CN113948732B - Gradient structure and pore anode, preparation method and battery - Google Patents

Gradient structure and pore anode, preparation method and battery Download PDF

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CN113948732B
CN113948732B CN202111034259.4A CN202111034259A CN113948732B CN 113948732 B CN113948732 B CN 113948732B CN 202111034259 A CN202111034259 A CN 202111034259A CN 113948732 B CN113948732 B CN 113948732B
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temperature
layer
anode
slurry
pore
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CN113948732A (en
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赵金保
张彦杰
寇聪聪
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Tan Kah Kee Innovation Laboratory
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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
    • 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
    • H01M8/0245—Composites in the form of layered or coated products
    • 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
    • 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
    • H01M8/0236—Glass; Ceramics; Cermets
    • 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
    • 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 gradient structure and pore anode, a preparation method and a battery. The anode is sequentially arranged into an outer layer, a transition layer and an inner layer; the outer layer is distributed with fiber holes, the transition layer is distributed with fiber holes, ball holes and holes communicated with the fiber holes and the ball holes, and the inner layer is distributed with ball holes; the aperture of the fiber hole is smaller than that of the ball hole, and the porosities of the outer layer, the transition layer and the inner layer are reduced in sequence. The solid oxide fuel cell adopting the gradient structure and the pore anode can effectively reduce the concentration polarization of the cell by utilizing the gradient structure and the pore anode while ensuring the sufficient mechanical strength of a single cell, thereby optimizing the performance of the cell. Meanwhile, the invention provides a method for preparing the solid oxide fuel cell with the gradient structure and the pore anode by adopting the technology of combining non-aqueous tape casting and demoulding with high-temperature co-sintering, which is beneficial to the application and the industrialized development of the solid oxide fuel cell technology.

Description

Gradient structure and pore anode, preparation method and battery
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to a gradient structure and pore anode, a preparation method thereof and a cell.
Background
With worldwide research and development focused on new, low-emission, sustainable, and cost-effective energy sources, fuel cells have become a potential research direction. Solid oxide fuel cells, which are electrochemical devices, can efficiently convert chemical energy into electrical energy by fuel oxidation while reducing the amount of oxidant.
Solid Oxide Fuel Cells (SOFC) have many advantages over other types of fuel cells, including high energy conversion efficiency, fuel flexibility, high quality waste heat, all-solid-state structure, high power density, low-temperature chamber gas emissions, low noise, and environmental impact. SOFCs consist of electrodes (anode and cathode) and an electrolyte. The anode receives fuel, the cathode receives oxidant, and the electrolyte allows oxide ions or protons to pass through. SOFCs typically operate at high temperatures (> 600℃.) and have power generation efficiencies in excess of 60% compared to the overall efficiency of conventional thermal power plants of no more than 35%, being the most efficient fuel cells. Furthermore, the fuel flexibility of SOFCs, particularly the ability to internally reform most carbonaceous fuels, and the promise of cogeneration, make it an important research direction in the field of new energy research.
An SOFC is a device that converts chemical energy (primarily hydrogen) directly into electrical energy through an electrochemical catalytic reaction. Unlike most other types of fuel cells, SOFCs do not require expensive catalysts. SOFCs employ solid oxides as the electrolyte. The solid oxide has the capability of transferring oxygen ions at high temperature, plays a role in transferring the oxygen ions and separating air and fuel in the cell, and obtains electrons from oxygen molecules on a cathode to be reduced into the oxygen ions. Under the action of the potential difference and the oxygen concentration difference driving force, oxygen ions are directionally transited through oxygen vacancies in the electrolyte and migrate to the anode three-phase interface to perform oxidation reaction with the fuel.
SOFCs may employ anode support, electrolyte support and cathode support, depending on which layer is used as mechanical support. In electrolyte-supported SOFCs, the electrolyte is the thickest component (> 150 μm), while the anode and cathode are very thin (about 50 μm), resulting in higher resistance. Therefore, most of the research work to date has focused on the application of electrolyte supported SOFCs at high operating temperatures. In an electrode supported SOFC one of the two electrodes, the cathode or anode, is the thickest component (about 1 mm) and the support structure. This reduces the impedance making the design more suitable for operation at lower temperatures. This system is called an "intermediate temperature solid oxide fuel cell" (IT-SOFC). Cathode-supported SOFCs have several advantages over anode-supported SOFCs, such as low cost cathode support materials, and a thinner anode prevents carbon deposition when operated with hydrocarbon fuels. However, since the sintering temperature of the cathode is greatly different from that of the electrolyte and the anode, it is difficult to prepare the electrolyte and the anode on the basis of the cathode, and thus, the current major research is focused on the anode-supported SOFC. However, anode-supported SOFCs require a thick anode, which requires hydrogen and water vapor transport in the anode porous electrode, and the thick anode is not conducive to gas transport, resulting in large concentration polarization and reduced cell performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a gradient structure and pore anode, a preparation method thereof and a battery, and solves the problems of an anode supported SOFC in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: providing a gradient structure and a pore anode which are sequentially arranged into an outer layer, a transition layer and an inner layer; the outer layer is distributed with fiber holes, part of the fiber holes extend to the surface of the outer layer, the transition layer is distributed with fiber holes, ball holes and holes communicated with the fiber holes and the ball holes, and the inner layer is distributed with ball holes; the porosity of the outer layer, the porosity of the transition layer and the porosity of the inner layer are decreased gradually.
