KR100394777B1 - Surface treatment of molten carbonate fuel cell separator - Google Patents
Surface treatment of molten carbonate fuel cell separator Download PDFInfo
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- KR100394777B1 KR100394777B1 KR1019960022387A KR19960022387A KR100394777B1 KR 100394777 B1 KR100394777 B1 KR 100394777B1 KR 1019960022387 A KR1019960022387 A KR 1019960022387A KR 19960022387 A KR19960022387 A KR 19960022387A KR 100394777 B1 KR100394777 B1 KR 100394777B1
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- aluminum
- fuel cell
- nickel
- coating
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- 239000000446 fuel Substances 0.000 title claims abstract description 30
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 238000004381 surface treatment Methods 0.000 title claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 230000007797 corrosion Effects 0.000 claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000009792 diffusion process Methods 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- -1 lithium aluminates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0048—Molten electrolytes used at high temperature
- H01M2300/0051—Carbonates
-
- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
본 발명은 용융탄산염 연료전지에 관한 것으로, 특히 스페인리스강의 모재에 니켈과 알루미늄을 적층코팅한 후 확산열처리하여 열변형을 방지하고 내구성을 향상한 용융탄산염 연료전지 분리판의 표면처리방법에 관한 것이다. 본 발명은 용융탄산염 연료전지의 분리판으로 사용했을 때 알루미늄의 코팅두께가 얇아도 기존의 알루미늄 단독코팅과 유사하거나 더 내식성이 우수하다. 뿐만 아니라, 열처리온도가 상대적으로 낮게 할 수 있어 연료전지 분리판과 같은 박판에 대한 열변형을방지하여 내구성을 향상할 수 있는 효과를 가지고 있다.The present invention relates to a molten carbonate fuel cell, and more particularly, to a surface treatment method of a molten carbonate fuel cell separator in which nickel and aluminum are laminated on a base material of a Spanish lease steel and diffusion heat treatment is performed to prevent thermal deformation and improve durability . When used as a separator of a molten carbonate fuel cell, the present invention is similar to or better in corrosion resistance than a conventional aluminum coating even when the thickness of the aluminum coating is small. In addition, since the heat treatment temperature can be relatively low, thermal deformation of the thin plate, such as the fuel cell separator, can be prevented and durability can be improved.
Description
본 발명은 용융탄산염 연료전지에 관한 것으로, 특히 스테인리스강의 모재에 니켈과 알루미늄을 적층코팅한 후 확산열처리하여 열변형을 방지하고 내구성을 향상시킨, 용융탄산염 연료전지 분리판의 표면처리방법에 관한 것이다.The present invention relates to a molten carbonate fuel cell, and more particularly, to a method for surface treatment of a molten carbonate fuel cell separator in which nickel and aluminum are laminated on a base material of stainless steel and then subjected to diffusion heat treatment to prevent thermal deformation and improve durability .
일반적으로, 연료전지란 연료가 가지고 있는 화학에너지(연료속의 수소)와 공기중의 산소를 전기화학반응시켜 전기를 발생시키는 장치로서, 수력, 화력, 원자력발전에 이은 제 4의 발전방식이다. 이러한 연료전지는 반응물의 화학에너지를 전기에너지로 직접 전환시키므로 고효율, 저공해란 잇점을 갖고 있다.Generally, a fuel cell is a fourth generation system that generates electricity by electrochemically reacting chemical energy (hydrogen in fuel) of fuel with oxygen in the air, and is a power generation system after hydropower, thermal power, and nuclear power generation. These fuel cells directly convert the chemical energy of the reactants into electrical energy, which has the advantage of high efficiency and low pollution.
