CN109841882B - Manufacturing method of solid fuel cell based on supporting structure - Google Patents
Manufacturing method of solid fuel cell based on supporting structure Download PDFInfo
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- CN109841882B CN109841882B CN201910280008.0A CN201910280008A CN109841882B CN 109841882 B CN109841882 B CN 109841882B CN 201910280008 A CN201910280008 A CN 201910280008A CN 109841882 B CN109841882 B CN 109841882B
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- 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
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Abstract
A manufacturing method of a solid fuel cell based on a supporting structure belongs to the field of fuel cells. The method comprises the following steps: a layered composite structure composed of a cathode and an electrolyte membrane was produced. The partition material is transferred to the electrolyte membrane to make a partition grid having a coefficient of thermal expansion equal to or less than that of the electrolyte membrane. The surface of the separator and/or the surface of the electrolyte are filled with a second material for forming an anode. The above method can suppress the problem of separation of the anode and the electrolyte membrane from each other, thereby improving the service life of the battery manufactured thereby.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a method for manufacturing a solid fuel cell based on a support structure.
Background
Solid Fuel cells (SOFCs) have relatively high service temperatures (e.g., 800-1000 ℃). As an all-solid-state device, only two-phase (gas-solid) reaction is involved in the fuel reaction process, so that the structure can be simplified to a certain extent without complicated electrolyte management.
Some SOFCs currently have a thin film structural design. The fabrication process of such an SOFC needs to be specifically examined, and the use thereof has a problem in combination with conditions such as the operating temperature. These have limited further development of plate-type SOFCs.
Currently, the main problems of SOFCs are: in actual production and use, cracks are likely to form and the layered structures are likely to be peeled from each other.
Disclosure of Invention
In view of the above-mentioned shortcomings, the present application provides a method for fabricating a solid state fuel cell based on a support structure to improve the above problems of SOFC cracks and spalling.
The invention is realized by the following steps:
in a first aspect, examples of the invention provide a method of fabricating a support structure-based solid state fuel cell.
The manufacturing method comprises the following steps:
attaching an electrolyte to a cathode electrode as a support structure to form a layered composite structure of the cathode electrode and an electrolyte membrane, wherein the electrolyte membrane is in contact with the cathode electrode with a first surface, and the cathode electrode is made of a first material;
transferring a partitioning material to a second surface of the electrolyte membrane opposite to the first surface to make a partition grid having a thermal expansion coefficient equal to or less than that of the electrolyte membrane, the partition grid partitioning the second surface of the electrolyte membrane into a first region and a second region, wherein the first region is not covered with the partitioning material and the second region is covered with the partitioning material;
filling a second material in one or both of the first region and the second region to form an anode electrode.
A separation grid is made in the anode electrode, and the form in which the anode electrode is independently in contact with the electrolyte membrane is changed. The anode electrode is divided into a plurality of pieces by a separation grid, and the individual portions can be bounded by the separation grid.
The anode electrode is separated into a plurality of pieces by the separation grid, so that the internal stress of the anode electrode caused by heat is dispersed, the electrolyte membrane and the anode electrode are more easily matched, and the electrolyte membrane and the anode electrode are not separated from each other due to large difference of deformation (such as thermal expansion) of the electrolyte and the anode electrode.
With reference to the first aspect, in a first possible implementation manner of the first aspect, the first material used for manufacturing the cathode electrode includes a p-type semiconductor or a perovskite oxide.
The use of a p-type semiconductor or perovskite oxide for the cathode electrode facilitates charge conduction.
With reference to the first aspect, in a second possible implementation manner of the first aspect, the cathode electrode is of a flat plate type structure or a tubular structure.
Depending on the fuel cell construction and the requirements of use, it is fabricated in a desired shape to facilitate handling and fabrication of subsequent components.
In a third possible embodiment of the first aspect in combination with the first or second possible embodiment, in the process of attaching the electrolyte to the cathode electrode to form the layered composite structure of the cathode electrode and the electrolyte membrane, the composite structure is subjected to sintering in an air atmosphere.
The cathode and the electrolyte membrane can be bonded together by sintering, so that the cathode and the electrolyte membrane are firmly and stably bonded.
