CN103641312B - Sealing material and preparation method thereof - Google Patents
Sealing material and preparation method thereof Download PDFInfo
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- CN103641312B CN103641312B CN201310648652.1A CN201310648652A CN103641312B CN 103641312 B CN103641312 B CN 103641312B CN 201310648652 A CN201310648652 A CN 201310648652A CN 103641312 B CN103641312 B CN 103641312B
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- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000003566 sealing material Substances 0.000 title abstract description 12
- 239000008393 encapsulating agent Substances 0.000 claims description 155
- 239000011573 trace mineral Substances 0.000 claims description 21
- 235000013619 trace mineral Nutrition 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 abstract description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052796 boron Inorganic materials 0.000 abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 13
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 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
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 41
- 150000001875 compounds Chemical class 0.000 description 38
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 24
- 238000002441 X-ray diffraction Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 239000000292 calcium oxide Substances 0.000 description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- 229910052791 calcium Inorganic materials 0.000 description 13
- 239000011575 calcium Substances 0.000 description 13
- 239000002210 silicon-based material Substances 0.000 description 10
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002241 glass-ceramic Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 230000003321 amplification Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000011056 performance test Methods 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate 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
- ZLTFJCVIWPRJEA-UHFFFAOYSA-H dialuminum azane trisulfate Chemical compound N.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZLTFJCVIWPRJEA-UHFFFAOYSA-H 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 239000006112 glass ceramic composition Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910003641 H2SiO3 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 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
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 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
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 235000013369 micronutrients Nutrition 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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, particularly relate to a kind of encapsulant and preparation method thereof.
Background technology
SOFC (SOFC) is a kind of under middle high temperature, directly will be stored in fuel and oxidant
Chemical energy efficiently, contamination-freely changes into all solid state chemical generated device of electric energy.
SOFC is mainly made up of monocell, connector and encapsulant.Under middle high temperature, SOFC has fuel gas (H2
Deng) and oxidizing gas (O2Deng) generation, if occurring between each connector of SOFC revealing, fuel gas and oxidizing gas occur
Mixing, then SOFC will be unable to work, will cause blast time serious.In order to prevent gas leakage, encapsulant needs and SOFC
Each parts keep good air-tightness.And, in SOFC Thermal Cycling, owing to difference and the chemistry of thermal coefficient of expansion are unstable
Qualitative, with connector, encapsulant will occur that gap, sealant surface come off or battery problems of crack, so sealing material
The connector that material also should be in contact with it keeps matched coefficients of thermal expansion and chemical stability.
In prior art, encapsulant conventional for SOFC include glass-ceramic base encapsulant, Metal Substrate encapsulant and
Mica-based encapsulant etc..Wherein, glass-ceramic seals is widely used because being prone to scale equipment and low cost.
The Chinese patent of Patent No. CN100536195C discloses a kind of battery pile encapsulant, including following components by weight percent: oxidation
Barium 40%～60%, aluminium 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 oxide 0.4%～2% and the high softening-point glass-ceramic of cerium oxide 0.2%～2% composition
Encapsulant；Barium monoxide 30%～40%, aluminium 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
The low softening point glass-ceramic seals of 0.2%～2.0% composition；High softening-point glass-ceramic material and low softening point glass
The mass ratio of glass-ceramic sealing material is (7～4): (3～6)；Ethanol；Terpineol；High softening-point glass-ceramic material is with low
The content of softening point glass-ceramic seals is 20%～40%.This encapsulant is preferable with the boundary moisture performance of connector,
There is the thermal circulation performance of excellence；But sealing temperature is required higher by this encapsulant, is unfavorable for the sealing-in of SOFC.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of encapsulant and preparation method thereof, it is close that the present invention provides
Closure material has relatively low nodularization point and wider nodularization temperature range so that sealing temperature is required relatively low by this encapsulant,
Be conducive to the sealing-in of SOFC.
The invention provides a kind of encapsulant, including following components:
The Al of 9wt.%～15wt.%2O3；
The SiO of 35wt.%～50wt.%2；
The CaO of 25wt.%～35wt.%；
The B of 5wt.%～15wt.%2O3。
Preferably, including the Al of 11wt.%～14wt.%2O3。
Preferably, including the SiO of 40wt.%～45wt.%2。
Preferably, including the CaO of 28wt.%～33wt.%.
