CN109411778B - Preparation process of solid oxide fuel cell stack - Google Patents

Preparation process of solid oxide fuel cell stack Download PDF

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CN109411778B
CN109411778B CN201811269936.9A CN201811269936A CN109411778B CN 109411778 B CN109411778 B CN 109411778B CN 201811269936 A CN201811269936 A CN 201811269936A CN 109411778 B CN109411778 B CN 109411778B
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tubular
air inlet
fuel cell
solid oxide
oxide fuel
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CN109411778A (en
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区定容
李致朋
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Nanjing Nernst Technology Co.,Ltd.
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Shenzhen Zhiyuan Power 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
    • H01M8/002—Shape, form of a fuel cell
    • H01M8/004—Cylindrical, tubular or wound
    • 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
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a preparation process of a solid oxide fuel cell pack, which comprises the following steps: (1) manufacturing the tubular inner electrodes of the tubular battery units and the air inlet cavity into an integrally formed blank body, and enabling an internal flow channel of each tubular inner electrode to be communicated with the air inlet cavity; (2) coating an electrolyte layer on the outer wall of each tubular inner electrode, and then performing primary sintering treatment; (3) and coating an outer electrode layer on the electrolyte layer, and performing secondary sintering treatment to obtain an integrated structure of the plurality of tubular battery units and the air inlet cavity. According to the preparation process of the solid oxide fuel cell pack, each tubular cell unit is assembled on the air inlet cavity one by one without positioning, so that the air inlet cavity and the first cell unit group are good in air tightness and high in stability, good isolation of anode gas and cathode gas is realized, and the power generation performance and long-term stability of the solid oxide fuel cell pack are effectively improved.

Description

Preparation process of solid oxide fuel cell stack
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation process of a solid oxide fuel cell stack.
Background
The Solid Oxide Fuel Cell (SOFC) has the advantages of high power generation efficiency, low emission, wide adaptability to various fuel gases, high waste heat utilization value and the like, and is one of important strategic technologies for providing clean and efficient energy, relieving energy and environmental crisis and realizing sustainable development in China.
Currently, SOFCs are mainly classified into plate type and tube type. The plate type SOFC cell stack is formed by laminating a plate type cell unit and a sheet bipolar plate, complete sealing of the plate type cell unit and the sheet bipolar plate under the high-temperature operation condition of the SOFC is required to be realized in order to isolate anode gas and cathode gas, and the requirements on thermal expansion matching, thermal stability, chemical stability and the like of a sealing material are very high. The sealing structure of the tubular SOFC is relatively simple compared to the plate type SOFC, but it is also necessary to seal the junction between the tubular cell unit and the internal gas inlet/outlet cavities to separate the anode gas and the cathode gas.
The prior art for sealing between the tube-type battery cell and the inlet/outlet cavity is more. Siemens-siemens corporation tubular SOFC cell stacks employ an incomplete seal structure between the cell unit and the air cavity. In the Mitsubishi heavy industry tubular SOFC stack, a more complex sealing structure is adopted between the cell and the air cavity: firstly, a ceramic sleeve is adhered to a part of the tubular battery unit needing sealing by adopting inorganic high-temperature glue, and then the ceramic sleeve and the air cavity are sealed. For small and medium-sized mobile power stations or power supplies, in order to meet the mobile requirements, the sealing is often required to be higher, and a glass sealing material with higher sealing performance is adopted for carrying out airtight sealing, for example, in a tubular SOFC (solid oxide fuel cell) stack of Toto company, a tubular cell unit is firstly sealed on an end metal sleeve by using a glass-based sealing material and then is connected with an air cavity.
In the prior art, tube-type fuel cell units and air inlet cavities are required to be prepared respectively, and then the dispersed tube-type fuel cell units are connected to the air inlet cavities according to a certain arrangement mode. The sealing method has the following defects: (1) the assembly workload of the battery pack is large, and the sealing effect is difficult to ensure; (2) because the connecting part is hermetically sealed by adopting different sealing materials, such as the inorganic high-temperature adhesive, the glass sealing material and the like, the connecting part is easy to crack due to thermal stress generated by the difference of the thermal expansion coefficients of different materials in the process of quick and repeated starting. The failure of the seal can not only lead to the performance reduction of the electric pile and the failure of the electric pile, but also even cause the electric pile to fire when the sealing failure is serious.
Disclosure of Invention
The inventor finds that the concentration of the reaction gas on the gas inlet cavity side is higher, and the sealing requirement is higher. In view of the above, the solid oxide fuel cell stack and the solid oxide fuel cell system provided by the invention better overcome the problems and defects in the prior art, and the gas inlet cavity and each tubular cell unit in the first cell unit group are designed into an integrated connection structure, and each tubular cell unit is assembled on the gas inlet cavity one by one without positioning, so that the gas tightness between the gas inlet cavity and the first cell unit group is good, the stability is high, the good isolation of anode gas and cathode gas is realized, the power generation performance and the long-term stability of the solid oxide fuel cell stack are effectively improved, and the assembly work of the solid oxide fuel cell stack is simplified.