With reference to the third possible embodiment, in a fourth possible embodiment of the first aspect, the electrolyte is attached to the cathode electrode by any one of coating, screen printing, and ink jet printing.
Coating, screen printing, ink jet printing are easy to implement and implement solutions that facilitate rapid, high quality production of electrolytes.
With reference to the first aspect, in a fifth possible embodiment of the first aspect, the electrolyte membrane has a thickness of 1 to 50 micrometers.
The thickness of the electrolyte membrane is adjusted correspondingly according to the size requirement of the fuel cell so as to meet the requirement of practical use.
With reference to the first aspect, in a sixth possible embodiment of the first aspect, the partition material comprises any one of rare earth doped ceria or rare earth doped zirconia, alumina, Mg — Al spinel, silicate.
The dividing material has various choices, and can be selected according to the requirements of the difficulty degree of the process and the manufacturing cost.
With reference to the first aspect, in a seventh possible embodiment of the first aspect, the thickness of the separation grid is 1 to 50 micrometers.
The thickness of the spacer grid is selected and implemented as desired to match the size of the fuel cell.
With reference to the first aspect, in an eighth possible implementation manner of the first aspect, the second material includes elemental nickel or a nickel alloy or a cermet.
Nickel and its alloys or cermets have desirable physical and electrical properties and can be advantageously used in the fabrication of fuel cells.
With reference to the eighth possible embodiment, in a ninth possible embodiment of the first aspect, the nickel alloy includes Ni-Co, Ni-Fe, Ni-Pt.
The above nickel alloy selection combines the advantages of cost and performance.
Has the advantages that:
the method for manufacturing the solid fuel cell based on the support structure separates the anode electrode in the fuel cell, so that the anode electrode forms a plurality of relatively independent areas. Adjacent two of the plurality of independent areas may be bounded by a separation grid. Based on the situation, the separation grids weaken the mismatch problem caused by the stress of the anode electrode and the electrolyte membrane, so that the problem that the anode electrode and the electrolyte membrane are mutually separated due to large deformation difference is greatly relieved or even solved.
Drawings
In order to more clearly illustrate the technical solutions in the examples or prior art of the present application, the drawings that are needed to be used in the description of the examples or prior art will be briefly introduced below.
FIG. 1 is a schematic view of a first perspective of a first fuel cell in an example of the present application;
FIG. 2 is a schematic diagram illustrating a second perspective of the fuel cell shown in FIG. 1;
FIG. 3 is a schematic diagram of a second perspective view of a second fuel cell in an example of the present application;
fig. 4 is a schematic diagram of a third fuel cell in an example of the present application from a second perspective;
FIG. 5 is a schematic diagram of a fourth fuel cell in an example of the present application from a second perspective;
fig. 6 is a schematic diagram of a fifth fuel cell in an example of the present application from a first perspective.
Icon: 100-a fuel cell; 102-a cathode electrode; 103-electrolyte membrane; 104-an anode electrode; 105-a separation grid; 1041 a-region; 1051 a-rectangular block; 1041 b-region; 1051 b-triangular blocks; 1041 c-region; 1051 c-round block; 1041 d-region; 1051 d-rectangular bar; 200-a fuel cell; 204-an anode electrode; 205-a separation grid; 401-higher layer; 402-supplemental layer.
Detailed Description
The following is a detailed explanation of implementations in examples, however, it will be understood by those skilled in the art that the following examples are only illustrative of the present application and should not be taken as limiting the scope of the present application. The example does not indicate specific conditions, and can be performed according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are conventional products available commercially.
The following is a detailed description of a method for manufacturing a solid-state fuel cell based on a support structure according to an example of the present invention:
referring to fig. 1 and 2, a fuel cell 100 in the example has a layered structure. In the view direction in fig. 1, the fuel cell 100 includes a cathode 102 (made of a first material), an electrolyte membrane 103 (made of an electrolyte), and an anode 104 (made of a second material) which are arranged in this order from the bottom to the top.
Specifically, a separation mesh 105 is distributed in the anode electrode 104, and the thermal expansion coefficient of the separation mesh is equal to or less than that of the electrolyte membrane.
Fig. 1 is a diagram of an exemplary structure, and therefore defines the relative positional relationship of the functional layers of the fuel cell 100, but the thicknesses of the layers themselves, as well as the relative thickness magnitudes of the layers, are not intended to be illustrative in a limiting sense. In other examples, other thickness configurations may be made. Wherein, the thickness refers to the extension length from the cathode electrode 102 to the anode electrode 104; or the length in the direction from the anode electrode 104 to the cathode electrode 102.
In fig. 1, the thickness of the cathode electrode 102 is smaller than the thickness of the electrolyte membrane 103, and in other examples, the thickness of the cathode electrode 102 may be smaller than the thickness of the electrolyte membrane 103.
Fig. 2 is a schematic diagram showing a structure of the fuel cell 100 of fig. 1 in a plan view (from the anode electrode 104 toward the cathode electrode 102). Referring to fig. 1, it can be seen from fig. 2 that the anode electrode 104 is separated into a plurality of portions by a separation grid 105. As is apparent from fig. 1 and 2, the anode electrode 104 has a plurality of portions, and the plurality of portions are in a continuous structure as a whole and form the region 1041 a. The partition grid 105 includes a plurality of (45) rectangular blocks 1051a arranged at intervals (in a crisscross array layout).
It should be noted that the separation grid 105 may also have other types of arrangements, so that the anode electrode can also be divided into various different configurations accordingly, some such divisions being illustrated in fig. 3-5.
Referring to fig. 3 in conjunction with fig. 1 and 3, it can be seen from fig. 3 that the anode electrode 104 is separated into a plurality of portions by a separation grid 105. Obviously, the anode electrode 104 has a plurality of portions, and the plurality of portions are in a continuous structure as a whole and form the region 1041 b. The partition grid 105 includes a plurality (56) of triangular blocks 1051b arranged at intervals (in a criss-cross array layout). In addition, it should be noted that, in the perspective as shown in fig. 1, only 5 columns of triangular blocks are shown in fig. 1, but there are 7 columns of triangular blocks in fig. 3.
Referring to fig. 4 in conjunction with fig. 1 and 4, it can be seen from fig. 4 that the anode electrode 104 is separated into a plurality of portions by a separation grid 105. Obviously, the anode electrode 104 has a plurality of portions, and the plurality of portions are in a continuous structure as a whole and form the region 1041 c. The partition grid 105 includes a plurality of (64) circular nubs 1051c arranged at intervals (in a criss-cross array layout). In addition, it should be noted that, in the perspective as shown in fig. 1, only 5 columns of circular blocks are shown in fig. 1, but there are 8 columns of circular blocks in fig. 4.
Referring to fig. 5 in conjunction with fig. 1 and 5, it can be seen from fig. 5 that the anode electrode 104 is separated into a plurality of portions by a separation grid 105. Obviously, the anode electrode 104 has a plurality of portions, and the plurality of portions are in a separation/isolation structure as a whole and form the region 1041 d. The partition grid 105 includes a plurality of (5) rectangular strips 1051d arranged at intervals (longitudinally spaced arrangement).
In the above exemplary fuel cell, the anode electrode is divided by the network division structure of different structures, and therefore, the anode electrode exhibits correspondingly different division patterns. The thickness of the separation grid is equal to the thickness of the anode electrode (the extension length from the cathode electrode to the anode electrode). Of course, the thickness of the separation grid may not be equal to the thickness of the anode electrode. For example, the thickness of the separation grid is greater than the thickness of the anode electrode. Alternatively, the thickness of the separation grid is smaller than the thickness of the anode electrode, an example of which may be illustrated in fig. 6, which will be mentioned later.
The above fuel cell 100 can be fabricated by the following method.
The preparation process comprises the following steps:
the method comprises a first step of attaching an electrolyte to a cathode to form a layered composite structure of the cathode and an electrolyte membrane, wherein the electrolyte membrane is in contact with the cathode on a first surface, and the cathode is made of a first material.
The cathode electrode may be a finished product manufactured in advance, and is used when manufacturing and assembling the fuel cell. Alternatively, the cathode electrode may be fabricated in situ. The material may be selected as desired, and the material used for the cathode electrode, i.e., the first material, may include, for example, a p-type semiconductor or a perovskite oxide. In addition, the configuration (shape) of the cathode electrode may be selected differently according to the type of the fuel cell, for example, the cathode electrode is a flat plate type or a tubular type. The preparation method of the cathode electrode can be distinguished according to different raw materials. Such as: tape casting or extrusion molding.
