CN115172833A - Lithium compound electrode ceramic fuel cell electrolyte, preparation method and application - Google Patents
Lithium compound electrode ceramic fuel cell electrolyte, preparation method and application Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 70
- 239000000446 fuel Substances 0.000 title claims abstract description 42
- 239000000919 ceramic Substances 0.000 title claims abstract description 25
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 229910021314 NaFeO 2 Inorganic materials 0.000 claims abstract description 31
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004449 solid propellant Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
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- 230000007423 decrease Effects 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
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- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000013112 stability test Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910002490 Ce0.9Gd0.1O2–δ Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017018 Ni0.8Co0.15Al0.05 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
-
- 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
-
- 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
Abstract
The invention relates to a lithium compound electrode ceramic fuel cell electrolyte, a preparation method and application. The electrolyte comprises NaFeO 2 And MgO. The method is used for preparing the lithium compound electrode ceramic fuel cell, comprises S1, and NaFeO is prepared by a high-temperature solid phase method 2 (ii) a S2, the NaFeO prepared in the step S1 2 Grinding and mixing the electrolyte with MgO powder to obtain composite electrolyte powder; and S3, preparing a foamed nickel-NCAL electrode by a coating method, and then pressing the composite electrolyte powder and the electrode into a battery under high pressure. The preparation method of the lithium compound electrode ceramic fuel cell provided by the invention is simple and easy to operate, low in cost, and high in stability and better in power density when the obtained solid fuel cell runs stably at 550 ℃.
Description
Technical Field
The invention relates to a lithium compound electrode ceramic fuel cell electrolyte, a preparation method and application, and belongs to the technical field of cell preparation.
Background
Solid Oxide Fuel Cells (SOFCs) are fuel cells of the type that operate at medium to high temperatures (C:)>400 ℃) capable of operating at H 2 、NH 3 、CH 4 The energy conversion device taking C and other energy carriers as fuels has the advantages of wide fuel application range and high comprehensive conversion efficiency (40-65% of power generation efficiency and comprehensive energy efficiency)Not less than 90%), and the like, and the solid oxide fuel cell has a very wide application prospect and can use various fuels, such as natural gas, methane, coal gas, methane and the like; the device can be used in stationary power stations, household power supplies, ship power, automobile power, space navigation and other fields. Due to the adoption of the all-solid-state battery structure, the corrosion and electrolyte loss caused by the use of liquid electrolyte are avoided. With the further breakthrough of solid oxide fuel cell technology, it is expected that the solid oxide fuel cell will be widely applied in the future.
Commercialization of SOFCs has been limited by cost and long-term stability over the last twenty years. Reducing the operating temperature of SOFCs to below 600 ℃, while ensuring stable power generation performance and low manufacturing cost of the cells, is one of the most promising technical routes for large-scale commercialization of SOFCs. However, as the operation temperature of the SOFC decreases, the ion conductivity of the electrolyte may significantly decrease and the electrode catalytic activity may deteriorate, which may result in significant decrease in the power generation performance and stability of the battery. Conventional electrolyte materials, such as: y is 2 O 3 Stabilized ZrO 2 (YSZ) Gd-doped CeO 2 The ionic conductivity of electrolytes such as (GDC) and strontium/magnesium doped lanthanum gallate (LSGM) decreases significantly with decreasing temperature; the ionic conductivity of YSZ is 0.1S-cm at 1000 DEG C -1 At 800 deg.C, the temperature is reduced to 0.03 S.cm -1 And then reduced to 0.002S-cm at 600 deg.C -1 . Therefore, the reduction of the operation temperature is restricted by the low temperature and the low conductivity of the electrolyte, and the catalytic activity of the cathode material to the oxygen reduction reaction is greatly reduced at the low operation temperature, so that the large-scale commercial application of the fuel cell is hindered, and how to solve the problem is a technical problem which needs to be solved urgently. In recent years, ni is used as a catalyst 0.8 Co 0.15 Al 0.05 LiO 2 (NCAL) and LiNiO 2 Ceramic fuel cells using lithium oxide as electrodes, such as (LNO), achieve very high maximum power densities in the medium and low temperature range (450-600 ℃). The cell uses lithium oxide as an electrode and some ceramic oxides such as La 0.25 Sr 0.75 TiO 3 (LST)、 Ce 0.9 Gd 0.1 O 2-δ (GDC)、SrTiO 3 (STO)、BaZr 0.9 Y 0.1 O 2.95 (BZY) and the like as electrolytes, and the electrolyte obtains very good power generation performance at about 500 ℃. However, there are some problems with the long-term stability of this new ceramic fuel cell with the NCAL as the electrode. In addition, the use of rare earth materials such as Ce, gd, la, and Sr as the electrolyte material has a problem of excessive cost.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides a lithium compound electrode ceramic fuel cell electrolyte, a preparation method and application. The invention provides MgO and NaFeO with lower cost 2 The prepared composite material is used as electrolyte of lithium compound electrode ceramic fuel cell. MgO/NaFeO 2 The composite electrolyte battery has the characteristics of low cost, and the weight ratio of MgO to NaFeO of 7-8:3-2 2 Batteries that are electrolytes also have comparable long-term stability.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a lithium compound electrode ceramic fuel cell electrolyte comprising NaFeO 2 And MgO.