Specifically, the present invention proposes the following specific embodiments:
a process for preparing a solid oxide fuel cell stack, comprising: the solid oxide fuel cell stack comprises an air inlet cavity and a first cell unit group connected with one end face of the air inlet cavity, the first cell unit group comprises a plurality of tubular cell units, and each tubular cell unit comprises a tubular inner electrode, an electrolyte layer coated on the outer surface of the tubular inner electrode and an outer electrode layer coated on the outer surface of the electrolyte layer;
the preparation process comprises the following steps:
(1) manufacturing the tubular inner electrodes of the tubular battery units and the air inlet cavity into an integrally formed blank body, and enabling an internal flow channel of each tubular inner electrode to be communicated with the air inlet cavity;
(2) coating an electrolyte layer on the outer wall of each tubular inner electrode, and then performing primary sintering treatment;
(3) and after the first sintering treatment, coating an outer electrode layer on the electrolyte layer, and performing second sintering treatment to obtain an integrated structure of the plurality of tubular battery units and the air inlet cavity.
The solid oxide fuel cell stack further comprises at least one group of second cell unit groups, the first cell unit group is communicated with the second cell unit groups and the two adjacent groups of second cell unit groups through intermediate air cavities, each second cell unit group comprises a plurality of tubular cell units, and each tubular cell unit comprises a tubular inner electrode, an electrolyte layer wrapping the outer surface of the tubular inner electrode and an outer electrode layer wrapping the outer surface of the electrolyte layer;
the step (1) comprises the following steps: and manufacturing the air inlet cavity, the plurality of tubular inner electrodes of the first battery cell group, the middle air cavity and the plurality of tubular inner electrodes of the at least one group of second battery cell groups into an integrally-formed blank.
Further, in the step (1), the integrally formed blank is prepared by adopting a 3D printing forming, slip casting or gel casting forming method.
Further, the step (1) further comprises performing a pre-sintering treatment on the obtained integrally-formed blank.
Further, the pre-sintering treatment temperature is 600-1000 DEG CoAnd C, pre-burning treatment time is 4-6 h.
Further, in the step (2), the temperature of the first sintering treatment is 1000-1500oC, the first sintering treatment time is 2-18 h;
in the step (3), the temperature of the second sintering treatment is 900-1300 DEGoAnd C, the second sintering treatment time is 8-20 h.
Further, the materials of the plurality of tubular inner electrodes are at least one of perovskite type composite oxides and spinel type oxides or cermets; the material of the air inlet cavity is the same as that of the tubular inner electrode.
Further, the material of the electrolyte layer is rare earth ion doped cerium oxide or rare earth ion doped zirconium oxide; the material of the outer electrode layer is at least one of perovskite type composite oxide and spinel type oxide or metal ceramic.
Further, in the step (3), before the second sintering treatment, a dense ceramic interlayer is coated on the outer surface of the air inlet cavity.
Further, the solid oxide fuel cell stack also comprises a gas outlet cavity;
after the step (3), the method further comprises the following steps: the solid oxide fuel cell stack further comprises an air outlet cavity; and the plurality of tubular inner electrodes of the tubular battery units, the air inlet cavity and the air outlet cavity are integrally formed.
Compared with the prior art, the preparation process of the solid oxide fuel cell stack has the beneficial effects that:
according to the preparation process of the solid oxide fuel cell pack, the air inlet cavity and each tubular cell unit in the first cell unit group are made into an integral connecting structure, and each tubular cell unit is assembled on the air inlet cavity one by one without positioning, so that the air inlet cavity and the first cell unit group are good in air tightness and high in stability, good isolation of anode gas and cathode gas is realized, the power generation performance and long-term stability of the solid oxide fuel cell pack are effectively improved, and meanwhile, the assembly work of the solid oxide fuel cell pack is simplified.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic view of a first structure of a solid oxide fuel cell stack according to the present invention;
FIG. 2 is a schematic view of a second structure of a solid oxide fuel cell stack according to the present invention;
FIG. 3 is a schematic view of a third structure of a solid oxide fuel cell stack according to the present invention;
fig. 4 is a schematic cross-sectional structure of a tube-type battery cell according to the present invention;
figure 5 is a schematic view of a configuration of the outlet chamber of the present invention.