연료전지의 본체를 구성하는 구성요소로는, 제 1도에 도시한 바와 같이, 전기 화학반응이 일어나는 전극들(10a,10b), 전극들(10a,10b) 사이에 개재되어 전해질인 용융탄산염을 지지하는 매트릭스(20a20b) 그리고, 반응에 의해 발생되는 전자의 이동을 원활하게 하는 전류집진체(30a,30b) 및, 반응가스의 유출입 및 전기의 흐름을 연결시켜 주는 분리판들(40a,40b)이 있다. 이중 전극(10a,10b)을 구성하는 물질로는 연료극에 니켈-크롬(Ni-Cr)을, 산화극에 니켈(NiO)을 사용하며, 전해질로는 62mol% Li2CO3- 38mol% K2CO3의 조성을 가지는 혼합탄산염을, 그리고 매트릭스(20a,20b)로는 리튬알루미네이트(LiAlO2)를 사용한다. 또한, 분리판(40a,40b)의 재질로는 AISI 316이나 AISI 310 등의 스테인리스 스틸이 적합하다.As shown in FIG. 1, constituent elements constituting the main body of the fuel cell include electrodes 10a and 10b where an electrochemical reaction takes place, and molten carbonate as an electrolyte interposed between the electrodes 10a and 10b The current collectors 30a and 30b for facilitating the movement of electrons generated by the reaction and the separators 40a and 40b for connecting the flow of the reactant gas and the flow of electricity, . Nickel (Ni-Cr) and nickel (NiO) are used for the fuel electrode and the oxidizing electrode, respectively, and 62 mol% Li 2 CO 3 - 38 mol% K 2 CO 3 , and lithium aluminates (LiAlO 2 ) are used as the matrices 20a and 20b. Stainless steel such as AISI 316 or AISI 310 is suitable as the material of the separator plates 40a and 40b.
용융탄산염형 연료전지는 산소극에 산화니켈의 용해와 부식에 의한 전해질의 손실이 가장 심각한 문제로 대두되고 있다. 특히, 용융탄산염형 연료전지는 650℃의 고온에서 작동하기 때문에 전해질과 접촉하게 되는 이른바 습식밀봉부(Wet-Seal Area)(41a,41b)의 분리판(40a,40b)의 부식이 심각하다. 이런 부식의 결과로서, 전해질의 소모에 따른 반응가스의 크로스-오버(Cross-Over)와 부식생성물에 의한 전지의 단락등이 발생하여 전지의 성능과 수명을 단축시키는 문제점이 있다.In a molten carbonate fuel cell, loss of electrolyte due to dissolution and corrosion of nickel oxide in the oxygen electrode is becoming the most serious problem. Particularly, since the molten carbonate fuel cell operates at a high temperature of 650 ° C, the corrosion of the separators 40a and 40b of the so-called wet seal areas 41a and 41b, which are in contact with the electrolyte, is serious. As a result of such corrosion, cross-over of the reaction gas due to the consumption of the electrolyte and short-circuiting of the battery due to corrosion products occur, shortening the performance and lifetime of the battery.
이와 같은 문제를 해소하기 위해서 습식밀봉부(41a,41b)에 내식처리를 하게되는 바, 그 방법으로는 알루미늄코팅이 가장 좋은 것으로 인식되고 있다. 알루미늄코팅의 일반적인 방법으로는 용융된 알루미늄에 모재를 침적시키는 용융알루미늄 도금법과, Al과 NH4Cl, Al2O3등을 혼합하여 열처리한 후, Al을 모재에 확산시키는 방법(카로라이징) 등이 있다. 또한, 알루미늄을 증기로 기화시켜 증착시키는 물리증착법과, 알루미늄 분말과 여러 용제를 혼합한 슬러리를 모재에 코팅시키는 방법, 즉 슬러리코팅법과, 알루미늄을 모재에 분사시키는 스프레이코팅법 등도 있다.In order to solve such a problem, the wet sealing portions 41a and 41b are subjected to the corrosion treatment, and it is recognized that the aluminum coating is the best method. As a general method of aluminum coating, there are a molten aluminum plating method in which a base material is immersed in molten aluminum, a method in which Al is mixed with NH 4 Cl, Al 2 O 3 , and the like, and then Al is diffused into the base material (carrowing) . There are also physical vapor deposition methods in which aluminum is vaporized and vaporized, a method in which a slurry obtained by mixing aluminum powder and various solvents is coated on a base material, that is, a slurry coating method, and a spray coating method in which aluminum is sprayed onto a base material.
