CN103641312A - Sealing material and preparation method thereof - Google Patents
Sealing material and preparation method thereof Download PDFInfo
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- CN103641312A CN103641312A CN201310648652.1A CN201310648652A CN103641312A CN 103641312 A CN103641312 A CN 103641312A CN 201310648652 A CN201310648652 A CN 201310648652A CN 103641312 A CN103641312 A CN 103641312A
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- 239000003566 sealing material Substances 0.000 title claims abstract description 178
- 238000002360 preparation method Methods 0.000 title claims description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 25
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims description 46
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- 229910052791 calcium Inorganic materials 0.000 claims description 17
- 239000011575 calcium Substances 0.000 claims description 17
- 239000002210 silicon-based material Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 13
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 2
- 239000001301 oxygen Substances 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 41
- 238000012360 testing method Methods 0.000 description 22
- 238000002441 X-ray diffraction Methods 0.000 description 21
- 239000000292 calcium oxide Substances 0.000 description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 17
- 239000011573 trace mineral Substances 0.000 description 17
- 238000005382 thermal cycling Methods 0.000 description 12
- 235000013619 trace mineral Nutrition 0.000 description 12
- 239000011521 glass Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 9
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 4
- 230000036962 time dependent Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000006112 glass ceramic composition Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011785 micronutrient Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
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- Fuel Cell (AREA)
Abstract
The invention provides a sealing material which comprises the following components in percentage by weight: 9-15wt% of Al2O3, 35-50wt% of SiO2, 25-35wt% of CaO and 5-15wt% of B2O3. The sealing material provided by the invention comprises B2O3. According to the invention, B2O3 serves as an adjusting component, and in the sealing process, a boron and oxygen triangle [BO3] bedding surface structure in B2O3 is converted into a boron and oxygen tetrahedron [BO4] frame structure. Under the synergistic effect with other components, the coefficient of thermal expansion of the obtained sealing material is improved, and the spheroidizing temperature and the converting temperature are reduced. The sealing material provided by the invention has a low spheroidizing point and a wide spheroidizing temperature range, is low in demand on the sealing temperature, and facilitates seal of SOFC (Solid Oxide Fuel Cell). In addition, the sealing material is nearly free from pores and has higher compactness, so that the sealing material has a good sealing effect.
Description
Technical field
The present invention relates to technical field of inorganic material, relate in particular to a kind of sealing material and preparation method thereof.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of under middle high temperature, directly will be stored in chemical energy in fuel and oxygenant and efficiently, contamination-freely change into all solid state chemical generated device of electric energy.
SOFC mainly consists of monocell, web member and sealing material.Under middle high temperature, in SOFC, there is fuel gas (H
2deng) and oxidizing gas (O
2deng) generation, if occur revealed between each web member of SOFC, fuel gas and oxidizing gas mix, SOFC cannot work, will be explosion caused in the time of seriously.In order to prevent gas leakage, sealing material need to keep good resistance to air loss with each parts of SOFC.And, in SOFC Thermal Cycling, difference and chemical instability due to thermal expansivity, sealing material will occur that gap, sealant surface come off or battery problems of crack with web member, so the web member that sealing material also should be in contact with it keeps matched coefficients of thermal expansion and chemical stability.
In prior art, the sealing material that SOFC is conventional comprises glass-ceramic base sealing material, metal matrix sealing material and mica-based sealing material etc.Wherein, because being easy to, mass-producing equipment and cost are low to be widely used glass to ceramic seal material.The patent No. is that the Chinese patent of CN100536195C discloses a kind of battery pile sealing material, comprises following components by weight percent: the high softening-point glass to ceramic seal material that barium oxide 40%～60%, aluminum oxide 2%～10%, boron oxide 10%～20%, silicon oxide 30%～50%, magnesium oxide 3%～5%, calcium oxide 4%～10%, strontium oxide 0.2%～2.0%, zirconium white 0.4%～2% and cerium oxide 0.2%～2% form; The low softening point glass to ceramic seal material that barium oxide 30%～40%, aluminum oxide 2%～10%, boron oxide 10%～30%, silicon oxide 40%～50%, magnesium oxide 3%～5%, calcium oxide 2%～5%, strontium oxide 0.2%～2.0%, nickel oxide 0.4%～2.0%, cobalt oxide 0.2%～2.0% and cerium oxide 0.2%～2.0% form; The mass ratio of high softening-point glass-ceramic material and low softening point glass to ceramic seal material is (7～4): (3～6); Ethanol; Terpineol 350; The content of high softening-point glass-ceramic material and low softening point glass to ceramic seal material is 20%～40%.The interface wet ability of sealing material and web member can better, have excellent thermal circulation performance; But sealing material is had relatively high expectations to sealing temperature, be unfavorable for the sealing-in of SOFC.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of sealing material and preparation method thereof, sealing material provided by the invention has lower nodularization point and wider nodularization temperature range, makes sealing material lower to sealing temperature requirement, is conducive to the sealing-in of SOFC.
