CN112853530B - Hollow fiber pore-forming agent and application thereof in fuel cell - Google Patents

Hollow fiber pore-forming agent and application thereof in fuel cell Download PDF

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CN112853530B
CN112853530B CN202011618795.4A CN202011618795A CN112853530B CN 112853530 B CN112853530 B CN 112853530B CN 202011618795 A CN202011618795 A CN 202011618795A CN 112853530 B CN112853530 B CN 112853530B
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赵金保
李雪
曾静
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Xiamen University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
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    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • 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
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • 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

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Abstract

The invention relates to a pore-forming agent for hollow fibers and application thereof in fuel cells, wherein the pore-forming agent is PAN-PVP coaxial hollow fibers, the preparation method comprises the steps of preparing polyacrylonitrile and polyvinylpyrrolidone into PAN-PVP mixed solution, then operating on a coaxial high-voltage electrostatic spinning machine, placing methyl silicone oil in an inner needle hole, placing the PAN-PVP mixed solution in an outer needle hole, and collecting the PAN-PVP coaxial hollow fibers by rotating a roller collector. The PAN-PVP hollow fiber can form a three-dimensional network cross-linking cavity after the anode of the fuel cell is fired to remove the fiber, is beneficial to improving the connection of the anode in the hole, increasing the specific surface area in the electrolyte, integrally reducing the activation polarization of the cell, enlarging the electrochemical reaction area, reducing the internal resistance of the cell and accelerating the diffusion of substances, thereby finally improving the output performance of the cell and slowing down the attenuation of specific capacity.

Description

Hollow fiber pore-forming agent and application thereof in fuel cell
Technical Field
The invention relates to the field of batteries, in particular to a pore-forming agent for hollow fibers and application thereof in a fuel battery.
Technical Field
A fuel cell is a chemical device that directly converts chemical energy of fuel into electrical energy, and is also called an electrochemical generator. It is a fourth power generation technology following hydroelectric power generation, thermal power generation and atomic power generation. The fuel cell converts the Gibbs free energy in the chemical energy of the fuel into electric energy through electrochemical reaction, and is not limited by the Carnot cycle effect, so the efficiency is high; in addition, fuel cells use fuel and oxygen as raw materials; meanwhile, no mechanical transmission part is arranged, so that no noise pollution is caused, and the discharged harmful gas is less. It follows that fuel cells are the most promising power generation technology from the viewpoint of energy conservation and ecological environment conservation. At present, the technology of utilizing hydrogen generated by oxidation-reduction reaction of a metal air battery as fuel and connecting electrodes of a fuel battery to generate discharge reaction has been proposed in countries such as Japan, and a great deal of research is carried out in China, but the problems of low actual efficiency conversion rate exist. Theoretically, the power generation efficiency of the fuel cell can reach 85% -90%, but due to the limitation of various polarizations in operation, the energy conversion efficiency of the current fuel cell is about 40% -60%, and the potential of the fuel cell has a great development space.
The anode of the fuel cell, i.e. the fuel electrode, is generally a supporting structure and has a larger thickness, however, the thicker fuel electrode brings difficulty to the diffusion of gas in the fuel electrode, and meanwhile, in the deep electrochemical reaction of the electrode, because of the microstructure of the fuel electrode and the relationship between the microstructure of the fuel electrode and the micro interface of the solid electrolyte, if the reaction product, i.e. water vapor, is not easy to smoothly diffuse away from the electrode region, thereby reducing the concentration polarization of the electrode, the capacity of the cell system is greatly attenuated, the rate performance is not good, and the temperature of the working interface is reduced by the water vapor, so that the electrochemical reaction rate is slowed down, and the activation polarization of the cell is increased. The development of fuel cells is therefore limited by the improvement of the microstructure of the fuel electrode and its micro-interfacial relationship with the solid-state electrolyte. In addition, the future development trend of fuel cells is bound to be low-temperature operation, the electrochemical reaction and the substance diffusion rate are slowed down by reducing the working temperature, the activation polarization of the cells is increased, the specific capacity is rapidly attenuated due to the generation of the polarization phenomenon, and the power performance is reduced, so that the key technology needed to overcome the low-temperature fuel cells is to deeply improve the microstructure of the fuel electrode and improve the vapor diffusion rate under the low-temperature condition.
