 혼합물을 사용하는데, 탄산리튬과 탄산칼륨의 혼합탄산염에 용제와 바인더 등을 첨가하여 0.3∼0.4㎜ 두께의 시트로 제작된다.The electrolyte plate 7 uses a mixture of lithium carbonate (Li 2 CO 3 ) and potassium carbonate (K 2 CO 3 ), which is 0.3 to 0.4 mm thick by adding a solvent and a binder to a mixed carbonate of lithium carbonate and potassium carbonate. Are made of sheets of.
매트릭스(8)는 다공성 세라믹판을 말하는 것으로, 그 제조방법은 감마-리튬 알루민산염(γ-LiAlO2) 분말에 용제와 바인더 등을 첨가하여 기공율이 55∼60%인 0.4∼0.5㎜ 두께의 시트로 제작된다.The matrix 8 refers to a porous ceramic plate, and a method of manufacturing the same is 0.4 to 0.5 mm thick having a porosity of 55 to 60% by adding a solvent and a binder to a gamma-lithium aluminate (γ-LiAlO 2 ) powder. It is made of sheets.
상기와 같은 구조의 단위셀을 다층으로 적층시켜 스택을 제조하며, 이 스택에는 공기압실린더(9)에서 발생된 일정 압력이 가압판(10)을 통해 전면에 골고루 전달되며, 앞에서 언급한 바와 같이 650℃ 부근의 온도에서 운전된다.A stack is manufactured by stacking unit cells having the above structure in a multi-layer, in which a predetermined pressure generated in the pneumatic cylinder 9 is evenly transmitted to the front surface through the pressure plate 10, and as mentioned above, 650 ° C. It is operated at a nearby temperature.
여기서, 스택의 온도를 조업온도로 올리는 이른바 전처리(pre-treatment) 기간동안에 전해질판(7)의 용제와 바인더 등은 산화되어 제거되며, 혼합탄산염 전해질은 상온에서 고체상태이다가 약 500℃의 온도에서 용융되고, 온도가 650℃로 올라가면 액체로 변화여 매트릭스(8)의 기공 사이로 침투하여 없어지며, 용융된 전해질은 매트릭스(8) 기공사이를 완전히 채우고 연료극(1) 및 산소극(2)의 기공으로 들어간다.Here, the solvent and binder of the electrolyte plate 7 are oxidized and removed during the so-called pre-treatment period in which the temperature of the stack is raised to the operating temperature, and the mixed carbonate electrolyte is solid at room temperature and then is about 500 ° C. At the temperature rises to 650 ° C., changes into a liquid and penetrates through the pores of the matrix 8 and disappears, and the molten electrolyte completely fills the pores of the matrix 8 and the pores of the fuel electrode 1 and the oxygen electrode 2. Enter
아울러, 매트릭스(8)에 사용된 용제 등은 전해질판(7)과 마찬가지로 전처리 기간동안 산화하여 제거된다.In addition, the solvent and the like used in the matrix 8 are oxidized and removed during the pretreatment period similarly to the electrolyte plate 7.
이와 같이, 전해질이 함침되면 연료극(1)에는 수소가스와 탄산가스 및 물이 들어가는데, 그 비율은 72:18:10으로 혼합된다. 산소극(2)에는 공기와 탄산가스를 70:30의 비율로 공급하고 단위면적당 연료극(1)에는 수소가스를 기준으로 2.88cc를 흘리며 산소극(2)에는 산소를 기준으로 1.44cc를 흘리면 o.c.v가 1.013V로 측정된다. 이때 로드(load)를 단위면적당 150㎃로 걸면 단위셀당 정격방전전압은 0.8V 이상으로 나타난다.As such, when the electrolyte is impregnated, hydrogen gas, carbon dioxide gas, and water enter the fuel electrode 1, and the ratio is mixed at 72:18:10. Air and carbon dioxide gas are supplied to the oxygen electrode 2 at a ratio of 70:30, 2.88cc of hydrogen gas is flowed to the fuel electrode 1 per unit area, and 1.44cc of oxygen to the oxygen electrode 2 is ocv. Is measured at 1.013V. At this time, if the load is applied at 150㎃ per unit area, the rated discharge voltage per unit cell is over 0.8V.
상기와 같은 종래 기술에 따른 용융탄산염 연료전지에서 본 발명의 용이한 이해를 위하여 주목하여야 할 것은 용융염을 함침시키기 위하여 매트릭스(8) 사이에 전해질판(7)이 배치된다는 점이다.It should be noted that for easy understanding of the present invention in the molten carbonate fuel cell according to the prior art as described above, an electrolyte plate 7 is arranged between the matrices 8 to impregnate the molten salt.
