CN110875479A - Boron fuel cell and manufacturing method thereof - Google Patents

Boron fuel cell and manufacturing method thereof Download PDF

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Publication number
CN110875479A
CN110875479A CN201811010940.3A CN201811010940A CN110875479A CN 110875479 A CN110875479 A CN 110875479A CN 201811010940 A CN201811010940 A CN 201811010940A CN 110875479 A CN110875479 A CN 110875479A
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China
Prior art keywords
boron
porous
fuel cell
plate
anode
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CN201811010940.3A
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Chinese (zh)
Inventor
温术来
李向红
孙亮
赵寰宇
范家斌
诺力格尔
李鹏斐
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Shanghai Railway Communication Co Ltd
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Shanghai Railway Communication Co Ltd
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Priority to CN201811010940.3A priority Critical patent/CN110875479A/en
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    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Fuel Cell (AREA)

Abstract

The invention relates to a boron fuel cell and a manufacturing method thereof, wherein the boron fuel cell comprises a porous cathode plate (2), a cathode catalyst layer (3), a solid oxide electrolyte layer (4), an anode catalyst layer (5) and a porous anode plate (6) which are sequentially connected in a stacked mode, and the solid oxide electrolyte layer (4) is a double electrolyte layer formed by mixing borate and solid oxide. Compared with the prior art, the invention adopts the boron simple substance with high energy density as the fuel, and can achieve higher energy output by combining with the high conversion rate of the fuel cell; the double electrolytes formed by combining borate and solid oxide can improve the effective combining area of the electrolytes and fuel boron powder and improve the conversion efficiency.

