CN110247074B - Composite anode powder using PVP-K30 pore-forming agent and preparation method thereof - Google Patents

Composite anode powder using PVP-K30 pore-forming agent and preparation method thereof Download PDF

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CN110247074B
CN110247074B CN201910416786.8A CN201910416786A CN110247074B CN 110247074 B CN110247074 B CN 110247074B CN 201910416786 A CN201910416786 A CN 201910416786A CN 110247074 B CN110247074 B CN 110247074B
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pore
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temperature
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CN110247074A (en
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刘媛媛
张睿轩
贺颖
杨艳娇
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Inner Mongolia University of Science and Technology
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0243—Composites in the form of mixtures
    • 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
    • H01M2008/1293—Fuel cells with solid oxide 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 discloses a composite anode powder using PVP-K30 pore-forming agent and a preparation method thereof, and the inventor researches a composite anode powder using PVP-K30 as a raw material through repeated experimental research, and provides a preparation method of the composite anode powder and an application method of the composite anode powder on SOFC batteries; through comparative experimental research, the SOFC prepared by applying the composite anode powder has more superiority than the SOFC prepared by using starch and carbon; furthermore, through experimental study on the influence of different PVP-K30 contents on the porosity microstructure and the electrochemical performance of the SOFC battery anode material, the study finds that the effect when the PVP-K30 is added in an amount of 5% is a more excellent scheme; compared with the traditional process for preparing the anode powder by using carbon and starch, the preparation process of the anode powder is simpler, and the synthesis period is shortened.

Description

Composite anode powder using PVP-K30 pore-forming agent and preparation method thereof
Technical Field
The invention relates to the field of solid oxide fuel cells, in particular to composite anode powder using PVP-K30 pore-forming agent, a preparation method thereof and application of the anode powder in SOFC cells.
Background
With the rapid development of global industrialization and the excessive consumption of fossil fuels, the development and the environment protection of new energy have become the current theme, and a Solid Oxide Fuel Cell (SOFC) is a novel green energy, is not only environment-friendly, but also efficient and portable; but still has partial problems, the SOFC battery consists of three parts, the research on electrolyte and cathode materials is mature, and the market has already provided corresponding material systems; under the development trend of low temperature in SOFC, the performance of the anode material is not ideal; the porosity generated by the anode in the sintering process is too low to meet the requirement of pore expansion; therefore, a pore-forming agent is added to increase the porosity, which can provide a diffusion channel for the fuel gas and the reaction product and can also increase the speed of the gas reaching the three-phase reaction interface.
The widely used pore-forming agents at present are starch and carbon powder; most SOFC anode powder is synthesized by a solid-phase mixing method, wherein anode-electrolyte matrix powder is prepared by a sol-gel method or a glycine-nitrate combustion method, then mixed with NiO, starch or active carbon and other pore-forming agents, and the raw materials are added into alcohol or isopropanol solvent by a solid-phase ball milling method and uniformly mixed; calcining the uniformly mixed powder at a certain temperature to obtain synthesized powder; the process has the disadvantages that the particle diameter ratio of the synthesized powder is larger (generally larger than 1 micron), the pore-forming agent is easy to agglomerate, larger and sparse holes are formed, and the anode structure (shown in figure 1) is easy to collapse; when the carbon-containing anode material is used, carbon deposition is easily formed on the anode in the working process of the battery, and finally the service life of the battery is short; starch is cheap in market but has low solubility, even water-soluble starch has low solubility, which makes the blending process difficult.
Polyvinylpyrrolidone (PVP) is a non-ionic polymer with molecular formula of (C)6H9NO)nMolecular weight 4 ten thousand, melting point: 130 ℃; is very soluble in water and halogenated hydrocarbon solvent, alcohols, amines, nitroalkane, low molecular weight fatty acid and the like, and is not soluble in acetone, diethyl ether, turpentine, aliphatic hydrocarbon, alicyclic hydrocarbon and other few solvents; can be compatible with most inorganic acid salts and various resins; it is a white or nearly white powder with hydrophilic free-flowing properties; the PVP is divided into four grades according to the average molecular weight, customarily represented by K value, and different K values respectively represent corresponding PVP average molecular weight ranges; the K value is actually a characteristic value related to the relative viscosity of the aqueous solution of PVP, which in turn is a physical quantity related to the molecular weight of the high polymer, and therefore the K value can be used to characterize the average molecular weight of PVP; generally, the greater the K value, the greater its viscosity,the stronger the adhesion;
the PVP has good solubility, solubilization, film-forming property, bonding capability, complexing capability and other properties, the inventor researches and discovers that the PVP used as the pore-forming agent for preparing the SOFC battery anode material has more advantages than the existing anode material prepared by using starch and carbon powder, and the research and discovery shows that the scheme of adopting the PVP with the K value of 30 is one of the schemes with superior effects, and is represented by PVP-K30, and as shown in figure 2, the PVP-K30 molecular structural formula is shown.
Through repeated experimental research, the inventor researches a composite anode powder using PVP-K30 as a raw material, and provides a preparation method of the composite anode powder and an application method of the composite anode powder on an SOFC battery; through comparative experimental research, the SOFC prepared by applying the composite anode powder has more superiority than the SOFC prepared by using starch and carbon; furthermore, through experimental study on the influence of different PVP-K30 contents on the microstructure of the porosity and the electrochemical performance of the SOFC anode material, the final study finds that the effect of adding 5% of PVP-K30 is a preferable scheme.
