CN107180978B - Tubular solid oxide fuel cell anode support and preparation method thereof - Google Patents
Tubular solid oxide fuel cell anode support and preparation method thereof Download PDFInfo
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- CN107180978B CN107180978B CN201710254609.5A CN201710254609A CN107180978B CN 107180978 B CN107180978 B CN 107180978B CN 201710254609 A CN201710254609 A CN 201710254609A CN 107180978 B CN107180978 B CN 107180978B
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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
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a tubular solid oxide fuel cell anode support and a preparation method thereof, wherein the preparation method comprises the following steps: preparing slurry with anode powder uniformly dispersed; carrying out spray granulation on the obtained slurry to obtain modified anode powder; injecting the modified anode powder into a tubular mold, and demolding and molding after isostatic pressing to obtain a molded body; and sintering the obtained molded body to obtain the solid oxide tubular fuel cell anode support. The solid oxide tubular fuel cell anode support body is obtained through spray granulation, isostatic pressing and sintering, the production process is simple, the operability is strong, the process stability is good, the current collection of the obtained solid oxide tubular fuel cell anode support body is simple and convenient, the power loss is small, the electricity collecting material and a straight anode reaction area have a good physical binding surface, and the electron collection efficiency is greatly improved.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cell manufacturing, and particularly relates to a tubular solid oxide fuel cell anode support and a preparation method thereof.
Background
The Solid Oxide Fuel Cell (SOFC) is an all-solid-state energy conversion device based on ceramic materials, chemical energy in fuel is directly converted into electric energy through high-temperature electrochemical reaction, and a clean and efficient energy supply mode of the SOFC is an urgent need for solving urban energy and environmental problems in China. The distributed energy system based on the SOFC technology can realize efficient and clean heat supply and power supply, replaces the traditional urban energy supply mode, and leads the revolution of energy supply, production and consumption modes. The SOFC has the outstanding advantages of high efficiency, low pollution, low noise, modularization, small volume, high reliability, wide fuel adaptability and the like, is widely applied to aspects of large-scale distributed power stations, household combined heat and power systems, military portable power supplies and the like, and is also one of important technologies for realizing efficient and clean utilization of fossil energy such as coal, petroleum, natural gas and the like.
Solid oxide fuel cells have all-solid-state component characteristics, and their research direction has mainly focused on two structural types: tubular and flat. The flat-plate solid oxide fuel cell has higher volume power density and is usually used as a large-scale distributed power station. The tubular solid oxide fuel cell has the advantages of fast starting time, good thermal shock resistance and the like, and is an ideal structure developed as a portable power supply.
At present, the published patent application No. 200510101487.3 discloses a tapered tube type anode supporting solid oxide fuel cell single cell, the anode supporting body prepared by the method is in a tapered tube shape with one large end and one small end, so that sealing is easy to realize when the anode supporting body is connected in series, but current collection of the tube type cell anode prepared by the method is difficult; the invention patent with the patent number of 99108725.9 discloses a method for preparing an electrolyte thin tube by adopting a gypsum mold grouting method, wherein the uniformity and the suspension property of slurry in the grouting forming process greatly influence the quality of a grouting product, and the batch preparation consistency is poor; the invention patent of publication No. CN 2547010Y discloses an anode-supported tubular solid oxide fuel cell, which adopts an extrusion-molded special-shaped tubular anode support body with seven tubes inside, and the special-shaped structure increases the effective reaction area and improves the power density, but the complex structure has strict requirements on the mold design and the extrusion process, and the success rate cannot be ensured, and is not beneficial to the industrial production; the invention patent with publication number CN 1700494A discloses a method for dip forming a tubular solid oxide fuel cell, which introduces a method for adjusting the thickness of different functional structure layers by controlling the dipping times through the processes of material preparation, ball milling, vacuumizing, dipping, demoulding, presintering, sintering, pretreatment and the like, and the method has long preparation time and cannot meet the requirements of industrial production.
Disclosure of Invention
The invention aims to provide an anode support body of a tubular solid oxide fuel cell, the tubular solid oxide fuel cell comprising the anode support body and a preparation method thereof, aiming at the difficult problems of unstable preparation process, low yield, difficult anode electricity collection, large industrialization difficulty and the like of the tubular Solid Oxide Fuel Cell (SOFC) in the prior preparation technology.