In a preferred embodiment of the invention, the pore diameter of the fiber pores is 5-15 μm, the pore diameter of the ball pores is 10-60 μm, and the porosity of the outer layer, the porosity of the transition layer and the porosity of the inner layer are 35% -45%, 25% -35% and 15% -25% in sequence.
In a preferred embodiment of the present invention, the thickness of the outer layer is 150-350 μm; the thickness of the transition layer is 50-250 μm; the thickness of the inner layer is 200-400 μm.
In a preferred embodiment of the invention, the anode comprises NiO and a ceramic substrate, wherein the mass fraction of the NiO is 45-65%.
In a preferred embodiment of the present invention, the ceramic substrate is yttria-stabilized zirconia, scandia-stabilized zirconia, doped ceria or perovskite-type LaGaO 3 A base material.
The second technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a gradient structure and a porous anode is provided, which comprises the following steps:
(1) Mixing an organic solvent, anode ceramic powder, a dispersing agent, an adhesive, a plastic agent and a pore-forming agent to prepare slurry of each layer of the anode; wherein the content of the first and second substances,
the outer layer slurry adopts micron carbon fibers and carbon nanotubes as pore-forming agents, the inner layer slurry adopts spherical graphite and starch as pore-forming agents, and the transition layer slurry adopts a mixture of the outer layer pore-forming agents and the inner layer pore-forming agents;
(2) Carrying out vacuum defoaming on the outer layer slurry, the transition layer slurry and the inner layer slurry of the anode;
(3) Respectively casting the outer layer slurry, the transition layer slurry and the inner layer slurry of the anode on the surface of the PET film, standing for 22-26h, and separating the inner layer slurry layer, the transition layer slurry layer, the outer layer slurry layer and the PET film;
(4) Sequentially stacking an inner layer slurry layer, a transition layer slurry layer and an outer layer slurry layer, applying pressure of 3-10KPa for pre-sintering, and then performing high-temperature co-sintering to obtain the gradient structure and the pore anode; wherein the content of the first and second substances,
the pre-sintering is that the temperature is increased to 700-900 ℃ from the room temperature at the heating rate of 0.5-2 ℃/min, the temperature is maintained for 55-65 min, then the temperature is increased to 1000-1200 ℃ at the heating rate of 1-2 ℃/min, the temperature is maintained for 1-3 h, then the temperature is reduced to the room temperature at the cooling rate of 1-3 ℃/min, and the pressurization pre-sintering is completed;
the high-temperature co-sintering is to raise the temperature to 700-900 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 1-3 h, then raise the temperature to 1100-1300 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 1-3 h, then raise the temperature to 1300-1500 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 2-4 h, then lower the temperature to 700-900 ℃ at a cooling rate of 0.5-2 ℃/min, and finally lower the temperature to room temperature for cooling.
In a preferred embodiment of the present invention, the organic solvent is at least one of ethanol and butanone mixture, ethanol and trichloroethylene mixture, trichloroethylene and methyl ethyl ketone mixture, terpineol;
the anode ceramic powder consists of NiO and a powdery ceramic base material, wherein the ceramic base material is yttria-stabilized zirconia, scandia-stabilized zirconia or doped ceriaOr perovskite type LaGaO 3 A base material;
the dispersant is glycerol trioleate and triethanolamine;
the adhesive is polyvinyl butyral and ethyl cellulose;
the plasticizer is a mixture of polyethylene glycol and diethyl phthalate.
In a preferred embodiment of the present invention, there is provided a solid oxide fuel cell comprising an anode, an electrolyte and a cathode; wherein, the anode is used as a support body, and the gradient structure and the pore anode are adopted; the battery comprises an outer layer, a transition layer, an inner layer, an electrolyte layer and a cathode layer which are arranged in sequence.
In a preferred embodiment of the present invention, the thickness of the electrolyte layer is 10-100 μm; the thickness of the cathode layer is 10-100 μm.
In a preferred embodiment of the present invention, the electrolyte layer is made of yttria-stabilized zirconia, scandia-stabilized zirconia, doped ceria, perovskite-type LaGaO 3 A base material.
In a preferred embodiment of the present invention, the cathode layer is composed of (La) 0.8 Sr 0.2 ) 0.95 MnO 3-δ (LSM)、La 0.6 Sr 0.4 FeO 3-δ (LSF) or La 0.8 Sr 0.2 Cr 0.5 Fe 0.5 O 3-δ (LSCF) and a ceramic substrate, wherein the mass fraction of the ceramic substrate is 40-60%.
The fourth technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a solid oxide fuel cell is provided, which comprises the following steps:
(1) Preparing slurry of each layer of the anode by mixing an organic solvent, anode ceramic powder, a dispersing agent, an adhesive, a plastic agent and a pore-forming agent; wherein the outer layer slurry adopts micron carbon fibers and carbon nanotubes as pore-forming agents, the inner layer slurry adopts spherical graphite and starch as pore-forming agents, and the transition layer slurry adopts a mixture of the outer layer pore-forming agents and the inner layer pore-forming agents;
using organic solvent, electrolyte ceramicsMixing the powder and the adhesive to prepare electrolyte layer slurry; the electrolyte ceramic powder adopts yttria-stabilized zirconia, scandia-stabilized zirconia, doped ceria and perovskite LaGaO 3 One of the base materials;
preparing cathode layer slurry by mixing an organic solvent, cathode ceramic powder and an adhesive; the cathode ceramic powder adopts (La) 0.8 Sr 0.2 ) 0.95 MnO 3-δ (LSM)、La 0.6 Sr 0.4 FeO 3-δ (LSF) or La 0.8 Sr 0.2 Cr 0.5 Fe 0.5 O 3-δ (LSCF) of yttria-stabilized zirconia, scandia-stabilized zirconia, doped ceria, perovskite-type LaGaO 3 A base material.