Disclosure of Invention
The invention aims to provide composite anode powder using PVP-K30 pore-forming agent and a preparation method thereof, which comprises the composite anode powder using PVP-K30 as a raw material, the preparation method of the composite anode powder and the application method of the powder on SOFC batteries; the SOFC cell prepared by the method has greater advantages than the SOFC cell prepared by using starch and carbon.
The technical scheme adopted by the invention is as follows: the composite anode powder using the PVP-K30 pore-forming agent is characterized by comprising the following raw materials: gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2O, Glycine (C)2H5NO2) And PVP-K30 pore former.
Further, Gd (NO) is contained in the above-mentioned raw materials3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2The mass ratio of O to glycine is 1:4:5:25, and the mass fraction of PVP-K30 pore-forming agent is 5%.
A preparation method of composite anode powder using PVP-K30 pore-forming agent is characterized by comprising the following steps:
(1) respectively weighing Gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2O and glycine, and PVP-K30 pore former, wherein Gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2Weighing O and glycine according to the mass ratio of 1:4:5:25 (namely the mass NiO: GDC =1:1 and the total metal ions: glycine =1: 2.5);
(2) adding Ce (NO) with deionized water3)3·6H2Dissolving O and glycine to prepare a first solution; adding Gd (NO) to deionized water3)3·6H2Dissolving O to prepare a second solution; adding Ni (NO) with deionized water3)2·6H2Dissolving O to prepare a third solution; dissolving PVP-K30 pore-forming agent by using deionized water to prepare a fourth solution;
(3) heating the first solution prepared in the step (2) and continuously stirring to enable the first solution to reach a micro-boiling state of 80-90 ℃, and keeping the micro-boiling state for 30 minutes to enable different components in the first solution to be uniformly distributed and fully combined to obtain a fifth solution;
(4) circularly dripping the prepared second solution, third solution and fourth solution into the fifth solution in the step (3) by using a dropper at the temperature of 80-90 ℃ under the condition of continuous stirring until the prepared three solutions are completely added to obtain a sixth solution; keeping the sixth solution at 80-90 ℃ for about 3 hours under the condition of continuous stirring until excessive water is evaporated, and enabling the sixth solution to become a colloidal viscous state to obtain a jelly;
(5) transferring the jelly obtained in the step (4) into a beaker, and placing the beaker in a universal resistance furnace to heat until the jelly is self-ignited and incinerated to obtain incinerated powder;
(6) taking the beaker in the step (5) out of the resistance furnace, transferring the ashed powder into a crucible, and putting the crucible into a muffle furnace for heating, wherein the temperature control system is as follows: the temperature was raised at 1 ℃/min from room temperature 25 ℃ to 700 ℃; keeping the temperature at 700 ℃ for 2 hours; then, the temperature is reduced by 2 ℃/min to 25 ℃; the resultant was sufficiently ground (dry-ground) with an agate mortar, and then sieved through a 200-mesh sieve to obtain anode powder.
Further, in the step (3) and the step (4), the temperature is controlled by a high-temperature water bath mode, a magnetic stirrer is adopted for continuous stirring, and the high rotating speed of the stirrer is kept.
A method for applying the composite anode powder to an SOFC battery is characterized in that the anode powder is placed in a mortar, and terpineol is gradually added into the prepared anode powder in the grinding process until the prepared anode powder is in a sticky wire drawing state, so that sticky materials are obtained; coating the sticky substance on one side surface of an electrolyte sheet by using a screen printing technology, placing the electrolyte sheet in a drying oven, and drying at 150 ℃; taking out, coating once again and drying; then, sintering the mixture in a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at the speed of 1 ℃/min; thereafter, the temperature was raised from 1000 ℃ to 1450 ℃ at 2 ℃/min; keeping the temperature at 1450 ℃ for 2 hours; then cooling to 25 ℃ at the speed of 2 ℃/min to obtain a half cell;
preparing a cathode on the other side surface of the obtained half cell: mixing lanthanum, strontium, cobalt and iron with GDC in a ratio of 7:3, adding 30wt% of starch, adding absolute ethyl alcohol, grinding into cathode slurry, coating the cathode slurry on the other side surface of an electrolyte sheet by using a screen printing technology, placing the electrolyte sheet in an oven, drying at 150 ℃, coating the cathode slurry again, drying the coating again, sintering by using a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at a speed of 1 ℃/min; increasing the temperature from 1000 ℃ to 1450 ℃ at a rate of 2 ℃/min; keeping the temperature at 1450 ℃ for 2 hours, and cooling to 25 ℃ at the speed of 2 ℃/min; and obtaining the battery.
The invention has the beneficial effects that: the invention provides composite anode powder using PVP-K30 pore-forming agent and a preparation method thereof, and the inventor researches out composite anode powder using PVP-K30 as a raw material through repeated experimental research, and provides a preparation method of the composite anode powder and an application method of the composite anode powder on SOFC batteries; through comparative experimental research, the SOFC prepared by applying the composite anode powder has more superiority than the SOFC prepared by using starch and carbon; furthermore, through experimental study on the influence of different PVP-K30 contents on the porosity microstructure and the electrochemical performance of the SOFC battery anode material, the study finds that the effect when the PVP-K30 is added in an amount of 5% is a more excellent scheme; compared with the traditional process for preparing the anode powder by using carbon and starch, the preparation process of the anode powder is simpler, and the synthesis period is shortened.
