CN105304917A - Metal connector for medium-temperature flat plate type solid oxide fuel cell - Google Patents
Metal connector for medium-temperature flat plate type solid oxide fuel cell Download PDFInfo
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- CN105304917A CN105304917A CN201510715702.2A CN201510715702A CN105304917A CN 105304917 A CN105304917 A CN 105304917A CN 201510715702 A CN201510715702 A CN 201510715702A CN 105304917 A CN105304917 A CN 105304917A
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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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/128—Fuel cells with solid halide electrolytes
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Abstract
The invention discloses a metal connector for a medium-temperature flat plate type solid oxide fuel cell. The metal connector is characterized by being prepared from, by mass, 2-2.5 parts of Mo, 1-1.1 parts of Mn, 16-17 parts of Cr, 0.1-0.12 part of Zr, 0.51-0.53 part of Ti, 0.018-0.019 part of Y, 0.0049-0.0050 part of La, 0.0020-0.0025 part of C, 0.0094-0.0095 part of P, 0.0038-0.0039 part of Si, 0.00095-0.00099 part of S and 70-78 parts of Fe. According to the metal connector manufactured according to the formula, a novel metal connector alloy material capable of resisting cell cathode Cr poison in the working environment of the solid oxide fuel cell is provided and has a thermal expansion coefficient matched with other components of the cell, good pyroconductivity, good oxidation resistance and a good machining property; on the polarization condition of simulating galvanic pile work, no Cr deposition phenomenon is found on the LSM cathode and the LSM/YSZ electrolyte interface basically, and it is proved that the alloy has excellent cathode Cr poison resistance.
Description
Technical field
The invention belongs to field of alloy steel, more specifically, relate to warm flat solid oxide fuel cell metal connector in one.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of energy conversion apparatus of clean and effective, and fuel-cell fuel transfer ratio is high, and its heat-electric energy conversion efficiency can reach 85%, have clean, efficiently, noise is little, fuel source is extensive, module degree high.Therefore, SOFC is at stationary electric power plant, and portable power source, there is boundless prospect in the fields such as communications and transportation and military affairs.But generally speaking, a monocell can only release 0.6-0.7V electricity under normal operation circumstances, therefore, multiple cells in series use just must can reach desirable power, and itself one by one monocell be in series by connector, therefore metallic interconnect materials is not only monocell and is one of the key components of large-scale pile.The Main Function of connector mainly contains the effect that two: the first is transmission electronic and separation fuel gas and oxic gas between adjacent monocell; Second is distribute air-flow, and removes electrochemical products.Generally speaking, in SOFCs, connector is realize its connection function in monocell must possess following performance: high conductivity and stability of material, and its thermal coefficient of expansion must match with the thermal coefficient of expansion of other assembly materials; Material is fine and close, has good air-tightness, does not react to each other and spread with other assemblies; Excellent anti-oxidant sulfuration resistant anti-carbonation properties, good comprehensive mechanical performance and to be easy to processing cost low etc.
The LaCrO that traditional metallic interconnect materials is mainly adulterated
3ceramic material, it has a lot of significantly advantage, but also there are some problems: sintering character is poor, necessary high temperature ability sinter molding; Thermal conductivity is bad, causes hot loss of energy; Machining property is poor, and manufacturing cost is high; Easy formation Lacking oxygen.
The filming technique of Novel electrolytic material and traditional YSZ in recent years, make the rise of intermediate temperature solid oxide fuel cell (600 DEG C-800 DEG C), high-temperature alloy becomes the material of the most potentiality of SOFC connector, compared with the ceramic material of doping, metal alloy compositions has better electron conduction, can ignore its ohmic loss, and conductive capability is not by the control of partial pressure of oxygen, and higher thermal conductivity and cheaper cost, it has very broad utilization prospect.