(2) Carrying out vacuum defoaming on the outer layer slurry, the transition layer slurry and the inner layer slurry of the anode, the electrolyte layer slurry and the cathode layer slurry;
(3) Respectively casting the outer layer slurry, the transition layer slurry and the inner layer slurry of the anode on the surface of the PET film, standing for 22-26h, and separating the inner layer slurry layer, the transition layer slurry layer, the outer layer slurry layer and the PET film;
(4) Sequentially stacking the inner slurry layer, the transition layer slurry layer and the outer slurry layer, and applying pressure of 3-10KPa to perform pre-sintering; then spin-coating the electrolyte layer slurry on the anode inner layer slurry layer, and then carrying out primary high-temperature co-sintering on the four slurry layers;
(5) And coating the cathode layer slurry on the sintered compact electrolyte layer by using a screen printing method, and carrying out secondary high-temperature co-sintering to prepare the solid oxide fuel cell with the gradient anode structure.
In a preferred embodiment of the present invention, the pre-sintering is performed by raising the temperature from room temperature to 700-900 ℃ at a heating rate of 0.5-2 ℃/min, maintaining the temperature for 55-65 min, raising the temperature to 1000-1200 ℃ at a heating rate of 1-2 ℃/min, maintaining the temperature for 1-3 h, and lowering the temperature to room temperature at a cooling rate of 1-3 ℃/min, thereby completing the pressurized pre-sintering.
In a preferred embodiment of the present invention, the first high temperature co-sintering is to raise the temperature to 700-900 ℃ at a heating rate of 0.5-2 ℃/min and maintain the temperature for 1-3 h, then raise the temperature to 1100-1300 ℃ at a heating rate of 0.5-2 ℃/min and maintain the temperature for 1-3 h, then raise the temperature to 1300-1500 ℃ at a heating rate of 0.5-2 ℃/min and maintain the temperature for 2-4 h, then lower the temperature to 700-900 ℃ at a cooling rate of 0.5-2 ℃/min, and finally lower the temperature to room temperature for cooling.
In a preferred embodiment of the present invention, the second high temperature pre-sintering is performed by raising the temperature to 350-450 ℃ at a temperature raising rate of 0.5-2 ℃/min, maintaining the temperature for 1-3 h, raising the temperature to 900-1100 ℃ at a temperature raising rate of 0.5-2 ℃/min, maintaining the temperature for 2-4 h, and then lowering the temperature to room temperature at a temperature lowering rate of 0.5-2 ℃/min for cooling.
Compared with the background technology, the technical scheme has the following advantages:
1. the gradient anode support body has changed porosity and pore structure, the porosity is reduced from outside to inside, meanwhile, the pore structure is gradually transited from a fibrous through hole structure to a spherical pore structure, the sufficient mechanical strength of the battery piece is ensured, the transportation resistance of gas passing through the support body layer is reduced, and the influence of concentration polarization on the performance of a single battery is favorably reduced:
the outer fibrous pore structure that uses, the fibre hole is rectangular shape and like fibrous dispersion in the outer or link up to outer surface formation intercommunication hole, and the aperture in fibre hole is less than the ball hole but length is greater than the ball hole to the outer porosity that keeps high is favorable to gas to pass through, has the important function to the concentration polarization that reduces the battery. The transition layer uses the mixture of fibrous pores and spherical pores as the transition layer, because the material properties formed by the fibrous pores and the spherical pores are different, and the porosity difference between the outer layer and the inner layer is larger, the stress between the two layers caused by the material property difference can be effectively relieved by using the transition layer. The inner layer uses spherical holes, the porosity is kept low, the strength of the material is increased due to the isotropic stress characteristic of the spherical holes, and finally the overall strength of the multilayer anode can achieve the effect of supporting the whole SOFC;
2. the invention adopts the technology of combining non-aqueous tape casting demoulding and high-temperature co-sintering to prepare the solid oxide fuel cell with the gradient anode structure, and is beneficial to the application and the industrialized development of the solid oxide fuel cell technology.
Drawings
Fig. 1 is a schematic view of the overall structure of a solid oxide fuel cell of example 1.
Fig. 2 is a schematic view of the operation of the solid oxide fuel cell of example 1.
Fig. 3 is a schematic flow chart of a process for manufacturing a solid oxide fuel cell of example 1.
FIG. 4 is an electron micrograph of the gradient anode structure of example 1.
Fig. 5 is a schematic diagram of fig. 4 and its corresponding structure.
FIGS. 6 and 7 are electron micrographs of the anode outer layer of example 1 at different magnifications.
FIGS. 8 and 9 are electron micrographs of the anode transition layer of example 1 at different magnifications.
FIGS. 10 and 11 are electron micrographs of the inner layer of the anode in example 1 at different magnifications.
Fig. 12 is a graph comparing the performance of the batteries of examples and comparative examples.
Wherein, 1 cathode layer, 2 compact electrolyte layer, 3 anode inner layer, 4 anode transition layer, 5 anode outer layer.
