CN109904497B - Anti-carbon-deposition metal-supported solid oxide fuel cell and preparation method thereof - Google Patents
Anti-carbon-deposition metal-supported solid oxide fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of solid oxide fuel cells, and discloses an anti-carbon deposition metal support solid oxide fuel cell and a preparation method thereof. The battery comprises a porous catalytic reforming layer, a porous metal supporting layer, a porous anode functional layer, a compact electrolyte layer and a porous cathode layer which are tightly combined in sequence, wherein the porous catalytic reforming layer comprises Ni-M alloy and oxygen storage-water absorption oxide; the porous metal support layer comprises a Ni-M alloy and MgO; the porous anode functional layer comprises Ni-M alloy and fluorite structure oxide or Ni-M alloy and (ion conduction type) perovskite structure oxide. The invention also discloses a preparation method of the corresponding battery. The fuel cell of the invention can stably run in hydrocarbon fuel for a long time when the hydrocarbon is used as the fuel, has low cost of the preparation process, is suitable for large-area single cells and large-scale production and manufacture, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to an anti-carbon deposition metal support solid oxide fuel cell and a preparation method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is an electrochemical device that converts chemical energy in fossil fuels (coal, oil, natural gas, and other hydrocarbons) directly into electrical energy. The SOFC has the advantages of high efficiency, environmental protection, silence, modularization and the like, has wide application prospects in the fields of fixed power stations, mobile transportation, military and the like, and has great significance in relieving energy crisis, meeting the requirements of human beings on the quantity and quality of electric power, protecting the living environment of human beings and the like when being successfully applied.
The structural types of conventional SOFC single cells typically include electrolyte-supported (ES-SOFC), cathode-supported (CS-SOFC), and anode-supported (AS-SOFC). In the above structures, the ceramic or cermet materials that provide the mechanical support, while being highly corrosion resistant at high temperatures, are susceptible to structural failure when subjected to stress, shock, vibration, and rapid thermal cycling. With the development of low temperature in SOFCs, inexpensive stainless steel materials have been used as connectors in SOFC stacks, and also metal materials can be used as supports for SOFCs. Metal supported SOFCs (MS-SOFCs), referred to as third generation SOFC technologies, have significant advantages over electrolyte supported and electrode supported SOFCs in terms of cost, fabrication, mechanical strength and durability: (1) the metal material with lower cost is used as the support body, so that the cost of the SOFC is greatly reduced; (2) the mechanical strength of the SOFC can be effectively improved, and the single cell and the cell stack bear stronger impact, vibration or mechanical load; (3) the improvement of the strength of the single cell is also beneficial to improving the processability of the single cell, and can bear violent or quick operation and processing; (4) the MS-SOFC has better oxidation reduction and thermal cycling performance, and the good thermal cycling performance can realize the quick start and stop of the SOFC.
MS-SOFC was first reported from the 60 s of the last century, and has attracted attention again to the middle of the 90 s, and has been studied and developed for nearly 20 years to date. The MS-SOFC technology is gradually improved, especially along with the low temperature of the SOFCThe development of the technology has more prominent advantages and is gradually becoming one of the research hotspots in the field of SOFCs. In recent years, many international research institutes have been working on the problems of metal oxidation, element diffusion, electrode poisoning, single cell preparation, and the like in MS-SOFC. However, the current research on MS-SOFCs is mainly limited to H2MS-SOFCs are not commonly studied for the fuel stage, using hydrocarbons as fuel. The direct use of hydrocarbons as fuel of SOFC can reduce the system complexity and expensive production cost caused by external reforming of fuel, and can avoid the technical difficulties in storage and transportation of fuel, which is beneficial to commercialization of SOFC technology, and is a hot spot and main attack direction in current SOFC technology research.
However, like other SOFCs, the problem of anode carbon deposition caused by using hydrocarbons as fuel is a critical problem to be solved in MS-SOFCs. On one hand, the carbon deposition can block the diffusion of fuel gas in the anode, reduce the active reaction area of the anode functional layer and enable the performance of the anode to be attenuated until the anode completely fails; on the other hand, carbon deposition can also cause pulverization of the metal support body, and destroy the structure of a single cell.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention provides an anti-carbon deposition metal-supported solid oxide fuel cell and a preparation method thereof, which aims to solve the problem that the metal-supported solid oxide fuel cell is easy to generate carbon deposition when using hydrocarbon as fuel, so that the metal-supported solid oxide fuel cell can stably operate in the hydrocarbon fuel for a long time.
In order to achieve the above object, according to one aspect of the present invention, there is provided an anti-carbon deposition metal supported solid oxide fuel cell, characterized by comprising a porous catalytic reforming layer, a porous metal support layer, a porous anode functional layer, a dense electrolyte layer and a porous cathode layer, which are closely combined in this order, wherein,
the porous catalytic reforming layer comprises a Ni-M alloy and an oxygen storage-water absorption oxide;
the porous metal support layer comprises a Ni-M alloy and MgO;
the porous anode functional layer comprises Ni-M alloy and fluorite structure oxide or Ni-M alloy and ion conductive perovskite structure oxide;
wherein the M element is one or more of Fe, Co, Cu and Sn.
Further, the oxygen storage-water absorption oxide is CeO doped with alkaline earth or rare earth2Base, BaCeO3Radical, BaZrO3Base L a2Ce2O7And one or more of oxides.