Generally speaking, in order to improve the antioxygenic property of metal connector, all can add Cr and Mn in the alloy and allowing alloy Surface Creation Cr when being oxidized
2o
3(Mn, Cr)
2o
3spinel layer forms matrix/Cr
2o
3/ (Mn, Cr)
2o
3double membrane structure is in case the continuation of oxidation layer increases, but can cannot avoid the gaseous state of Cr under hot conditions and solid-state volatilization containing Cr in alloy, containing under the condition of moisture, this situation is especially serious, chemical reaction or electrochemical reaction can be there is and produce deposition in the volatilization state material containing Cr on negative electrode, thus cause the decay of cathode performance, cause the Cr of negative electrode to poison.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides warm flat solid oxide fuel cell metal connector in one, its object is to.
For achieving the above object, according to one aspect of the present invention, provide warm flat solid oxide fuel cell metal connector in one, it is characterized in that, in this metal connector: molybdenum (Mo) 2-2.5 mass fraction, manganese (Mn) 1-1.1 mass fraction, chromium (Cr) 16-17 mass fraction, zirconium (Zr) 0.1-0.12 mass fraction, titanium (Ti) 0.51-0.53 mass fraction, yttrium (Y) 0.018-0.019 mass fraction, lanthanum (La) 0.0049-0.0050 mass fraction, carbon (C) 0.0020-0.0025 mass fraction, phosphorus (P) 0.0094-0.0095 mass fraction, silicon (Si) 0.038-0.0039 mass fraction, sulphur (S) 0.00095-0.00099 mass fraction, iron (Fe) 70-78 mass fraction.
Further, described metal connector TEC between 35 ~ 800 DEG C is about 12.23 × 10
-6/ DEG C-12.25 × 10
-6/ DEG C.
Further, the parabola oxidation rate constant of described metal connector is positioned at 5.1 ~ 7.6 × 10
-14g
2cm
-4s
-1between.
Further, described metal connector forms thickness of oxidation film 2-4 μm after oxidation.
Further, the side namely near described metal connector inside described oxide-film is rich Cr oxide Cr
2o
3, outside is rich Mn oxide layer.
In general, the above technical scheme conceived by the present invention compared with prior art, can obtain following beneficial effect:
(1) provide a kind of metal connector novel alloy material having electrical resistance method negative electrode Cr and poison in Solid Oxide Fuel Cell operational environment, it has the thermal coefficient of expansion and good pyroconductivity, antioxygenic property and machining property that match with other component of battery;
(2) under the polarization condition of simulation pile work, LSM negative electrode and LSM/YSZ electrolyte interface do not find Cr depositional phenomenon substantially, illustrates that this alloy has good antikathode Cr and poisons performance.
Accompanying drawing explanation
Fig. 1 is the alloy material thermal coefficient of expansion curve chart at different temperatures realized according to the present invention;
Fig. 2 is the kinetic curve figure of alloy material isothermal and cyclic oxidation 1000h under 750 DEG C of negative electrode atmosphere according to the present invention's realization;
Fig. 3 be according to the present invention realize alloy material under 750 DEG C of negative electrode atmosphere, area specific resistance (ASR) figure after pre-oxidation different time;
Fig. 4 (a) is the Cross Section Morphology figure of alloy material under 750 DEG C of negative electrode atmosphere after cyclic oxidation 1000h realized according to the present invention;
Fig. 4 (b) is the EDS analysis chart of alloy material after cyclic oxidation 1000h under 750 DEG C of negative electrode atmosphere realized according to the present invention;
Fig. 5 (a) is the impedance spectrum comparison diagram of LSM negative electrode under 200mAcm-2 current density directly contacted with the alloy material realized according to the present invention;
Fig. 5 (b) is the impedance spectrum comparison diagram of LSM negative electrode under 200mAcm-2 current density directly contacted with SUS430;
Fig. 6 (a) is that the LSM negative electrode that directly contacts at 850 DEG C with the alloy material realized according to the present invention is at 200mAcm
-2polarization behavior figure under current density;
Fig. 6 (b) is that the LSM negative electrode that directly contacts at 850 DEG C with SUS430 is at 200mAcm
-2polarization behavior figure under current density;
