CN114388838A - Flat tube type solid oxide fuel cell and preparation method thereof - Google Patents

Flat tube type solid oxide fuel cell and preparation method thereof Download PDF

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Publication number
CN114388838A
CN114388838A CN202111662239.1A CN202111662239A CN114388838A CN 114388838 A CN114388838 A CN 114388838A CN 202111662239 A CN202111662239 A CN 202111662239A CN 114388838 A CN114388838 A CN 114388838A
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layer
sealing
support body
electrolyte
electrolyte layer
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CN114388838B (en
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应梦涛
曹宝华
官万兵
杨钧
王建新
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Zhejiang Hydrogen Technology Co ltd
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Zhejiang Hydrogen Technology Co ltd
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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
    • 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
    • H01M8/0276—Sealing means characterised by their form
    • 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
    • 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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • 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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
    • 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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1266—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing bismuth oxide
    • 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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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 flat tube type solid oxide fuel cell and a preparation method thereof, which solve the problems that in the sintering process of an electrolyte layer of the traditional flat tube type solid oxide fuel cell, the electrolyte layer used for sealing the side edge of a generated support body is not easy to be compact, the sealing performance is weakened, fuel is easy to leak, the width of the side edge of the support body cannot be unified through machining, and finally the sealing is difficult and the yield is low after a later-stage electric pile is integrated; the method effectively solves the problems by adding the methods of secondary mechanical processing, adjusting the preparation sequence of each functional layer, changing the sealing structure and material of side sealing, reducing the sintering temperature of the sealing layer and the like; the problem of original preparation technology is solved, the width size and the side flatness of the side edge can be controlled by machining after the side edge is sintered at high temperature, the side edge sealing effect is excellent, and the method has the advantages of being simple to operate, good in universality, high in product yield and safety, easy to standardize, capable of achieving large-scale production and the like.

Description

Flat tube type solid oxide fuel cell and preparation method thereof
Technical Field
The invention relates to the technical field of fuel cells, in particular to a flat tube type solid oxide fuel cell and a preparation method thereof.
Background
A solid oxide fuel cell (hereinafter, referred to as SOFC) is a power generation device having a high efficiency, no pollution, and an all-solid-state structure, and is capable of accommodating a variety of fuel gases without requiring an additional reformer. The SOFC is mainly composed of a support, an anode layer, an electrolyte layer, a barrier layer, and a cathode layer, wherein the anode layer, the electrolyte layer, the barrier layer, and the cathode layer are collectively referred to as a functional layer. SOFCs can be broadly classified into tubular, plate, and tubular types, wherein the flat-tube SOFC is a combination of a flat-plate SOFC and a tubular SOFC, and a common structure is to provide a hollow hole in an anode support layer, the hollow hole having an open end on a side of the anode support layer.
Patent CN201510104627.6 discloses a flat tube type solid oxide fuel cell with a symmetric structure, in which an anode layer, an electrolyte layer, a barrier layer, and a cathode layer are sequentially distributed on both the upper surface and the lower surface of a support, and the cell is of a symmetric structure with the support as the center. The preparation process comprises the following steps: preparing an anode layer, wherein the anode layer comprises a first anode layer and a second anode layer, the first anode layer is positioned on the upper surface of a support body, the second anode layer is positioned on the lower surface of the support body, the first anode layer is not connected with the second anode layer, and an electrolyte layer is prepared after low-temperature sintering; the electrolyte layer comprises a first electrolyte layer and a second electrolyte layer, the first electrolyte layer is positioned on the surface of the first anode layer, the second electrolyte layer is positioned on the surface of the second anode layer, the electrolyte layer is prepared on the side edge of the support body, the first electrolyte layer and the second electrolyte layer are connected through the electrolyte layers on the two sides, and a dense electrolyte is formed after high-temperature sintering, so that fuel in the porous support body is not leaked; preparing a barrier layer, wherein the first barrier layer is positioned on the surface of the first electrolyte layer, the second barrier layer is positioned on the surface of the second electrolyte layer, the first barrier layer is not connected with the second barrier layer, and the cathode layer is prepared after high-temperature sintering; the first cathode layer is positioned on the surface of the first barrier layer, the second cathode layer is positioned on the surface of the second barrier layer, the first cathode layer is not connected with the second cathode layer, and the full cell is obtained by high-temperature sintering.
Patent CN201180006685.5 discloses a flat-tube type solid oxide fuel cell with an asymmetric structure, in which an anode layer, an electrolyte layer, a barrier layer, and a cathode layer are sequentially distributed on the upper surface of a support, and the lower surface is an anode current collecting layer and an electrolyte layer distributed around the anode current collecting layer. The preparation process comprises the following steps: preparing an anode layer and an anode current collecting layer, wherein the anode layer is positioned on the upper surface of a support body, the anode current collecting layer is positioned on the lower surface of the support body, and the electrolyte layer is prepared after low-temperature sintering; the electrolyte layer comprises a first electrolyte layer and a second electrolyte layer, the first electrolyte layer is positioned on the surface of the anode layer, and the second electrolyte layer is positioned on the peripheral surface of the anode current collecting layer; preparing electrolyte layers on the side surfaces of the support body, connecting the first electrolyte layer with the second electrolyte layer through the electrolyte layers on the two sides, and forming a dense electrolyte after high-temperature sintering so as to prevent fuel in the porous support body from leaking; and the prepared barrier layer is positioned on the surface of the first electrolyte layer, a cathode layer is prepared on the surface of the barrier layer after high-temperature sintering, and the full cell is obtained after high-temperature sintering again.
