CN105397340A - Composite brazing filler material system for self-adaptive sealing of medium-temperature solid oxide fuel battery and brazing method of composite brazing filler material system - Google Patents
Composite brazing filler material system for self-adaptive sealing of medium-temperature solid oxide fuel battery and brazing method of composite brazing filler material system Download PDFInfo
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- CN105397340A CN105397340A CN201511023752.0A CN201511023752A CN105397340A CN 105397340 A CN105397340 A CN 105397340A CN 201511023752 A CN201511023752 A CN 201511023752A CN 105397340 A CN105397340 A CN 105397340A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/008—Soldering within a furnace
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
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Abstract
The invention discloses a composite brazing filler material system for self-adaptive sealing of a medium-temperature solid oxide fuel battery and a brazing method the composite brazing filler material system, belongs to the field of solid oxide fuel batteries and aims to solve the problems that the existing brazing-connected and brazing-sealed SOFC is relatively high in connection temperature and the reliability is not enough because of mismatching of thermal expansion coefficients of components. The composite brazing filler material system is composed of a prefabricated layer and a middle layer, wherein the middle layer takes an Ag-CuO brazing filler material as a base body; the base body contains two types of glass phases which are different in glass softening temperature. The brazing method comprises the following steps: (1) performing vapor deposition to obtain a Cu film; (2) preparing a mixed glass phase; (3) adding the mixed glass phase into the Ag-CuO brazing filler material to prepare brazing filler material mixed powder; (4) preparing an adhesive; (5) mixing the brazing filler material mixed powder with the adhesive; (6) coating composite brazing filler material paste; (7) performing high-temperature brazing. According to the composite brazing filler material system and the brazing method disclosed by the invention, two types of glass phases are added to improve the plastic deformation capability of the composite brazing filler material system, so the reliability of sealed batch production of the SOFC.
Description
Technical field
The invention belongs to SOFC technical field, be specifically related to a kind of composite soldering and the method for welding thereof that realize the reliable self adaptation sealing-in of intermediate temperature solid oxide fuel cell.
Background technology
SOFC (SolidOxideFuelCell, SOFC), it is a kind of novel energy technology, the reaction between fuel and oxide is realized by ion conduction in the electrolyte, directly converts chemical energy is become electric energy, substitute traditional fuel combustion process, not needing the energy conversion process through fuel chemical energy → heat energy → mechanical energy → electric energy, is a kind of all solid state chemical devices of clean and effective.But higher operating temperature causes SOFC length start-up time and sealing difficulty, and the reaction that high temperature accelerates between battery component simultaneously also can affect battery life, so reduction operating temperature is the key that SOFC obtains extensive use.Current, middle temperature (~ 800 DEG C) SOFC is widely studied, and is expected to obtain large-scale practical application.In solid-oxide fuel cell stack, multiple monocell is joined together to obtain desired voltage and exports, and connector is placed between independent battery, and repetitive forms battery pile.The positiver sealing realizing fuel cell is that SOFC obtains the key used reliably and with long-term.The seal request of battery avoids the leakage of mixing between fuel gas and oxidizing gas and gas.
Good fuel encapsulation needs sealing position to keep good heat endurance and electrical insulating property in use procedure, and possess the thermal coefficient of expansion matched with battery component, seal process needs to carry out at a lower temperature, avoids high temperature to cause damage to battery component.Meanwhile, encapsulant will keep the balance between wetability and viscosity, and while ensureing that encapsulant can well fill, sealing station of avoiding trickling pollutes SOFC.In order to meet these instructions for uses, a large amount of sealing systems is developed.Mainly comprise glass capsulation, compression seal and brazing.But all there is inherent shortcoming in above three kinds of encapsulating methods, cannot meet the instructions for use of SOFC completely.Recently, research reports a kind of sealing theory-self-adapting seal completely newly, namely allows encapsulant to produce certain plastic deformation at service temperatures, to eliminate the thermal stress because variations in temperature produces, improves the operational reliability of SOFC battery pile.But also insufficient about the research of self-adapting seal at present, be still in the exploratory stage.