Fig. 7 (a) to contact and through 200mA.cm at 850 DEG C of metal connectors prepared with the alloy material realized according to the present invention
-2the cathode surface shape appearance figure of current polarizing;
Fig. 7 (b) to contact and through 200mA.cm at 850 DEG C of metal connectors prepared with the alloy material realized according to the present invention
-2the shape appearance figure of the deposition ring of the cathode surface of current polarizing;
Fig. 8 (a) be according to the present invention realize novel alloy material under on negative electrode deposition ring microscopic appearance figure;
Fig. 8 (b) be according to the present invention realize novel alloy material under on electrolyte deposition ring microscopic appearance figure mono-;
Fig. 8 (c) be according to the present invention realize novel alloy material under on electrolyte deposition ring microscopic appearance figure bis-;
Fig. 9 (a) be the schematic surface of the YSZ of novel alloy material after washing negative electrode off that realizes according to the present invention and its correspondence can spectrogram;
Fig. 9 (b) is energy spectrogram corresponding behind the surface according to the YSZ of novel alloy material after washing negative electrode off of the present invention's realization.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each execution mode of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Metallic Interconnect Materials Used conventionally, uses and many relates to following alloy material:
Ni base alloy: there is very high heat-resisting and high temperature strength, and there is the spontaneous oxide-film NiO of oxidation in Ni-Cr base alloy, Cr
2o
3there is good oxidation resistance, but comparatively large (17-20 × 10 of the thermal coefficient of expansion of Ni base alloy
-6/ DEG C), so when start battery and stopping because temperature distributing disproportionation generation thermal stress causes the destruction of dielectric film.
Cr base alloy: this alloy has good high-temperature corrosion resistance, antioxygenic property, thermal coefficient of expansion (9-10 × 10
-6/ DEG C) mate well with YSZ, the oxide layer that surface is formed is Cr
2o
3, conductivity is high.But when working temperature is higher than 700 DEG C, the diffusion rate of Cr obviously increases thus makes oxidation rate increase; In addition on the one hand, during high temperature, there is serious volatilization problems in Cr, and in application process, this alloy connector can cause the rapid decay of cell cathode performance, thus causes the failure of pile.Therefore, this kind of alloy is only limited to and uses at 700 DEG C, causes the limitation that it uses.
Fe base alloy: wide material sources, has good ductility, and be easy to processing, cheap for manufacturing cost, thermal coefficient of expansion mates with YSZ more than Ni base alloy.But there is the problem of non-oxidizability difference, therefore, generally add Cr in the alloy and cause it to form Cr at alloy surface
2o
3layer, solves the problem of oxidizability difference.Therefore, no matter from economy or practical standpoint, Fe base alloy is all the potential Metallic Interconnect Materials Used of most.
Under SOFC working temperature, Cr
2o
3main and O
2there is following reaction:
2Cr
2o
3+ 3O
2(g)=4CrO
3in (g) dry air (1)
2Cr
2o
3+ 3O
2(g)+4H
2o (g)=4CrO
2(OH)
2in (g) wet air (2)
In dry air, CrO
3g () is main volatile oxidn; When there is a certain amount of steam, CrO
2(OH)
2g () is main volatile oxidn, and will cause Cr
2o
3the rate of volatilization of film significantly increases.And the reaction of its negative electrode is generally electrochemical reaction and chemical reaction.Electrochemical reaction model is thought: Cr poisons usually relevant to cathodic polarization and by it owing to reducing at electrochemical cathode containing Cr gas phase, forms Cr by following reaction
2o
3phase:
CrO
3+3VO”＝Cr
2O
3+3Oo
x+6h’(3)
2CrO
2(OH)
2+3Vo”＝Cr
2O
3+2H
2O+3Oo
x+6h’(4)
The overvoltage of negative electrode increases with the increase of polarization current and the prolongation of polarization time.There is no the electrode that electric current flows through, Cr is in electrode interior random distribution, and the electrode having electric current to pass through, the deposition of Cr mainly concentrates on electrode/electrolyte interface district, and preferential deposition is at three-phase reaction interface place (TPB), embodies the feature of electrochemical reducting reaction.
