CN107959036B - Preparation method of solid oxide fuel cell with flat plate structure - Google Patents
Preparation method of solid oxide fuel cell with flat plate structure Download PDFInfo
- Publication number
- CN107959036B CN107959036B CN201610898228.6A CN201610898228A CN107959036B CN 107959036 B CN107959036 B CN 107959036B CN 201610898228 A CN201610898228 A CN 201610898228A CN 107959036 B CN107959036 B CN 107959036B
- Authority
- CN
- China
- Prior art keywords
- layer
- electrolyte
- barrier layer
- anode
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 39
- 239000007787 solid Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000004888 barrier function Effects 0.000 claims abstract description 99
- 239000003792 electrolyte Substances 0.000 claims abstract description 96
- 238000005245 sintering Methods 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 22
- 238000007650 screen-printing Methods 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000006257 cathode slurry Substances 0.000 claims description 9
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000002001 electrolyte material Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 230000008646 thermal stress Effects 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 195
- 239000000758 substrate Substances 0.000 description 8
- 238000003487 electrochemical reaction Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- -1 oxygen ion Chemical class 0.000 description 2
- 229910002230 La2Zr2O7 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
Landscapes
- 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 provides a preparation method of a solid oxide fuel cell with a flat plate structure. The solid oxide fuel cell takes an anode layer as a supporting layer, and a barrier layer material between an electrolyte and a cathode is GDC; according to the invention, the anode support body, the electrolyte and the barrier layer green body are co-sintered, so that the preparation process is greatly simplified, the electrolyte and the barrier layer can achieve a good compact effect at the sintering temperature of 1300 ℃, and the interface bonding effect between the electrolyte and the barrier layer is good. The preparation method is particularly suitable for the solid oxide fuel cell with a hollow upper-lower distribution flat plate structure in consideration of the problems of thermal stress and sintering flatness.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to a preparation method of a solid oxide fuel cell with a flat plate type structure.
Background
Due to climate change and fossil energy constraints, solid oxide fuel cell technology has received much attention. The basic structure of the solid oxide fuel cell comprises an electrolyte, a porous anode and a porous cathode, wherein fuel is introduced into the anode, oxidant gas is introduced into the cathode, electrons are generated through electrochemical reaction at a three-phase interface of the electrolyte and the electrode, an external electronic loop is formed, and electric energy and heat energy are finally generated.
In recent years, the high temperature anode, electrolyte and cathode materials which are researched and applied relatively mature in solid oxide fuel cells are Ni-YSZ, YSZ and LSM, respectively. However, as the operating temperature of the high-temperature solid oxide fuel cell is reduced from 800-1000 ℃ to 500-800 ℃, compared with the pure electronic conductor cathode material LSM, the mixed ion conductor LSCF has higher catalytic activity on oxygen, so that the discharge performance of the cell is better. However, when operated at high temperatures of 1200 ℃ or higher, the LSCF cathode material is susceptible to interfacial reaction with the YSZ electrolyte material to form an insulating SrZrO phase3And La2Zr2O7And the like, and a problem of a mismatch in expansion coefficient or the like occurs, causing instability of the battery.
To address this problem, researchers have introduced a barrier layer between LSCF and YSZ that should satisfy: 1) the electrolyte YSZ and the cathode LSCF have good chemical compatibility, and can prevent the electrolyte YSZ and the cathode LSCF from generating a high-impedance phase through chemical reaction;
2) the expansion coefficient of the material of the barrier layer is between that of YSZ and LSCF of the cathode, so that the expansion coefficient between the cathode and the electrolyte is improved;
3) the barrier layer material has good compactness and high oxygen ion conductivity at medium and low temperature.
By adding cerium oxide (CeO)2) Doping rare earth metal oxide Gd with proper concentration in the base material2O3Can greatly increase the oxygen ion vacancy and obviously improve the ionic conductivity, thereby becoming a good oxygen ion conductor. Such doped CeO2The base material is called GDC, and the base material is prepared into a compact film layer, so that the requirements of the barrier layer can be met.