Summary of the invention
The connection temperature that the object of the invention is to solve existing brazing sealing SOFC is higher, the problem of the reliability deficiency that inter-module coefficient of thermal expansion mismatch causes, and be provided for composite soldering system and the method for welding thereof of the sealing-in of intermediate temperature solid oxide fuel cell self adaptation.
The composite soldering system that the present invention is used for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation is made up of preformed layer and intermediate layer, preformed layer is evaporation at the Cu thin layer of cell piece and connector sealing station, the Ag-CuO solder that intermediate layer mixes with Ag powder and CuO powder is for matrix, to be added with glass transition temperature be in the base the glassy phase A of 650 ~ 700 DEG C and glass transition temperature is the glassy phase B of 750 ~ 800 DEG C, and wherein in Ag-CuO solder, the content of CuO is 1 ~ 15mol%.
The method for welding that the present invention is used for the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in realizes according to following steps:
One, Cu thin layer in vacuum evaporation respectively on the sealing surface of connector and cell piece, obtains plated film connector and plated film cell piece;
Two, to be the glassy phase A of 650 ~ 700 DEG C and glass transition temperature by glass transition temperature be, and the glassy phase B mixing of 750 ~ 800 DEG C is pulverized, and obtains hybrid glass phase after crossing 300 ~ 400 mesh sieves;
Three, the Ag powder taken and the mixing of CuO powder, obtain Ag-CuO solder, in Ag-CuO solder, then add the hybrid glass phase that step 2 obtains, add absolute ethyl alcohol and carry out ball milling, cross 300 ~ 400 mesh sieves, obtain solder mixed-powder after drying;
Four, ethyl cellulose is dissolved in terpinol, obtains terpineol solution of ethyl cellulose bonding agent;
Five, solder mixed-powder step 3 obtained joins in terpineol solution of ethyl cellulose bonding agent, mixes and obtains intermediate layer composite soldering cream;
Six, adopt the method for serigraphy to be coated on the sealing surface of plated film cell piece by intermediate layer composite soldering cream, obtain the cell piece being coated with intermediate layer composite soldering cream;
Seven, the sealing surface of plated film connector is fitted with the sealing surface of cell piece being coated with intermediate layer composite soldering cream assemble, then Muffle furnace is put into, first 200 DEG C of insulation 30 ~ 50min degasification is warming up to, continue to be warming up to 300 ~ 400 DEG C of insulation 30 ~ 50min plastic removals, be warming up to the scope inside holding 5 ~ 30min of 1000 ~ 1050 DEG C again, be cooled to room temperature subsequently, complete the soldering of the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in;
The content of the glassy phase A wherein described in step 2 accounts for 1 ~ 20wt% of Ag-CuO solder, and the content of glassy phase B accounts for 1 ~ 20wt% of Ag-CuO solder, and in step 3, the content of CuO accounts for 1 ~ 15mol% of Ag-CuO solder.
The advantage of self adaptation composite soldering system of the present invention is: the two kinds of glassy phases added, can in the actual use procedure of SOFC, occur softening after reaching corresponding glass softening point temperature, increase the plastic deformation ability of composite soldering system, the thermal stress produced due to SOFC inter-module coefficient of thermal expansion mismatch in heating process can be absorbed.Add the two kinds of glassy phases possessing different softening point, composite soldering system can be allowed to possess post deformation failure deformability, absorb thermal stress stage by stage, avoid composite soldering system plastic deformation ability to increase suddenly, the structural stability of SOFC is impacted.And the object of evaporation prefabricated Cu thin layer contacts in order to avoid glassy phase with by sealing the direct of matrix, because glassy phase can in use soften produce plastic deformation, if glassy phase appears on seal interface, can the performance that is tightly connected be reduced after softening, cause the slow leakage of gas.
Step 7 of the present invention adopts the method for air reaction brazing then can quantize technical process, add the reliability of SOFC sealing batch production, in air ambient, carry out the method connected simultaneously with Muffle furnace, reduce manufacturing cost, there is good commercial application prospect.
Accompanying drawing explanation
Fig. 1 is the structural representation of the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation of the present invention sealing-in;
The schematic diagram that plastic deformation absorbs thermal stress is there is in Fig. 2 after analog composite solder system reaches the softening temperature of glassy phase A and B;
Shearing strength of joint resolution chart after intermediate temperature solid oxide fuel cell self adaptation sealing-in soldered fitting 800 DEG C of elevated temperature thermal cycles that Fig. 3 obtains for embodiment one.
