CN116813202B - Microcrystalline glass material and preparation method and application thereof - Google Patents
Microcrystalline glass material and preparation method and application thereof Download PDFInfo
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- CN116813202B CN116813202B CN202310721683.9A CN202310721683A CN116813202B CN 116813202 B CN116813202 B CN 116813202B CN 202310721683 A CN202310721683 A CN 202310721683A CN 116813202 B CN116813202 B CN 116813202B
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- 239000011521 glass Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 239000006112 glass ceramic composition Substances 0.000 claims description 32
- 239000000956 alloy Substances 0.000 claims description 27
- 229910045601 alloy Inorganic materials 0.000 claims description 25
- 239000002241 glass-ceramic Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052705 radium Inorganic materials 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 32
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000008646 thermal stress Effects 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 238000002474 experimental method Methods 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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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
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
Abstract
The application discloses a microcrystalline glass material, a preparation method and application thereof, and belongs to the field of fuel cells. The application controls Ra in the main body part and the connecting part in the microcrystalline glass material 1 Element, ra 2 Element mass ratio of element, al element and M element, and Ra in regulating main body part and connecting part 1 Element and Ra 2 Element, ra 1 The mass ratio of the elements of the element and the B element, the Al element and the M element, and the Si element and the Re element ensures that the main body part has certain strength and the connecting part has better thermal stress; the connecting part made of the microcrystalline glass material has high-temperature sealing insulation characteristics, good high-temperature mechanical characteristics, no poor performance and other conditions even if the connecting part runs under the working condition of long-term high temperature, and no point leakage problem occurs when the connecting part runs for a long time; the connecting component made of the microcrystalline glass material provides technical support for commercial application of the fuel cell system.
Description
Technical Field
The application belongs to the field of fuel cells, and particularly relates to a microcrystalline glass material and a preparation method and application thereof.
Background
A fuel cell is a chemical device that directly converts chemical energy possessed by fuel into electric energy. The device converts the Gibbs free energy part in the fuel chemical energy into electric energy through electrochemical reaction, is not limited by the Carnot cycle effect, and therefore has higher efficiency.
The fuel cell comprises a phosphoric acid fuel cell, an alkaline fuel cell, a proton exchange membrane fuel cell, a molten carbonate fuel cell, a solid oxide fuel cell and a direct methanol fuel cell, the working principles of the fuel cells are the same, the fuel cell power generation system generally comprises two or more electric stacks, and the electric stacks are connected and used for conveying gas through pipe fittings; therefore, the connecting pipe fitting between the stacks must have good sealing performance and insulating property to prevent the occurrence of short circuit between the positive electrode and the negative electrode of the stacks during operation, and at the same time, in order to satisfy the characteristic that part of fuel cells operate at high temperature, the connecting pipe fitting also has the characteristic that no microcracking or air leakage occurs in the joint area under the use condition of high temperature (600-800 ℃) for a long time.
Aiming at the performance requirements of connecting pipe fittings among all electric stacks of the fuel cell, finding a sealing insulating connecting part with good mechanical property at high temperature is the key point of the current research in the field of fuel cells.
Disclosure of Invention
The purpose of the application is to overcome the defects of the prior art and provide a microcrystalline glass material, a preparation method and application thereof, wherein a connecting part prepared from the microcrystalline glass material is sealed and insulated, and the connecting part can have good high-temperature mechanical property when being applied to a fuel cell, and can not cause problems of poor performance and point leakage when running under the working condition of long-term high temperature.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the microcrystalline glass material comprises a main body part and a connecting part; the connecting part and the main body part comprise the following components: alkaline earth metal oxide Ra 1 O, alkaline earth metal oxide Ra 2 O、B 2 O 3 、Al 2 O 3 、MO 2 、SiO 2 And rare earth metal oxide ReO; the mass ratio of each element in the connecting part and the main body part satisfies the following relation: x is X Ra1 :Y Ra1 ＝1-1.8:1，X Ra2 :Y Ra2 ＝0.55-1:1，X Al :Y Al ＝0.3-5:1，X M :Y M =0-10:1; wherein Ra is 1 And Ra (Ra) 2 Selected from different alkaline earth metals, M is selected from at least one of Ti and Zr, X Ra1 、X Ra2 、X Al 、X M Respectively represents Ra per unit area in the connecting part 1 、Ra 2 Mass of Al, M element, Y Ra1 、Y Ra2 、Y Al 、Y M Respectively represents Ra per unit area in the main body part 1 、Ra 2 Mass of Al and M elements.