In one aspect, the present invention provides a method for preparing an anode support of a tubular solid oxide fuel cell, comprising the following steps:
preparing slurry with anode powder uniformly dispersed;
carrying out spray granulation on the obtained slurry to obtain modified anode powder;
injecting the modified anode powder into a tubular mold, and demolding and molding after isostatic pressing to obtain a molded body;
and sintering the obtained molded body to obtain the solid oxide tubular fuel cell anode support.
The solid oxide tubular fuel cell anode support body is obtained through spray granulation, isostatic pressing and sintering, the production process is simple, the operability is strong, the process stability is good, the current collection of the obtained solid oxide tubular fuel cell anode support body is simple and convenient, the power loss is small, the electricity collecting material and a straight anode reaction area have good physical binding surfaces, and the collection efficiency of electrons is greatly improved; the electrochemical performance is good; the cost is low, the utilization rate of the anode support powder is improved to the maximum extent, and the cost of raw materials is reduced. Specifically, the method comprises the following steps: in the aspect of process, after grouting and dip forming, drying is needed, and the temperature and humidity of the environment are controlled, and after spray granulation, the direct isostatic compaction of solid particles is simpler and more efficient than the grouting and dip forming process; in the aspect of products, the materials after grouting and dip forming have low strength, are easy to deform and wrinkle, and have high strength after isostatic pressing forming, and meanwhile, the rigid core rod in the die ensures that the inner surface of the tubular blank has good roundness and straightness, and the tubular blank is better attached to an anode charge collecting layer and more convenient to prepare; in the aspect of cost, the raw material loss is inevitably generated by the processes of ball milling, filtering, defoaming and the like during the preparation of the slurry or pug for grouting and dipping, the loss of the spray granulation preparation process is relatively small, and the cost is lower.
Preferably, the slurry comprises: the anode powder, the adhesive, the dispersant and the pore-forming agent are mixed according to the following ratio:
anode powder: 100 parts by mass;
pore-forming agent: 0 to 20 parts by mass;
adhesive agent: 1-10 parts by mass;
dispersing agent: 1 to 5 parts by mass.
Preferably, the solvent of the slurry is water, and the solid content of the slurry is 50-60 wt%.
Preferably, the anode powder is a mixed powder of NiO and yttrium-stabilized zirconia or a mixed powder of NiO and scandium-stabilized zirconia;
the pore-forming agent is wheat flour or graphite powder;
the binder is polyvinyl alcohol;
the dispersant is triethanolamine.
Preferably, the temperature of spray granulation is 0 to 250 ℃, preferably 100 to 250 ℃, and more preferably 120 to 180 ℃.
Preferably, the working medium used for isostatic pressing is hydraulic oil, the pressure is 160-200 MPa, and the pressure maintaining time is 15-60 minutes.
Preferably, the sintering temperature is 800-1000 ℃, and the heat preservation time is 1-3 hours.
Preferably, the tubular mold comprises:
the flexible sleeve is open at one end and closed at the other end;
the rigid core rod is arranged inside the flexible sleeve in a coaxial mode with the flexible sleeve, and a material injection cavity is formed between the rigid core rod and the flexible sleeve; and
and the material injection member is arranged at the opening end of the flexible sleeve and fixes the rigid core rod, and the material injection member is provided with a material injection hole for injecting materials into the material injection cavity.
According to the tubular mold, the material injection hole can be used for injecting powder into the material injection cavity. The flexible sleeve can be automatically separated from the outer surface of the blank after isostatic pressing, so that the demoulding is convenient and fast. The rigid core rod in the die ensures that the inner surface of the tubular blank has good roundness and straightness, and the tubular blank is better attached to the anode charge collecting layer and more convenient to prepare.
Preferably, the closed end of the flexible sleeve is a hemispherical end socket, and the tip end of the rigid core rod close to the closed end of the flexible sleeve is hemispherical. Thus, a tubular support body having one end closed by a hemispherical surface can be prepared.
Preferably, the flexible sleeve is made of a soft rubber or silicone rubber material. The soft rubber or silicon rubber material has good elastic memory performance, is more beneficial to the automatic separation of the isostatic pressing and the outer surface of the blank, and leads the demoulding to be more convenient and faster.
Preferably, the thickness of the flexible sleeve is 5-10 mm. The flexible sleeve with a certain thickness can keep good demoulding performance and simultaneously ensure the straightness and roundness of the blank.