이상과 같은 일반적인 알루미늄 코닝방법에서는 900℃이상에서 확산열처리를 하게 되는데, 분리판이 박판이다 보니 고열에 의한 변형이 발생하고, 표면층에 고온열처리로 인한 결함이 생겨 스테인리스의 모재까지 부식됨으로 인해 전지의 수명을 단축시키는 결과를 초래하는 문제점이 있다. 또한, 일정두께(최저 30㎛)이상 알루미늄을 코팅하지 않으면 내식성이 충분하지 못하게 되는데, 알루미늄의 두께를 높이기 위해서는 결국 코팅비를 높이지 않으면 안되는 문제가 발생한다.In the general aluminum corning process as described above, diffusion heat treatment is performed at 900 ° C. or more. When the separator plate is a thin plate, deformation due to high temperature occurs, defects due to high temperature heat treatment are generated in the surface layer, Resulting in shortening the time required for the operation. In addition, if aluminum is not coated to a certain thickness (at least 30 탆), corrosion resistance becomes insufficient. However, in order to increase the thickness of aluminum, the coating ratio must be increased.
본 발명의 목적은 상술한 제결점을 해소하기 위한 것으로서, 모재에 니켈과 알루미늄을 복합코팅한 후, 최적의 온도와 분위기에서 확산열처리하여 박판인 분리판의 열변형을 방지하고 내구성을 향상시킨, 용융탄산염 연료전지 분리판의 표면처리방법을 제공함에 있다.An object of the present invention is to solve the above-described drawbacks, and it is an object of the present invention to provide a method of manufacturing a nickel-aluminum composite plate by nickel-aluminum composite coating on a base material, followed by diffusion heat treatment at an optimal temperature and atmosphere to prevent thermal deformation of the plate- And a method for surface treatment of a molten carbonate fuel cell separator.
이와 같은 목적을 달성하기 위한 본 발명에 따른 용융탄산염 연료전지 분리판의 표면처리방법은, 소정넓이의 모재에 니켈을 소정두께로 코팅하는 단계를 구비하고 있으며, 상기 니켈코팅층위에 적정두께로 알루미늄을 코팅하는 단계를 구비하고 있으며, 상기 니켈과 알루미늄이 적층코팅된 모재를 600~1000℃ 온도하에 10%수소분위기에서 10분이상 열처리하여 확산층을 형성하는 단계를 구비하고 있다.According to an aspect of the present invention, there is provided a method for surface treatment of a molten carbonate fuel cell bipolar plate, the method comprising: coating nickel with a predetermined thickness on a base material having a predetermined width; And a step of forming a diffusion layer by heat treating the base material in which the nickel and aluminum are laminated and coated at a temperature of 600 to 1000 DEG C in a 10% hydrogen atmosphere for 10 minutes or more.
본 발명은 제 1도에 나타난 분리판의 구성부분 중 탄산염과 직접 접촉하는 습식밀봉부에 대한 내식처리방법에 관한 것으로, 이하 본 발명에 의한 용융탄산염연료전지 분리판의 표면처리방법에 대해 구체적으로 설명한다.The present invention relates to a corrosion-resistant treatment method for a wet-type sealing part which is in direct contact with a carbonate among constituent parts of the separating plate shown in FIG. 1, and a method for surface treatment of a molten carbonate fuel cell separator according to the present invention will be described in detail Explain.
먼저, 모재에 니켈을 적정두께로 코팅하고, 그 위에 다시 알루미늄을 코팅하게 된다. 이와 같은 적층코팅을 하기 위한 첫번째 방법으로는, 분리판의 모재인 소정넓이의 스테인리스강판에 니켈을 2㎛이상의 두께(최적두께 5∼20㎛)로 전기도금하여 코팅하고, 그리고 니켈이 코팅된 위에 알루미늄을 물리증착법에 의해 두께 4㎛이상(최적두께10~ 60㎛)로 코팅하는 방법이 있다. 또한, 두번째 방법으로는 소정넓이의 스테인리스강판에 니켈을 5㎛이상의 두께(최적두께10∼50㎛)로 스프레이 코팅하고, 그 위에 스프레이코팅법으로 알루미늄 10㎛이상의 두께(최적두께 20∼100㎛)로 코팅하는 방법이 있다.First, nickel is coated on the base material to an appropriate thickness, and then aluminum is coated thereon. As a first method for such a multilayer coating, nickel is electroplated with a thickness of 2 탆 or more (optimum thickness: 5 to 20 탆) on a stainless steel plate having a predetermined width, which is a base material of the separator plate, There is a method of coating aluminum with a thickness of 4 탆 or more (optimum thickness 10 to 60 탆) by physical vapor deposition. As a second method, nickel is spray-coated on a stainless steel plate having a predetermined width to a thickness of 5 탆 or more (optimum thickness 10 to 50 탆), and aluminum is coated thereon with a thickness of 10 탆 or more (optimal thickness 20 to 100 탆) .