Patent CN201510104627.6 and patent CN201180006685.5 disclose flat tube type solid oxide fuel cells with two different structures, respectively, but the sealing of the side edges of the support in the two structures is achieved by covering the electrolyte and connecting with the electrolyte layers on the upper and lower surfaces, and the material is yttria-stabilized zirconia. When the side electrolyte and the upper and lower surface electrolytes are co-sintered at a high temperature, the following problems occur:
the electrolyte material yttria-stabilized zirconia needs to be sintered at the temperature of not less than 1320 ℃, the support body is easy to deform due to high temperature and inconsistent shrinkage of each part of the support body in the sintering process, and the deformation quantity of the side edge of the support body cannot be controlled in the prior art, so that an electrolyte layer used for sealing the side edge of the support body is not easy to compact, the sealing performance is weakened, and fuel is easy to leak.
Usually, the thickness of the electrolyte used for sealing the side edge of the support body is 5-15um, after the support body is sintered at a high temperature on a subsequent functional layer, particularly an electrolyte layer, the difference between the widths of different support body after deformation or the difference between the side deformation amounts is often larger than the thickness of the side electrolyte layer, so that the side width uniformity of the SOFC support body cannot be realized through machining, and finally the problems of difficult sealing, low yield and the like after the later-stage integrated electric pile are caused.
Disclosure of Invention
The invention aims to provide a novel preparation method of a flat tube type solid oxide fuel cell, which effectively solves the problem of the original preparation process in the background technology and has the advantages of simple operation, good universality, high product yield and safety, easiness in large-scale production and the like.
In order to achieve the above object, the present invention provides a novel flat tubular solid oxide, a support; a through hole is arranged in the supporting body;
an anode layer comprising a first anode layer and a second anode layer; the lower side of the first anode layer is positioned on the upper surface of the support; a second anode layer, the upper side of the second anode layer is positioned on the lower surface of the support;
the electrolyte layer comprises a first electrolyte layer and a second electrolyte layer, the first electrolyte layer is positioned on the upper surface of the first anode layer, and the second electrolyte layer is positioned on the lower surface of the second anode layer; a sealing layer is arranged between the first electrolyte layer and the second electrolyte layer, one end of the sealing layer is connected with the first electrolyte layer, and the other end of the sealing layer is connected with the second electrolyte layer;
a barrier layer including a first barrier layer and a second barrier layer, the first barrier layer being located on an upper surface of the first electrolyte layer; the second barrier layer is positioned on the lower surface of the first electrolyte layer;
a cathode layer including a first cathode layer and a second cathode layer, the first cathode layer being located on an upper surface of the first barrier layer; the second cathode layer is located on the lower surface of the second barrier layer.
As a further preference, the barrier layer includes a first barrier layer and a second barrier layer, the first barrier layer being located on an upper surface of the first electrolyte layer; the second barrier layer is positioned on the lower surface of the first electrolyte layer; the barrier layer comprises a first cathode layer and a second cathode layer, and the first cathode layer is positioned on the upper surface of the first barrier layer; the second cathode layer is located on the lower surface of the second barrier layer.
A preparation method of a flat tube type solid oxide fuel cell comprises the steps as follows:
step S1: mixing the raw materials of the support body; adding a liquid raw material into a support body powder raw material, and mixing to obtain a mixture; wherein, the support body powder raw materials comprise 30-60% of nickel oxide powder and 30-70% of yttria-stabilized zirconia powder, and the liquid raw materials comprise 3-10% of pore-forming agent, 3-35% of plasticizer and 0.5-15% of dispersant;
step S2: preparing a support body blank: drying the support body blank, and then sintering at high temperature to obtain the support body blank;
step S3: first mechanical processing: carrying out first mechanical processing on the support body blank, and processing the three-dimensional size of the blank to a set value;
step S4: preparing an anode layer: arranging nickel oxide or a mixture of copper oxide and yttria-stabilized zirconia on the upper surface of the support body, arranging nickel oxide and other easily reducible metal oxides on the lower surface of the support body, and sintering at 800-1000 ℃ for 2 h; a first anode layer is formed on the upper surface of the support body, and a second anode layer is formed on the lower surface of the support body;
step S5: preparing an electrolyte layer: arranging metal oxide on the upper surface of the first anode layer, arranging metal oxide on the lower surface of the second anode layer, and sintering at the high temperature of not less than 1300 ℃ for 2-5h to ensure that the electrolyte layer is compact and the support body is greatly shrunk; a first electrolyte layer is formed on the upper surface of the first anode layer, a second electrolyte layer is formed on the lower surface of the second anode layer, the first electrolyte layer and the second electrolyte layer are compact, and the volume amplitude of the support body is shrunk;
step S6: preparing a sealing layer: disposing a silicate between the first electrolyte and the second electrolyte layer; then sintering and compacting at 600-1300 ℃ to form a sealing layer, wherein the thickness of the sealing layer is preferably 3-15 um;
step S7: preparing a barrier layer: cerium oxide is arranged on the upper surface of the first electrolyte layer, cerium oxide is arranged on the lower surface of the second electrolyte layer, and sintering is carried out at 1200-1300 ℃ for 1-5 h; a first barrier layer is formed on the upper surface of the support body, and a second barrier layer is formed on the lower surface of the support body;
step S8: preparing a cathode layer: setting lanthanum perovskite cobaltate on the upper surface of the first barrier layer, setting lanthanum perovskite cobaltate on the lower surface of the second barrier layer, and sintering at the temperature of 800-; the upper surface of the support body forms a first cathode layer, and the lower surface of the support body forms a second cathode layer.