Glass-ceramic materials are often used as sealing materials for metal-to-metal, metal-to-ceramic, ceramic-to-ceramic, and the like; glass-ceramic materials offer higher service temperatures, superior mechanical properties and corrosion resistance, and have a very wide range of Coefficients of Thermal Expansion (CTE) compared to glass.
The inventors found that due to Ra in the present invention 1 Element and Ra 2 The elements are main elements of the main body part and the connecting part, and Ra in the main body part and the connecting part is controlled 1 Element and Ra 2 The mass ratio of the elements is in the range, the consistency of the system of the connecting part and the main body part can be ensured, the matching performance of the microcrystalline glass material in the subsequent sintering and using processes can be ensured to be better, and the problems of performance deterioration and the like in the using process caused by different thermal stress of each part can be avoided.
The inventors have also found that in the present invention, al element can play a role in stabilizing the network structure of the glass-ceramic material, and that an excessive Al element content in the connection portion may cause a phase-separation crystallization phenomenon in the melting process of the final glass-ceramic material, which is unfavorable for the stabilization of the glass-ceramic material, so that it is necessary to control the mass ratio of Al element per unit area in the connection portion and the main body portion within the above-mentioned range.
The inventors have also found that in the present invention, the main body portion is a portion that provides strength of the glass-ceramic material, the higher content of the M element is advantageous for controlling the precipitated phase, the phase does not need to be strictly controlled as the connecting portion is used as the window, and the required M content is small because of the requirement of use, so that the mass ratio of the M element per unit area in the connecting portion and the main body portion needs to be controlled within the above range.
To sum up, ra 1 Element, ra 2 The element, B element, al element, M element, si element and Re element are all main elements for separating out crystal phases in the microcrystalline glass material, and the microcrystalline glass material can keep better stability by regulating and controlling the element mass ratio of the main body part and the elements in the unit area of the connecting part in the microcrystalline glass material, so that the connecting part manufactured by the invention is sealed and insulated, has better high-temperature mechanical property, and can not cause the problems of poor performance and point leakage when operated under the working condition of long-term high temperature.
Preferred embodiments as the glass-ceramic Material of the present applicationThe Ra is 1 Is at least one of Mg, ca and Sr.
As a preferred embodiment of the glass ceramic material of the present application, the Ra 2 Is at least one of Ca, sr and Ba.
As a preferred embodiment of the glass ceramic material of the present application, re in the rare earth metal oxide ReO is at least one of La and Ce.
As a preferred embodiment of the glass ceramic material of the present application, the connecting portion comprises the following components in percentage by weight: ra (Ra) 1 O 30％-35％、Ra 2 O 20％-30％、B 2 O 3 10％-30％、Al 2 O 3 0-0.5％、MO 2 0-1％、SiO 2 10% -28% of ReO and 0.5% -5% of ReO, wherein the main body part comprises the following components in percentage by weight: ra (Ra) 1 O 20％-30％、Ra 2 O 30％-35％、B 2 O 3 10％-30％、Al 2 O 3 0-5％、MO 2 0-5％、SiO 2 10％-28％、ReO 0.5％-5％；
As a preferred embodiment of the glass ceramic material of the present application, ra in the connecting portion 1 Element and Ra 2 The mass ratio of the elements is Ra 1 :Ra 2 =0.8-1.5:1; the inventors found through a large number of experiments that by controlling the Ra1 element and Ra 2 The mass ratio of the elements is within the above range, and it is ensured that most of the phase precipitated in the glass-ceramic material contains Ra 1 The phase, make the connecting portion keep good stability to strengthen the high temperature mechanical properties of the final connecting part that prepares.
As a preferred embodiment of the glass ceramic material of the present application, ra in the connecting portion 1 The mass ratio of the element and the B element is Ra 1 B=1.8-7:1; the inventors found through a number of experiments that by controlling Ra 1 The mass ratio of the element to the element B in the above range ensures that most of the phase precipitated in the glass-ceramic material contains Ra 1 The phase, make the connecting portion keep good stability to strengthen the high temperature mechanical properties of the final connecting part that prepares.