Detailed description of the invention
Detailed description of the invention one: the composite soldering system that present embodiment is used for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation is made up of preformed layer and intermediate layer, preformed layer is evaporation at the Cu thin layer of cell piece and connector sealing station, the Ag-CuO solder that intermediate layer mixes with Ag powder and CuO powder is for matrix, also to be added with glass transition temperature be in the base the glassy phase A of 650 ~ 700 DEG C and glass transition temperature is the glassy phase B of 750 ~ 800 DEG C, and wherein in Ag-CuO solder, the content of CuO is 1 ~ 15mol%.
Detailed description of the invention two: present embodiment and detailed description of the invention one are 1 ~ 2 μm unlike the thickness of described copper lamina.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two account for 1 ~ 20wt% of Ag-CuO solder unlike the addition of glassy phase A, this glassy phase A by mass percentage by 5% ~ 15% Li
2o, 25% ~ 35% SiO
2, the BeO of 15% ~ 25%, the B of 20% ~ 30%
2o
3form with the MgO of 10% ~ 15%.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three account for 1 ~ 20wt% of Ag-CuO solder unlike the addition of glassy phase B, and this glassy phase B is by mass percentage by 10% ~ 15%Na
2o, 30% ~ 40%SiO
2, 20% ~ 25%CaO, 10% ~ 20%B
2o
3with 10% ~ 20%Al
2o
3composition.
Detailed description of the invention five: the method for welding that present embodiment is used for the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in is implemented according to following steps:
One, Cu thin layer 3 in vacuum evaporation respectively on the sealing surface of connector 1 and cell piece 2, obtains plated film connector and plated film cell piece;
Two, to be the glassy phase A4 of 650 ~ 700 DEG C and glass transition temperature by glass transition temperature be, and the glassy phase B5 mixing of 750 ~ 800 DEG C is pulverized, and obtains hybrid glass phase after crossing 300 ~ 400 mesh sieves;
Three, the Ag powder taken and the mixing of CuO powder, obtain Ag-CuO solder 6, in Ag-CuO solder, then add the hybrid glass phase that step 2 obtains, add absolute ethyl alcohol and carry out ball milling, cross 300 ~ 400 mesh sieves, obtain solder mixed-powder after drying;
Four, ethyl cellulose is dissolved in terpinol, obtains terpineol solution of ethyl cellulose bonding agent;
Five, solder mixed-powder step 3 obtained joins in terpineol solution of ethyl cellulose bonding agent, mixes and obtains intermediate layer composite soldering cream;
Six, adopt the method for serigraphy to be coated on the sealing surface of plated film cell piece by intermediate layer composite soldering cream, obtain the cell piece being coated with intermediate layer composite soldering cream;
Seven, the sealing surface of plated film connector is fitted with the sealing surface of cell piece being coated with intermediate layer composite soldering cream assemble, then Muffle furnace is put into, first 200 DEG C of insulation 30 ~ 50min degasification is warming up to, continue to be warming up to 300 ~ 400 DEG C of insulation 30 ~ 50min plastic removals, be warming up to the scope inside holding 5 ~ 30min of 1000 ~ 1050 DEG C again, be cooled to room temperature subsequently, complete the soldering of the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in;
The content of the glassy phase A wherein described in step 2 accounts for 1 ~ 20wt% of Ag-CuO solder, and the content of glassy phase B accounts for 1 ~ 20wt% of Ag-CuO solder, and in step 3, the content of CuO accounts for 1 ~ 15mol% of Ag-CuO solder.
The web plate that the serigraphy of present embodiment step 6 is used, need previously prepared printed pattern, printed pattern is according to waiting that the actual graphical of sealing position is carried out prefabricated, and printed pattern and battery will be treated that envelope position is strictly aimed at by printing process, avoid other positions of solder paste pollution feul cell piece.
Detailed description of the invention six: present embodiment and detailed description of the invention five maintain 5 × 10 unlike vacuum in step one evaporate process
-2more than Pa, Current Control is at 120 ~ 150A, and Control of Voltage is at 10 ~ 15V.Other step and parameter identical with detailed description of the invention five.