At this stage, the steps for preparing the solid oxide fuel cell with the anode, electrolyte, cathode material and barrier layer of Ni-YSZ, LSCF and GDC respectively are generally as follows: after the anode functional layer and the electrolyte layer are prepared at 1300 ℃ by co-firing, printing GDC slurry on the surface of a compact electrolyte substrate in a silk-screen manner for sintering, wherein the GDC barrier layer is generally sintered at 1200 ℃, and finally printing cathode slurry on the surface of the GDC barrier layer in a silk-screen manner for sintering at about 1100 ℃.
The method has the following defects: (1) the sintered half-cell is sintered for the second time, so that the complexity of the cell preparation is increased; (2) the section SEM image of the GDC barrier layer prepared by screen printing GDC slurry on the surface of the hard electrolyte substrate and performing secondary sintering is shown in figure 1, which shows that the compact effect is poor, the requirement of barrier layer compactness is difficult to meet, and the interface bonding effect between the hard electrolyte substrate and the electrolyte is poor, so that larger interface resistance can be caused, and simultaneously, the diffusion reaction between a cathode material and the electrolyte is not favorably avoided, and the operation stability of the battery is influenced.
Disclosure of Invention
Aiming at the technical current situation of the solid oxide fuel cell, the invention provides the preparation method of the solid oxide fuel cell, the process is simple, the cost is low, and the prepared GDC barrier layer has good compactness and good interface bonding property with an electrolyte.
Therefore, after a large number of experiments and researches, the inventor discovers that the preparation process can be simplified and the cost can be saved by adopting a flat plate type structure taking the anode layer as a supporting layer and co-sintering the anode layer, the electrolyte layer and the barrier layer green body, the GDC barrier layer and the electrolyte layer which are prepared when the sintering temperature is increased to 1300 ℃ can achieve a compact effect, and meanwhile, the interface bonding effect between the GDC barrier layer and the electrolyte layer is good.
Namely, the technical scheme of the invention is as follows: a method for preparing a solid oxide fuel cell with a flat plate structure, wherein the solid oxide fuel cell takes an anode layer as a supporting layer, the anode layer is made of Ni-YSZ, an electrolyte material is YSZ, a cathode material is LSCF, and a barrier layer between the electrolyte and the cathode is GDC, and is characterized in that: the barrier layer is made by sintering, and the anode layer, the electrolyte layer and the green body of the barrier layer are co-sintered at a sintering temperature of 1300 ℃ or higher.
As one implementation, the electrolyte paste and the barrier layer GDC paste are coated, impregnated, or screen printed on the anode layer surface, followed by co-sintering.
Preferably, the electrolyte layer has a thickness of 1 to 10 μm, more preferably 5 μm.
Preferably, the barrier layer has a thickness of 1 to 5 μm m, more preferably 3 μm.
Preferably, the co-sintering procedure is as follows: heating to 600 deg.C at 0.5-3 deg.C/min, maintaining for 0.5-3 h, heating to sintering temperature at 0.5-3 deg.C/min, maintaining for 1-5 h, and naturally cooling to room temperature.
And after the anode layer, the electrolyte layer and the green body of the barrier layer are sintered together, coating or screen printing cathode slurry on the surface of the barrier layer, and then sintering, wherein the sintering temperature is cathode sintering temperature. The cathode sintering temperature is 1000-1200 ℃.
At present, a problem of the solid oxide fuel cell of the flat plate type structure is that the cell structure is asymmetric. When the cell is operated at a higher temperature, the introduction of fuel, electrochemical reaction, and electron transfer all generate heat, and the coexistence of these heats causes the internal thermal balance to be extremely uneven, and particularly when the cell structure is asymmetric, the thermal stress due to such uneven heat is more negligible, which may cause cracks between the thin electrolyte and the electrode, thereby damaging the cell and causing operation failure. In addition, when the cell structure is asymmetric, denaturation is likely to occur during the sintering process for preparing the cell, which affects the flatness of the cell.