Description

Boron fuel cell and manufacturing method thereof
Technical Field
The present invention relates to a fuel cell, and more particularly, to a boron fuel cell and a method of manufacturing the same.
Background
The fuel cell is a device for converting chemical energy in fuel into electric energy, has the main advantage of high conversion efficiency which can reach 50-80 percent and theoretically can reach 100 percent, is mainly used in the fields of traffic, fixed power stations and portable power sources, and has been developed for automobiles taking the fuel cell as a core power source at present. The energy output of a fuel cell depends, in addition to its conversion efficiency, on the energy density of the fuel chosen. For a fuel cell of the same conversion efficiency, the greater the energy density of the fuel, the greater its energy output. The fuel source of the fuel cell is very wide, mainly comprises carbon, alcohol, hydrogen and the like, wherein the energy density of the hydrogen is the largest and can reach 142MJ/kg, but the combustible range of the hydrogen is 4-75%, the explosion range is 18-59%, the safety and reliability are poor, and no widely acceptable solution is found at present, so that the application of the high-energy-density fuel is limited. The carbon fuel mainly comprises graphite, carbon black, coal and the like, and the fuel has high safety and reliability, but has low energy density, for example, the energy density of the coal is only about 16.8 MJ/kg. The energy density of the alcohol substances is slightly higher than that of coal, for example, the energy density of methanol is about 21.6MJ/kg, and the energy density of ethanol is about 29.7 MJ/kg. The energy density of boron is 58.28MJ/kg, the boron is a non-metal simple substance with the energy density second to that of hydrogen, is one of the most promising high-energy metal fuel components in the research field of solid oxygen-poor propellants, is a main energy source of boron-containing oxygen-poor propellants, but is not applied to the field of fuel cells as fuel.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a boron fuel cell and a method for manufacturing the same, which fully utilize the high conversion efficiency of the fuel cell to obtain high power output.
The purpose of the invention can be realized by the following technical scheme:
a boron fuel cell comprises a porous cathode plate, a cathode catalyst layer, a solid oxide electrolyte layer, an anode catalyst layer and a porous anode plate which are sequentially connected in a stacked mode, wherein the solid oxide electrolyte layer is a double-electrolyte layer formed by mixing borate and solid oxide.
The cathode collector net is arranged on the outer side of the porous cathode plate, and the anode collector net is arranged on the outer side of the porous anode plate.
The porous cathode plate, the cathode catalyst layer, the solid oxide electrolyte layer, the anode catalyst layer and the porous anode plate are positioned in the ceramic tube.
The porous anode plate is a porous NiO-YSZ flat plate.
The porous cathode plate is porous La0.85Sr0.15MnO3And (4) flat plate.
And the cathode lead is connected with the porous cathode plate, and the anode lead is connected with the porous anode plate.
And depositing YSZ on the porous anode plate by adopting an ion beam vapor deposition or electron beam vapor deposition method to form an electrolyte layer, wherein the structure of the electrolyte layer is columnar.
The borate contains sodium borate, potassium borate and aluminum oxide.
The borate composition is as follows: 46-62 wt% of sodium borate, 18-32 wt% of potassium borate and 6-36 wt% of aluminum oxide.
The manufacturing method of the boron fuel cell comprises the following steps:
1) sequentially stacking a porous cathode plate, a cathode catalyst layer, a solid oxide electrolyte layer, an anode catalyst layer and a porous anode plate in a ceramic tube, respectively placing a pole current collecting net and an anode current collecting net at the outer sides of the porous cathode plate and the porous anode plate, and leading out a cathode lead and an anode lead;
2) placing a boron powder layer outside the anode current collecting net, and placing a borate layer outside the boron powder layer to finish the assembly of the fuel cell;
3) and (2) putting the assembled boron fuel cell into a heating furnace, heating and preserving heat to enable a boron salt layer to be molten and to infiltrate into a boron powder layer, the boron salt layer reaches a solid oxide electrolyte layer through holes of a porous anode plate, a boron simple substance loses electrons under the action of an anode catalyst layer to form boron ions, the lost electrons reach a porous cathode plate from an external circuit, oxygen in the air passes through the porous cathode plate at the moment, the oxygen is catalyzed by a cathode catalyst layer and then receives the electrons to form oxygen ions, and the oxygen ions penetrate through the solid oxide electrolyte layer to reach the porous anode plate to react with the boron ions to generate boron oxide.
Compared with the prior art, the invention has the following advantages:
(1) the boron simple substance with high energy density is used as fuel, and high energy output can be achieved by combining with the high conversion rate of the fuel cell.
(2) The double electrolytes formed by combining borate and solid oxide can improve the effective combining area of the electrolytes and fuel boron powder and improve the conversion efficiency.
(3) YSZ is deposited on the porous anode plate by adopting a plasma beam vapor deposition or electron beam vapor deposition method to form an electrolyte layer, the organization structure of the electrolyte layer is columnar, a directional channel vertical to the pole plate is formed for oxygen ion transmission, the transmission time of oxygen ions can be shortened, and the working efficiency of the whole boron fuel cell is improved.
Drawings
FIG. 1 is a schematic structural view of the present invention;
reference numerals:
1-a cathode current collector; 2-a porous cathode plate; 3-a cathode catalyst layer; 4-a solid oxide electrolyte layer; 5-anode catalyst layer; 6-a porous anode plate; 7-anode current collecting net; 8-anode lead; 9-borate layer; a 10-boron powder layer; 11-a ceramic tube; 12-cathode lead.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Examples
As shown in fig. 1, the boron fuel cell comprises a cathode current collecting net 1, a porous cathode plate 2, a cathode catalyst layer 3, a solid oxide electrolyte layer 4, an anode catalyst layer 5, a porous anode plate 6 and an anode current collecting net 7 which are sequentially connected in a stacked manner, wherein the solid oxide electrolyte layer 4 is a double electrolyte layer formed by mixing borate and solid oxide.