Preferably, including the B of 8wt.%～12wt.%2O3。
The invention provides the preparation method of a kind of encapsulant, comprise the following steps:
Boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound are mixed, the mixture obtained is melted
Rear cooling, obtains encapsulant.
Preferably, described boron-containing compound includes Na2B4O7、B2O3、H3BO3And K2B4O7In one or more.
Preferably, the boron in described boron-containing compound, the aluminum in aluminum contained compound, the calcium in calcium containing compound and silicide-comprising
The mol ratio of the silicon in compound is (0.1～0.5): (0.1～0.6): (0.3～1.0): (0.2～1.2).
Preferably, described aluminum contained compound includes Al2O3、Al(OH)3, one in boehmite and aluminum sulfate ammonia or
Multiple.
Preferably, described melted temperature is 1400 DEG C～1500 DEG C；
The described melted time is 1.5h～2.5h.
The invention provides a kind of encapsulant, including following components: the Al of 9wt.%～15wt.%2O3；35wt.%～
The SiO of 50wt.%2；The B of CaO and 5wt.%～15wt.% of 25wt.%～35wt.%2O3.The encapsulant that the present invention provides includes
B2O3, B2O3As modifying ingredients, during sealing-in, B2O3In boron oxygen triangle body [BO3] deck structure is to boron oxygen on four sides
Body [BO4] rack-like structural transformation, under the synergism with other components, improve the thermal expansion system of the encapsulant obtained
Number, reduces nodularization temperature and the transition temperature of encapsulant.The present invention provide encapsulant have relatively low nodularization point and
Wider nodularization temperature range, the requirement to sealing temperature reduces, the sealing-in of beneficially SOFC.It addition, this encapsulant is almost
Do not find that pore, higher compactness make it have preferable sealing effectiveness.Test result indicate that, the sealing material that the present invention provides
Minimum 850 DEG C of the nodularization point of material, nodularization temperature range is 850 DEG C～960 DEG C.
Accompanying drawing explanation
Fig. 1 is the image sintering figure of the encapsulant that the embodiment of the present invention 1 obtains；
Fig. 2 is the XRD spectra of the encapsulant that the embodiment of the present invention 1 obtains；
Fig. 3 is that 5 element cells prepared by the encapsulant that the embodiment of the present invention 1 obtains pile up the I-V curve at 750 DEG C
Figure；
Fig. 4 is the V-t curve chart of 5 element cell heaps prepared by the encapsulant that the embodiment of the present invention 1 obtains；
Fig. 5 is the I-V curve before and after 5 element cell heap thermal cycles prepared by the encapsulant that the embodiment of the present invention 1 obtains
Figure；
Fig. 6 is the V-t curve before and after 5 element cell heap thermal cycles prepared by the encapsulant that the embodiment of the present invention 1 obtains
Figure；
Fig. 7 is the SEM figure of amplification 200 times after the encapsulant that the embodiment of the present invention 1 obtains is tested；
Fig. 8 is the SEM figure of amplification 1500 times after the encapsulant that the embodiment of the present invention 1 obtains is tested；
Fig. 9 is the encapsulant that obtains of the embodiment of the present invention 2 image sintering figure between 750 DEG C～1000 DEG C；
Figure 10 is the encapsulant that obtains of the embodiment of the present invention 3 image sintering figure between 750 DEG C～1000 DEG C.
Detailed description of the invention
The invention provides a kind of encapsulant, including following components:
The Al of 9wt.%～15wt.%2O3；
The SiO of 35wt.%～50wt.%2；
The CaO of 25wt.%～35wt.%；
The B of 5wt.%～15wt.%2O3。
The encapsulant that the present invention provides includes B2O3, B2O3As modifying ingredients, during sealing-in, B2O3In boron
Oxygen triangle body [BO3] deck structure is to boron oxygen tetrahedron [BO4] rack-like structural transformation, under the synergism with other components, carry
The thermal coefficient of expansion of the high encapsulant obtained, reduces nodularization temperature and the transition temperature of the encapsulant obtained.This
The encapsulant of bright offer has relatively low nodularization point and wider nodularization temperature range, and the requirement to sealing temperature reduces, and has
It is beneficial to the sealing-in of SOFC.It addition, this encapsulant does not almost find that pore, higher compactness make encapsulant have preferably
Sealing effectiveness.