As a preferred embodiment of the glass ceramic material, in the connecting part, the mass ratio of the Al element to the M element is Al:M=0-4:1; the inventor finds through a large number of experiments that the content of the Al element can ensure the stability of the microcrystalline glass system in the range, the mass ratio of the Al element to the M element in the range can ensure that the microcrystalline glass material cannot be crystallized prematurely, and the process stability of a final product can be ensured.
As a preferred embodiment of the glass ceramic material, in the connecting part, the mass ratio of Si element to Re element is Si:Re=2-65:1; the inventor finds through a large number of experiments that the matching property of each phase in the microcrystalline glass material can be ensured only when the element mass ratio of the Si element to the Re element is within the range, and if the element mass ratio of the Si element to the Re element is not within the range, more Re-containing crystal phase is precipitated during crystallization, and the matching property among final phases is affected.
As a preferred embodiment of the glass ceramic material of the present application, ra in the main body portion 1 Element and Ra 2 The mass ratio of the elements is Ra 1 :Ra 2 =0.4-1:1; the inventors found through a number of experiments that the Ra1 element and Ra in the main body portion 2 The element mass ratio of the elements is within the above range, so that the glass ceramic material containing Ra required by the invention can be formed 2 And contains Ra 1 A phase.
As a preferred embodiment of the glass ceramic material of the present application, ra in the main body portion 1 The mass ratio of the element and the B element is Ra 1 B=1-6:1; the inventors found through a number of experiments that by controlling Ra 1 The mass ratio of the element to the element B in the above range can avoid excessive B acid salt precipitated in the glass ceramic material, and excessive B acid salt is easy to cause the stability of the final glass ceramic material to be poor.
As a preferred embodiment of the glass ceramic material, in the main body part, the mass ratio of the Al element to the M element is Al:M=0-50:1; the inventors found through a large number of experiments that in the main body part of the invention, the mass of the elements of Al element and M element is easier than that of the above range to ensure the phase control of precipitation.
As a preferred embodiment of the glass ceramic material of the present application, the mass ratio of Si element to Re element in the main body is Si: re=2 to 65:1; the inventor finds through a large number of experiments that the matching property of each phase in the microcrystalline glass material can be ensured only when the element mass ratio of the Si element to the Re element is within the range, and if the element mass ratio of the Si element to the Re element is not within the range, more Re-containing crystal phase is precipitated during crystallization, and the matching property among final phases is affected.
As a preferred embodiment of the glass ceramic material of the present application, the connection portion is composed of a connection portion a and a connection portion B, and the connection portion a and the connection portion B are respectively joined to both ends of the main body portion.
In a second aspect, the present application provides a connecting member comprising a glass-ceramic portion made of a glass-ceramic material according to the first aspect.
As a preferred embodiment of the connecting member of the present application, the connecting member further includes an alloy portion.
As a preferred embodiment of the connecting member of the present application, the end portion of the alloy portion in the connecting member is in end-to-end sealing engagement with the connecting portion in the glass ceramic portion.
As a more preferred embodiment of the connecting member of the present application, the alloy portion is made of an alloy material.
In a more preferred embodiment of the connecting member of the present application, the glass ceramic portion and the alloy portion have tubular shapes.
As a more preferable embodiment of the connecting member of the present application, both ends of the glass ceramic portion have grooves or bosses.
As a most preferred embodiment of the connecting member of the present application, the alloy portion is a burring tubular alloy portion or a bellows-like alloy portion burring inwardly or outwardly.
As a preferred embodiment of the connecting member of the present application, the burring length of the burring tubular alloy portion is 0 to 50mm;
preferably, the flanging length of the flanging tubular alloy part is 2-10mm;
more preferably, the burring length of the burring tubular alloy portion is 4-5mm.
As a preferred embodiment of the connecting member of the present application, the burring thickness of the burring tubular alloy portion is 0.1 to 5mm;
preferably, the flanging thickness of the flanging tubular alloy part is 0.1-2mm;
more preferably, the burring thickness of the burring tubular alloy portion is 0.2 to 0.4mm.