Description of the main element symbols:
100-an air inlet cavity;
200-a first cell stack;
300-an air outlet cavity;
310-connecting hole;
400-second cell stack;
500-intermediate air cavity;
a 600-tube type battery cell;
610-inner electrode layers;
620-electrolyte layer;
630-outer electrode layer.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention.
This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms as used herein:
the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, temperature, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Referring to fig. 1 to 5, the solid oxide fuel cell stack includes an air inlet chamber 100 and a first cell unit 200 connected to an end surface of the air inlet chamber 100, the air inlet chamber 100 has an air inlet (not shown), and the first cell unit 200 includes a plurality of tube-type cell units 600. Each tube-type battery cell 600 includes a tube-type inner electrode 610, an electrolyte layer 620 coated on an outer surface of the tube-type inner electrode 610, and an outer electrode layer 630 coated on an outer surface of the electrolyte layer 620. The hollow center portion of the tubular inner electrode 610 is an internal flow passage.
The preparation process of the solid oxide fuel cell stack comprises the following steps:
step (1): the tube-type internal electrodes 610 of the plurality of tube-type battery cells 600 and the air inlet chamber 100 are manufactured into an integrally formed blank body, and the internal flow channel of each tube-type internal electrode 610 is communicated with the air inlet chamber 100.
Preferably, the present invention may adopt an existing method for integrally forming several tube-type inner electrodes 610 of the tube-type battery cells 600 and the air inlet cavity 100 into an integrally formed blank by laser light-cured 3D printing, slip casting, vacuum gel casting, or the like.
Preferably, the preparation process further comprises cleaning, drying and pre-sintering the obtained integrally-formed blank. Wherein, the drying process can be natural drying or 60-80 times of dryingoC is as 60oC、65oC、70oC、75oC or 80oC, drying in an oven to remove possible residual solvent in the integrally formed blank; in the pre-sintering treatment process: the pre-sintering temperature is preferably 600 to 1000 deg.CoC is as in 600oC、700oC、800oC、900oC or 1000oC, and the pre-sintering treatment time is preferably 4-6 h, such as 4h, 4.5h, 5h, 5.5h or 6 h.
Step (2): an electrolyte layer 620 is coated on the outer wall of each tube-type inner electrode 610, and then a first sintering process is performed.
Preferably, the present invention may apply a layer of electrolyte layer 620 on the outer wall of each tubular inner electrode 610 by using a conventional process such as slurry dipping, physical deposition, chemical deposition or electrophoretic deposition, or may apply a layer of electrolyte layer 620 on the outer wall of each tubular inner electrode 610 by using other application methods, and the thickness of the electrolyte layer 620 may be set according to actual requirements.
Preferably, the temperature of the first sintering treatment is 1000-1500oC is as 1000oC、1100oC、1200oC、1300oC、1400oC or 1500oC, and the like; the first sintering treatment time is 2-18 h, such as 2h, 5h, 8h, 10h, 12h, 15h or 18 h.
And (3): after the first sintering process, an outer electrode layer 630 is coated on the electrolyte layer 620, and a second sintering process is performed to obtain an integrated structure of the plurality of tubular battery cells 600 and the air inlet cavity 100, even if the air inlet cavity 100 and each tubular battery cell 600 in the first battery cell group 200 are in an integrated connection structure.
Preferably, the temperature of the second sintering treatment is 900-1300 DEG CoC is as in 900oC、1000oC、1100oC、1200oC or 1300oC, and the time of the second sintering treatment is 8-20 h, such as 8h, 10h, 12h, 15h, 18h or 20 h.
Preferably, as shown in fig. 2, 3 and 4, the solid oxide fuel cell stack further includes at least one second cell stack 400, the first cell stack 200 and the second cell stack 400 and the two adjacent second cell stacks 400 are communicated with each other through an intermediate air cavity 500, each second cell stack 400 includes a plurality of tubular cell units 600, and each tubular cell unit 600 includes a tubular inner electrode 610, an electrolyte layer 620 coated on an outer surface of the tubular inner electrode 610, and an outer electrode layer 630 coated on an outer surface of the electrolyte layer 620.
It should be noted that the number of the second cell lines 400 may be designed into one, two, three, five or more second cell lines 400 according to actual needs. The number of the tube-type battery cells 600 in each second battery cell group 400 may be the same or different, and may also be the same or different from the number of the tube-type battery cells 600 in the first battery cell group 200. Preferably, the number of the tube-type battery cells 600 in each set of the second cell line 400 is the same as the number of the tube-type battery cells 600 in the first cell line 200, and they are arranged in one-to-one correspondence.