For this reason, the solid oxide fuel cell with a flat plate structure is preferably designed into an upper and lower distribution type taking the anode supporting layer as the center, namely the electrolyte layer is divided into two layers which are respectively positioned on the upper and lower surfaces of the anode supporting layer; the barrier layer is also divided into two layers which are respectively positioned on the surfaces of the two electrolyte layers; the cathode layer is also divided into two layers which are respectively positioned on the surfaces of the two barrier layers; and the anode supporting layer is provided with holes for introducing gas, and the holes are provided with open ends on the side surface of the anode supporting layer. The design takes the anode supporting layer as a center, gas is introduced into the inner hole of the anode supporting layer from the side opening and then diffused to the upper side and the lower side, and the three-phase interface with electrochemical reaction is positioned on the upper side and the lower side of the supporting electrode layer, so that the generated thermal stress is effectively offset, and the thermal stress is greatly reduced. In addition, in the process of preparing the battery, the battery structure is in an up-and-down distribution type, so that the flatness of the battery is kept in the process of sintering the battery.
That is, the solid oxide fuel cell is preferably a hollow vertically distributed flat plate structure, and as shown in fig. 2, the anode layer is used as a support layer, and the anode layer, the electrolyte layer, the barrier layer, and the cathode layer are stacked vertically in the thickness direction; the electrolyte layer comprises a first electrolyte layer and a second electrolyte layer, the first electrolyte layer is positioned on the lower surface of the support anode layer, and the second electrolyte layer is positioned on the upper surface of the support anode layer; the barrier layer comprises a first barrier layer and a second barrier layer, the first barrier layer is positioned on the lower surface of the first electrolyte layer, and the second barrier layer is positioned on the upper surface of the second electrolyte layer; the cathode layer comprises a first cathode layer and a second cathode layer, the first cathode layer is positioned on the lower surface of the first barrier layer, and the second cathode layer is positioned on the upper surface of the second barrier layer; the support anode layer is provided with hollow channels (or holes) having an access end at the side of the support anode layer.
Further preferably, when the anode layer is used as a center, and the first electrolyte layer and the second electrolyte layer are symmetrically distributed, that is, the shapes, thicknesses, and the like of the first electrolyte layer and the second electrolyte layer are completely consistent, the effect of reducing the thermal stress is better, and the flatness maintenance of the sintering process is more facilitated.
Further preferably, the anode support layer is used as a center, and when the first barrier layer and the second barrier layer are symmetrically distributed, that is, the shapes, thicknesses and the like of the first barrier layer and the second barrier layer are completely consistent, the effect of reducing the thermal stress is better, and the flatness maintenance of the sintering process is more facilitated.
Further preferably, the anode supporting layer is used as a center, and when the first cathode layer and the second cathode layer are symmetrically distributed, that is, the shapes, thicknesses and the like of the first cathode layer and the second cathode layer are completely consistent, the effect of reducing the thermal stress is better, and the flatness maintenance of the sintering process is more facilitated.
In the above-described hollow anode-supported structure distributed vertically, as an implementation manner, the method for manufacturing a solid oxide fuel cell of the present invention is as follows:
(1) taking an anode support body as a raw material, burying a high-temperature volatile substance with a certain size as a pore-forming agent in the anode support body, forming and sintering to obtain a forming body, wherein the pore-forming agent volatilizes to obtain a support electrode layer with a pore structure, and the pore has an opening end on the side surface of the support electrode layer;
the pore-forming agent material is not limited, and includes carbon rods, carbon materials with other shapes such as graphite, carbon nanotubes and the like.
The molding method is not limited, and includes hot pressing, casting and the like.
(2) Sequentially coating, dipping or screen printing first electrolyte slurry and first barrier layer slurry on the lower surface of the anode support body; sequentially coating, dipping or screen printing a second electrolyte slurry and a second barrier layer slurry on the upper surface of the anode support body; and then co-sintering.
(3) Coating or screen printing first cathode slurry on the lower surface of the first barrier layer; coating or screen printing second cathode slurry on the lower surface of the second barrier layer; and then sintering is performed.