Preferably, the rigid core rod is made of a zirconia material. In this way, the molding process can be made free of contamination.
Preferably, the rigid core rod is a polished rigid core rod. This ensures that the inner wall of the anode support remains straight while maintaining good release properties.
Preferably, the material injection member is formed in an annular shape, and the material injection holes are formed in a plurality of numbers and are uniformly distributed on the annular material injection member. Therefore, the loose packing density of the powder in the material injection cavity can be kept uniform, the outer surface has better roundness after isostatic pressing, and a good foundation is provided for the subsequent preparation of a compact electrolyte thin layer.
Preferably, the number of the material injection holes is 3-5. Thus, the apparent density of the powder in the material injection cavity can be kept uniform.
In a second aspect, the present invention provides a method for preparing a tubular solid oxide fuel cell, comprising the steps of:
preparing an anode support of the solid oxide tube type fuel cell according to the preparation method;
soaking the obtained anode support body in electrolyte slurry, drying and sintering to obtain a solid oxide tubular fuel half cell;
and (3) soaking the obtained half cell in a cathode material, drying and sintering to obtain the solid oxide tubular fuel cell.
In a third aspect, the present invention provides a tubular solid oxide fuel cell anode support prepared according to the above preparation method.
In a fourth aspect, the present invention provides a tubular solid oxide fuel cell, which comprises, in order from inside to outside: the tubular solid oxide fuel cell comprises an anode support, an electrolyte layer and a cathode layer.
Drawings
Fig. 1 is a structural sectional view of a molding die for manufacturing an anode support of a tubular fuel cell according to the present invention, in which:
1 flexible sleeve (outer die sleeve), 2 core rod, 3 material injection cavity, 4 material injection ring and 5 material injection hole;
FIG. 2 is a schematic view of the anode support of a tubular fuel cell prepared according to the present invention, wherein (a) is a physical diagram and (b) is a schematic cross-sectional structural diagram;
FIG. 3 is a schematic diagram of a tubular fuel cell made in accordance with the present invention;
FIG. 4 is a pictorial view of an anode-supported tubular fuel cell made in accordance with the present invention;
FIG. 5 is a scanning electron microscope image of the microstructure of the anode-supported tubular cell;
FIG. 6 is a view of a test object in a furnace of the anode-supported tubular cell;
FIG. 7 is an I-V-P curve of the above tubular cell at various temperatures;
FIG. 8 is an EIS curve of the tubular cell at different temperatures;
FIG. 9 is a V-t curve of constant current discharge of the above tubular battery
FIG. 10 is a comparison of the performance of anode supports made by different forming processes;
FIG. 11 is a comparison of impedance spectra of anode supports prepared by different forming processes;
FIG. 12 is an I-V-P curve of a battery test under different pore former contents of anode powder;
FIG. 13 is EIS curves of cell tests with different pore former contents for anode powders.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting.
The solid oxide tubular fuel cell anode support is obtained through spray granulation, isostatic pressing and sintering. The production method of the present invention will be specifically described below as an example.
First, a slurry in which anode powder is uniformly dispersed (anode powder slurry) is prepared. In the present invention, the anode powder may be any anode material powder suitable for a tubular solid oxide fuel cell, and for example, nickel oxide (NiO) and yttrium-stabilized zirconia (YSZ) (the molar doping amount of yttrium is 3% to 10%) may be mixed, or nickel oxide (NiO) and scandium-stabilized zirconia (ScSZ or SSZ) (the molar doping amount of scandium is 0% to 15%) may be mixed. The mass percentage of the nickel oxide (NiO) can be 30-70%.
The slurry may also contain a pore-forming agent. The pore-forming agent is wheat flour or graphite powder, for example. The mass portion of the pore-forming agent is generally within 20 percent. Within the range of 20%, the more pore-forming agent content, the better. The pore-forming agent generates pores after being completely combusted in the sintering process so as to increase the three-phase reaction interface area of the anode functional layer and improve the diffusion speed and the electrochemical reaction rate of gas.
The slurry may also contain a binder, such as polyvinyl alcohol (PVA). The mass portion of the binder is generally 1 to 10 percent. The binder is used for resisting intermolecular resistance in the forming process, so that the forming is easier, and simultaneously, the formed blank keeps the space geometry.