Detailed Description
Example 1
The present embodiment is a solid oxide fuel cell with a flat plate type gradient anode structure, and the preparation method is as follows:
(1) 4.5g of yttria-stabilized zirconia (YSZ) and 5.5g of nickel oxide (NiO) were weighed into a ball mill pot, 7.75mL of ethanol and 3.75mL of butanone were added and stirred, and 0.2mL of triolein was added thereto. Ball milling is carried out for 20h by a planetary ball mill, then the mixture is taken out, appropriate amount of 0.99g of polyvinyl butyral (PVB), 0.75g of polyethylene glycol (PEG) and 0.55mL of diethyl Phthalate (PHT) are weighed, and the mixture is fully stirred and then ball milled for 24h, then the mixture is taken out. 0.6g of micron carbon fiber is dispersed in 5mL of ethanol solution, and then the mixture is mixed with the slurry after ball milling, and the mixture is fully stirred until the viscosity is 5 pas, so that the slurry of the outer layer 5 of the anode is obtained.
(2) 4.5g yttria-stabilized zirconia (YSZ) and 5.5g nickel oxide (NiO) were weighed into a ball mill jar, 7.75mL ethanol and 3.75mL butanone were added and stirred, and 0.2mL triolein was added thereto. Ball milling is carried out for 20h by a planetary ball mill, then the mixture is taken out, appropriate amount of 0.99g of polyvinyl butyral (PVB), 0.75g of polyethylene glycol (PEG) and 0.55mL of diethyl Phthalate (PHT) are weighed, and the mixture is fully stirred and then ball milled for 24h, then the mixture is taken out. 0.2g of micron carbon fiber and 0.4g of starch are dispersed in 5mL of ethanol solution, then the mixture is mixed with the slurry after ball milling, and the mixture is fully stirred until the viscosity is 5 pas to obtain the slurry of the anode transition layer 4.
(3) 4.5g yttria-stabilized zirconia (YSZ) and 5.5g nickel oxide (NiO) were weighed into a ball mill jar, 7.75mL ethanol and 3.75mL butanone were added and stirred, and 0.2mL triolein was added thereto. Ball milling is carried out for 20h by a planetary ball mill, then the mixture is taken out, appropriate amount of 0.99g of polyvinyl butyral (PVB), 0.75g of polyethylene glycol (PEG) and 0.55mL of diethyl Phthalate (PHT) are weighed, and the mixture is fully stirred and then ball milled for 24h, then the mixture is taken out. Dispersing 0.375g of starch in 5mL of ethanol solution, then mixing with the slurry after ball milling, and fully stirring until the viscosity is 5 pas to obtain the slurry of the inner layer 3 of the anode.
(4) And (3) carrying out vacuum defoaming on the slurry of the anode outer layer 5, the slurry of the anode transition layer 4 and the slurry of the anode inner layer 3 for 10min.
(5) On a polyester film carrier tape, respectively casting slurry of an anode outer layer 5, slurry of an anode transition layer 4 and slurry of an anode inner layer 3 on the surface of the carrier tape, standing the carrier tape for 24 hours, and separating a solidified ceramic slurry layer from the surface of the carrier tape.
(6) And stacking the slurry layer 3 on the anode inner layer, the slurry layer 4 on the anode transition layer and the slurry layer 5 on the anode outer layer in sequence, and applying pressure 5KPa to prevent the slurry layers from deforming. Then the temperature was raised from room temperature to 700 ℃ at a ramp rate of 1 ℃/min and maintained at this temperature for 60min, then raised to 1100 ℃ at a ramp rate of 2 ℃/min and maintained at this temperature for 2h, and then lowered to room temperature at a ramp rate of 2 ℃/min, completing the pressurized pre-sintering.
(7) Weighing 18.9g of terpineol and 1.1g of ethyl cellulose, mixing, heating to 80 ℃, stirring, adding 10.7g of YSZ after uniformly mixing, ball-milling for 24 hours after uniformly stirring, and then carrying out vacuum defoaming for 10 minutes to obtain the slurry of the compact electrolyte layer 2.
(8) And (3) adsorbing the three-layer anode plate subjected to pressurized pre-sintering on a tray of a spin coater, dripping slurry of the compact electrolyte layer 2 on the surface of the three-layer anode plate to fully cover the three-layer anode plate, then operating at the rotating speed of 6000r/s for 40s, then heating to 80 ℃ and preserving heat for 20min, then heating to 450 ℃ and preserving heat for 20min, and repeating the step (8) for a plurality of times.
(9) Sintering the gradient anode and the electrolyte by adopting a high-temperature co-sintering method, wherein a heating program firstly raises the temperature to 800 ℃ at a heating rate of 1 ℃/min and maintains the temperature for 1h, then raises the temperature to 1200 ℃ at a heating rate of 2 ℃/min and maintains the temperature for 2h, then raises the temperature to 1400 ℃ at a heating rate of 2 ℃/min and maintains the temperature for 4h, then lowers the temperature to 800 ℃ at a cooling rate of 2 ℃/min, and finally lowers the temperature to room temperature for cooling.
(10) Weighing 13.2g of terpineol and 0.77g of ethyl cellulose, mixing, heating to 80 ℃, stirring, adding 4g of YSZ and 4g of LSCF after uniform mixing, ball-milling for 24h after uniform stirring, and then carrying out vacuum defoaming for 10min to obtain cathode layer 1 slurry.
