Semiconductor ionic solid oxide fuel cell with single-component structure and preparation method of semiconductor ionic solid oxide fuel cell

Abstract

The invention discloses a semiconductor ionic solid oxide fuel cell with a single-component structure and a preparation method of the semiconductor ionic solid oxide fuel cell, and belongs to the technical field of solid oxide fuel cells. Comprising an intermediate layer of a GDC ion conductor material coated with a nano SiC semiconductor material and current collecting layers located on the two sides of the intermediate layer. The preparation method comprises the following steps: mixing a Gd source, a Ce source, citric acid monohydrate, ethylene glycol and SiC, uniformly stirring to obtain viscous gel, and sequentially drying, calcining and grinding to obtain GDC coated SiC powder; the preparation method comprises the following steps: mixing NCAL and terpilenol to prepare slurry, uniformly coating foamed nickel with the slurry, and drying to obtain foamed nickel-NCAL; taking GDC coated SiC powder as an intermediate layer, taking foamed nickel-NCAL as collector layers at two ends, and tabletting by using a tablet press to prepare the semiconductor ion type solid oxide fuel cell. The preparation process is simple and easy to implement, and the solid oxide fuel cell obtained by the preparation method has excellent electrochemical efficiency and stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid oxide fuel cells, and in particular relates to a semiconductor ion type solid oxide fuel cell with a single component structure and a preparation method thereof. Background Art

[0002] At present, fossil energy still occupies a dominant position in the global energy consumption structure, and over-reliance on fossil energy has posed a severe challenge to the living environment of mankind. Solid oxide fuel cells (SOFCs) are an efficient and environmentally friendly energy conversion device with broad application prospects. The operating temperature of traditional SOFCs is between 600-1000℃, which is the highest operating temperature of all fuel cells. Excessive temperature will cause material aging, structural deformation and other problems, resulting in battery performance degradation and shortened life.

[0003] In 2010, a team led by Professor Zhu Bin of the Royal Institute of Technology in Sweden developed an electrolyte-free fuel cell (Electrolyte-Free Fuel Cell, EFFC). Its uniqueness lies in integrating the anode, cathode, and electrolyte functions of traditional solid oxide fuel cells into the same layer of semiconductor ion materials to form a single-component structure. Compared with the traditional three-layer SOFC, there is no need to consider the matching of the anode and cathode with the electrolyte. The preparation method is simpler and the manufacturing cost is lower. It can effectively reduce interface losses and avoid thermal stress and other problems, thereby improving the stability of the battery. The single-component SOFC is usually mixed with semiconductor materials and ion conductor materials into a homogeneous material, so that the mixed material has both ion conduction properties and semiconductor properties. The ion conductor material has the ability to conduct ions in the ion body and on its surface at the same time, while the semiconductor material produces a synergistic effect with the ions, electrons, and holes in the ion conductor material, ultimately improving the overall conductivity of the battery material, thereby reducing the operating temperature of the battery and improving the stability of the battery. Semiconductor ion solid oxide fuel cell is an energy device with great structural innovation. Its core technology lies in finding a suitable uniform layer of mixed conductivity of semiconductor-ion heterogeneous structure materials, so that the prepared solid oxide fuel cell has excellent electrochemical efficiency and stability.

[0004] Therefore, there is an urgent need to provide a medium- and low-temperature SOFC with a simple preparation process, high power generation efficiency, and a new structure, and a preparation method thereof. Summary of the invention

[0005] In view of the above technical problems, the present invention proposes a semiconductor ion-type solid oxide fuel cell with a single-component structure and a preparation method thereof.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention:

[0008] A semiconductor ion type solid oxide fuel cell having a single-component structure, comprising:

[0009] GDC (Ce) is coated with nano-SiC semiconductor material 0.9 G 0.1 O2) an intermediate layer of an ion conductor material (the coating structure is described as GDC@SiC) and current collecting layers located on both sides of the intermediate layer;

[0010] The GDC ion conductor material is Ce x G 1-x O2; wherein x is 0 to 1, and x is not 0, and x is not 1.

[0011] Beneficial effects: The present invention uses nano-SiC semiconductor materials to coat GDC ion conductor materials (the coating structure is described as GDC@SiC). On the one hand, by introducing nano-sized materials, the specific surface area is increased. On the other hand, this core-shell structure can give full play to the synergistic effect of the heterogeneous interface, which is beneficial to improve the output power. Then GDC@SiC powder is used as an intermediate layer with Ni-Ni foam. 0.8 Co 0.15 Al 0.05 LiO2 (NCAL for short) is used as the current collecting layers at both ends for sheet pressing, ultimately forming a new semiconductor ion-type solid oxide fuel cell with a single-component structure.