Compared with the traditional preparation method, the preparation method disclosed by the invention is more flexible in preparation process, convenient to adjust according to actual production conditions, applicable to more production conditions and has certain universality.
As a further preference, the method further comprises the step a of performing second machining: and carrying out secondary mechanical processing on the three-dimensional size of the support body to process the size to a set value.
Preferably, in the step B, the sealing layer is prepared by using a material comprising an oxide-doped silicate of a metal element such as aluminum, iron, calcium, magnesium, sodium, and the like with a powder particle size D50 in the range of 1-2um, and a combination of the above materials, and sealing is performed by using the material, wherein the thickness of the sealing layer is 3-5 um;
or manganese and calcium doped nickel base alloy with the powder grain diameter D50 ranging from 0.6 um to 1um and the combination of the materials, the material is adopted for sealing, and the thickness of the sealing layer is 4 um to 8 um;
or low temperature densification ceramic oxide material with high sintering activity, such as yttrium, scandium, gadolinium, cerium and one or more of zirconia, bismuth oxide, cerium oxide doped with different rare earth elements, and the combination of the above materials, and the sealing layer is sealed by adopting the material, and the thickness of the sealing layer is 3-15 um; when sintering is carried out, the sintering temperature is 600-1300 ℃, and the sintering time is 1-3 hours.
The sealing layer material with lower sintering temperature is selected, so that the shrinkage degree of the battery unit is reduced in the sintering process, and the yield of products is improved.
As a further preference, the preparation of the sealing layer slurry in step S6 is mainly prepared by a high-speed dispersion method, a ball milling method, and the like, and further includes step B, where step B is divided into step 1 and step 2, and step 1: adding the sealed powder, the ethyl fiber and the terpineol into a container, wherein the mixture is prepared from 3-20 parts of the sealed powder, 1-6 parts of the ethyl fiber and 5-25 parts of the terpineol, putting the mixed solution into the sealed container, and dispersing for 10-15h by adopting a high-speed dispersion machine or a ball mill, and the step 2: grinding the dispersed slurry to be less than 2um by a three-roll grinder;
preferably, the material composition of the sealing layer in step S6 is silicate, and the raw material ratio is as follows: 30-35 parts of MgO, 360-65 parts of Al2O, 30.1-0.4 part of Fe2O30, 3-3 parts of SiO21, 0.2-0.8 part of CaO and 0.1-0.4 part of Na2O 0.1. The solid content of the prepared sealing layer slurry is 40-50%, and the viscosity of the slurry is 300-500Pa S.
The sealing layer adopts nickel-based alloy powder as a material component, and the raw materials are as follows: 0.1-5 parts of Mn, 0-0.3 part of CaO and 95-99 parts of iron-nickel alloy powder, wherein the solid content of the prepared sealing layer slurry is 50-70%, and the viscosity of the slurry is 200-400Pa S.
The sealing layer adopts ceramic oxide materials as the material components, and the raw material ratio is as follows: 85-99 parts of ZrO, 8-8 parts of Y2O33 and 3-3 parts of Al2O31, wherein ZrO can be replaced by BiO, and the mixture ratio is unchanged. The solid content of the prepared sealing layer slurry is 30-80%, and the viscosity of the slurry is 100-600Pa S.
As a further preference, the method for preparing the sealing layer by the sealing slurry in the step S6 is as follows: the silicate sealing slurry adopts a pulling and dipping method, the nickel-based alloy sealing slurry adopts a transfer printing method, and the ceramic oxide sealing slurry adopts a screen printing film forming method.
Preferably, in step S6, the sealing layer is made of a ceramic oxide, and the second machining is performed between step S5 and step S6. The sealing layer material is prepared by selecting silicate slurry and nickel base alloy slurry, and the second machining and the step 6 are carried out after the step 8.
Preferably, in the step S1, the support raw material is mixed and includes support powder raw material and liquid raw material, where the powder raw material includes the following components: 30-60 parts of nickel oxide powder, 30-70 parts of yttria-stabilized zirconia powder and 3-10 parts of pore-forming agent; the liquid raw materials comprise the following components in percentage by weight: 3-35 parts of plasticizer, 0.5-15 parts of dispersant, 0.5-3 parts of defoamer and 0.5-15 parts of lubricant.
Preferably, the material used for the first anode layer comprises a mixture of nickel oxide, copper oxide or other metal oxides and yttria-stabilized zirconia, wherein the mass ratio of yttria-stabilized zirconia powder is 30-75%;
the material of the second anode layer comprises metal oxide which is easy to reduce such as nickel oxide and the like and the combination of the materials.