In order to improve the microstructure of the fuel electrode, pore-forming agents are required to be added in the process of preparing the metal ceramic anode support in the traditional technology, and usually, the pore-forming agents are burnt in the high-temperature treatment process, so that large pores are formed in the anode, reaction gas can rapidly enter an inner-layer anode to participate in electrochemical reaction, meanwhile, product gas can rapidly exit the anode, and the shape of the pore-forming agents determines the appearance of pores in the anode. Pore formers commonly added to the anode include organic pore formers such as flour, starch, tapioca flour, and the like, and carbon pore formers such as graphite, carbon black, and the like, or combinations thereof, which leave spherical or other irregular shaped pores in the anode, and if a small amount of conventional pore formers are used, they will form a large number of isolated pores in the anode, which is detrimental to gas diffusion because interconnected pores in the electrode are necessary that allow the reactant to diffuse into the active reaction zone and the reaction product to diffuse out of the active reaction zone. The use of a large amount of pore former is generally required to form the pores formed by the conventional pore former so as to form the connected gas transport channels, but the use of a large amount of pore former will destroy the mechanical strength of the anode, so the use of a fibrous pore former is considered. Based on the advantage of the shape of the fiber pore-forming agent in length, elongated holes are formed in the anode after high-temperature calcination, and the elongated holes are easy to form communicated gas channels, so that reaction gas can quickly enter the inner-layer anode to participate in electrochemical reaction, and meanwhile, product gas can be quickly discharged out of the anode. Common methods for preparing fiber pore formers include Chemical Vapor Deposition (CVD), solid phase synthesis, and electrospinning. The method adopts an electrostatic spinning technology in the Panwept doctor paper of the university of Harbin industry, namely research on influence of anode pores and interface microstructures on electrode polarization and performance of SOFC, and introduces NiO-containing anode initial powder in the fiber collection process, so that a relatively ideal fuel cell anode microstructure is obtained.
Disclosure of Invention
In order to solve the problems, the invention provides a hollow fiber pore-forming agent and application thereof in a fuel cell.
The invention provides a hollow fiber pore-forming agent, which is PAN-PVP coaxial hollow fiber prepared by taking polyacrylonitrile and polyvinylpyrrolidone as raw materials.
The invention discloses a preparation method of a fuel cell anode, which comprises the following steps:
s1, preparing anode initial powder: pre-sintering the metal oxide powder containing nickel at 600 ℃ for 2h, and then mixing and grinding the metal oxide powder with 8 mol% of YSZ electrolyte powder for 2h to obtain anode initial powderWherein the mass ratio of the nickel-containing metal oxide to YSZ is 1: 1; the nickel-containing metal oxide is NiO or Ni2O3One or a mixture of the two;
s2, preparing PAN-PVP coaxial hollow fiber:
dissolving PAN and PVP in solvent, stirring at 35-90 deg.C for 12 hr with stirring speed of 90rmin-1Forming a uniform PAN-PVP mixed solution;
operating on a high-voltage electrostatic spinning machine, adopting a common medical injector to manufacture a coaxial spinneret, wherein the diameter of an inner needle hole is 0.7mm, the diameter of an outer needle hole is 1.6mm, methyl silicone oil is placed in the inner needle hole, a PAN-PVP mixed solution is placed in the outer needle hole, and the advancing speed of a spinning sample injector is 2-4 mu ms-1The distance between the collecting roller and the spinning nozzle is 10-15cm, and the voltage is 20-22 kV; the roller collector is made of aluminum sheets and copper wires and is 25-50rmin under the condition of 12-20V direct current voltage-1The speed of the cylinder drives the cylinder to rotate and collect the PAN-PVP coaxial hollow fiber;
s3, mixing the anode initial powder and the PAN-PVP coaxial hollow fiber: when a thin layer of PAN-PVP coaxial hollow fibers is distributed on a roller collector, the anode initial powder prepared by S1 is quickly and uniformly scattered on the surface of the fibers, the newly prepared PAN-PVP coaxial hollow fibers have viscosity on the surface, so the anode initial powder can be attached to the fibers, then the PAN-PVP coaxial hollow fibers are continuously collected on the fiber mixture with the anode initial powder scattered on the surface, after the fiber layer adhered with the powder is completely covered by the newly received fibers, the anode initial powder is quickly and uniformly scattered on the surface of a second layer of PAN-PVP coaxial hollow fibers, and the operation is repeated for multiple times to obtain a mixture of the fuel anode initial powder and the PAN-PVP coaxial hollow fibers, wherein the PAN-PVP coaxial hollow fibers account for 2-10wt% of the total mass of the mixture;
s4, preparing a fuel cell anode: and (3) putting the mixture of the anode initial powder obtained in the step (S3) and the PAN-PVP coaxial hollow fiber into a steel mold, pressing into a fuel cell anode blank with the thickness of about 0.1-1mm under the pressure condition of 50-500 MPa, and sintering the anode blank at 1000 ℃ for 2 hours to obtain the fuel cell anode.