Accordingly, in step (1): the air intake cavity 100, the plurality of tubular internal electrodes 610 of the first cell unit group 200, the intermediate air cavity 500, and the plurality of tubular internal electrodes 610 of the at least one second cell unit group 400 are manufactured into an integrally molded embryo body, and the air intake cavity 100, the internal flow channels of the plurality of tubular internal electrodes 610 of the first cell unit group 200, the intermediate air cavity 500, and the internal flow channels of the plurality of tubular internal electrodes 610 of the at least one second cell unit group 400 are communicated.
In the anode-supported SOFC, the tubular inner electrode 610 is made of a cermet, preferably a cermet in which a transition group element such as Ni, Co, Fe, Mn, etc. is combined with a metal oxide, the content of the transition group element such as Ni, Co, Fe, Mn, etc. in the cermet is 20 to 80wt%, for example, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, or 80wt%, and the metal oxide is rare earth ion-doped ceria, rare earth ion-doped zirconia, alumina, or the like. Correspondingly, the material of the outer electrode layer 630 may be at least one of a perovskite type composite oxide and a spinel type oxide, that is, the material of the outer electrode 630 may be any one of a perovskite type composite oxide and a spinel type oxide, or a composite of the perovskite type composite oxide and the spinel type oxide in any ratio.
For the cathode-supported SOFC, the tubular inner electrode 610 may be made of at least one of a perovskite-type composite oxide and a spinel-type oxide, that is, the tubular inner electrode 610 may be made of any one of a perovskite-type composite oxide and a spinel-type oxide, or a composite of a perovskite-type composite oxide and a spinel-type oxide at any ratio; the material of the tubular inner electrode 610 may also be a mixture of a perovskite-type composite oxide and rare earth ion-doped ceria. Correspondingly, the material of the outer electrode layer 630 may be cermet.
Preferably, the material of the electrolyte layer 620 is rare earth ion doped ceria or rare earth ion doped zirconia or the like. The rare earth ion-doped ceria includes, for example, yttrium (Y) -doped ceria, gadolinium (Gd) -doped ceria, samarium (Sm) -doped ceria, or lanthanum (La) -doped ceria; the rare earth ion-doped zirconia may be specifically yttrium (Y) -doped zirconia or scandium (Sc) -doped zirconia.
The material of the air inlet chamber 100 and the material of the intermediate air chamber 500 may be the same as or different from the material of the tubular inner electrode 610. When the material of the air intake chamber 100 and the intermediate air chamber 500 is different from that of the tubular inner electrode 610, the material may be alumina, zirconia, or ceria. Preferably, the material of the air inlet chamber 100 and the intermediate air chamber 500 is the same as that of the tubular inner electrode 610.
Further, in order to ensure the air tightness of the intake cavity 100, a dense ceramic interlayer may be coated on the outer wall surface of the intake cavity 100. The ceramic interlayer can be made of alumina, zirconia, ceria and other ceramic materials. Preferably, the ceramic barrier layer is made of the same material as the electrolyte layer 620 in the tube-type battery cell 600.
Preferably, all the tube-shaped battery cells 600 of the first cell line group 200 are the same in size and arranged in parallel with each other, all the tube-shaped battery cells 600 of each second cell line group 400 are the same in size and arranged in parallel with each other, and each tube-shaped battery cell 600 is arranged perpendicular to the air intake chamber 100. The cross-section of the first cell line 200 and each of the second cell lines 400 may be a quadrangle, a hexagon, a circle, or the like.
Of course, the present invention is not limited to the size and arrangement of all the tube-type battery cells 600 of the first cell line 200 and all the tube-type battery cells 600 in each set of the second cell line 400, and may also be arranged in a non-parallel manner, such as in a radial arrangement or a spiral arrangement, and preferably in a fibonacci spiral arrangement that can more effectively utilize space.
In addition, the tube-type battery units 600 with different tube diameters and different cross-sectional shapes can be mixed and arranged, so that the space density of the tube-type battery units 600 is further improved.
Further, the solid oxide fuel cell stack further comprises a gas outlet chamber 300.
Preferably, the outlet chamber 300 may be integrally formed with the inlet chamber 100 and the plurality of tube-type battery cells 600.
Of course, a plurality of connection holes 310 corresponding to the plurality of tubular battery cells 600 of the first battery cell group 200 one to one may also be designed on one end surface of the air outlet cavity 300, as shown in fig. 5, one end of each tubular battery cell 600 of the first battery cell group 200, which is far away from the air inlet cavity 100, is bonded to the periphery of the corresponding connection hole 310 of the air outlet cavity 300 by using a high temperature adhesive, or a cylindrical connection member (not shown in the figure) is welded at the connection hole 310 of the air outlet cavity 300, the outer diameter of the connection member is slightly larger than the outer diameter of the tubular battery cell 600, then one end of each tubular battery cell 600, which is far away from the air inlet cavity 100, is inserted into the connection.