The battery manufacturing method comprises the following steps:
1) the porous cathode plate 2, the cathode catalyst layer 3, the solid oxide electrolyte 4, the anode catalyst layer 5 and the porous anode plate 6 are solid oxidant fuel cells and are placed in a ceramic tube 11. When the porous cathode plate is placed, the porous cathode plate 2 is outward, the porous anode plate 6 is inward, the cathode current collecting net 1 is placed on the outer side of the porous cathode plate 1, the cathode lead 12 is led out, the current collecting net 7 is placed on the outer side of the porous anode plate 6, and the anode lead 8 is led out;
2) and (3) placing a boron powder layer 10 outside the anode current collecting net 7, and placing a borate layer 9 outside the boron powder layer 10 to finish the installation of the boron fuel cell.
3) And (3) putting the assembled boron fuel cell into a heating furnace, heating to a preset temperature, and preserving heat for 10-30 minutes to enable the boron salt layer 9 to be in a molten state, wherein due to gravity and capillary action, the molten boron salt layer 9 can infiltrate into the boron powder layer 10 to reach a porous anode layer and reach the solid electrolyte layer through holes of the anode layer. Under the action of an anode catalyst, the elemental boron loses electrons to form boron ions, the lost electrons reach the porous cathode layer from an external circuit, oxygen in the air passes through the porous cathode layer at the moment, the oxygen is catalyzed by the cathode catalyst layer and then receives the electrons to form oxygen ions, and the oxygen ions penetrate through the solid oxide electrolyte layer to reach the porous anode layer to react with the boron ions to generate boron oxide.
In this embodiment, the boron powder is elemental boron powder, and amorphous boron powder and crystalline boron powder can be used, and amorphous boron powder is preferred. The amorphous boron powder has disordered structure and a large number of internal defects, so that the amorphous boron powder has poor thermal stability, is easy to react, and is beneficial to improving the performance of the boron fuel cell.
The particle size of the boron powder is controlled between 6 and 52 mu m, the reaction is incomplete when the particle size is too large, the reaction efficiency is reduced, the fuel waste is caused, and in addition, the specific surface area of the boron particles is small and the activity is reduced because of the too large particle size, so the reaction is not facilitated, and the battery performance is reduced. The boron powder with too small particle size has the advantages of improved specific surface area, increased activity, accelerated reaction speed and unfavorable reaction control, and meanwhile, because the activity is increased due to the too small particle size, oxides are easy to appear on the surface, a protective layer is formed on the surface of the boron powder, the boron powder is isolated from contacting with the outside, and the reaction is slowed down.
The boron salt layer mainly comprises sodium borate, potassium borate and aluminum oxide, wherein the weight percentage of the sodium borate is 46-62%, the weight percentage of the potassium borate is 18-32%, and the weight percentage of the aluminum oxide is 6-36%; the aluminum oxide plays a role of a diluent, and the excessive high concentration of borate is avoided, so that the content is controlled to be between 6 and 36 percent. The melting point of the mixture of the sodium borate and the potassium borate is influenced by the matching proportion of the sodium borate and the potassium borate, the matching proportion of the sodium borate and the potassium borate is controlled, the melting point of the mixture is favorably adjusted, and the reaction temperature of the battery is controlled within a reasonable range. If the reaction temperature of the battery is too high, the battery reacts too fast and is difficult to control; if the cell reaction temperature is too low, the reaction does not proceed easily, and the cell efficiency is lowered. In addition, too low a reaction temperature affects the ability of the solid electrolyte to transport the load. Therefore, the matching ratio of the two is required to be adjusted, and the reaction temperature of the battery is controlled between 650 ℃ and 1100 ℃.
The anode of the solid oxide cell is a porous NiO-YSZ flat plate, Y2O 3-doped ZrO2(YSZ) is deposited on the porous anode flat plate by adopting a plasma beam physical vapor deposition or electron beam physical vapor deposition method to form an electrolyte layer with the thickness of 2-280 microns, and the cathode is a La0.85Sr0.15MnO3 flat plate, wherein the electron beam physical vapor deposition process parameters are taken as examples: putting the porous anode plate into a cavity of electron beam physical deposition equipment, vacuumizing with the vacuum degree of 0.01-0.1Pa, raising the temperature to 700-900 ℃, electrifying with the current of 1.0-2.0A to ensure that the deposition surface layer is uniform, cooling the sample to room temperature at the rotation speed of 5-30rpm after the deposition process is finished, and taking out the sample. The plasma beam physical vapor deposition or the electron beam physical vapor deposition is mainly characterized in that a high-energy beam 'rapid temperature rise and rapid temperature fall' principle is utilized to deposit a zirconia-doped yttrium oxide material on an anode plate to form a solid electrolyte layer, the deposition process is controlled to enable the deposition material to form uniformly distributed columnar structures on the surface of the anode, a directional channel perpendicular to the anode plate is formed for oxygen ion transfer, the transfer time of oxygen ions can be shortened, and the working efficiency of the whole boron fuel cell is improved.
The performance of the boron fuel cell tends to increase firstly and then decrease along with the increase of the working temperature, and when the working temperature is too low, the output current density of the boron fuel cell decreases due to slow reaction speed; the output current density of the boron fuel cell rises along with the rise of the working temperature; when the working temperature is too high, the reaction is too fast, and the product cannot fall off from the polar plate in time, so that the subsequent reaction is difficult to carry out, and the performance of the battery is reduced. The working temperature of the boron fuel cell of the embodiment is 650-1100 ℃, so that the performance of the cell can reach the best.