The encapsulant that the present invention provides includes the Al of 9wt.%～15wt.%2O3, preferably 11wt.%～14wt.%, more excellent
Elect 12wt.%～13wt.% as.The present invention is to described Al2O3Source there is no a special restriction, use those skilled in the art ripe
The Al known2O3?.In the present invention, described Al2O3Add encapsulant mobility during sealing-in and caking property.
The encapsulant that the present invention provides includes the SiO of 35wt.%～50wt.%2, preferably 40wt.%～45wt.%, more
It is preferably 42wt.%～44wt.%.The present invention is to described SiO2Source there is no a special restriction, use those skilled in the art
Known to SiO2?.
The encapsulant that the present invention provides includes CaO, preferably 28wt.%～33wt.% of 25wt.%～35wt.%, more excellent
Elect 30wt.%～32wt.% as.The present invention does not has special restriction to the source of described CaO, uses those skilled in the art to know
CaO.In the present invention, described CaO adds the thermal coefficient of expansion of encapsulant.
The encapsulant that the present invention provides includes the B of 5wt.%～15wt.%2O3, preferably 8wt.%～12wt.%, more preferably
For 9wt.%～11wt.%.The present invention is to described B2O3Source there is no special restriction, use well known to those skilled in the art
B2O3?.In the present invention, described B2O3Reduce the viscosity of encapsulant, softening temperature and transition temperature.
The encapsulant that the present invention provides the most also includes trace element.In the present invention, described trace element include Zn,
One or more in Mg and F；Described trace element content in the seal material is preferably 0.1wt.%～2.5wt.%,
More preferably 0.2wt.%～1.0wt.%.In the present invention, described trace element adds, for preparing described sealing without artificial
By preparing what raw material was brought into during material.
The invention provides the preparation method of a kind of encapsulant, comprise the following steps:
Boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound are mixed, the mixture obtained is melted
Rear cooling, obtains encapsulant.
Boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound are mixed by the present invention, obtain mixture.
The present invention does not has special restriction to the order of described mixing, preferably boron-containing compound and aluminum contained compound is first mixed, then to
Wherein it is sequentially added into calcium containing compound and silicon-containing compound.The present invention is to described boron-containing compound, aluminum contained compound, calcic chemical combination
Container used when thing and silicon-containing compound mixing does not has special restriction, uses container well known to those skilled in the art i.e.
Can, as crucible well known to those skilled in the art can be used.
In the present invention, described boron-containing compound is preferably Na2B4O7、H3BO3、B2O3And K2B4O7In one or more,
More preferably B2O3And H3BO3In one or both；Described aluminum contained compound is preferably Al2O3、Al(OH)3, boehmite
With one or more in aluminum sulfate ammonia, more preferably Al2O3；Described calcium containing compound is preferably CaCO3With the one in CaO
Or multiple, more preferably CaO；Described silicon-containing compound is preferably SiO2And H2SiO3In one or both, more preferably
SiO2.It is special that the source of described boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound is not had by the present invention
Limit, use above-mentioned boron-containing compound well known to those skilled in the art, aluminum contained compound, calcium containing compound and silicon-containing compound
, the commercial goods of above-mentioned boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound can be used.At this
In invention, described boron-containing compound, aluminum contained compound, calcium containing compound and silicon-containing compound are inevitable when mixing as raw material
Brought trace element into, described trace element preferably includes one or more in Zn, Mg and F.
In the present invention, the boron in described boron-containing compound, the aluminum in aluminum contained compound, the calcium in calcium containing compound and contain
The mol ratio of the silicon in silicon compound is preferably (0.1～0.5): (0.1～0.6): (0.3～1.0): (0.2～1.2), more excellent
Elect as (0.15～0.3): (0.15～0.5): (0.4～0.8): (0.4～1.0).
After obtaining mixture, the present invention cools down after melted for described mixture, obtains encapsulant.The present invention is preferably by institute
State mixture and rise to described melted temperature with the heating rate of 1 DEG C/min～8 DEG C/min, more preferably with 3 DEG C/min～5 DEG C/
The heating rate of min rises to described melted temperature, cools down, obtain encapsulant after melting.The present invention is to described melted setting
Standby do not have special restriction, preferably melts in high temperature furnace；Described melted temperature is preferably 1400 DEG C～1500 DEG C, more
It is preferably 1430 DEG C～1470 DEG C；The described melted time is preferably 1.5h～2.5h, more preferably 2h.