The invention provides a kind of sealing material, comprise following component:
The Al of 9wt.%～15wt.%
2o
3;
The SiO of 35wt.%～50wt.%
2;
The CaO of 25wt.%～35wt.%;
The B of 5wt.%～15wt.%
2o
3.
Preferably, the Al that comprises 11wt.%～14wt.%
2o
3.
Preferably, the SiO that comprises 40wt.%～45wt.%
2.
Preferably, the CaO that comprises 28wt.%～33wt.%.
Preferably, the B that comprises 8wt.%～12wt.%
2o
3.
The preparation method who the invention provides a kind of sealing material, comprises the following steps:
Boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound are mixed, by cooling after the mixture melting obtaining, obtain sealing material.
Preferably, described boron-containing compound comprises Na
2b
4o
7, B
2o
3, H
3bO
3and K
2b
4o
7in one or more.
Preferably, the mol ratio of the boron in described boron-containing compound, the aluminium in aluminum contained compound, the calcium in calcium containing compound and the silicon in silicon-containing compound is (0.1～0.5): (0.1～0.6): (0.3～1.0): (0.2～1.2).
Preferably, described aluminum contained compound comprises Al
2o
3, Al (OH)
3, one or more in pseudo-boehmite and Tai-Ace S 150 ammonia.
Preferably, the temperature of described melting is 1400 ℃～1500 ℃;
The time of described melting is 1.5h～2.5h.
The invention provides a kind of sealing material, comprise the Al of following component: 9wt.%～15wt.%
2o
3; The SiO of 35wt.%～50wt.%
2; The CaO of 25wt.%～35wt.% and the B of 5wt.%～15wt.%
2o
3.Sealing material provided by the invention comprises B
2o
3, B
2o
3as regulating composition, in the process of sealing-in, B
2o
3in boron oxygen triangle body [BO
3] deck structure is to boron oxygen tetrahedron [BO
4] the structural transformation of frame shape, under the synergy with other components, improved the thermal expansivity of the sealing material obtaining, reduced nodularization temperature and the transition temperature of sealing material.Sealing material provided by the invention has lower nodularization point and wider nodularization temperature range, and the requirement of sealing temperature is reduced, and is conducive to the sealing-in of SOFC.In addition, sealing material is not almost found pore, and higher compactness makes it have good sealing effectiveness.Experimental result shows, the nodularization point of sealing material provided by the invention is minimum is 850 ℃, and nodularization temperature range is 850 ℃～960 ℃.
Accompanying drawing explanation
Fig. 1 is the image sintering figure of the sealing material that obtains of the embodiment of the present invention 1;
Fig. 2 is the XRD spectra of the sealing material that obtains of the embodiment of the present invention 1;
Fig. 3 is that 5 elementary cells prepared by sealing material that the embodiment of the present invention 1 obtains pile up the I-V graphic representation at 750 ℃;
Fig. 4 is the V-t graphic representation of the 5 elementary cells heaps prepared of sealing material that the embodiment of the present invention 1 obtains;
Fig. 5 is the I-V graphic representation before and after the 5 elementary cells heap thermal cyclings prepared of sealing material that the embodiment of the present invention 1 obtains;
Fig. 6 is the V-t graphic representation before and after the 5 elementary cells heap thermal cyclings prepared of sealing material that the embodiment of the present invention 1 obtains;
Fig. 7 is the rear SEM figure that amplifies 200 times of sealing material test that the embodiment of the present invention 1 obtains;
Fig. 8 is the rear SEM figure that amplifies 1500 times of sealing material test that the embodiment of the present invention 1 obtains;
Fig. 9 is the image sintering figure of the sealing material that obtains of the embodiment of the present invention 2 between 750 ℃～1000 ℃;
Figure 10 is the image sintering figure of the sealing material that obtains of the embodiment of the present invention 3 between 750 ℃～1000 ℃.