The material used for the anode current collecting layer comprises metal oxide which is easy to reduce such as nickel oxide and the combination of the materials; when high-temperature sintering is carried out, the sintering temperature is 800-1000 ℃, and the sintering time is 2 hours.
As a further preferred example, in the step S6, the material used for the electrolyte layer in preparing the electrolyte layer includes zirconium oxide, bismuth oxide or cerium oxide doped with one or more different rare earth elements, such as yttrium, scandium, gadolinium and cerium, and combinations thereof.
As a further preference, the step S2 further includes a step S21, and the method for preparing the mixture includes an extrusion molding method, an isostatic pressing method, an injection method, a slip casting method or a 3D printing method.
Compared with the prior art, the preparation technology of the invention has the following main advantages:
1) the side sealing layer is sealed after the electrolyte or the barrier layer is sintered at high temperature, so that the side can control the width size and the side flatness of the side through machining after the side is sintered at high temperature, and the production standardization of the solid oxide fuel cell is facilitated.
2) The side sealing material used in the invention can be sintered and compacted at the temperature of 600-1300 ℃ by adjusting different components, has wider sintering and compacting temperature range, can be flexibly adjusted according to the battery preparation process, and has extremely strong universality.
3) The battery preparation method used by the invention greatly improves the consistency, the yield and the safety of the battery, has low requirement on equipment, is simple to operate and is beneficial to large-scale production.
Drawings
Fig. 1 is a structural view of a single cell functional layer having a symmetrical structure in a first embodiment of the present invention;
FIG. 2 is a graph showing the sintering effect of the side sealing layers of the single cells having the symmetrical structure according to the first embodiment of the present invention;
fig. 3 is a structural view of a single cell functional layer having an asymmetric structure in a second embodiment of the present invention;
fig. 4 is a graph showing the sintering effect of the side sealing layer of the single cell having the asymmetric structure in the second embodiment of the present invention.
101. A sealing layer; 102. a first anode layer; 103. a first electrolyte layer; 104. a first barrier layer; 105. a first cathode layer; 106. a second anode layer; 107. a second electrolyte layer; 108. a second barrier layer; 109. a second cathode layer; 110. and a support body.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", and the like, which indicate orientations or positional relationships, are based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Referring to fig. 1 and 3, a flat tube type solid oxide fuel cell includes:
a support body 110; a through hole is arranged in the supporting body 110;
an anode layer including a first anode layer 102 and a second anode layer 106; the underside of the first anode layer 102 is located on the upper surface of the support 110; a second anode layer 106, an upper side of the second anode layer 106 being positioned on a lower surface of the support 110;
electrolyte layers including a first electrolyte layer 103 and a second electrolyte layer 107, the first electrolyte layer 103 being located on the upper surface of the first anode layer 102, the second electrolyte layer 107 being located on the lower surface of the second anode layer 106; a sealing layer 101 is arranged between the first electrolyte layer 103 and the second electrolyte layer 107, one end of the sealing layer 101 is connected with the first electrolyte layer 103, and the other end of the sealing layer 101 is connected with the second electrolyte layer 107; a barrier layer on an upper surface of the first electrolyte layer 103; and the cathode layer is positioned on the upper surface of the barrier layer.
As shown in fig. 1, further, as a preferred embodiment, the barrier layer includes a first barrier layer 104 and a second barrier layer 108, the first barrier layer 104 is located on the upper surface of the first electrolyte layer 103; the second barrier layer 108 is located on the lower surface of the first electrolyte layer 103; the barrier layer includes a first cathode layer 105 and a second cathode layer 109, the first cathode layer 105 being located on an upper surface of the first barrier layer 104; the second cathode layer 109 is located on the lower surface of the second barrier layer 108.
A flat tube type solid oxide fuel cell and a preparation method thereof, comprising the flat tube type solid oxide fuel cell,
the method comprises the following steps:
step S1: mixing the support 110 raw materials; adding a liquid raw material into a powder raw material of a support body 110 and mixing to obtain a mixture; wherein, the support body 110 comprises 30-60% of nickel oxide powder, 30-70% of yttria-stabilized zirconia powder, and liquid raw materials of 3-10% of pore-forming agent, 3-35% of plasticizer and 0.5-15% of dispersant;
step S2: preparing a support body 110 blank: drying the support body 110 blank, and then sintering at high temperature to obtain a support body 110 blank;
step S3: first mechanical processing: carrying out first mechanical processing on a support body 110 blank, and processing the three-dimensional size of the blank to a set value;
step S4: preparing an anode layer: arranging nickel oxide or a mixture of copper oxide and yttria-stabilized zirconia on the upper surface of the support body 110, arranging metal oxides which are easy to reduce such as nickel oxide on the lower surface of the support body 110, and sintering at the temperature of 800-; the first anode layer 102 is formed on the upper surface of the support 110, and the second anode layer 106 is formed on the lower surface of the support 110;
step S5: preparing an electrolyte layer: arranging metal oxide on the upper surface of the first anode layer 102 and the lower surface of the second anode layer 106, and sintering at a high temperature of not less than 1300 ℃ for 2-5h to ensure that the electrolyte layer is compact and the support 110 is greatly shrunk; a first electrolyte layer 103 is formed on the upper surface of the first anode layer 102, a second electrolyte layer 107 is formed on the lower surface of the second anode layer 106, the first electrolyte layer 103 and the second electrolyte layer 107 are compact, and the support 110 shrinks in volume;
step S6: preparing a sealing layer 101: a silicate is provided between the first electrolyte and the second electrolyte layer 107; then sintering and compacting at 600-1300 ℃ to form a sealing layer 101;
step S7: preparing a barrier layer: cerium oxide is arranged on the upper surface of the first electrolyte layer 103, cerium oxide is arranged on the lower surface of the second electrolyte layer 107, and sintering is carried out at 1200-1300 ℃ for 1-5 h; the upper surface of the support 110 forms a first barrier layer 104, and the lower surface of the support 110 forms a second barrier layer 108;
step S8: preparing a cathode layer: the lanthanum perovskite cobaltate is arranged on the upper surface of the first barrier layer 104, the lanthanum perovskite cobaltate is arranged on the lower surface of the second barrier layer 108, and sintering is carried out at the temperature of 800-; the upper surface of the support 110 forms the first cathode layer 105, and the lower surface of the support 110 forms the second cathode layer 109.