Preferably, the solvent comprises: one of dimethyl sulfoxide, dimethylformamide, deionized water, polyethylene glycol and ethylene glycol.
Preferably, the step S2 is:
dissolving 1g of PAN and 1g of PVP in 20ml of dimethylformamide, and stirring at 45 ℃ for 12h at the stirring speed of 90rmin-1Forming a uniform PAN-PVP mixed solution;
operating on a high-voltage electrostatic spinning machine, adopting a common medical injector to manufacture a coaxial spinneret, wherein the diameter of an inner needle hole is 0.7mm, the diameter of an outer needle hole is 1.6mm, methyl silicone oil is placed in the inner needle hole, a PAN-PVP mixed solution is placed in the outer needle hole, and the advancing speed of a spinning sample injector is 2 mu ms-1The distance between the collecting roller and the spinning nozzle is 15cm, and the voltage is 20 kV; the roller collector is made of aluminum sheets and copper wires and is at 40rmin under the condition of 12V direct current voltage-1The speed of the cylinder drives the cylinder to rotate and collect the PAN-PVP coaxial hollow fiber;
the method for preparing the fuel cell anode coated with the solid electrolyte on one side by the fuel cell anode comprises the following steps: firstly preparing electrolyte slurry, then adopting a slurry spin-coating method to place a drop of electrolyte slurry in the center of the outer surface of one side of the anode of the fuel cell, and the rotating speed of a spin coater is 6000r min-1Setting the running time to be 60s, driving the fuel cell anode to rotate at a high speed through a spin coater to generate centrifugal force to enable the electrolyte slurry to be uniformly coated on the outer surface of one side of the fuel cell anode, then drying the fuel cell anode attached with a layer of electrolyte slurry at 400 ℃, continuously spin-coating a second layer and a third layer on the formed first layer of electrolyte film after drying, drying each layer at 400 ℃, and finally sintering the fuel cell anode with three layers of electrolyte films at 1400 ℃ for 4h to obtain the fuel cell anode with one side coated with solid electrolyte.
Preferably, the preparation method of the electrolyte slurry comprises the following steps: putting electrolyte powder into a mortar for grinding for about 30min, adding a binder, continuously grinding until the electrolyte powder and the binder are uniformly mixed, wherein the electrolyte powder accounts for 30wt% of the total mass of the electrolyte slurry, the binder is prepared from ethyl cellulose and terpineol, the ethyl cellulose accounts for 5wt% of the total mass of the binder, and the ethyl cellulose is continuously dissolved in the terpineol under the heating condition until the electrolyte slurry is uniformly mixed to obtain the electrolyte slurry.
The invention has the following beneficial effects:
1. in the electrostatic spinning process, the PAN-PVP hollow fiber with a hollow structure, long nanometer and uniform physicochemical properties can be prepared by utilizing a coaxial spinning technology, and after the anode of the fuel cell is fired to remove the fiber, a three-dimensional reticular cross-linking cavity can be formed, which is beneficial to improving the connection of the anode in the hole, increasing the internal specific surface area of electrolyte, integrally reducing the activation polarization of the cell, increasing the electrochemical reaction area, reducing the internal resistance of the cell and accelerating the diffusion of substances, thereby finally improving the output performance of the cell and slowing down the attenuation of specific capacity.