In conclusion, in the preparation process of the solid oxide fuel cell with the flat plate structure, the anode support body, the electrolyte and the barrier layer green body are sintered together, so that the preparation process is greatly simplified, the electrolyte and the barrier layer can achieve good compact effect at the sintering temperature of 1300 ℃, and meanwhile, the interface bonding effect between the electrolyte and the barrier layer is good. The preparation method is particularly suitable for the solid oxide fuel cell with a hollow upper-lower distribution flat plate structure in consideration of the problems of thermal stress and sintering flatness.
Drawings
FIG. 1 is a sectional SEM image of a GDC barrier layer obtained on the surface of an electrolyte substrate by secondary sintering;
FIG. 2 is a schematic structural view of a hollow solid oxide fuel cell of a vertically distributed flat plate type structure in example 1 of the present invention;
fig. 3(a) is a surface SEM image of a GDC barrier layer obtained on the surface of an electrolyte substrate by co-sintering in the preparation of a solid oxide fuel cell of a hollow top-bottom distribution plate type structure in example 1 of the present invention;
fig. 3(b) is a sectional SEM image of a GDC barrier layer obtained on the surface of an electrolyte substrate by co-sintering in the preparation of a solid oxide fuel cell of a hollow top-bottom distribution plate type structure in example 1 of the present invention;
fig. 4(a) is a surface SEM image of a GDC barrier layer obtained on the surface of an electrolyte substrate by secondary sintering in the preparation of a solid oxide fuel cell of a hollow top-bottom distribution plate-type structure in comparative example 1 of the present invention;
fig. 4(b) is a sectional SEM image of a GDC barrier layer obtained on the surface of an electrolyte substrate by secondary sintering in the production of a solid oxide fuel cell of a hollow vertically distributed flat plate type structure in comparative example 1 of the present invention.
Detailed Description
The invention will be described in further detail below with reference to the embodiments of the drawing, which are intended to facilitate the understanding of the invention and are not intended to limit the invention in any way.
The reference numerals in fig. 2 are: 1-an anode support layer; 21-a first electrolyte layer; 22-a second electrolyte layer; 31-a first barrier layer; 32-a second barrier layer; 41-a first cathode layer; 42-a second cathode layer; 5-pore canal.
Example 1:
in this embodiment, the solid oxide fuel cell is a hollow flat plate structure distributed vertically, as shown in fig. 2, the anode layer 1 is used as a support layer, and the anode layer, the electrolyte layer, the barrier layer, and the cathode layer are stacked vertically along the thickness direction; the electrolyte layer comprises a first electrolyte layer 21 and a second electrolyte layer 22, the first electrolyte layer 21 is positioned on the lower surface of the support anode layer 1, and the second electrolyte layer 22 is positioned on the upper surface of the support anode layer 1; the barrier layers comprise a first barrier layer 31 and a second barrier layer 32, the first barrier layer 31 is positioned on the lower surface of the first electrolyte layer 21, and the second barrier layer 32 is positioned on the upper surface of the second electrolyte layer 22; the cathode layer comprises a first cathode layer 41 and a second cathode layer 42, the first cathode layer 41 is positioned on the lower surface of the first barrier layer 31, and the second cathode layer 42 is positioned on the upper surface of the second barrier layer 32; the support anode layer 1 is provided with a number of holes 4 having an inlet and an outlet end at the side of the support anode layer 1.
The first electrolyte layer 21 and the second electrolyte layer 22 are symmetrically distributed with the support anode layer 1 as the center, that is, the shapes, thicknesses, etc. of the first electrolyte layer 21 and the second electrolyte layer 22 are completely consistent.
The first barrier layer 31 and the second barrier layer 32 are symmetrically distributed with the support anode layer 1 as the center, that is, the shapes, thicknesses, etc. of the first barrier layer 31 and the second barrier layer 32 are completely consistent.
The first cathode layer 41 and the second cathode layer 42 are symmetrically distributed with the support anode layer 1 as the center, that is, the shapes, thicknesses, etc. of the first cathode layer 41 and the second cathode layer 42 are completely the same.
The material of the support anode layer 1 is Ni-YSZ.