Further, as a preferred embodiment, the method further comprises a step a of performing a second machining: performing a second machining process on the three-dimensional size of the support body 110 to a set value; step a may be performed between or after any of steps 6-8.
Further, as a preferred embodiment, the silicate used for the sealing layer 101: comprises silicate doped with oxides of metal elements such as aluminum, iron, calcium, magnesium, sodium and the like with the powder grain diameter D50 ranging from 1um to 2um and the combination of the materials;
or manganese and calcium doped nickel base alloy with powder grain diameter D50 in the range of 0.6-1um and the combination of the materials;
or low temperature densified materials with high sintering activity, such as yttrium, scandium, gadolinium, cerium and other one or more of zirconia, bismuth oxide, cerium oxide doped with different rare earth elements, and combinations thereof.
Further, as a preferred embodiment, step S6 further includes step B, step B: preparation of sealing layer 101 slurry: adding silicate, ethyl fiber and terpineol into a ball milling tank, wherein the silicate, the ethyl fiber and the terpineol are in a corresponding mass ratio of 9:3:8, and grinding the mixed solution in a ball mill for 10 hours until the fineness is less than 2 um; wherein the silicate comprises the following components:
MgO:Al2O3:Fe2O3:SiO2:CaO:Na2O＝33.29:64.05:0.25:1.56:0.55:0.3。
further, as a preferred embodiment, in the step S1, the raw material of the support 110 is mixed, and the raw material of the support 110 includes powder raw material and liquid raw material of the support 110, wherein the powder raw material includes the following components: 30-60 parts of nickel oxide powder, 30-70 parts of yttria-stabilized zirconia powder and 3-10 parts of pore-forming agent; the liquid raw materials comprise the following components in percentage by weight: 3-35 parts of plasticizer, 0.5-15 parts of dispersant, 0.5-3 parts of defoamer and 0.5-15 parts of lubricant.
Further, as a preferred embodiment, the material used for the first anode layer 102 includes a mixture of nickel oxide, copper oxide or other metal oxide and yttria-stabilized zirconia, wherein the mass ratio of the yttria-stabilized zirconia powder is 30-75%;
the material of the second anode layer 106 includes a metal oxide such as nickel oxide which is easily reduced, and a combination of these materials.
Further, in a preferred embodiment, in the step S6, the electrolyte layer is prepared by using materials including zirconium oxide, bismuth oxide or cerium oxide doped with one or more different rare earth elements, such as yttrium, scandium, gadolinium, cerium, and combinations thereof.
Further, as a preferred embodiment, the step S2 further includes a step S21, and the method for preparing the mixture includes extrusion molding, isostatic pressing, injection, slip casting, or 3D printing.
The material used by the barrier layer comprises samarium, neodymium, scandium and other one or more of cerium oxide doped with different rare earth elements and the combination of the materials, and the range of the powder particle size D50 is 0.2-0.5 um.
The cathode layer is made of materials including lanthanum perovskite cobaltate doped with one or more different rare earth elements such as barium and strontium and the combination of the materials, and the powder particle size D50 ranges from 0.2um to 0.5 um.
According to the embodiments shown in FIGS. 1-2
A method for preparing a flat tube type solid oxide fuel cell with a symmetrical structure,
silicate, ethyl fiber and terpineol are used as sealing layer 101 slurry;
the method comprises the following steps:
step S1: mixing the support 110 raw materials; wherein the support body 110 comprises the following raw materials in percentage by weight: 46 parts of nickel oxide powder, 46 parts of yttria-stabilized zirconia powder and 3 parts of starch pore-forming agent; the liquid raw materials comprise the following components in percentage by weight: 3 parts of di (2-ethylhexyl) phthalate plasticizer, 0.5 part of polyolefin dispersant, 1 part of defoamer and 0.5 part of lubricant.
Step S2: preparing a support body 110 blank; and preparing a blank of the support body 110 by using an extrusion compression molding method, wherein the blank has a hollow hole structure, drying the blank of the support body 110, and sintering at a high temperature to obtain a blank of the support body 110, wherein the sintering temperature is 1000 ℃.