The slurry may also contain a dispersant such as triethanolamine. The mass portion of the dispersant is generally 1 to 5 percent. The dispersant keeps good uniformity of the aqueous solution in the process of preparing the mixed powder into the aqueous solution.
The solvent of the slurry can be water or alcohol, so that the use of an organic solvent can be avoided, the preparation environment is healthy and environment-friendly, and the cost is low. The solid content of the slurry is generally controlled to be 50-60%, so that the slurry can be ensured to have good fluidity, the spray gun of a spray granulation dryer is prevented from being blocked, and granulation and molding are easy to realize.
In one example, the slurry is formulated by: the mixed powder material (anode powder) of the fuel cell anode, the pore-forming material (pore-forming agent), the binder and the dispersant are uniformly mixed according to the proportion (for example, uniformly mixed by a mortar) to obtain an anode mixed powder material, and the anode mixed powder material is prepared into an aqueous solution by pure water. The anode mixed powder comprises the following components in percentage by weight:
100 parts by mass of anode powder
0 to 20 parts by mass (preferably not 0)
1 to 10 parts by mass of an adhesive
1-5 parts by mass of a dispersant.
And then, carrying out spray granulation on the anode powder slurry by using a high-temperature spray granulator to obtain the modified anode mixed powder. The working temperature range of the high-temperature spray granulator is 0-250 ℃, preferably 100-250 ℃, more preferably 120-180 ℃, for example 150 ℃. In the working temperature range, the solvent can be quickly evaporated, and simultaneously the vaporific slurry can be quickly formed. The slurry spraying speed of the spray granulator can be 0-100 ml/min (preferably not 0), and preferably 20-30 ml/min. By spray granulation, a mixed powder having a concentrated particle size distribution and good fluidity can be obtained. In the present invention, the particle size of the mixed powder may be 1 to 100. mu.m.
Injecting the modified anode mixed powder into a tubular mold, vibrating and filling, pressurizing by an isostatic press, and demolding and molding.
Fig. 1 shows a sectional view of an exemplary structure of a tubular mold. As shown in fig. 1, the mold comprises a flexible sleeve 1 which is open at one end and closed at the other end. The rigid core rod 2 is arranged inside the flexible sleeve 1 and forms a material injection cavity 3 with the flexible sleeve 1. The rigid core rod 2 is arranged coaxially with the flexible sleeve 1 and its tip end is at a distance from the closed end of the flexible sleeve 1. The base end of the rigid core rod 2 is close to the open end of the flexible sleeve 1. The injection member, which may be formed in a ring shape, i.e., the injection ring 4 shown in fig. 1, is provided at the open end of the flexible sleeve 1 and fixes the base end of the rigid core rod 2. That is, the mold is assembled from a flexible sleeve 1 and a rigid core rod 2 through an injection ring 4. The material injection ring 4 is provided with a material injection hole 5 for injecting materials into the material injection cavity.
As shown in fig. 1, the flexible sleeve 1 may be cylindrical, and the closed end thereof may be a hemisphere surface. The rigid mandrel 2 may be cylindrical and its tip may also be hemispherical. Therefore, the material injection cavity 3 can be formed into a U-shaped cross section, and the formed blank is in a cylindrical tube shape with one hemispherical end closed and the other end open. The size of the material injection cavity 3 can be changed by adjusting the sizes of the flexible sleeve 1 and the rigid core rod 2, so that the size of the formed blank body can be adjusted.
The flexible sleeve 1 can be made of elastic material, such as soft rubber or silicon rubber material, and has good elastic memory performance, and can be automatically separated from the outer surface of a blank after isostatic pressing, so that demoulding is convenient and rapid. The thickness of the flexible sleeve 1 can be 5-10 mm.
The rigid core rod 2 may be made of a ceramic material, preferably a zirconia material, so that the forming process does not cause contamination. The rigid mandrel bar 2 is preferably polished to ensure that the inner wall of the anode support remains straight while maintaining good releasability.
The material injection ring 4 may be made of metal. The injection ring 4 is detachably arranged at the open end of the flexible sleeve 1. The base end of the rigid mandrel 2 may be fixed to the shot ring 4, or may be detachable therefrom. For example, the shot ring 4 may be engaged with the base end of the rigid core rod 2 and the open end of the flexible sleeve 1. The material injection ring 4 is provided with a material injection hole 5 communicated with the material injection cavity 3 so as to inject the material to be molded, such as powder, into the material injection cavity 3. The material injection holes 5 are preferably uniformly distributed in a plurality, for example, 3-5, more specifically, 4, so that the loose packing density of powder in the material injection cavity can be kept uniform, the outer surface has better roundness after isostatic pressing, and a good foundation is provided for the subsequent preparation of a compact electrolyte thin layer. The aperture of the material injection hole 5 can be 2-5 mm.