Compared with the prior anode material prepared by using starch and carbon as pore-forming agents, the invention has the advantages that: experiments show that the addition of the PVP-K30 water-soluble organic macromolecular pore-forming agent is more beneficial to the formation of anode pores, and the water-soluble characteristic is utilized, so that the water-soluble organic macromolecular pore-forming agent can be doped during the primary synthesis of the powder, the agglomeration of the pore-forming agent can be avoided, the pore-forming agent can be distributed more uniformly, and the pore-forming shrinkage of the powder is natural. On the other hand, long-chain macromolecules are adopted, so that the working procedures of later grinding and doping are reduced, and the synthesis period is shortened. Compared with the carbon pore-forming agent, the carbon-forming agent can effectively avoid carbon deposition, reduce concentration polarization, improve the pore-forming efficiency, prolong the service life of the battery and obtain higher power density.
By comparing doping results of the three pore-forming agents in different proportions, the porosity of the anode is gradually increased along with the increase of the content of the PVP-K30 pore-forming agent, the mass transfer resistance of anode fuel gas is reduced, the number of TPB is increased, and the working efficiency of the anode is improved.
Drawings
FIG. 1 is a microtopography of an anode structure synthesized in a conventional manner.
FIG. 2 shows the molecular structure of PVP-K30.
FIG. 3 is a diagram of the result of XRD test in the example of the present invention.
FIG. 4 is a micro-topography of an anode with 3%, 5%, 7% PVP-K30 pore former added in the embodiment of the present invention; wherein, the (a) and the (d) are anode strips added with 3 percent of PVP-K30, and the (b) and the (e) are anode strips added with 5 percent of PVP-K30; (c) and (f) is an anode sheet added with 7% PVP-K30, wherein (a), (b) and (c) are anode surfaces, and (d), (e) and (f) are anode sections.
FIG. 5 is a micro-morphology of an anode when 3%, 5%, 7% activated carbon pore-forming agent is added respectively in the embodiment of the present invention; wherein, (g) and (j) are anode sheets added with 3 percent of active carbon; (h) and (k) 5% of active carbon anode sheet is added; (i) and (l) is an anode sheet added with 7 percent of active carbon, wherein (g), (h) and (i) are anode surfaces, and (j), (k) and (l) are anode sections.
FIG. 6 is a micro-topography of an anode when 3%, 5%, 7% starch pore formers are added, respectively, in an embodiment of the present invention; wherein (m) and (p) are anode strips added with 3% of starch; (n) and (q) are anode strips added with 5% of starch; and (o) and (r) are anode sheets added with 7% of starch, wherein (m), (n) and (o) are anode surfaces, and (p), (q) and (r) are anode sections.
FIG. 7 is a graph comparing I-V-P curves at 600 ℃ of a single cell formed by doping NiO-GDC composite anode materials with different pore formers according to the optimal ratio in the embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments, which are only used for illustrating the technical solution of the present invention and are not limited.
The invention provides composite anode powder using PVP-K30 pore-forming agent and a preparation method thereof, and the composite anode powder comprises composite anode powder using PVP-K30 as a raw material, and provides a preparation method of the composite anode powder and an application method of the composite anode powder on SOFC batteries.
A composite anode powder using PVP-K30 pore former comprises the following raw materials: gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2O, Glycine (C)2H5NO2) And PVP-K30 pore former.
Further, Gd (NO) is contained in the above-mentioned raw materials3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2The mass ratio of O to glycine is 1:4:5:25, and the mass fraction of PVP-K30 pore-forming agent is 5%.