Chemical model is thought: in cathodic polarization process, and LSM electrode surface will produce Mn
2+, it and Cr steam react by formula (5) and form Cr-Mn-O condensation nucleus.
CrO
2(OH)
2+Mn
Mn’＝Cr-Mn-O+H
2O(5)
These condensation nucleus further with Cr
6+reaction generates Cr
2o
3(Mn, Cr)
3o
4spinel, chemical reactions at the same time model indicates that Cr-Mn-O condensation nucleus is mobile on YSZ, is occurring Cr away from the position of TPB
2o
3phase.Cr
2o
3phase range of deposition extends to 500 μm from 40 ~ 50 μm, widely beyond TPB width (≤1 μm).When there is no polarization or anode polarization, the appearance of Cr deposition further demonstrates the correctness of Chemical Reaction Model, according to Chemical Reaction Model, Cr-Mn-O condensation nucleus is the principal element determining Cr deposition, and the existence of polarization advances the migration of deposit to TPB.
Cr Poisoning cathode is main relevant with the volatilization of Cr in alloy and the reaction mechanism of Cr, and the volatilization of structure to Cr therefore changing the composition regulation and control alloy in-situ growth oxide-film of alloy has very large inhibition.The lifting of the antioxygenic property of Cr alloy is must be obligato, but oxide layer must have the normal transmission of higher conductance guarantee electronics, add a certain amount of Al and Si in alloy and effectively can improve non-oxidizability, but under high temperature, alloy surface generates Al
2o
3and SiO
2conductance is lower, therefore, only has formation Cr
2o
3the alloy of oxide layer just possesses the condition becoming SOFC connector.Adding a small amount of Mn more in the alloy makes alloy surface form Cr
2o
3/ (Mn, Cr)
3o
4double layer oxide film effectively can reduce the volatilization of Cr.Add the elements such as La, Ti of trace also can suppress Cr to a certain extent volatilization with the structure changing oxide-film in the alloy.But these can not suppress volatilization and the Poisoning cathode of Cr completely.
Summary of the invention: the object of the invention is to provide a kind of metal connector alloy material having electrical resistance method negative electrode Cr and poison in Solid Oxide Fuel Cell operational environment, and this alloy material is:
Chemical composition is (unit is mass fraction):
Molybdenum (Mo) 2-2.5 mass fraction, manganese (Mn) 1-1.1 mass fraction, chromium (Cr) 16-17 mass fraction, zirconium (Zr) 0.1-0.12 mass fraction, titanium (Ti) 0.51-0.53 mass fraction, yttrium (Y) 0.018-0.019 mass fraction, lanthanum (La) 0.0049-0.0050 mass fraction, carbon (C) 0.0020-0.0025 mass fraction, phosphorus (P) 0.0094-0.0095 mass fraction, silicon (Si) 0.038-0.0039 mass fraction, sulphur (S) 0.00095-0.00099 mass parts, iron (Fe) 70-78 mass fraction.
The effect of above-mentioned element is according to as follows:
Fe, as matrix element, forms stable austenite structure, the more alloying element of solid solution.
The effect of Mo mainly adjusts the thermal coefficient of expansion of alloy, itself and other ceramic compositions of SOFC is matched, and improves high temperature resistant property.
The effect of Mn, Si mainly keeps the processing characteristics that alloy is good, but the content of Si can not more than 0.05%, if too much can form SiO
2oxide layer, causes the electric conductivity of connector sharply to reduce.And the effect of Mn also has at metal connector surface formation (Mn, Cr)
3o
4spinel, can hinder the outside volatilization of Cr.
Heavy alloyed high-temperature oxidation resistance and structure stability are mainly put forward in the effect of Cr, put forward heavy alloyed mechanical performance, and too much Cr can cause the performance of negative electrode to decay rapidly, therefore, consider, the limit content of Cr meets SOFC metal connector most 17% and requires.
Low-alloyed conductivity can fall in Ti, Zr.
Y, the thermal coefficient of expansion that La mainly can adjust alloy makes itself and YSZ match, also heavy alloyed high-temperature oxidation resistance can be carried, the more important thing is, this rare earth element can remove gas and impurity when alloy smelting as purifying agent, improve alloy purity, improve crystal boundary structure, play the Microalloying Effect of strengthening crystal boundary.