Step S3: first mechanical processing: carrying out first mechanical processing on a support body 110 blank, and processing the three-dimensional size of the blank to a set value;
step S4: preparing an anode layer: arranging nickel oxide or a mixture of copper oxide and yttria-stabilized zirconia on the upper surface of the support body 110, arranging metal oxides which are easy to reduce such as nickel oxide on the lower surface of the support body 110, and sintering at the temperature of 800-; the first anode layer 102 is formed on the upper surface of the support 110, and the second anode layer 106 is formed on the lower surface of the support 110;
step S5: preparing an electrolyte layer: arranging metal oxide on the upper surface of the first anode layer 102 and the lower surface of the second anode layer 106, and sintering at a high temperature of not less than 1300 ℃ for 2-5h to ensure that the electrolyte layer is compact and the support 110 is greatly shrunk; a first electrolyte layer 103 is formed on the upper surface of the first anode layer 102, a second electrolyte layer 107 is formed on the lower surface of the second anode layer 106, the first electrolyte layer 103 and the second electrolyte layer 107 are compact, and the support 110 shrinks in volume;
step S6: preparing a sealing layer 101: a silicate is provided between the first electrolyte and the second electrolyte layer 107; then sintering and compacting at 600-1300 ℃ to form a sealing layer 101;
step S7: preparing a barrier layer: preparing barrier layers on the surfaces of the electrolyte layers, wherein the first barrier layer 104 is positioned on the surface of the first electrolyte layer 103, the second barrier layer 108 is positioned on the surface of the second electrolyte layer 107, the first barrier layer 104 is not connected with the second barrier layer 108, and then sintering at a high temperature of 1280 ℃ for 2 hours; the barrier layer is prepared from samarium-doped cerium oxide, and the particle size D50 of the powder is 0.2 um.
Step S8: preparing a cathode layer: preparing cathode layers on the surfaces of the barrier layers, wherein the first cathode layer 105 is positioned on the surface of the first barrier layer 104, the second cathode layer 109 is positioned on the surface of the second barrier layer 108, the first cathode layer 105 is not connected with the second cathode layer 109, and then high-temperature sintering is carried out, wherein the sintering temperature is 1000 ℃, and the sintering time is 1 hour; the cathode layer is prepared from barium-doped lanthanum perovskite cobaltate, and the powder particle size D50 is 0.2 um.
Step A: and (3) second mechanical processing: performing a second machining of the three-dimensional dimensions of the support body 110, in particular the length and width, to set the dimensions to the set values;
and B: preparing a sealing layer 101: and (3) preparing the sealing layer 101 on the side surface of the support body 110 by adopting a dip-coating method, wherein the material of the sealing layer 101 is derived from the material in the slurry for preparing the sealing layer 101 in the step (C), the sealing layer 101 is connected with the first electrolyte layer 103 and the second electrolyte layer 107, and sintering is carried out at the sintering temperature of 900 ℃ for 1 hour so as to ensure that the sealing layer 101 is compact.
The finished single cell with a symmetrical structure is finally obtained, the structure of the single cell is shown in figure (1), and the sintering effect of the sealing layer 101101 is shown in figure (2).
Referring to FIGS. 3-4, the second embodiment
A method for preparing a flat tube type solid oxide fuel cell with an asymmetric structure,
preparing sealing layer 101 slurry: ceramic oxide powder, ethyl fiber and terpineol are used as sealing layer slurry.
The method comprises the following steps:
step S1: mixing the support 110 raw materials; wherein the support body 110 comprises the following raw materials in percentage by weight: 49 parts of nickel oxide powder, 39 parts of yttria-stabilized zirconia powder and 5 parts of graphite pore-forming agent; the liquid raw materials comprise the following components in percentage by weight: 3.5 parts of di (2-ethylhexyl) phthalate plasticizer, 1.5 parts of polypropylene dispersant, 0.5 part of defoaming agent and 1.5 parts of lubricant.
Step S2: preparing a support body 110 blank; an isostatic pressing method is used to prepare a blank of the support body 110, and the blank has a hollow hole structure. Preparing a support body 110 blank: and drying the support body 110 blank, and then sintering at high temperature to obtain a support body 110 blank, wherein the sintering temperature is 1000 ℃.
Step S4: first mechanical processing: carrying out first mechanical processing on a support body 110 blank, and processing the three-dimensional size of the blank to a set value;
step S5: preparing an anode layer: preparing an anode layer and an anode current collecting layer on the surface of the support body 110, wherein the anode layer is positioned on the upper surface of the support body 110, the anode current collecting layer is positioned on the lower surface of the support body 110, and then sintering at the high temperature of 900 ℃ for 2 hours; the anode layer is prepared from a mixture of copper oxide and yttria-stabilized zirconia, wherein the mass ratio of yttria-stabilized zirconia powder is 70%; the material for preparing the anode current collecting layer is nickel oxide.
Step S6: preparing an electrolyte layer: preparing electrolyte layers on the surfaces of the anode layers, wherein a first electrolyte layer 103 is prepared on the surface of a first anode layer 102, a second electrolyte layer 107 is prepared on the peripheral surface of an anode current collecting layer, the first electrolyte layer 103 is not connected with the second electrolyte layer 107, and then sintering is carried out at a high temperature, wherein the sintering temperature is 1360 ℃ and the sintering time is 5 hours; the material for preparing the electrolyte layer is gadolinium and cerium element doped zirconia.