2. Compared with carbon fiber with the same outer diameter, the PAN-PVP hollow fiber has higher molecular orientation degree and larger breaking elongation, the composite material which can be modified by the PAN-PVP hollow fiber has stronger impact toughness, can maintain the original structure when being compounded with a solid electrolyte, is not easy to break, enhances the processability and the flexibility of the anode of the fuel cell coated with the solid electrolyte on one side, reduces the microporosity of the composite interface of the solid electrolyte and the anode of the fuel cell, increases the electrochemical reaction area, reduces the internal resistance of the cell, accelerates the diffusion of substances, finally improves the output performance of the cell and slows down the attenuation of specific capacity.
3. When the PAN-PVP hollow fiber is adopted to manufacture the pore canals with the same pore diameter in the anode of the fuel cell, the consumption of organic matters is less, and the PAN-PVP hollow fiber has the unique advantages of environmental protection and production cost reduction.
Drawings
FIG. 1 is a schematic view of a metal air/fuel cell for electrochemical performance testing in example 11 of the present invention;
FIG. 2 is a morphology chart of the PAN-PVP coaxial hollow fiber prepared in the embodiment 1 of the invention under an electron microscope.
Detailed Description
The present invention is further illustrated by the following examples.
Comparative example preparation of Fuel cell Anode from PVA electrospun fibers of the prior art
(1) Preparing an electrostatic spinning solution: 1g of PVA is dissolved in 20mL of deionized water, and the mixture is stirred for 4 hours at 90 ℃ and the stirring speed is 150 r/min.
(2) High-voltage electrostatic spinning: the advancing speed of the spinning sample injector is 2 mu ms < -1 >, the distance between the collecting roller and the spinning spray head is 15cm, and the voltage is 20 kV.
(3) Collecting electrostatic spinning: the roller collector is made of aluminum sheets and copper wires and can collect a large amount of dispersed fibers, and 12V direct current drives the roller to receive, rotate and collect electrostatic spinning at the speed of 30 rmin-1.
(4) Electrostatic spinning composite solid electrolyte: and (3) pre-burning the anode NiO powder for 2h at 600 ℃ and mixing and grinding 8% mol of yttria-stabilized zirconia electrolyte powder for 2h, wherein the mass ratio of NiO to YSZ is 1: 1. When the roller receiver is full of a thin layer of fiber, the anode initial powder is quickly and uniformly scattered on the surface of the fiber, and the anode initial powder can be attached to the fiber due to the viscosity of the surface of the fiber which is just prepared. Then continue to collect PVA fiber on the mixture of fiber whose surface is sprinkled with anode initial powder, when the fiber layer adhered with powder is completely covered by the newly received fiber, the anode initial powder is sprinkled on the surface of the second layer fiber rapidly and uniformly, thus, a large amount of mixture of anode initial powder and PVA fiber can be obtained by repeating the operation for many times.
(5) And putting the mixture of the anode initial powder and the PVA fiber into a steel mould, pressing into an anode blank with the thickness of about 0.5mm under the pressure of 200MPa, and sintering the anode blank at 1000 ℃ for 2h to obtain the fuel cell anode.
