CN104810536A - Half cell of solid oxide fuel cell, fuel cell and their manufacturing methods - Google Patents

Half cell of solid oxide fuel cell, fuel cell and their manufacturing methods Download PDF

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Publication number
CN104810536A
CN104810536A CN201410043562.4A CN201410043562A CN104810536A CN 104810536 A CN104810536 A CN 104810536A CN 201410043562 A CN201410043562 A CN 201410043562A CN 104810536 A CN104810536 A CN 104810536A
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dielectric substrate
carrier band
sintering
functional layer
anode
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张磊
谢斌
李明
籍伟杰
姜友松
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Kyrgyzstan Shier (hefei) Energy Technology Co Ltd
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Kyrgyzstan Shier (hefei) Energy Technology Co Ltd
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Priority to CN201410043562.4A priority Critical patent/CN104810536A/en
Publication of CN104810536A publication Critical patent/CN104810536A/en
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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
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a half cell of solid oxide fuel cell, a fuel cell and their manufacturing methods. The half cell orderly comprises an electrolyte layer, an optional functional layer and a supporting layer. The outer surface of the electrolyte layer is flat in a micrometer level. Preferably, the outer surface has a submicron or nanometer microstructure, or has a submicron or nanometer raised, undulating or branched structure. Preferably, the electrolyte layer is formed on the surface of a carrier tape by a spray-drying method so that an electrolyte green compact utilizes the carrier tape as a template and copies microscopic morphology of the surface of the carrier tape. The surface of the carrier tape is flat in a micrometer level. Preferably, through processing and modification, the surface of the carrier tape forms a submicron or nanometer microstructure so that the surface of the electrolyte layer contacting with the carrier tape forms a submicron or nanometer microstructure after sintering.

Description

The half-cell, fuel cell and preparation method thereof of Solid Oxide Fuel Cell
Technical field
The present invention relates to the half-cell of Solid Oxide Fuel Cell, Solid Oxide Fuel Cell and preparation method thereof.Specifically, the invention belongs to metal oxide ceramic thin film technique field, relate to more specifically and adopt spraying and curtain coating to combine to prepare the half-cell of Solid Oxide Fuel Cell and Solid Oxide Fuel Cell.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of fuel cell of structure of whole solid state, works using the metal oxide ceramic film with ionic conductivity as electrolyte at the higher temperature of 600 DEG C-1000 DEG C.Solid Oxide Fuel Cell has all solid state, more energy-efficient and to outstanding advantages such as the extensive adaptability of pluralities of fuel gas such as coal gas, natural gas, blenders, both large-scale stationary power generation factory had been suitable as, be suitable as again the small-sized electric generating apparatus of hospital, market, dormitory and outlying mountain area, the drive system of accessory power supply as vehicle steamer can also be used for.
Solid Oxide Fuel Cell monocell is sandwich structure, also known as anodolyte negative electrode sandwich construction (Positive-pole, Electrolyte and Negative-pole), forms primarily of the electrolyte of densification, the anode of porous and negative electrode.Anode and negative electrode mainly provide the place of fuel reaction, to the chemical reaction catalysis that electrode occurs and conduction current.Negative electrode and anode are not originally depleted and corrode in fuel cell use procedure.Fuel cell requirements electrode microstructure has conductive phase UNICOM and the large feature of reaction activated interfaces area, need simultaneously electrolyte and electrode thermal matching good, between electrode and dielectric substrate, usually add one deck electrode function layer.
Electrolyte Main Function is transport tape electron ion between the anode and cathode, thus the electric transmission of balance external circuit finally completes cell circuit, and electrolyte also plays a part to separate fuel gas and oxic gas simultaneously.Fuel cell requirements dielectric substrate air-tightness is good and conductance is high, free from flaw and pore on microcosmic; In order to reduce bath resistance, Solid Oxide Fuel Cell adopts 10 microns ~ 50 microns electrolytic thin-membranes.Electrolyte and electrode contact interface requirements good without laminar contact.The performance of microstructure on fuel cell of electrolyte and electrode has conclusive impact, and a key challenge of development Solid Oxide Fuel Cell adopts suitable preparation method to obtain the electrolyte-electrode microstructure meeting fuel cell requirements.
As film forming method; there is the physical methods such as ion plating method, plasma spraying, physical vaporous deposition; but the apparatus expensive that these methods use, cost are high, and the rate of film build of ion plating method and physical vaporous deposition is lower, is difficult to form the large production of scale.
In addition, also there is the chemical methodes such as chemical vapour deposition technique, electrochemical vapor deposition, sol-gel process, spray pyrolysis, but wherein the apparatus expensive, the cost that use of chemical vapour deposition technique, electrochemical vapor deposition is high, and reaction temperature is higher, and the gas that is corrosive is released.Although sol-gel process, spray pyrolysis cost are lower, sol-gel method craft procedure parameter is many, easily forms crackle in dry run, and coating is thin, and production efficiency is low; The salt reacted in spray pyrolysis has corrosivity, usually must heat-treat.
In addition, as lower-cost shaping method of ceramics, also there is the methods such as electrophoretic deposition, the tape casting, silk screen print method, slip casting/pressure filtration molding method, centrifugal casting.But the thickness evenness of electrophoretic deposition is not so good; Easily there is crackle in the tape casting silk and reticulated printing method; The production efficiency of slip casting/pressure filtration molding method is low, more easily forms crackle; Centrifugal casting reaction temperature is higher, and the gas that is corrosive is released.
Therefore, the factors such as comprehensive production technology, cost and rate of film build, the tape casting and spray-on process are the method for manufacturing thin film receiving more concern.
The tape casting production technology is simple, and with short production cycle, cost is lower, is applicable to preparation large area thin layer tabular ceramic material, has the low feature being applicable to preparing multi-layer compound structure material of cost; But traditional the tape casting is applicable to the film preparation of 25 ~ 2000 μm usually, be difficult to preparation 20 microns and following thin dense electrolyte film.Spray-on process technique is easy to control, cost is low, film forming area large, is applicable to preparation less than 20 microns films, is suitable for industrial production; But in existing fuel cell preparation technology, spray method needs usually using metallic salt as predecessor, the metallic salt predecessor of needs is mixed in proportion, sintering after spraying, predecessor is reacted and obtains ceramic membrane; Simultaneously easily there is cracking, delamination, the defect such as to peel off in existing spray method.The tape casting that single use is traditional and spray-on process prepare fuel cell, and processing step is complicated, and cost high finished product rate is low, limits the promotion and application of Solid Oxide Fuel Cell.
The open CN101515651A of Chinese patent application discloses a kind of preparation method of Solid Oxide Fuel Cell, and it adopts spraying and curtain coating to combine preparation Solid Oxide Fuel Cell.Specifically, it comprises following processing step: slurry of anode functional layer being sprayed is sprayed onto on substrate and obtains anode functional layer green compact under the drive of carrier gas; By anode slurry curtain coating in anode functional layer green compact, after drying, take off substrate, obtain functional layer-anode green compact; By the electrolyte sprays slurry prepared with metal-oxide powder, be sprayed onto under the drive of carrier gas on functional layer-anode green compact, obtain three-decker green compact; The three-decker green sintering of preparation is obtained anodic half-cell; The dielectric substrate of half-cell is prepared negative electrode and obtains fuel-cell single-cell.