Impurity element C, S, P content preferably controls within 0.005%, ensures that alloy has good smelting quality and degree of purity.
Embodiment one
Relate to middle temperature flat solid oxide fuel cell metal connector Fe-Mn-Cr alloy in the present embodiment one, Cr content is about 16.5wt.%, guarantees that alloy surface can form the Cr of protectiveness
2o
3oxide-film; Make the adding of 1wt.%Mn surface energy form Mn-Cr type spinelle or rich Mn type conductive oxide, reduce Cr volatilize Poisoning cathode may and improve the conductivity of oxide-film; A small amount of Zr, Ti and rare-earth elements La, adding of Y can put forward heavy alloyed oxidation drag and the adhesiveness improving alloy oxide film and matrix.And the impurity such as the C in alloy, S, P are all in control range, alloy has very high degree of purity.
The composition of the alloy material realized according to the present embodiment one is as shown in the table:
Table 1. alloy of the present invention and prior art alloy SUS430 constituent chemical composition contrast table (mass fraction unit be gram)
| Cr | Mn | Ti | La | Y | Zr | Mo | C | S | P | Si | Fe |
| 16.56 | 1.05 | 0.52 | 0.005 | 0.018 | 0.11 | 2.09 | 0.002 | 0.00095 | 0.0094 | 0.038 | 70 |
| 16.68 | 0.26 | 78 |
As shown above, the element that upper style representatives alloy material of the present invention uses and part by weight thereof, and in next style representatives prior art, prepare the element and part by weight thereof that alloy material uses, wherein mainly Cr in prior art can be found out, the simple three kinds of elements of Mn and Fe, and in the present invention, according to the ratio increasing Mn within the scope of limited mass parts, make metal connector surface energy form Mn-Cr type spinelle or rich Mn type conductive oxide, reduce Cr volatilize Poisoning cathode may and improve the conductivity of oxide-film.
The present embodiment, compared with prior art in Solid Oxide Fuel Cell operational environment, has the good thermal expansion matching performance with other adjacent material, and has good high-temperature electric conduction performance, antioxygenic property and machining property.
Between 35 ~ 800 DEG C, TEC is about 12.23 × 10
-6/ DEG C, be typical ferritic stainless steel TEC, (be generally 10 ~ 13 × 10 with other assembly of SOFC
-6/ DEG C) there is good thermal expansion compatibility, meet the requirement of SOFC Metallic Interconnect Materials Used to thermal expansion matching.Have excellent high-temperature oxydation drag and electric conductivity according to the alloy of the present embodiment proportioning, the parabola oxidation rate constant under 750 DEG C of negative electrode atmosphere is positioned at 5.1 ~ 7.6 × 10
-14g
2cm
-4s
-1between.ASR value after pre-oxidation 1000h is about 10m Ω cm
2, Mn
2o
3with Ti doping Cr
2o
3be formed to be beneficial to and improve oxide-film electric conductivity.Thermal cycle is conducive to carrying heavy alloyed oxidation drag and electric conductivity, and significantly improves the adhesiveness of oxide-film and matrix.The more important thing is under the polarization condition of simulation pile work, LSM negative electrode and LSM/YSZ electrolyte interface there is no and find Cr depositional phenomenon, illustrate that this alloy has good antikathode Cr and poisons performance.
The processing technology that the alloy that the present embodiment relates to adopts: vacuum induction melting alloy, 1150 DEG C of forging square billets, are hot-rolled down to 3mm slab, are cold-rolled to 1mm sheet material, 1050 DEG C of vacuum annealings, Performance Detection.
The normal temperature mechanical property of the alloy that table 2. is prepared for the present embodiment and alloy of the prior art
Fig. 1 is the present embodiment one composition alloy thermal coefficient of expansion curve at different temperatures, illustrate the thermal expansion of alloy material involved in the present invention and adjacent components do match good, some that can not occur because thermal stress causes are destroyed.