By utilizing the tubular mold, the prepared anode support body has simple and convenient current collection and small power loss, and the electricity collecting material and a straight anode reaction area have good physical binding surfaces, so that the collection efficiency of electrons is greatly improved; the electrochemical performance is good; the cost is low, the utilization rate of the anode supporting powder is improved to the maximum extent, and the cost of raw materials is reduced; the production process is simple, strong in operability and good in process stability.
After the mould is filled with the anode mixed material and is filled in a vibrating way, the mould is exhausted by a plastic bag and then is wrapped by a plurality of layers to prevent a hydraulic medium from permeating.
The working medium of the isostatic press may be hydraulic oil. The working pressure of the isostatic press can be 160-200 MPa, for example 200MPa, the pressure can completely break the powder particles, and the formed blank has good strength. The working temperature of the isostatic pressing machine can be 10-35 ℃. The pressure can be applied to the working pressure in a slope mode, for example, 10-15 MPa/min. The pressure can be maintained at the working pressure for 30-60 minutes, such as 30 minutes. And (4) removing the pressure and demoulding to obtain the tubular solid oxide fuel cell anode support body blank. Fig. 2 shows a photograph and a schematic cross-sectional view of the anode support blank of the tubular solid oxide fuel cell of the present invention after being demolded, and it can be seen that the support blank has a cylindrical appearance, one end of which is closed by a hemispherical surface and the other end of which is open.
And supporting the obtained blank by using an alumina tube, horizontally putting the blank into a muffle furnace (such as a high-temperature muffle furnace at 1200 ℃), and pre-sintering at 800-1000 ℃ for 1-3 hours to obtain the molded tubular solid oxide fuel cell anode support.
The obtained tubular solid oxide fuel cell anode support body is of a tubular structure with one end closed and the other end open, and the thickness of the anode support tube is generally 200-2000 mu m. The thickness is adjustable, the total amount of the powder filled is controlled by changing the space between the flexible sleeve and the rigid core rod, namely the thickness of the anode supporting tube is adjusted by matching the flexible outer die sleeves with different sizes and the rigid core rod.
And preparing an electrolyte layer and a cathode layer on the basis of the tubular solid oxide anode support body, thus preparing the anode-supported tubular solid oxide fuel cell.
For example, the tubular solid oxide fuel cell anode support may be impregnated with an electrolyte slurry such as Yttrium Stabilized Zirconia (YSZ) (the molar doping amount of yttrium is 3% to 8%) or scandium stabilized zirconia (ScSZ), dried, and then sintered at 1350 to 1450 ℃ for 2 to 4 hours (e.g., 4 hours) to form a tubular fuel cell half cell with a bright surface.
The half cell can be impregnated with a porous cathode material of lanthanum strontium manganese (La)0.75Sr0.25)0.95MnO3(LSM) or Lanthanum Strontium Gallium Magnesium (LSGM), drying, keeping the temperature at 1150-1200 ℃ for 2-3 hours (for example 2 hours), and sintering to obtain the tubular solid oxide fuel cell unit.
Fig. 3 shows a structural diagram of a tubular solid oxide fuel cell (single cell) of the present invention, which is an anode support layer, an electrolyte layer, and a cathode layer in this order from inside to outside. Fuel gas may be passed into the anode support layer from an open end thereof. The anode support body prepared by the method has better roundness, and is beneficial to preparing a compact electrolyte thin layer on the anode support body.
The tubular solid oxide fuel cell unit cell of the present invention can be used for an integrated tubular stack or a tubular fuel cell system.