[0012] Optionally, the diameter of the solid oxide fuel cell is 13 mm.

[0013] Optionally, the particle size of the SiC semiconductor material in the GDC@SiC is 40 nm, and the particle size of the GDC is 100 nm.

[0014] Optionally, the current collecting layers at both ends are Ni-Ni foam 0.8 Co 0.15 Al 0.05 LiO2 (abbreviated as NCAL).

[0015] The second technical solution of the present invention:

[0016] A method for preparing a semiconductor ion type solid oxide fuel cell having a single-component structure comprises the following steps:

[0017] Gd source, Ce source, monohydrated citric acid, ethylene glycol and SiC were mixed and stirred evenly to obtain a viscous gel, which was then dried, calcined and ground in sequence to obtain GDC@SiC powder;

[0018] NCAL(Ni 0.8 Co 0.15 Al 0.05 LiO2) and pinene alcohol are mixed to form a slurry, which is evenly coated on the nickel foam and dried to obtain nickel foam-NCAL;

[0019] GDC@SiC powder was used as the middle layer and nickel foam-NCAL was used as the current collecting layers at both ends. A semiconductor ion-type solid oxide fuel cell (nickel foam-NCAL|GDC@SiC powder|nickel foam-NCAL) was prepared by tableting using a tablet press.

[0020] Optionally, the Gd source is at least one of gadolinium nitrate hexahydrate (Gd(NO3)2·6H2O), gadolinium acetate or gadolinium oxide; preferably Gd(NO3)2·6H2O;

[0021] The Ce source is at least one of cerium nitrate hexahydrate (Ce(NO3)2·6H2O), cerium acetate or cerium oxide, preferably Ce(NO3)2·6H2O.

[0022] Among them, when cerium oxide and gadolinium oxide are selected as raw materials, they need to be oxidized with dilute nitric acid to obtain metal cations.

[0023] Optionally, the molar ratio of Gd(NO3)2·6H2O, Ce(NO3)2·6H2O, citric acid monohydrate and ethylene glycol is: 0.1:0.9:2:4.

[0024] Optionally, the mass ratio of SiC to GDC in the GDC@SiC powder is (2:3)-(3:2), preferably 2:3, 3:2, 1:1; more preferably 2:3.

[0025] Optionally, the calcination process is carried out under the following conditions: calcination at 700° C. for 5 hours.

[0026] The mass ratio of NCAL to terpineol is 3:1.

[0027] Compared with the prior art, the present invention has the following advantages and technical effects:

[0028] The single homogeneous layer (i.e., the middle layer, a uniform layered structure composed of the same structure) of the solid oxide fuel cell of the present invention is composed of a GDC-SiC semiconductor ion material with a coating structure as a battery, and a current collecting layer made of NCAL-coated nickel foam is formed on both end surfaces, forming a semiconductor ion type solid oxide fuel cell with the advantages of safety, high efficiency, environmental friendliness, and simple manufacturing process.

[0029] The solid oxide fuel cell obtained by the preparation method of the present invention has excellent electrochemical efficiency and stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0031] Figure 1 This is a schematic diagram of the structure of the solid oxide fuel cell prepared in Example 1 of the present invention;

[0032] Among them, 1-single homomorphic layer, 2-collector layer;

[0033] Figure 2 This is a working schematic diagram of the solid oxide fuel cell prepared in Example 1 of the present invention;

[0034] Figure 3 XRD patterns of SiC, GDC-SiC and GDC prepared in Example 1 of the present invention;

[0035] Figure 4 This is a SEM image of the GDC@SiC powder prepared in Example 1 of the present invention;

[0036] Figure 5 This is the EDS image of the GDC@SiC powder prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0037] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0038] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0039] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0040] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0041] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0042] The embodiment of the present invention discloses a novel method for preparing a single-component semiconductor ion-type solid oxide fuel cell, comprising the following steps:

[0043] (1) Preparation of semiconductor ion homogeneous material, GDC@SiC powder by sol-gel method:

[0044] Gd(NO3)2·6H2O, Ce(NO3)2·6H2O and water are used as raw materials, monohydrated citric acid is added in a molar ratio of 1:2 (ratio of the sum of the two metal ions to citric acid), ethylene glycol is added in a molar ratio of 1:2 (ratio of citric acid to ethylene glycol), SiC is added in a mass ratio of GDC:SiC of 3:2, the formed mixed solution is ultrasonically treated and then placed on a constant temperature stirrer, heated and stirred for 8 hours to form a viscous gel, the viscous gel is placed in a blast drying oven for blast drying to form a dry gel, and then the dry gel is calcined at 700°C for 5 hours, and the obtained mixed powder is ball milled to obtain GDC@SiC powder;

[0045] (2) NCAL and pinene alcohol are made into a slurry, which is evenly coated on nickel foam and dried to obtain nickel foam-NCAL. The nickel foam-NCAL is used as a current collecting layer and a tablet press is used to form a new type of single-component structure semiconductor ion-type solid oxide fuel cell according to nickel foam-NCAL|GDC@SiC powder|nickel foam-NCAL.

[0046] The embodiment of the present invention also discloses a novel single-component structure semiconductor ion type solid oxide fuel cell, comprising: GDC (Ce 0.9 G 0.1 O2) ion conductor material (the coating structure is described as GDC@SiC) Figure 1 A single homogeneous layer 1) in the middle layer and current collecting layers 2 located at both ends of the middle layer.

[0047] The "room temperature" in the present invention refers to 20-30°C unless otherwise specified.

[0048] The raw materials used in the present invention are all purchased from the market.

[0049] The technical solution of the present invention is further illustrated by the following embodiments.

[0050] Example 1

[0051] A method for preparing a semiconductor ion type solid oxide fuel cell having a single-component structure comprises the following steps:

[0052] (1) Synthesis of GDC@SiC powder

[0053] Add 120mL of deionized water to a beaker, then add 0.002mol Gd(NO3)2·6H2O and 0.018mol Ce(NO3)2·6H2O and dissolve them in the deionized water, and mix them evenly at room temperature; then add citric acid monohydrate at a molar ratio of 1:2 (ratio of metal ions to citric acid), add 4.9656g (0.08mol) of ethylene glycol at a molar ratio of 1:2 (ratio of citric acid to ethylene glycol), add nano-SiC powder to the mixed solution at a mass ratio of 3:2 (ratio of GDC to SiC) to form a mixed solution A, and after ultrasonic treatment of the mixed solution A for 60min, place it on a constant temperature magnetic stirrer, heat (temperature is 80°C) and stir for 8h until a viscous gel is formed, transfer the gel to a blast drying oven and dry and heat at 250°C for 10h, and calcine the obtained GDC / SiC dry gel at 700°C in a muffle furnace for 5h. The sintered GDC / SiC powder was dry-milled for 2 h. After dry-milling, ethanol was added as a dispersion medium for wet-milling for 12 h and dried to form GDC@SiC powder.

[0054] (2) Preparation of nickel foam-NCAL / GDC@SiC / nickel foam-NCAL battery components

[0055] NCAL slurry is prepared by mixing NCAL and pinene alcohol in a mass ratio of 3:1, and coated on the surface of nickel foam. The nickel foam coated with NCAL is then placed in a blast drying oven for drying, and then sprayed and dried again until the surface of the nickel foam presents a uniform black color, thereby forming a nickel foam-NCAL current collecting layer.

[0056] The materials were placed into a tablet press mold in the order of nickel foam-NCAL / GDC@SiC powder / nickel foam-NCAL to form a single-component structure nickel foam-NCAL|GDC@SiC powder|nickel foam-NCAL semiconductor ion-type solid oxide fuel cell with a diameter of 13 mm.

[0057] Comparative Example 1

[0058] The difference from Example 1 is that the raw material ratio in step (1) is different, and the mass ratio of GDC to SiC is 1:4. Other conditions are the same as in Example 1.

[0059] Comparative Example 2

[0060] The difference from Example 1 is that silicon carbide is not added. Other conditions are the same as Example 1.

[0061] Comparative Example 3

[0062] The difference from Example 1 is that silicon carbide is replaced by copper oxide. Other conditions are the same as Example 1.

[0063] Comparative Example 4

[0064] The difference from Example 1 is that no calcination treatment is performed in step (1), and other conditions are the same as in Example 1.

[0065] Figure 1 This is a schematic diagram of the structure of the solid oxide fuel cell prepared in Example 1 of the present invention. It can be seen from the figure that the solid oxide fuel cell device is a single-component structure, without anode and cathode in the traditional sense, and only uses nickel foam-NCAL as the current collecting layer of the battery component and GDC@SiC powder as a single isomorphous layer (middle layer).

[0066] Figure 2 The working diagram of the solid oxide fuel cell is shown in the figure. As can be seen from the figure, when the solid oxide fuel cell is working, at the fuel gas input side, the fuel gas is catalytically oxidized and loses electrons in the reaction; at the oxygen input side, the oxygen obtains electrons from the external circuit to generate oxygen ions. The oxygen ions will migrate from the oxygen input side to the fuel gas input side, H + It will migrate from the fuel gas input side to the oxygen input side, completing the entire electrochemical reaction process inside the battery and realizing the conversion of chemical energy into electrical energy.