(11) The cathode layer 1 slurry was printed on the dense electrolyte layer 2 using a screen printer and then dried at 80 ℃ for 20min, and step (11) was repeated several times.
(12) The solid oxide fuel cell with the gradient anode structure is prepared by adopting a high-temperature co-sintering method, wherein a temperature rise program firstly raises the temperature to 450 ℃ at a temperature rise rate of 1 ℃/min and maintains the temperature for 2h, then raises the temperature to 1050 ℃ at a temperature rise rate of 1 ℃/min and maintains the temperature for 4h, and then lowers the temperature to room temperature at a temperature drop rate of 2 ℃/min and cools the temperature, so that the solid oxide fuel cell with the gradient anode structure is obtained.
The solid oxide fuel cell prepared in this example includes an outer layer 5, a transition layer 4, an inner layer 3, an electrolyte layer 2, and a cathode layer 1, which are sequentially disposed. Fiber holes are distributed in the outer layer, fiber holes, ball holes and holes communicated with the fiber holes and the ball holes are distributed in the transition layer, and ball holes are distributed in the inner layer; the aperture of the fiber hole is 5-15 μm, the aperture of the ball hole is 10-60 μm, and the porosities of the outer layer, the transition layer and the inner layer are 35-45%, 25-35% and 15-25% in sequence. The thickness of the outer layer is 250 μm; the thickness of the transition layer is 150 μm; the thickness of the inner layer is 300 mu m; the thickness of the electrolyte layer is 20 μm; the thickness of the cathode layer was 20 μm.
Fig. 4 and 5 are electron micrographs of the gradient anode structure of the solid oxide fuel cell with the gradient anode structure according to the embodiment of the present invention corresponding to the schematic diagrams, wherein the three layers of the anode outer layer 5, the anode transition layer 4 and the anode inner layer 3 are well defined and are tightly combined.
Fig. 6 and 7 are electron micrographs of the anode outer layer 5 in the solid oxide fuel cell having a gradient anode structure according to the embodiment of the present invention, from which a large number of fibrous pore structures can be seen, the circular cross-sectional pore diameter of the fiber pores being 9 μm, and the porosity being 41% as measured.
Fig. 8 and 9 are electron micrographs of the anode transition layer 4 in the solid oxide fuel cell having the gradient anode structure according to the embodiment of the present invention, in which spherical pores and fibrous pores are mixed, and the porosity is measured to be 28%, and the fibrous pores are connected to the spherical pores, thereby combining the advantages of the two pore structures.
Fig. 10 and 11 are electron micrographs of the anode inner layer 3 in the solid oxide fuel cell having the gradient anode structure according to the embodiment of the present invention, in which the porosity is 19%, the pore diameter is 10 to 60 μm, and the entire pore structure is spherical, and the material strength is improved.
Example 2
A method for preparing a gradient structure and pore anode comprises the following steps:
(1) 4.5g of yttria-stabilized zirconia (YSZ) and 5.5g of nickel oxide (NiO) were weighed into a ball mill pot, 7.75mL of ethanol and 3.75mL of butanone were added and stirred, and 0.2mL of triolein was added thereto. Ball milling is carried out for 20h by a planetary ball mill, then the mixture is taken out, appropriate amount of 0.99g of polyvinyl butyral (PVB), 0.75g of polyethylene glycol (PEG) and 0.55mL of diethyl Phthalate (PHT) are weighed, and the mixture is fully stirred and then ball milled for 24h, then the mixture is taken out. 0.6g of micron carbon fiber is dispersed in 5mL of ethanol solution, and then the mixture is mixed with the slurry after ball milling, and the mixture is fully stirred until the viscosity is 5 pas, so that the slurry of the outer layer 5 of the anode is obtained.
(2) 4.5g of yttria-stabilized zirconia (YSZ) and 5.5g of nickel oxide (NiO) were weighed into a ball mill pot, 7.75mL of ethanol and 3.75mL of butanone were added and stirred, and 0.2mL of triolein was added thereto. Ball milling is carried out for 20h by a planetary ball mill, then the mixture is taken out, appropriate amount of 0.99g of polyvinyl butyral (PVB), 0.75g of polyethylene glycol (PEG) and 0.55mL of diethyl Phthalate (PHT) are weighed, and the mixture is fully stirred and then ball milled for 24h, then the mixture is taken out. 0.2g of micron carbon fiber and 0.4g of starch are dispersed in 5mL of ethanol solution, and then the mixture is mixed with the slurry after ball milling, and the mixture is fully stirred until the viscosity is 5 pas, so that the slurry of the anode transition layer 4 is obtained.
(3) 4.5g of yttria-stabilized zirconia (YSZ) and 5.5g of nickel oxide (NiO) were weighed into a ball mill pot, 7.75mL of ethanol and 3.75mL of butanone were added and stirred, and 0.2mL of triolein was added thereto. Ball milling is carried out for 20h by a planetary ball mill, then the mixture is taken out, appropriate amount of 0.99g of polyvinyl butyral (PVB), 0.75g of polyethylene glycol (PEG) and 0.55mL of diethyl Phthalate (PHT) are weighed, and the mixture is fully stirred and then ball milled for 24h, then the mixture is taken out. 0.375g of starch is dispersed in 5mL of ethanol solution, and then the mixture is mixed with the slurry after ball milling, and the mixture is fully stirred until the viscosity is 5 pas, so as to obtain the slurry of the inner layer 3 of the anode.