따라서, 전해질판(7)이 고온에서 녹아 전극(1,2)과 매트릭스(8)에 함침되면 전해질판(7)의 두께차이만큼 단위셀이 아래로 내려앉는데, 통상 단위셀을 100장정도 적층하면 약 10㎝ 가량 아래로 내려앉는다.Therefore, when the electrolyte plate 7 is melted at a high temperature and impregnated with the electrodes 1, 2 and the matrix 8, the unit cell is lowered by the thickness difference of the electrolyte plate 7, and the unit cell is generally about 100 sheets. Lay down about 10 cm when stacked.
전술한 바와 같이 종래 기술에 의하면, 전해질판이 시트의 형태로 제작되어두 장의 매트릭스 사이에 배치되며, 고온에서 전해질판이 녹으면 스택의 높이가 전해질판의 두께만큼 내려앉는 것을 알 수 있다.As described above, according to the related art, an electrolyte plate is manufactured in the form of a sheet and disposed between two sheets, and when the electrolyte plate melts at a high temperature, the height of the stack falls by the thickness of the electrolyte plate.
그러므로, 스택 적층 시에 전해질판의 수축에 의한 높이 감소를 감안하여야 하므로 그 작업이 매우 번거로운 문제점이 있었다.Therefore, since the height reduction due to shrinkage of the electrolyte plate must be taken into account when stacking, the work has been very troublesome.
아울러, 전해질판이 녹으면서 전극과 전해질 및 전극과 매트릭스의 접촉 저항이 증가되어 이는 연료전지의 성능 저하를 유발하는 하나의 요인으로 제공되었으며, 전해질판이 수축될 때에 매트릭스가 열충격에 의하여 깨질 수 있는 문제점이 있었다.In addition, as the electrolyte plate melts, the contact resistance between the electrode and the electrolyte and the electrode and the matrix is increased, which is one of the factors causing the deterioration of the fuel cell, and when the electrolyte plate shrinks, the matrix may be broken by thermal shock. there was.
따라서, 본 발명은 상기와 같은 종래 기술의 문제점들을 해결하기 위하여 제안한 것으로서, 단위셀의 제조과정에서 산소극 및 매트릭스의 기공 속에 전해질을 미리 함침시켜 제작함으로써 스택 적층 작업의 용이성이 향상되고 전극과 매트릭스와의 접촉 저항이 감소되게 하는 데 그 목적이 있다.Therefore, the present invention has been proposed to solve the above problems of the prior art, by fabricating the electrolyte in the pores of the oxygen electrode and the matrix in the manufacturing process of the unit cell in advance to facilitate the stack stacking operation and improve the electrode and matrix The purpose is to reduce the contact resistance with the.
도 1은 종래 기술에 따른 용융탄산염 연료전지의 단위셀 단면도.1 is a cross-sectional view of a unit cell of a molten carbonate fuel cell according to the prior art.
도 2는 본 발명에 따른 용융탄산염 연료전지의 단위셀 단면도.2 is a unit cell cross-sectional view of a molten carbonate fuel cell according to the present invention.
*도면의 주요 부분에 대한 부호의 설명** Description of the symbols for the main parts of the drawings *
1 : 연료극 2,102 : 산소극1: fuel electrode 2,102: oxygen electrode
3 : 상분리판 4 : 하분리판3: phase separation plate 4: lower separation plate
5 : 연료극집전판 6 : 산소극집전판5: anode collector plate 6: oxygen collector plate
7 : 전해질판 8,108 : 매트릭스7: electrolyte plate 8,108 matrix
9 : 공기압실린더 10 : 가압판9: pneumatic cylinder 10: pressure plate
이러한 목적을 달성하기 위한 본 발명에 따른 용융탄산염 연료전지의 전해질 함침방법은, 수소의 산화가 일어나는 연료극과, 산소의 환원이 일어나는 산소극과, 상기 연료극과 산소극과의 사이에 위치하여 이온의 이동통로를 제공하는 매트릭스를 포함하는 용융탄산염 연료전지를 제조하는 방법에 있어서:The electrolyte impregnation method of the molten carbonate fuel cell according to the present invention for achieving this object is located between the fuel electrode in which the oxidation of hydrogen occurs, the oxygen electrode in which the reduction of oxygen occurs, and the ions are located between the fuel electrode and the oxygen electrode A method of making a molten carbonate fuel cell comprising a matrix providing a travel passage:
성형 및 소결 단계를 거쳐 상기 연료극 및 산소극을 만드는 과정과,Forming a fuel electrode and an oxygen electrode through a forming and sintering step;
주성분에 전해질을 혼합한 후 성형 과정을 거쳐 상기 매트릭스를 만드는 과정과,Mixing the electrolyte with the main component and forming the matrix through a molding process;
상기 연료극과 산소극 및 매트릭스를 적층하는 과정을 포함한다.And laminating the fuel electrode, the oxygen electrode, and the matrix.