The electrolyte as described above, preferably, the NaFeO 2 The mass ratio of MgO to MgO is 7-8:3-2.
The electrolyte as described above, preferably, the NaFeO 2 The preparation method comprises the following steps of mixing Fe with Na according to the molar ratio of 1.1 2 O 3 And Na 2 CO 3 After mixing, adding absolute ethyl alcohol for ball milling, drying after even mixing, and then roasting to obtain NaFeO 2 And (3) powder.
A lithium compound electrode ceramic fuel cell has a electrolyte containing NaFeO 2 And MgO.
Preferably, the NaFeO 2 The mass ratio of MgO to MgO is 7-8:3-2; the preferred material for the electrodes is nickel foam-NCAL.
A method for preparing a lithium compound electrode ceramic fuel cell comprises the following steps:
s1, preparing NaFeO by using high-temperature solid phase method 2 ；
S2, the NaFeO prepared in the step S1 2 Grinding and mixing the electrolyte with MgO powder to obtain composite electrolyte powder;
and S3, preparing a foamed nickel-NCAL electrode by a coating method, and then pressing the composite electrolyte powder and the electrode into a battery under high pressure.
In the above production method, preferably, in step S1, the high-temperature solid-phase method is performed by mixing Fe in a molar ratio of Fe to Na of 1.05 to 1.2 2 O 3 And Na 2 CO 3 After mixing, adding absolute ethyl alcohol for ball milling, drying after even mixing, and then roasting to obtain NaFeO 2 And (3) powder.
In the preparation method, the rotation speed of the ball milling is preferably 300-800 r/min, the ball milling time is 10-12 h, the drying temperature is 50-80 ℃, the drying time is 12-30 min, the roasting temperature is 700-900 ℃, and the roasting time is 8-10 h.
The production method as described above, preferably, in step S2, naFeO 2 The weight ratio of the MgO to the MgO powder is 7-8:3-2, and the grinding time is 15-40 minutes.
In the above manufacturing method, preferably, in step S3, the nickel foam-NCAL electrode is prepared by mixing terpineol and NCAL powder and stirring them to a viscous slurry, then uniformly coating the mixture on the nickel foam, drying and cutting the mixture to obtain the electrode; the composite electrolyte powder was placed between two electrodes and pressed to obtain a battery.
In the above production method, the pressure for pressing is preferably 360MPa.
(III) advantageous effects
The invention has the beneficial effects that:
the lithium compound electrode ceramic fuel cell electrolyte provided by the invention has the advantages of low cost and good stability.
The preparation method of the lithium compound electrode ceramic fuel cell provided by the invention is simple and easy to operate, and low in cost, and the obtained ceramic fuel cell has good power density and good stability when running stably at 550 ℃.
Drawings
FIG. 1 shows the NaFeO prepared 2 XRD spectrogram of the powder;
FIG. 2 is an IV-IP curve of composite electrolyte cells of different mass ratios under a hydrogen fuel test;
FIG. 3 is an AC impedance plot for cells with different mass ratios of composite electrolyte under a hydrogen fuel test;
FIG. 4 is a graph of short term stability tests performed on batteries of composite electrolytes of different mass ratios at 550 ℃;
FIG. 5 shows MgO/NaFeO in a mass ratio of 8:2 2 Cross-sectional view of the cell after testing of the composite electrolyte cell fuel cell.
Detailed Description
The invention provides a preparation method of a lithium compound electrode ceramic fuel cell, which comprises the following steps:
s1, preparing NaFeO by using high-temperature solid phase method 2 ；
S2, the NaFeO prepared in the step S1 2 Grinding and mixing the electrolyte with MgO powder to obtain composite electrolyte powder;
and S3, preparing a foamed nickel-NCAL electrode by a coating method, and then pressing the composite electrolyte powder and the electrode into a battery under high pressure.