The first electrolyte layer 21 and the second electrolyte layer 22 are made of the same material, YSZ.
The first barrier layer 31 and the second barrier layer 32 are made of the same material and are GDC.
The first cathode layer 41 is made of the same material as the second cathode layer 42 and is LSCF.
The preparation method of the solid oxide fuel cell comprises the following steps:
(1) filling a carbon rod in the raw material by taking the material of the support anode layer as the raw material, hot-pressing the raw material for forming, and then sintering at the sintering temperature of 1000 ℃ to obtain the support anode layer with the hole structure, wherein the hole has an opening end on the side surface of the support electrode layer;
(2) sequentially screen-printing first electrolyte slurry and first barrier layer slurry on the lower surface of the support anode layer; sequentially screen-printing a second electrolyte slurry and a second barrier layer slurry on the upper surface of the anode support body to obtain a half-cell blank; then, the semi-cell blank is placed in a resistance furnace for co-sintering (vertical sintering), and the sintering procedure is as follows: heating to 600 ℃ at a speed of 1 ℃/min, preserving heat for 2h, heating to 1300 ℃ at a speed of 1 ℃/min, preserving heat for 4h, naturally cooling to room temperature, and taking out the half cell after the resistance furnace is cooled to room temperature.
SEM representation is carried out on the surface and the section of the GDC of the half-cell, the structure is shown in figures 3(a) and 3(b), the density of the electrolyte layer and the barrier layer is high, the interface combination effect between the electrolyte and the barrier layer is very good, only a few holes are formed, the holes are closed, and the surface of the GDC barrier layer is fully compact.
(3) Screen printing first cathode slurry on the lower surface of the first barrier layer; screen printing second cathode slurry on the lower surface of the second barrier layer; then sintering is carried out, and the sintering temperature is 1100 ℃.
In the sintering process, the prepared battery is flat due to the symmetrical structure.
In the working state, oxidant gas is introduced to the lower surface of the first cathode layer 41 and the upper surface of the second cathode layer 42; introducing fuel into the opening end of the hole on the side surface of the support anode 1, introducing the fuel into the support anode 1 through the hole 4, and then diffusing the fuel to the upper side and the lower side; the oxidant gas diffuses to the first electrolyte layer 21 through the first barrier layer 31 and diffuses to the second electrolyte layer 22 through the second barrier layer 32; the electrochemical reaction occurs through the first electrolyte layer 21 to generate electric energy and heat energy, and the electrochemical reaction occurs through the second electrolyte layer 22 to generate electric energy and heat energy. Because the three-phase interface where the electrochemical reaction occurs is located at the upper and lower sides of the support electrode layer 1, the generated thermal stress is effectively offset, and the thermal stress is greatly reduced.
Comparative example 1:
this example is a comparative example to example 1 above.
In this example, the solid oxide fuel cell has a hollow flat plate structure distributed vertically, and has the same structure as that of example 1.
In this embodiment, the method for manufacturing the solid oxide fuel cell includes the following steps:
(1) same as in step (1) in example 1;
(2) screen printing a first electrolyte paste on a lower surface of the support anode layer; printing a second electrolyte slurry on the upper surface of the anode support body through a screen printing manner to obtain a half-cell blank; then, the half-cell blank
Then, screen printing first barrier layer slurry on the lower surface of the first electrolyte layer; screen printing a second barrier layer paste on the upper surface of the second electrolyte layer; then, placing the mixture into a resistance furnace for co-sintering (vertical sintering), wherein the sintering procedure is as follows: heating to 600 ℃ at a speed of 1 ℃/min, preserving heat for 2h, heating to 1300 ℃ at a speed of 1 ℃/min, preserving heat for 4h, naturally cooling to room temperature, and taking out the half cell after the resistance furnace is cooled to room temperature.
SEM characterization of the GDC surface and cross-section of the half cell, the structure of which is shown in fig. 4(a) and 4(b), shows that the barrier layer is less dense, has a large number of voids on the surface and cross-section, and has poor bonding effect with the electrolyte, resulting in a large interface resistance.