본 발명의 실시예로는 다수개가 존재할 수 있으며, 이하에서는 가장 바람직한 실시예에 대하여 상세히 설명하기로 한다.There may be a plurality of embodiments of the present invention, hereinafter, the most preferred embodiments will be described in detail.
본 발명에 따른 용융탄산염 연료전지의 전해질 함침방법을 채용한 제조법을 대분하면, 니켈을 주성분으로 하고 크롬을 첨가물질로 하여 혼합·볼밀링·테이프 캐스팅·건조하는 성형 단계와 환원분위기로 열처리하는 소결 단계를 거쳐 연료극을 만드는 과정과; 산화니켈을 주성분으로 하여 성형 단계와 소결 단계를 거친 후 그 위에 전해질을 고르게 얹고 소정의 온도로 가열하여 기공내로 함침시켜 산소극을 만드는 과정과; 전해질과 결합제를 혼합하여 분산시키는 단계, 감마-리튬 알루민산염을 주성분으로 사용하여 상기 분산된 혼합물과 함께 혼합하여 슬러리를 만드는 단계, 이 슬러리를 박판으로 성형하는 단계를 거쳐 매트릭스를 만드는 과정과; 연료극과 산소극 및 매트릭스를 적층하여 단위셀을 만드는 과정과; 이 단위셀을 여러 단으로 적층하여 스택을 만드는 과정으로 이루어진다.The manufacturing method employing the electrolyte impregnation method of the molten carbonate fuel cell according to the present invention is largely divided into a molding step of mixing, ball milling, tape casting, drying with nickel as a main component and chromium as an additive, and sintering heat treatment with a reducing atmosphere. Making a fuel electrode through the steps; After the forming step and the sintering step using nickel oxide as a main component, an electrolyte is evenly placed thereon, heated to a predetermined temperature, and impregnated into pores to form an oxygen electrode; Mixing and dispersing an electrolyte and a binder, mixing with the dispersed mixture using gamma-lithium aluminate as a main component to form a slurry, and forming the matrix by forming the slurry into a thin plate; Stacking a fuel electrode, an oxygen electrode, and a matrix to form a unit cell; The unit cells are stacked in multiple stages to form a stack.
상기의 여러 과정 중에서 종래 기술, 즉 통상의 방법이 적용된 과정은 그 상세 설명을 생략하기로 하고, 본 발명의 기술 요지인 산소극 제조과정과 매트릭스 제조과정은 아래에서 보다 상세히 설명하기로 한다.Among the above processes, a detailed description of the prior art, that is, the process to which the conventional method is applied will be omitted, and an oxygen electrode manufacturing process and a matrix manufacturing process, which are the technical gist of the present invention, will be described in more detail below.
산소극 제조과정은, 먼저 산화니켈을 주성분으로 하고 용제 등을 혼합하여 슬러리를 만들며, 이 슬러리를 테이프 캐스팅 및 건조하여 다공성의 시트로 성형하고, 시트를 고온에서 열처리하는 소결 단계를 거친다.The production process of the oxygen electrode is first made of nickel oxide and mixed with a solvent to form a slurry. The slurry is tape cast and dried to form a porous sheet, and the sheet is subjected to a sintering step of heat treatment at a high temperature.
이후, 소결된 시트 위에 적정량의 전해질, 즉 미리 전극기공(연료극 및 산소극)에 함침될 양으로 계산한 탄산리튬과 탄산칼륨의 혼합물을 얹고 550∼650℃의 온도조건에서 대략 30분간 가열한다.Thereafter, a suitable amount of electrolyte, that is, a mixture of lithium carbonate and potassium carbonate calculated in advance in the amount of the electrode impregnated in the electrode pores (fuel electrode and oxygen electrode) is placed on the sintered sheet and heated at a temperature of 550 to 650 ° C for about 30 minutes.
그러면, 전해질이 소결된 시트의 기공 내로 함침되어 산소극의 제작이 완료된다.Then, the electrolyte is impregnated into the pores of the sintered sheet to complete the production of the oxygen electrode.
매트릭스의 제조과정은, 먼저 산소극의 제조과정에서 사용된 동종의 전해질과 결합제를 혼합하여 분산시킨다. 이때, 전해질의 양은 이후에 제작 완료될 매트릭스의 기공을 100% 함침하는 양으로서 이는 선행 시험제작의 결과값을 기초로 얻을 수 있다.In the manufacturing process of the matrix, first, the same electrolyte and binder used in the preparation of the oxygen electrode are mixed and dispersed. At this time, the amount of the electrolyte is an amount to impregnate the pores of the matrix to be produced later, which can be obtained based on the result of the previous test production.