After completing to melt described mixture, the melt substance obtained is cooled down by the present invention, obtains encapsulant.
Described melt substance is preferably cooled down in water by the present invention, obtains encapsulant.In the present invention, the temperature of described cooling
It is preferably 10 DEG C～40 DEG C, more preferably 15 DEG C～30 DEG C, most preferably 20 DEG C～25 DEG C.
The present invention encapsulant to preparing carries out softening performance test, and test process is as follows:
The encapsulant prepared is pressed into sequin by the present invention, and the sequin obtained is placed in SJY type high temperature shadow
As, in sintering instrument, according to 1 DEG C/min temperature programming to 1100 DEG C, the softening process of encapsulant being carried out record, is sealed
The softening performance test result of material.
The present invention encapsulant to preparing carries out X-ray diffraction (XRD) and analyzes, and detailed process is as follows:
Encapsulant is placed in x-ray diffractometer by the present invention, carries out XRD test from room temperature to being warming up to 1100 DEG C.
Test result shows: minimum 850 DEG C of the nodularization point of the encapsulant that the present invention provides, nodularization temperature range is
850 DEG C～950 DEG C, having relatively low nodularization point and wider nodularization temperature range, the requirement to sealing temperature reduces, and is conducive to
The sealing-in of SOFC；In XRD test process, temperature is in the range of room temperature to 1100 DEG C, and encapsulant does not has crystallize, does not has new phase
Generate, be amorphous glass phase in this temperature range always, be conducive to carrying out the sealing-in of SOFC.
The invention provides a kind of encapsulant, including following components: the Al of 9wt.%～15wt.%2O3；35wt.%～
The SiO of 50wt.%2；The CaO of 25wt.%～35wt.%；The B of 5wt.%～15wt.%2O3.The encapsulant that the present invention provides includes
B2O3, B2O3As modifying ingredients, during sealing-in, B2O3Middle boron oxygen triangle body [BO3] deck structure is to boron oxygen tetrahedron
[BO4] rack-like structural transformation, under the synergism with other components, improve the thermal coefficient of expansion of the encapsulant obtained,
Reduce nodularization temperature and transition temperature.The encapsulant that the present invention provides has relatively low nodularization point and wider nodularization temperature
Scope, the requirement to sealing temperature reduces, the sealing-in of beneficially SOFC.It addition, the encapsulant that the present invention provides almost is not sent out
Existing pore, higher compactness makes encapsulant have preferable sealing effectiveness.
In order to further illustrate the present invention, a kind of encapsulant present invention provided below in conjunction with embodiment and preparation thereof
Method is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
The present invention weighs the Al of the component of following mass content: 12.7wt.%2O3, the SiO of 43.5wt.%2, 31.6wt.%
The B of CaO and 10wt.%2O3, micronutrient levels is 2.2wt%, and described trace element includes Zn, Mg and F, said components is mixed
It is placed in crucible, then the crucible that will be equipped with said components is placed in high temperature furnace, is warming up to 1450 with the heating rate of 5 DEG C/min
DEG C, at 1450 DEG C, melted 2h is in a liquid state to all components, opens the most rapidly high temperature furnace, is placed in cold by liquid composition in crucible
Water is cooled to room temperature rapidly, obtains encapsulant.
The encapsulant obtained is pressed into by the present inventionSequin, be placed in SJY type high temperature image sintering instrument
In, according to 1 DEG C/min temperature programming to 1100 DEG C, its softening performance to be observed, result is as it is shown in figure 1, Fig. 1 is the present invention
The encapsulant that embodiment 1 obtains image sintering figure between 750 DEG C～1000 DEG C, wherein, a1 is that encapsulant is at 750 DEG C
Under image sintering figure；B1 is encapsulant image sintering figure at 800 DEG C；C1 is encapsulant image at 835 DEG C
Sintering figure；D1 is encapsulant image sintering figure at 860 DEG C；E1 is encapsulant image sintering figure at 870 DEG C；f1
For encapsulant image sintering figure at 880 DEG C；G1 is encapsulant image sintering figure at 900 DEG C；H1 is sealing material
Material image sintering figure at 920 DEG C；I1 is encapsulant image sintering figure at 950 DEG C；J1 is that encapsulant is 1000
Image sintering figure at DEG C.
From figure 1 it appears that the encapsulant 835 DEG C that the present invention provides begins with the sign of softening, 860 DEG C start ball
Changing, nodularization temperature range is 860 DEG C～950 DEG C.