Example 1 (best case): the preparation method of the fuel cell anode comprises the following steps:
s1, preparing fuel anode initial powder: pre-sintering the nickel-containing metal oxide powder at 600 ℃ for 2h, and then mixing and grinding the nickel-containing metal oxide powder and 8 mol% of YSZ electrolyte powder for 2h to obtain anode initial powder, wherein the mass ratio of the nickel-containing metal oxide to the YSZ is 1: 1; the nickel-containing metal oxide is NiO or Ni2O3One or a mixture of bothAn agent;
s2, preparing PAN-PVP coaxial hollow fiber:
dissolving 1g of PAN and 1g of PVP in 20ml of dimethylformamide, and stirring at 45 ℃ for 12h at the stirring speed of 90rmin-1Forming a uniform PAN-PVP mixed solution;
operating on a high-voltage electrostatic spinning machine, adopting a common medical injector to manufacture a coaxial spinneret, wherein the diameter of an inner needle hole is 0.7mm, the diameter of an outer needle hole is 1.6mm, methyl silicone oil is placed in the inner needle hole, a PAN-PVP mixed solution is placed in the outer needle hole, and the advancing speed of a spinning sample injector is 2 mu ms-1The distance between the collecting roller and the spinning nozzle is 15cm, and the voltage is 20 kV; the roller collector is made of aluminum sheets and copper wires and is at 40rmin under the condition of 12V direct current voltage-1The speed of the cylinder drives the cylinder to rotate and collect the PAN-PVP coaxial hollow fiber;
s3, mixing the anode initial powder and the PAN-PVP coaxial hollow fiber: when a thin layer of PAN-PVP coaxial hollow fibers is fully distributed on a roller collector, the anode initial powder prepared by S1 is quickly and uniformly scattered on the surface of the fibers, the surface of the PAN-PVP coaxial hollow fibers which are just prepared has viscosity, so the anode initial powder can be attached to the fibers, then the PAN-PVP coaxial hollow fibers are continuously collected on the fiber mixture with the anode initial powder scattered on the surface, after the fiber layer with the powder adhered to the fiber layer is completely covered by the newly received fibers, the anode initial powder is quickly and uniformly scattered on the surface of a second layer of PAN-PVP coaxial hollow fibers, and the operation is repeated for multiple times to obtain a mixture of the fuel anode initial powder and the PAN-PVP coaxial hollow fibers, wherein the PAN-PVP coaxial hollow fibers account for 5wt% of the total mass of the mixture;
s4, preparing a fuel cell anode: and (3) putting the mixture of the anode initial powder obtained in the step (S3) and the PAN-PVP coaxial hollow fiber into a steel mold, pressing the mixture into a fuel cell anode blank with the thickness of about 0.5mm under the pressure condition of 50-500 MPa, and sintering the anode blank at 1000 ℃ for 2 hours to obtain the fuel cell anode.
Examples 2 to 10: the preparation method of the fuel cell anode comprises the following steps:
s1, preparing anode initial powder: the same as example 1;
s2, preparing PAN-PVP coaxial hollow fiber: the procedure is the same as example 1, and the specific experimental parameter design is shown in table 1;
s3, mixing the anode initial powder and the PAN-PVP coaxial hollow fiber: the same as example 1;
s4, preparing a fuel cell anode: the same as example 1;
TABLE 1 comparison of preparation Process parameters for the examples
Figure GDA0003261970530000091
Figure GDA0003261970530000101
Example 11 electrochemical Performance test
The fuel cell anode prepared in each of the above examples was used to prepare a fuel cell anode coated with a solid electrolyte on one side by: firstly preparing electrolyte slurry, then adopting a slurry spin-coating method to place a drop of electrolyte slurry in the center of the outer surface of one side of the anode of the fuel cell, and the rotating speed of a spin coater is 6000r min-1Setting the running time to be 60s, driving a fuel electrode to rotate at a high speed through a spin coater to generate centrifugal force to enable electrolyte slurry to be uniformly coated on the outer surface of one side of the anode of the fuel cell, then drying the anode of the fuel cell attached with a layer of electrolyte slurry at 400 ℃, continuously spin-coating a second layer and a third layer on a formed first layer of electrolyte film after drying, drying each layer at 400 ℃, and finally sintering the fuel cell anode with three layers of electrolyte films at 1400 ℃ for 4h to obtain the fuel cell anode with one side coated with solid electrolyte.
The preparation method of the electrolyte slurry comprises the following steps: putting electrolyte powder into a mortar for grinding for about 30min, adding a binder, continuously grinding until the electrolyte powder and the binder are uniformly mixed, wherein the electrolyte powder accounts for 30wt% of the total mass of the electrolyte slurry, the binder is prepared from ethyl cellulose and terpineol, the ethyl cellulose accounts for 5wt% of the total mass of the binder, and the ethyl cellulose is continuously dissolved in the terpineol under the heating condition until the electrolyte slurry is uniformly mixed to obtain the electrolyte slurry.