(3) Same as step (3) in example 1;
in the sintering process, the prepared battery is flat due to the symmetrical structure.
The above embodiments are provided to explain the technical solutions of the present invention in a detailed manner, and it should be understood that the above examples are only specific embodiments of the present invention, and are not intended to limit the present invention. Any modification, addition or equivalent substitution made within the scope of the present invention shall be included in the protection scope of the present invention.
Claims (6)
1. The solid oxide fuel cell takes an anode layer as a supporting layer, the anode layer is made of Ni-YSZ, an electrolyte material is YSZ, a cathode material is LSCF, and a barrier layer between the electrolyte and the cathode is GDC, and is characterized in that: the barrier layer is prepared by sintering, and the anode layer, the electrolyte layer and the green body of the barrier layer are sintered together, wherein the sintering temperature is higher than or equal to 1300 ℃; the co-sintering procedure is as follows: heating to 600 deg.C at a rate of 0.5-3 deg.C/min, maintaining for 0.5-3 h, heating to sintering temperature at a rate of 0.5-3 deg.C/min, maintaining for 1-5 h, and naturally cooling to room temperature;
the solid oxide fuel cell is a hollow and vertically distributed flat plate type structure, takes the anode layer as a supporting layer, and supports the anode layer, the electrolyte layer, the barrier layer and the cathode layer which are vertically stacked along the thickness direction; the electrolyte layer comprises a first electrolyte layer and a second electrolyte layer, the first electrolyte layer is positioned on the lower surface of the support anode layer, and the second electrolyte layer is positioned on the upper surface of the support anode layer; the barrier layer comprises a first barrier layer and a second barrier layer, the first barrier layer is positioned on the lower surface of the first electrolyte layer, and the second barrier layer is positioned on the upper surface of the second electrolyte layer; the cathode layer comprises a first cathode layer and a second cathode layer, the first cathode layer is positioned on the lower surface of the first barrier layer, and the second cathode layer is positioned on the upper surface of the second barrier layer; the anode supporting layer is provided with a plurality of holes, and the holes are provided with inlet and outlet ends on the side surface of the anode supporting layer;
taking the anode supporting layer as a center, the first electrolyte layer and the second electrolyte layer are symmetrically distributed, the first barrier layer and the second barrier layer are symmetrically distributed, and the first cathode layer and the second cathode layer are symmetrically distributed;
the preparation method of the solid oxide fuel cell comprises the following steps:
(1) taking an anode support as a raw material, burying a high-temperature volatile substance with a certain size as a pore-forming agent in the anode support, forming and sintering to obtain a forming body, wherein the pore-forming agent volatilizes to obtain a support anode layer with a pore structure, and the pores have open ends on the side surfaces of the support electrode layer;
the pore-forming agent material comprises a carbon rod, graphite and a carbon nano tube;
(2) sequentially coating, dipping or screen printing first electrolyte slurry and first barrier layer slurry on the lower surface of the anode support body; sequentially coating, dipping or screen printing a second electrolyte slurry and a second barrier layer slurry on the upper surface of the anode support body; then carrying out the co-sintering;
(3) coating or screen printing first cathode slurry on the lower surface of the first barrier layer; coating or screen printing second cathode slurry on the lower surface of the second barrier layer; and then sintering is performed.