A preparation method of composite anode powder using PVP-K30 pore-forming agent, wherein the used reagents are analytically pure reagents, and NiO-GDC composite anode powder is synthesized by adopting a glycine-nitrate method; the method comprises the following specific steps:
(1) respectively weighing Gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2O and glycine, and PVP-K30 pore former, wherein Gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2Weighing O and glycine according to the mass ratio of 1:4:5:25 (namely the mass NiO: GDC =1:1 and the total metal ions: glycine =1: 2.5);
(2) adding Ce (NO) with deionized water3)3·6H2Dissolving O and glycine to prepare a first solution; adding Gd (NO) to deionized water3)3·6H2Dissolving O to prepare a second solution; adding Ni (NO) with deionized water3)2·6H2Dissolving O to prepare a third solution; dissolving PVP-K30 pore-forming agent by using deionized water to prepare a fourth solution; the four solutions are prepared into saturated solutions or slightly diluted with the saturated solutions for standby;
(3) heating the first solution prepared in the step (2) and continuously stirring to enable the first solution to reach a micro-boiling state of 80-90 ℃, and keeping the micro-boiling state for 30 minutes to enable different components in the first solution to be uniformly distributed and fully combined to obtain a fifth solution;
(4) circularly dripping the prepared second solution, third solution and fourth solution into the fifth solution in the step (3) by using a dropper at the temperature of 80-90 ℃ under the condition of continuous stirring until the prepared three solutions are completely added to obtain a sixth solution; keeping the sixth solution at 80-90 ℃ for about 3 hours under the condition of continuous stirring until excessive water is evaporated, and enabling the sixth solution to become a colloidal viscous state to obtain a jelly;
the circulating dropping mode is as follows: dripping any one of the second solution, the third solution and the fourth solution, dripping any one of the remaining two solutions, and finally dripping the remaining one solution, and then repeating the dripping sequence until the addition of the prepared three solutions is finished; for example, a drop of the second solution is added, a drop of the third solution is added, a drop of the fourth solution is added, the dropping sequence is repeated, a drop of the second solution is added, and the process is repeated until the addition of the prepared three solutions is finished;
(5) transferring the jelly obtained in the step (4) into a 2000ml big beaker, placing the beaker in a universal resistance furnace for heating, slowly increasing the power of the universal resistance furnace until the power reaches 1000W, stopping power regulation, and heating until the jelly is self-ignited and incinerated to obtain incinerated powder;
(6) taking the beaker in the step (5) out of the resistance furnace, transferring the ashed powder into a crucible, and putting the crucible into a muffle furnace for heating, wherein the temperature control system is as follows: the temperature was raised at 1 ℃/min from room temperature 25 ℃ to 700 ℃; keeping the temperature at 700 ℃ for 2 hours; then, the temperature is reduced by 2 ℃/min to 25 ℃; the resultant was sufficiently ground (dry-ground) with an agate mortar, and then sieved through a 200-mesh sieve to obtain anode powder.
Further, in the step (3) and the step (4), the temperature can be controlled by a high-temperature water bath mode, a magnetic stirrer is adopted for continuous stirring, and the high rotating speed of the stirrer is kept.
Further, the jelly formed in the step (4) is transferred in time and is subjected to subsequent operations, otherwise, the jelly may be burnt in advance, so that the feed liquid is lost, and the yield is reduced.
Further, in the step (6), grinding can be omitted or shortened according to actual particle size requirements, for example, the prepared anode powder is used for pressing an anode blank without grinding; if the prepared anode powder is coated on the surface of an electrolyte sheet, grinding is needed.
A method for applying composite anode powder of PVP-K30 pore-forming agent to SOFC battery comprises placing anode powder in a mortar, adding terpineol to the prepared anode powder gradually during grinding process to obtain viscous material; coating the sticky substance on one side surface of an electrolyte sheet by using a screen printing technology, placing the electrolyte sheet in a drying oven, and drying at 150 ℃; taking out, coating once again and drying; then, sintering the mixture in a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at the speed of 1 ℃/min; thereafter, the temperature was raised from 1000 ℃ to 1450 ℃ at 2 ℃/min; keeping the temperature at 1450 ℃ for 2 hours; then cooling to 25 ℃ at the speed of 2 ℃/min to obtain a half cell;
preparing a cathode on the other side surface of the obtained half cell: mixing lanthanum, strontium, cobalt and iron with GDC in a ratio of 7:3, adding 30wt% of starch, adding absolute ethyl alcohol, grinding into cathode slurry, coating the cathode slurry on the other side surface of an electrolyte sheet by using a screen printing technology, placing the electrolyte sheet in an oven, drying at 150 ℃, coating the cathode slurry again, drying the coating again, sintering by using a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at a speed of 1 ℃/min; increasing the temperature from 1000 ℃ to 1450 ℃ at a rate of 2 ℃/min; keeping the temperature at 1450 ℃ for 2 hours, and cooling to 25 ℃ at the speed of 2 ℃/min; and obtaining the battery.
Example 1
In order to illustrate the advantages of the anode material prepared by the present invention compared with the prior anode material prepared by using carbon and starch, a detailed description of the comparative experiment is provided below.