그리고, 혼합된 전해질 및 결합제를 주성분인 감마-리튬 알루민산염과 다시 혼합하여 1차로 볼밀링한다.Then, the mixed electrolyte and the binder are mixed again with gamma-lithium aluminate as a main component and ball milled firstly.
그리고, 볼밀링한 혼합물에 용제를 첨가한 후 2차로 볼밀링하여 슬러리를 만든다.Then, a solvent is added to the ball milled mixture and then ball milled secondly to form a slurry.
이후, 슬러리에 포함된 기포를 제거하며, 탈포된 슬러리를 테이프 캐스팅 및 건조시켜 박판으로 성형하면 매트릭스의 제작이 완료된다.Thereafter, bubbles contained in the slurry are removed, and the degassed slurry is tape cast and dried to form a thin plate, thereby completing the preparation of the matrix.
이와 같은 과정을 거쳐 연료극과 산소극 및 매트릭스의 제작이 완료되면, 이들을 적층하여 단위셀을 만들며, 이 단위셀을 여러 단으로 적층하여 스택이 만들어진다.When the production of the fuel electrode, the oxygen electrode and the matrix is completed through such a process, the unit cells are stacked to form unit cells, and the unit cells are stacked to form a stack.
상술한 본 발명에 따른 용융탄산염 연료전지의 전해질 함침방법으로 제작된단위셀의 단면 구조를 도 2에 나타내었다. 도 2에서 부호 102는 산소극이며, 108은 매트릭스이고, 이외의 미설명 부호는 종래 기술에서 참조한 도 1의 구성요소와 동일한 요소이다.2 is a cross-sectional structure of a unit cell manufactured by the electrolyte impregnation method of the molten carbonate fuel cell according to the present invention. In FIG. 2, reference numeral 102 denotes an oxygen electrode, 108 denotes a matrix, and other reference numerals denote the same elements as those of FIG.
도 2를 도 1과 비교하면 본 발명의 단위셀은 종래의 단위셀과는 달리 전해질판이 없는 구조임을 쉽게 알 수 있다. 이는 산소극(102)과 매트릭스(108)에 전해질이 이미 함침된 상태이므로 별도의 전해질판이 필요하지 않기 때문이다.Comparing FIG. 2 with FIG. 1, it can be easily seen that the unit cell of the present invention has a structure without an electrolyte plate unlike the conventional unit cell. This is because an electrolyte plate is already impregnated with the oxygen electrode 102 and the matrix 108, and thus a separate electrolyte plate is not required.
이와 같이, 본 발명에 의해 제작된 스택은 공기압실린더(9) 및 가압판(10)을 통해 압력이 가해지고, 조업온도인 650℃ 부근의 온도에서 운전되면, 산소극(102)과 매트릭스(108)의 기공내에 함침된 전해질이 녹아 자연적으로 연료극(1) 및 산소극(102)에 골고루 이동되며, 전해질판이 없는 구조이므로 전처리 기간 및 운전 중에 스택의 높이는 내려앉지 않는다.As described above, when the stack manufactured according to the present invention is pressurized through the pneumatic cylinder 9 and the pressure plate 10 and operated at a temperature around 650 ° C. which is an operating temperature, the oxygen electrode 102 and the matrix 108 are operated. The electrolyte impregnated in the pores of the melt melts and naturally moves evenly to the fuel electrode 1 and the oxygen electrode 102, and because the structure does not have an electrolyte plate, the stack height does not fall during the pretreatment period and operation.
상술한 바와 같이 본 발명의 전해질 함침방법으로 제작된 연료전지는 전해질판이 없는 구조이므로 스택 적층 시에 전해질판의 수축에 의한 높이 감소를 감안할 필요가 없어 그 작업이 매우 용이하며, 종래 기술에서 전해질판이 녹을 때에 발생되던 접촉 저항의 증가현상은 완전히 방지되고, 전해질판이 수축될 때에 열충격에 의해 매트릭스가 깨질 우려도 말끔히 해소된다.As described above, since the fuel cell manufactured by the electrolyte impregnation method of the present invention has no electrolyte plate structure, it is not necessary to consider the height reduction due to shrinkage of the electrolyte plate when stacking, and the operation is very easy. The increase in contact resistance generated during melting is completely prevented, and the possibility of the matrix being broken by thermal shock when the electrolyte plate shrinks is also completely eliminated.
아울러, 매트릭스의 제조과정에서 전해질이 혼합되므로 전해질이 고르게 분포되어 부식발생이 억제되어 내구성이 향상되므로 연료전지의 수명이 연장되는 효과가 있다.In addition, since the electrolyte is mixed in the manufacturing process of the matrix, the electrolyte is evenly distributed and corrosion is suppressed, thereby improving durability, thereby extending the life of the fuel cell.
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