Detailed description of the invention seven: present embodiment and detailed description of the invention five or six are 2 ~ 8wt% unlike the content of ethyl cellulose in step 4 terpineol solution of ethyl cellulose bonding agent.Other step and parameter identical with detailed description of the invention five or six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention five to seven are (2 ~ 4) unlike step 5 by weight: 1 solder mixed-powder step 3 obtained joins in terpineol solution of ethyl cellulose bonding agent.Other step and parameter identical with one of detailed description of the invention five to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention five to eight adopt 300 ~ 400 object web plates unlike in the method for the serigraphy described in step 6, and screen thickness is 100 ~ 200 μm.Other step and parameter identical with one of detailed description of the invention five to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention five to nine are 100 ~ 200 μm unlike the thickness of the intermediate layer composite soldering cream described in step 6.Other step and parameter identical with one of detailed description of the invention five to nine.
Embodiment one: the method for welding that the present embodiment is used for the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in realizes according to following steps:
One, on the sealing surface of connector and cell piece respectively in vacuum evaporation thickness be the Cu thin layer of 1 μm, obtain plated film connector and plated film cell piece;
Two, to be the glassy phase A of 680 DEG C and glass transition temperature by glass transition temperature be, and the glassy phase B mixing of 780 DEG C is pulverized, and obtains hybrid glass phase after crossing 300 mesh sieves;
Three, the Ag powder taken and the mixing of CuO powder, obtain Ag-CuO solder, in Ag-CuO solder, then add the hybrid glass phase that step 2 obtains, add absolute ethyl alcohol and carry out ball milling 3 hours, cross 300 mesh sieves, obtain solder mixed-powder at 100 DEG C after drying;
Four, be dissolved in terpinol by ethyl cellulose, obtain terpineol solution of ethyl cellulose bonding agent, wherein the addition of ethyl cellulose is 2wt%;
Five, join in terpineol solution of ethyl cellulose bonding agent by weight solder mixed-powder step 3 obtained for 2:1, mix and obtain intermediate layer composite soldering cream;
Six, use thickness to be that the 300 order web plates of 100 μm adopt the method for serigraphys to be coated on the sealing surface of plated film cell piece by intermediate layer composite soldering cream, the thickness controlling intermediate layer is 100 μm, obtains the cell piece being coated with intermediate layer composite soldering cream;
Seven, the sealing surface of plated film connector is fitted with the sealing surface of cell piece being coated with intermediate layer composite soldering cream assemble, then Muffle furnace is put into, first 200 DEG C of insulation 30min degasification is warming up to, continue to be warming up to 300 DEG C of insulation 30min plastic removals, be warming up to the scope inside holding 5min of 1000 DEG C again, be cooled to room temperature subsequently, complete the soldering of the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in;
Wherein in step 3 Ag-CuO solder, the content of CuO is 1mol%, and the addition of glassy phase A accounts for the 1wt% of Ag-CuO solder, and the addition of glassy phase B accounts for the 1wt% of Ag-CuO solder.
In order to intuitively show the quality of connection of battery component, Crofer22APU ferritic stainless steel (SOFC commonly uses metallic interconnect materials) and cell piece are processed into shearing sample, then carry out 800 DEG C of thermal cycle shear strength tests to soldered fitting, experimental result as shown in Figure 3.Result shows, soldered fitting maintains more than 150MPa 80 Thermal Cycling center tap shear strengths, and long term high temperature thermal cycle does not have butt joint performance and causes obvious impact.