The term "a plurality of roots" may be exemplified by 2, 10, 50, 100, 200, 500, 800, 1000, etc.
It should be noted that the inlet chamber 100, the outlet chamber 300, and the intermediate air chamber 500 may be each cylindrical, rectangular or other shapes.
According to the preparation process of the solid oxide fuel cell stack, the air inlet cavity 100 and each tubular cell unit 600 in the first cell unit group 200 are made into an integral connecting structure, and each tubular cell unit 600 is assembled on the air inlet cavity one by one without positioning, so that the air tightness between the air inlet cavity 100 and the first cell unit group 200 is good, the stability is high, the anode gas and the cathode gas are well isolated, the power generation performance and the long-term stability of the solid oxide fuel cell stack are effectively improved, and the assembly work of the solid oxide fuel cell stack is simplified.
In addition, in the prior art, the tubular battery units and the air inlet cavity are required to be prepared respectively, then the dispersed tubular battery units are connected to the air cavity according to a certain arrangement mode, and the distance between every two adjacent tubular battery units is large because the positions of pipe end connectors, the sealing positions and the assembly space between every two adjacent tubular battery units are reserved. For example, in the case of a tube-type cell having a diameter of 8mm, the distance between the centers of two adjacent tube-type cells is at least 18 mm. In the invention, the air inlet cavity 100 and each tubular battery cell 600 in the first battery cell group 200 are integrally connected, and similarly, taking a tubular battery cell with a diameter of 8mm as an example, the center distance between adjacent tubular battery cells can be reduced to 10mm, so that the assembly space between the tubular battery cells 600 is effectively saved, and the battery density can be greatly improved.
It should be noted that the solid oxide fuel cell pack obtained by the preparation process of the present invention can be applied to various solid oxide fuel cell systems, including distributed power generation, portable power sources and fuel cell power systems, the air inlet of the air inlet cavity 100 is connected with the system air path through an external pipeline, and the air outlet cavity 300 is also connected with the system air path through a cavity socket or an external pipeline. Preferably, air distribution and heat exchange structures may also be provided in the inlet chamber 100 and the outlet chamber 300.
Example 1
(1) After an integrated model of the 100 tubular inner electrodes 610 and the air inlet cavity 100 is established by using three-dimensional modeling software, the 100 tubular inner electrodes 610 are the same in size and are arranged in parallel, the whole cross section is square, and the air inlet cavity 100 and the air outlet cavity 300 are respectively positioned at two ends of the 100 tubular inner electrodes 610 and are vertical to the 100 tubular inner electrodes 610; then, an integrally formed blank body comprising a plurality of tubular inner electrodes 610 and the air inlet cavity 100 is obtained through a laser photocuring 3D printing forming technology, and an internal flow channel of each tubular inner electrode 610 is communicated with the air inlet cavity 100; the air inlet cavity 100 is obtained by printing yttrium-doped cerium oxide slurry, and the 100 tubular inner electrodes 610 are obtained by printing a mixture of strontium-doped lanthanum cobaltate (LSM) and yttrium-doped cerium oxide (wherein the LSM content is 60 wt%).
(2) Cleaning the integrally formed blank obtained in the step (1), naturally drying in a shady and ventilated environment, and dryingPre-burning the integrally formed blank at 600 deg.CoAnd C, pre-sintering for 6 h.
(3) Preparing yttrium-doped cerium oxide films with the thickness of 5 microns on the outer surface of the air inlet cavity 100 and the outer wall of each tubular inner electrode 610 by adopting a chemical deposition method, and then sintering the yttrium-doped cerium oxide films at the high temperature of 1000 ℃ for 18 hours to form an electrolyte layer 620 on the outer wall of each tubular inner electrode 610 and a ceramic interlayer on the outer surface of the air inlet cavity 100.
(4) A layer of nickel oxide (NiO) and yttrium-doped ceria compound (the content of nickel oxide (NiO) accounts for 50 wt%) is coated on the outer surface of the electrolyte layer 620, and then sintering treatment is performed at 900 ℃ for 20 hours to form the outer electrode layer 630, so that 100 tubular battery cells 600 composed of the tubular inner electrode 610, the electrolyte layer 620 coated on the outer surface of the tubular inner electrode 610, and the outer electrode layer 630 coated on the outer surface of the electrolyte layer 620 are obtained, wherein the diameter of each tubular battery cell 600 is 8mm, and the center distance between two adjacent tubular battery cells 600 is 12 mm.
(5) Preparing the air outlet cavity 300, designing 100 connecting holes 310 corresponding to 100 tubular battery units 600 one by one on one end face of the air outlet cavity 300, welding cylindrical connecting pieces at the connecting holes 310 of the air outlet cavity 300, wherein the outer diameter of each connecting piece is slightly larger than that of each tubular battery unit 600, inserting one end of each tubular battery unit 600 far away from the air inlet cavity 100 into the connecting piece, and sealing and connecting gaps through high-temperature glue or glass.