According to the invention, an isostatic pressing forming process is adopted, powder with good forming performance, namely good fluidity and crushing performance, is prepared through spray granulation, uniform density and convenient demolding can be ensured through a proper forming die, and finally an excellent forming effect is realized through isostatic pressing process control. Compared with the prior art, the invention has the advantages that: the current collection is simple and convenient, the power loss is small, the electricity collecting material and a straight anode reaction area have good physical binding surfaces, and the collection efficiency of electrons is greatly improved; the electrochemical performance is good; the cost is low, the utilization rate of the anode supporting powder is improved to the maximum extent, and the cost of raw materials is reduced; the production process is simple, strong in operability and good in process stability.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1: preparation and performance characterization of anode support tube type solid oxide fuel cell
Mixing powder (NiO and 8YSZ), PVA, triethanolamine and graphite powder of the anode of the fuel cell according to the mass ratio of 100: 10: 3: 10, after being uniformly mixed, preparing a slurry suspension with pure water, wherein the solid content of the slurry suspension is 60%; spraying and granulating the anode powder slurry by using a high-temperature spray granulator, setting the working temperature of a spray dryer to be 180 ℃, setting the spraying speed of the slurry to be 20ml/min, granulating to obtain modified anode mixed powder, and testing the particle size distribution of the modified anode mixed powder to be 1-10 mu m by using an electron scanning microscope; injecting the anode granulation powder into a tubular mold, filling the tubular mold, vibrating and beating the mold, performing isostatic pressing, loading the pressure of the isostatic pressing machine to 200MPa at a pressurizing rate of 10MPa/min, maintaining the pressure for 30 minutes, removing the pressure, and demolding to obtain a tubular solid oxide fuel cell anode support body blank; and (3) putting the blank into a muffle furnace, pre-sintering at 1000 ℃ for 2 hours to obtain a solid oxide fuel cell anode support body with one end closed and the other end open, and measuring the thickness of the anode support tube to be 1200 mu m.
Coating a layer of ScSZ electrolyte slurry on the obtained anode support body by using a dipping method, drying, putting the anode support body into a muffle furnace, preserving heat for 3 hours at 1400 ℃, and sintering to obtain a tubular fuel cell half cell with a bright surface; then impregnating porous cathode material lanthanum strontium manganese (La)0.75Sr0.25)0.95MnO3(LSM) and finally preparing the tubular solid oxide fuel single cell.
Fig. 4 is a diagram of a microtube type anode-supported tube type single cell prepared in this embodiment, and it can be seen that the microtube type cell prepared by the method has good linearity and good process stability, and is suitable for mass production; fig. 5 is a scanning electron microscope image of the cross section microstructure of the anode-supported tubular single cell prepared in this embodiment, and it can be seen that the tubular cell has a multilayer structure along the thickness direction, and the anode-supported layer, the electrolyte layer, and the cathode layer are sequentially arranged from left to right.
Performing electrochemical performance characterization according to a universal test method of the tubular cell, wherein the cathode side electricity collecting material is a silver mesh&Platinum paste, NiO paste and nickel felt on the anode side, and the in-furnace test condition of the anode-supported tubular cell is shown in FIG. 6; the test conditions are 100sccm hydrogen and 200sccm air, the test is carried out at 850 ℃, 800 ℃ and 750 ℃, the electrochemical performance is shown in figure 7, and the alternating current impedance spectrum is shown in figure 8; then, the stability of the tubular cell was examined by selecting a constant current mode at 750 ℃ and setting the current density at 187mA cm-2The voltage change with time is shown in fig. 9.
The test results of this example show that: the output power at 850, 800 and 750 ℃ is 225, 200 and 175mW cm respectively-2Ohmic impedances of 0.55, 0.65 and 0.75. omega. cm2Polarization impedances 3.50, 3.65, 2.75. omega. cm2The good stability was maintained under the constant current load condition for a long period of time, and the result indicates that the process for preparing the anode support of this example was effective. The preparation process of the tubular anode support is stable and easy to industrialize, the micro-tubular battery prepared by the method can be used for a portable power system, and the prepared large-size tubular battery is suitable for a distributed power generation system.
Example 2: the performance comparison of the tubular anode supported battery prepared by the extrusion, impregnation and isostatic pressing method is that the mixed powder (NiO and 8YSZ), PVA, triethanolamine and graphite powder of the anode of the fuel battery are mixed according to the mass ratio of 100: 10: 3: 10, uniformly mixing, taking three parts with equal mass, preparing a tubular anode support body respectively according to the modes of extrusion, impregnation and isostatic pressing, namely preparing pug, then carrying out extrusion forming, preparing slurry, then carrying out lifting, impregnation, drying and forming, carrying out spray granulation, then carrying out isostatic pressing (see example 1), adjusting the size and the thickness of an anode support blank by controlling the size of an extrusion die head, the impregnation frequency and the size of an isostatic pressing die so as to enable blanks obtained by the three methods to be consistent in size and thickness (taking three blanks with consistent size and thickness respectively), putting the blanks into a muffle furnace, pre-sintering for 2 hours at 1000 ℃ to obtain the solid oxide fuel cell anode support body with one end closed and the other end open, and selecting the anode support blanks with the thickness of about 800 mu m prepared by the methods respectively to carry out subsequent comparison experiments.