이상과 같이 적층코팅한 후, 모재와 알루미늄 및 니켈을 반응시켜 확산층을 형성하기 위해 600~1000℃의 온도(최적온도 650∼900℃)하에 10% 수소(질소 발란스)에서 10분이상(최적시간 1-5시간) 열처리를 한다.In order to form a diffusion layer by reacting the base material with aluminum and nickel after the lamination coating as described above, the base material is reacted with 10% hydrogen (nitrogen balance) at a temperature of 600 to 1000 ° C. (optimum temperature 650 to 900 ° C.) 1-5 hours).
만약, 알루미늄-니켈코팅된 분리판을 열처리하지 않고 연료전지에 사용하게 되면, 알루미늄의 융점이 645℃이므로 전지조업과정에서 녹아 버리거나, 탄산염과 격렬히 반응해서 탄산염의 손실을 크게 일으켜 전지의 성능을 떨어뜨리게 된다. 니켈의 코팅두께가 2㎛이하이거나 알루미늄의 코팅두께가 4㎛이하이면, 탄산염에 대한 내부식 효과가 현저히 떨어지게 된다.If the aluminum-nickel coated separator is used in a fuel cell without heat treatment, the melting point of the aluminum is 645 ° C., which melts in the course of the battery operation or reacts violently with the carbonate to cause a significant loss of carbonate, . If the coating thickness of nickel is 2 탆 or less, or if the coating thickness of aluminum is 4 탆 or less, the corrosion effect on the carbonate is remarkably deteriorated.
그리고, 열처리온도를 600℃이하로 하면, 알루미늄-니켈과 모재의 원자간에 확산이 거의 일어나지 않아, 이런 분리판을 연료전지에 사용하면 전해질의 소모가 많고 모재에 부식이 일어나게 된다.If the heat treatment temperature is lower than 600 ° C, diffusion between the aluminum-nickel and the atoms of the base material hardly occurs. If such a separator is used in a fuel cell, the electrolyte is consumed and corrosion occurs in the base material.
또한, 열처리 온도를 1000℃이상으로 하면 모재의 변형이 생기고 표면층에 결함이 생겨 모재의 부식이 일어나게 된다.When the heat treatment temperature is 1000 ° C or higher, deformation of the base material occurs and defects are formed in the surface layer, causing corrosion of the base material.
한편, 열처리시간을 10분이하로 하면 알루미늄과 모재와의 반응이 제대로 일어나지 않는 문제가 발생한다.On the other hand, if the heat treatment time is less than 10 minutes, there arises a problem that the reaction between aluminum and the base material does not occur properly.
다음 실시예들은 본 발명의 효과를 입증해 준다.The following examples demonstrate the effectiveness of the present invention.
실시예 1Example 1
2mm 두께의 스테인리스 강판316L(이하, 모재라고 함)의 표면에 잔류하고 있는 기름기와 불순물을 물, 유기용제 및, 산등으로 깨끗이 세척한다. 이 세척된 모재를 질산니켈수용액속에 넣고 2㎛ 또는 5㎛의 두께로 니켈을 전기도금한다. 전기도금된 모재를 다시 위의 방법으로 세척하고, 진공도 5 ×10-6torr인 진공로속에 넣고 물리증착법의 일종인 이온 스퍼터링으로 알루미늄을 증착시킨다. 이때, 알루미늄코팅의 두께는 10㎛으로 한다. 알루미늄-니켈이 코팅된 모재를 10%수소(질소 발란스)가 흐르는 분위기로에 넣고 830℃에서 1시간동안 열처리한다. 분위기로를 질소로 완전히 채우고 나서 열처리된 강판을 꺼내고, 표면에 산화된 알루미늄을 제거한다.Clean the grease and impurities remaining on the surface of the 2 mm thick stainless steel plate 316L (hereinafter referred to as "base material") with water, organic solvents, and acid. The washed base material is placed in an aqueous nickel nitrate solution and electroplated with nickel to a thickness of 2 탆 or 5 탆. The electroplated base material is again cleaned by the above method and placed in a vacuum furnace having a vacuum degree of 5 × 10 -6 torr, and aluminum is deposited by ion sputtering, which is one kind of physical vapor deposition method. At this time, the aluminum coating has a thickness of 10 mu m. The aluminum-nickel coated base material is placed in an atmosphere of 10% hydrogen (nitrogen balance) and heat-treated at 830 ° C for 1 hour. The furnace is completely filled with nitrogen, the annealed steel plate is taken out, and the oxidized aluminum is removed on the surface.