The application also provides a preparation method of the connecting component, which comprises the following steps: and (3) contacting the alloy part with the glass-ceramic part and heating until crystallization occurs in the glass-ceramic part, so that the connecting part in the glass-ceramic part is connected with the alloy part, and the connecting part is obtained.
In a third aspect, the present application provides a fuel cell system comprising a gas delivery pipe made of the connecting member according to the second aspect.
As a preferred embodiment of the fuel cell system of the present application, the fuel cell system further comprises a manifold and a fuel cell stack.
As a more preferable embodiment of the fuel cell system of the present application, the connection modes of the gas delivery pipe, the manifold and the fuel cell stack are as follows: the gas delivery pipe is connected with one end of the manifold, and the fuel cell stack is connected with the other end of the manifold.
Compared with the prior art, the beneficial effect of this application lies in:
the application controls Ra in the main body part and the connecting part in the microcrystalline glass material 1 Element, ra 2 Elemental mass ratio of element, al element, and M element, ra in main body portion and connecting portion 1 Element and Ra 2 Element, ra 1 The mass ratio of the elements of the element and the B element, the Al element and the M element, and the Si element and the Re element ensures that the main body part has certain strength and the connecting part has better thermal stress; the connecting part made of the microcrystalline glass material has high-temperature sealing and insulating properties, good high-temperature mechanical properties, and no performance failure even if the connecting part runs under the working condition of long-term high temperatureGood conditions and the like, and no point leakage problem exists in long-time operation; the connecting component made of the microcrystalline glass material provides technical support for commercial application of the fuel cell system.
Drawings
FIG. 1 is a schematic diagram of a stack module of a fuel cell system according to the present disclosure;
the glass ceramic part (1), the alloy part (2) and the fuel cell stack (3).
Detailed Description
For a better description of the objects, technical solutions and advantages of the present application, the present application will be further described with reference to specific examples.
Reagents, methods and apparatus employed in this application, unless otherwise indicated, are those conventionally employed in the art.
In the present invention, the formulation of the connecting portions a and B is the same, and the following examples are denoted by "connecting portions".
Examples 1 to 25
The formulation of the connection part in the glass-ceramic material of examples 1 to 25 is shown in Table 1, the formulation of the main body part in the glass-ceramic material is shown in Table 2, the mass ratio X of the connection part to the mass ratio X of the elements in the main body part are shown in Table 3, and the mass ratio X of the elements in the connection part and the mass ratio X of the elements in the main body part are calculated from tables 1 and 2 Ra1 :Y Ra1 、X Ra2 :Y Ra2 、X Al :Y Al And X M :Y M As shown in table 4; wherein Ra in examples 1-14 1 Is Mg, ra 2 Ca, M is Zr, re is La; ra in examples 15 to 19 1 Is Mg, ra 2 Ca, M is Ti, re is La; ra in example 20 1 Is Sr, ra 2 Ba, M is Ti, re is Ce; ra in example 21 1 Is Mg, ra 2 Sr, M is Ti, re is Ce; ra in example 22 1 Is Mg and Ca, ra 2 Sr, M is Ti, re is Ce; ra in example 23 1 Is Mg, ca and Sr, ra 2 Ba, M is Ti, re is Ce; ra in example 24 1 Mg and Sr, ra 2 Ba, M is Ti, re is Ce; ra in example 25 1 Is Ca, ra 2 Sr, M is Ti, re is Ce.
In the embodiments 1-25, the connecting part comprises an alloy part and a microcrystalline glass part, the alloy part is prepared by heating and sintering an alloy material iron-based alloy SUS 444 in a die, and the alloy part is a flanging tube with the inner diameter of 24mm, the outer diameter of 32mm, the flanging length of 4mm and the flanging thickness of 0.4 mm; the glass ceramics part is prepared by placing the connecting part and the main body part in the tables 1 and 2 in a mould for heating and sintering, the glass ceramics part comprises a connecting part and a main body part, the connecting part comprises a connecting part A and a connecting part B, and the end part of an alloy part in the connecting part is in head-to-tail sealing joint with the connecting part in the glass ceramics part; the glass ceramic part is a glass tube with the inner diameter of 16mm, the outer diameter of 32mm, one end provided with a boss, the inner diameter of the boss is 16mm, the outer diameter of the boss is 22mm, and the height of the boss is 2 mm.