Further, the mass of the MgO is 0.05-0.1% of that of the porous metal support layer;
preferably, the thickness of the porous catalytic reforming layer is 20-40 μm, and the porosity is 40-60%;
preferably, the thickness of the porous metal supporting layer is 500-1000 μm, and the porosity is 40-60%;
preferably, the thickness of the porous anode functional layer is 10-20 μm, and the porosity is 40-60%;
preferably, the thickness of the dense electrolyte layer is 10 μm to 20 μm;
preferably, the thickness of the porous cathode layer is 5-20 μm, and the porosity is 40-60%.
According to another aspect of the invention, a method for preparing an anti-carbon deposition metal-supported solid oxide fuel cell is provided, which comprises the following steps:
s1, uniformly mixing absolute ethyl alcohol and xylene, adding a dispersing agent serving as a solvent, adding a mixed powder formed by a first precursor and a pore-forming agent into the solvent, carrying out ball milling, sequentially adding a plasticizer, a first binder and a defoaming agent, carrying out ball milling again to form a casting slurry, carrying out casting molding after defoaming, and drying to obtain a support voxel blank layer;
s2, uniformly mixing a second precursor and a fluorite structure oxide or the second precursor and an ion conduction type perovskite structure oxide, adding a second binder, grinding to obtain slurry of an anode functional layer, and printing the slurry of the anode functional layer on the support biscuit to prepare an anode functional layer thick film biscuit layer;
s3, adding the electrolyte oxide powder into a second binder, grinding to obtain electrolyte layer slurry, and printing the electrolyte layer slurry on the anode functional layer thick film green layer to obtain an electrolyte layer thick film green layer;
s4, degreasing and sintering the prepared support voxel blank layer, the anode function layer thick film blank layer and the electrolyte layer thick film blank layer which are sequentially in close contact with one another in an air atmosphere, and then cooling to room temperature to obtain a metal oxide supported half cell;
s5, mixing the electronic conductive perovskite structure oxide with electrolyte powder, adding a second binder, grinding to obtain slurry of a cathode functional layer, printing the slurry of the cathode functional layer on one side of an electrolyte layer of the half cell, drying, sintering, and cooling to room temperature to obtain a single cell supported by metal oxide;
s6, uniformly mixing the third precursor and the oxygen storage-water absorption oxide powder, adding a second binder, grinding to obtain slurry of the catalytic reforming layer, and printing the slurry of the catalytic reforming layer on one side of the support layer of the single cell to prepare the catalytic reforming layer.
Further, the first precursor is NiO, MgO and MOxThe second precursor is NiO and MOxThe third precursor is NiO and MOxWherein, the M element is one or more of Fe, Co, Cu and Sn.
Further, in step S1, the first binder is polyvinyl butyral;
the mass of the MgO powder is 0.05-0.1% of that of the first precursor.
Further, in step S2, the second binder is a terpineol solution of ethyl cellulose, wherein the mass fraction of the ethyl cellulose is 3.5% -4.5%,
the content of the second binder in the slurry of the anode functional layer is 30-40 wt.%,
the mass ratio of the fluorite or ionic conduction type perovskite structure oxide to the second precursor is 3:7-4: 6.
Further, in step S3, the content of the second binder in the slurry of the electrolyte layer is 30 wt.% to 40 wt.%.
Further, in step S4, the degreasing time is 4h to 6h, the sintering temperature is 1400 ℃ to 1500 ℃, and the sintering temperature rising and cooling rates are 0.5 ℃/min to 5 ℃/min;
in step S5, the sintering temperature is 900 ℃ to 1100 ℃, the sintering temperature rise and cooling rate is 3 ℃/min to 5 ℃/min, and the content of the second binder in the slurry of the cathode functional layer is 40 wt.% to 60 wt.%.
Further, in step S6,
the amount of the second binder in the slurry of the catalytic reforming layer is 40 wt.% to 60 wt.%,
the mass ratio of the oxygen storage-water absorption oxide to the third precursor is 1:9-3: 7. .
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the anti-carbon-deposition metal-supported solid oxide fuel cell effectively solves the problem that the metal-supported solid oxide fuel cell is easy to generate carbon deposition when a hydrocarbon is used as fuel, so that the metal-supported solid oxide fuel cell can stably run in the hydrocarbon fuel for a long time, has low preparation process cost, is suitable for large-area monocells and large-scale production and manufacture, and has wide application prospect.
(2) According to the invention, MgO is added into the porous metal supporting layer, so that sintering shrinkage among metal particles after the supporting layer is reduced can be effectively inhibited, the structural stability of the single cell in-situ reduction is enhanced, and the porous supporting layer has better dimensional stability when the single cell is subjected to thermal cycling;
(3) according to the invention, the oxygen storage-water absorption oxide is added into the porous catalytic reforming layer, so that the carbon deposition resistance of the catalytic reforming layer can be effectively improved, and meanwhile, the fuel components reaching the porous metal supporting layer and the porous anode functional layer are changed after the hydrocarbon fuel is reformed by the porous catalytic reforming layer, so that the carbon deposition generated between the supporting body and the anode is avoided;
(3) the porous catalytic reforming layer does not need an independent sintering step in the preparation process, can be subjected to in-situ reduction and sintering when a single cell operates, is favorable for enhancing the interface contact between the current collecting material and the anode side, and improves the current collecting performance;
(4) the single cell preparation process is low in cost, is suitable for large-area single cells and large-scale production and manufacture, adopts metal oxide as a precursor, and is sintered and formed in the air, so that the use of inert atmosphere or reducing atmosphere is avoided, the manufacturing cost is reduced, and the single cell preparation process has wide application prospect.