Embodiment
The invention provides a kind of sealing material, comprise following component:
The Al of 9wt.%～15wt.%
2o
3;
The SiO of 35wt.%～50wt.%
2;
The CaO of 25wt.%～35wt.%;
The B of 5wt.%～15wt.%
2o
3.
Sealing material provided by the invention comprises B
2o
3, B
2o
3as regulating composition, in the process of sealing-in, B
2o
3in boron oxygen triangle body [BO
3] deck structure is to boron oxygen tetrahedron [BO
4] structural transformation of frame shape, under the synergy with other components, improved the thermal expansivity of the sealing material obtaining, reduced nodularization temperature and the transition temperature of the sealing material obtaining.Sealing material provided by the invention has lower nodularization point and wider nodularization temperature range, and the requirement of sealing temperature is reduced, and is conducive to the sealing-in of SOFC.In addition, sealing material is not almost found pore, and higher compactness makes sealing material have good sealing effectiveness.
Sealing material provided by the invention comprises the Al of 9wt.%～15wt.%
2o
3, be preferably 11wt.%～14wt.%, more preferably 12wt.%～13wt.%.The present invention is to described Al
2o
3source there is no special restriction, adopt Al well known to those skilled in the art
2o
3.In the present invention, described Al
2o
3increased mobility and the cohesiveness of sealing material in sealing-in process.
Sealing material provided by the invention comprises the SiO of 35wt.%～50wt.%
2, be preferably 40wt.%～45wt.%, more preferably 42wt.%～44wt.%.The present invention is to described SiO
2source there is no special restriction, adopt SiO well known to those skilled in the art
2.
Sealing material provided by the invention comprises the CaO of 25wt.%～35wt.%, is preferably 28wt.%～33wt.%, more preferably 30wt.%～32wt.%.The present invention does not have special restriction to the source of described CaO, adopts CaO well known to those skilled in the art.In the present invention, described CaO has increased the thermal expansivity of sealing material.
Sealing material provided by the invention comprises the B of 5wt.%～15wt.%
2o
3, be preferably 8wt.%～12wt.%, more preferably 9wt.%～11wt.%.The present invention is to described B
2o
3source there is no special restriction, adopt B well known to those skilled in the art
2o
3.In the present invention, described B
2o
3viscosity, softening temperature and the transition temperature of sealing material have been reduced.
Sealing material provided by the invention preferably also comprises trace element.In the present invention, described trace element comprises one or more in Zn, Mg and F; The content of described trace element in described sealing material is preferably 0.1wt.%～2.5wt.%, more preferably 0.2wt.%～1.0wt.%.In the present invention, described trace element is without artificial interpolation, for what brought into by raw materials in the process at the described sealing material of preparation.
The preparation method who the invention provides a kind of sealing material, comprises the following steps:
Boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound are mixed, by cooling after the mixture melting obtaining, obtain sealing material.
The present invention mixes boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound, obtains mixture.The present invention does not have special restriction to the order of described mixing, preferably boron-containing compound and aluminum contained compound is first mixed, then adds successively calcium containing compound and silicon-containing compound wherein.When the present invention mixes described boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound, container used does not have special restriction, adopts container well known to those skilled in the art, as adopted crucible well known to those skilled in the art.
In the present invention, described boron-containing compound is preferably Na
2b
4o
7, H
3bO
3, B
2o
3and K
2b
4o
7in one or more, B more preferably
2o
3and H
3bO
3in one or both; Described aluminum contained compound is preferably Al
2o
3, Al (OH)
3, one or more in pseudo-boehmite and Tai-Ace S 150 ammonia, more preferably Al
2o
3; Described calcium containing compound is preferably CaCO
3with one or more in CaO, CaO more preferably; Described silicon-containing compound is preferably SiO
2and H
2siO
3in one or both, SiO more preferably
2.The present invention does not have special restriction to the source of described boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound, adopt above-mentioned boron-containing compound well known to those skilled in the art, aluminum contained compound, calcium containing compound and silicon-containing compound, can adopt the commercial goods of above-mentioned boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound.In the present invention, when described boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound mix as raw material, inevitably brought trace element into, described trace element preferably includes one or more in Zn, Mg and F.
In the present invention, the mol ratio of the boron in described boron-containing compound, the aluminium in aluminum contained compound, the calcium in calcium containing compound and the silicon in silicon-containing compound is preferably (0.1～0.5): (0.1～0.6): (0.3～1.0): (0.2～1.2), more preferably (0.15～0.3): (0.15～0.5): (0.4～0.8): (0.4～1.0).