(4) And (3) carrying out vacuum defoaming on the slurry of the anode outer layer 5, the slurry of the anode transition layer 4 and the slurry of the anode inner layer 3 for 10min.
(5) On a polyester film carrier tape, respectively casting slurry of an anode outer layer 5, slurry of an anode transition layer 4 and slurry of an anode inner layer 3 on the surface of the carrier tape, standing the carrier tape for 24 hours, and separating a solidified ceramic slurry layer from the surface of the carrier tape.
(6) And stacking the slurry layer 3 of the anode inner layer, the slurry layer 4 of the anode transition layer and the slurry layer 5 of the anode outer layer in sequence, and applying pressure 5KPa to prevent the slurry layers from deforming. Then the temperature was raised from room temperature to 700 ℃ at a ramp rate of 1 ℃/min and maintained at this temperature for 60min, then raised to 1100 ℃ at a ramp rate of 2 ℃/min and maintained at this temperature for 2h, and then lowered to room temperature at a ramp rate of 2 ℃/min, completing the pressurized pre-sintering.
(7) Sintering the gradient anode by adopting a high-temperature co-sintering method, wherein a heating program firstly raises the temperature to 800 ℃ at a heating rate of 1 ℃/min and maintains the temperature for 1h, then raises the temperature to 1200 ℃ at a heating rate of 2 ℃/min and maintains the temperature for 2h, then raises the temperature to 1400 ℃ at a heating rate of 2 ℃/min and maintains the temperature for 4h, then lowers the temperature to 800 ℃ at a cooling rate of 2 ℃/min, and finally lowers the temperature to room temperature for cooling.
The gradient structure and pore anode prepared in this example includes an outer layer 5, a transition layer 4, and an inner layer 3, which are sequentially disposed. Fiber holes are distributed in the outer layer 5, fiber holes, ball holes and holes communicated with the fiber holes and the ball holes are distributed in the transition layer 4, and ball holes are distributed in the inner layer 3; the pore diameter of the fiber pores is 9 μm, the pore diameter of the ball pores is 10-60 μm, and the porosities of the outer layer 5, the transition layer 4 and the inner layer 3 are 41%, 28% and 19% in sequence. The thickness of the outer layer 5 is 250 μm; the thickness of the transition layer 4 is 150 μm; the thickness of the inner layer 3 is 300 mu m; the thickness of the electrolyte layer is 20 μm; the thickness of the cathode layer was 20 μm.
Comparative example 1
Comparative example 1 a solid oxide fuel cell having no gradient change in both porosity and pore structure was used, and was prepared as follows:
(1) 4.5g yttria-stabilized zirconia (YSZ) and 5.5g nickel oxide (NiO) were weighed into a ball mill jar, 7.75mL ethanol and 3.75mL butanone were added and stirred, and 0.2mL triolein was added thereto. Ball milling is carried out for 20h by a planetary ball mill, then the mixture is taken out, appropriate amount of 0.99g of polyvinyl butyral (PVB), 0.75g of polyethylene glycol (PEG) and 0.55mL of diethyl Phthalate (PHT) are weighed, and the mixture is fully stirred and then ball milled for 24h, then the mixture is taken out. Dispersing 0.375g of starch in 5mL of ethanol solution, then mixing with the slurry after ball milling, and fully stirring until the viscosity is 5 pas to obtain the anode slurry.
(4) And (4) carrying out vacuum defoaming on the anode slurry for 10min.
(5) On a polyester film carrier tape, anode slurry is cast on the surface of the carrier tape, then the carrier tape is kept still for 24 hours, and then the solidified ceramic slurry layer is separated from the surface of the carrier tape.
(6) 3 anode slurry layers were stacked and a pressure of 5KPa was applied to prevent the slurry layers from being deformed. Then, the temperature was raised from room temperature to 700 ℃ at a ramp-up rate of 1 ℃/min and maintained at this temperature for 60min, then raised to 1100 ℃ at a ramp-up rate of 2 ℃/min and maintained at this temperature for 2h, and then lowered to room temperature at a ramp-down rate of 2 ℃/min, completing the pressurized pre-sintering.
(7) Weighing 18.9g of terpineol and 1.1g of ethyl cellulose, mixing, heating to 80 ℃, stirring, adding 10.7g of YSZ after uniform mixing, ball-milling for 24 hours after uniform stirring, and then carrying out vacuum defoaming for 10min to obtain the compact electrolyte layer slurry.
(8) And (3) adsorbing the three-layer anode plate subjected to pressurized pre-sintering on a tray of a spin coater, dripping the compact electrolyte layer slurry on the surface of the three-layer anode plate to fully cover the three-layer anode plate, then operating at the rotating speed of 6000r/s for 40s, then heating to 80 ℃ and preserving heat for 20min, then heating to 450 ℃ and preserving heat for 20min, and repeating the step (8) for a plurality of times.
(9) Sintering the anode and the electrolyte by adopting a high-temperature co-sintering method, wherein a heating program firstly raises the temperature to 800 ℃ at a heating rate of 1 ℃/min and maintains the temperature for 1h, then raises the temperature to 1200 ℃ at a heating rate of 2 ℃/min and maintains the temperature for 2h, then raises the temperature to 1400 ℃ at a heating rate of 2 ℃/min and maintains the temperature for 4h, then lowers the temperature to 800 ℃ at a cooling rate of 2 ℃/min, and finally lowers the temperature to room temperature for cooling.