The preparation method of the connecting part comprises the following steps: and (3) contacting the alloy part with the glass-ceramic part, and heating to the crystallization temperature of the glass-ceramic part in an air atmosphere, so that the connection part of the glass-ceramic part and the alloy part are sealed and connected together end to end, and the connection part is obtained.
TABLE 1
TABLE 2
| wt％ | Al 2 O 3 | Ra 2 O | Ra 1 O | MO 2 | SiO 2 | ReO | B 2 O 3 |
| Example 1 | 1 | 35 | 25 | 2 | 25 | 2 | 10 |
| Example 2 | 1 | 32 | 25 | 2 | 25 | 4 | 11 |
| Example 3 | 1 | 30 | 25 | 2 | 20 | 2 | 20 |
| Example 4 | 1 | 30 | 25 | 2 | 16 | 1 | 25 |
| Example 5 | 0.5 | 32 | 25 | 2 | 14 | 1.5 | 25 |
| Example 6 | 0.1 | 32 | 25 | 2 | 10 | 0.9 | 30 |
| Example 7 | 1 | 32 | 20 | 2 | 10 | 5 | 30 |
| Example 8 | 1 | 32 | 25 | 2 | 15 | 5 | 20 |
| Example 9 | 1 | 32 | 30 | 2 | 24.5 | 0.5 | 10 |
| Example 10 | 1 | 32 | 20 | 2 | 28 | 0.5 | 16.5 |
| Example 11 | 1 | 32 | 25 | 5 | 15 | 2 | 20 |
| Example 12 | 1 | 32 | 25 | 0.2 | 16.8 | 5 | 20 |
| Example 13 | 1 | 32 | 25 | 0.5 | 16.5 | 5 | 20 |
| Example 14 | 1 | 32 | 25 | 0.1 | 16.9 | 5 | 20 |
| Example 15 | 1 | 35 | 25 | 2 | 25 | 2 | 10 |
| Example 16 | 1 | 32 | 25 | 2 | 25 | 4 | 11 |
| Example 17 | 1 | 30 | 25 | 2 | 20 | 2 | 20 |
| Example 18 | 1 | 30 | 25 | 2 | 16 | 1 | 25 |
| Example 19 | 1 | 35 | 25 | 2 | 25 | 2 | 10 |
| Example 20 | 1 | 35 | 25 | 2 | 25 | 2 | 10 |
| Example 21 | 1 | 20 | 30 | 2 | 25 | 2 | 20 |
| Example 22 | 1 | 20 | 30 | 2 | 25 | 2 | 20 |
| Example 23 | 1 | 20 | 30 | 2 | 25 | 2 | 20 |
| Example 24 | 1 | 20 | 30 | 2 | 25 | 2 | 20 |
| Example 25 | 1 | 20 | 30 | 2 | 25 | 2 | 20 |
TABLE 3 Table 3
TABLE 4 Table 4
Comparative examples 1 to 10
The formulation of the connection part in the glass-ceramic material of comparative examples 1 to 10 is shown in Table 5, the formulation of the main body part in the glass-ceramic material is shown in Table 6, the mass ratio X of the connection part to the mass ratio X of the elements in the main body part are shown in Table 7, and the mass ratio X of the elements in the connection part and the mass ratio X of the elements in the main body part are calculated from tables 5 and 6 Ra1 :Y Ra1 、X Ra2 :Y Ra2 、X Al :Y Al And X M :Y M As shown in table 8; wherein Ra in comparative examples 1 to 10 1 Is Mg, ra 2 Ca, M, zr and Re La.
The preparation methods of the connection members described in comparative examples 1 to 10 were the same as those of examples 1 to 25.
