CN110380078A - Low-temperature sealing structure and method for sealing for metallic support type solid oxide fuel cell - Google Patents
Low-temperature sealing structure and method for sealing for metallic support type solid oxide fuel cell Download PDFInfo
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- CN110380078A CN110380078A CN201910656202.4A CN201910656202A CN110380078A CN 110380078 A CN110380078 A CN 110380078A CN 201910656202 A CN201910656202 A CN 201910656202A CN 110380078 A CN110380078 A CN 110380078A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0286—Processes for forming seals
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Low-temperature sealing structure and method for sealing for metallic support type solid oxide fuel cell, the invention belongs to metallic support type solid oxide fuel cell sealing technology fields, it causes metal support severe oxidation to damage to solve the problems, such as that existing method for sealing sealing temperature is excessively high.The low temperature sealing method carries out surface in the prefabricated nickel coating of cell piece metal support and stainless steel connector surface and is modified, the diffusion connection of matrix heat treatment reinforcement coating and matrix after nickel plating, sealing-in surface coating nanometer soldering paste is waited in cell piece, it waits for that sealing-in position is assembled with stainless steel connector, forms low-temperature sealing structure.The present invention selects small size nano-solder paste, under 250~350 DEG C of cryogenic conditions, realize the reliable sealing-in of low temperature of metallic support type solid oxide fuel cell, silver and nickel coating constitute sealing-in connector, the fabulous high temperature resistant anti-oxidation of plasticity avoids oxidative damage of cell piece metal support during sealing-in.
Description
Technical field
The invention belongs to metallic support type solid oxide fuel cell sealing technology fields, are mainly concerned with a kind of realization
The method for sealing and its sealing-in material of metallic support type fuel cell low-temperature sealing.
Background technique
With the aggravation of energy problem, probes into environmentally friendly energy development and become increasingly important.Solid oxide fuel
Battery (Solid Oxide Fuel Cell, SOFC) is since it is high with energy conversion efficiency, fuel tolerance is strong, power is close
Degree is high, pollutes the advantages that small and is paid close attention to by researcher.
It is supporter that traditional SOFC, which generallys use thicker YSZ electrolyte or Ni-YSZ anode, and ceramic material is as branch
The problems such as all there is battery processing difficulties, thermal-shock resistance difference and be not easily assembled in support body.In recent years, in order to overcome ceramic supporting body
Metallic support type solid oxide fuel cell (Metal- is prepared as supporter using metal material in existing defect
Suported Solid Oxide Fuel Cell, MS-SOFC) become research hotspot.It uses cheap stainless steel etc.
Metal greatly reduces the production and processing cost of SOFC as metal support material, while also strong with excellent machinery
Degree and thermal shock resistance, the technology of preparing of MS-SOFC monocell has tended to be mature at present, but must incite somebody to action in actual use
Single battery group sealing-in forms battery pile, to meet higher output voltage and demanded power output.
The sealing technology of mainstream includes glass compaction sealing, crunch seal and air reaction soldering at present.Compressing sealing-in is
Battery component and high temperature resistant packing material are compressed by load mechanical force load to realize sealing-in, easily operated and maintenance, still
Its defect is more, poor air-tightness, the poor influence practical application of long-term working stability.Glass ceramics sealing-in is by close to adjust
The CTE match degree of closure material and cell device, the method have many advantages, such as that easy to operate, air-tightness is good, property is easily adjusted, but it connects
Jointing temp is usually more than 850 DEG C, and the metal support of MS-SOFC can not be suitable for MS- by severe oxidation under the conditions of the temperature
The sealing-in of SOFC.Air reaction soldering, as connecting material, connects temperature more than 1000 using noble metal-metal oxide
DEG C, MS-SOFC metal support not only can be by severe oxidation under the condition of contact, while the oxide in solder and metal support
Body, which reacts, causes cell performance decay.
Oxidization burning loss of MS-SOFC cell piece functional layer during sealing-in in order to prevent need to seek new method and realize
The sealing-in of cell piece at a lower temperature, and fire-resistant oxidation resistant and the excellent connector of mechanical performance can be obtained.The burning of nano silver
Junction temperature is much lower compared to conventional powder, is applied to the law temperature joining of high power electronic device at present, is being lower than 400
DEG C connection at a temperature of can be obtained and have high-temperature service performance jointing, realize that the low temperature of MS-SOFC can using nano silver
It can avoid its oxidation during the connection process by connection while obtained jointing can be on active service under the high temperature conditions.Exploitation is suitable
Low temperature sealing method for metallic support type solid oxide fuel cell, it will help the commercialization of MS-SOFC battery pile
Operation realizes that high efficiency of energy is developed using promotion green low-carbon.
Summary of the invention
It is an object of the present invention to overcome the sealing temperature of existing method for sealing excessively high, lead to MS-SOFC metal support
The problem of severe oxidation, structure and medium temperature (~600 DEG C) military service demand for MS-SOFC, the invention proposes one kind to be applicable in
In the method for MS-SOFC battery pile nano silver low-temperature sealing, by the prefabricated nickel coating in sealing-in position to improve interface quality of connection.
Low-temperature sealing structure of the present invention for metallic support type solid oxide fuel cell is in metal connector
To the prefabricated connector Ni coating in sealing-in position, electronickelling processing is carried out in connector Ni coating surface, makes metal connector surface
Obtain crest array structure；In cell piece to electroplated Ni in the metal support of sealing-in position, cell piece Ni coating is obtained, in electricity
Pond piece Ni coating surface carries out electronickelling processing, so that cell piece surface is obtained crest array structure, in metal connector and battery
Soldering paste is applied between the sealing-in position of piece, forms the low-temperature sealing structure for being used for metallic support type solid oxide fuel cell；
Wherein the soldering paste is mixed by metal nanoparticle and ethylene glycol solution, metal nanoparticle Ag, Au,
Pt, Ag@Cu, Cu@Ag or Ag-Cu alloying pellet.
Nanometer Ag soldering paste of the present invention for low-temperature sealing is using ferrous sulfate solution as reducing agent, and silver nitrate solution is oxygen
The nano mattisolda with citric acid package of agent preparation.Electricity is all passed through on cell piece foam metal supporter and connector surface
Plating forms one layer of fine and close electroless nickel layer, electroplated structural is heat-treated a few hours under an inert atmosphere, promotes electroplated layer and base
Counterdiffusion between body improves the bonding strength of coating and matrix.Nano mattisolda is applied to cell piece and connector waits connecting
Surface is connect, cell piece-nano mattisolda-connector structure is formed, to realize cell piece and metal connector in cryogenic conditions
Lower sintering forms stable sealing-in connector.
Low temperature sealing method of the present invention for metallic support type solid oxide fuel cell is realized according to the following steps:
One, aqueous slkali is carried out to metal connector and MS-SOFC cell piece and cleans oil removing, the metal connection after obtaining alkali cleaning
Body and cell piece；
Two, by after cleaning metal connector and MS-SOFC cell piece be put into hydrochloric acid solution and carry out surface activation process,
Metal connector and MS-SOFC cell piece after being activated；
Three, preplating Ni is handled on the metal connector of activation and MS-SOFC cell piece surface respectively, is obtained with preplating
Ni layers of metal connector and cell piece；
Four, electronickelling processing is carried out to the metal connector and cell piece that have preplating Ni layers respectively, in Ni layers of table of preplating
It looks unfamiliar and grows the Ni coating with nano-chip arrays structure, obtain plating Ni metal connector and plate Ni cell piece；
Five, plating Ni metal connector and plating Ni cell piece that step 4 obtains are put into inert gas tubular type furnace, 400
It is heat-treated at~500 DEG C, obtains the metal connector with electroless nickel layer and cell piece；
Six, metal nanoparticle is uniformly mixed with ethylene glycol, obtains nano metal soldering paste；
Seven, by nano metal soldering paste by silk screen print method even application metal connector with electroless nickel layer to
Sealing-in surface of position obtains the metal connector coated with nano-solder paste；
Eight, the metal connector for being coated with nano-solder paste is dried in vacuo in drying box, the gold after being dried
Belong to connector；
Nine, Ni cell piece and the metal connector sandwich structure consisting after nano-solder paste and drying will be plated, applies assembly
Pressure carries out sealing-in, is put into Muffle furnace and carries out sealing-in, sealing-in process is to be warming up to 250~350 DEG C with 10~15 DEG C/min
Sealing temperature cools to room temperature with the furnace after 20~60min of soaking time, completes metallic support type solid oxide fuel cell
Low-temperature sealing.
Low temperature seal method of the present invention suitable for metallic support type solid oxide fuel cell includes following
The utility model has the advantages that
(a) for the present invention using the nano silver of organic matter package as sealing material, seal temperature need to only meet organic matter point
Sealing-in can be realized in solution temperature, and MS-SOFC metal support is avoided under 250~350 DEG C of cryogenic conditions in high intermediate temperature sealing
Oxidation corrosion, while production cost is reduced, the encapsulating method is easy to operate to be easy to mass production, is conducive to metallic support type
The popularization of solid oxide fuel cell.
(b) sealing material is fine silver material, and seal nipple dense structure is uniformly intermediate not to generate other phases, air-tightness and disconnected
Resistance to spalling is promoted.Silver and nickel coating composition sealing-in connector, the fabulous high temperature resistant anti-oxidation of plasticity, tissue with higher are steady simultaneously
It is qualitative.
(c) three-dimensional Ni nanometers of chip architectures of stainless steel connector and the preparation of cell piece surface, improve a nanometer connection procedure
Median surface bonding strength and reliability, while certain protective effect is played to stainless steel connector and battery sheet matrix, it keeps away
The excessive oxidation during being on active service is exempted from, it is therefore prevented that the Cr of fuel cell is poisoned, and improves the reliability of fuel cell.
Detailed description of the invention
Fig. 1 is the schematic diagram that the present invention is used for metallic support type solid oxide fuel cell low-temperature sealing structure；
Fig. 2 is the joint microstructure that embodiment one selects nanometer Ag soldering paste to obtain in 350 DEG C of low-temperature sealing MS-SOFC；
Fig. 3 is the jointing shear strength test figure that embodiment one obtains.
Specific embodiment
Specific embodiment 1: present embodiment is used for the low-temperature sealing knot of metallic support type solid oxide fuel cell
Structure is to carry out electronickelling on 4 surface of connector Ni coating to the prefabricated connector Ni coating 4 in sealing-in position in metal connector 3
Processing makes metal connector surface obtain crest array structure 5；In cell piece to be electroplated in sealing-in position metal support 1
Ni obtains cell piece Ni coating 2, carries out electronickelling processing on 2 surface of cell piece Ni coating, 1 surface of cell piece is made to obtain crest
Array structure 5 applies soldering paste 6 between metal connector 3 and the sealing-in position of cell piece 1, is formed solid for metallic support type
The low-temperature sealing structure of oxide body fuel cell；
Wherein the soldering paste 6 is mixed by metal nanoparticle and ethylene glycol solution, metal nanoparticle Ag,
Au, Pt, Ag@Cu, Cu@Ag or Ag-Cu alloying pellet.
Ag@Cu and Cu@Ag described in present embodiment are core-shell structured nanomaterials, and it is Cu that Ag@Cu expression core, which is Ag shell,
Cu@Ag indicates that core is Cu, and shell is Ag.Two kinds of Core-shell structure materials can be commercially available.
Specific implementation method two: the present embodiment is different from the first embodiment in that the partial size of metal nanoparticle is
5~30nm.
Specific implementation method three: the present embodiment is different from the first and the second embodiment in that the applied thickness of soldering paste 6
It is 30~50 μm.
Specific implementation method four: present embodiment is used for the low-temperature sealing side of metallic support type solid oxide fuel cell
Method follows the steps below to implement:
One, aqueous slkali is carried out to metal connector and MS-SOFC cell piece and cleans oil removing, the metal connection after obtaining alkali cleaning
Body and cell piece；
Two, by after cleaning metal connector and MS-SOFC cell piece be put into hydrochloric acid solution and carry out surface activation process,
Metal connector and MS-SOFC cell piece after being activated；
Three, preplating Ni is handled on the metal connector of activation and MS-SOFC cell piece surface respectively, is obtained with preplating
Ni layers of metal connector and cell piece；
Four, electronickelling processing is carried out to the metal connector and cell piece that have preplating Ni layers respectively, in Ni layers of table of preplating
It looks unfamiliar and grows the Ni coating with nano-chip arrays structure, obtain plating Ni metal connector and plate Ni cell piece；
Five, plating Ni metal connector and plating Ni cell piece that step 4 obtains are put into inert gas tubular type furnace, 400
It is heat-treated at~500 DEG C, obtains the metal connector with electroless nickel layer and cell piece；
Six, metal nanoparticle is uniformly mixed with ethylene glycol, obtains nano metal soldering paste；
Seven, by nano metal soldering paste by silk screen print method even application metal connector with electroless nickel layer to
Sealing-in surface of position obtains the metal connector coated with nano-solder paste；
Eight, the metal connector for being coated with nano-solder paste is dried in vacuo in drying box, the gold after being dried
Belong to connector；
Nine, Ni cell piece and the metal connector sandwich structure consisting after nano-solder paste and drying will be plated, applies assembly
Pressure carries out sealing-in, is put into Muffle furnace and carries out sealing-in, sealing-in process is to be warming up to 250~350 DEG C with 10~15 DEG C/min
Sealing temperature cools to room temperature with the furnace after 20~60min of soaking time, completes metallic support type solid oxide fuel cell
Low-temperature sealing.
Specific implementation method five: present embodiment and aqueous slkali described in step 1 unlike specific embodiment four with
Water is solution, and the component and content in alkali wash water are the NaOH, the Na of 20~30g/L of 10~25g/L2CO3With 20~45g/L's
Na3PO4。
Specific implementation method six: present embodiment uses temperature for 70~80 DEG C unlike specific embodiment five
Aqueous slkali impregnates 15~25min to metal connector and MS-SOFC cell piece and carries out cleaning oil removing.
Specific implementation method seven: unlike one of present embodiment and specific embodiment four to six described in step 2
Hydrochloric acid solution be in every liter of water be added 150~200mL mass concentration be 37% concentrated hydrochloric acid.
Specific implementation method eight: described in step 3 unlike one of present embodiment and specific embodiment four to seven
Pre-plating solution in preplating Ni processing takes water as a solvent, pre-plating solution component and content are as follows: the HCl and 80~120g/ of 80~100mL/L
The NiCl of L2·6H2O is under room temperature 3~5A/dm in current density2Under conditions of the metal connector and MS- that activate
5~6min is electroplated in SOFC cell piece in pre-plating solution.
Specific implementation method nine: described in step 4 unlike one of present embodiment and specific embodiment four to eight
Electroplate liquid in electronickelling processing takes water as a solvent, the component in electroplate liquid are as follows: the NiCl of 220~280g/L2·6H240 O ,~
The H of 80g/L3BO3With the C of 0.10~0.20g/L12H25SO4Na is 4~8A/dm in current density2Under conditions of have preplating Ni
5~7min is electroplated in the metal connector and cell piece of layer in electroplate liquid.
The temperature of present embodiment electroplate liquid is 45~55 DEG C, pH value 4~5.
Specific implementation method ten: step 5 vacuum is dry unlike one of present embodiment and specific embodiment four to nine
Dry temperature is 40~50 DEG C, and the dry time is 30~60min.
Specific implementation method 11: heat in step 5 unlike one of present embodiment and specific embodiment four to ten
The processing time is 1~3h.
Specific implementation method 12: present embodiment from unlike specific embodiment four to one of 11 in step 6
The mass ratio of metal nanoparticle and ethylene glycol is 8~10:1.
Specific implementation method 13: present embodiment from unlike specific embodiment four to one of 12 in step 9
The assembling pressure of application is 3~5MPa.
Embodiment one: the present embodiment for metallic support type solid oxide fuel cell low temperature sealing method according to
Lower step is implemented:
One, aqueous slkali is carried out to metal connector and MS-SOFC cell piece and cleans oil removing, the metal connection after obtaining alkali cleaning
Body and cell piece, for aqueous slkali using water as solution, the group in alkali wash water is divided into the NaOH of 10g/L, the Na of 20g/L2CO3With 20g/L's
Na3PO4, it the use of temperature is 80 DEG C, soaking time 20min；
Two, by after cleaning metal connector and MS-SOFC cell piece be put into the hydrochloric acid solution of concentration 1mol/L and carry out
Surface activation process 30s, metal connector and MS-SOFC cell piece after being activated；
Three, preplating Ni is handled on the metal connector of activation and MS-SOFC cell piece surface respectively, is obtained with preplating
Ni layers of metal connector and cell piece, wherein the pre-plating solution in preplating Ni processing takes water as a solvent, the component in pre-plating solution are as follows:
The NiCl of HCl and 100g/L that the mass concentration of 100mL/L is 37%2·6H2O is under room temperature 3A/ in current density
dm2Under conditions of the metal connector that activates and MS-SOFC cell piece 5min is electroplated in pre-plating solution；
Four, electronickelling processing is carried out to the metal connector and cell piece that have preplating Ni layers respectively, in Ni layers of table of preplating
It looks unfamiliar and grows the Ni coating with nano-chip arrays structure, obtain plating Ni metal connector and plate Ni cell piece；
Five, plating Ni metal connector and plating Ni cell piece that step 4 obtains are put into inert gas tubular type furnace, 450
Heat treatment 2h is carried out at DEG C, obtains the metal connector with electroless nickel layer and cell piece；
Six, nano-silver powder is uniformly mixed with ethylene glycol according to mass ratio 9:1, obtains nano metal soldering paste；
Seven, by nano metal soldering paste by silk screen print method even application metal connector with electroless nickel layer to
Sealing-in surface of position obtains the metal connector coated with nano-solder paste, and applied thickness is at 50 μm or so；
Eight, the metal connector for being coated with nano-solder paste is dried in vacuo in drying box, and drying temperature is 50 DEG C,
Drying time is 60min, the metal connector after being dried；
Nine, Ni cell piece and the metal connector sandwich structure consisting after nano-solder paste and drying will be plated, applies 5MPa
Assembling pressure carries out sealing-in, is put into Muffle furnace and carries out sealing-in, sealing-in process is the sealing-in temperature for being warming up to 350 DEG C with 10 DEG C/min
It spends, cools to room temperature with the furnace after soaking time 30min, complete the low-temperature sealing of metallic support type solid oxide fuel cell.
Electroplate liquid in the present embodiment step 4 takes water as a solvent, the component in electroplate liquid are as follows: the NiCl of 250g/L2·
6H2O, the H of 60g/L3BO3With the C of 0.15g/L12H25SO4Na is 5A/dm in current density2Under conditions of with preplating Ni layer
5min is electroplated in metal connector and cell piece in electroplate liquid, and temperature of electroplating solution is 45 DEG C.
The present embodiment battery sheet material is metallic support type cell piece, and anode layer is doped with Ce0.8Gd0.2O1.9With Ni's
ScYSZ ceramics, electrolyte are mixed electrolyte (the mixed ionic and electronic of ion and electronic conductor
Conductor, MIEC), cathode material is (La0.6Sr0.4)0.99CoO3-δ(LSC), metal support material is a kind of Fe22Cr
Ferritic stainless steel, metal connector are Fe23Cr ferritic stainless steel.
In order to intuitively show the mass effect of the present embodiment low-temperature sealing, to stainless steel connector and MS-SOFC cell piece
Joint microstructure after sealing-in is observed.The Typical Joints macrograph of 350 DEG C of acquisitions is as shown in Figure 2, the results showed that, nano silver
Close with two sides interface cohesion, pore-free flawless, welding point nano silver sintering degree is higher, forms fine and close connector group
It knits.Shear strength test is carried out to jointing, the result of acquisition is as shown in Figure 3.The result shows that can be real at 350 DEG C -400 DEG C
Existing cell piece and Metallic Interconnect Materials Used are reliably connected, and strength of joint reaches 12MPa.
Embodiment two: the present embodiment and step 6 unlike embodiment one are 9:1 by Au nano particle according to mass ratio
It is uniformly mixed with ethylene glycol solution.
Embodiment three: the present embodiment and step 6 unlike embodiment one are 9:1 by Pt nano particle according to mass ratio
It is uniformly mixed with ethylene glycol solution.
Example IV: the present embodiment is 9:1 by Ag@Cu nanometers according to mass ratio from step 6 unlike embodiment one
Grain and ethylene glycol solution uniformly mix.
Ag@Cu nucleocapsid connector nano particle in the present embodiment is commercially available.
Embodiment five: the present embodiment is 9:1 by Cu@Ag nanometers according to mass ratio from step 6 unlike embodiment one
Grain and ethylene glycol solution uniformly mix.
Cu@Ag nucleocapsid connector nano particle in the present embodiment is commercially available.
Embodiment six: the present embodiment receives Ag-Cu alloy for 9:1 according to mass ratio from step 6 unlike embodiment one
Rice grain and ethylene glycol solution uniformly mix.
Claims (10)
1. being used for the low-temperature sealing structure of metallic support type solid oxide fuel cell, it is characterised in that this is used for metal support
The low-temperature sealing structure of type solid oxide fuel cell is in metal connector (3) to the prefabricated connector Ni plating in sealing-in position
Layer (4) carries out electronickelling processing on connector Ni coating (4) surface, metal connector surface is made to obtain crest array structure
(5)；In cell piece to electroplated Ni in sealing-in position metal support (1), obtain cell piece Ni coating (2), in cell piece Ni
Coating (2) surface carries out electronickelling processing, so that cell piece (1) surface is obtained crest array structure (5), in metal connector (3)
Soldering paste (6) are applied between the sealing-in position of cell piece (1), are formed for the low of metallic support type solid oxide fuel cell
Intermediate temperature sealing structure；
Wherein the soldering paste (6) is mixed by metal nanoparticle and ethylene glycol solution, metal nanoparticle Ag, Au,
Pt, Ag@Cu, Cu@Ag or Ag-Cu alloying pellet.
2. the low-temperature sealing structure according to claim 1 for metallic support type solid oxide fuel cell, special
Sign is that the partial size of metal nanoparticle is 5~30nm.
3. the low-temperature sealing structure according to claim 1 for metallic support type solid oxide fuel cell, special
Sign is that the applied thickness of soldering paste (6) is 30~50 μm.
4. being used for the low temperature sealing method of metallic support type solid oxide fuel cell, it is characterised in that the method for sealing is pressed
Column step is realized:
One, aqueous slkali is carried out to metal connector and MS-SOFC cell piece and cleans oil removing, metal connector after obtaining alkali cleaning and
Cell piece；
Two, by after cleaning metal connector and MS-SOFC cell piece be put into hydrochloric acid solution and carry out surface activation process, obtain
Metal connector and MS-SOFC cell piece after activation；
Three, preplating Ni is handled on the metal connector of activation and MS-SOFC cell piece surface respectively, is obtained with preplating Ni layers
Metal connector and cell piece；
Four, electronickelling processing is carried out to the metal connector and cell piece that have preplating Ni layers respectively, it is raw in preplating Ni layer surface
The Ni coating with nano-chip arrays structure is grown, plating Ni metal connector is obtained and plates Ni cell piece；
Five, plating Ni metal connector that step 4 obtains and plating Ni cell piece are put into inert gas tubular type furnace, 400~
It is heat-treated at 500 DEG C, obtains the metal connector with electroless nickel layer and cell piece；
Six, metal nanoparticle is uniformly mixed with ethylene glycol, obtains nano metal soldering paste；
Seven, nano metal soldering paste is passed through into silk screen print method even application in the metal connector with electroless nickel layer to sealing-in
Surface of position obtains the metal connector coated with nano-solder paste；
Eight, the metal connector for being coated with nano-solder paste is dried in vacuo in drying box, and the metal after being dried connects
Junctor；
Nine, Ni cell piece and the metal connector sandwich structure consisting after nano-solder paste and drying will be plated, applies assembling pressure
Sealing-in is carried out, is put into Muffle furnace and carries out sealing-in, sealing-in process is the sealing-in for being warming up to 250~350 DEG C with 10~15 DEG C/min
Temperature cools to room temperature with the furnace after 20~60min of soaking time, completes the low temperature of metallic support type solid oxide fuel cell
Sealing-in.
5. the low temperature sealing method according to claim 4 for metallic support type solid oxide fuel cell, special
Sign is aqueous slkali described in step 1 using water as solution, and the component and content in alkali wash water are the NaOH of 10~25g/L, 20~
The Na of 30g/L2CO3With the Na of 20~45g/L3PO4。
6. the low temperature sealing method according to claim 4 for metallic support type solid oxide fuel cell, special
Sign is that the pre-plating solution in the processing of preplating Ni described in step 3 takes water as a solvent, pre-plating solution component and content are as follows: 80~
The NiCl of the HCl and 80~120g/L of 100mL/L2·6H2O is under room temperature 3~5A/dm in current density2Under conditions of
5~6min is electroplated in the metal connector and MS-SOFC cell piece of activation in pre-plating solution.
7. the low temperature sealing method according to claim 4 for metallic support type solid oxide fuel cell, special
Sign is that the electroplate liquid in the processing of electronickelling described in step 4 takes water as a solvent, the component in electroplate liquid are as follows: 220~280g/L
NiCl2·6H2O, the H of 40~80g/L3BO3With the C of 0.10~0.20g/L12H25SO4Na is 4~8A/dm in current density2
Under conditions of with preplating Ni layers metal connector and cell piece 5~7min is electroplated in electroplate liquid.
8. the low temperature sealing method according to claim 4 for metallic support type solid oxide fuel cell, special
Sign is in step 5 that heat treatment time is 1~3h.
9. the low temperature sealing method according to claim 4 for metallic support type solid oxide fuel cell, special
Sign is in step 6 that the mass ratio of metal nanoparticle and ethylene glycol is 8~10:1.
10. the low temperature sealing method according to claim 4 for metallic support type solid oxide fuel cell, special
Sign is that the assembling pressure applied in step 9 is 3~5MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403767A (en) * | 2020-03-31 | 2020-07-10 | 西安交通大学 | Solid oxide fuel cell/electrolyzer and stack structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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Application publication date: 20191025 |