The present invention will obtain encapsulant and carry out X-ray diffraction (XRD) analysis, and result is as in figure 2 it is shown, Fig. 2 is the present invention
The encapsulant that embodiment 1 obtains is from the XRD spectra of room temperature to 1100 DEG C.Wherein, curve 1 be encapsulant at room temperature
XRD spectra；Curve 2 is encapsulant XRD spectra at 700 DEG C；Curve 3 is encapsulant XRD spectra at 750 DEG C；
Curve 4 is encapsulant XRD spectra at 800 DEG C；Curve 5 is encapsulant XRD spectra at 850 DEG C；Curve 6 is close
Closure material XRD spectra at 900 DEG C；Curve 7 is encapsulant XRD spectra at 950 DEG C；Curve 8 is that encapsulant exists
XRD spectra at 1000 DEG C；Curve 9 is encapsulant XRD spectra at 1050 DEG C；Curve 10 is 1100 DEG C of lower seal materials
XRD spectra.As seen from Figure 2, in the range of room temperature to 1100 DEG C, the encapsulant that the present invention provides does not has crystallize, does not has
There is new generation mutually, be amorphous glass phase in this temperature range always, be conducive to carrying out the sealing-in of SOFC.
Image sintering experiment and XRD test show, the nodularization point of the encapsulant that the present invention provides is low, nodularization temperature range
Scope is wide, the sealing-in of beneficially SOFC.
5 element cell heaps made by the encapsulant that the present invention uses the present embodiment to prepare, and seal temperature is 880 DEG C.
This 5 element cell heap includes monocell, connector and encapsulant, at the encapsulant of connector surrounding point glue desired thickness,
Then being coupled together piecemeal for 5 monocells by connector for dispensing glue, impressed pressure is 100kg, finally with 1 DEG C/
The heating rate of min is raised to 880 DEG C and seals, and is persistently incubated four hours at 880 DEG C, and cooling i.e. can get 5 unit electricity
Chi Dui.The performance of the 5 element cell heaps that the present embodiment is obtained by the present invention is tested, and concrete test process and test result are such as
Under:
The 5 element cell heaps prepared by the present embodiment carry out sealing property test, and test result is as it is shown on figure 3, Fig. 3 is this
5 element cells prepared by the encapsulant that inventive embodiments 1 obtains pile up the I-V curve figure at 750 DEG C, and wherein, 1 represents 750
At DEG C, 5 element cells pile up H2/ air=4.8/14sccm cm-2Under I-V curve；At 2 expressions 750 DEG C, 5 element cells pile up
H2/ air=6.3/19sccm cm-2Under I-V curve；At 3 expressions 750 DEG C, 5 element cells pile up H2/ air=9.5/
29sccm·cm-2Under I-V curve.As seen from Figure 5, at 750 DEG C, H2/ air=9.5/29sccm cm-2Under the conditions of, 5
Element 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, power
Density reaches 0.55W cm-2, illustrate that 5 element cell heaps have good sealing property.
The encapsulant that the present embodiment is prepared by the present invention is used in 5 element cell heaps carrying out sealing property test, test
As shown in Figure 4, Fig. 4 is the V-t curve chart of 5 element cell heaps prepared by the encapsulant that the embodiment of the present invention 1 obtains to result, its
In, 1 is the time dependent curve of voltage, and 2 is the time dependent curve of electric current.As seen from Figure 4,5 element cell heap
At 750 DEG C, H2/ air=6.3/19sccm cm-2Under with 35A constant-current discharge, working voltage 3.77V, monomer average voltage is
0.75V, runs power 132W, and 5 element cell heap stable operation 20h are undamped, show in running, favorable sealing property.