TABLE 5
| wt％ | Al 2 O 3 | CaO | MgO | ZrO 2 | SiO 2 | La 2 O 3 | B 2 O 3 |
| Comparative example 1 | 0.2 | 23 | 35 | 0.1 | 25 | 1.7 | 15 |
| Comparative example 2 | 5 | 23 | 35 | 0.1 | 28 | 0.9 | 8 |
| Comparative example 3 | 0.3 | 10 | 35 | 0.1 | 30 | 16.6 | 8 |
| Comparative example 4 | 0.3 | 35 | 45 | 0.1 | 5 | 4.6 | 10 |
| Comparative example 5 | 0.3 | 23 | 20 | 0.1 | 35 | 11.6 | 10 |
| Comparative example 6 | 0.3 | 23 | 10 | 0.1 | 26.6 | 10 | 30 |
| Comparative example 7 | 0.3 | 23 | 35 | 15 | 9 | 2.7 | 15 |
| Comparative example 8 | 0.3 | 23 | 35 | 4 | 25 | 2.7 | 10 |
| Comparative example 9 | 0.3 | 23 | 20 | 15 | 15 | 0.2 | 26.5 |
| Comparative example 10 | 0.3 | 23 | 10 | 4 | 25 | 2.7 | 35 |
TABLE 6
TABLE 7
TABLE 8
| Mass ratio of elements per unit area | X Mg ：Y Mg | X Ca ：Y Ca | X Al ：Y Al | X Zr ：Y Zr |
| Comparative example 1 | 1.40 | 0.72 | 0.03 | 0.05 |
| Comparative example 2 | 1.40 | 0.72 | 10.00 | 0.05 |
| Comparative example 3 | 1.40 | 0.33 | 0.30 | 0.05 |
| Comparative example 4 | 1.80 | 1.75 | 0.30 | 0.05 |
| Comparative example 5 | 2.00 | 0.72 | 0.30 | 0.05 |
| Comparative example 6 | 0.33 | 0.72 | 0.30 | 0.05 |
| Comparative example 7 | 1.40 | 0.72 | 0.30 | 15.00 |
| Comparative example 8 | 1.40 | 0.72 | 0.30 | 20.00 |
| Comparative example 9 | 2.00 | 0.72 | 0.30 | 15.00 |
| Comparative example 10 | 0.33 | 0.72 | 0.30 | 20.00 |
Effect example
The gas delivery pipe prepared by the connection members prepared in the above examples and comparative examples was connected to one end of a fuel cell manifold, and the other end of the manifold was connected to a fuel cell, to prepare a fuel cell system, and the following performance test was performed, and the test results are shown in table 9:
1. thermal shock performance test: raising the temperature at 5 ℃/min, preserving the temperature at 800 ℃ for 2 hours, circulating for 20 times, and observing the appearance of the product; performing normal-temperature air leak detection, maintaining the pressure at 6000Pa, and judging that the leakage is less than 10 Pa/min;
2. aging performance test: raising the temperature at 1 ℃/min, preserving the temperature at 800 ℃ for 2000 hours, and observing the appearance of the product; performing normal-temperature air leak detection, maintaining the pressure at 6000Pa, and judging that the leakage is less than 10 Pa/min;
3. insulation test: the resistivity was measured by applying a voltage of 1000V continuously for at least 15s with the voltage value stable 4 Omega cm is qualified;
4. mechanical property test: according to the national standard GB-T4338-2006 high temperature tensile test method, the test is carried out under the high temperature working condition of 800 ℃, the maximum tensile force which can be borne by the test piece on the premise of no leakage is tested, and the tensile force of at least 40N of qualified products can be borne without leakage.
TABLE 9
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As can be seen from the data in Table 9, the connecting parts made of the glass-ceramic materials of examples 1 to 25 of the present application can bear at least 50N and above tensile force and 20N and above shearing force under the high temperature condition of 800 ℃, have good high temperature mechanical properties, have no leakage after impact resistance test and aging performance test, have good thermal shock resistance and high temperature reliability, can withstand 1000V voltage to be continuously applied for at least 15s, have stable and unchanged voltage value, and have resistivity larger than 1×10 4 Omega cm, has better high-temperature voltage resistance and insulativity. Comparative examples 1 and 2 were each produced by the mass ratio of Al element per unit area of the connecting portion to the main body portion, the mass ratio of Al element to Zr element in the connecting portion, and the mass ratio of Al element to Zr element in the main body portion 1 And B is outside the range provided by the present invention, resulting in poor thermal shock resistance and high temperature reliability of the final joint member; comparative examples 3 to 10 also were poor in high-temperature mechanical properties or thermal shock resistance and high-temperature reliability of the finally produced connection member because the mass ratio of the elements in the connection portion and the main body portion of the glass ceramic material was not within the range provided by the present invention.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present application and not for limiting the scope of protection of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application.