One) and an experimental group are the anode powder prepared by the invention and an anode blank and an SOFC battery prepared by the powder:
(1) preparing anode powder: in the preparation method, in the step (1), PVP-K30 pore-forming agents are respectively weighed to be 3%, 5% and 7% in mass fraction; obtaining three anode powders with doping mass fractions of 3%, 5% and 7% of PVP-K30 respectively;
(2) preparing an anode blank: weighing 3%, 5% and 7% of PVP-K30 anode powder according to 0.5g of each part, pressing the weighed anode powder into a circular anode blank with the diameter of 16mm under the pressure of 2MPa by using a powder tablet press, slowly heating the anode blank from room temperature to 1450 ℃, preserving heat for 2 hours for pre-sintering, avoiding the phenomenon that the outer ring is warped and bent or even cracked due to the overhigh heating speed of the anode blank, and finally preparing 3 anode blanks;
(3) preparation of SOFC cell:
the method comprises the following steps:
preparing an electrolyte sheet: synthesis of Gd by sol-gel method0.2Ce0.8O1.9Powder, namely heating the powder from 25 ℃ to 700 ℃ at the speed of 1 ℃/min, keeping the temperature of 700 ℃ for 2 hours, cooling to room temperature, and grinding the powder by using absolute ethyl alcohol until the powder is dried and can pass through a 200-mesh sieve, so as to obtain electrolyte powder; taking 0.3g of electrolyte powder, pressing into a round blank with the diameter of 15mm under the pressure of 2MPa by using a powder tablet press, slowly heating the electrolyte blank in a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at the speed of 1 ℃/min; raising the temperature from 1000 ℃ to 1450 ℃ at the speed of 2 ℃/min, and preserving the temperature for 5 hours at 1450 ℃ to obtain an electrolyte sheet;
step two:
preparing an anode on one side surface of an electrolyte sheet: putting 5% PVP-K30 anode powder into a mortar, and gradually adding terpineol into the prepared anode powder in the grinding process until the anode powder is in a sticky wire drawing state to obtain a sticky material; coating the sticky substance on one side surface of an electrolyte sheet by using a screen printing technology, placing the electrolyte sheet in a drying oven, and drying at 150 ℃; taking out, coating once again and drying; then, sintering the mixture in a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at the speed of 1 ℃/min; thereafter, the temperature was raised from 1000 ℃ to 1450 ℃ at 2 ℃/min; keeping the temperature at 1450 ℃ for 2 hours; then cooling to 25 ℃ at the speed of 2 ℃/min to obtain a half cell;
preparing a cathode on the other side surface of the electrolyte sheet: mixing lanthanum, strontium, cobalt and iron with GDC in a ratio of 7:3, adding 30wt% of starch, adding absolute ethyl alcohol, grinding into cathode slurry, coating the cathode slurry on the other side surface of an electrolyte sheet by using a screen printing technology, placing the electrolyte sheet in an oven, drying at 150 ℃, coating the cathode slurry again, drying the coating again, sintering by using a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at a speed of 1 ℃/min; increasing the temperature from 1000 ℃ to 1450 ℃ at a rate of 2 ℃/min; keeping the temperature at 1450 ℃ for 2 hours, and cooling to 25 ℃ at the speed of 2 ℃/min; and obtaining the battery.
A3%, 7% PVP-K30 cell was prepared in the same manner as described above.
And secondly) the comparison group 1 is anode powder prepared by taking carbon as a pore-forming agent, and an anode blank and an SOFC battery prepared by applying the powder:
(1) preparing carbon-doped anode powder: all reagents used in the experiment are analytically pure reagents, and NiO-GDC composite anode powder is synthesized by a glycine-nitrate method; the specific preparation process comprises the following steps:
the method comprises the following steps: with Gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2Weighing corresponding mass according to the mass ratio of 1:4:5:15 (namely the mass NiO of the substance: GDC =1:1 and the total metal ion: glycine =1: 2.5) by using O and glycine as raw materials, completely dissolving the raw materials by using deionized water to prepare a solution, putting the solution on a magnetic stirrer, adding magnetons, continuously heating and stirring the solution to ensure that different components are uniformly and fully combined; heating for several hours until the solution becomes a colloidal viscous state; transferring the mixture into a 2000ml big beaker, heating the mixture by using a resistance furnace until the mixture spontaneously combusts and is ashed, putting the mixture into a muffle furnace, slowly heating the mixture to 700 ℃, and preserving the temperature for two hours to obtain anode powder preliminarily;
step two: mixing the synthesized anode powder with pore-forming agents (activated carbon) with the mass fractions of 3%, 5% and 7%, ball-milling for 24 hours by using a ball mill, and adding absolute ethyl alcohol in the milling process to uniformly mix the mixture to obtain anode powder doped with three carbon-doped pore-forming agents of 3%, 5% and 7%;
(2) preparing a carbon-doped anode blank: weighing 3%, 5% and 7% of three carbon-doped pore-forming agent anode powders according to 0.5g per part, pressing the weighed anode powders into a circular anode blank with the diameter of 16mm under the pressure of 2MPa by using a powder tablet press, slowly heating the anode blank from room temperature to 1450 ℃, preserving heat for 2 hours for pre-sintering, avoiding the phenomenon that the outer ring is warped and bent or even cracked due to the overhigh heating speed of the anode blank, and finally preparing the required 3 carbon-doped anode blanks;
(3) preparation of carbon-doped SOFC cell: the steps of the method are the same as the preparation method of the SOFC battery, and the method is different in that anode powder doped with 3%, 5% and 7% of carbon is adopted.
And thirdly) the comparison group 2 is anode powder prepared by taking starch as a pore-forming agent, and an anode blank and an SOFC battery prepared by applying the powder:
(1) preparing the starch-doped anode powder: the preparation method is the same as that of the carbon-doped anode powder, and the difference is that 3%, 5% and 7% of starch pore-forming agent is adopted;
(2) preparing a starch-doped anode blank: the preparation method is the same as that of the carbon-doped anode blank, and the difference is that 3%, 5% and 7% of three types of anode powder doped with starch pore-forming agents are adopted;
(3) preparation of starch doped SOFC cells: the steps of the method are the same as the preparation method of the SOFC battery, and the method is different in that anode powder doped with 3%, 5% and 7% of starch is adopted.