[0067] Figure 3 The XRD diagrams of SiC, GDC-SiC and GDC are measured at an angle of 10 to 80°. As can be seen from the figure, by comparing the PDF standard card, after mixing GDC and SiC, GDC and SiC are in a two-phase mode, indicating that there is no reaction between the two materials. Due to the long ball milling time and the low content of other compounds, some compounds have amorphous phenomena during the ball milling process or some characteristic peaks overlap with other characteristic peaks, resulting in the XRD results not detecting the characteristic peaks of other substances.

[0068] Figure 4 This is a SEM image of the GDC@SiC powder prepared in Example 1 of the present invention. From the image, it can be seen that nano-scale SiC (diameter of about 40 nm) is coated with GDC (diameter of about 100 nm).

[0069] Figure 5This is the EDS image of the GDC@SiC powder prepared in Example 1 of the present invention, confirming the presence of Ce, Gd, Si and C elements.

[0070] Effect verification

[0071] The samples prepared in Example 1 and Comparative Examples 1-4 were subjected to electrochemical effect tests. The test conditions of the electrochemical data were as follows: the flow rates of hydrogen and air were both 100 mL / min; the measurement temperature was 550°C; the application frequency range was 0.1 Hz to 100 kHZ, and the measurement started from the high frequency; the vibration voltage signal amplitude was 10 mV. The corresponding electrochemical effect data are shown in Table 1:

[0072] Table 1

[0073] OCV (open circuit voltage) / V <![CDATA[Maximum output power / mW·cm -2 > Example 1 1.0 834 Comparative Example 1 0.3 103 Comparative Example 2 0.5 405 Comparative Example 3 0.8 610 Comparative Example 4 0.4 —

[0074] It can be seen from Table 1 that the semiconductor ion-type solid oxide fuel cell prepared in Example 1 of the present invention has a high open circuit voltage and a high output power, which reflects its excellent electrochemical performance.

[0075] The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A semiconductor ion type solid oxide fuel cell having a single component structure, characterized in that: include: The intermediate layer of the GDC ion conductor material and the current collecting layers on both sides of the intermediate layer are coated with nano-SiC semiconductor material; the GDC ion conductor material is Ce x G 1-x O2; wherein x is 0 to 1, and x is not 0, and x is not 1.

2. A semiconductor ion type solid oxide fuel cell with a single component structure according to claim 1, characterized in that: The intermediate layer is GDC@SiC, in which the particle size of SiC is 40 nm and the particle size of GDC is 100 nm.

3. A semiconductor ion type solid oxide fuel cell with a single component structure according to claim 1, characterized in that: The current collecting layers at both ends are Ni-Ni foam 0.8 Co 0.15 Al 0.05 LiO2.

4. A method for preparing a semiconductor ion-type solid oxide fuel cell having a single-component structure, characterized in that: The following steps are involved: Gd source, Ce source, monohydrated citric acid, ethylene glycol and SiC were mixed and stirred evenly to obtain a viscous gel, which was then dried, calcined and ground in sequence to obtain GDC@SiC powder; NCAL and pinene alcohol are mixed to form a slurry, which is evenly coated on the nickel foam and dried to obtain the nickel foam-NCAL; The semiconductor ion-type solid oxide fuel cell according to any one of claims 1 to 3 is prepared by using a tablet press to form a GDC@SiC powder as an intermediate layer and nickel foam-NCAL as current collecting layers at both ends.

5. The method for preparing a semiconductor ion type solid oxide fuel cell having a single component structure according to claim 4, characterized in that: The Gd source is Gd(NO3)2·6H2O; The Ce source is Ce(NO3)2·6H2O.

6. The method for preparing a semiconductor ion type solid oxide fuel cell having a single component structure according to claim 5, characterized in that: The molar ratio of Gd(NO3)2·6H2O, Ce(NO3)2·6H2O, citric acid monohydrate and ethylene glycol is 0.1:0.9:2:

4.

7. The method for preparing a semiconductor ion type solid oxide fuel cell having a single component structure according to claim 4, characterized in that: The mass ratio of SiC to GDC in the GDC@SiC powder is (2:3)-(3:2).

8. The method for preparing a semiconductor ion type solid oxide fuel cell having a single component structure according to claim 4, characterized in that: The calcination process was carried out under the conditions of 700° C. for 5 h.

9. The method for preparing a semiconductor ion type solid oxide fuel cell having a single component structure according to claim 4, characterized in that: The mass ratio of NCAL to terpineol is 3:1.

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