But the electrolyte layer surface out-of-flatness using the method to obtain has a lot of projection and spherical agglomeration, and dielectric substrate has hole and crack, and compactness is bad.
In addition, in order to increase electrolyte and electrode contact, reduce interface resistance and increase catalytic activity, usually can control the microscopic appearance of bath surface.But common method of modifying carries out after blank sintering, and the electrolyte meter surface hardness after sintering is high, blank sintering becomes pottery, and complex process difficulty is large, particularly also needs to carry out again the microstructure that high-sintering process could modify bath surface.Bath surface such as after sintering by silk screen printing electrolyte powder, and then through high temperature sintering, obtains the bath surface with certain roughness.
Therefore, need a kind of preparation method of Solid Oxide Fuel Cell of improvement, to obtain thinner and that air-tightness is good dielectric substrate, and can control bath surface microstructure.
Summary of the invention
The present inventor studies in detail in order to solve the problem, found that, if employing spray-on process formation dielectric substrate and alternatively functional layer (comprising anode functional layer and cathode functional), then on spraying base substrate, form supporting layer (comprising anode support and cathode support layers), then dielectric substrate table green compact take carrier band as template duplicating carrier band surface microscopic topographic, bath surface microscopic appearance can be accurately controlled by the microscopic appearance controlling carrier band surface, not only can reduce the defects such as unsound crack and hole, the contact that can also increase electrolyte and electrode improves battery performance.In addition, as another advantage, the supporting layer base substrate of curtain coating shrinks in dry run, produces pressure, can increase the density of electrolyte base substrate to dielectric substrate base substrate, and high blank density is also conducive to improving the rear electrolytical compactness of sintering.
One object of the present invention is the half-cell providing a kind of Solid Oxide Fuel Cell, and it comprises dielectric substrate, optional functional layer and supporting layer successively, and described dielectric substrate is one or more layers; Described functional layer is one or more layers anode functional layer or one or more layers cathode functional; Described supporting layer is one or more layers anode support or one or more layers cathode support layers, wherein
The outer surface of described dielectric substrate is smooth on micro-meter scale, and preferably, described outer surface has sub-micron or nanocrystailine microstructures, and further preferably, described outer surface has the projection of sub-micron or Nano grade, fluctuating or dendritic morphology;
Preferably, described dielectric substrate uses spray drying process to be formed at carrier band on the surface, thus make electrolyte green compact take carrier band as template, copy the microscopic appearance on carrier band surface, the surface of described carrier band is smooth on micro-meter scale, preferably carrier band surface is through reprocessing and modification, be formed with sub-micron or nanocrystailine microstructures, thus the surface that dielectric substrate is contacted with carrier band forms sub-micron or nanocrystailine microstructures after sintering.
Another object of the present invention is the manufacture method of the half-cell providing a kind of Solid Oxide Fuel Cell, and it comprises:
1) spray drying process, described spray drying process comprises:
(a). use spray drying process to form one or more layers dielectric substrate on the surface at carrier band, make electrolyte green compact take carrier band as the microscopic appearance on template duplicating carrier band surface, and
(b). alternatively, dielectric substrate after the drying use spray drying process form one or more layers anode functional layer or one or more layers cathode functional,
Thus form spraying base substrate;
(2). curtain coating operation, described curtain coating operation is included in direct curtain coating on spraying base substrate and forms the anode support or cathode support layers that correspond to anode functional layer or cathode functional, and makes curtain coating body drying;
(3). separation circuit, described separation circuit comprises makes dried base substrate be separated with carrier band;
(4). sintering circuit, described sintering circuit comprises isolated for institute blank sintering, forms the half-cell of described Solid Oxide Fuel Cell.
Present invention also offers a kind of manufacture method of Solid Oxide Fuel Cell, described method be included in said method obtain Solid Oxide Fuel Cell half-cell on prepare corresponding negative electrode or anode.
In addition, the invention provides a kind of half-cell of Solid Oxide Fuel Cell, it is obtained by said method.
In addition, the invention provides a kind of Solid Oxide Fuel Cell, it is obtained by said method.
The half-cell of the Solid Oxide Fuel Cell made by the inventive method and battery, had the following advantages:
1. electrolyte thin and fine and close, ensure that its air-tightness and mechanical strength, decreases the internal resistance of cell simultaneously.It is believed that, this is because electrolyte is in preparation process, surface contacts with carrier band, and dielectric substrate table green compact take carrier band as template duplicating carrier band surface microscopic topographic, therefore can accurately control bath surface microscopic appearance by the microscopic appearance controlling carrier band surface.First carrier band surface is smooth on micro-meter scale, copies the defects such as the bath surface free from flaw of acquisition and hole, is conducive to improving electrolyte density; Secondly, control the sub-micron on carrier band surface or the microstructure of nanometer, the bath surface of preparation also tool sub-micron in need or nanocrystailine microstructures can be made; In addition, the supporting layer base substrate of curtain coating shrinks in dry run, produces pressure to dielectric substrate base substrate, can increase the density of electrolyte base substrate on the one hand, and it is fine and close that high blank density is also conducive to sintering rear electrolyte; Make on the other hand dielectric substrate billet surface and carrier band surface contact more closely, dielectric substrate is more accurate take carrier band as the microscopic appearance on template duplicating surface.
2. be easy to the microstructure in controlling functions layer and composition.Because employing spray-on process forms functional layer, therefore can by changing microstructure and the composition of parameter (spraying paste composition, spray time, spray rate etc.) the accurate controlling functions layer of spray process.
3. electrolyte, optional functional layer and supporting layer one step sintering can be made to obtain, thus Production Time and cost can be saved.
Accompanying drawing explanation
Fig. 1 is that anode support dry run shrinks the schematic diagram producing the densification of pressure promotion electrolyte base substrate.
Fig. 2 is the section of positive electrode support solid oxide fuel cell and the SEM picture of bath surface that prepare according to embodiment 1 method, and it has the three-decker of dielectric substrate-anode functional layer-anode support.
Fig. 3 is the section SEM picture of the cathode support Solid Oxide Fuel Cell prepared according to embodiment 2 method, and it has the three-decker of dielectric substrate-cathode functional-cathode support layers.
Fig. 4 is the SEM picture with the Solid Oxide Fuel Cell section of the anode function Rotating fields of Ni gradient distribution obtained according to embodiment 5 method, and it has the four-layer structure of electrolyte-anode functional layer one-anode functional layer two-anode support.
Fig. 5 is the impact of dispersant for the viscosity of electrolyte sprays slurry.
To be different binder content fine and close for electrolyte and the impact of evenness for Fig. 6.
Fig. 7 for a change obtains the SEM picture of bath surface and section after operating sequence according to embodiment 7 method.
Fig. 8 is the electrolyte green compact schematic diagram obtained according to the different operating mode of embodiment 1 method and embodiment 7 method.
Fig. 9 is the SEM picture of the electrolyte-anode support adopting embodiment 8 method to make according to the double-deck curtain coating of prior art.
Figure 10 is the monocell section and the SEM picture of bath surface that make according to embodiment 9, and it has the four-layer structure of SDC dielectric substrate-YSZ dielectric substrate-anode functional layer-anode-supported.
Figure 11 is the monocell section and the SEM picture of bath surface that make according to embodiment 10, and it has the double-decker of dielectric substrate-cathode support layers.