Obtain after mixture, the present invention, by cooling after described mixture melting, obtains sealing material.The present invention preferably rises to the temperature of described melting by described mixture with the temperature rise rate of 1 ℃/min～8 ℃/min, and more preferably the temperature rise rate with 3 ℃/min～5 ℃/min rises to the temperature of described melting, cooling after melting, obtains sealing material.The present invention does not have special restriction to the equipment of described melting, preferably in High Temperature Furnaces Heating Apparatus, carries out melting; The temperature of described melting is preferably 1400 ℃～1500 ℃, more preferably 1430 ℃～1470 ℃; The time of described melting is preferably 1.5h～2.5h, more preferably 2h.
Complete after the melting of described mixture, the present invention carries out the melt substance obtaining cooling, obtains sealing material.The present invention preferably carries out described melt substance cooling in water, obtains sealing material.In the present invention, described cooling temperature is preferably 10 ℃～40 ℃, more preferably 15 ℃～30 ℃, most preferably is 20 ℃～25 ℃.
The present invention carries out softening performance test to the sealing material preparing, and test process is as follows:
The present invention is pressed into sequin by the sealing material preparing, the sequin obtaining is placed in SJY type high temperature image sintering instrument, according to 1 ℃/min temperature programming to 1100 ℃, the softening process of sealing material is carried out to record, obtain the softening performance test result of sealing material.
The present invention carries out X-ray diffraction (XRD) analysis to the sealing material preparing, and detailed process is as follows:
The present invention is placed in sealing material in x-ray diffractometer, from room temperature, to being warming up to 1100 ℃, carries out XRD test.
Test result shows: the nodularization point of sealing material provided by the invention is minimum is 850 ℃, and nodularization temperature range is 850 ℃～950 ℃, has lower nodularization point and wider nodularization temperature range, and the requirement of sealing temperature is reduced, and is conducive to the sealing-in of SOFC; In XRD test process, temperature is within the scope of room temperature to 1100 ℃, and sealing material does not have crystallization, there is no new generation mutually, in this temperature range, is amorphous glass phase always, is conducive to carry out the sealing-in of SOFC.
The invention provides a kind of sealing material, comprise the Al of following component: 9wt.%～15wt.%
2o
3; The SiO of 35wt.%～50wt.%
2; The CaO of 25wt.%～35wt.%; The B of 5wt.%～15wt.%
2o
3.Sealing material provided by the invention comprises B
2o
3, B
2o
3as regulating composition, in the process of sealing-in, B
2o
3middle boron oxygen triangle body [BO
3] deck structure is to boron oxygen tetrahedron [BO
4] structural transformation of frame shape, under the synergy with other components, improved the thermal expansivity of the sealing material obtaining, reduced nodularization temperature and transition temperature.Sealing material provided by the invention has lower nodularization point and wider nodularization temperature range, and the requirement of sealing temperature is reduced, and is conducive to the sealing-in of SOFC.In addition, sealing material provided by the invention is not almost found pore, and higher compactness makes sealing material have good sealing effectiveness.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of sealing material provided by the invention and preparation method thereof is described in detail, but they can not be interpreted as to limiting the scope of the present invention.
The present invention takes the Al of the component of following mass content: 12.7wt.%
2o
3, 43.5wt.% SiO
2, the CaO of 31.6wt.% and the B of 10wt.%
2o
3micronutrient levels is 2.2wt%, described trace element comprises Zn, Mg and F, said components is mixed and to be placed in crucible, then the crucible that said components is housed is placed in to High Temperature Furnaces Heating Apparatus, with the temperature rise rate of 5 ℃/min, be warming up to 1450 ℃, at 1450 ℃, melting 2h is in a liquid state to all components, then open rapidly High Temperature Furnaces Heating Apparatus, liquid composition in crucible is placed in to cold water and is cooled to rapidly room temperature, obtain sealing material.
The present invention is pressed into the sealing material obtaining
sequin, be placed in SJY type high temperature image sintering instrument, according to 1 ℃/min temperature programming to 1100 ℃, its softening performance is observed, result as shown in Figure 1, Fig. 1 is the image sintering figure of the sealing material that obtains of the embodiment of the present invention 1 between 750 ℃～1000 ℃, and wherein, a1 is the image sintering figure of sealing material at 750 ℃; B1 is the image sintering figure of sealing material at 800 ℃; C1 is the image sintering figure of sealing material at 835 ℃; D1 is the image sintering figure of sealing material at 860 ℃; E1 is the image sintering figure of sealing material at 870 ℃; F1 is the image sintering figure of sealing material at 880 ℃; G1 is the image sintering figure of sealing material at 900 ℃; H1 is the image sintering figure of sealing material at 920 ℃; I1 is the image sintering figure of sealing material at 950 ℃; J1 is the image sintering figure of sealing material at 1000 ℃.
As can be seen from Figure 1,835 ℃ of sealing materials provided by the invention start there is softening sign, and 860 ℃ start nodularizations, and nodularization temperature range is 860 ℃～950 ℃.
The present invention will obtain sealing material and carry out X-ray diffraction (XRD) and analyze, and as shown in Figure 2, Fig. 2 is the sealing material that obtains of the embodiment of the present invention 1 from the XRD spectra of room temperature to 1100 ℃ to result.Wherein, curve 1 is sealing material XRD spectra at room temperature; Curve 2 is the XRD spectra of sealing material at 700 ℃; Curve 3 is the XRD spectra of sealing material at 750 ℃; Curve 4 is the XRD spectra of sealing material at 800 ℃; Curve 5 is the XRD spectra of sealing material at 850 ℃; Curve 6 is the XRD spectra of sealing material at 900 ℃; Curve 7 is the XRD spectra of sealing material at 950 ℃; Curve 8 is the XRD spectra of sealing material at 1000 ℃; Curve 9 is the XRD spectra of sealing material at 1050 ℃; Curve 10 is the XRD spectra of 1100 ℃ of lower seal materials.As seen from Figure 2, within the scope of room temperature to 1100 ℃, sealing material provided by the invention does not have crystallization, there is no new generation mutually, in this temperature range, is amorphous glass phase always, is conducive to carry out the sealing-in of SOFC.
Image sintering experiment and XRD test and show, the nodularization point of sealing material provided by the invention is low, and nodularization temperature range scope is wide, is conducive to the sealing-in of SOFC.
The present invention adopts the sealing material that the present embodiment prepares to make 5 elementary cell heaps, and seal temperature is 880 ℃.This 5 elementary cell heap comprises monocell, web member and sealing material, sealing material at web member surrounding point glue desired thickness, then the web member by a glue is by 5 piecemeal coupling together of monocell, impressed pressure is 100kg, finally with the temperature rise rate of 1 ℃/min, being raised to 880 ℃ seals, at 880 ℃, continue insulation four hours, cooling can obtain 5 elementary cell heaps.The performance of the 5 elementary cell heaps that the present invention obtains the present embodiment is tested, and concrete test process and test result are as follows:
5 elementary cell heaps prepared by the present embodiment carry out sealing property test, test result as shown in Figure 3, Fig. 3 is that 5 elementary cells prepared by sealing material that the embodiment of the present invention 1 obtains pile up the I-V graphic representation at 750 ℃, wherein, 1 represent 750 ℃ at 5 elementary cells pile up H
2/ air=4.8/14sccmcm
-2under I-V curve; At 2 750 ℃ of expressions, 5 elementary cells pile up H
2/ air=6.3/19sccmcm
-2under I-V curve; At 3 750 ℃ of expressions, 5 elementary cells pile up H
2/ air=9.5/29sccmcm
-2under I-V curve.As seen from Figure 5, at 750 ℃, H
2/ air=9.5/29sccmcm
-2under condition, 5 elementary cell heap open circuit voltage 6.032V, average open-circuit voltage is up to 1.206V, and monomer power under 0.7V is 173.6W, and power density reaches 0.55Wcm
-2, illustrate that 5 elementary cell heaps have good sealing property.
The sealing material that the present invention prepares the present embodiment carries out sealing property test for 5 elementary cell heaps, test result as shown in Figure 4, Fig. 4 is the V-t graphic representation of the 5 elementary cells heaps prepared of sealing material that the embodiment of the present invention 1 obtains, wherein, 1 is the time dependent curve of voltage, and 2 is the time dependent curve of electric current.As seen from Figure 4,5 elementary cells pile up 750 ℃, H
2/ air=6.3/19sccmcm
-2under with 35A constant-current discharge, running voltage 3.77V, monomer average voltage is 0.75V, service rating 132W, 5 elementary cells heaps steady running 20h are undamped, show in operational process favorable sealing property.