표면층의 조성을 확인하기 위해 시편으로 자르고 표면가공을 한 후 표면의 원소분석 및 X-선 회절기로 표면조성분석을 실행하였다. 표면조성분석을 한 결과, 표면층의 성분은 Ni-Al 과 Ni2Al3화합물이었으며, 표면층의 두께와 조성은 표 1에 나타내었다.In order to confirm the composition of the surface layer, it was cut into specimens and surface-processed, and elemental analysis of the surface and analysis of the surface composition with an X-ray diffractometer were carried out. As a result of surface composition analysis, Ni-Al and Ni 2 Al 3 compounds were found in the surface layer, and the thickness and composition of the surface layer are shown in Table 1.
시편위에 62mol% Li2CO3- 38mol% K2CO3의 조성을 가지는 탄산염 가루를 올리고, CO2분위기의 650℃의 로속에서 200시간동안 부식시켰다. 부식실험후의 시편의 표면을 주사전자현미경과 X-선 회전기로 관찰해 보았다. 이 800℃나 900℃에서 열처리된 시편은 부식이 전혀 발견되지 않았다.Carbonate powder having a composition of 62 mol% Li 2 CO 3 - 38 mol% K 2 CO 3 was placed on the specimen and etched for 200 hours at a speed of 650 ° C. in CO 2 atmosphere. The surface of the specimen after the corrosion test was observed with a scanning electron microscope and an X-ray machine. The specimens annealed at 800 ℃ and 900 ℃ showed no corrosion at all.
실시예 2Example 2
실시예 1 과 같은 방법으로 하되, 2mm강판 316L(모재)에 샌드블라스팅을 하고 니켈분말을 스프레이코팅법으로 20㎛의 두께로 입혔다. 여기에 스프레이법에 의해 알루미늄을 70㎛ 두께로 코팅한 후 830℃에서 열처리하였다. 이 시편을 실시예 1과 같은 방법으로 분석하고 부식시켰다. 분석한 결과는 표 1에 나타냈으며, 부식실험결과 모재에 대한 부식은 없는 것으로 나타났다.In the same manner as in Example 1, a 2 mm steel plate 316L (base material) was sandblasted and nickel powder was coated with a thickness of 20 탆 by a spray coating method. Aluminum was coated thereon by spraying to a thickness of 70 탆 and then heat-treated at 830 캜. This specimen was analyzed and etched in the same manner as in Example 1. The results of the analysis are shown in Table 1, and the corrosion test results showed no corrosion of the base metal.
비교예Comparative Example
실시예 1에서와 같은 방법으로 하되, 니켈코팅을 하지 않고 알루미늄코팅만을 10㎛두께로 한 시편을 830℃에서 열처리 하였다. 이 시편을 실시예 1과 같은 방법으로 분석하고 부식시켰다. 분석한 결과는 표 1과 같으며, 부식실험결과 시편은 알루미늄코팅층이 얇고 치밀하지 못하여 국부적으로 모재까지 부식이 일어남이 관찰되었다.The same procedure as in Example 1 was carried out except that the nickel coating was not applied and the aluminum coating was only 10 μm thick. This specimen was analyzed and etched in the same manner as in Example 1. The results of the analysis are as shown in Table 1. As a result of the corrosion test, it was observed that the aluminum coating layer was thin and not densified and corrosion was locally caused to the base metal.
이상 부식실험결과 니켈-알루미늄 표면충의 조성이 알루미늄 몰비 25∼75%, 니켈 몰비 25~75% 일때 탄산염에 대한 내식성이 우수한 것으로 판명되었다.As a result of the abnormal corrosion test, it was proved that the composition of the nickel-aluminum surface layer is excellent in corrosion resistance against carbonate when the aluminum molar ratio is 25 to 75% and the nickel molar ratio is 25 to 75%.