The bath surface that Figure 12 (a) prepares for the polyethylene film carrier band surface implementation having nano projection on surface according to embodiment 1 method.
Figure 12 (b) is for having through processing the bath surface that surface of aluminum plate that nanometer rises and falls continuously is prepared acquisition on surface according to embodiment 1 method.
Figure 12 (c) is for having the surperficial bath surface being prepared acquisition of macromolecule membrane carrier band of sub-micron dendritic microstructure on surface according to embodiment 1 method.
Embodiment
The present invention is described in detail below.
One, the half-cell of Solid Oxide Fuel Cell and the manufacture method of Solid Oxide Fuel Cell
1. spray-drying process
The manufacture method of the half-cell of Solid Oxide Fuel Cell of the present invention, comprises and adopts spray drying process to form dielectric substrate on carrier band, or form dielectric substrate and functional layer.
1.1. the formation of dielectric substrate
First spray drying process is used to form one or more layers dielectric substrate on the surface at carrier band.
As carrier band, any suitable carrier band can be used.Specifically, it can be organic polymer film, glass, metal or marble, but for cost, easily acquired and be convenient to the reasons such as suitability for industrialized production, is preferably polyethylene film or plate glass.
The key of Solid Oxide Fuel Cell is solid electrolyte, and the quality of solid electrolyte performance will determine the quality of fuel battery performance.Electrolyte plays a part to separate fuel gas and oxic gas.Fuel cell requirements dielectric substrate air-tightness is good, free from flaw and pore on microcosmic; In order to reduce bath resistance, Solid Oxide Fuel Cell needs to adopt thinner electrolytic thin-membrane.In addition, also require electrolyte and electrode contact interface good without laminar contact.
In a word, invention technician is known, as the electrolyte in Solid Oxide Fuel Cell, usually requires that it is fine and close as much as possible, thin as much as possible.This is the requirement of a contradiction.If the out-of-flatness on micro-meter scale of electrolyte surface, than if any the fluctuating or crack etc. of 5 μm, be just difficult to densification.In addition in order to the contact increased between electrolyte and electrode improves battery performance, usually bath surface is processed, sub-micron or nanoscale control microscopic appearance.
The present invention reaches above-mentioned requirements by using spray drying process to form dielectric substrate on the surface at carrier band.Reason is, by making electrolyte green compact be template with carrier band, can copy the microscopic appearance on carrier band surface.The surface of carrier band used is smoothly (namely do not comprise hole or the crack of diameter more than 5 μm on micro-meter scale, preferably do not comprise hole or the crack of diameter more than 2 μm, more preferably hole or the crack of diameter more than 1 μm is not comprised), thus the surface that dielectric substrate is contacted with carrier band is also smooth after sintering on micro-meter scale.
Preferably carrier band surface is through reprocessing and modification, form sub-micron in need or nanocrystailine microstructures, thus the surface making dielectric substrate contact with carrier band forms corresponding sub-micron or nanocrystailine microstructures after sintering, thus the contact added between electrolyte and electrode, improve battery performance.Further preferably, the surface that dielectric substrate contacts with carrier band has the projection of sub-micron or Nano grade, fluctuating or dendritic morphology after sintering.
More specifically, on the one hand owing to using spray-on process to form dielectric substrate, easily can control the thickness of dielectric substrate, obtain thin dielectric substrate; On the other hand because the carrier band that dielectric substrate is smooth on micro-meter scale is formed on the surface, which ensure that the planarization of electrolyte layer surface on micro-meter scale, easily obtain fine and close dielectric substrate; Particularly by controlling the sub-micron on carrier band surface or the microstructure of nanoscale, the microstructure of bath surface can also be controlled, promotes electrolyte and electrode contact and improve battery performance., smooth electrolyte layer surface is defined as the hole not comprising diameter more than 5 μm or crack herein, does not preferably comprise hole or the crack of diameter more than 2 μm, more preferably do not comprise hole or the crack of diameter more than 1 μm.
Usually, as well known to those skilled in the art, 0.1nm ~ 100nm is nanoscale, and 100nm ~ 1000nm is submicron-scale.
As electrolyte, it can be yttrium stable zirconium oxide (YSZ), gadolinium doped-ceria, samarium doping barium cerate or samarium doping cerium oxide (SDC).
Before spraying, preparation dielectric substrate spraying slurry, this dielectric substrate spraying slurry except containing except yttrium stable zirconium oxide (YSZ), gadolinium doped-ceria, samarium doping barium cerate or samarium doping cerium oxide (SDC), also comprises dispersant and binding agent and suitable solvent.As dispersant, it is preferably triethanolamine.As binding agent, it is preferably polyvinyl butyral resin.Relative to the gross weight of dielectric substrate spraying slurry, the content of dispersant is 0.4 ~ 2.4%, is preferably 0.5 ~ 2.2wt%, be more preferably 1.6 ~ 2%, most preferably be 1.8wt%, the content of binding agent is 0.6 ~ 3%, be preferably 0.7 ~ 2wt%, be also preferably 1.5 ~ 2.26%, most preferably be 1.88wt%.When the content of dispersant is in above-mentioned scope, the viscosity of the slurry obtained is low, has excellent dispersiveness and stability, and the electrolyte density after sintering is high.When the content of binding agent is in above-mentioned scope, electrolytical density is high, and the evenness of the bath surface after sintering reduces.As solvent, can be selected from ethanol, butanone, dibutyl phthalate, polyethylene glycol one or more.
Specifically, during configuration dielectric substrate spraying slurry, can adopt and add suitable solvent, dispersant and binding agent in the materials such as yttrium stable zirconium oxide (YSZ), gadolinium doped-ceria, samarium doping barium cerate or samarium doping cerium oxide (SDC), mixing also ball milling forms.For example, can by ball milling after the mixing of ethanol, triethanolamine and YSZ powder, the mass ratio of ethanol, triethanolamine and YSZ powder is 5 ~ 10:0.05 ~ 0.15:1, and be preferably 6:0.1:1, Ball-milling Time is 12 ~ 48h, is preferably 18 ~ 24h; Then dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin is added, continue ball milling, the mass ratio of dibutyl phthalate, polyethylene glycol and binding agent and YSZ powder is 0.05 ~ 0.15:0.05 ~ 0.5:0.07 ~ 0.2:1, be preferably 0.1:0.1:0.14:1, Ball-milling Time is 12 ~ 48h, is preferably 18 ~ 24h.
The dielectric substrate obtained by the way spraying slurry is sprayed on carrier band by carrier gas (such as compressed air).For example, the pressure of carrier gas can be 0.05 ~ 0.25MPa, be preferably 0.12 ~ 0.15MPa, spray rate is 5 ~ 15mL/min, and be preferably 10mL/min, spray time is 5 ~ 45min, be preferably 15min, carrier band temperature is 20 ~ 50 DEG C, is preferably 40 ~ 45 DEG C, forms dielectric substrate green layer after dry.
After spraying blank sintering, the thickness of dielectric substrate is 3 μm ~ 20 μm, is preferably 5 μm ~ 10 μm.When the thickness of rear for sintering dielectric substrate is remained on this scope, can be ensure the air-tightness of dielectric substrate and there is certain mechanical strength, also make to decrease the internal resistance of cell simultaneously.