Respectively coating a layer of ScSZ electrolyte slurry on the three anode supports by using a dipping method, drying, putting the dried ScSZ electrolyte slurry into a muffle furnace, preserving heat for 3 hours at 1400 ℃, and sintering to form a tubular fuel cell half cell with a bright surface; then respectively impregnating porous cathode materials with lanthanum strontium manganese (La)0.75Sr0.25)0.95MnO3(LSM) and finally preparing the tubular fuel cell unit cells with three different anode forming modes.
The electrochemical performance characterization of the three tubular batteries is respectively carried out according to a general test method of the tubular batteries, wherein the electricity collecting materials on the anode side are NiO slurry and nickel felt, the cathode side is silver mesh and platinum slurry, the test conditions are 100sccm hydrogen and 200sccm air, the test is respectively carried out at the temperature of 750 ℃, the electrochemical performance pair chart is shown in figure 10, and the electrochemical alternating current impedance spectrum comparison is shown in figure 11.
The results of this example show that: the output power of the anode supporting tube type fuel cell prepared by isostatic pressing, extrusion and dipping process forming modes at 750 ℃ is 328, 280 and 240mW cm-2Ohmic impedance: 0.55, 0.70, 0.8. omega. cm2The tubular battery anode receives electricity and realizes current conduction through the contact of the foam nickel inserted into the tube and the anode surface, and the ohmic resistance is subtracted from the ohmic resistance of the electrolyte layer to be regarded as the contact resistance, so that the contact resistance is sequentially from large to small: dipping forming, extrusion forming and spray granulation forming. Because the shape retention capacity of the anode support body prepared by dip forming is poor, the strength of the anode support body blank prepared by extrusion forming is poor, the bending strength of the isostatic pressing forming blank prepared by the invention is about 0.3MPa, and the dip forming and the extrusion forming are carried outThe strength of the blank is poor, the strength of the blank is at least one magnitude different from that of the isostatic pressing blank, and the tubular battery prepared by the method has good straightness and roundness, so that the electricity-receiving nickel felt can be smoothly inserted into a tube, good contact between the foamed nickel and the whole anode surface is ensured, and larger contact resistance is caused by poor contact; therefore, the isostatic pressing is more efficient in electricity collection and excellent in electrochemical performance than the tubular fuel cell prepared by the extrusion and dip forming process.
Example 3: comparing the performances of the anode-supported tubular solid oxide fuel cell under different pore-forming agent contents, namely mixing powder (NiO and 8YSZ), PVA, triethanolamine and graphite powder of the anode of the fuel cell according to the mass ratio of 100: 10: 3: 12, uniformly mixing to obtain an anode mixed powder sample I, and mixing the anode mixed powder sample I with the anode mixed powder sample I according to the mass ratio of 100: 10: 3: 8, uniformly mixing to obtain a second anode mixed powder sample, and respectively preparing slurry suspension with the solid content of 60% by using pure water; respectively carrying out spray granulation on the anode powder slurry by using a high-temperature spray granulator, setting the working temperature of a spray dryer to be 180 ℃, setting the spraying speed of the slurry to be 25ml/min, respectively granulating to obtain two modified anode mixed powder materials, and testing by using an electron scanning microscope that the particle sizes of the two modified anode mixed powder materials are uniformly distributed in a range of 1-10 mu m; respectively injecting the anode granulation powder into tubular molds with the same specification, filling the tubular molds with the anode granulation powder, performing isostatic pressing after full shaking, loading the powders to 200MPa at a pressurization rate of 10MPa/min by using an isostatic pressing machine, maintaining the pressure for 30 minutes, and demolding after pressure is removed to obtain a tubular solid oxide fuel cell anode support body blank; and (3) putting the two blank samples into a muffle furnace, pre-burning for 2 hours at 1000 ℃ to obtain two solid oxide fuel cell anode support bodies, and testing the thickness of the anode support tube to be about 1000 mu m.