2. The method of claim 1, further comprising: the thickness of the electrolyte layer is 1-10 μm.
3. The method of claim 1, further comprising: the thickness of the electrolyte layer is 5 μm.
4. The method of claim 1, further comprising: the thickness of the barrier layer is 1-5 μm.
5. The method of claim 1, further comprising: the thickness of the barrier layer is 3 μm.
6. The method of claim 1, further comprising: after the anode layer, the electrolyte layer and the green body of the barrier layer are sintered together, coating or screen printing cathode slurry on the surface of the barrier layer, and then sintering, wherein the sintering temperature is cathode sintering temperature which is 1000-1200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610898228.6A CN107959036B (en) | 2016-10-14 | 2016-10-14 | Preparation method of solid oxide fuel cell with flat plate structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610898228.6A CN107959036B (en) | 2016-10-14 | 2016-10-14 | Preparation method of solid oxide fuel cell with flat plate structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107959036A CN107959036A (en) | 2018-04-24 |
| CN107959036B true CN107959036B (en) | 2021-11-30 |
Family
ID=61953130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610898228.6A Active CN107959036B (en) | 2016-10-14 | 2016-10-14 | Preparation method of solid oxide fuel cell with flat plate structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107959036B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111224139B (en) * | 2018-11-27 | 2021-07-20 | 中国科学院大连化学物理研究所 | A composite structure proton ceramic membrane fuel cell and its preparation |
| CN109860677A (en) * | 2019-04-09 | 2019-06-07 | 深圳市致远动力科技有限公司 | With the production method of the battery of positive electricity extremely supporter |
| CN109841882B (en) * | 2019-04-09 | 2021-03-02 | 深圳市致远动力科技有限公司 | Manufacturing method of solid fuel cell based on supporting structure |
| CN112993267A (en) * | 2019-12-18 | 2021-06-18 | 中国科学院宁波材料技术与工程研究所 | Direct methane dry reforming power generation method based on solid oxide fuel cell with symmetrical double-cathode structure |
| CN114204044A (en) * | 2020-09-17 | 2022-03-18 | 浙江氢邦科技有限公司 | Preparation method of supported anode in anode-supported solid oxide fuel cell with symmetrical structure |
| CN112467164B (en) * | 2020-11-25 | 2021-09-24 | 浙江臻泰能源科技有限公司 | A solid oxide battery chip with dual electrolyte structure and preparation method thereof |
| CN114725461A (en) * | 2020-12-21 | 2022-07-08 | 宁波材料所杭州湾研究院 | Low-temperature sintered densified samarium-neodymium-doped cerium oxide-based barrier layer, preparation method thereof and solid oxide fuel cell |
| CN113540489B (en) * | 2021-05-15 | 2022-09-09 | 山东工业陶瓷研究设计院有限公司 | Barrier layer slurry, preparation method, barrier layer preparation method and battery monomer |
| CN113381048B (en) * | 2021-05-28 | 2022-11-11 | 山东工业陶瓷研究设计院有限公司 | Solid oxide fuel cell and preparation method thereof |
| CN113445061B (en) * | 2021-06-07 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | Flat-tube type solid oxide electrolytic cell, seawater electrolysis hydrogen production device and seawater electrolysis hydrogen production process |
| CN113471493B (en) * | 2021-07-26 | 2022-07-15 | 中国科学技术大学 | Production process and half cell of a solid oxide fuel cell half cell |
| CN113346118B (en) * | 2021-08-05 | 2021-11-05 | 北京思伟特新能源科技有限公司 | Method for preparing metal support monomer by adopting co-casting method |
| CN114388838B (en) * | 2021-12-31 | 2024-01-23 | 浙江氢邦科技有限公司 | Flat tube type solid oxide fuel cell and preparation method thereof |
| CN114400356B (en) * | 2021-12-31 | 2024-04-05 | 浙江氢邦科技有限公司 | Fuel cell and preparation method thereof |
| CN115020716B (en) * | 2021-12-31 | 2024-04-05 | 浙江氢邦科技有限公司 | Fuel cell and preparation method of flat tube solid oxide fuel cell functional layer thereof |
| CN114335586A (en) * | 2022-01-04 | 2022-04-12 | 苏州华清京昆新能源科技有限公司 | Method for improving flatness of product after sintering of semi-cell isolation layer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101399352A (en) * | 2007-09-25 | 2009-04-01 | 中国科学院宁波材料技术与工程研究所 | Producing method for a high strength ultra-thin anode supporting type solid oxide fuel cell |