1.2. the formation of functional layer
Secondly, alternatively dielectric substrate after the drying use spray drying process to form one or more layers functional layer.
Functional layer is optional layer.Functional layer can reduce the stress of electrolyte and supporting layer, improves the performance of battery, improves rate of finished products.In addition, functional layer can also be prepared into the distribution of the catalytic active component made in male or female in gradient, thus increase contacting of electrolyte and supporting layer, improve reactivity.
Usually, functional layer and supporting layer have identical or close one-tenth and are grouped into.But compared with supporting layer, functional layer has meticulous microstructure, larger specific area is good with each general character that is connected, and its reacting catalytic performance is high.Add functional layer and can significantly improve battery output.
Therefore, in a preferred embodiment of the invention, spray drying process is used to form one or more layers functional layer on the electrolyte layer.
Functional layer can be anode functional layer or cathode functional.
As anode functional layer, NiO/YSZ material can be adopted.Ni wherein except anode current conductive capability is provided, also to H 2deng fuel gas, there is good catalytic activity.YSZ wherein, can make itself and dielectric substrate have close thermal coefficient of expansion on the one hand, increases the tack of anode on electrolyte, can prevent the undue sintering of Ni particle on the other hand and cause its active reduction; In addition, YSZ can also provide ionic conductance component in the anode, increases gas phase/electrolyte/Metal Phase three phase boundary (TPB), i.e. response area of electrode.In addition, as anode functional layer, also other materials can be adopted, such as gadolinium doped-ceria.
As cathode functional, La can be adopted 1-Xsr xmnO 3-δ(LSM, x are 0.15 ~ 0.3)/YSZ material.La 1-Xsr xmnO 3there is strong reducing power thus guarantee oxygen ions migrate number, higher electronic conductivity and ionic conductivity, good thermo-chemical stability and the chemical compatibility with electrolyte.The effect of YSZ as hereinbefore.In addition, as cathode functional, also other materials can be adopted, the cobalt acid samarium of such as strontium doping.
Before spraying function layer, preparation male or female functional layer spraying slurry.
Such as, for the spraying slurry of anode functional layer, can add suitable solvent, dispersant and binding agent in NiO/YSZ material, mixing also ball milling forms.For example, ethanol, triethanolamine, YSZ powder, NiO powder are preferably 10 ~ 15:0.15 ~ 0.25:0.5 ~ 1:1 according to mass ratio, are more preferably the rear ball milling 18 ~ 24h of 13:0.18:0.8:1 mixing.Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, its quality and NiO powder ratio are respectively 0.05 ~ 0.15:0.05 ~ 0.15:0.05 ~ 0.15:1, are preferably 0.1:0.1:0.1:1, continue ball milling 18 ~ 24h.
For the spraying slurry of cathode functional, can at La 1-Xsr xmnO 3add suitable solvent, dispersant and binding agent in/YSZ material, mixing also ball milling forms.For example, by ethanol, triethanolamine, YSZ powder, La 0.8sr 0.2mnO 3powder is 10 ~ 15:0.15 ~ 0.25:0.5 ~ 1:1 according to mass ratio, is preferably the rear ball milling 18 ~ 24h of 13:0.18:1:1 mixing.Then dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin is added, its quality and La 0.8sr 0. 2mnO 3powder ratio is respectively 0.05 ~ 0.15:0.05 ~ 0.15:0.05 ~ 0.15:1, is preferably 0.1:0.1:0.1:1, continues ball milling 18 ~ 24h.
Functional layer can be one or more layers anode functional layer or one or more layers cathode functional.When functional layer is multilayer, the concentration of the catalyst component in functional layer can distribution gradient, can reduce the difference with electrolyte in thermal property further, avoid occurring bonding during sintering.For the object reducing cost and Simplified flowsheet, functional layer is preferably two-layer.
Typically, for the making that functional layer makes, require to control microstructure and composition, such as along with thickness increases, in functional layer, the ratio of the catalyst component such as nickel oxide improves, and particle is greatly thicker, and porosity improves.By controlling microstructure and composition, catalytic activity and the structural stability of functional layer can be improved.
Because the present invention prepares functional layer by spray-on process, therefore can by changing the parameter (spraying paste composition, spray time, spray rate etc.) of spray process and the accurately microstructure of controlling functions layer and composition.
The functional layer obtained by the way spraying slurry is sprayed on electrolyte green layer by carrier gas (such as compressed air).For example, the pressure of carrier gas can be 0.05 ~ 0.25MPa, and be preferably 0.12 ~ 0.15MPa, spray rate is 5 ~ 15mL/min, be preferably 10mL/min, spray time is 5 ~ 45min, is preferably 15min, carrier band temperature is 20 ~ 50 DEG C, is preferably 40 ~ 45 DEG C, forms functional layer after drying.
After spraying blank sintering, the thickness of functional layer is for being preferably 10 ~ 30 μm, is more preferably 15 ~ 25 μm.This is because catalytic activity region mainly concentrates in above-mentioned scope, particularly concentrate within 25 μm.Blocked up functional layer can hinder reacting gas to be diffused into active region.
In spray-drying process, by the circulation of spray-drying-spray-drying repeatedly, achieve the multilayer base substrate of heterogeneity and thickness, thus define dielectric substrate and functional layer successively on carrier band.Solvent and the additive level of the slurry of wherein spraying are controlled, the composition of the ceramic powder contained by slurry is controlled, slurry spray amount with spraying body drying after thickness there is proportionate relationship, after spraying blank sintering, thickness (when not using function layer, refers to the thickness of dielectric substrate; When using function layer, refer to the gross thickness of dielectric substrate and functional layer) be 3-100 μm, be preferably 10 ~ 40 μm, most preferably be 25 ~ 30 μm.
2. casting processes
This process to be included on spraying base substrate that step 1 formed directly curtain coating and to form anode support or cathode support layers, and makes curtain coating body drying.
Specifically, when not forming functional layer, can on dielectric substrate after the drying directly curtain coating form above-mentioned supporting layer; And when forming functional layer, in functional layer after the drying, curtain coating forms above-mentioned supporting layer.It is pointed out that, when not forming functional layer, supporting layer itself can play the effect of functional layer.
As anode support or cathode support layers, it adopts the material identical with anode functional layer or cathode functional.Such as anode support, can adopt NiO/YSZ material, and cathode support layers can adopt La 1-Xsr xmnO 3(LSM, x are 0.15 ~ 0.3)/YSZ material.By such mode, make their thermal property substantially identical, thus avoid the stripping sintering rear interlayer.But typically, the particle diameter of functional layer is less, and the particle diameter of supporting layer is larger.
For the slurry of anode support, also can add suitable solvent, dispersant and binding agent in NiO/YSZ material, mixing also ball milling forms.For example, be 1.2 ~ 1.6:0.06 ~ 0.1:0.6 ~ 1.0:1 by ethanol, triethanolamine, YSZ powder, NiO powder according to mass ratio, be preferably ball milling 18 ~ 24h after 1.44:0.08:0.8:1 mixing.Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, its quality and NiO powder ratio are respectively 0.12 ~ 0.16:0.12 ~ 0.16:0.2 ~ 0.3:1, are preferably 0.14:0.14:0.27:1, continue ball milling 18 ~ 24h.