The sealing material that the present invention prepares the present embodiment is for the thermal circulation performance test of 5 elementary cell heaps, test result as shown in Figure 5, Fig. 5 is the I-V graphic representation before and after the 5 elementary cells heap thermal cyclings prepared of sealing material that the embodiment of the present invention 1 obtains, wherein curve 1 is the I-V curve before 5 elementary cell heap thermal cyclings, and curve 2 is the I-V curve after 5 elementary cell heap thermal cyclings.As seen from Figure 5,5 elementary cells pile up 750 ℃, H
2/ air=9.5/29sccmcm
-2under with 35A constant-current discharge, record 5 elementary cells heaps open circuit voltage 5.936V, monomer average voltage is 1.187V, service rating 156W under monomer 0.7V; 5 elementary cell heaps are through once thoroughly thermal cycling, and 5 elementary cells pile up 750 ℃, H
2/ air=9.5/29sccmcm
-2under with 35A constant-current discharge, record 5 elementary cells heaps open circuit voltage 6.043V, average open-circuit voltage 1.209V, service rating 136W under monomer 0.7V, power density 0.43Wcm
-2; As seen from Figure 5, through once thoroughly thermal cycling, 5 elementary cell heap open circuit voltages do not decline, and favorable sealing property is described.
The sealing material that the present invention prepares the present embodiment is for the thermal circulation performance test of 5 elementary cell heaps, test result as shown in Figure 6, Fig. 6 is the V-t graphic representation before and after the 5 elementary cells heap thermal cyclings prepared of sealing material that the embodiment of the present invention 1 obtains, wherein, curve 1 is the time dependent curve of voltage, and curve 2 is the time dependent curve of electric current.As seen from Figure 6,5 elementary cells pile up 750 ℃, H
2/ air=6.3/19sccmcm
-2under with 35A constant-current discharge, record 5 elementary cells heaps open circuit voltage 3.848V, monomer average voltage 0.770V, service rating 134.7W, 5 elementary cell stack operation 20h stablize undamped; 5 elementary cell heaps are through once thoroughly thermal cycling, first from 750 ℃, be down to 30 ℃, then from 30 ℃, being warming up to 750 ℃ tests, under the same conditions with 35A constant-current discharge, 5 elementary cell stack operation voltage 3.788V, monomer average voltage is 0.758V, service rating 132.5W, 5 elementary cell stack operation 17h; As seen from Figure 6, the service rating 2.2W that only declines before than thermal cycling after 5 elementary cells heaps thermal cyclings, illustrates the favorable sealing property of sealing material.
The sealing material that the present invention prepares the present embodiment is applied to test in 5 elementary cell heaps, sealing material after test is carried out to sem analysis, result as shown in Figure 7 and Figure 8, Fig. 7 is the rear SEM figure that amplifies 200 times of sealing material test that the embodiment of the present invention 1 obtains, Fig. 8 is the rear SEM figure that amplifies 1500 times of sealing material test that the embodiment of the present invention 1 obtains, wherein, M is sealing material.By Fig. 7 and Fig. 8, can be found out, sealing material is not almost found pore, very fine and close, illustrates that the resistance to air loss of sealing material is fine.
The present invention takes the Al of the component of following mass content: 13.4wt.%
2o
3, 45.9wt.% SiO
2, the CaO of 33.4wt.% is, the B of 5wt.%
2o
3trace element with 2.2wt.%, wherein trace element comprises Zn, Mg and F, said components is mixed and is placed in crucible, again the crucible that said components is housed is placed in to High Temperature Furnaces Heating Apparatus, temperature rise rate with 5 ℃/min is warming up to 1500 ℃, and at 1500 ℃, melting 1.5h is in a liquid state to all components, then opens rapidly High Temperature Furnaces Heating Apparatus, liquid composition in crucible is placed in to cold water and is cooled to rapidly room temperature, obtain sealing material.
The present invention is pressed into the sealing material obtaining
sequin, be placed in SJY type high temperature image sintering instrument, according to 1 ℃/min temperature programming to 1100 ℃, its softening performance is observed, result as shown in Figure 9, Fig. 9 is the image sintering figure of the sealing material that obtains of the embodiment of the present invention 2 between 750 ℃～1000 ℃, and wherein, a2 is the image sintering figure of sealing material at 800 ℃; B2 is the image sintering figure of sealing material at 830 ℃; C2 is the image sintering figure of sealing material at 850 ℃; D2 is the image sintering figure of sealing material at 860 ℃; E2 is the image sintering figure of sealing material at 870 ℃; F2 is the image sintering figure of sealing material at 880 ℃; G2 is the image sintering figure of sealing material at 910 ℃; H2 is the image sintering figure of sealing material at 920 ℃; I2 is the image sintering figure of sealing material at 950 ℃; J2 is the image sintering figure of sealing material at 1040 ℃.
As can be seen from Figure 9, about 910 ℃ beginning nodularizations of sealing material provided by the invention, nodularization temperature range is 910 ℃～950 ℃, nodularization temperature range is wide in range, is all beneficial to the sealing-in of carrying out SOFC in this temperature range.
The sealing material temperature that the present embodiment provides shows that from the original position XRD of room temperature to 1100 ℃ sealing material provided by the invention does not have crystallization, there is no new generation mutually, in this temperature range, is amorphous glass phase always, is conducive to carry out the sealing-in of SOFC.
Image sintering experiment and XRD test and show, the nodularization point of sealing material provided by the invention is low, and nodularization temperature range scope is wide, is conducive to the sealing-in of SOFC.
The present invention takes the Al of the component of following mass content: 12wt.%
2o
3, 41wt.% SiO
2, the CaO of 29.8wt.% is, the B of 15wt.%
2o
3trace element with 2.2wt.%, wherein trace element comprises Zn, Mg or F, said components is mixed and is placed in crucible, again the crucible that said components is housed is placed in to High Temperature Furnaces Heating Apparatus, heating rate with 5 ℃/min is warming up to 1500 ℃, and at 1500 ℃, melting 2h is in a liquid state to all components, then opens rapidly High Temperature Furnaces Heating Apparatus, liquid composition in crucible is placed in to cold water and is cooled to rapidly room temperature, obtain sealing material.
The present invention is pressed into the sealing material obtaining
sequin, be placed in SJY type high temperature image sintering instrument, according to 1 ℃/min temperature programming to 1100 ℃, its softening performance is observed, result is as shown in figure 10, Figure 10 is the image sintering figure of the sealing material that obtains of the embodiment of the present invention 3 between 750 ℃～1000 ℃, and wherein, a3 is the image sintering figure of sealing material at 800 ℃; B3 is the image sintering figure of sealing material at 830 ℃; C3 is the image sintering figure of sealing material at 850 ℃; D3 is the image sintering figure of sealing material at 860 ℃; E3 is the image sintering figure of sealing material at 870 ℃; F3 is the image sintering figure of sealing material at 880 ℃; G3 is the image sintering figure of sealing material at 920 ℃; H3 is the image sintering figure of sealing material at 950 ℃.
As can be seen from Figure 10, about 850 ℃ beginning nodularizations of the sealing material of the present embodiment, nodularization temperature range is 850 ℃～950 ℃.
The sealing material that the present embodiment provides does not have crystallization from the XRD sealing material provided by the invention of room temperature to 1100 ℃, there is no new generation mutually, in this temperature range, is amorphous glass phase always, is conducive to carry out the sealing-in of SOFC.
Image sintering experiment and XRD test and show, the nodularization point of sealing material provided by the invention is low, and nodularization temperature range scope is wide, is conducive to the sealing-in of SOFC.
Embodiment 4
The present invention takes the Al of the component of following mass content: 9.0wt.%
2o
3, 48.9wt.% SiO
2, the CaO of 27.0wt.% is, the B of 13wt.%
2o
3trace element with 2.1wt.%, wherein trace element comprises Zn, Mg and F, said components is mixed and is placed in crucible, again the crucible that said components is housed is placed in to High Temperature Furnaces Heating Apparatus, heating rate with 8 ℃/min is warming up to 1500 ℃, and then melting 2h at 1500 ℃ opens rapidly High Temperature Furnaces Heating Apparatus, liquid composition in crucible is placed in to cold water and is cooled to rapidly room temperature, obtain sealing material.
The nodularization point of the sealing material that the embodiment of the present invention 4 prepares is 900 ℃, and nodularization temperature range is 900 ℃～960 ℃, and nodularization temperature range is wide in range, is conducive to the sealing-in of SOFC in this temperature range.
The present invention takes the Al of the component of following mass content: 14.8wt.%
2o
3, 35.0wt.% SiO
2, the CaO of 33.4wt.% is, the B of 15wt.%
2o
3trace element with 1.8wt.%, wherein trace element comprises Zn, Mg and F, said components is mixed and is placed in crucible, again the crucible that said components is housed is placed in to High Temperature Furnaces Heating Apparatus, heating rate with 5 ℃/min is warming up to 1500 ℃, and then melting 2h at 1500 ℃ opens rapidly High Temperature Furnaces Heating Apparatus, liquid composition in crucible is placed in to cold water and is cooled to rapidly room temperature, obtain sealing material.