Claims (3)
1. The microcrystalline glass material is characterized by comprising a main body part and a connecting part; the connecting part and the main body part are both composed of the following components: alkaline earth metal oxide Ra 1 O, alkaline earth metal oxide Ra 2 O、B 2 O 3 、Al 2 O 3 、MO 2 、SiO 2 And rare earth metal oxide ReO; the mass ratio of each element in the connecting part and the main body part satisfies the following relation: x is X Ra1 :Y Ra1 ＝1-1.8:1，X Ra2 :Y Ra2 ＝0.55-1:1，X Al :Y Al ＝0.3-5:1，X M :Y M =0-10:1; wherein Ra is 1 And Ra (Ra) 2 Selected from different alkaline earth metals, X Ra1 、X Ra2 、X Al 、X M Respectively represents Ra per unit area in the connecting part 1 、Ra 2 Mass of Al, M element, Y Ra1 、Y Ra2 、Y Al 、Y M Respectively represents Ra per unit area in the main body part 1 、Ra 2 The mass of Al and M elements; the Ra (Ra) 1 Is at least one of Sr, mg and Ca, and Ra is 2 Is Sr or Ba, M is Ti, and Re is Ce; wherein, in the connecting part, ra 1 Element and Ra 2 The mass ratio of the elements is Ra 1 :Ra 2 ＝0.8-1.5:1，Ra 1 The mass ratio of the element and the B element is Ra 1 :B＝1.8-7:1；
Wherein, in the connecting part, the mass ratio of the Al element to the M element is Al:M=0-4:1, and the mass ratio of the Si element to the Re element is Si:Re=2-65:1;
in the main body, ra 1 Element and Ra 2 The mass ratio of the elements is Ra 1 :Ra 2 ＝0.4-1:1，Ra 1 The mass ratio of the element and the B element is Ra 1 The mass ratio of the element B=1-6:1, the element Al and the element M is Al:M=0-50:1, and the mass ratio of the element Si and the element Re is Si:Re=2-65:1.
2. A connecting member comprising a glass-ceramic portion and an alloy portion made of the glass-ceramic material according to claim 1.
3. The joining component of claim 2 wherein the ends of the alloy portion of the joining component are in end-to-end sealing engagement with the joining portion of the glass-ceramic portion.
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| WO1999021803A2 (en) * | 1997-10-29 | 1999-05-06 | The Westaim Corporation | Dielectric glasses for low dielectric loss, low temperature cofired ceramics with medium dielectric constants |
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| CN101801873A (en) * | 2007-08-22 | 2010-08-11 | 日本山村硝子株式会社 | Glass composition for sealing |
| CN112047638A (en) * | 2020-08-28 | 2020-12-08 | 潮州三环（集团）股份有限公司 | Glass and preparation method and application thereof |
| CN112521011A (en) * | 2020-11-04 | 2021-03-19 | 中国科学院上海硅酸盐研究所 | Solid oxide fuel cell composite sealing material and preparation method and application thereof |
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| WO1999021803A2 (en) * | 1997-10-29 | 1999-05-06 | The Westaim Corporation | Dielectric glasses for low dielectric loss, low temperature cofired ceramics with medium dielectric constants |
| CN101801873A (en) * | 2007-08-22 | 2010-08-11 | 日本山村硝子株式会社 | Glass composition for sealing |
| CN101684034A (en) * | 2008-09-26 | 2010-03-31 | 中国科学院过程工程研究所 | Sealing glass powder, sealing glass ceramic powder and application |
| CN112047638A (en) * | 2020-08-28 | 2020-12-08 | 潮州三环（集团）股份有限公司 | Glass and preparation method and application thereof |
| CN112521011A (en) * | 2020-11-04 | 2021-03-19 | 中国科学院上海硅酸盐研究所 | Solid oxide fuel cell composite sealing material and preparation method and application thereof |
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