Embodiment two: the method for welding that the present embodiment is used for the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in realizes according to following steps:
One, on the sealing surface of connector and cell piece respectively in vacuum evaporation thickness be the Cu thin layer of 1 μm, obtain plated film connector and plated film cell piece;
Two, to be the glassy phase A of 680 DEG C and glass transition temperature by glass transition temperature be, and the glassy phase B mixing of 780 DEG C is pulverized, and obtains hybrid glass phase after crossing 300 mesh sieves;
Three, the Ag powder taken and the mixing of CuO powder, obtain Ag-CuO solder, in Ag-CuO solder, then add the hybrid glass phase that step 2 obtains, add absolute ethyl alcohol and carry out ball milling 3 hours, cross 300 mesh sieves, obtain solder mixed-powder at 100 DEG C after drying;
Four, be dissolved in terpinol by ethyl cellulose, obtain terpineol solution of ethyl cellulose bonding agent, wherein the addition of ethyl cellulose is 2wt%;
Five, join in terpineol solution of ethyl cellulose bonding agent by weight solder mixed-powder step 3 obtained for 2:1, mix and obtain intermediate layer composite soldering cream;
Six, use thickness to be that the 300 order web plates of 100 μm adopt the method for serigraphys to be coated on the sealing surface of plated film cell piece by intermediate layer composite soldering cream, the thickness controlling intermediate layer is 100 μm, obtains the cell piece being coated with intermediate layer composite soldering cream;
Seven, the sealing surface of plated film connector is fitted with the sealing surface of cell piece being coated with intermediate layer composite soldering cream assemble, then Muffle furnace is put into, first 200 DEG C of insulation 30min degasification is warming up to, continue to be warming up to 300 DEG C of insulation 40min plastic removals, be warming up to the scope inside holding 10min of 1000 DEG C again, be cooled to room temperature subsequently, complete the soldering of the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in;
Wherein in step 3 Ag-CuO solder, the content of CuO is 4mol%, and the addition of glassy phase A accounts for the 2wt% of Ag-CuO solder, and the addition of glassy phase B accounts for the 5wt% of Ag-CuO solder.
Embodiment three: the method for welding that the present embodiment is used for the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in realizes according to following steps:
One, on the sealing surface of connector and cell piece respectively in vacuum evaporation thickness be the Cu thin layer of 1 μm, obtain plated film connector and plated film cell piece;
Two, to be the glassy phase A of 680 DEG C and glass transition temperature by glass transition temperature be, and the glassy phase B mixing of 780 DEG C is pulverized, and obtains hybrid glass phase after crossing 300 mesh sieves;
Three, the Ag powder taken and the mixing of CuO powder, obtain Ag-CuO solder, in Ag-CuO solder, then add the hybrid glass phase that step 2 obtains, add absolute ethyl alcohol and carry out ball milling 3 hours, cross 300 mesh sieves, obtain solder mixed-powder at 100 DEG C after drying;
Four, be dissolved in terpinol by ethyl cellulose, obtain terpineol solution of ethyl cellulose bonding agent, wherein the addition of ethyl cellulose is 2wt%;
Five, join in terpineol solution of ethyl cellulose bonding agent by weight solder mixed-powder step 3 obtained for 3:1, mix and obtain intermediate layer composite soldering cream;
Six, use thickness to be that the 400 order web plates of 100 μm adopt the method for serigraphys to be coated on the sealing surface of plated film cell piece by intermediate layer composite soldering cream, the thickness controlling intermediate layer is 100 μm, obtains the cell piece being coated with intermediate layer composite soldering cream;
Seven, the sealing surface of plated film connector is fitted with the sealing surface of cell piece being coated with intermediate layer composite soldering cream assemble, then Muffle furnace is put into, first 200 DEG C of insulation 40min degasification is warming up to, continue to be warming up to 300 DEG C of insulation 40min plastic removals, be warming up to the scope inside holding 15min of 1000 DEG C again, be cooled to room temperature subsequently, complete the soldering of the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in;
Wherein in step 3 Ag-CuO solder, the content of CuO is 4mol%, and the addition of glassy phase A accounts for the 5wt% of Ag-CuO solder, and the addition of glassy phase B accounts for the 5wt% of Ag-CuO solder.
Claims (10)
1. for the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in, it is characterized in that this composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation is made up of preformed layer and intermediate layer, preformed layer is evaporation at the Cu thin layer of cell piece and connector sealing station, the Ag-CuO solder that intermediate layer mixes with Ag powder and CuO powder is for matrix, to be added with glass transition temperature be in the base the glassy phase A of 650 ~ 700 DEG C and glass transition temperature is the glassy phase B of 750 ~ 800 DEG C, wherein in Ag-CuO solder, the content of CuO is 1 ~ 15mol%.
2. the composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation according to claim 1, is characterized in that the thickness of described copper lamina is 1 ~ 2 μm.
3. the composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation according to claim 1, is characterized in that the addition of glassy phase A accounts for 1 ~ 20wt% of Ag-CuO solder, this glassy phase A by mass percentage by 5% ~ 15% Li
2o, 25% ~ 35% SiO
2, the BeO of 15% ~ 25%, the B of 20% ~ 30%
2o
3form with the MgO of 10% ~ 15%.
4. the composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation according to claim 1, it is characterized in that the addition of glassy phase B accounts for 1 ~ 20wt% of Ag-CuO solder, this glassy phase B is by mass percentage by 10% ~ 15%Na
2o, 30% ~ 40%SiO
2, 20% ~ 25%CaO, 10% ~ 20%B
2o
3with 10% ~ 20%Al
2o
3composition.
5., for the method for welding of the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in, it is characterized in that following these steps to realize:
One, Cu thin layer in vacuum evaporation respectively on the sealing surface of connector and cell piece, obtains plated film connector and plated film cell piece;
Two, to be the glassy phase A of 650 ~ 700 DEG C and glass transition temperature by glass transition temperature be, and the glassy phase B mixing of 750 ~ 800 DEG C is pulverized, and obtains hybrid glass phase after crossing 300 ~ 400 mesh sieves;
Three, the Ag powder taken and the mixing of CuO powder, obtain Ag-CuO solder, in Ag-CuO solder, then add the hybrid glass phase that step 2 obtains, add absolute ethyl alcohol and carry out ball milling, cross 300 ~ 400 mesh sieves, obtain solder mixed-powder after drying;
Four, ethyl cellulose is dissolved in terpinol, obtains terpineol solution of ethyl cellulose bonding agent;
Five, solder mixed-powder step 3 obtained joins in terpineol solution of ethyl cellulose bonding agent, mixes and obtains intermediate layer composite soldering cream;
Six, adopt the method for serigraphy to be coated on the sealing surface of plated film cell piece by intermediate layer composite soldering cream, obtain the cell piece being coated with intermediate layer composite soldering cream;
Seven, the sealing surface of plated film connector is fitted with the sealing surface of cell piece being coated with intermediate layer composite soldering cream assemble, then Muffle furnace is put into, first 200 DEG C of insulation 30 ~ 50min degasification is warming up to, continue to be warming up to 300 ~ 400 DEG C of insulation 30 ~ 50min plastic removals, be warming up to the scope inside holding 5 ~ 30min of 1000 ~ 1050 DEG C again, be cooled to room temperature subsequently, complete the soldering of the composite soldering system of intermediate temperature solid oxide fuel cell self adaptation sealing-in;
The content of the glassy phase A wherein described in step 2 accounts for 1 ~ 20wt% of Ag-CuO solder, and the content of glassy phase B accounts for 1 ~ 20wt% of Ag-CuO solder, and in step 3, the content of CuO accounts for 1 ~ 15mol% of Ag-CuO solder.
6. the method for welding of the composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation according to claim 5, is characterized in that in step one evaporate process, vacuum maintains 5 × 10
-2more than Pa, Current Control is at 120 ~ 150A, and Control of Voltage is at 10 ~ 15V.
7. the method for welding of the composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation according to claim 5, is characterized in that the content of ethyl cellulose in step 4 terpineol solution of ethyl cellulose bonding agent is 2 ~ 8wt%.
8. the method for welding of the composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation according to claim 5, is characterized in that step 5 is (2 ~ 4) by weight: 1 solder mixed-powder step 3 obtained joins in terpineol solution of ethyl cellulose bonding agent.
9. the method for welding of the composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation according to claim 5, it is characterized in that adopting 300 ~ 400 object web plates in the method for the serigraphy described in step 6, screen thickness is 100 ~ 200 μm.