Fig. 2 is the kinetic curve of alloy isothermal and cyclic oxidation 1000h under 750 DEG C of negative electrode atmosphere according to the present embodiment one preparation.The parabola Oxidation Law that diffusion process controls followed by this alloy under SOFC working temperature.As can be seen from Figure 2, the oxidation rate under cyclic oxidation condition slightly lower than the oxidation rate under isothermal oxidation condition, will show that this alloy has excellent cyclic oxidation drag.Think, the transformation of oxidation rate and the continuous fine and close Mn of alloy surface under cyclic oxidation condition
2o
3the formation of oxide layer is relevant.Alloy surface forms continuous fine and close Mn
2o
3oxide-film is conducive to the inside diffusion process to outdiffusion and anion (as O ion) suppressing cation (as Cr ion), thus reduces the growth rate of oxide-film, improves alloy oxidation drag.
Fig. 3 is that the alloy of the present embodiment one preparation is under 750 DEG C of negative electrode atmosphere, area specific resistance (ASR) figure after pre-oxidation different time, as can be seen from the figure the ASR value of alloy increases gradually, the relation and log (ASR/T) and 1/T are obviously in line, show that the conductive characteristic of oxidation sample meets the semiconductor conductive characteristic shown in Arrhenius relation, and the electric conductivity of this Fe-Cr alloy is better than traditional Fe-Cr Metallic Interconnect Materials Used, also substantially suitable with the electric conductivity of some Ni base alloy, this Fe-Cr-Mn alloy still has good electric conductivity, meet SOFC metal connector conduction needs.The electric conductivity of its excellence can ascribe the raising of alloy oxidation drag to, and forms the Mn of high conductivity
2o
3with the Cr of Ti doping
2o
3.
Fig. 4 is Cross Section Morphology figure (a) under present component alloy 750 DEG C of negative electrode atmosphere after cyclic oxidation 1000h and EDS analysis chart (b), as shown in figure (a), and the thickness of oxidation film of even compact about 2 μm.Be rich Cr oxide Cr inside oxide-film
2o
3, outside is rich Mn oxide layer (Mn-Cr spinelle and Mn
2o
3), be distributed with TiO in the matrix of premature/interfacial oxide film
2inner oxide particle.It is smooth that the oxide-film formed is straight, and the adhesiveness of oxide layer and matrix is also improved, and whole oxide-film surface coverage has the Mn of one deck even compact
2o
3layer, be conducive to suppressing Cr volatilization Poisoning cathode, therefore this alloy has the ability that better antikathode Cr poisons.
Fig. 5 is that the LSM negative electrode that directly contacts with novel alloy and SUS430 at 850 DEG C is at 200mAcm
-2impedance spectrum comparison diagram (a) under current density, (b), along with the growth of polarization time, the cathode ohmic impedance contacted with novel alloy there is no change, and contrastingly increase along with the increase of time with the cathode ohmic impedance of traditional SUS430 alloy contact.LSM negative electrode under novel alloy is proved not to be subject to strong impact that Cr poisons and to cause interface to deposit serious.
Fig. 6 is that the LSM negative electrode that directly contacts with novel alloy and SUS430 at 850 DEG C is at 200mAcm
-2polarization behavior comparison diagram (a) under current density, (b), as can be seen from figure (a), along with the growth of time, the electromotive force of the LSM negative electrode contacted with novel alloy there is no change, until the later stage just slowly increases, and overpotential presents the trend of reduction, this is that the cathode overpotential of Late Cambrian and Fe-Cr-Mn alloy contact reduces.Ohmic resistance there is no change, and polarization resistance reduces along with the applying of electric current, meets the anticathode polarization impact of electric current.Comparison diagram (b), the cathode potential contacted with SUS430 significantly increases along with the increase polarized, overpotential held stationary and have the trend of increase, meets in the past to the variation characteristic of the negative electrode with alloy contact.
Fig. 7 to contact with metal connector and through 200mAcm at 850 DEG C
-2the cathode surface (a) of current polarizing, cathode surface is very clean, without any deposit, the existence (b) of deposition ring has been found around negative electrode, and narrow than with other alloy contact of deposition ring, prove that this alloy poisoning on negative electrode will weaken much than other commercial alloy.