Drawings
FIG. 1 is a schematic structural diagram of a single cell of an anti-carbon deposition metal-supported solid oxide fuel cell according to the present invention;
fig. 2 is a cross-sectional microscopic structure diagram of a single cell of an anti-carbon metal-supported solid oxide fuel cell prepared and implemented according to the present invention.
The same reference numbers will be used throughout the drawings to refer to the same structure, wherein: 1-porous catalytic reforming layer, 2-porous metal supporting layer, 3-porous anode functional layer, 4-compact electrolyte layer and 5-porous cathode layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, the anti-carbon deposition metal supported solid oxide fuel cell of the present invention comprises a porous catalytic reforming layer 1, a porous metal supporting layer 2, a porous anode functional layer 3, a dense electrolyte layer 4 and a porous cathode layer 5 which are tightly combined in sequence. Wherein: the porous catalytic reforming layer mainly comprises Ni-M alloy and oxygen storage-water absorption oxide; the porous metal supporting layer mainly comprises Ni-M alloy and MgO; the porous anode functional layer mainly comprises Ni-M alloy and fluorite or Ni-M alloy and perovskite structure oxide; wherein the M element is one or more of Fe, Co, Cu and Sn.
The oxygen storage-water absorption oxide is CeO doped with alkaline earth or rare earth2Base, BaCeO3Radical, BaZrO3Base L a2Ce2O7And one or more of oxides. The mass of the MgO is 0.05-0.1% of that of the porous metal support layer; preferably, the thickness of the porous catalytic reforming layer is 20-40 μm, and the porosity is 40-60%; preferably, the thickness of the porous metal supporting layer is 500-1000 μm, and the porosity is 40-60%; preferably, the thickness of the porous anode functional layer is 10-20 μm, and the porosity is 40-60%; preferably, the thickness of the dense electrolyte layer is 10 μm to 20 μm; preferably, the thickness of the porous cathode layer is 5-20 μm, and the porosity is 40-60%.
According to another aspect of the invention, a method for preparing an anti-carbon deposition metal-supported solid oxide fuel cell is provided, which comprises the following steps:
s1, uniformly mixing absolute ethyl alcohol and xylene, adding a dispersing agent serving as a solvent, adding a mixed powder formed by a first precursor and a pore-forming agent into the solvent, carrying out ball milling, sequentially adding a plasticizer, a first binder and a defoaming agent, carrying out ball milling again to form a casting slurry, carrying out casting molding after defoaming, and drying to obtain a support voxel blank layer; the first binder is polyvinyl butyral; the mass of the MgO powder is 0.05-0.1% of that of the first precursor.
S2, uniformly mixing a second precursor and a fluorite structure oxide or the second precursor and an ion conduction type perovskite structure oxide, adding a second binder, grinding to obtain slurry of an anode functional layer, and printing the slurry of the anode functional layer on the support biscuit to prepare an anode functional layer thick film biscuit layer; the second binder is a terpineol solution of ethyl cellulose, wherein the mass fraction of the ethyl cellulose is 3.5-4.5%, the content of the second binder in the slurry of the anode functional layer is 30-40 wt.%, and the mass ratio of the fluorite or ionic conduction type perovskite structure oxide to the second precursor is 3:7-4: 6.
S3, adding the electrolyte oxide powder into a second binder, grinding to obtain electrolyte layer slurry, and printing the electrolyte layer slurry on the anode functional layer thick film green layer to obtain an electrolyte layer thick film green layer; the second binder is contained in the slurry for the electrolyte layer in an amount of 30 wt.% to 40 wt.%.
S4, degreasing and sintering the prepared support voxel blank layer, the anode function layer thick film blank layer and the electrolyte layer thick film blank layer which are sequentially in close contact with one another in an air atmosphere, and then cooling to room temperature to obtain a metal oxide supported half cell; the degreasing time is 4-6h, the sintering temperature is 1400-1500 ℃, and the sintering temperature rising and cooling rates are 0.5-5 ℃/min.
S5, mixing the electronic conductive perovskite structure oxide with electrolyte powder, adding a second binder, grinding to obtain slurry of a cathode functional layer, printing the slurry of the cathode functional layer on one side of an electrolyte layer of the half cell, drying, sintering, and cooling to room temperature to obtain a single cell supported by metal oxide; the sintering temperature is 900-1100 ℃, the sintering temperature rise and cooling rate is 3-5 ℃/min, and the content of the second binder in the slurry of the cathode functional layer is 40-60 wt.%.
S6, uniformly mixing a third precursor and the oxygen storage-water absorption oxide powder, adding a second binder, grinding to obtain slurry of a catalytic reforming layer, printing the slurry of the catalytic reforming layer on one side of a support layer of the single cell to prepare the catalytic reforming layer, wherein the content of the second binder in the slurry of the catalytic reforming layer is 40-60 wt%, and the mass ratio of the oxygen storage-water absorption oxide to the third precursor is 1:9-3: 7.
Wherein the first precursor is NiO, MgO and MOxThe second precursor isNiO and MOxThe third precursor is NiO and MOx。
Specifically, the preparation method comprises the following steps:
(1) preparation of support layer by tape casting method
Uniformly mixing absolute ethyl alcohol and xylene according to the volume ratio of 1:1 to obtain a solvent, adding a certain amount of fish oil as a dispersing agent, and uniformly stirring; NiO powder, MgO powder and MOxPouring the powder into the solvent, uniformly stirring, adding starch or carbon powder as a pore-forming agent, sequentially adding a plasticizer, a first binder and a defoaming agent after ball milling for 24 hours, forming casting slurry after ball milling for 24 hours, carrying out vacuum defoaming, carrying out casting molding, drying to obtain a support body biscuit, and cutting according to the required specification; the MgO powder accounts for 0.05-0.1% of the mixed powder by mass; the MO isxThe powder accounts for 10 to 50 percent of the mass of the mixed powder; the plasticizer is Butyl Benzyl Phthalate (BBP) and polyalkyl glycol (PAG); the first binder is polyvinyl butyral (PVB); the defoaming agent is cyclohexanone.
(2) Method for preparing anode functional layer by silk-screen printing method
NiO and MO are addedxAdding a second binder into the mixed powder of fluorite or the oxide with the ionic conduction type perovskite structure, grinding to obtain slurry of the anode functional layer, and printing the slurry of the anode functional layer on a support body biscuit by adopting a screen printing method to prepare an anode functional layer thick film biscuit; the second binder is an ethyl cellulose terpineol solution having an ethyl cellulose content of 3 wt.% to 5 wt.%; the content of the second binder is 30-40 wt.%; the fluorite or the ionic conduction type perovskite structure oxide accounts for 30-40% of the mass of the mixed powder.
(3) Preparation of electrolyte layer by screen printing method
Adding the selected electrolyte oxide powder into a second binder, grinding to obtain electrolyte layer slurry, and printing the electrolyte layer slurry on an anode functional layer biscuit by adopting a screen printing method to prepare an electrolyte layer thick film biscuit; the content of the second binder is 30-40 wt.%; the content of the electrolyte oxide powder is 60-70 wt.%.
(4) Sintering and forming of half-cell
Degreasing the semi-cell blank obtained in the steps (1) - (3) for 4-6h at 240 ℃ in air atmosphere, then co-sintering at the temperature of 1400 ℃ and 1500 ℃ for 4-6h, controlling the heating and cooling rates to be 0.5 ℃/min-5 ℃/min, and cooling to room temperature to obtain the semi-cell supported by the metal oxide.
(5) Preparation of cathode layer by screen printing method
Adding a second binder into the mixed powder of the oxide with the electronic conductivity and the electrolyte, grinding to obtain slurry of a cathode functional layer, printing the slurry of the cathode functional layer on one side of the electrolyte of the half-cell obtained in the step (4) by adopting a screen printing method to prepare a cathode layer thick film biscuit, drying, sintering at 900-1100 ℃ for 2-3 h in an air atmosphere, controlling the heating and cooling rates to be 3-5 ℃/min, and cooling to room temperature to obtain a single cell supported by the metal oxide; the content of the second binder is 40-60 wt.%; the electrolyte powder accounts for 40-60% of the mixed powder by mass.
(6) Preparation of catalytic reforming layer by screen printing method
NiO and MO are addedxAnd (3) adding a second binder into the oxygen storage-water absorption oxide mixed powder, grinding to obtain slurry of the catalytic reforming layer, and printing the slurry of the catalytic reforming layer on one side of the support body of the single cell obtained in the step (5) by adopting a screen printing method; the content of the second binder is 40-60 wt.%; the oxygen storage-water absorption oxide powder accounts for 10-30% of the mass of the mixed powder.
The catalytic reforming layer, the supporting layer and the anode functional layer jointly form a multi-layer anode structure, and are reduced in situ under the working condition of the battery to form the porous catalytic reforming layer, the porous metal supporting layer and the porous anode functional layer; after in-situ reduction, the catalytic reforming layer can be sintered in situ under the working condition of the battery and form good interface contact with the porous metal supporting layer.
The porous catalytic reforming layer mainly comprises Ni-M alloy and a small amount of oxygen storage-water absorption oxides, wherein M element is one or more of Fe, Co, Cu, Sn and the likeSeed growing; the oxygen storage-water absorption oxide is CeO doped with alkaline earth or rare earth2Base, BaCeO3Radical, BaZrO3Base L a2Ce2O7And one or more of oxides.
The porous anode functional layer mainly comprises Ni-M alloy and fluorite or ion conduction type perovskite structure oxide, wherein M element is one or more of Fe, Co, Cu, Sn and the like; the fluorite structure oxide is alkaline earth or rare earth doped ZrO2、CeO2Or L a2Ce2O7The ionic conduction type perovskite structure oxide is L aGaO doped with alkaline earth or rare earth3、BaCeO3Or BaZrO3One or more of them. The content of the fluorite-structured or ion-conductive perovskite-structured oxide is 30 wt.% to 50 wt.% to provide ion conductivity. The material of the dense electrolyte layer is selected from alkaline earth or rare earth doped ZrO2、CeO2Or L a2Ce2O7、LaGaO3、BaCeO3Or BaZrO3One or more of them. The thickness of the compact electrolyte layer is 10-20 μm, and the ohmic resistance of the battery can be effectively reduced by reducing the thickness of the electrolyte layer under the realizable preparation conditions.
The porous cathode layer mainly comprises perovskite structure oxide with electronic conductivity and electrolyte material, wherein the perovskite structure oxide with electronic conductivity is L aCoO doped by alkaline earth elements, transition group elements or rare earth elements3、SrCoO3、LaFeO3、SrMnO3、SmCoO3One or more of the following; the electrolyte material is the same as the above-described electrolyte material. The content of the perovskite structure oxide having electronic conductivity is 50 wt.% to 80 wt.%.
Example 1
(1) Weighing anhydrous ethanol and xylene 60ml each, uniformly mixing as solvent, adding 4.5g fish oil as dispersant, weighing 207g NiO powder and 23g Fe2O3Adding powder and 1.15g of MgO powder into the solvent, adding 5g of starch as a pore-forming agent, stirringBall milling is carried out for 24 hours after the mixture is evenly mixed; then, 9g Butyl Benzyl Phthalate (BBP), 9g polyalkyl glycol (PAG), 21g polyvinyl butyral (PVB) and 0.2g cyclohexanone are added in sequence, stirred uniformly and ball-milled for 24 h. And (3) carrying out vacuum defoaming treatment on the slurry obtained after ball milling for 30 minutes, and carrying out tape casting and drying on a casting machine to obtain a support body biscuit with the thickness of 1 mm.
(2) Dissolving ethyl cellulose in terpineol to prepare an ethyl cellulose terpineol solution with the ethyl cellulose content of 4 wt%, wherein the ethyl cellulose is used as a binder for preparing the screen printing slurry for later use.
(3) 1.8g of NiO powder and 1.2gCe g of NiO powder0.8Gd0.2O2Adding the powder into 2g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on a support body biscuit by adopting a screen printing method to prepare an anode functional layer thick film biscuit, naturally drying, and repeating the printing step for 3 times;
(4) 3.4gCe0.8Gd0.2O2Adding the powder into 1.6g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on an anode functional layer biscuit by adopting a screen printing method to prepare an electrolyte layer thick film biscuit, naturally drying, and repeating the printing step for 3 times;
(5) degreasing the semi-cell biscuit obtained in the steps (1) to (4) for 4 to 6 hours at 240 ℃ in air atmosphere, then co-sintering the semi-cell biscuit for 4 hours at a high temperature of 1450 ℃, controlling the heating and cooling rates to be 0.5 to 5 ℃/min, and cooling the semi-cell biscuit to room temperature to obtain a metal oxide supported semi-cell;
(6) 1.5g of L a0.6Sr0.4Co0.2Fe0.8O3Powder and 1gCe0.8Gd0.2O2Adding the powder into 2.5g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on one side of the electrolyte of the half-cell obtained in the step (5) by adopting a screen printing method to prepare a cathode layer thick film biscuit, naturally drying, repeating the printing step for 2 times, sintering at 1050 ℃ for 3h in air atmosphere, controlling the heating and cooling rates to be 3-5 ℃/min, and cooling to room temperature to prepare a single cell supported by metal oxide;
(7) 2.8gNi0.8Cu0.2Powder of O and 0.7gCe0.8Gd0.2O2And (3) adding the powder into 1.5g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on one side of the support body of the single cell obtained in the step (6) by adopting a screen printing method, naturally drying, and repeating the printing step for 4-6 times to obtain the single cell containing the catalytic reforming layer, wherein the single cell can be reduced into a metal-supported solid oxide fuel cell single cell in situ under the working condition.
Example 2
(1) Weighing anhydrous ethanol and xylene 60ml each, mixing well as solvent, adding fish oil 4.5g as dispersant, weighing 115gNiO powder and 115gFe2O3Adding powder and 1.15g of MgO powder into the solvent, adding 5g of starch serving as a pore-forming agent, uniformly stirring, and carrying out ball milling for 24 hours; then, 11g of Butyl Benzyl Phthalate (BBP), 11g of Polyalkylglycol (PAG), 23g of polyvinyl butyral (PVB) and 0.25g of cyclohexanone are added in sequence, stirred uniformly and ball-milled for 24 hours. And (3) carrying out vacuum defoaming treatment on the slurry obtained after ball milling for 30 minutes, and carrying out tape casting and drying on a casting machine to obtain a support body biscuit with the thickness of 1 mm.
(2) Dissolving ethyl cellulose in terpineol to prepare an ethyl cellulose terpineol solution with the ethyl cellulose content of 4 wt%, wherein the ethyl cellulose is used as a binder for preparing the screen printing slurry for later use.
(3) 1.8g of NiO powder and 1.2gCe g of NiO powder0.9Sm0.1O2Adding the powder into 2g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on a support body biscuit by adopting a screen printing method to prepare an anode functional layer thick film biscuit, naturally drying, and repeating the printing step for 3 times;
(4) 3.4gCe0.9Sm0.1O2Adding the powder into 1.6g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on an anode functional layer biscuit by adopting a screen printing method to prepare an electrolyte layer thick film biscuit, naturally drying, and repeating the printing step for 3 times;
(5) degreasing the semi-cell biscuit obtained in the steps (1) to (4) for 4 to 6 hours at 240 ℃ in air atmosphere, then co-sintering the semi-cell biscuit for 4 hours at a high temperature of 1450 ℃, controlling the heating and cooling rates to be 0.5 to 5 ℃/min, and cooling the semi-cell biscuit to room temperature to obtain a metal oxide supported semi-cell;
(6) 1.5gBa0.5Sr0.5Co0.8Fe0.2O3Powder and 1gCe0.9Sm0.1O2Adding the powder into 2.5g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on one side of the electrolyte of the half-cell obtained in the step (5) by adopting a screen printing method to prepare a cathode layer thick film biscuit, naturally drying, repeating the printing step for 2 times, sintering for 3h at the temperature of 900-1100 ℃ in the air atmosphere, controlling the heating and cooling rates to be 3-5 ℃/min, and cooling to room temperature to prepare a single cell supported by metal oxide;
(7) will be 3gNi0.5Cu0.5Fe2O4Powder and 0.5gCe0.9Sm0.1O2And (3) adding the powder into 1.5g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on one side of the support body of the single cell obtained in the step (6) by adopting a screen printing method, naturally drying, and repeating the printing step for 4-6 times to obtain the single cell containing the catalytic reforming layer, wherein the single cell can be reduced into a metal-supported solid oxide fuel cell single cell in situ under the working condition.
Example 3
(1) Weighing anhydrous ethanol and xylene, mixing 60ml each, adding 4.5g fish oil as dispersant, weighing 184g NiO powder and 46g Fe2O3Adding powder and 1.15g of MgO powder into the solvent, adding 5g of starch serving as a pore-forming agent, uniformly stirring, and carrying out ball milling for 24 hours; then, 10g Butyl Benzyl Phthalate (BBP), 10g polyalkyl glycol (PAG), 22g polyvinyl butyral (PVB) and 0.23g cyclohexanone are added in sequence, stirred uniformly and ball-milled for 24 h. And (3) carrying out vacuum defoaming treatment on the slurry obtained after ball milling for 30 minutes, and carrying out tape casting and drying on a casting machine to obtain a support body biscuit with the thickness of 1 mm.
(2) Dissolving ethyl cellulose in terpineol to prepare an ethyl cellulose terpineol solution with the ethyl cellulose content of 4 wt%, wherein the ethyl cellulose is used as a binder for preparing the screen printing slurry for later use.
(3) 1.8g of NiO powder and 1.2g of BaZr0.1Ce0.7Y0.1Yb0.1O3Adding the powder into 2g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on a support body biscuit by adopting a screen printing method to prepare an anode functional layer thick film biscuit, naturally drying, and repeating the printing step for 3 times;
(4) 3.4g of BaZr0.1Ce0.7Y0.1Yb0.1O3Adding the powder into 1.6g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on an anode functional layer biscuit by adopting a screen printing method to prepare an electrolyte layer thick film biscuit, naturally drying, and repeating the printing step for 3 times;
(5) degreasing the semi-cell biscuit obtained in the steps (1) to (4) for 4 to 6 hours at 240 ℃ in air atmosphere, then co-sintering the semi-cell biscuit for 4 hours at a high temperature of 1450 ℃, controlling the heating and cooling rates to be 0.5 to 5 ℃/min, and cooling the semi-cell biscuit to room temperature to obtain a metal oxide supported semi-cell;
(6) 1.5g of PrBa0.5Sr0.5Co1.5Fe0.5O6Powder and 1gBaZr0.1Ce0.7Y0.1Yb0.1O3Adding the powder into 2.5g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on one side of the electrolyte of the half-cell obtained in the step (5) by adopting a screen printing method to prepare a cathode layer thick film biscuit, naturally drying, repeating the printing step for 2 times, sintering for 3h at the temperature of 900-1100 ℃ in the air atmosphere, controlling the heating and cooling rates to be 3-5 ℃/min, and cooling to room temperature to prepare a single cell supported by metal oxide;
(7) 2.8gNi0.8Cu0.2O powder and 0.7gBaZr0.1Ce0.7Y0.1Yb0.1O3Adding the powder into 1.5g ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on one side of the support body of the single cell obtained in the step (6) by adopting a screen printing method, naturally drying, and repeating the printing step for 4-6 times to obtain the product containingA catalytic reforming layer cell that can be reduced in situ under operating conditions to a metal supported solid oxide fuel cell.
Example 4
The steps (1), (2), (3), (4), (5) and (6) in the preparation of the anti-carbon deposition metal-supported solid oxide fuel cell related to the embodiment are the same as the embodiment 1, except that the step (7): (7) 2.8gNi0.5Cu0.5Fe2O4Powder and 0.7g L a1.95Sm0.05Ce2O7And (3) adding the powder into 1.5g of ethyl cellulose terpineol solution, grinding for 1-2h to obtain stable and uniform slurry, printing the slurry on one side of the support body of the single cell obtained in the step (6) by adopting a screen printing method, naturally drying, and repeating the printing step for 4-6 times to obtain the single cell containing the catalytic reforming layer, wherein the single cell can be reduced into a metal-supported solid oxide fuel cell single cell in situ under the working condition.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An anti-carbon deposition metal support solid oxide fuel cell is characterized by comprising a porous catalytic reforming layer, a porous metal support layer, a porous anode functional layer, a compact electrolyte layer and a porous cathode layer which are tightly combined in sequence,
the porous catalytic reforming layer comprises a Ni-M alloy and an oxygen storage-water absorption oxide;
the porous metal support layer comprises a Ni-M alloy and MgO;
the porous anode functional layer comprises Ni-M alloy and fluorite structure oxide or Ni-M alloy and ion conductive perovskite structure oxide;
wherein the M element is one or more of Fe, Co, Cu and Sn.
2. According toThe anti-carbon deposition metal supported solid oxide fuel cell as recited in claim 1, wherein the oxygen storage-water absorbing oxide is CeO doped with alkaline earth or rare earth2Base, BaCeO3Radical, BaZrO3Base L a2Ce2O7One or more of the oxide bases.
3. The anti-carbon deposition metal supported solid oxide fuel cell as claimed in claim 1 or 2,
the mass of the MgO is 0.05-0.1% of that of the porous metal support layer;
the thickness of the porous catalytic reforming layer is 20-40 μm, and the porosity is 40-60%;
the thickness of the porous metal supporting layer is 500-1000 μm, and the porosity is 40-60%;
the thickness of the porous anode functional layer is 10-20 μm, and the porosity is 40-60%;
the thickness of the compact electrolyte layer is 10-20 μm;
the thickness of the porous cathode layer is 5-20 μm, and the porosity is 40-60%.
4. The preparation method of the anti-carbon deposition metal support solid oxide fuel cell is characterized by comprising the following steps:
s1, uniformly mixing absolute ethyl alcohol and xylene, adding a dispersing agent serving as a solvent, adding a mixed powder formed by a first precursor and a pore-forming agent into the solvent, carrying out ball milling, sequentially adding a plasticizer, a first binder and a defoaming agent, carrying out ball milling again to form a casting slurry, carrying out casting molding after defoaming, and drying to obtain a support voxel blank layer;
s2, uniformly mixing a second precursor and a fluorite structure oxide or the second precursor and an ion conduction type perovskite structure oxide, adding a second binder, grinding to obtain slurry of an anode functional layer, and printing the slurry of the anode functional layer on the support biscuit to prepare an anode functional layer thick film biscuit layer;
s3, adding the electrolyte oxide powder into a second binder, grinding to obtain electrolyte layer slurry, and printing the electrolyte layer slurry on the anode functional layer thick film green layer to obtain an electrolyte layer thick film green layer;
s4, degreasing and sintering the prepared support voxel blank layer, the anode function layer thick film blank layer and the electrolyte layer thick film blank layer which are sequentially in close contact with one another in an air atmosphere, and then cooling to room temperature to obtain a metal oxide supported half cell;
s5, mixing the electronic conductive perovskite structure oxide with electrolyte powder, adding a second binder, grinding to obtain slurry of a cathode functional layer, printing the slurry of the cathode functional layer on one side of an electrolyte layer of the half cell, drying, sintering, and cooling to room temperature to obtain a single cell supported by metal oxide;
s6, uniformly mixing the third precursor, the oxygen storage-water absorption oxide powder and the second binder, grinding to obtain slurry of the catalytic reforming layer, and printing the slurry of the catalytic reforming layer on one side of the support layer of the single cell to prepare the catalytic reforming layer.
5. The method according to claim 4, wherein the first precursor is NiO, MgO, and MOxThe second precursor is NiO and MOxThe third precursor is NiO and MOxWherein, the M element is one or more of Fe, Co, Cu and Sn.
6. The method according to claim 5, wherein in step S1, the first binder is polyvinyl butyral;
the mass of the MgO powder is 0.05-0.1% of that of the first precursor.
7. The method according to claim 4, wherein in step S2, the second binder is terpineol solution of ethyl cellulose, wherein the mass fraction of the ethyl cellulose is 3.5% -4.5%,
the content of the second binder in the slurry of the anode functional layer is 30-40 wt.%,
the mass ratio of the fluorite or ionic conduction type perovskite structure oxide to the second precursor is 3:7-4: 6.
8. The method according to claim 4, wherein the second binder is contained in the slurry for the electrolyte layer in an amount of 30 wt.% to 40 wt.% in step S3.
9. The preparation method according to claim 4, wherein in step S4, the degreasing time is 4-6h, the sintering temperature is 1400-1500 ℃, and the sintering temperature rise and cooling rate is 0.5-5 ℃/min;
in step S5, the sintering temperature is 900 ℃ to 1100 ℃, the sintering temperature rise and cooling rate is 3 ℃/min to 5 ℃/min, and the content of the second binder in the slurry of the cathode functional layer is 40 wt.% to 60 wt.%.
10. The production method according to any one of claims 4 to 9,
in step S6, the second binder is present in the slurry of the catalytic reforming layer in an amount of 40 wt.% to 60 wt.%,
the mass ratio of the oxygen storage-water absorption oxide to the third precursor is 1:9-3: 7.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560951A (en) * | 2004-03-05 | 2005-01-05 | 厦门大学 | Intermediat-temp solid oxide fuel cell electrolytic of high-efficient preventing carbon deposit and its preparation method |
| CN1960047A (en) * | 2006-11-23 | 2007-05-09 | 上海交通大学 | Method for preparing low temperature solid oxide fuel cell supported by porous metal |
| CN1985397A (en) * | 2004-06-10 | 2007-06-20 | 丹麦科技大学 | Solid oxide fuel cell |
| CN101562255A (en) * | 2009-05-19 | 2009-10-21 | 华中科技大学 | Method for preparing metallic support type solid oxide fuel cell |
| CN101771149A (en) * | 2008-12-29 | 2010-07-07 | 中国科学院大连化学物理研究所 | Composite anode of magnesium-modified and nickel-based solid-oxide fuel cell and preparation and application thereof |
| CN102290580A (en) * | 2011-07-18 | 2011-12-21 | 上海交通大学 | Solid oxide fuel cell anode/electrolyte double-layered membrane and preparation method thereof |
| CN102437358A (en) * | 2011-11-30 | 2012-05-02 | 中国科学技术大学 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
| CN102881929A (en) * | 2012-10-26 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Structure of flat-plate type metal-support solid oxide fuel cell for immersing electrodes |
| CN102903945A (en) * | 2012-10-26 | 2013-01-30 | 中国科学院上海硅酸盐研究所 | Method for preparing large-size flat plate type metal supporting solid oxide fuel cell |
| CN103872366A (en) * | 2012-12-12 | 2014-06-18 | 中国科学院上海硅酸盐研究所 | Metal-supported solid oxide fuel cell and preparation method thereof |
| CN103928693A (en) * | 2014-03-21 | 2014-07-16 | 上海交通大学 | Metal support half-cell of solid oxide fuel cell and preparation method thereof |
| CN104157893A (en) * | 2013-05-13 | 2014-11-19 | 中国科学院大连化学物理研究所 | Low temperature solid oxide fuel cell supported by porous metal and preparation method thereof |
| CN104638277A (en) * | 2015-01-30 | 2015-05-20 | 陕西煤业化工技术研究院有限责任公司 | Gradient functional anode electrode for carbon-based solid oxide fuel battery and preparation method of gradient functional anode electrode |
| CN104779409A (en) * | 2015-04-27 | 2015-07-15 | 上海邦民新能源科技有限公司 | Solid oxide fuel cell and preparation method thereof |
| CN104916857A (en) * | 2015-06-16 | 2015-09-16 | 华中科技大学 | Planar solid oxide fuel cell |
| CN105244523A (en) * | 2015-08-28 | 2016-01-13 | 山西大学 | Solid oxide fuel cell with anti-carbon function |
| KR20180097924A (en) * | 2017-02-24 | 2018-09-03 | 한국과학기술원 | Method for fabricating metal-supported solid oxide fuel cell using ex-situ bonding and metal-supported solid oxide fuel cell fabricated by the same |
-
2019
- 2019-01-09 CN CN201910018604.1A patent/CN109904497B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560951A (en) * | 2004-03-05 | 2005-01-05 | 厦门大学 | Intermediat-temp solid oxide fuel cell electrolytic of high-efficient preventing carbon deposit and its preparation method |
| CN1985397A (en) * | 2004-06-10 | 2007-06-20 | 丹麦科技大学 | Solid oxide fuel cell |
| CN1960047A (en) * | 2006-11-23 | 2007-05-09 | 上海交通大学 | Method for preparing low temperature solid oxide fuel cell supported by porous metal |
| CN101771149A (en) * | 2008-12-29 | 2010-07-07 | 中国科学院大连化学物理研究所 | Composite anode of magnesium-modified and nickel-based solid-oxide fuel cell and preparation and application thereof |
| CN101562255A (en) * | 2009-05-19 | 2009-10-21 | 华中科技大学 | Method for preparing metallic support type solid oxide fuel cell |
| CN102290580A (en) * | 2011-07-18 | 2011-12-21 | 上海交通大学 | Solid oxide fuel cell anode/electrolyte double-layered membrane and preparation method thereof |
| CN102437358A (en) * | 2011-11-30 | 2012-05-02 | 中国科学技术大学 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
| CN102903945A (en) * | 2012-10-26 | 2013-01-30 | 中国科学院上海硅酸盐研究所 | Method for preparing large-size flat plate type metal supporting solid oxide fuel cell |
| CN102881929A (en) * | 2012-10-26 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Structure of flat-plate type metal-support solid oxide fuel cell for immersing electrodes |
| CN103872366A (en) * | 2012-12-12 | 2014-06-18 | 中国科学院上海硅酸盐研究所 | Metal-supported solid oxide fuel cell and preparation method thereof |
| CN104157893A (en) * | 2013-05-13 | 2014-11-19 | 中国科学院大连化学物理研究所 | Low temperature solid oxide fuel cell supported by porous metal and preparation method thereof |
| CN103928693A (en) * | 2014-03-21 | 2014-07-16 | 上海交通大学 | Metal support half-cell of solid oxide fuel cell and preparation method thereof |
| CN104638277A (en) * | 2015-01-30 | 2015-05-20 | 陕西煤业化工技术研究院有限责任公司 | Gradient functional anode electrode for carbon-based solid oxide fuel battery and preparation method of gradient functional anode electrode |
| CN104779409A (en) * | 2015-04-27 | 2015-07-15 | 上海邦民新能源科技有限公司 | Solid oxide fuel cell and preparation method thereof |
| CN104916857A (en) * | 2015-06-16 | 2015-09-16 | 华中科技大学 | Planar solid oxide fuel cell |
| CN105244523A (en) * | 2015-08-28 | 2016-01-13 | 山西大学 | Solid oxide fuel cell with anti-carbon function |
| KR20180097924A (en) * | 2017-02-24 | 2018-09-03 | 한국과학기술원 | Method for fabricating metal-supported solid oxide fuel cell using ex-situ bonding and metal-supported solid oxide fuel cell fabricated by the same |
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