Example 2
(1) The method comprises the following steps of establishing an integrated model of the air inlet cavity 100, the 500 tubular inner electrodes 610 and the air outlet cavity 300 by using three-dimensional modeling software, wherein the 500 tubular inner electrodes 610 are identical in size and are arranged in parallel, the whole cross section of the integrated model is square, and the air inlet cavity 100 and the air outlet cavity 300 are respectively positioned at two ends of the 500 tubular inner electrodes 610 and are vertical to the 500 tubular inner electrodes 610; then, an integrally formed blank body comprising a plurality of tubular inner electrodes 610 and the air inlet cavity 100 is obtained through a laser photocuring 3D printing forming technology, and an internal flow channel of each tubular inner electrode 610 is communicated with the air inlet cavity 100; the air inlet cavity 100 is obtained by printing yttrium-doped cerium oxide slurry, and the 500 tubular inner electrodes 610 are obtained by printing a mixture of strontium-doped lanthanum cobaltate (LSM) and yttrium-doped cerium oxide (wherein the LSM content is 60 wt%).
(2) Cleaning the integrally formed blank obtained in the step (1), naturally drying in a shady and ventilated environment, and pre-burning the dried integrally formed blank at the pre-burning temperature of 800oAnd C, pre-sintering for 5 h.
(3) Preparing yttrium-doped cerium oxide films with the thickness of 5 microns on the outer surface of the air inlet cavity 100 and the outer wall of each tubular inner electrode 610 by adopting a chemical deposition method, and then sintering at the high temperature of 1200 ℃ for 10 hours to form an electrolyte layer 620 on the outer wall of each tubular inner electrode 610 and a ceramic interlayer on the outer surface of the air inlet cavity 100.
(4) A layer of nickel oxide (NiO) and yttrium-doped ceria composite (the content of nickel oxide (NiO) accounts for 50 wt%) was coated on the outer surface of the electrolyte layer 620, and then, sintering treatment was performed at 1100 ℃ for 13 hours to form the outer electrode layer 630, thereby obtaining 500 tubular battery cells 600 each composed of a tubular inner electrode 610, an electrolyte layer 620 coated on the outer surface of the tubular inner electrode 610, and an outer electrode layer 630 coated on the outer surface of the electrolyte layer 620, each tubular battery cell 600 having a diameter of 6mm, and the distance between the centers of two adjacent tubular battery cells 600 was 8 mm.
Example 3
(1) Obtaining an integrally formed blank body comprising 100 tubular inner electrodes 610 and the air inlet cavity 100 by adopting a vacuum gel injection molding method, wherein an internal flow channel of each tubular inner electrode 610 is communicated with the air inlet cavity 100; the 100 tubular inner electrodes 610 are identical in size and are arranged in parallel, the whole cross section of the 100 tubular inner electrodes 610 is square, and the air inlet cavity 100 and the air outlet cavity 300 are respectively located at two ends of the 100 tubular inner electrodes 610 and are perpendicular to the 100 tubular inner electrodes 610; wherein, the gas inlet cavity 100 and the 100 tubular inner electrodes 610 both adopt a cermet material formed by compounding Ni and yttrium-doped cerium oxide (the content of Ni is 50 wt%).
(2) Cleaning the integrally formed blank obtained in the step (1), naturally drying in a shady and ventilated environment, and drying the integrally formed blankPerforming pre-sintering treatment at 1000 deg.CoAnd C, pre-sintering for 4 h.
(3) Preparing a yttrium-doped zirconia film with the thickness of 20 microns on the outer surface of the air inlet cavity 100 and the outer wall of each tubular inner electrode 610 by adopting a slurry dipping method, and then sintering at 1500 ℃ for 4 hours to form an electrolyte layer 620 on the outer wall of each tubular inner electrode 610 and a ceramic interlayer on the outer surface of the air inlet cavity 100.
(4) Coating a layer of strontium-doped lanthanum cobaltite on the outer surface of an electrolyte layer 620, and then performing sintering treatment at 1300 ℃ for 10h to form an outer electrode layer 630, thereby obtaining 100 tubular battery cells 600 composed of tubular inner electrodes 610, the electrolyte layer 620 coated on the outer surface of the tubular inner electrodes 610, and the outer electrode layer 630 coated on the outer surface of the electrolyte layer 620, wherein the diameter of each tubular battery cell 600 is 8mm, and the center distance between two adjacent tubular battery cells 600 is 12 mm.