For cathode support layers, can at La 1-Xsr xmnO 3add suitable solvent, dispersant and binding agent in/YSZ material, mixing also ball milling forms.For example, can by ethanol, triethanolamine, YSZ powder, La 0.8sr 0.2mnO 3powder is 1.2 ~ 1.6:0.06 ~ 0.1:0.6 ~ 1.0:1 according to mass ratio, is preferably the rear ball milling 18 ~ 24h of 1.44:0.08:1:1 mixing.Then dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin is added, its quality and La 0.8sr 0.2mnO 3powder ratio is respectively 0.12 ~ 0.16:0.12 ~ 0.16:0.2 ~ 0.3:1, is preferably 0.14:0.14:0.27:1, continues ball milling 18 ~ 24h.
After above-mentioned casting slurry deaeration, on spraying base substrate, directly curtain coating forms anode support or cathode support layers.Casting technique can be water-based tape casting or non-aqueous tape-casting, and casting processes can be a curtain coating or repeatedly curtain coating, and after curtain coating blank sintering, thickness is 100-1200 μm.
3. sintering process
By the body drying after curtain coating, base substrate is separated with carrier band, by the multilayer base substrate one step co-sintering after separation, obtains the half-cell of anode-supported or the half-cell of cathode support.
For example, sintering process can for being warming up to 200-500 DEG C with the heating rate of 1 DEG C/min ~ 5 DEG C/min, keep a period of time, come unstuck to make base substrate, then be warming up to 1100-1500 DEG C (herein not to data) with the heating rate of 2 DEG C/min ~ 6 DEG C/min, keep 120-600min, preferred 200-400min.
Be included in the scouring processes in 200-500 DEG C of temperature range in sintering process of the present invention, described scouring processes accounts for the 10-25% of overall sintering time.
The object of coming unstuck occurs bubble and crackle to prevent in sintering procedure, makes burned product fine and close, do not occur peeling off.
After curtain coating, after overall blank sintering, thickness is 100-1200 μm, is preferably 300 μm ~ 1000 μm, most preferably is 500 μm ~ 750 μm.
By above-mentioned steps, electrolyte, optional functional layer and supporting layer one step sintering can be made to obtain, thus Production Time and cost can be saved.
Obtain after half-cells through above-mentioned 1,2,3 steps, by preparing corresponding negative electrode or anode can obtain complete Solid Oxide Fuel Cell on half-cell.
Two, soild oxide semi-fuel cell and Solid Oxide Fuel Cell
The present invention also provides a kind of half-cell of Solid Oxide Fuel Cell, comprise dielectric substrate, optional functional layer and supporting layer successively, described dielectric substrate is one or more layers, described functional layer is one or more layers anode functional layer or one or more layers cathode functional, described supporting layer is one or more layers supporting layer functional layer or one or more layers cathode support layers, and the outer surface of wherein said dielectric substrate is smooth on micro-meter scale.
Battery performance is improved in order to the contact increased between electrolyte and electrode, preferably, the outer surface of dielectric substrate has sub-micron or nanocrystailine microstructures, and further preferably, described outer surface has the projection of sub-micron or Nano grade, fluctuating or dendritic morphology.The outer surface of dielectric substrate is defined as the face relative with the contact-making surface of dielectric substrate and optional functional layer or dielectric substrate and supporting layer.When multilayer electrolyte layer, it is the face with functional layer or supporting layer distance dielectric substrate farthest.And when being assembled into Solid Oxide Fuel Cell, it is the face with negative electrode or positive contact.
In order to form said structure, dielectric substrate can use spray drying process to be formed at carrier band on the surface, thus make electrolyte green compact take carrier band as template, copy the microscopic appearance on carrier band surface, the surface of described carrier band is smooth on micro-meter scale, preferably carrier band surface is through reprocessing and modification, be formed with sub-micron or nanocrystailine microstructures, thus the surface that dielectric substrate is contacted with carrier band forms sub-micron or nanocrystailine microstructures after sintering.
Further preferably, the half-cell of Solid Oxide Fuel Cell of the present invention is prepared from by the manufacture method described in above-mentioned Part I.
The present invention also provides a kind of Solid Oxide Fuel Cell, and it for preparing corresponding negative electrode or anode and obtaining on the half-cell of above-mentioned Solid Oxide Fuel Cell.
Embodiment
In more detail the present invention is described by the following examples, but this and do not mean that protection scope of the present invention limits by these embodiments.
Embodiment 1:
The present embodiment is the Making programme of the Solid Oxide Fuel Cell of anode-supported, specifically realizes in such a way:
1) dielectric substrate spraying slurry preparation:
By ethanol, triethanolamine and YSZ powder according to mass ratio be 6:0.1:1 mixing after ball milling 18 ~ 24h; Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, the ratio of its quality and YSZ powder is respectively 0.1:0.1:0.14:1, continues ball milling 18 ~ 24h.
2) anode functional layer spraying slurry preparation:
By ethanol, triethanolamine, YSZ powder, NiO powder according to mass ratio be 13:0.18:0.8:1 mixing after ball milling 18 ~ 24h.Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, its quality and NiO powder ratio are respectively 0.1:0.1:0.1:1, continue ball milling 18 ~ 24h.
3) anode support casting slurry preparation:
By ethanol, triethanolamine, YSZ powder, NiO powder according to mass ratio be 1.44:0.08:0.8:1 mixing after ball milling 18 ~ 24h.Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, its quality and NiO powder ratio are respectively 0.14:0.14:0.27:1, continue ball milling 18 ~ 24h.
4) dielectric substrate spraying:
By step 1) dielectric substrate that obtains spraying slurry is sprayed on using compressed air as carrier gas on polyethylene carrier band, compressed-air actuated pressure is 0.12 ~ 0.15MPa, spray rate is 10mL/min, and spray time is 15min, and polyethylene carrier band remains on 40 ~ 45 DEG C.Dielectric substrate green layer is formed after dry.
5) anode functional layer spraying:
By step 2) anode functional layer that obtains spraying slurry is sprayed on the electrolyte green layer that step 4 obtains using compressed air as carrier gas, compressed-air actuated pressure 0.14 ~ 0.2MPa, spray rate is 10mL/min, and spray time is 20min, and polyethylene carrier band remains on 45 ~ 50 DEG C.Anode functional layer-dielectric substrate dual-layer green body layer is formed after drying.
6) anode support curtain coating:
By step 3) after the anode support casting slurry deaeration that obtains, on the anode functional layer that curtain coating obtains in step 5-dielectric substrate dual-layer green body layer, after drying, form anode support-anode functional layer-dielectric substrate three layers green compact.
7) green compact cut and sinter:
By step 6) three layers of green compact obtaining are separated with polyethylene carrier band, cut into the size of needs, obtain half-cells at 1350 ~ 1400 DEG C of sintering.
8) negative electrode makes:
In step 7) half-cell that obtains adopt the method for silk screen printing to make negative electrode green layer, then after 1100 ~ 1150 DEG C of sintering, obtain positive electrode support solid oxide fuel cell monocells.
Fig. 1 is employing the present embodiment mode processing step, to the schematic diagram that electrolyte densification promotes.Can be seen by figure, in anode support green compact dry run, can form the pressure to electrolyte green compact direction, this pressure can promote the densification of electrolyte green compact, thus improves sintered rear electrolyte compactness.