The encapsulant that the present embodiment is prepared by the present invention is used for the thermal circulation performance test of 5 element cell heaps, test knot
Fruit is as it is shown in figure 5, I-V before and after 5 element cell heap thermal cycles that Fig. 5 is the encapsulant that the embodiment of the present invention 1 obtains to be prepared
Curve chart, the I-V curve before wherein curve 1 is 5 element cell heap thermal cycles, curve 2 is the I-after 5 element cell heap thermal cycles
V curve.As seen from Figure 5,5 element cells pile up 750 DEG C, H2/ air=9.5/29sccm cm-2Under put with 35A constant current
Electricity, records 5 element cell heap open-circuit voltage 5.936V, and monomer average voltage is 1.187V, runs power 156W under monomer 0.7V；
5 element cell heaps are through once thoroughly thermal cycle, and 5 element cells pile up 750 DEG C, H2/ air=9.5/29sccm cm-2Under with
35A constant-current discharge, records 5 element cell heap open-circuit voltage 6.043V, average open-circuit voltage 1.209V, runs merit under monomer 0.7V
Rate 136W, power density 0.43W cm-2；As seen from Figure 5, through once thoroughly thermal cycle, 5 element cell heap open circuit electricity
Pressure does not declines, and favorable sealing property is described.
The encapsulant that the present embodiment is prepared by the present invention is used for the thermal circulation performance test of 5 element cell heaps, test knot
As shown in Figure 6, Fig. 6 is the V-t before and after 5 element cell heap thermal cycles prepared by the encapsulant that the embodiment of the present invention 1 obtains to fruit
Curve chart, wherein, curve 1 is the time dependent curve of voltage, and curve 2 is the time dependent curve of electric current.Permissible by Fig. 6
Finding out, 5 element cells pile up 750 DEG C, H2/ air=6.3/19sccm cm-2Under with 35A constant-current discharge, record 5 element cells
Heap open-circuit voltage 3.848V, monomer average voltage 0.770V, run power 134.7W, 5 element cell stack operation 20h stable without declining
Subtract；5 element cell heaps, through once thoroughly thermal cycle, are first down to 30 DEG C from 750 DEG C, are then warming up to 750 DEG C from 30 DEG C and carry out
Test, under the same conditions with 35A constant-current discharge, 5 element cell stack operation voltage 3.788V, monomer average voltage is
0.758V, runs power 132.5W, 5 element cell stack operation 17h；As seen from Figure 6, transport after 5 element cell heap thermal cycles
Row power only declines 2.2W than before thermal cycle, and the favorable sealing property of encapsulant is described.
The encapsulant that the present embodiment is prepared by the present invention is applied in 5 element cell heaps test, to the sealing after test
Material carries out sem analysis, and as shown in Figure 7 and Figure 8, Fig. 7 is amplification after the encapsulant test that the embodiment of the present invention 1 obtains to result
The SEM figure of 200 times, Fig. 8 is the SEM figure of amplification 1500 times after the encapsulant that the embodiment of the present invention 1 obtains is tested, and wherein, M is
Encapsulant.By Fig. 7 and Fig. 8 it can be seen that encapsulant does not almost find pore, the finest and close, the gas of encapsulant is described
Close property is fine.
Embodiment 2
The present invention weighs the Al of the component of following mass content: 13.4wt.%2O3, the SiO of 45.9wt.%2, 33.4wt.%
The B of CaO, 5wt.%2O3With the trace element of 2.2wt.%, wherein trace element includes Zn, Mg and F, said components is mixed rearmounted
In crucible, then the crucible that will be equipped with said components is placed in high temperature furnace, is warming up to 1500 DEG C with the heating rate of 5 DEG C/min,
At 1500 DEG C, melted 1.5h is in a liquid state to all components, opens the most rapidly high temperature furnace, is placed in cold by liquid composition in crucible
Water is cooled to room temperature rapidly, obtains encapsulant.
The encapsulant obtained is pressed into by the present inventionSequin, be placed in SJY type high temperature image sintering instrument
In, according to 1 DEG C/min temperature programming to 1100 DEG C, its softening performance to be observed, result is as it is shown in figure 9, Fig. 9 is the present invention
The encapsulant that embodiment 2 obtains image sintering figure between 750 DEG C～1000 DEG C, wherein, a2 is that encapsulant is at 800 DEG C
Under image sintering figure；B2 is encapsulant image sintering figure at 830 DEG C；C2 is encapsulant image at 850 DEG C
Sintering figure；D2 is encapsulant image sintering figure at 860 DEG C；E2 is encapsulant image sintering figure at 870 DEG C；f2
For encapsulant image sintering figure at 880 DEG C；G2 is encapsulant image sintering figure at 910 DEG C；H2 is sealing material
Material image sintering figure at 920 DEG C；I2 is encapsulant image sintering figure at 950 DEG C；J2 is that encapsulant is 1040
Image sintering figure at DEG C.
From fig. 9, it can be seen that the encapsulant about 910 DEG C that the present invention provides starts nodularization, nodularization temperature range is 910
DEG C～950 DEG C, nodularization temperature range is wide in range, is all beneficial to carry out the sealing-in of SOFC in this temperature range.
The encapsulant temperature that the present embodiment provides shows, from the in-situ TiC particles of room temperature to 1100 DEG C, the sealing that the present invention provides
Material does not has crystallize, does not has new generation mutually, is amorphous glass phase always, is conducive to carrying out the envelope of SOFC in this temperature range
Connect.
Image sintering experiment and XRD test show, the nodularization point of the encapsulant that the present invention provides is low, nodularization temperature range
Scope is wide, the sealing-in of beneficially SOFC.
Embodiment 3
The present invention weighs the Al of the component of following mass content: 12wt.%2O3, the SiO of 41wt.%2, the CaO of 29.8wt.%,
The B of 15wt.%2O3With the trace element of 2.2wt.%, wherein trace element includes Zn, Mg or F, said components mixing is placed on
In crucible, then the crucible that will be equipped with said components is placed in high temperature furnace, is warming up to 1500 DEG C with the rate of heat addition of 5 DEG C/min,
At 1500 DEG C, melted 2h is in a liquid state to all components, opens the most rapidly high temperature furnace, in liquid composition is placed in cold water in crucible
It is cooled to room temperature rapidly, obtains encapsulant.
The encapsulant obtained is pressed into by the present inventionSequin, be placed in SJY type high temperature image sintering instrument
In, according to 1 DEG C/min temperature programming to 1100 DEG C, its softening performance to be observed, as shown in fig. 10, Figure 10 is this to result
The encapsulant that inventive embodiments 3 obtains image sintering figure between 750 DEG C～1000 DEG C, wherein, a3 is that encapsulant exists
Image sintering figure at 800 DEG C；B3 is encapsulant image sintering figure at 830 DEG C；C3 is that encapsulant is at 850 DEG C
Image sintering figure；D3 is encapsulant image sintering figure at 860 DEG C；E3 is encapsulant image sintering at 870 DEG C
Figure；F3 is encapsulant image sintering figure at 880 DEG C；G3 is encapsulant image sintering figure at 920 DEG C；H3 is close
Closure material image sintering figure at 950 DEG C.
From fig. 10 it can be seen that the encapsulant about 850 DEG C of the present embodiment starts nodularization, nodularization temperature range is 850
DEG C～950 DEG C.
The encapsulant that the encapsulant that the present embodiment provides provides from the XRD present invention of room temperature to 1100 DEG C is not analysed
Crystalline substance, does not has new generation mutually, is amorphous glass phase always, is conducive to carrying out the sealing-in of SOFC in this temperature range.
Image sintering experiment and XRD test show, the nodularization point of the encapsulant that the present invention provides is low, nodularization temperature range
Scope is wide, the sealing-in of beneficially SOFC.
Embodiment 4
The present invention weighs the Al of the component of following mass content: 9.0wt.%2O3, the SiO of 48.9wt.%2, 27.0wt.%
The B of CaO, 13wt.%2O3With the trace element of 2.1wt.%, wherein trace element includes Zn, Mg and F, after said components being mixed
It is placed in crucible, then the crucible that will be equipped with said components is placed in high temperature furnace, is warming up to 1500 with the rate of heat addition of 8 DEG C/min
DEG C, at 1500 DEG C, melted 2h, opens the most rapidly high temperature furnace, is cooled to room rapidly in liquid composition is placed in cold water in crucible
Temperature, obtains encapsulant.
The nodularization point of the encapsulant that the embodiment of the present invention 4 prepares is 900 DEG C, nodularization temperature range be 900 DEG C～
960 DEG C, nodularization temperature range is wide in range, is conducive to the sealing-in of SOFC in this temperature range.
Embodiment 5
The present invention weighs the Al of the component of following mass content: 14.8wt.%2O3, the SiO of 35.0wt.%2, 33.4wt.%
The B of CaO, 15wt.%2O3With the trace element of 1.8wt.%, wherein trace element includes Zn, Mg and F, after said components being mixed
It is placed in crucible, then the crucible that will be equipped with said components is placed in high temperature furnace, is warming up to 1500 with the rate of heat addition of 5 DEG C/min
DEG C, at 1500 DEG C, melted 2h, opens the most rapidly high temperature furnace, is cooled to room rapidly in liquid composition is placed in cold water in crucible
Temperature, obtains encapsulant.