Step A: and (3) second mechanical processing: performing a second machining of the three-dimensional dimensions of the support body 110, in particular the length and width, to set the dimensions to the set values;
and B: preparing sealing layer 101 slurry: taking 17 parts of powder ZrO, Y2O30.6 parts of powder Al2O 30.4 parts of powder terpineol and 3 parts of ethyl cellulose, and dispersing in a ball milling tank for 10 hours, wherein the particle size D50 of each powder is 1-2 um; grinding the dispersed slurry in a three-roller grinder until the fineness is less than 2um, preparing the sealing slurry and the side surface of the support by adopting a screen printing method, and drying.
Step S7: preparing a barrier layer: preparing a barrier layer on the surface of the first electrolyte layer 103, and then sintering at a high temperature, wherein the sintering temperature is 1300 ℃, and the sintering time is 1 hour; the material for preparing the barrier layer is cerium oxide doped with neodymium, and the particle size D50 of the powder is 0.2-0.5 um.
Step S8: preparing a cathode layer: preparing a cathode layer on the surface of the barrier layer, wherein the cathode layer is made of strontium-doped lanthanum perovskite cobaltate, and the powder particle size D50 is 0.2-0.5 um; and meanwhile, preparing the sealing layer 101 on the side surface of the support body 110 by adopting a screen printing method, wherein the material of the sealing layer 101 is derived from the material in the slurry for preparing the sealing layer 101 in the step C, the sealing layer 101 is connected with the first electrolyte layer 103 and the second electrolyte layer 107, and the cathode layer and the sealing layer 101 are sintered together at the sintering temperature of 900 ℃.
Wherein the second anode layer 106 is an anode current collector layer;
the finished single cell with an asymmetric structure is finally obtained, the structure of the single cell is shown in fig. 3, and the sintering effect of the sealing layer 101101 is shown in fig. 4.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

Claims (10)

1. A flat tube solid oxide fuel cell, comprising:
a support body (110); a through hole is arranged in the support body (110);
an anode layer comprising a first anode layer (102) and a second anode layer (106); the underside of the first anode layer (102) is located on the upper surface of the support (110); a second anode layer (106), an upper side of the second anode layer (106) being located at a lower surface of the support (110);
electrolyte layers including a first electrolyte layer (103) and a second electrolyte layer (107), the first electrolyte layer (103) being located on an upper surface of the first anode layer (102), the second electrolyte layer (107) being located on a lower surface of the second anode layer (106); a sealing layer (101) is arranged between the first electrolyte layer (103) and the second electrolyte layer (107), one end of the sealing layer (101) is connected with the first electrolyte layer (103), and the other end of the sealing layer (101) is connected with the second electrolyte layer (107);
a barrier layer on an upper surface of the first electrolyte layer (103);
a cathode layer on an upper surface of the barrier layer.
2. The flat tube solid oxide fuel cell of claim 1, wherein the barrier layer comprises a first barrier layer (104) and a second barrier layer (108), the first barrier layer (104) being located on an upper surface of the first electrolyte layer (103); the second barrier layer (108) is located on the lower surface of the first electrolyte layer (103); the barrier layer comprises a first cathode layer (105) and a second cathode layer (109), the first cathode layer (105) being located on an upper surface of the first barrier layer (104); the second cathode layer (109) is located on a lower surface of the second barrier layer (108).
3. A method for preparing a flat tube type solid oxide fuel cell is characterized in that,
the method comprises the following steps:
step S1: mixing the support (110) raw materials; adding a liquid raw material into a support body (110) powder raw material, and mixing to obtain a mixture; wherein, the powder raw materials of the support body (110) are 30-60% of nickel oxide powder and 30-70% of yttria-stabilized zirconia powder, and the liquid raw materials are 3-10% of pore-forming agent, 3-35% of plasticizer and 0.5-15% of dispersant;
step S2: preparing a support body (110) blank: drying the blank body of the support body (110), and then sintering at high temperature to obtain a blank of the support body (110);
step S3: first mechanical processing: carrying out first mechanical processing on a blank of a support body (110), and processing the three-dimensional size of the blank to a set value;
step S4: preparing an anode layer: arranging nickel oxide or a mixture of copper oxide and yttria-stabilized zirconia on the upper surface of the support body (110), arranging easily reducible metal oxide such as nickel oxide on the lower surface of the support body (110), and sintering at 800-; the upper surface of the support body (110) forms a first anode layer (102), and the lower surface of the support body (110) forms a second anode layer (106);
step S5: preparing an electrolyte layer: arranging metal oxide on the upper surface of the first anode layer (102), arranging metal oxide on the lower surface of the second anode layer (106), and sintering at the high temperature of not less than 1300 ℃ for 2-5h to ensure that the electrolyte layer is compact and the support body (110) is greatly shrunk; a first electrolyte layer (103) is formed on the upper surface of the first anode layer (102), a second electrolyte layer (107) is formed on the lower surface of the second anode layer (106), and the first electrolyte layer (103) and the second electrolyte layer (107) are compact;
step S6: preparation of sealing layer (101): -providing a silicate between the first electrolyte and the second electrolyte layer (107); then sintering and densifying at 600-1300 ℃ to form a sealing layer (101), wherein the thickness of the sealing layer is preferably 3-15 um;
step S7: preparing a barrier layer: cerium oxide is arranged on the upper surface of the first electrolyte layer (103), cerium oxide is arranged on the lower surface of the second electrolyte layer (107), and sintering is carried out at 1200-1300 ℃ for 1-5 h; a first barrier layer (104) is formed on the upper surface of the support body (110), and a second barrier layer (108) is formed on the lower surface of the support body (110);
step S8: preparing a cathode layer: setting lanthanum perovskite cobaltate on the upper surface of the first barrier layer (104), setting lanthanum perovskite cobaltate on the lower surface of the second barrier layer (108), and sintering at 800-1000 ℃ for 1 h; the upper surface of the support body (110) forms a first cathode layer (105), and the lower surface of the support body (110) forms a second cathode layer (109).