Four) performance testing:
(4.1) porosity measurement
(4.1.1) porosity was measured by placing the prepared anode blank in a balance using Archimedes drainage method and weighing to obtain its mass m1(ii) a Placing the anode blank in a beaker filled with absolute ethyl alcohol, and weighing the anode blank to obtain the suspended weight m2Taking out the anode blank, wiping the surface, measuring the mass of the anode blank again by using the balance, and weighing the anode blank to obtain the anode blank with the mass m3. The density ρ is calculated according to the formula (1)0，
Figure DEST_PATH_IMAGE001
(4.1.2) calculating the theoretical density rho of the blank according to the NiO and GDC PDF card, calculating the porosity p of the anode blank according to the formula (2),
Figure 780407DEST_PATH_IMAGE002
(4.2) X-ray diffraction (XRD) powder characterization
The specific parameters of the bench X-ray diffractometer are as follows: and (3) a CuKalpha target (lambda =0.15418 nm), a scanning angle of 10-90 degrees, a working current of 15mA and a working voltage of 40KV, carrying out X-ray diffraction at a speed of 2 DEG/min on the anode powder, and analyzing a diffraction pattern of the anode powder to obtain information such as components of the anode powder, structures or forms of atoms or molecules in the material. X-ray diffraction is the most effective and widely used technique for studying the structure of matter. When a monochromatic X-ray is incident on the crystal, the distance between atoms regularly arranged in the crystal and the wavelength of the incident X-ray have the same order of magnitude, so that X-rays scattered by different atoms interfere with each other, strong X-ray diffraction is generated in certain special directions, and the diffraction peaks with different diffraction intensities are reflected on an XRD (X-ray diffraction) spectrum.
(4.3) Observation of microstructure
The experiment was microscopically characterized using a scanning electron microscope (JEOLJSM-6510). The scanning electron microscope is characterized in that electron cross spots emitted by an electron gun are changed into focused electron beams after passing through a secondary condenser, the electron beams are subjected to grid-type drawing on the surface of a test sample according to a certain time and space sequence, the electron beams interact with the sample in the drawing process, a secondary electron signal emission phenomenon is generated on the surface of the sample, and the energy and the intensity of the secondary electrons can indirectly reflect the morphological structure and the phase composition of each point on the surface of the sample. The signal emitted by secondary electron is collected by detector, converted into optical signal by scintillator, and converted into electric signal by photomultiplier and amplifier to control the intensity of electron beam on fluorescent screen and display the scanned image synchronous with electron beam.
(4.4) measurement of electrochemical Properties
Synthesis of Gd by sol-gel method0.2Ce0.8O1.9And pressing into a blank under the pressure of 2MPa by using a powder tablet press, taking the blank as the electrolyte of the prepared single cell, and respectively coating the LSCF cathode and the prepared anode powder on two sides of the electrolyte sheet by using a screen printing technology. Using the IVIUMSTAT electrochemical workstation of the Netherlands, will prepareThe good monocell is fixed on a cell testing device self-made in a laboratory by conductive adhesive, moist hydrogen is introduced into the anode end of the cell, and the cathode is exposed in the outside air. Controlling the flow rate of the hydrogen at 40ml-min', raising the temperature to 650 ℃, and starting to test the I-V curve of the battery after the performance of the battery is stable.
Five) comparative analysis
(5.1) measurement of porosity
Three different types of pore formers were used in the experiment: PVP-K30, active carbon, starch, the addition amount of three pore-forming agents and the porosity measured by anode blanks with different components are specifically shown in Table 1;
TABLE 1 anodic pore-forming agent dosage, green body composition and porosity comparison
Figure DEST_PATH_IMAGE003
By comparing the porosities measured after the anodes of the pore-forming agents with different mass fractions are respectively added and sintered, the porosity is in an increasing trend along with the increase of the content of the pore-forming agent under the condition of adding the same pore-forming agent; however, the PVP-K30 is not stable when added in an excessive amount, and is partially precipitated, so that the concentration and the porosity cannot be approximated in a linear relationship.
When the pore-forming agent with the mass fraction of 3% is added respectively, the anode porosity of the added PVP-K30 pore-forming agent, the anode porosity of the added activated carbon pore-forming agent and the anode porosity of the added starch pore-forming agent are respectively 3.30%, 2.82% and 3.26%, and the anode porosity of the added PVP-K30 is slightly higher than the anode porosity of the added activated carbon pore-forming agent and the anode porosity of the added starch pore-forming agent, but is very close to the anode porosity.
When the PVP-K30 pore-forming agent with the mass fraction of 7% is added, the measured anode porosity reaches 9.13%, and the measured anode porosity is the maximum porosity obtained in the experiment; when the active carbon pore-forming agent and the starch pore-forming agent with the same mass fraction are added, the porosity is only 4.48 percent and 5.02 percent, the values are far different, and the effect is relatively poor. The highest porosity can be obtained by adding PVP-K30 with the mass fraction of 7%, but the actual high porosity can cause the collapse of an anode structure, the number of three-phase reaction interfaces is reduced, and the concentration polarization of the battery can be generated, so that the electrical property of the battery is reduced; experimental studies have found that the anode porosity reaches 9.13% and the electrical performance is rather inferior to that of 7.54% porosity;
compared with the experimental data that the mass fraction of each pore-forming agent is 3% and 7%, the mass fraction of the pore-forming agent is increased by 4%, the porosity of the anode added with the activated carbon pore-forming agent and the starch pore-forming agent is increased by 1.76% and 1.66%, and the porosity of the anode added with the PVP-K30 pore-forming agent is increased by 5.83%, which is 4 times of the former, which shows that the PVP-K30 pore-forming agent has better effect, and the efficiency of the PVP-K30 pore-forming agent is far greater than that of the activated carbon pore-forming agent and the starch pore-forming agent.