Fig. 2 is the SEM picture of monocell section and the bath surface adopting the present embodiment mode to make.The three-decker of dielectric substrate-anode functional layer-anode support can be seen from section; Dielectric substrate thickness is 15 μm, and anode function layer thickness is 20 μm; The thickness of anode support is 700 microns.Layering is not had, dielectric substrate dense non-porous hole between three layers.The smooth dense non-porous hole of bath surface can be seen from surface.
The present embodiment technological process is simple, and rate of finished products is high, the fine and close and surfacing of the single-celled electrolyte of acquisition.
Embodiment 2:
The present embodiment is the Making programme of the Solid Oxide Fuel Cell of cathode support, specifically realizes in such a way:
1) dielectric substrate spraying slurry preparation:
By ethanol, triethanolamine and YSZ powder according to mass ratio be 6:0.1:1 mixing after ball milling 18 ~ 24h; Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, the ratio of its quality and YSZ powder is respectively 0.1:0.1:0.14:1, continues ball milling 18 ~ 24h.
2) cathode functional spraying slurry preparation:
By ethanol, triethanolamine, YSZ powder, La 0.8sr 0.2mnO 3powder is the rear ball milling 18 ~ 24h of 13:0.18:1:1 mixing according to mass ratio.Then dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin is added, its quality and La 0.8sr 0.2mnO 3powder ratio is respectively 0.1:0.1:0.1:1, continues ball milling 18 ~ 24h.
3) cathode support layers casting slurry preparation:
By ethanol, triethanolamine, YSZ powder, La 0.8sr 0.2mnO 3powder is the rear ball milling 18 ~ 24h of 1.44:0.08:1:1 mixing according to mass ratio.Then dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin is added, its quality and La 0.8sr 0.2mnO 3powder ratio is respectively 0.14:0.14:0.27:1, continues ball milling 18 ~ 24h.
4) dielectric substrate spraying:
By step 1) dielectric substrate that obtains spraying slurry is sprayed on using compressed air as carrier gas on polyethylene carrier band, compressed-air actuated pressure 0.12 ~ 0.15MPa, spray rate is 10mL/min, and spray time is 15min, and polyethylene carrier band remains on 40 ~ 45 DEG C.Dielectric substrate green layer is formed after dry.
5) cathode functional spraying:
By step 2) anode functional layer that obtains spraying slurry is sprayed on step 4 using compressed air as carrier gas) on the electrolyte green layer that obtains, compressed-air actuated pressure 0.14 ~ 0.2MPa, spray rate is 10mL/min, and spray time is 10min, and polyethylene carrier band remains on 45 ~ 50 DEG C.Cathode functional-dielectric substrate dual-layer green body layer is formed after drying.
6) cathode support layers curtain coating:
By step 3) after the anode support casting slurry deaeration that obtains, on the cathode functional that curtain coating obtains in step 5)-dielectric substrate dual-layer green body layer, after drying, form cathode support layers-cathode functional-dielectric substrate three layers green compact.
7) green compact cut and sinter:
By step 6) three layers of green compact obtaining are separated with polyethylene carrier band, cut into the size of needs, obtain half-cells at 1150 ~ 1250 DEG C of sintering.
8) anode makes:
In step 7) half-cell that obtains adopt the method for silk screen printing to make anode green bodies layer, then after 1100 ~ 1150 DEG C of sintering, obtain cathode support Solid Oxide Fuel Cell monocells.
Fig. 3 is the SEM picture of monocell section and the bath surface adopting the present embodiment mode to make.The three-decker of dielectric substrate-cathode functional-cathode support layers can be seen from section; Dielectric substrate thickness is 15 μm, and cathode function layer thickness is 10 μm; The thickness of cathode support layers is 1000 μm, does not have layering between three layers, dielectric substrate dense non-porous hole.
The technological process of the present embodiment mode is simple, and rate of finished products is high, the fine and close and surfacing of the single-celled electrolyte of acquisition.
Embodiment 3:
The present embodiment mode and way of example one (i.e. the mode of embodiment 1) difference are: the spray rate of step 4) is 25mL/min, and spray time is 40min; The spray rate of step 5) is 10mL/min, and spray time is 3min.Other steps are identical with way of example one.
The present embodiment changes the amount of spraying, and the electrolyte thickness of acquisition is 100 μm, and anode function layer thickness is 3 μm, and the thickness of anode support is 800 μm.
Embodiment 4:
The present embodiment mode and way of example one difference are: step 4) is sprayed at surface of plate glass.Other steps are identical with way of example one.
Embodiment 5:
The present embodiment mode and way of example one difference are: step 2) and step 5)
2) anode functional layer spraying slurry preparation:
By ethanol, triethanolamine, YSZ powder, NiO powder according to mass ratio be 13:0.18:0.8:0.5 mixing after ball milling 18 ~ 24h.Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, its quality and NiO powder ratio are respectively 0.1:0.1:0.1:1, continue ball milling 18 ~ 24h, obtain anode functional layer spraying slurry 1.
By ethanol, triethanolamine, YSZ powder, NiO powder according to mass ratio be 13:0.18:0.8:1 mixing after ball milling 18 ~ 24h.Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, its quality and NiO powder ratio are respectively 0.1:0.1:0.1:1, continue ball milling 18 ~ 24h, obtain anode functional layer spraying slurry 2.
5) anode functional layer spraying:
By step 2) anode functional layer that obtains spraying slurry 1 is sprayed on step 4 using compressed air as carrier gas) on the electrolyte green layer that obtains, compressed-air actuated pressure 0.14 ~ 0.2MPa, spray rate is 10mL/min, and spray time is 5min, and polyethylene carrier band remains on 45 ~ 50 DEG C.Electrolyte-anode functional layer one green compact are obtained after drying.By step 2) anode functional layer that obtains spraying slurry 2 is sprayed on anode functional layer 1 green compact using compressed air as carrier gas, compressed-air actuated pressure 0.14 ~ 0.2MPa, spray rate is 10mL/min, and spray time is 5min, and polyethylene carrier band remains on 45 ~ 50 DEG C.Electrolyte-anode functional layer one-anode functional layer two green compact are obtained after drying.
Fig. 4 is SEM picture and the results of elemental analyses of the battery section that the present embodiment obtains.As we can see from the figure, section presents electrolyte-anode functional layer one-anode functional layer two-anode support four-layer structure.Wherein dielectric substrate thickness is about 20 μm, and anode functional layer one thickness is about 10 μm, and anode function layer thickness two is about 10 μm, and the thickness of anode support is 300 μm.The Ni content of anode functional layer one is lower than anode functional layer two, and the Ni content of anode functional layer two is similar to anode support.
The anode functional layer that the present embodiment mode obtains has Ni distribution feature in gradient, and this functional layer can improve reactivity, and increase electrolyte contacts with supporting layer, improves the rate of finished products of preparation.
Embodiment 6:
The present embodiment mode embodies the electrolyte in order to obtain smooth densification, the optimizing process for electrolyte sprays slurry:
1) dispersant (triethanolamine) content optimization: refer to Fig. 5, the content of dispersant has impact for spraying slurry, and the slurry that viscosity is minimum has best dispersiveness and stability, and the electrolyte density of preparation is the highest.
2) binding agent (polyvinyl butyral resin) content optimization: refer to Fig. 6, different binder content has impact for the electrolyte planarization prepared and density.As shown in Figure 6, when binder content brings up to 1.88% from 0.72%, electrolyte density improves, but after binder content increases above 1.88% further, electrolyte meter surface evenness reduces.