Coating a layer of ScSZ electrolyte slurry on the obtained anode support by using an immersion method, drying, putting the anode support into a muffle furnace, preserving heat for 3 hours at 1400 ℃, and sintering to obtain a tubular fuel cell half cell with a bright surface; then impregnating porous cathode material lanthanum strontium manganese (La)0.75Sr0.25)0.95MnO3(LSM) to finally prepare two tubular solid oxide fuel cell single cells, namely: the mass ratio of the pore-forming agent is 12% of that of the sample I, and the mass ratio of the pore-forming agent is 8% of that of the sample II.
The electrochemical performance characterization is carried out according to the test method commonly used for tubular batteries, the electrochemical performance of two samples is shown in figure 12, and the alternating current impedance spectroscopy test result is shown in figure 13.
The results of this example show that: the output power of a sample I with the pore-forming agent mass ratio of 12 percent and a sample II with the pore-forming agent mass ratio of 8 percent are respectively 300 mW and 255mW cm-2The ohmic impedance and the polarization impedance are respectively: 0.70, 0.71. omega. cm2The ohmic resistance is basically close to be consistent with the electrolyte preparation process and the test electricity receiving process, and the polarization impedance is respectively as follows: 1.50, 1.70. omega. cm2The method has the advantages that the pore-forming agent generates pores after the sintering process, the content of the pore-forming agent is increased, namely the three-phase reaction interface area of the anode functional layer is increased, and the diffusion speed and the electrochemical reaction rate of gas are improved, so that the higher content of the pore-forming agent has smaller polarization impedance, and the beneficial effect is better output performance, therefore, the method is an effective forming method of the tubular cell anode support.
Claims (10)
1. A preparation method of a tubular solid oxide fuel cell anode support body is characterized by comprising the following steps:
uniformly mixing mixed anode powder of a fuel cell anode, a pore-forming agent, a binder and a dispersing agent according to a ratio to obtain an anode mixed powder material, and preparing slurry in which the anode powder is uniformly dispersed by using a solvent, wherein the mixed anode powder is mixed powder of NiO and yttrium-stabilized zirconia or mixed powder of NiO and scandium-stabilized zirconia, and the pore-forming agent is wheat flour or graphite powder; the slurry comprises: the anode powder, the adhesive, the dispersant and the pore-forming agent are mixed according to the following ratio: anode powder: 100 parts by mass of a pore-forming agent: 0 to 20 parts by mass and not 0, adhesive: 1-10 parts by mass of a dispersant: 1-5 parts by mass;
carrying out spray granulation on the obtained slurry to obtain modified anode powder;
injecting the modified anode powder into a tubular mold, and demolding and molding after isostatic pressing to obtain a molded body;
and sintering the obtained molded body to obtain the solid oxide tubular fuel cell anode support.
2. The method according to claim 1, wherein the solvent of the slurry is water, and the solid content of the slurry is 50 to 60 wt%.
3. The production method according to claim 1 or 2, characterized in that the binder is polyvinyl alcohol; the dispersant is triethanolamine.
4. The method according to claim 1 or 2, wherein the temperature of the spray granulation is 0 to 250 ℃.
5. The method according to claim 4, wherein the temperature of the spray granulation is 120 to 180 ℃.
6. The preparation method according to claim 1 or 2, wherein the working medium used for isostatic pressing is hydraulic oil, the pressure is 160 to 200MPa, and the pressure maintaining time is 15 to 60 minutes.
7. The method according to claim 1 or 2, wherein the sintering temperature is 800 to 1000 ℃ and the holding time is 1 to 3 hours.
8. A method for preparing a tubular solid oxide fuel cell, comprising the steps of:
preparing a solid oxide tube fuel cell anode support according to the production method of any one of claims 1 to 7;
soaking the obtained anode support body in electrolyte slurry, drying and sintering to obtain a solid oxide tubular fuel half cell;
and (3) soaking the obtained half cell in a cathode material, drying and sintering to obtain the solid oxide tubular fuel cell.
9. A tubular solid oxide fuel cell anode support prepared according to the preparation method of any one of claims 1 to 7.
10. A tubular solid oxide fuel cell, comprising in order from the inside to the outside: the tubular solid oxide fuel cell anode support of claim 9, an electrolyte layer, and a cathode layer.
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