(5.2) XRD test results
XRD (X-ray diffraction) tests are carried out on the prepared anode powder with the doping content of PVP-K30 being 3%, 5% and 7%, the prepared anode powder with the doping content of carbon being 3%, 5% and 7% and the prepared anode powder with the doping content of starch being 3%, 5% and 7% to obtain an XRD pattern, and the XRD pattern is shown in figure 3;
it can be seen from fig. 3 that, although the types and contents of the added pore-forming agents are different, the added pore-forming agents present diffraction peaks at almost the same positions, and the relative intensities and angles of the diffraction peaks of the samples prepared by the glycine-nitrate method are consistent with the positions of NiO-GDC peaks in the JCPDS standard card, which indicates that no new diffraction peak appears in the XRD spectrum, the prepared samples present a better crystalline state and have a higher purity, and the anode powder added with the pore-forming agents does not have other new phases generated and existed, so that the function of the anode in the battery is not interfered. The half-peak width of the pore-forming agent of the same kind is gradually increased along with the increase of the mass fraction, and the grain size of the pore-forming agent is presumed to be slightly reduced according to the Sheer formula; for example, the content of PVP (polyvinyl pyrrolidone) serving as a pore forming agent is increased, the diffraction peak of GDC shifts to a low angle, the lattice constant is increased, and uniform through holes are easy to form; in summary, PVP-K30 was used as the pore former.
(5.3) SEM test results
4-6 are anode micro-topography images with different contents of PVP-K30, activated carbon pore former and starch pore former, and it can be seen from scanning electron microscope images that the used pore former largely affects the micro-topography of the anode substrate; comparing the figures, the most and most uniform holes are added with 5% PVP-K30, the holes are regular in spherical shape and uniform in size distribution, and the microstructure can greatly reduce the diffusion resistance of airflow, which is beneficial to the transportation of gas phase reactants and products; with the same porosity, such a structure allows for higher electrical conductivity of the anode substrate;
compared with 4 (d), 5 (j), 4 (e), 5 (k), 4 (f) and 5 (l), when the activated carbon pore-forming agent is added as the pore-forming agent of the anode substrate, only a small amount of large holes exist in the anode, and most of the other holes are small and are unevenly distributed because the carbon decomposition temperature is high and the analysis temperature section is long, so that the formed hole diameter is small, which brings difficulty to the diffusion of gas in the anode, and forms serious concentration polarization, thus easily causing the cell fracture;
as shown in fig. 6 (m), (n), (o), (p), (q), (r), when the pore-forming agent is added as the anode substrate for pore-forming, there is a phenomenon of non-uniform pores in the anode because the starch is not uniformly ball-milled during the ball-milling process, which has an effect on the stability and operation of the battery structure;
in conclusion, the carbon and the starch are used as pore-forming agents, so that the required addition amount is large, the obtained pores are small and uneven, and the diffusion of gas-phase substances is not facilitated; the PVP with different contents is added to the anode substrate to be used as a pore-forming agent, so that a better microstructure can be obtained, a single large and complete hole and a large hole which is connected with each other can be formed in the anode, and the holes are beneficial to increasing the effective reaction area of the fuel gas.
(5.4) electrochemical Performance test
5% of pore-forming agents (PVP-K30, activated carbon and starch) are respectively added into the same anode substrate to be used as an anode, and three pore-forming agent single cells are prepared in parallel by using the same LSCF cathode and GDC electrolyte. The electrochemical test shows that the performance test results of the single cell with different pore-forming agents are shown in FIG. 7. As can be seen from FIG. 7, the maximum open circuit voltages of the single cells consisting of 5% PVP-K30, 5% C, and 5% starch pore former were about 0.91V, 0.83V, and 0.85V, respectively, at 600 deg.C, indicating that the cell consisting of the 5% PVP-K30 hybrid anode achieved higher open circuit voltages. In NiWhen the mass ratio of O-GDC is 5:5, the power densities of single cells corresponding to 5 percent of PVP-K30, 5 percent of C and 5 percent of starch pore-forming agent are respectively 0.113W/Cm2、0.092W/Cm2And 0.099W/Cm2It shows that the battery formed by the 5% PVP-K30 mixed anode has higher output power.
Obviously, the adjustment of the type and the content of the pore-forming agent has certain influence on the power density of a single cell, and compared with the carbon and starch pore-forming agent, the addition of a small amount of PVP-K30 pore-forming agent can make the power density reach the maximum peak value. The main reason is that the carbonaceous anode material is easy to form carbon deposit, block the anode pores and is not beneficial to the progress of the anodic oxidation reaction, so that the performance of the single cell is relatively low. The PVP-K30 pore-forming agent is a non-ionic surfactant, has good solubility, film-forming property, binding capacity and complexing capacity, and the like, so that the aperture of the anode is smaller, the pore channels are increased, the porosity is increased, the diffusion speed of gas is increased, and the concentration polarization of the anode is reduced, thereby improving the electrochemical performance of the battery.