| CN102217125A (en) * | 2008-10-09 | 2011-10-12 | 塞拉米克燃料电池有限公司 | A solid oxide fuel cell or solid oxide fuel cell sub-component and methods of preparing same |
| CN106025317A (en) * | 2016-05-27 | 2016-10-12 | 清华大学 | Efficient power generation device coupled by automobile exhaust temperature difference cells and automobile exhaust fuel cells |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101359746B (en) * | 2008-09-19 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Large size tubular solid oxide fuel cell and preparation thereof |
| US9153831B2 (en) * | 2009-10-06 | 2015-10-06 | University Of South Carolina | Electrode design for low temperature direct-hydrocarbon solid oxide fuel cells |
| JP5343836B2 (en) * | 2009-12-10 | 2013-11-13 | 株式会社ノリタケカンパニーリミテド | Solid oxide fuel cell and method for producing the same |
-
2016
- 2016-10-14 CN CN201610898228.6A patent/CN107959036B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101399352A (en) * | 2007-09-25 | 2009-04-01 | 中国科学院宁波材料技术与工程研究所 | Producing method for a high strength ultra-thin anode supporting type solid oxide fuel cell |
| CN102217125A (en) * | 2008-10-09 | 2011-10-12 | 塞拉米克燃料电池有限公司 | A solid oxide fuel cell or solid oxide fuel cell sub-component and methods of preparing same |
| CN106025317A (en) * | 2016-05-27 | 2016-10-12 | 清华大学 | Efficient power generation device coupled by automobile exhaust temperature difference cells and automobile exhaust fuel cells |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107959036A (en) | 2018-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107959036B (en) | Preparation method of solid oxide fuel cell with flat plate structure | |
| JP4986623B2 (en) | Solid oxide fuel cell stack and fuel cell system | |
| JP6599998B2 (en) | Electrolyte formation method | |
| KR102077682B1 (en) | Electrolyte formation process | |
| JP6398647B2 (en) | Method for producing anode for solid oxide fuel cell and method for producing electrolyte layer-electrode assembly for fuel cell | |
| US20070015045A1 (en) | High performance anode-supported solid oxide fuel cell | |
| CN101359746B (en) | Large size tubular solid oxide fuel cell and preparation thereof | |
| CN106033819B (en) | A kind of ceramic electrolyte battery and preparation method thereof of flat pole support | |
| JP6140733B2 (en) | Design and manufacturing technology for solid oxide fuel cells with improved output performance in medium and low temperature operation | |
| CN101577341A (en) | Method for preparing solid oxide fuel cell and entire cell thereof at low temperature | |
| JP2019509615A (en) | Solid oxide fuel cell with cathode functional layer | |
| KR101637917B1 (en) | Protonic conducting solid oxide fuel cell and method for preparing thereof | |
| JP7021787B2 (en) | Proton conductive electrolyte | |
| KR101685386B1 (en) | Anode Supported Solid Oxide Fuel Cell by using low temperature co-firing and manufacturing method thereof | |
| JP4876363B2 (en) | Current collector, method for producing the same, and solid oxide fuel cell | |
| KR102719579B1 (en) | Method for manufacturing electrochemical element and electrochemical element | |
| JP2009218126A (en) | Manufacturing method for completely-dense electrolyte layer laminated on high-performance solid oxide type fuel-cell membrane-electrode assembly (sofc-mea) | |
| JP4304889B2 (en) | Solid oxide fuel cell | |
| JP2008234927A (en) | Manufacturing method of solid oxide fuel cell | |
| CN114583226B (en) | Metal-supported proton conductor solid oxide battery and preparation method thereof | |
| US12027728B2 (en) | Methods and devices for preventing thermally-induced stress cracks in large footprint solid oxide fuel cell columns | |
| CN113497266B (en) | A kind of electrolyte layer, preparation method and application thereof | |
| US20240014407A1 (en) | Monolithic Electrode Supported Electro-Chemical Device Stack | |
| KR20190100610A (en) | Method for fabricating solid oxide fuel cell | |
| JP2002358976A (en) | Solid electrolyte fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210824 Address after: 315201 1219 Zhongguan West Road, Zhenhai District, Ningbo City, Zhejiang Province Applicant after: Zhejiang Hydrogen Technology Co.,Ltd. Address before: 315201, No. 519, Zhuang Avenue, Zhenhai District, Zhejiang, Ningbo Applicant before: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |