CN111048814A - Film hydrogen electrode solid oxide battery and preparation method thereof - Google Patents

Film hydrogen electrode solid oxide battery and preparation method thereof Download PDF

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CN111048814A
CN111048814A CN201911087937.6A CN201911087937A CN111048814A CN 111048814 A CN111048814 A CN 111048814A CN 201911087937 A CN201911087937 A CN 201911087937A CN 111048814 A CN111048814 A CN 111048814A
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electrolyte
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朱腾龙
吕秋秋
宋佳宁
钟秦
韩敏芳
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Nanjing University of Science and Technology
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    • H—ELECTRICITY
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H01M4/8835—Screen printing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
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Abstract

The invention discloses a solid oxide cell of a film hydrogen electrode and a preparation method thereof, wherein the invention prepares an integrated half cell with a compact YSZ film electrolyte layer and a porous YSZ thick film supporting layer by a tape casting method; and finally, dipping the nano perovskite oxygen electrode in a porous YSZ thick film supporting layer by adopting a solution dipping method to finally obtain the solid oxide battery simultaneously provided with the thin film hydrogen electrode and the thin film electrolyte. The cell with the structure can reduce the ohmic impedance of an electrolyte and the diffusion impedance of gas components in a hydrogen electrode, and improve the fuel utilization efficiency in a fuel cell mode and the electric efficiency in an electrolysis mode.

Description

Film hydrogen electrode solid oxide battery and preparation method thereof
Technical Field
The invention relates to a solid oxide cell with a thin film hydrogen electrode and a preparation method thereof, in particular to the field of cell preparation.
Background
At present, 96% of hydrogen is prepared by taking stone resources such as coal, petroleum, natural gas and the like as raw materials, such as coal gasification, natural gas reforming hydrogen production and the like, and has the disadvantages of large scale, high technical maturity, complex process flow, huge equipment and insufficient energy conversion efficiency. Moreover, the oil gas resources in China are relatively poor, and the hydrogen production technology can also generate certain environmental hidden dangers, so that a novel hydrogen production concept and a novel hydrogen production technical approach need to be developed. Among many electrolytic hydrogen production technologies, Solid Oxide Electrolysis Cells (SOEC) work at high temperature (700-.
Most of the existing SOC single cells are in electrolyte supporting and hydrogen electrode supporting structures: the electrolyte supported battery has stable long-term operation, but has large ohmic resistance and poor performance, and generally needs to work at the temperature of 850 ℃ below zero and above. The hydrogen electrode supporting battery has smaller ohmic resistance, and the operating temperature can be reduced to 750 ℃ and 850 ℃; however, when used for hydrogen production by electrolysis of water, a thicker hydrogen electrode support layer will produce a greater diffusion polarization resistance. Therefore, when water is electrolyzed to produce hydrogen, the oxygen electrode supporting structure with a thinner electrolyte and a hydrogen electrode is selected as the best scheme.
Most of the existing commercial application monocells are first-generation electrolyte supporting structures, the mechanical strength of the monocells is provided by a thicker electrolyte layer, and the monocells are high in stability and strong in thermal cycling and oxidation reduction resistance; however, the operating temperature is higher, typically at 850-. The second generation anode supporting single cell adopts thicker Ni-YSZ as a mechanical supporting layer, but the anode supporting layer is thicker, so that the diffusion resistance of fuel and oxidation products thereof on the anode side is higher, and higher fuel utilization efficiency is not favorably obtained. Therefore, it is necessary to design a Solid Oxide Fuel Cell (SOFC) having both an electrolyte membrane and an anode membrane, to reduce anode polarization diffusion resistance, and to improve fuel efficiency.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a thin film hydrogen electrode solid oxide fuel cell and a method for manufacturing the same, wherein when the thin film hydrogen electrode solid oxide fuel cell is used for hydrogen production by electrolysis, a thin hydrogen electrode and a thin electrolyte layer can greatly reduce diffusion polarization resistance and improve electrolysis efficiency. When the membrane hydrogen electrode solid oxide fuel cell is used for a solid oxide fuel cell, the anode layer and the electrolyte layer which are thinner can greatly reduce the polarization diffusion resistance of the anode and improve the utilization efficiency of fuel.
The technical scheme for realizing the purpose of the invention is as follows:
a membrane hydrogen electrode solid oxide fuel cell, the electrolyte layer of the cell is YSZ, the isolating layer is GDC, the anode layer is LSCFN, the cathode layer is LSCF; the YSZ is 8% molY2O3 stabilized ZrO2The GDC is Gd2O3Doped CeO2Of the general formula Ce0.9Gd0.1O2-m0 < m < 0.5; the general formula of the LSCFN is La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ0 < delta < 1, and LSCFN is a pure perovskite structure.
Preparing an integrated half cell with a compact YSZ thin film electrolyte layer and a porous YSZ thick film supporting layer by a tape casting method; and finally, dipping the nano perovskite oxygen electrode in a porous YSZ thick film supporting layer by adopting a solution dipping method to finally obtain the solid oxide battery simultaneously provided with the thin film hydrogen electrode and the thin film electrolyte.
Further, the invention provides a preparation method of the membrane hydrogen electrode solid oxide fuel cell, which comprises the following steps:
step 1, preparing a YSZ electrolyte sheet, punching a cast YSZ electrolyte blank into a small round sheet with the diameter of 19mm, and sintering at 1400 ℃ for 5h to obtain a porous YSZ-supported half-cell support body;
step 2, selecting the integrated half-cell support body for screen printing of the GDC barrier layer, screen printing of the GDC barrier layer on the surface of the compact YSZ electrolyte sheet, and calcining at 1300 ℃ for 3 hours with the thickness of 5 microns;
step 3, selecting and using the silk-screen oxygen electrode LSCFN as La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ(LSCFN) perovskite oxide material is deposited on the surface of the GDC isolating layer by a screen printing method and then calcined at 1075 ℃ for 2 hours to form a working area of 0.5cm2The thickness of the anode of (2) is 40 μm;
step 4, preparing a cathode in the porous YSZ support body by dipping the LSCF hydrogen electrode by using an LSCF dipping solution, wherein the cathode is dipped for about 15 times until the solution cannot automatically permeate into the porous layer, and the cathode is calcined at 750 ℃ for 0.5h and has the thickness of 400 microns after dipping each time;
step 5, manufacturing a single cell, and finally, silk-screening silver grids on the surfaces of the cathode and the anode respectively to collect current, wherein the effective working area of the single cell is 0.5cm2。
The invention also provides a preparation method of the hydrogen electrode LSCFN, which comprises the following steps:
step 1, according to La (NO)3)6·6H2O：SrCO3：Co(NO3)2·6H2O：Fe2O3：Nb2O50.4: 0.6: 0.2: 0.35: 0.1, putting the mixture into a ball milling tank, adding ethanol, and ball milling for 48 hours;
and 2, drying the ball-milled mixture in an oven, calcining the dried ball-milled mixture in a crucible at 1100 ℃ for 5 hours, and sieving the calcined ball-milled mixture with a 200-mesh sieve to obtain the hydrogen electrode material.
The oxygen electrode and the electrolyte structure are integrated, the porous YSZ is used as an oxygen electrode supporting layer and is co-sintered with the compact YSZ electrolyte film, the interface between the oxygen electrode and the electrolyte is eliminated, the service life and the thermal cycle stability are improved, and meanwhile, the nano oxygen electrode can be prepared in the porous YSZ by adopting an impregnation technology, so that high-performance output is realized.
When the cell is used for fuel cells and electrolytic cells, the electrolyte thinning and the anode thinning greatly reduce ohmic impedance and hydrogen electrode diffusion polarization impedance, and higher energy conversion efficiency is obtained. Because YSZ has poor chemical compatibility with many high-activity cathode and anode perovskite materials, it is easy to react during high-temperature preparation and long-term operation, and is doped with cerium oxide (e.g. 10-20 mol% Gd)2O3Or Sm2O3Doped CeO2: GDC or SDC) has higher ionic conductivity at low temperature (600 ℃), and the cerium oxide-based electrolyte has good chemical compatibility with the existing electrode material. The cerium oxide-based electrolyte material often forms a double electrolyte layer with an electrolyte such as YSZ or the like, or serves as an isolation layer to prevent a reaction between an electrode material and an electrolyte during high-temperature preparation and long-term operation. When the Ni-YSZ hydrogen electrode is directly adopted, a GDC isolating layer is not needed, and when the ceramic oxide hydrogen electrode is used, the GDC isolating layer is needed. The ceramic oxide includes both perovskite-structured and layered perovskite-structured, double perovskite-structured, spinel-structured, and the like.
In summary, compared with the prior art, the invention has the following technical effects:
(1) the thin film electrolyte and the thin film hydrogen electrode are provided, so that low ohmic resistance loss and low hydrogen electrode diffusion loss are obtained.
(2) The oxygen electrode and the electrolyte structure are integrated, the porous YSZ is used as an oxygen electrode supporting layer and is co-sintered with the compact YSZ electrolyte film, the interface between the oxygen electrode and the electrolyte is eliminated, the service life and the thermal cycle stability are improved, and meanwhile, the nano oxygen electrode can be prepared in the porous YSZ by adopting an impregnation technology, so that high-performance output is realized.
(3) The electrolyte and the anode of the battery are thinned, and the interfaces are tightly connected and are not easy to fall off.
Drawings
Fig. 1 is a cell structure diagram of a membrane hydrogen electrode solid oxide fuel cell.
FIG. 2 is a cross-sectional micro-topography of a thin film hydrogen electrode solid oxide fuel cell.
Fig. 3 is a graph of power density of a membrane hydrogen electrode solid oxide fuel cell at 750 ℃ and different hydrogen partial pressures.
Fig. 4 is a graph of power density of a membrane hydrogen electrode solid oxide fuel cell at 750 ℃ and different hydrogen flow rates.
Fig. 5 is an electrochemical ac spectrum of a thin film hydrogen electrode solid oxide fuel cell as a fuel cell.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1: preparation of membrane hydrogen electrode solid oxide fuel cell
Step 1, preparing a YSZ electrolyte sheet, stamping a cast YSZ electrolyte blank into a small round sheet with the diameter of 19mm, and sintering at 1400 ℃ for 5h to obtain an integrated semi-cell support body supported by porous YSZ;
step 2, selecting the integrated half-cell support body for screen printing of the GDC barrier layer, screen printing of the GDC barrier layer on the surface of the compact YSZ electrolyte sheet, and then calcining at 1300 ℃ for 3h with the thickness of 5 microns;
step 3, selecting and using the silk-screen oxygen electrode LSCFN as La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ(LSCFN) of perovskite oxide material, with a thickness of 40 μm. Depositing on the surface of GDC isolation layer by screen printing method, and calcining at 1075 deg.C for 2 hr to form a working area of 0.5cm2The anode of (1);
step 4, preparing a cathode in the porous YSZ support body by impregnating the LSCF hydrogen electrode with an LSCF impregnating solution, wherein the impregnated cathode needs to be impregnated for about 15 times until the solution cannot automatically permeate into the porous layer, and the impregnated cathode is calcined at 750 ℃ for 0.5h each time;
step 5, the single cell is manufactured and finally, the cathodeThe surfaces of the electrode and the anode are respectively silk-screened with silver grids, and the effective working area of a single cell is 0.5cm2。
As can be seen from fig. 3, the anode (hydrogen electrode) of the cell is thin, but the phase interface contact is good, and the exfoliation phenomenon is not likely to occur.
At present, electrolyte supporting and anode supporting single batteries widely adopted in other laboratories have thicker anode layers and electrolyte layers, and a cathode porous layer and the electrolyte layers are integrally prepared, so that the electrolyte layers and the cathode layers are not easy to fall off, and the electrolyte layers can be very thin and are 40 mu m in the integral preparation process, and compared with the conventional 100-micron and 400 mu m thick batteries, the ohmic resistance can be greatly reduced by the thin electrolyte layers. The porous layer is used for obtaining the cathode by adopting an immersion method, so that the cathode is used as a functional layer and also used as a supporting layer, and the battery has better mechanical property.
Testing of membrane hydrogen electrode solid oxide Fuel cells
Used as electrolytic cell
Sealing the cathode side of the single cell on the top of the alumina ceramic tube by using conductive adhesive (Ag), exposing the oxygen electrode in static air, and introducing 5% H to the hydrogen electrode side2Water vapor carrying/Ar, gas passing through a water-containing gas cylinder heated by a constant-temperature water tank to generate the required amount of vapor. In order to prevent the influence of water vapor condensation on gas components in the electrolytic process, the external pipeline is insulated by using a heating belt, and a silver wire is used as a lead to connect an electrode and electrochemical test equipment. An operating temperature of 800 ℃ was selected and tested at various steam contents (3% H)2O-5％H2/Ar、10％H2O-5％H2/Ar、20％H2O-5％H2I-V curve and EIS curve under/Ar).
Used as fuel cell
Fixing the film hydrogen electrode solid oxide fuel cell in a test tube by silver paste, conducting and lengthening by silver wires, calcining for one hour at 600 ℃ in a muffle furnace, taking out, sealing the periphery of the cell by sealing slurry, and uniformly smearing during sealing. And sealing again after drying for 1h to ensure the absolute sealing of the battery. Then, the electric signal is accessed into the system for detection through the silver wires of the cathode and the anodeAnd (6) measuring. Open circuit voltage OCV, electrochemical ac impedance spectroscopy EIS and power density LSV were tested separately. The obtained power density chart is shown in fig. 4, and the electrochemical ac impedance spectrum is shown in fig. 5. As can be seen from the power density chart, the maximum power density of the battery is 0.114W/cm2(ii) a The electrochemical alternating-current impedance spectrum shows that the ohmic impedance is small and is about 1.5 omega cm2。

Claims (6)

1. A membrane hydrogen electrode solid oxide fuel cell, comprising: the electrolyte layer of the battery is YSZ, the isolating layer is GDC, the anode layer is LSCFN, and the cathode layer is LSCF; the YSZ is 8% molY2O3 stabilized ZrO2The GDC is Gd2O3Doped CeO2Of the general formula Ce0.9Gd0.1O2-m0 < m < 0.5; the general formula of the LSCFN is La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ0 < delta < 1, and LSCFN is a pure perovskite structure.
2. A membrane hydrogen electrode solid oxide fuel cell, comprising:
preparing an integrated half cell with a compact YSZ thin film electrolyte layer and a porous YSZ thick film supporting layer by a tape casting method; and finally, dipping the nano perovskite oxygen electrode in a porous YSZ thick film supporting layer by adopting a solution dipping method to finally obtain the solid oxide battery simultaneously provided with the thin film hydrogen electrode and the thin film electrolyte.
3. The preparation method of the membrane hydrogen electrode solid oxide fuel cell according to claim 2, characterized by comprising the following steps:
step 1, preparing a YSZ electrolyte sheet, punching a cast YSZ electrolyte blank into a small round sheet with the diameter of 19mm, and sintering at 1400 ℃ for 5 hours to obtain a porous YSZ-supported half-cell support body;
step 2, selecting the integrated half-cell support body for screen printing of the GDC barrier layer, screen printing of the GDC barrier layer on the surface of the compact YSZ electrolyte sheet, and calcining at 1300 ℃ for 3 hours with the thickness of 5 microns;
step 3, selecting and using the silk-screen anode layer LSCFN as La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ(LSCFN) perovskite oxide material is deposited on the surface of the GDC isolating layer by a screen printing method and then calcined at 1075 ℃ for 2 hours to form a working area of 0.5cm2The anode layer has a thickness of 40 μm;
step 4, preparing a cathode in the porous YSZ support body by dipping the LSCF hydrogen electrode by using an LSCF dipping solution, wherein the cathode is dipped for about 15 times until the solution cannot automatically permeate into the porous layer, the cathode is calcined at 750 ℃ for 0.5h after each dipping, and the thickness of the cathode is 400 microns;
and 5, manufacturing a single cell, and finally, silk-screening silver grids on the surfaces of the cathode and the anode respectively to collect current.
4. The method for preparing the membrane hydrogen electrode solid oxide fuel cell according to claim 2, wherein the method for preparing the hydrogen electrode material of the membrane hydrogen electrode solid oxide fuel cell comprises the following steps:
step 1, according to La (NO)3)6·6H2O：SrCO3：Co(NO3)2·6H2O：Fe2O3：Nb2O50.4: 0.6: 0.2: 0.35: 0.1, putting the mixture into a ball milling tank, adding ethanol, and ball milling for 48 hours;
and 2, drying the ball-milled mixture in an oven, calcining the dried ball-milled mixture in a crucible at 1100 ℃ for 5 hours, and sieving the calcined ball-milled mixture with a 200-mesh sieve to obtain the hydrogen electrode material.
5. The preparation method according to claim 4, wherein in the step 2, the ball milling media are zirconia balls and absolute ethyl alcohol, and the ball milling time is 48 hours.
6. Use of a membrane hydrogen electrode solid oxide fuel cell, characterized in that the cell can be used in an electrolysis cell or in a fuel cell.
CN201911087937.6A 2019-11-08 2019-11-08 Film hydrogen electrode solid oxide battery and preparation method thereof Pending CN111048814A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112599826A (en) * 2020-12-03 2021-04-02 山东科技大学 High-performance solid oxide fuel cell and preparation method thereof
CN113258111A (en) * 2021-06-30 2021-08-13 中国矿业大学(北京) Zirconium-based anode-supported solid oxide battery without isolation layer
CN113445061A (en) * 2021-06-07 2021-09-28 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
CN114890787A (en) * 2022-05-31 2022-08-12 南京理工大学 Oxygen electrode supporting type solid oxide electrolytic cell and preparation method thereof
CN115966713A (en) * 2023-01-13 2023-04-14 华北电力大学 Solid oxide battery and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1960047A (en) * 2006-11-23 2007-05-09 上海交通大学 Method for preparing low temperature solid oxide fuel cell supported by porous metal
CN101577341A (en) * 2009-06-10 2009-11-11 中国矿业大学(北京) Method for preparing solid oxide fuel cell and entire cell thereof at low temperature

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Application publication date: 20200421