Preferably, naFeO obtained by a high-temperature solid phase method 2 Has the advantages of simple preparation process, environmental protection and the like, and further, the high-temperature solid phase method is to use Fe 2 O 3 And Na 2 CO 3 After mixing, adding absolute ethyl alcohol for ball milling, drying after even mixing, and then roasting to obtain NaFeO 2 Powder; preferably, the molar ratio of Fe to Na element is 1.05-1.2 2 O 3 And Na 2 CO 3 The ratio of (a) is selected such that the reason for the excess of Na element is to compensate for the volatilization loss of Na during the high-temperature sintering. Preference is given toSetting the rotation speed of the ball mill to be 300-800 r/min, the ball milling time to be 10-12 h, the drying temperature to be 50-80 ℃ and the drying time to be 12-30 min, so that the powder is fully dried, the roasting temperature to be 700-900 ℃ and the roasting time to be 10 h. Further, the rotation speed of the ball milling is preferably 500r/min, the ball milling time is 12 hours, the drying temperature is 60 ℃, the drying time is 30 minutes, the roasting temperature is 800 ℃, and the roasting time is 10 hours.
The preparation method as described above, preferably, in step S2, naFeO 2 The weight ratio of the MgO to the MgO powder is 7-8:3-2, and the grinding time is 15-40 minutes. NaFeO 2 Too high or too low content of (B) causes deterioration of battery stability, so NaFeO is preferable 2 The mass ratio of the MgO powder to the MgO powder is 7-8:3-2.
Preferably, in step S3, the nickel foam-NCAL electrode is prepared by mixing terpineol: NCAL powder is mixed and stirred according to the mass ratio of 1:7 to viscous slurry, then the viscous slurry is evenly coated on foamed nickel, and the electrode is obtained after drying and cutting; and placing the composite electrolyte powder between two electrodes, and pressing under the pressure of 360MPa to obtain the battery.
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1
A preparation method of a lithium compound electrode ceramic fuel cell is carried out by adopting the following steps:
(1) High-temperature solid phase method for preparing NaFeO 2 : firstly, respectively weighing certain mass of Fe according to the atomic ratio of Fe to Na = 1.1 2 O 3 And Na 2 CO 3 Wherein a slight excess of Na is added to compensate for the Na volatilization loss during high temperature firing. Then mixing the zirconia balls with the weighed Fe 2 O 3 And Na 2 CO 3 Placing the mixture into a ball milling tank according to the volume ratio of 1.5 to 1.5, using absolute ethyl alcohol as a dispersing agent to disperse powder materials into the ethyl alcohol, and mainly aiming at fully mixing the two powder materials, and carrying out ball milling on the mixed powder for 12 hours at the rotating speed of 500r/min to ensure that Fe is dispersed in the mixed powder 2 O 3 And Na 2 CO 3 Mixing evenly, taking out the mixed powder after ball milling, and drying in an electrothermal constant-temperature drying oven at 60 ℃ until drying. Finally, the powder is made into strips and is placed in a crucible, the strips are roasted for 10 hours at the temperature of 800 ℃, and the blackish green NaFeO is obtained after grinding 2 And (3) powder.
(2) Preparing a composite electrolyte: taking NaFeO 2 And MgO powder are respectively put into a mortar according to the mass ratio of 6:4, 7:3, 8:2 and 9:1 to be ground for 30 minutes to obtain the composite electrolyte powder.
(3) Preparing a single cell: a nickel foam-NCAL electrode was first prepared by a coating method. The specific preparation method comprises the following steps: ni 0.8 Co 0.15 Al 0.05 LiO 2 (NCAL) is mixed and stirred to be viscous according to the mass ratio of 1:7, the slurry is evenly smeared on foamed nickel, the foamed nickel is placed into an oven to be dried for 60 minutes at the temperature of 80 ℃, the foamed nickel is taken out after surface liquid is solidified, and a wafer with the diameter of 13mm is cut to be used as an electrode. Then NaFeO with different mass proportions processed in the step (2) is added 2 And the MgO composite electrolyte powder and the foamed nickel-NCAL electrode are pressed into a disk-shaped single cell under the pressure of 360MPa, the thickness of the electrolyte can be made to be 0.3-1.5 mm, the thickness of the electrolyte can be adjusted by the using amount of the composite electrolyte, and one foamed nickel-NCAL electrode is respectively arranged on two sides of the single cell. The battery structure is as follows: foamed nickel-NCAL/NaFeO 2 + MgO composite electrolyte/nickel foam-NCAL.
For NaFeO prepared in the step (1) 2 The X-ray diffraction method is used for detection, the result is shown in figure 1, and the prepared NaFeO can be seen from the figure 2 No significant hetero-phase formation is evident.