Claims (10)

1. The boron fuel cell is characterized by comprising a porous cathode plate (2), a cathode catalyst layer (3), a solid oxide electrolyte layer (4), an anode catalyst layer (5) and a porous anode plate (6) which are sequentially connected in a stacked mode, wherein the solid oxide electrolyte layer (4) is a double-electrolyte layer formed by mixing borate and solid oxide.
2. A boron fuel cell according to claim 1, further comprising a cathode current collector mesh (1) outside the porous cathode plate (2) and an anode current collector mesh (7) outside the porous anode plate (6).
3. A boron fuel cell according to claim 1, further comprising a ceramic tube (11), wherein the porous cathode plate (2), cathode catalyst layer (3), solid oxide electrolyte layer (4), anode catalyst layer (5) and porous anode plate (6) are located inside the ceramic tube (11).
4. The boron fuel cell according to claim 1, wherein the porous anode plate (6) is a porous NiO-YSZ plate.
5. A boron fuel cell according to claim 1, characterized in that the porous cathode plate (2) is porous La0.85Sr0.15MnO3And (4) flat plate.
6. A boron fuel cell according to claim 1, further comprising a cathode lead (12) connected to the porous cathode plate (2) and an anode lead (8) connected to the porous anode plate (6).
7. The boron fuel cell according to claim 1, wherein YSZ is deposited on the porous anode plate (6) by ion beam vapor deposition or electron beam vapor deposition to form an electrolyte layer, and the structure of the electrolyte layer is columnar.
8. The boron fuel cell of claim 1, wherein said borate comprises sodium borate, potassium borate and aluminum oxide.
9. A boron fuel cell according to claim 8, wherein said borate composition is as follows: 46-62 wt% of sodium borate, 18-32 wt% of potassium borate and 6-36 wt% of aluminum oxide.
10. A method of manufacturing a boron fuel cell according to any one of claims 1 to 9, comprising the steps of:
1) sequentially stacking a porous cathode plate (2), a cathode catalyst layer (3), a solid oxide electrolyte layer (4), an anode catalyst layer (5) and a porous anode plate (6) in a ceramic tube (11), respectively placing a pole current collecting net (1) and an anode current collecting net (7) at the outer sides of the porous cathode plate (2) and the porous anode plate (6), and leading out a cathode lead (12) and an anode lead (8);
2) a boron powder layer is arranged on the outer side of the anode current collecting net (7), and a borate layer is arranged outside the boron powder layer to finish the assembly of the fuel cell;
3) and (2) putting the assembled boron fuel cell into a heating furnace, heating and preserving heat to melt a boron salt layer and infiltrate the boron powder layer, the boron salt layer reaches the solid oxide electrolyte layer (4) through the holes of the porous anode plate (6), the boron simple substance loses electrons under the action of the anode catalyst layer (5) to form boron ions, the lost electrons reach the porous cathode plate (2) from an external circuit, oxygen in the air passes through the porous cathode plate (2) at the moment and receives the electrons after being catalyzed by the cathode catalyst layer to form oxygen ions, and the oxygen ions penetrate through the solid oxide electrolyte layer (4) to reach the porous anode plate (6) to react with the boron ions to generate boron oxide.
CN201811010940.3A 2018-08-31 2018-08-31 Boron fuel cell and manufacturing method thereof Pending CN110875479A (en)

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CN201811010940.3A CN110875479A (en) 2018-08-31 2018-08-31 Boron fuel cell and manufacturing method thereof

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Application Number Priority Date Filing Date Title
CN201811010940.3A CN110875479A (en) 2018-08-31 2018-08-31 Boron fuel cell and manufacturing method thereof

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CN110875479A true CN110875479A (en) 2020-03-10

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