The nodularization point of the sealing material that the embodiment of the present invention 5 prepares is 850 ℃, and nodularization temperature range is 850 ℃～930 ℃, and nodularization temperature range is wide in range, is conducive to the sealing-in of SOFC in this temperature range.
The present invention takes the Al (OH) of the component of following mass content: 10wt.%
3, 39wt.% H
2siO
3, 35wt.% CaCO
3, 15wt.% H
3bO
3trace element with 1wt.%, wherein trace element comprises Zn, Mg and F, said components is mixed and is placed in crucible, again the crucible that said components is housed is placed in to High Temperature Furnaces Heating Apparatus, heating rate with 5 ℃/min is warming up to 1500 ℃, and then melting 2h at 1500 ℃ opens rapidly High Temperature Furnaces Heating Apparatus, liquid composition in crucible is placed in to cold water and is cooled to rapidly room temperature, obtain sealing material.
The nodularization point of the sealing material that the embodiment of the present invention 6 prepares is 870 ℃, and nodularization temperature range is 870 ℃～950 ℃, and nodularization temperature range is wide in range, is conducive to the sealing-in of SOFC in this temperature range.
As seen from the above embodiment, the invention provides a kind of sealing material, comprise the Al of following component: 9wt.%～15wt.%
2o
3; The SiO of 35wt.%～50wt.%
2; The CaO of 25wt.%～35wt.% and the B of 5wt.%～15wt.%
2o
3.Sealing material provided by the invention comprises B
2o
3, B
2o
3as regulating composition, in the process of sealing-in, B
2o
3in boron oxygen triangle body [BO
3] deck structure is to boron oxygen tetrahedron [BO
4] structural transformation of frame shape, under the synergy with other components, improved the thermal expansivity of the sealing material obtaining, reduced nodularization temperature and transition temperature.Sealing material provided by the invention has lower nodularization point and wider nodularization temperature range, and sealing material is reduced the requirement of sealing temperature, is conducive to the sealing-in of SOFC.In addition, sealing material provided by the invention is not almost found pore, and higher compactness makes sealing material have good sealing effectiveness.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a sealing material, comprises following component:
The Al of 9wt.%～15wt.%
2o
3;
The SiO of 35wt.%～50wt.%
2;
The CaO of 25wt.%～35wt.%;
The B of 5wt.%～15wt.%
2o
3.
2. sealing material according to claim 1, is characterized in that, comprises the Al of 11wt.%～14wt.%
2o
3.
3. sealing material according to claim 1, is characterized in that, comprises the SiO of 40wt.%～45wt.%
2.
4. sealing material according to claim 1, is characterized in that, comprises the CaO of 28wt.%～33wt.%.
5. sealing material according to claim 1, is characterized in that, comprises the B of 8wt.%～12wt.%
2o
3.
6. a preparation method for sealing material, comprises the following steps:
Boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound are mixed, by cooling after the mixture melting obtaining, obtain sealing material.
7. preparation method according to claim 6, is characterized in that, described boron-containing compound comprises Na
2b
4o
7, B
2o
3, H
3bO
3and K
2b
4o
7in one or more.
8. preparation method according to claim 6, it is characterized in that, the mol ratio of the boron in described boron-containing compound, the aluminium in aluminum contained compound, the calcium in calcium containing compound and the silicon in silicon-containing compound is (0.1～0.5): (0.1～0.6): (0.3～1.0): (0.2～1.2).
9. preparation method according to claim 6, is characterized in that, described aluminum contained compound comprises Al
2o
3, Al (OH)
3, one or more in pseudo-boehmite and Tai-Ace S 150 ammonia.
10. preparation method according to claim 6, is characterized in that, the temperature of described melting is 1400 ℃～1500 ℃;
The time of described melting is 1.5h～2.5h.
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Effective date of registration: 20240319 Address after: No. 11-1-1-1, Building 1, East Zone, Ningbo New Material Innovation Center, High tech Zone, Ningbo City, Zhejiang Province, 315048 Patentee after: Zhejiang Industrial Research Institute Development Co.,Ltd. Country or region after: Zhong Guo Address before: 315201 No. 1219 Zhongguan West Road, Zhenhai District, Ningbo City, Zhejiang Province Patentee before: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Country or region before: Zhong Guo |