And (3) electrochemical performance testing: the single cell prepared by the above method, wherein the thickness of the prepared fuel cell is 2.8mm, wherein the thicknesses of the vertically symmetrical electrodes are both 0.8mm, and the thickness of the intermediate electrolyte is 1.2mm. And placing the sample on a performance test fixture for clamping, placing the sample in a tubular resistance furnace, heating to 550 ℃, and carrying out electrochemical performance test. In the experiment, hydrogen is used as the fuel of the anode side, and oxygen is introduced to the cathode side to be used as the oxidant. Hydrogen is provided by a hydrogen generator, oxygen is provided by a gas cylinder, a rubber tube for supplying gas is connected to one side of the clamp, and the other side of the clamp is correspondingly connected with a rubber tubeThe hydrogen gas is discharged. The gas flow on both sides was 120mL/min. The electrochemical performance test was performed by a preston electrochemical workstation. After the fuel is introduced into the two sides of the cell, the IP-IV curve of the cell is firstly measured, then the alternating current impedance of the cell is measured, and finally the long-term stability of the cell is measured (the current is constant at 200 mA/cm) 2 ). The test frequency range of the alternating current impedance spectrum is 0.1Hz-1000000Hz, and the amplitude of the disturbance voltage is 20mV.
FIG. 2 shows the composite electrolytes and MgO and NaFeO in different mass ratios 2 The electrochemical performance of the electrolyte cell alone in a 550 ℃ fuel cell atmosphere was tested. As can be seen from the figure, mgO and NaFeO 2 The mass ratio of (A) is 6:4, 7:3, 8:2, 9:1 and MgO and NaFeO 2 The open circuit voltages of the batteries which are used as the electrolyte independently are 1.07, 1.02, 1.08, 1, 1.04 and 1V respectively; the maximum power density is 329, 550, 660, 504, 393, 274mW cm -2 . The electrochemical performance test result shows that MgO and NaFeO 2 The mass ratio of (A) to (B) is 8: the maximum power density of the electrolyte cell of 2 was the highest.
FIG. 3 shows the composite electrolytes and MgO and NaFeO in different mass ratios 2 The alternating current impedance spectrum of the electrolyte cell alone under the test atmosphere of the fuel cell. In the impedance spectrum, the focus of the left side of the impedance arc and the X axis represents the ohmic resistance of the battery. Since the principal product of the NCAL electrode after reduction includes Ni, the ohmic impedance of the cell is negligible to the contribution of the electrode. That is to say the ohmic resistance R of the cell in FIG. 3 o Primarily representative of the ohmic resistance of the electrolyte in the cell. MgO and NaFeO 2 The mass ratio of (A) is 6:4, 7:3, 8:2, 9:1 and MgO and NaFeO 2 The ohmic impedance of the cell as the electrolyte alone was 0.17, 0.15, 0.23, 0.37. Omega. Cm 2 The ion conductivity of the electrolyte of the corresponding battery is about 0.7, 0.8, 0.52 and 0.31 S.cm according to the rough calculation of the thickness of the electrolyte -1 。
FIG. 4 shows MgO/NaFeO in different mass ratios 2 The result of constant current stability test of the composite electrolyte cell, in which the current density was constant at 0.2A/cm 2 . As can be seen from FIG. 4, mgO/NaFeO 2 The composite electrolyte cell is at 0.2A/cm 2 In the constant current test process, the output voltage has a rapid reduction process within 1 hour in the initial test period, and then the voltage attenuation tends to be flat. Wherein the mass ratio of MgO/NaFeO is 7:3 2 After 4 hours, the output voltage of the composite electrolyte battery is reduced from 1V to 0.85V, then slowly reduced to about 0.79V after 6 hours, and then stabilized at 0.79V for 30 hours. During the period of 40 to 74h, the battery performance is slowly decayed, and the voltage is decayed from 0.79V to 0.75V. MgO and NaFeO 2 The output voltage of the battery respectively and independently used as the electrolyte can be rapidly reduced to 0.2V, the stability is poor, and the MgO and NaFeO are proved 2 The composite electrolyte prepared by compounding the components according to a certain proportion can effectively improve the stability of the battery, and MgO and NaFeO 2 The optimal ratio is about 7-8:3-2.