Installing a prepared fuel cell anode coated with a solid electrolyte on one side of each example as a fuel cell, and as shown in fig. 1, the fuel cell comprises a fuel cell unit 1 and a metal gas cell unit 2, the fuel cell unit 1 is composed of an air electrode 3, a solid electrolyte 5 and an anode 4, the air electrode 3 and the anode 4 are connected through a line, the line is respectively connected into a discharge line and a charging line through a conversion head 8, the discharge line is provided with a discharge port 6, and the charging line is provided with a charging port 7; the metal-gas battery unit 2 is of a closed structure with an opening at one side, the opening side is directly connected with one side of the anode 4, a metal-metal oxide layer 10 is arranged at one side of the metal-gas battery unit 2, the metal-metal oxide layer is Fe-FeO, a gas cavity 9 is formed between the metal-gas battery unit 2 and the anode 4, and the metal-gas battery unit 2 is provided with H2A flow channel.
In the electrochemical performance test, the fuel cell was set such that 5% H was put into one side of the metal gas cell unit 22And N2Is heated to a temperature of 650 ℃ once 5% H2-N2The gas is converted to 3% H2O humidified pure H2Gas, after conversion of iron oxide to iron, H2The inlet and outlet of the flow are closed so that the anode 4 and the metal-gas cell unit 2 become closed chambers. To generate iron-redox couples from pure iron, the cells were galvanostatically discharged using a blue electrochemical test system with a small discharge current of 10mA cm-2, and H was programmed by the RSOFC program2Conversion to H2O and further converting the iron to ferrous oxide, and monitoring the open circuit voltage of the battery system using a blue electrochemical test system. The electrochemical performance parameters obtained for each example were tested as follows:
TABLE 2 electrochemical data for fuel electrode self-supports prepared for each experimental group
Figure GDA0003261970530000121
According to the hollow fiber pore-forming agent for the fuel cell anode, disclosed by the invention, the microstructure of the reaction interface of the fuel cell anode is improved, and the electrochemical efficiency of a metal air/fuel cell is obviously improved, wherein in the embodiment 1 as an optimal example, compared with a comparative example in the prior art, the first discharge specific capacity is improved by 39%, the cycle 200 cycle specific capacity at 0.1C rate is improved by 134%, and the cycle 200 cycle capacity retention rate at 0.1C rate is improved by 68%; the efficiency of the metal air/fuel cell system adopting the interface microstructure is greatly promoted, and the PAN-PVP coaxial hollow fiber has the unique advantages of less organic matter consumption, environmental protection and production cost reduction when pore channels with the same pore diameter are manufactured in the anode of the fuel cell. .
From the experimental data, the solvent adopted when preparing the PAN-PVP coaxial hollow fiber is better than dimethylformamide, and dimethyl sulfoxide, deionized water, polyethylene glycol, ethanol and the like are adopted.
The sizes of the inner and outer pinholes influence the size of the later formed pinholes. The optimal is 1mm of inner needle hole and 2mm of outer needle hole. The pinhole is too small, the spinning is easy to break, and a cross-linked and communicated hole structure is not easy to form. The pinholes are too large, the formed holes are too large, and the interfacial impedance of the electrochemical reaction is increased.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (5)

1. A method of making a fuel cell anode, comprising the steps of:
s1, preparing anode initial powder: pre-sintering the nickel-containing metal oxide powder at 600 ℃ for 2h, and then mixing and grinding the nickel-containing metal oxide powder and 8 mol% of YSZ electrolyte powder for 2h to obtain anode initial powder, wherein the mass ratio of the nickel-containing metal oxide to the YSZ is 1: 1; the nickel-containing metal oxide is NiO or Ni2O3One or a mixture of the two;
s2, preparing PAN-PVP coaxial hollow fiber:
dissolving PAN and PVP in solvent, stirring at 35-90 deg.C for 12 hr with stirring speed of 90rmin-1Forming a uniform PAN-PVP mixed solution;
operating on a high-voltage electrostatic spinning machine, adopting a common medical injector to manufacture a coaxial spinneret, wherein the diameter of an inner needle hole is 0.7mm, the diameter of an outer needle hole is 1.6mm, methyl silicone oil is placed in the inner needle hole, a PAN-PVP mixed solution is placed in the outer needle hole, and the advancing speed of a spinning sample injector is 2-4 mu ms-1The distance between the collecting roller and the spinning nozzle is 10-15cm, and the voltage is 20-22 kV; the roller collector is made of aluminum sheets and copper wires and is 25-50rmin under the condition of 12-20V direct current voltage-1The speed of the cylinder drives the cylinder to rotate and collect the PAN-PVP coaxial hollow fiber;