(5) Preparing the air outlet cavity 300, designing 100 connecting holes 310 corresponding to 100 tubular battery units 600 one by one on one end face of the air outlet cavity 300, welding cylindrical connecting pieces at the connecting holes 310 of the air outlet cavity 300, wherein the outer diameter of each connecting piece is slightly larger than that of each tubular battery unit 600, inserting one end of each tubular battery unit 600 far away from the air inlet cavity 100 into the connecting piece, and sealing and connecting gaps through high-temperature glue or glass.
Example 4
(1) Adopting a slip casting method to obtain an integrally formed blank body comprising the air inlet cavity 100, 100 tubular inner electrodes 610 and the air outlet cavity 300, wherein an internal flow channel of each tubular inner electrode 610 is communicated with the air inlet cavity 100 and the air outlet cavity 300; wherein, the 100 tubular inner electrodes 610 have the same size and are arranged in parallel, and the whole cross section is square; the air inlet cavity 100 and the air outlet cavity 300 are respectively positioned at two ends of the 100 tubular inner electrodes 610 and are vertical to the 100 tubular inner electrodes 610; wherein, the gas inlet cavity 100, the 100 tubular inner electrodes 610 and the gas outlet cavity 300 are made of metal ceramic materials formed by compounding Ni and yttrium-doped cerium oxide (the content of Ni is 50 wt%).
(2) Cleaning the integrally formed blank obtained in the step (1), and thenNaturally drying in a shady and ventilated environment, and pre-sintering the dried integrally formed blank at 800 deg.CoAnd C, pre-sintering for 5 h.
(3) Preparing yttrium-doped cerium oxide films with the thickness of 5 microns on the outer surface of the air inlet cavity 100 and the outer wall of each tubular inner electrode 610 by adopting a slurry dipping method, and then sintering at the high temperature of 1200 ℃ for 10 hours to form an electrolyte layer 620 on the outer wall of each tubular inner electrode 610 and a ceramic interlayer on the outer surface of the air inlet cavity 100.
(4) Coating a layer of strontium-doped lanthanum cobaltite on the outer surface of an electrolyte layer 620, and then performing sintering treatment at 1300 ℃ for 10h to form an outer electrode layer 630, thereby obtaining 100 tubular battery cells 600 composed of tubular inner electrodes 610, the electrolyte layer 620 coated on the outer surface of the tubular inner electrodes 610, and the outer electrode layer 630 coated on the outer surface of the electrolyte layer 620, wherein the diameter of each tubular battery cell 600 is 8mm, and the center distance between two adjacent tubular battery cells 600 is 12 mm.
Example 5
(1) After an integrated model of the air inlet cavity 100, the two groups of tubular inner electrode groups, the middle air cavity 500 and the air outlet cavity 300 is established by using three-dimensional modeling software, each group of tubular inner electrode groups comprises 50 tubular inner electrodes 610 which are same in size and are arranged in parallel, the overall cross section of each group is square, the middle air cavity 500 is positioned between the two groups of tubular inner electrode groups, the air inlet cavity 100 and the air outlet cavity 300 are respectively positioned at two ends, and the middle air cavity 500, the air inlet cavity 100 and the air outlet cavity 300 are all perpendicular to the two groups of tubular inner electrodes 610; then, obtaining an integrally formed blank body comprising an air inlet cavity 100, two groups of tubular inner electrode groups, a middle air cavity 500 and an air outlet cavity 300 by using a laser photocuring 3D printing technology, wherein an internal flow channel of each tubular inner electrode 610 is communicated with the air inlet cavity 100, the middle air cavity 500 and the air outlet cavity 300; wherein, the air inlet cavity 100, the middle air cavity 500, each tubular inner electrode 610 and the air outlet cavity 300 are obtained by printing metal ceramic slurry (the content of Ni is 50 wt%) formed by compounding cerium oxide doped with Ni and yttrium.
(2) And (2) cleaning the integrally formed blank obtained in the step (1), and naturally drying in a cool and ventilated environment.
(3) Preparing yttrium-doped zirconia films with the thickness of 5 microns on the outer surface of the air inlet cavity 100 and the outer wall of each tubular inner electrode 610 by adopting an electrophoretic deposition method, and then sintering for 12 hours at the high temperature of 1200 ℃, so that an electrolyte layer 620 is formed on the outer wall of each tubular inner electrode 610 and a ceramic interlayer is formed on the outer surface of the air inlet cavity 100.
(4) Coating a layer of strontium-doped lanthanum cobaltite on the outer surface of the electrolyte layer 620, and then performing sintering treatment at 1000 ℃ for 15h to form an outer electrode layer 630, so that each group of cell units comprises 50 tubular cell units 600 consisting of tubular inner electrodes 610, the electrolyte layer 620 coated on the outer surface of the tubular inner electrodes 610 and the outer electrode layer 630 coated on the outer surface of the electrolyte layer 620, the diameter of each tubular cell unit 600 is 8mm, and the distance between the centers of two adjacent tubular cell units 600 is 12 mm.
The solid oxide fuel cell stacks obtained in examples 1 and 2 need to be 500 to 800 before they are used in a solid oxide fuel cell system to generate electricityoAnd C, heating in a reducing atmosphere to reduce the nickel oxide in the outer electrode layer as an anode into metallic Ni.
When the solid oxide fuel cell stack prepared in the embodiments 1 to 5 of the present invention is applied to a solid oxide fuel cell system using hydrogen as a fuel, the initial open-circuit voltage value of each tubular cell unit in the solid oxide fuel cell stack prepared in the embodiments 1 to 5 of the present invention is 1.05 to 1.15V, and the open-circuit voltage value after 1000 hours of operation is not significantly reduced (the reduction ratio is less than 5%); under the same test condition, the initial open-circuit voltage value of each tubular battery unit in the prior art (the air inlet cavity and each tubular battery unit are hermetically assembled by high-temperature glue) is 0.95-1.0V, and the open-circuit voltage value after running for 1000 hours is obviously reduced (the reduction ratio is 20% -26%).
Therefore, the power generation performance and stability of the solid oxide fuel cell stack prepared by the method are obviously improved compared with the power generation performance and stability of the solid oxide fuel cell stack prepared by the prior art (the air inlet cavity and each tubular cell unit are hermetically assembled by high-temperature glue).
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.

Claims (9)

1. A process for preparing a solid oxide fuel cell stack, comprising: the solid oxide fuel cell stack comprises an air inlet cavity, a first cell unit group and at least one second cell unit group, wherein the first cell unit group is connected with one end face of the air inlet cavity, the second cell unit groups are communicated with each other through an intermediate air cavity, the first cell unit group and each second cell unit group respectively comprise a plurality of tubular cell units, each tubular cell unit comprises a tubular inner electrode, an electrolyte layer and an outer electrode layer, the electrolyte layer wraps the outer surface of the tubular inner electrode, and the outer electrode layer wraps the outer surface of the electrolyte layer;
the preparation process comprises the following steps:
(1) manufacturing the air inlet cavity, the plurality of tubular inner electrodes of the first battery cell group, the middle air cavity and the plurality of tubular inner electrodes of at least one group of second battery cell groups into an integrally-formed blank body, and enabling an internal flow channel of each tubular inner electrode to be communicated with the air inlet cavity;
(2) coating an electrolyte layer on the outer wall of each tubular inner electrode, and then performing primary sintering treatment;
(3) and after the first sintering treatment, coating an outer electrode layer on the electrolyte layer, and performing second sintering treatment to obtain an integrated structure of the plurality of tubular battery units and the air inlet cavity.
2. The process for preparing a solid oxide fuel cell stack according to claim 1, wherein: in the step (1), the integrally formed blank is prepared by adopting a 3D printing forming, grouting forming or vacuum gel casting forming method.
3. The process for preparing a solid oxide fuel cell stack according to claim 1, wherein: and (1) pre-burning the obtained integrally-formed blank.
4. The process of manufacturing a solid oxide fuel cell stack according to claim 3, characterized in that: the pre-sintering treatment temperature is 600-1000 DEG CoAnd C, pre-burning treatment time is 4-6 h.
5. The process for preparing a solid oxide fuel cell stack according to claim 1, wherein: in the step (2), the temperature of the first sintering treatment is 1000-1500oC, the first sintering treatment time is 2-18 h;
in the step (3), the temperature of the second sintering treatment is 900-1300 DEGoAnd C, the second sintering treatment time is 8-20 h.
6. The process for preparing a solid oxide fuel cell stack according to claim 1, wherein: the materials of the plurality of tubular inner electrodes are at least one of perovskite type composite oxides and spinel type oxides or metal ceramics; the material of the air inlet cavity is the same as that of the tubular inner electrode.
7. The process for preparing a solid oxide fuel cell stack according to claim 1, wherein: the electrolyte layer is made of rare earth ion doped cerium oxide or rare earth ion doped zirconium oxide; the material of the outer electrode layer is at least one of perovskite type composite oxide and spinel type oxide or metal ceramic.
8. The process for preparing a solid oxide fuel cell stack according to claim 1, wherein: and (3) before the second sintering treatment, coating a compact ceramic interlayer on the outer surface of the air inlet cavity.
9. The process for preparing a solid oxide fuel cell stack according to claim 1, wherein: the solid oxide fuel cell stack further comprises an air outlet cavity; and the plurality of tubular inner electrodes of the tubular battery units, the air inlet cavity and the air outlet cavity are integrally formed.
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