In order to research the microstructure of the battery prepared in the invention, the prepared single battery is processed by embedding epoxy resin and polishing the section, and is analyzed in the cross section morphology of a Scanning Electron Microscope (SEM), so that the mass ratio of MgO/NaFeO of 8:2 is used 2 The results are shown in FIG. 5, using a battery as an example. It can be seen from FIG. 5 that the cell has a symmetrical structure, the upper and lower sides are nickel foam-NCAL electrodes, and the middle layer is MgO/NaFeO 2 A composite electrolyte, wherein the electrolyte thickness is about 1.2mm. It can be seen from the figure that the electrolyte is denser and has no significant porosity; and a nickel foam-NCAL electrode and MgO/NaFeO 2 The composite electrolyte is tightly connected, and obvious layering and cracking phenomena do not occur.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any person skilled in the art can change or modify the technical content disclosed above into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A lithium compound electrode ceramic fuel cell electrolyte, characterized in that it comprises NaFeO 2 And MgO.
2. The lithium compound electrode ceramic fuel cell electrolyte of claim 1, wherein the NaFeO 2 The mass ratio of MgO to MgO is 7-8:3-2.
3. The lithium compound electrode ceramic fuel cell electrolyte of claim 1 or 2, wherein the NaFeO 2 The preparation method comprises the following steps of mixing Fe with Na according to the molar ratio of 1.1 2 O 3 And Na 2 CO 3 After mixing, adding absolute ethyl alcohol for ball milling, drying after even mixing, and then roasting to obtain NaFeO 2 And (3) powder.
4. A lithium compound electrode ceramic fuel cell is characterized in that the electrolyte of the fuel cell contains NaFeO 2 And MgO.
5. The lithium compound electrode ceramic fuel cell according to claim 4, wherein the NaFeO 2 The mass ratio of MgO to MgO is 7-8:3-2.
6. A preparation method of a lithium compound electrode ceramic fuel cell is characterized by comprising the following steps:
s1, preparing NaFeO by using high-temperature solid phase method 2 ；
S2, the NaFeO prepared in the step S1 2 Grinding and mixing the electrolyte with MgO powder to obtain composite electrolyte powder;
and S3, preparing a foamed nickel-NCAL electrode by a coating method, and then pressing the composite electrolyte powder and the electrode into a battery under high pressure.
7. The method according to claim 6, wherein the high-temperature solid phase method comprises, in step S1, mixing Fe in a molar ratio of Fe to Na of 1.05 to 1.2 2 O 3 And Na 2 CO 3 Mixing, adding absolute ethyl alcohol, ball milling, mixing, drying and dryingThen roasting to obtain NaFeO 2 And (3) powder.
8. The preparation method of claim 7, wherein the ball milling time is 10-12 h, the drying temperature is 50-80 ℃, the drying time is 12-30 min, the roasting temperature is 700-900 ℃, and the roasting time is 8-10 h.
9. The production method according to claim 6, wherein, in step S2, naFeO 2 The mass ratio of the MgO powder to the MgO powder is 7-8:3-2, and the grinding time is 15-40 minutes.
10. The method of claim 6, wherein the nickel foam-NCAL electrode is prepared by mixing terpineol and NCAL powder and stirring to form a viscous slurry, then uniformly coating the viscous slurry on the nickel foam, drying and cutting to obtain the electrode; the composite electrolyte powder was placed between two electrodes and pressed to obtain a battery.
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|---|---|---|---|---|
| CN103493268A (en) * | 2011-04-12 | 2014-01-01 | Toto株式会社 | Solid electrolyte fuel cell |
| JP2014049270A (en) * | 2012-08-31 | 2014-03-17 | Ti:Kk | Fuel battery |
| CN104937763A (en) * | 2012-11-15 | 2015-09-23 | 康宁股份有限公司 | Solid ceramic electrolytes |
| US20210242470A1 (en) * | 2020-01-30 | 2021-08-05 | Samsung Electronics Co., Ltd. | Cathode, lithium-air battery including the same, and method of preparing the same |
| CN114649527A (en) * | 2022-02-24 | 2022-06-21 | 南京工业大学 | Four-phase conductor proton conductor oxygen electrode material, preparation method and application |
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|---|---|---|---|---|
| CN103493268A (en) * | 2011-04-12 | 2014-01-01 | Toto株式会社 | Solid electrolyte fuel cell |
| JP2014049270A (en) * | 2012-08-31 | 2014-03-17 | Ti:Kk | Fuel battery |
| CN104937763A (en) * | 2012-11-15 | 2015-09-23 | 康宁股份有限公司 | Solid ceramic electrolytes |
| US20210242470A1 (en) * | 2020-01-30 | 2021-08-05 | Samsung Electronics Co., Ltd. | Cathode, lithium-air battery including the same, and method of preparing the same |
| CN114649527A (en) * | 2022-02-24 | 2022-06-21 | 南京工业大学 | Four-phase conductor proton conductor oxygen electrode material, preparation method and application |
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