Sixth) conclusion
Experiments show that the addition of the PVP-K30 water-soluble organic macromolecular pore-forming agent is more beneficial to the formation of anode pores, and the water-soluble characteristic is utilized, so that the water-soluble organic macromolecular pore-forming agent can be doped during the primary synthesis of the powder, the agglomeration of the pore-forming agent can be avoided, the pore-forming agent can be distributed more uniformly, and the pore-forming shrinkage of the powder is natural. On the other hand, long-chain macromolecules are adopted, so that the working procedures of later grinding and doping are reduced, and the synthesis period is shortened. Compared with a carbon pore forming agent, the carbon-deposited carbon-doped carbon material can effectively avoid carbon deposition, reduce concentration polarization, improve the pore forming efficiency, prolong the service life of a battery and obtain higher power density;
by comparing doping results of the three pore-forming agents in different proportions, the porosity of the anode is gradually increased along with the increase of the content of the PVP-K30 pore-forming agent, the mass transfer resistance of anode fuel gas is reduced, the number of TPB is increased, and the working efficiency of the anode is improved;
the solubility of PVP-K30 decreased with increasing temperature, and at high concentrations, partial precipitation occurred. In practical application, the concentration of PVP-K30 should not be too high, so the experiment studies the pore-forming effect and electrochemical performance of the anode when PVP-K30 is used as the pore-forming agent in a low concentration range.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made, and equivalents can be substituted for elements thereof without departing from the scope of the invention.

Claims (3)

1. A preparation method of composite anode powder using PVP-K30 pore-forming agent is characterized by comprising the following steps:
(1) respectively weighing Gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2O and glycine, and PVP-K30 pore former, wherein Gd (NO)3)3·6H2O，Ce(NO3)3·6H2O，Ni(NO3)2·6H2Weighing O and glycine according to the mass ratio of 1:4:5: 25;
(2) adding Ce (NO) with deionized water3)3·6H2Dissolving O and glycine to prepare a first solution; adding Gd (NO) to deionized water3)3·6H2Dissolving O to prepare a second solution; adding Ni (NO) with deionized water3)2·6H2Dissolving O to prepare a third solution; dissolving PVP-K30 pore-forming agent by using deionized water to prepare a fourth solution;
(3) heating the first solution prepared in the step (2) and continuously stirring to enable the first solution to reach a micro-boiling state of 80-90 ℃, and keeping the micro-boiling state for 30 minutes to enable different components in the first solution to be uniformly distributed and fully combined to obtain a fifth solution;
(4) circularly dripping the prepared second solution, third solution and fourth solution into the fifth solution in the step (3) by using a dropper at the temperature of 80-90 ℃ under the condition of continuous stirring until the prepared three solutions are completely added to obtain a sixth solution; keeping the sixth solution at 80-90 ℃ for about 3 hours under the condition of continuous stirring until excessive water is evaporated, and enabling the sixth solution to become a colloidal viscous state to obtain a jelly;
(5) transferring the jelly obtained in the step (4) into a beaker, and placing the beaker in a universal resistance furnace to heat until the jelly is self-ignited and incinerated to obtain incinerated powder;
(6) taking the beaker in the step (5) out of the resistance furnace, transferring the ashed powder into a crucible, and putting the crucible into a muffle furnace for heating, wherein the temperature control system is as follows: the temperature was raised at 1 ℃/min from room temperature 25 ℃ to 700 ℃; keeping the temperature at 700 ℃ for 2 hours; then, the temperature is reduced by 2 ℃/min to 25 ℃; and fully grinding the product by using an agate mortar, and then sieving the product by a 200-mesh sieve to obtain anode powder.
2. The method for preparing a composite anode powder using PVP-K30 pore former as claimed in claim 1, wherein the temperature in step (3) and step (4) is controlled by high temperature water bath, and the stirring is continued by magnetic stirrer while maintaining the high rotation speed of the stirrer.
3. A method for applying the composite anode powder prepared by the preparation method of claim 1 to SOFC batteries is characterized in that the anode powder is taken and placed in a mortar, and the terpineol is gradually added into the prepared anode powder in the grinding process until the prepared anode powder is in a sticky wire-drawing state, so that a sticky material is obtained; coating the sticky substance on one side surface of an electrolyte sheet by using a screen printing technology, placing the electrolyte sheet in a drying oven, and drying at 150 ℃; taking out, coating once again and drying; then, sintering the mixture in a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at the speed of 1 ℃/min; thereafter, the temperature was raised from 1000 ℃ to 1450 ℃ at 2 ℃/min; keeping the temperature at 1450 ℃ for 2 hours; then cooling to 25 ℃ at the speed of 2 ℃/min to obtain a half cell;
preparing a cathode on the other side surface of the obtained half cell: mixing lanthanum, strontium, cobalt and iron with GDC in a ratio of 7:3, adding 30wt% of starch, adding absolute ethyl alcohol, grinding into cathode slurry, coating the cathode slurry on the other side surface of an electrolyte sheet by using a screen printing technology, placing the electrolyte sheet in an oven, drying at 150 ℃, coating the cathode slurry again, drying the coating again, sintering by using a muffle furnace, and raising the temperature from 25 ℃ to 1000 ℃ at a speed of 1 ℃/min; increasing the temperature from 1000 ℃ to 1450 ℃ at a rate of 2 ℃/min; keeping the temperature at 1450 ℃ for 2 hours, and cooling to 25 ℃ at the speed of 2 ℃/min; and obtaining the battery.
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