Embodiment 7:
The present embodiment mode is compare the impact of different operating order for electrolyte planarization and density.The present embodiment mode is similar to the method adopted in CN101515651A, they are different from way of example one (i.e. the method for embodiment 1) is: carry out step 4) electrolyte sprays, and first carry out the spraying of step 5) anode functional layer and step 6) anode support curtain coating, then the just dry rear anode function-anode support green compact obtained are separated with carrier band, carry out electrolyte sprays process on anode functional layer surface.
Fig. 7 is the SEM picture that the present embodiment mode obtains bath surface and section.Can see that bath surface out-of-flatness has a lot of projection and spherical agglomeration, and dielectric substrate has hole and crack, compactness is bad.
Fig. 8 is the schematic diagram that way of example one and way of example seven (i.e. the method for embodiment 7) cause obtaining electrolyte different-shape.The electrolyte green compact that spraying obtains form by forming bead accumulation after many spherical droplet dryings.According to way of example one, when being contacted with smooth carrier band by electrolyte layer surface, bath surface is smooth.According to way of example seven, when electrolyte Direct spraying is on functional layer surface, projection and spherical agglomeration can be formed.
Embodiment 8:
Fig. 9 is the SEM picture of the electrolyte-anode support using the double-deck curtain coating of prior art to make.Can see that ceramic material has double-layer structure, but use common casting technology, the structure of more than three layers or three layers cannot be made.The three-decker with anode functional layer can be prepared according to way of example one, add anode functional layer, the performance of battery can be improved, reduce the stress of electrolyte and supporting layer, improve rate of finished products.
Embodiment 9:
The present embodiment is the Making programme of the Solid Oxide Fuel Cell of anode-supported, specifically realizes in such a way:
1) samarium doping cerium oxide (SDC) dielectric substrate spraying slurry preparation:
By ethanol, triethanolamine and SDC powder according to mass ratio be 6:0.1:1 mixing after ball milling 18 ~ 24h; Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, the ratio of its quality and YSZ powder is respectively 0.1:0.1:0.14:1, continues ball milling 18 ~ 24h.
2) YSZ dielectric substrate spraying slurry preparation:
By ethanol, triethanolamine and YSZ powder according to mass ratio be 6:0.1:1 mixing after ball milling 18 ~ 24h; Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, the ratio of its quality and YSZ powder is respectively 0.1:0.1:0.14:1, continues ball milling 18 ~ 24h.
3) anode functional layer spraying slurry preparation:
By ethanol, triethanolamine, YSZ powder, NiO powder according to mass ratio be 13:0.18:0.8:1 mixing after ball milling 18 ~ 24h.Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, its quality and NiO powder ratio are respectively 0.1:0.1:0.1:1, continue ball milling 18 ~ 24h.
4) anode support casting slurry preparation:
By ethanol, triethanolamine, YSZ powder, NiO powder according to mass ratio be 1.44:0.08:0.8:1 mixing after ball milling 18 ~ 24h.Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, its quality and NiO powder ratio are respectively 0.14:0.14:0.27:1, continue ball milling 18 ~ 24h.
5) SDC dielectric substrate spraying:
By step 1) the SDC dielectric substrate that obtains spraying slurry is sprayed on using compressed air as carrier gas on polyethylene carrier band, compressed-air actuated pressure is 0.12 ~ 0.15MPa, spray rate is 10mL/min, and spray time is 3min, and polyethylene carrier band remains on 40 ~ 45 DEG C.Dielectric substrate green layer is formed after dry.
6) YSZ dielectric substrate spraying:
By step 2) the YSZ dielectric substrate that obtains spraying slurry is sprayed on using compressed air as carrier gas on SDC dielectric substrate, compressed-air actuated pressure is 0.12 ~ 0.15MPa, spray rate is 10mL/min, and spray time is 7min, and polyethylene carrier band remains on 40 ~ 45 DEG C.Dielectric substrate green layer is formed after dry.
7) anode functional layer spraying:
By step 3) anode functional layer that obtains spraying slurry is sprayed on the electrolyte green layer that step 4 obtains using compressed air as carrier gas, compressed-air actuated pressure 0.14 ~ 0.2MPa, spray rate is 10mL/min, and spray time is 10min, and polyethylene carrier band remains on 45 ~ 50 DEG C.Anode functional layer-dielectric substrate dual-layer green body layer is formed after drying.
8) anode support curtain coating:
By step 3) after the anode support casting slurry deaeration that obtains, on the anode functional layer that curtain coating obtains in step 5-dielectric substrate dual-layer green body layer, after drying, form anode support-anode functional layer-dielectric substrate three layers green compact.
9) green compact cut and sinter:
By step 8) three layers of green compact obtaining are separated with polyethylene carrier band, cut into the size of needs, obtain half-cells at 1350 ~ 1400 DEG C of sintering.
10) negative electrode makes:
In step 9) half-cell that obtains adopt the method for silk screen printing to make negative electrode green layer, then after 1100 ~ 1150 DEG C of sintering, obtain positive electrode support solid oxide fuel cell monocells.
Figure 10 is the SEM picture of monocell section and the bath surface adopting the present embodiment mode to make.The four-layer structure of SDC dielectric substrate-YSZ dielectric substrate-anode functional layer-anode support can be seen from section; SDC dielectric substrate thickness is 3 μm, and YSZ dielectric substrate thickness is 7 μm, and anode function layer thickness is 10 μm, and the thickness of anode support is 750 μm; Layering is not had, dielectric substrate dense non-porous hole between four layers.
The present embodiment technological process is simple, and rate of finished products is high, the fine and close and surfacing of the single-celled electrolyte of acquisition.
Embodiment 10:
The present embodiment is the Making programme of the Solid Oxide Fuel Cell of cathode support, specifically realizes in such a way:
1) dielectric substrate spraying slurry preparation:
By ethanol, triethanolamine and YSZ powder according to mass ratio be 5:0.1:1 mixing after ball milling 18 ~ 20h; Then add dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin, the ratio of its quality and YSZ powder is respectively 0.1:0.1:0.15:1, continues ball milling 18 ~ 20h.
2) cathode support layers casting slurry preparation:
By ethanol, triethanolamine, YSZ powder, La 0.8sr 0.2mnO 3powder is the rear ball milling 18 ~ 20h of 1.5:0.1:1:1 mixing according to mass ratio.Then dibutyl phthalate, polyethylene glycol and polyvinyl butyral resin is added, its quality and La 0.8sr 0.2mnO 3powder ratio is respectively 0.15:0.15:0.3:1, continues ball milling 18 ~ 20h.
3) dielectric substrate spraying:
By step 1) dielectric substrate that obtains spraying slurry is sprayed on using compressed air as carrier gas on polyethylene carrier band, compressed-air actuated pressure 0.12 ~ 0.15MPa, spray rate is 10mL/min, and spray time is 15min, and polyethylene carrier band remains on 40 ~ 45 DEG C.Dielectric substrate green layer is formed after dry.
4) cathode support layers curtain coating:
By step 2) after the cathode support layers casting slurry deaeration that obtains, on the dielectric substrate green layer that curtain coating obtains in step 3), after dry, form cathode support layers dielectric substrate dual-layer green body.