The nodularization point of the encapsulant that the embodiment of the present invention 5 prepares is 850 DEG C, nodularization temperature range be 850 DEG C～
930 DEG C, nodularization temperature range is wide in range, is conducive to the sealing-in of SOFC in this temperature range.
Embodiment 6
The present invention weighs the Al (OH) of the component of following mass content: 10wt.%3, the H of 39wt.%2SiO3, 35wt.%
CaCO3, the H of 15wt.%3BO3With the trace element of 1wt.%, wherein trace element includes Zn, Mg and F, after said components being mixed
It is placed in crucible, then the crucible that will be equipped with said components is placed in high temperature furnace, is warming up to 1500 with the rate of heat addition of 5 DEG C/min
DEG C, at 1500 DEG C, melted 2h, opens the most rapidly high temperature furnace, is cooled to room rapidly in liquid composition is placed in cold water in crucible
Temperature, obtains encapsulant.
The nodularization point of the encapsulant that the embodiment of the present invention 6 prepares is 870 DEG C, nodularization temperature range be 870 DEG C～
950 DEG C, 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 encapsulant, including following components: 9wt.%～15wt.%
Al2O3；The SiO of 35wt.%～50wt.%2；The B of CaO and 5wt.%～15wt.% of 25wt.%～35wt.%2O3.The present invention carries
The encapsulant of confession includes B2O3, B2O3As modifying ingredients, during sealing-in, B2O3In boron oxygen triangle body [BO3] layer
Face structure is to boron oxygen tetrahedron [BO4] rack-like structural transformation, under the synergism with other components, improve the sealing obtained
The thermal coefficient of expansion of material, reduces nodularization temperature and transition temperature.The encapsulant that the present invention provides has relatively low nodularization
Point and wider nodularization temperature range so that the requirement of sealing temperature is reduced by this encapsulant, the sealing-in of beneficially SOFC.Separately
Outward, the encapsulant that the present invention provides almost does not finds that pore, higher compactness make encapsulant have preferably and seal effect
Really.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (1)
1. an encapsulant, composed of the following components:
The Al of 12wt.%2O3；
The SiO of 41wt.%2；
The CaO of 29.8wt.%；
The B of 15wt.%2O3；
The trace element of 2.2wt.%；Described trace element is Zn；
Or
Composed of the following components:
The Al of 14.8wt.%2O3；
The SiO of 35.0wt.%2；
The CaO of 33.4wt.%；
The B of 15wt.%2O3；
The trace element of 1.8wt.%；Described trace element is Zn, Mg and F；
The preparation method of described encapsulant comprises the steps of:
The mixing of described component is placed in crucible, more described crucible is placed in high temperature furnace, with the rate of heat addition liter of 5 DEG C/min
Temperature is to 1500 DEG C, and at 1500 DEG C, melted 2h, opens the most rapidly high temperature furnace, the liquid composition in crucible is placed in cold water anxious
Speed is cooled to room temperature, obtains described encapsulant.
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| CN112331893B (en) * | 2020-10-28 | 2022-02-15 | 华中科技大学 | Flat-plate type solid oxide fuel cell and sealing method thereof |
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| US7964523B2 (en) * | 2008-06-19 | 2011-06-21 | Nihon Yamamura Glass Co., Ltd. | Composition for sealing glass |
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| US8691470B2 (en) * | 2008-11-12 | 2014-04-08 | Bloom Energy Corporation | Seal compositions, methods, and structures for planar solid oxide fuel cells |
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| CN1494176A (en) * | 2003-09-03 | 2004-05-05 | �й���ѧԺ�����о��� | Medium and high temperature sealing method of plate type solid oxide fuel battery and its sealing material |
| CN101801873A (en) * | 2007-08-22 | 2010-08-11 | 日本山村硝子株式会社 | Glass composition for sealing |
| CN101557007A (en) * | 2008-04-07 | 2009-10-14 | 托普索燃料电池股份有限公司 | Fuel cell stack |
| US7964523B2 (en) * | 2008-06-19 | 2011-06-21 | Nihon Yamamura Glass Co., Ltd. | Composition for sealing glass |
| CN101841052A (en) * | 2009-03-13 | 2010-09-22 | 托普索燃料电池股份有限公司 | Fuel cell pack |
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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 |