10. the method for welding of the composite soldering system for the sealing-in of intermediate temperature solid oxide fuel cell self adaptation according to claim 5, is characterized in that the thickness of the intermediate layer composite soldering cream described in step 6 is 100 ~ 200 μm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107359499A (en) * | 2017-07-09 | 2017-11-17 | 湖南省众精细陶瓷制造有限公司 | The packaging technology of ceramic discharge tube |
| CN108258263A (en) * | 2018-01-10 | 2018-07-06 | 哈尔滨工业大学 | For the low-temperature sealing structure and its method for sealing of solid oxide fuel cell |
| CN110405379A (en) * | 2018-04-27 | 2019-11-05 | 哈尔滨工业大学 | A kind of Ag-CuO-B2O3Its sapphire method of connection of solder, preparation method and utilization |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61143538A (en) * | 1984-12-17 | 1986-07-01 | Tanaka Kikinzoku Kogyo Kk | Silver material for ornament |
| JPH0917232A (en) * | 1995-06-30 | 1997-01-17 | Tanaka Kikinzoku Internatl Kk | Conductor paste composition |
| US20060239765A1 (en) * | 2005-04-22 | 2006-10-26 | Battelle Memorial Institute | Joint with application in electrochemical devices |
| US20100218875A1 (en) * | 2007-06-11 | 2010-09-02 | Battelle Memorial Institute | Diffusion barriers in modified air brazes |
| CN102699561A (en) * | 2012-06-21 | 2012-10-03 | 上海交通大学 | Composite brazing alloy for sealing solid oxide fuel cell and brazing technology of composite brazing alloy |
| CN102699558A (en) * | 2012-06-29 | 2012-10-03 | 哈尔滨工业大学 | Flexible composite middle layer brazing alloy and method of utilizing brazing ceramic and metal |
| CN103343247A (en) * | 2013-07-08 | 2013-10-09 | 深圳市亿铖达工业有限公司 | Method for adding trace elements during preparation of composite lead-free solder |
-
2015
- 2015-12-30 CN CN201511023752.0A patent/CN105397340B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61143538A (en) * | 1984-12-17 | 1986-07-01 | Tanaka Kikinzoku Kogyo Kk | Silver material for ornament |
| JPH0917232A (en) * | 1995-06-30 | 1997-01-17 | Tanaka Kikinzoku Internatl Kk | Conductor paste composition |
| US20060239765A1 (en) * | 2005-04-22 | 2006-10-26 | Battelle Memorial Institute | Joint with application in electrochemical devices |
| US20100218875A1 (en) * | 2007-06-11 | 2010-09-02 | Battelle Memorial Institute | Diffusion barriers in modified air brazes |
| CN102699561A (en) * | 2012-06-21 | 2012-10-03 | 上海交通大学 | Composite brazing alloy for sealing solid oxide fuel cell and brazing technology of composite brazing alloy |
| CN102699558A (en) * | 2012-06-29 | 2012-10-03 | 哈尔滨工业大学 | Flexible composite middle layer brazing alloy and method of utilizing brazing ceramic and metal |
| CN103343247A (en) * | 2013-07-08 | 2013-10-09 | 深圳市亿铖达工业有限公司 | Method for adding trace elements during preparation of composite lead-free solder |
Non-Patent Citations (1)
| Title |
|---|
| 刘泳良: "中温固体氧化物燃料电池密封材料的设计与性能研究", 《中国优秀硕士学位论文全文数据库-工程科技Ⅱ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107359499A (en) * | 2017-07-09 | 2017-11-17 | 湖南省众精细陶瓷制造有限公司 | The packaging technology of ceramic discharge tube |
| CN108258263A (en) * | 2018-01-10 | 2018-07-06 | 哈尔滨工业大学 | For the low-temperature sealing structure and its method for sealing of solid oxide fuel cell |
| CN108258263B (en) * | 2018-01-10 | 2020-04-24 | 哈尔滨工业大学 | Low temperature sealing method for solid oxide fuel cell |
| CN110405379A (en) * | 2018-04-27 | 2019-11-05 | 哈尔滨工业大学 | A kind of Ag-CuO-B2O3Its sapphire method of connection of solder, preparation method and utilization |
| CN110405379B (en) * | 2018-04-27 | 2020-11-13 | 哈尔滨工业大学 | Ag-CuO-B2O3Brazing filler metal, preparation method thereof and method for connecting sapphire by using brazing filler metal |
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