이상 서술한 바와 같이, 본 발명은 용융탄산염 연료전지의 분리판으로 사용했을 때 알루미늄의 코팅두께가 얇아도 기존의 알루미늄 단독코팅과 유사하거나 내식성이 더 우수한 효과가 있다. 뿐만아니라, 열처리온도를 상대적으로 낮게 할 수 있어 연료전지 분리판과 같은 박판에서의 열변형을 방지하여 내구성을 향상할 수 있는 효과를 가지고 있다.As described above, according to the present invention, when used as a separator of a molten carbonate fuel cell, even if the coating thickness of aluminum is thin, it is similar to or better in corrosion resistance than conventional aluminum coatings. In addition, since the heat treatment temperature can be relatively lowered, thermal deformation of the thin plate such as the fuel cell separator can be prevented and durability can be improved.
제 1도는 일반적인 용융탄산염 연료전지의 구성도이다.FIG. 1 is a block diagram of a typical molten carbonate fuel cell.
* 도면의 주요부분에 대한 부호의 설명 *Description of the Related Art [0002]
10a,10b : 전극 20a,20b : 매트릭스10a, 10b: electrodes 20a, 20b: matrix
30a,3b : 전류집진체 40a,40b : 분리판30a, 3b: Current collectors 40a, 40b:
41a,41b : 습식밀봉부41a, 41b: wet seal part
Claims (3)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019960022387A KR100394777B1 (en) | 1996-06-19 | 1996-06-19 | Surface treatment of molten carbonate fuel cell separator |
| IT97MI001264A IT1292033B1 (en) | 1996-05-31 | 1997-05-29 | ANTICORROSIVE TREATMENT METHOD FOR A MOLTEN CARBONATE FUEL CELL SEPARATOR |
| US08/864,745 US6090228A (en) | 1996-05-31 | 1997-05-29 | Anticorrosive treatment method for a separator of molten carbonate fuel cell |
| NL1006185A NL1006185C2 (en) | 1996-05-31 | 1997-05-30 | Anti-corrosion treatment method for a fuel cell separator with molten carbonate. |
| JP14421597A JP3423574B2 (en) | 1996-05-31 | 1997-06-02 | Corrosion resistant treatment method for separator of molten carbonate fuel cell |
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| KR1019960022387A KR100394777B1 (en) | 1996-06-19 | 1996-06-19 | Surface treatment of molten carbonate fuel cell separator |
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| KR980006586A KR980006586A (en) | 1998-03-30 |
| KR100394777B1 true KR100394777B1 (en) | 2003-11-17 |
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| TWI641175B (en) * | 2016-11-28 | 2018-11-11 | 財團法人工業技術研究院 | Anti-corrosion structure and fuel cell employing the same |
| US10511030B2 (en) | 2016-11-28 | 2019-12-17 | Industrial Technology Research Institute | Anti-corrosion structure and fuel cell employing the same |
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| KR100761645B1 (en) * | 2006-12-01 | 2007-10-04 | 서준택 | Nickel-plated separator for fuel cell and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63138663A (en) * | 1986-11-29 | 1988-06-10 | Toshiba Corp | Manufacture of fused carbonate corrosion-resistant material |
| JPH0417267A (en) * | 1990-05-10 | 1992-01-22 | Nisshin Steel Co Ltd | Separator plate of molten carbonate fuel cell |
| JPH0652868A (en) * | 1992-06-19 | 1994-02-25 | Sumitomo Special Metals Co Ltd | Separator masking material for molten carbonate fuel cell and manufacture thereof |
-
1996
- 1996-06-19 KR KR1019960022387A patent/KR100394777B1/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63138663A (en) * | 1986-11-29 | 1988-06-10 | Toshiba Corp | Manufacture of fused carbonate corrosion-resistant material |
| JPH0417267A (en) * | 1990-05-10 | 1992-01-22 | Nisshin Steel Co Ltd | Separator plate of molten carbonate fuel cell |
| JPH0652868A (en) * | 1992-06-19 | 1994-02-25 | Sumitomo Special Metals Co Ltd | Separator masking material for molten carbonate fuel cell and manufacture thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI641175B (en) * | 2016-11-28 | 2018-11-11 | 財團法人工業技術研究院 | Anti-corrosion structure and fuel cell employing the same |
| US10511030B2 (en) | 2016-11-28 | 2019-12-17 | Industrial Technology Research Institute | Anti-corrosion structure and fuel cell employing the same |
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