4. The method for manufacturing a flat tube solid oxide fuel cell according to claim 3, further comprising a step A of second machining: and carrying out secondary mechanical processing on the three-dimensional size of the support body (110) to process the size to a set value.
5. The method for preparing the flat tube type solid oxide fuel cell according to claim 3, wherein the sealing powder used by the sealing layer (101) can be silicate: comprises silicate doped with oxide of metal elements such as aluminum, iron, calcium, magnesium, sodium and the like with the powder grain diameter D50 ranging from 1um to 2um and the combination of the materials, and is sealed by adopting the material, and the thickness of a sealing layer is 3 um to 5 um;
sealing the powder or the combination of the manganese-calcium-doped nickel-based alloy with the powder grain diameter D50 ranging from 0.6 um to 1um and the multiple materials, adopting the material for sealing, and ensuring that the thickness of the sealing layer is 4 um to 8 um;
the sealing powder or low-temperature densification ceramic oxide material with high sintering activity, such as yttrium, scandium, gadolinium, cerium, aluminum and one or more of zirconia, bismuth oxide, cerium oxide doped with different rare earth elements, and the combination of the above materials, is sealed by adopting the material, and the thickness of the sealing layer is 3-15 um.
6. The method of claim 3, wherein the sealing layer slurry in step S6 is prepared mainly by a high-speed dispersion method, a ball milling method, or the like, and the preparation step includes step B, and the step B is divided into step 1 and step 2, step 1: adding the sealed powder, the ethyl fiber and the terpineol into a container, wherein the mixture is prepared from 3-20 parts of the sealed powder, 1-6 parts of the ethyl fiber and 5-25 parts of the terpineol, putting the mixed solution into the sealed container, and dispersing for 10-15h by adopting a high-speed dispersion machine or a ball mill, and the step 2: and grinding the dispersed slurry to be less than 2um by using a three-roll grinder.
7. The method for preparing a flat tube type solid oxide fuel cell according to claim 3, wherein the material component of the sealing layer in the step S6 is silicate, and the raw material ratio is as follows: the sealing layer slurry comprises, by weight, 30-35 parts of MgO, 360-65 parts of Al2O, 30.1-0.4 part of Fe2O30, 21-3 parts of SiO, 0.2-0.8 part of CaO and 0.1-0.4 part of Na2O 0.1, wherein the solid content of the prepared sealing layer slurry is 40-50%, and the viscosity of the slurry is 300-500Pa S;
the sealing layer adopts nickel-based alloy powder as a material component, and the raw materials are as follows: 0.1-5 parts of Mn, 0.3-0.78 part of Ca0 and 95-99 parts of iron-nickel alloy powder, wherein the solid content of the prepared sealing layer slurry is 50-70%, and the viscosity of the slurry is 200-400Pa S;
the sealing layer adopts ceramic oxide materials as the material components, and the raw material ratio is as follows: 85-99 parts of ZrO, 33-8 parts of Y2O, 31-3 parts of Al2O, wherein ZrO can be replaced by BiO, the mixture ratio is unchanged, the solid content of the prepared sealing layer slurry is 30-80%, and the viscosity of the slurry is 100-600Pa S.
8. The method for manufacturing a flat tube type solid oxide fuel cell according to claim 3, wherein the method for preparing the sealing layer by the sealing slurry in the step S6 is as follows: the silicate sealing slurry adopts a pulling and dipping method, the nickel-based alloy sealing slurry adopts a transfer printing method, and the ceramic oxide sealing slurry adopts a screen printing film forming method.
9. The method according to claim 3, wherein the sealing layer is made of ceramic oxide in step S6, the second mechanical processing is performed between step 5 and step 6, and the sealing layer is sintered at 1300 ℃ to be dense; the sealing layer material is prepared by selecting silicate slurry and nickel-based alloy slurry, the second mechanical processing and the step 6 are carried out after the step 8, and the sealing layer is sintered at low temperature of 900 ℃ to be compact.
10. The method of claim 6, wherein the step S2 further comprises a step S21, and the mixture is prepared by extrusion molding, isostatic pressing, injection, slip casting, or 3D printing.
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CN102084527A (en) * 2008-03-20 2011-06-01 丹麦科技大学 A composite glass seal for a solid oxide electrolyser cell stack
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