In some examples, the electrode material of the cathode electrode may be selected to be a metal oxide, such as LaxSryCoFeOz(LSCF). In some specific examples, the quaternary alloy oxide may be La1-xSrxCo0.2Fe0.8O3(wherein 0.1)<x<0.6)。
Accordingly, a method of manufacturing an electrolyte membrane with a cathode electrode as a support structure includes: the electrolyte fluid or dope (slurry) is transferred to the surface of the cathode electrode and the electrolyte is allowed to solidify. Optionally, the method of transferring the electrolyte to the surface of the cathode electrode comprises: magnetron sputtering, electrophoretic deposition, screen printing, dip coating, electrophoretic method, plasma deposition. Further, in the example, in order to solidify the electrolyte and improve the bonding firmness with the cathode electrode, the composite structure of the cathode electrode and the electrolyte may be sintered in an air atmosphere. In one example, the electrolyte membrane is formed as a thin film, and the thickness of the electrolyte membrane can be set as desired, for example, 1 to 50 micrometers, 11 to 40 micrometers, or 23 to 30 micrometers.
And a second step of transferring the partitioning material to a second surface of the electrolyte membrane opposite to the first surface to make a partition grid having a thermal expansion coefficient equal to or less than that of the electrolyte membrane, the partition grid partitioning the second surface of the electrolyte membrane into a first region and a second region, wherein the first region is not covered with the partitioning material and the second region is covered with the partitioning material.
As described above, the partition mesh is bonded to the surface (second surface) of the electrolyte membrane, and the cathode electrode is bonded to the surface (first surface) of the electrolyte membrane. Therefore, in the thickness direction of the electrolyte membrane, it is sandwiched by the cathode electrode and the separation mesh.
The material of the separation mesh may be treated in the form of a dispersion and then transferred to the surface of the electrolyte membrane. The method of transfer may be, for example: screen printing, ink jet printing, paste coating (providing a mask at a position where the application of the network partition material is not required), and the like. The separation grid can adopt CeO obtained by doping rare earth elements2Or zirconium oxide, Al2O3Magnesium-aluminum spinels, silicates, and the like. The thickness of the division grid can be 1-50 microns, for example; or 11-46 μm; or 23-40 microns; or 30 to 39 μm.
The anode electrode to be mentioned later has physical contact with the electrolyte membrane, and the anode electrode is divided by the separation mesh, and therefore, when the separation mesh is manufactured as described above, it is not attached to the surface (second surface) of the electrolyte membrane in a completely covering manner. In contrast, a part of the second face of the electrolyte membrane is covered, and the other part is not covered. Accordingly, the second face of the electrolyte membrane has a portion (the second region, which is subsequently covered with the second material for making the anode electrode) covered with the separation mesh, and a portion (the first region, which is subsequently covered with the second material for making the anode electrode) not covered with the separation mesh.
And a third step of filling a second material in one or both of the first region and the second region to manufacture an anode electrode.
For example, the second material for forming the anode electrode may be selected from elemental nickel or nickel alloy (Ni alloy includes Ni — Co,Ni-Fe, Ni-Pt, etc.), or the second material may be a cermet. The cermet is, for example, made of Ni or a nickel alloy and CeO2Zirconium oxide, etc., and the volume fraction of metal is between 20 and 80%.
In the fuel cell illustrated in fig. 1 to 5, the second face of the electrolyte membrane is covered commonly with the separation mesh and the anode electrode, and the separation mesh and the anode electrode are independent of each other. That is, the network partition structure and the anode electrode cover different regions of the electrolyte membrane, respectively. The separation grid covers the second area, the anode electrode covers the first area, and the anode electrode does not cover the separation grid.
Unlike the above-described manner of covering the electrolyte membrane and the separation mesh with the second material for manufacturing the anode electrode (only the electrolyte membrane is covered), the second electrode material can also cover both the electrolyte membrane and the separation mesh. Such a structural example can be clearly understood from that illustrated in fig. 6.
In fig. 6, the fuel cell 200 includes a cathode electrode 102, an electrolyte membrane 103, an anode electrode 204, and a separation mesh 205 is distributed in the anode electrode 204. The anode electrode 204 includes two portions, an equipotential layer 401 and a complementary layer 402. Wherein the higher layer 401 covers the first area of the electrolyte membrane 103 that is reserved after the provision of the separation grid 205, and the supplementary layer 402 covers the separation grid 205.
As described above, the higher layer 401 is a portion having the same height (thickness) as the anode electrode 204; the supplemental layer 402 is a structural layer that covers the separation grid 205, and the thickness of the supplemental layer 402 is the same as the sum of the heights of the separation grid 205 (any one of them) and the height of the higher-level layer 401. In other words, the height of the separation grid 205 is less than the thickness of the higher level layer 401.
The fuel cell which can be used for the fuel cell is manufactured based on the mode, the problems of cracking and falling of the anode electrode are well inhibited and solved, and the yield of the electrode and the fuel cell manufactured by the electrode is improved to more than 95%. The yield of some fuel cells (without division) and fuel cells made therefrom known to the inventors is only 40-60%.
A method of fabricating a support structure-based solid state fuel cell of the present invention is described in further detail below with reference to examples.
Example 1
The example provides a flat-type fuel cell (cathode electrode support, anode electrode split). The manufacturing method comprises the following steps:
and S101, preparing a cathode electrode.
The cathode electrode has micropores and is made of strontium-doped lanthanum manganite with a P-type semiconductor structure. Preparing solid raw materials of a cathode electrode into slurry by using an organic solvent, casting the slurry into a flat structure (with the thickness of 1mm and the thickness of 5cm multiplied by 5cm), sintering the slurry for 1 hour at the temperature of 960 ℃ in air, and cooling the sintered slurry to room temperature.
Step S102, preparing an electrolyte membrane.
The electrolyte membrane was made of La1-xSrxGa1-yMgyOz. Fabricated by spin coating to a thickness of 20 microns. The cathode electrode is used as a support structure, and an electrolyte material is made into slurry and coated on one surface of the support structure.
And S103, preparing a separation grid.
The material of the partition mesh was selected as alumina, and configured as a slurry (organic solvent was a dispersant), and brushed onto the surface of the electrolyte membrane by a dip coating method (a mask was provided at a position where the application of the mesh partition material was not required) to a thickness of 30 μm.
And S104, heating and sintering.
And (3) sintering the cathode electrode, the electrolyte membrane and the separation grid obtained in the steps 101 to 103 at the temperature of 1200 ℃ for 1 hour in the air condition, and then cooling to room temperature.
And step S105, preparing an anode electrode.
The anode is made of nickel metal ceramic, organic dispersant is made into slurry, the slurry is coated on the surface of the network partition layer in the cathode, the electrolyte membrane and the network partition layer, sintering is carried out at the temperature of 1000 ℃, and then cooling is carried out to reduce the temperature to room temperature.
Example 2
An example provides a tubular fuel cell (cathode electrode support, anode electrode split). The manufacturing method comprises the following steps:
and S101, preparing a cathode electrode.
The cathode electrode is made of ABO3LSM (La) as an electrode of perovskite structure1-xSrxMn3E.g. La0.7Sr0.3Mn3) It can be prepared by solid phase synthesis or combustion or sol-gel method, in this example by dissolving lanthanum nitrate, strontium nitrate and manganese nitrate in water, adding glycine, heating and burning, and then baking at 1000 ℃.
The LSM powder was dispersed in an organic dispersant (5 wt% ethyl cellulose and 95 wt% terpineol), and ground in a mortar to obtain a slurry, which was formed into a cathode tube 10cm (cm) thick, 5cm high and 5cm inner diameter by extrusion.
Step S102, preparing an electrolyte membrane.
The electrolyte membrane is made of an element composition LaSrGaMgO. It was made by dip coating and had a thickness of 30 μm. The LSM cathode electrode is used as a supporting structure, electrolyte raw materials are prepared into slurry, and the slurry is coated on the outer surface of the supporting structure.
And S103, preparing a separation grid.
Use of Al for separating grids2O3The slurry was prepared using an organic solvent, and applied to the surface of an electrolyte membrane by printing, and the thickness was 30 μm.
And step S104, sintering.
And (4) sintering the cathode electrode, the electrolyte membrane and the separation grid prepared in the steps from the step S101 to the step S103 for 1 hour at the temperature of 1300 ℃ in the air condition, and then cooling to reduce the temperature to the room temperature.
And step S105, preparing an anode electrode.
The anode electrode is porous and made of nickel ceramic. The nickel ceramics is blended into slurry with an organic solvent, the slurry is coated on the surface of the separation grid among the cathode electrode, the electrolyte membrane and the separation grid prepared in step S104, and then sintered at 1200 degrees centigrade for 1 hour under air conditions, and then cooled to room temperature.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A method of fabricating a support structure based solid state fuel cell, the method comprising:
attaching an electrolyte to a cathode electrode as a support structure to form a layered composite structure of the cathode electrode and an electrolyte membrane, wherein the electrolyte membrane is in contact with the cathode electrode with a first surface, and the cathode electrode is made of a first material;
transferring a partitioning material to a second face of the electrolyte membrane, which is opposite to the first face, to make a partitioning grid having a coefficient of thermal expansion equal to or less than that of the electrolyte membrane, the partitioning grid partitioning the second face of the electrolyte membrane into a first region and a second region, wherein the first region is not covered with the partitioning material and the second region is covered with the partitioning material;
filling a second material in one or both of the first region and the second region to manufacture an anode electrode.
2. The method of claim 1, wherein the first material comprises a p-type semiconductor or a perovskite oxide.
3. The method of claim 1, wherein the cathode is a plate or tube structure.
4. The support structure-based solid fuel cell fabrication method according to claim 2 or 3, wherein in attaching the electrolyte to the cathode electrode to form a layered composite structure of the cathode electrode and the electrolyte membrane, the composite structure is subjected to sintering in an air atmosphere.
5. The method of claim 4, wherein the electrolyte is attached to the cathode electrode by any one of coating, screen printing, and ink jet printing.
6. The method of claim 1, wherein the electrolyte membrane has a thickness of 1 to 50 microns.
7. The method of making a support structure based solid state fuel cell according to claim 1, wherein the partitioning material comprises any one of rare earth doped ceria or rare earth doped zirconia, alumina, Mg-Al spinel, silicates.
8. The method of claim 1, wherein the spacer grid has a thickness of 1-50 μm.
9. The method of claim 1, wherein the second material comprises elemental nickel or a nickel alloy or a cermet.
10. The method of claim 9, wherein the nickel alloy comprises Ni-Co, Ni-Fe, Ni-Pt.
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| CN101304092A (en) * | 2007-05-11 | 2008-11-12 | 中国科学院大连化学物理研究所 | Cathode material of mid-temperature solid-oxide fuel battery and uses thereof |
| CN107959036A (en) * | 2016-10-14 | 2018-04-24 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the solid oxide fuel cell of flat structure |
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| CN1323459C (en) * | 2005-04-07 | 2007-06-27 | 天津大学 | Fuel battery structure and process for preparing same |
| EP2031684B1 (en) * | 2007-08-31 | 2016-08-10 | Technical University of Denmark | Metal supported solid oxide fuel cell |
| US20120251917A1 (en) * | 2011-04-04 | 2012-10-04 | Korea Institute Of Science And Technology | Solid oxide fuel cell comprising nanostructure composite cathode and fabrication method thereof |
| CN102881929B (en) * | 2012-10-26 | 2015-06-03 | 中国科学院上海硅酸盐研究所 | Structure of flat-plate type metal-support solid oxide fuel cell for immersing electrodes |
| CN104638287A (en) * | 2015-01-28 | 2015-05-20 | 潮州三环（集团）股份有限公司 | Method for preparing anode-supported type solid oxide fuel battery |
| CN109004283B (en) * | 2018-07-26 | 2022-02-01 | 京东方科技集团股份有限公司 | All-solid-state lithium battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101304092A (en) * | 2007-05-11 | 2008-11-12 | 中国科学院大连化学物理研究所 | Cathode material of mid-temperature solid-oxide fuel battery and uses thereof |
| CN107959036A (en) * | 2016-10-14 | 2018-04-24 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the solid oxide fuel cell of flat structure |
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