Fig. 8 is deposition ring microscopic appearance figure under novel alloy, and as can be seen from figure (a), the deposition on negative electrode is very loose, also assembles seldom, and on electrolyte, near cathode side, as shown in figure (b), deposit is less; Until do not deposit completely away from cathode side, shown in figure (c).
Fig. 9 (a) be the schematic diagram on YSZ surface after washing negative electrode off and correspondence can spectrogram.As can be seen from SEM schematic diagram, the YSZ surface below negative electrode is very clean, without any deposition, by EDS spectrogram as Fig. 9 (b) just can infer, this alloy inhibits Cr in the deposition of interface.Comprehensive, the novel alloy that the present invention relates to affects seldom on poisoning of LSM negative electrode, can as very potential intermediate temperature SOFC Metallic Interconnect Materials Used.
The metal connector alloy prepared according to the present invention, by regulating and controlling the composition of alloy, coordinating suitable preparation technology, having prepared the intermediate temperature SOFC metal connector Fe base alloy possessing premium properties.This alloy has the thermal coefficient of expansion matched with electrolyte, good mechanical performance, high-temperature oxidation resistance, high-temperature electric conduction performance, the most important thing is that having antikathode Cr poisons performance.
Other embodiment realized according to the present invention is as follows:
And the characteristic test result of the alloy realized according to above-described embodiment is as follows:
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. warm flat solid oxide fuel cell metal connector in a kind, it is characterized in that, in this metal connector: molybdenum (Mo) 2-2.5 mass fraction, manganese (Mn) 1-1.1 mass fraction, chromium (Cr) 16-17 mass fraction, zirconium (Zr) 0.1-0.12 mass fraction, titanium (Ti) 0.51-0.53 mass fraction, yttrium (Y) 0.018-0.019 mass fraction, lanthanum (La) 0.0049-0.0050 mass fraction, carbon (C) 0.0020-0.0025 mass fraction, phosphorus (P) 0.0094-0.0095 mass fraction, silicon (Si) 0.038-0.0039 mass fraction, sulphur (S) 0.00095-0.00099 mass fraction, iron (Fe) 70-78 mass fraction.
2. warm flat solid oxide fuel cell metal connector in as claimed in claim 1, it is characterized in that, described metal connector TEC between 35 ~ 800 DEG C is about 12.23 × 10
-6/ DEG C-12.25 × 10
-6/ DEG C.
3. warm flat solid oxide fuel cell metal connector in as claimed in claim 1 or 2, it is characterized in that, the parabola oxidation rate constant of described metal connector is positioned at 5.1 ~ 7.6 × 10
-14g
2cm
-4s
-1between.
4. warm flat solid oxide fuel cell metal connector in as claimed in claim 3, it is characterized in that, described metal connector forms thickness of oxidation film 2-4 μm after oxidation.
5. warm flat solid oxide fuel cell metal connector in as claimed in claim 4, it is characterized in that, the side namely near described metal connector inside described oxide-film is rich Cr oxide Cr
2o
3, outside is rich Mn oxide layer.