s3, mixing the anode initial powder and the PAN-PVP coaxial hollow fiber: when a thin layer of PAN-PVP coaxial hollow fibers is fully distributed on a roller collector, the anode initial powder prepared by S1 is quickly and uniformly scattered on the surface of the fibers, the newly prepared PAN-PVP coaxial hollow fibers have viscosity on the surface, so the anode initial powder can be attached to the fibers, then the PAN-PVP coaxial hollow fibers are continuously collected on the fiber mixture with the anode initial powder scattered on the surface, after the fiber layer with the powder adhered on the fiber layer is completely covered by the newly received fibers, the anode initial powder is quickly and uniformly scattered on the surface of a second layer of PAN-PVP coaxial hollow fibers, and the operation is repeated for multiple times to obtain a mixture of the anode initial powder and the PAN-PVP coaxial hollow fibers, wherein the PAN-PVP coaxial hollow fibers account for 2-10wt% of the total mass of the mixture;
s4, preparing a fuel cell anode: and (3) putting the mixture of the anode initial powder obtained in the step (S3) and the PAN-PVP coaxial hollow fiber into a steel mold, pressing into a fuel cell anode blank with the thickness of 0.1-1mm under the pressure condition of 50-500 MPa, and sintering the anode blank at 1000 ℃ for 2 hours to obtain the fuel cell anode.
2. The method of manufacturing a fuel cell anode according to claim 1, wherein the solvent includes: one of dimethyl sulfoxide, dimethylformamide, deionized water, polyethylene glycol and ethylene glycol.
3. The method for producing a fuel cell anode according to claim 2, wherein the step S2 is:
dissolving 1g of PAN and 1g of PVP in 20ml of dimethylformamide, and stirring at 45 ℃ for 12h at the stirring speed of 90rmin-1Forming a uniform PAN-PVP mixed solution;
operating on a high-voltage electrostatic spinning machine, adopting a common medical injector to manufacture a coaxial spinneret, wherein the diameter of an inner needle hole is 0.7mm, the diameter of an outer needle hole is 1.6mm, methyl silicone oil is placed in the inner needle hole, a PAN-PVP mixed solution is placed in the outer needle hole, and the advancing speed of a spinning sample injector is 2 mu ms-1The distance between the collecting roller and the spinning nozzle is 15cm, and the voltage is 20 kV; the roller collector is made of aluminum sheets and copper wires and is at 40rmin under the condition of 12V direct current voltage-1The speed of the cylinder drives the cylinder to rotate to collect the PAN-PVP coaxial hollow fiber.
4. The use of the fuel cell anode produced by the method for producing a fuel cell anode according to claim 1 for producing a fuel cell anode coated on one side with a solid electrolyte, in a fuel cell, by: first, an electrolyte slurry is preparedThen, a drop of electrolyte slurry is placed in the center of the outer surface of one side of the anode of the fuel cell by adopting a slurry spin coating method, and the rotating speed of a spin coater is 6000r min-1Setting the running time to be 60s, driving the fuel cell anode to rotate at a high speed through a spin coater to generate centrifugal force to enable the electrolyte slurry to be uniformly coated on the outer surface of one side of the fuel cell anode, then drying the fuel cell anode attached with a layer of electrolyte slurry at 400 ℃, continuously spin-coating a second layer and a third layer on the formed first layer of electrolyte film after drying, drying each layer at 400 ℃, and finally sintering the fuel cell anode with three layers of electrolyte films at 1400 ℃ for 4h to obtain the fuel cell anode with one side coated with solid electrolyte.
5. The use of a fuel cell anode according to claim 4 in a fuel cell, wherein the electrolyte slurry is prepared by: putting electrolyte powder into a mortar for grinding for about 30min, adding a binder, continuously grinding until the electrolyte powder and the binder are uniformly mixed to obtain electrolyte slurry, wherein the electrolyte powder accounts for 30wt% of the total mass of the electrolyte slurry, the binder is prepared from ethyl cellulose and terpineol, the ethyl cellulose accounts for 5wt% of the total mass of the binder, and the ethyl cellulose is continuously dissolved in the terpineol under the heating condition until the electrolyte powder and the binder are uniformly mixed.
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