(10) Weighing 13.2g of terpineol and 0.77g of ethyl cellulose, mixing, heating to 80 ℃, stirring, adding 4g of YSZ and 4g of LSCF after uniform mixing, ball-milling for 24h after uniform stirring, and then carrying out vacuum defoaming for 10min to obtain cathode layer slurry.
(11) The cathode layer slurry was printed on top of the dense electrolyte layer using a screen printer and then dried at 80 ℃ for 20min, repeating step (11) several times.
(12) The solid oxide fuel cell is prepared by adopting a high-temperature co-sintering method, wherein a temperature rise program firstly raises the temperature to 450 ℃ at a temperature rise rate of 1 ℃/min and maintains the temperature for 2h, then raises the temperature to 1050 ℃ at the temperature rise rate of 1 ℃/min and maintains the temperature for 4h, and then lowers the temperature to room temperature at a temperature drop rate of 2 ℃/min and cools the temperature to obtain the solid oxide fuel cell.
Fig. 12 is a graph comparing the performance of examples and comparative examples of a solid oxide fuel cell of a gradient anode structure according to an embodiment of the present invention, both curves being measured at 800 c, hydrogen flow rate being 100sccm, and the other end of the cell being exposed to air using oxygen in air as an oxidizing gas. Fig. 12 shows that, compared to a conventional solid oxide fuel cell having no gradient change in porosity and pore structure, the solid oxide fuel cell having a gradient anode structure according to the embodiment of the present invention has a higher output voltage at the same current density, has a higher power density, reduces concentration polarization of the cell, and improves electrical properties of the cell. Meanwhile, the gradient structure, the porosity and the gradient pore structure are adopted, so that the porosity can be reduced in the inner layer of the anode, the spherical pores are used, and the strength of the battery is improved. Compared with the traditional anode supporting type solid oxide fuel cell, the gradient anode structure provided by the invention has more advantages.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.

Claims (15)

1. A gradient structure and pore anode, characterized by: the outer layer, the transition layer and the inner layer are sequentially arranged; the outer layer is distributed with fiber holes, part of the fiber holes extend to the surface of the outer layer, the transition layer is distributed with fiber holes, ball holes and holes communicated with the fiber holes and the ball holes, and the inner layer is distributed with ball holes; the porosity of the outer layer, the porosity of the transition layer and the porosity of the inner layer are sequentially decreased;
the preparation method of the gradient structure and the pore anode comprises the following steps:
(1) Mixing an organic solvent, anode ceramic powder, a dispersing agent, an adhesive, a plastic agent and a pore-forming agent to prepare slurry of each layer of the anode; wherein the content of the first and second substances,
the outer layer slurry adopts micron carbon fibers and carbon nanotubes as pore-forming agents, the inner layer slurry adopts spherical graphite and starch as pore-forming agents, and the transition layer slurry adopts a mixture of the outer layer pore-forming agents and the inner layer pore-forming agents;
(2) Carrying out vacuum defoaming on the outer layer slurry, the transition layer slurry and the inner layer slurry of the anode;
(3) Respectively casting the outer layer slurry, the transition layer slurry and the inner layer slurry of the anode on the surface of the PET film, standing for 22-26h, and separating the inner layer slurry layer, the transition layer slurry layer, the outer layer slurry layer and the PET film;
(4) Sequentially stacking an inner layer slurry layer, a transition layer slurry layer and an outer layer slurry layer, applying pressure of 3-10KPa for pre-sintering, and then performing high-temperature co-sintering to obtain the gradient structure and the pore anode; wherein the content of the first and second substances,
the pre-sintering is that the temperature is increased to 700-900 ℃ from the room temperature at the heating rate of 0.5-2 ℃/min, the temperature is maintained for 55-65 min, then the temperature is increased to 1000-1200 ℃ at the heating rate of 1-2 ℃/min, the temperature is maintained for 1-3 h, then the temperature is reduced to the room temperature at the cooling rate of 1-3 ℃/min, and the pressurization pre-sintering is completed;
the high-temperature co-sintering is to raise the temperature to 700-900 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 1-3 h, then raise the temperature to 1100-1300 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 1-3 h, then raise the temperature to 1300-1500 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 2-4 h, then lower the temperature to 700-900 ℃ at a cooling rate of 0.5-2 ℃/min, and finally lower the temperature to room temperature for cooling.
2. A gradient structure and pore anode according to claim 1, wherein: the thickness of the outer layer is 150-350 μm; the thickness of the transition layer is 50-250 μm; the thickness of the inner layer is 200-400 μm.
3. A gradient structure and pore anode according to claim 1, wherein: the outer layer, the transition layer and the inner layer have the porosity of 35-45%, 25-35% and 15-25% respectively.
4. A gradient structure and pore anode according to claim 1, wherein: the pore diameter of the fiber pores is 5-15 μm, and the pore diameter of the ball pores is 10-60 μm.
5. A gradient structure and pore anode according to claim 1, wherein: the anode comprises NiO and a ceramic substrate, wherein the mass fraction of the NiO is 45-65%.
6. A gradient structure and pore anode according to claim 5, wherein: the ceramic substrate is yttria-stabilized zirconia, scandia-stabilized zirconia, doped ceria or perovskite LaGaO 3 A base material.
7. A gradient structure and pore anode according to claim 1, wherein:
the organic solvent is at least one of a mixture of ethanol and butanone, a mixture of ethanol and trichloroethylene, a mixture of trichloroethylene and methyl ethyl ketone and terpineol;
the anode ceramic powder consists of NiO and a powdery ceramic base material, wherein the ceramic base material is yttria-stabilized zirconia, scandia-stabilized zirconia, doped ceria or perovskite LaGaO 3 A base material;
the dispersant is triolein and triethanolamine;
the adhesive is polyvinyl butyral and ethyl cellulose;
the plasticizer is a mixture of polyethylene glycol and diethyl phthalate.
8. A solid oxide fuel cell, characterized by: comprises an anode, an electrolyte and a cathode; wherein the anode is used as a support body, and the gradient structure and pore anode of any one of claims 1 to 7 are adopted; the battery comprises an outer layer, a transition layer, an inner layer, an electrolyte layer and a cathode layer which are arranged in sequence.
9. A solid oxide fuel cell according to claim 8, wherein: the thickness of the electrolyte layer is 10-100 μm; the thickness of the cathode layer is 10-100 μm.
10. A solid oxide fuel cell according to claim 8, wherein: the electrolyte layer is made of yttria-stabilized zirconia, scandia-stabilized zirconia, doped ceria and perovskite LaGaO 3 A base material.
11. A solid oxide fuel cell according to claim 8, wherein: the cathode layer is composed of (La) 0.8 Sr 0.2 ) 0.95 MnO 3-δ (LSM)、La 0.6 Sr 0.4 FeO 3-δ (LSF) or La 0.8 Sr 0.2 Cr 0.5 Fe 0.5 O 3-δ (LSCF) and a ceramic substrate, wherein the mass fraction of the ceramic substrate is 40-60%.
12. The method for producing a solid oxide fuel cell according to any one of claims 8 to 11, characterized in that: the method comprises the following steps:
(1) Mixing an organic solvent, anode ceramic powder, a dispersing agent, an adhesive, a plastic agent and a pore-forming agent to prepare slurry of each layer of the anode; the outer layer slurry adopts micron carbon fibers and carbon nanotubes as pore-forming agents, the inner layer slurry adopts spherical graphite and starch as pore-forming agents, and the transition layer slurry adopts a mixture of the outer layer pore-forming agents and the inner layer pore-forming agents;
preparing electrolyte layer slurry by mixing an organic solvent, electrolyte ceramic powder and an adhesive;
preparing cathode layer slurry by mixing an organic solvent, cathode ceramic powder and an adhesive;
(2) Carrying out vacuum defoaming on the outer layer slurry, the transition layer slurry and the inner layer slurry of the anode, the electrolyte layer slurry and the cathode layer slurry;
(3) Respectively casting the outer layer slurry, the transition layer slurry and the inner layer slurry of the anode on the surface of the PET film, standing for 22-26h, and separating the inner layer slurry layer, the transition layer slurry layer, the outer layer slurry layer and the PET film;
(4) Sequentially stacking the inner layer slurry layer, the transition layer slurry layer and the outer layer slurry layer, and applying pressure of 3-10KPa to perform pre-sintering; then spin-coating the electrolyte layer slurry on the anode inner layer slurry layer, and then carrying out primary high-temperature co-sintering on the four slurry layers;
(5) And coating the cathode layer slurry on the sintered compact electrolyte layer by using a screen printing method, and carrying out secondary high-temperature co-sintering to prepare the solid oxide fuel cell with the gradient anode structure.
13. The method of manufacturing a solid oxide fuel cell according to claim 12, wherein: the pre-sintering is that the temperature is increased to 700-900 ℃ from the room temperature at the heating rate of 0.5-2 ℃/min, the temperature is maintained for 55-65 min, then the temperature is increased to 1000-1200 ℃ at the heating rate of 1-2 ℃/min, the temperature is maintained for 1-3 h, then the temperature is reduced to the room temperature at the cooling rate of 1-3 ℃/min, and the pressurization pre-sintering is completed.
14. The method of manufacturing a solid oxide fuel cell according to claim 12, wherein: the first high-temperature co-sintering is to raise the temperature to 700-900 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 1-3 h, then raise the temperature to 1100-1300 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 1-3 h, then raise the temperature to 1300-1500 ℃ at a heating rate of 0.5-2 ℃/min, maintain the temperature for 2-4 h, then lower the temperature to 700-900 ℃ at a cooling rate of 0.5-2 ℃/min, and finally lower the temperature to room temperature for cooling.
15. The method of manufacturing a solid oxide fuel cell according to claim 12, wherein: the second high-temperature pre-sintering is to raise the temperature to 350-450 ℃ at the heating rate of 0.5-2 ℃/min, maintain the temperature for 1-3 h, raise the temperature to 900-1100 ℃ at the heating rate of 0.5-2 ℃/min, maintain the temperature for 2-4 h, and then lower the temperature to room temperature at the cooling rate of 0.5-2 ℃/min for cooling.
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JP2009059524A (en) * 2007-08-30 2009-03-19 Panasonic Corp Fuel cell, gas diffusion layer for the same, method of manufacturing the same
CN101894956A (en) * 2010-08-17 2010-11-24 哈尔滨工业大学 Method for preparing anode support with columnar orientation pores
CN108598493A (en) * 2018-06-04 2018-09-28 西安交通大学 A kind of solid oxide fuel cell gradient porosity anode and fuel cell

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