5) green compact cut and sinter:
By step 4) three layers of green compact obtaining are separated with polyethylene carrier band, cut into the size of needs, obtain half-cells at 1150 ~ 1250 DEG C of sintering.
6) anode makes:
In step 5) half-cell that obtains adopt the method for silk screen printing to make anode green bodies layer, then after 1100 ~ 1150 DEG C of sintering, obtain cathode support Solid Oxide Fuel Cell monocells.
Figure 11 is the SEM picture of monocell section and the bath surface adopting the present embodiment mode to make.The double-decker of dielectric substrate-cathode support layers can be seen from section; Dielectric substrate thickness is 15 μm, and the thickness of cathode support layers is 1000 μm, does not have layering between dielectric substrate and cathode support layers, and dielectric substrate is fine and close in connected holes.
The technological process of the present embodiment mode is simple, and rate of finished products is high, the fine and close and surfacing of the single-celled electrolyte of acquisition.
Embodiment 11:
The present embodiment is the microstructure by controlling carrier band surface, realizes controlling the microstructure of bath surface.The present embodiment manufacturing process is identical with embodiment 1, and difference is that the carrier band used is different.
Figure 12 (a) is for carrying out the bath surface prepared in the polyethylene film carrier band surface on surface with nano projection.As we can see from the figure, bath surface has nanometer projection.
Figure 12 (b) is for having through processing the bath surface that surface of aluminum plate that nanometer rises and falls continuously is prepared acquisition on surface.As we can see from the figure, bath surface has nano level continuous fluctuating.
The macromolecule membrane carrier band surperficial bath surface that be prepared acquisition of Figure 12 (c) for having sub-micron dendritic microstructure on surface.As we can see from the figure, bath surface has special sub-micron microstructure.
As can be seen here, adopting preparation method provided by the invention, by controlling the microstructure on carrier band surface, accurately can control sub-micron or the nanostructure of bath surface.

Claims (10)

1. a half-cell for Solid Oxide Fuel Cell, is characterized in that, comprise dielectric substrate, optional functional layer and supporting layer successively, described dielectric substrate is one or more layers; Described functional layer is one or more layers anode functional layer or one or more layers cathode functional; Described supporting layer is one or more layers anode support or one or more layers cathode support layers, wherein
The outer surface of described dielectric substrate is smooth on micro-meter scale, and preferably, described outer surface has sub-micron or nanocrystailine microstructures, and further preferably, described outer surface has the projection of sub-micron or Nano grade, fluctuating or dendritic morphology;
Preferably, described dielectric substrate uses spray drying process to be formed at carrier band on the surface, thus make electrolyte green compact take carrier band as template, copy the microscopic appearance on carrier band surface, the surface of described carrier band is smooth on micro-meter scale, preferably carrier band surface is through reprocessing and modification, be formed with sub-micron or nanocrystailine microstructures, thus the surface that dielectric substrate is contacted with carrier band forms sub-micron or nanocrystailine microstructures after sintering.
2. a manufacture method for the half-cell of Solid Oxide Fuel Cell, is characterized in that, described method comprises:
1) spray drying process, described spray drying process comprises:
(a). use spray drying process to form one or more layers dielectric substrate on the surface at carrier band, make electrolyte green compact be template with carrier band, copy the microscopic appearance on carrier band surface, and
(b). alternatively, dielectric substrate after the drying uses spray drying process form one or more layers anode functional layer or one or more layers cathode functional, thus form spraying base substrate;
(2). curtain coating operation, described curtain coating operation is included in direct curtain coating on spraying base substrate and forms the anode support or cathode support layers that correspond to anode functional layer or cathode functional, and makes curtain coating body drying;
Wherein said direct curtain coating adopts a curtain coating or repeatedly curtain coating;
(3). separation circuit, described separation circuit comprises makes dried base substrate be separated with carrier band;
(4). sintering circuit, described sintering circuit comprises isolated for institute blank sintering, forms the half-cell of described Solid Oxide Fuel Cell.
3. the manufacture method of half-cell as claimed in claim 2, it is characterized in that, described carrier band is organic polymer film, glass, metal, marble, is preferably polyethylene film, polypropylene film or plate glass,
Preferably, described electrolytical active component is yttrium stable zirconium oxide (YSZ), gadolinium doped-ceria, samarium doping barium cerate or samarium doping cerium oxide (SDC);
Preferably, described anode functional layer is NiO/YSZ material, and described cathode functional is La 1-Xsr xmnO 3/ YSZ material, x is 0.15 ~ 0.3,
Preferably, described anode support is NiO/YSZ material, and described cathode support layers is La 1-Xsr xmnO 3/ YSZ material, x is 0.15 ~ 0.3.
4. the manufacture method of half-cell as claimed in claim 2, it is characterized in that, the surface of described carrier band is smooth on micro-meter scale, thus the surface that dielectric substrate is contacted with carrier band is smooth after sintering on micro-meter scale,
Preferably, carrier band surface is through reprocessing and modify, and be formed with sub-micron or nanocrystailine microstructures, thus the surface that dielectric substrate is contacted with carrier band forms sub-micron or nanocrystailine microstructures after sintering,
It is further preferred that the surface that contacts with carrier band of described dielectric substrate sub-micron after sintering or nanocrystailine microstructures are the projection of sub-micron or Nano grade, fluctuating or dendritic morphology.
5. the manufacture method of half-cell as claimed in claim 2, it is characterized in that, described dielectric substrate thickness is after sintering 3 ~ 20 μm, is preferably 5 ~ 10 μm;
When there is functional layer, described functional layer thickness is after sintering 10 ~ 30 μm, is preferably 15 ~ 25 μm;
Preferably, after sintering, the thickness of spraying base substrate is 3 ~ 100 μm, is preferably 10 ~ 40 μm, most preferably is 25 ~ 30 μm;
Preferably, after curtain coating blank sintering, thickness is 100-1200 μm; Be preferably 300 μm ~ 1000 μm, most preferably be 500 μm ~ 750 μm;
Further preferably, after curtain coating, after overall blank sintering, thickness is 100-1200 μm, is preferably 300 μm ~ 1000 μm, most preferably is 500 μm ~ 750 μm.
6. the manufacture method of half-cell as claimed in claim 2, it is characterized in that, after described functional layer sintering, the content playing the composition of catalytic action in functional layer increases in gradient along from dielectric substrate to the direction of supporting layer, and preferably the described composition playing catalytic action is Ni or La 1-xsr xmnO 3.
7. the manufacture method of half-cell as claimed in claim 2, it is characterized in that, by curtain coating base substrate one step co-sintering during sintering, and be included in the scouring processes in 200-500 DEG C of temperature range, described scouring processes accounts for the 10-25% of overall sintering time.
8. a manufacture method for Solid Oxide Fuel Cell, is characterized in that, described method to be included in any one of claim 2 ~ 7 the half-cell of Solid Oxide Fuel Cell that obtains prepares corresponding negative electrode or anode.
9. a half-cell for Solid Oxide Fuel Cell, is characterized in that, it is obtained by the method according to any one of claim 2 ~ 7.
10. a Solid Oxide Fuel Cell, is characterized in that, it is obtained by method according to claim 8.
CN201410043562.4A 2014-01-28 2014-01-28 Half cell of solid oxide fuel cell, fuel cell and their manufacturing methods Pending CN104810536A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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