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| CN201510715702.2A CN105304917A (en) | 2015-10-29 | 2015-10-29 | Metal connector for medium-temperature flat plate type solid oxide fuel cell |
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| CN201510715702.2A CN105304917A (en) | 2015-10-29 | 2015-10-29 | Metal connector for medium-temperature flat plate type solid oxide fuel cell |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355591A (en) * | 2018-11-19 | 2019-02-19 | 深圳市致远动力科技有限公司 | A kind of high-temperature alloy |
| CN109881127A (en) * | 2017-12-06 | 2019-06-14 | 宜兴市乐华冶金辅助材料有限公司 | A kind of contact arm material of pipeline chain scraper conveyor |
| CN110447136A (en) * | 2017-03-31 | 2019-11-12 | 大阪瓦斯株式会社 | Electrochemical element, electrochemical module, electrochemical appliance, energy system, solid oxide fuel cell and electrochemical element manufacturing method |
| CN110574197A (en) * | 2017-03-27 | 2019-12-13 | 日铁不锈钢株式会社 | Stainless steel material, structural member, single cell, and fuel cell stack |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333613A (en) * | 2008-08-06 | 2008-12-31 | 钢铁研究总院 | Nickel-based expansion alloy for metal connector of medium temperature plate type solid-oxide fuel battery |
| CN101503780A (en) * | 2009-03-27 | 2009-08-12 | 钢铁研究总院 | Iron based expanding metal for middle temperature plate type solid-oxide fuel battery metal connector |
| CN101519740A (en) * | 2009-04-03 | 2009-09-02 | 钢铁研究总院 | Ni-Mo-Cr alloy for metal connecting body of cathode Cr poison resisting intermediate-temperate solid oxide fuel battery |
| CN101597719A (en) * | 2009-07-02 | 2009-12-09 | 东北大学 | Flat intermediate temperature solid oxide fuel cell low Cr connector alloy |
| US20100310405A1 (en) * | 2009-06-05 | 2010-12-09 | Toyota Jidosha Kabushiki Kaisha | Ferrous sintered alloy, process for producing ferrous sintered alloy and connecting rod |
| CN102482745A (en) * | 2009-09-16 | 2012-05-30 | 日立金属株式会社 | Steel For Solid Oxide Fuel Cell Having Excellent Oxidation Resistance |
| CN103492601A (en) * | 2011-04-22 | 2014-01-01 | 日立金属株式会社 | Steel for solid oxide fuel cells having excellent oxidation resistance, and member for solid oxide fuel cells using same |
-
2015
- 2015-10-29 CN CN201510715702.2A patent/CN105304917A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333613A (en) * | 2008-08-06 | 2008-12-31 | 钢铁研究总院 | Nickel-based expansion alloy for metal connector of medium temperature plate type solid-oxide fuel battery |
| CN101503780A (en) * | 2009-03-27 | 2009-08-12 | 钢铁研究总院 | Iron based expanding metal for middle temperature plate type solid-oxide fuel battery metal connector |
| CN101519740A (en) * | 2009-04-03 | 2009-09-02 | 钢铁研究总院 | Ni-Mo-Cr alloy for metal connecting body of cathode Cr poison resisting intermediate-temperate solid oxide fuel battery |
| US20100310405A1 (en) * | 2009-06-05 | 2010-12-09 | Toyota Jidosha Kabushiki Kaisha | Ferrous sintered alloy, process for producing ferrous sintered alloy and connecting rod |
| CN101597719A (en) * | 2009-07-02 | 2009-12-09 | 东北大学 | Flat intermediate temperature solid oxide fuel cell low Cr connector alloy |
| CN102482745A (en) * | 2009-09-16 | 2012-05-30 | 日立金属株式会社 | Steel For Solid Oxide Fuel Cell Having Excellent Oxidation Resistance |
| CN103492601A (en) * | 2011-04-22 | 2014-01-01 | 日立金属株式会社 | Steel for solid oxide fuel cells having excellent oxidation resistance, and member for solid oxide fuel cells using same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110574197A (en) * | 2017-03-27 | 2019-12-13 | 日铁不锈钢株式会社 | Stainless steel material, structural member, single cell, and fuel cell stack |
| CN110574197B (en) * | 2017-03-27 | 2023-03-31 | 日铁不锈钢株式会社 | Stainless steel material, structural member, single cell, and fuel cell stack |
| CN110447136A (en) * | 2017-03-31 | 2019-11-12 | 大阪瓦斯株式会社 | Electrochemical element, electrochemical module, electrochemical appliance, energy system, solid oxide fuel cell and electrochemical element manufacturing method |
| CN109881127A (en) * | 2017-12-06 | 2019-06-14 | 宜兴市乐华冶金辅助材料有限公司 | A kind of contact arm material of pipeline chain scraper conveyor |
| CN109355591A (en) * | 2018-11-19 | 2019-02-19 | 深圳市致远动力科技有限公司 | A kind of high-temperature alloy |
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