CN113097512B - Proton conductor fuel cell and preparation method thereof - Google Patents
Proton conductor fuel cell and preparation method thereof Download PDFInfo
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- CN113097512B CN113097512B CN202110347500.2A CN202110347500A CN113097512B CN 113097512 B CN113097512 B CN 113097512B CN 202110347500 A CN202110347500 A CN 202110347500A CN 113097512 B CN113097512 B CN 113097512B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
Abstract
The invention discloses a proton conductor fuelThe proton conductor fuel cell comprises a proton conductor electrolyte and LSFM-CeO positioned on two sides of the proton conductor electrolyte 2 A composite anode and cathode; the LSFM-CeO 2 The composite anode is coated with CeO on the surface 2 A perovskite precursor material of nanoparticles, the perovskite precursor material having the chemical formula La 0.5 Sr 0.5 Fe 0.9 Mo 0.1 O 3‑δ . The invention firstly uses LSFM-CeO 2 The composite anode is applied to the proton conductor fuel cell, can obviously improve the discharge power of the cell, and effectively solves the problem of anode carbon deposition.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a proton conductor fuel cell and a preparation method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is a green energy conversion device that directly converts chemical energy stored in fuel into electrical energy through electrochemical reaction, and has received much attention due to its characteristics of cleanliness, high efficiency, strong fuel adaptability, modularity, and the like. One common application is the use of SOFCs for the electrochemical conversion of ethane.
The electrolyte in the ethane fuel cell can be oxygen ion conductive electrolyte, but due to the conduction of oxygen ions, ethane is easily oxidized deeply in the reaction process to generate carbon monoxide and carbon dioxide, and water generated at the anode dilutes the fuel concentration, so that the reaction efficiency is reduced. Therefore, a proton conductive electrolyte is generally used, but since ethane is easily cracked at high temperature, a large amount of carbon deposit is generated to adhere to the anode catalyst to cause its failure, which in turn causes rapid degradation of the battery. Therefore, the search for suitable anode catalysts to solve the problem of anode carbon deposition has been a trend in the hydrocarbon fuel field of SOFC.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a proton conductor fuel cell and a preparation method thereof, and aims to solve the problems of anode carbon deposit, low cell performance and high possibility of deep oxidation in the prior ethane proton conductor fuel cell.
The technical scheme of the invention is as follows:
a proton conductor fuel cell comprises a proton conductor electrolyte and LSFM-CeO on two sides of the proton conductor electrolyte 2 A composite anode and cathode; the LSFM-CeO 2 The composite anode is coated with CeO on the surface 2 A perovskite precursor material of nanoparticles, the perovskite precursor material having the chemical formula La 0.5 Sr 0.5 Fe 0.9 Mo 0.1 O 3-δ 。
The proton conductor fuel cell, wherein the CeO 2 The particle size of the nano-particles is 20-50nm.
The proton conductor fuel cell is characterized in that the material of the proton conductor electrolyte is BaZr 0.2 Ce 0.7 Y 0.1 O 3-δ 。
The proton conductor fuel cell, wherein the cathode is a LSCF-SDC composite cathode, and the chemical formula of the LSCF is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ The chemical formula of SDC is Sm 0.2 Ce 0.8 O 1.9 。
A method of making a proton conductor fuel cell, comprising the steps of:
providing LSFM-CeO 2 A composite anode, said LSFM-CeO 2 The composite anode is coated with CeO on the surface 2 A perovskite precursor material of nanoparticles, the perovskite precursor material having the chemical formula La 0.5 Sr 0.5 Fe 0.9 Mo 0.1 O 3-δ ；
Subjecting the LSFM-CeO 2 The composite anode and cathode are arranged on both sides of proton conductor electrolyte, and the LSFM-CeO is connected with the composite anode and cathode through wires 2 And communicating the composite anode with the cathode to obtain the proton conductor fuel cell.
The preparation method of the proton conductor fuel cell comprises the step of preparing the composite anode material LSFM-CeO 2 The preparation method comprises the following steps:
preparing LSFM anode powder by a citric acid combustion method;
adding polyethylene glycol and alcohol into the LSFM anode powder, and grinding and mixing to obtain anode slurry;
coating the anode slurry on one side of a proton conductor electrolyte, and carrying out primary calcination treatment to obtain an LSFM porous anode on one side of the proton conductor electrolyte;
weighing a certain amount of cerous nitrate medicine, dissolving the cerous nitrate medicine in deionized water, adding glycine serving as a complexing agent, and mixing to obtain Ce (NO) 3 ) 3 Impregnating liquid;
the Ce (NO) is vacuumized 3 ) 3 Impregnating the LSFM porous anode with an impregnating solution, and performing a second calcination treatment in an air atmosphere to obtain Ce (NO) impregnated in the LSFM porous anode 3 ) 3 Decomposition to CeO 2 And attaching the composite anode material to the LSFM porous anode to prepare the composite anode material LSFM-CeO 2 。
The preparation method of the proton conductor fuel cell comprises the following steps of:
dissolving lanthanum nitrate, strontium nitrate, ferric nitrate and ammonium molybdate in dilute nitric acid heated to a first temperature to prepare a mixed metal ion solution;
adding citric acid serving as a complexing agent into the mixed metal ion solution, stirring, and adding ammonia water to adjust the mixed metal ion solution to be alkaline;
heating the mixed metal ion solution at a first temperature to continuously evaporate water in the mixed metal ion solution to obtain wet gel; continuously heating the wet gel to obtain dry gel; continuously heating the xerogel, and performing self-propagating combustion on the gel when the gel reaches an ignition point to obtain uniformly dispersed LSFM precursor powder;
and carrying out calcination pretreatment on the LSFM precursor powder to obtain the LSFM anode powder with a pure phase.
The preparation method of the proton conductor fuel cell comprises the step of controlling the first temperature to be 80-100 ℃.
The preparation method of the proton conductor fuel cell comprises the following steps of calcining and pretreating at 1000-1200 ℃ for 4-6 hours; and/or the temperature of the first calcination treatment is 1000-1200 ℃, and the time is 1-3h; and/or the temperature of the second calcination treatment is 700-900 ℃ and the time is 1-3h.
The preparation method of the proton conductor fuel cell comprises the steps of adding citric acid serving as a complexing agent into the mixed metal ion solution, stirring, adding ammonia water to adjust the mixed metal ion solution to be alkaline, wherein the molar ratio of the citric acid to the total metals in the mixed metal ion solution is 1.5:1, adding ammonia water to adjust the pH value of the mixed metal ion solution to 7-7.5 after stirring.
Has the advantages that: compared with the prior art, the invention firstly uses the LSFM-CeO 2 The composite anode is applied to the proton conductor fuel cell, can obviously improve the discharge power of the cell and effectively solve the problem of carbon deposition of the anode.
Drawings
Fig. 1 is a schematic view of a proton conductor fuel cell according to the present invention.
Fig. 2 is a flow chart of a preferred embodiment of a method for manufacturing a proton conductor fuel cell according to the present invention.
In FIG. 3, a is the phase of the LSFM powder after neutralization and reduction in air, and CeO is impregnated 2 XRD spectrogram of the post composite anode; b is the XRD pattern of the composite electrolyte powder.
In fig. 4, a is an SEM picture of the surface of the composite anode after impregnation; b is an SEM picture of the cross section of the composite anode after impregnation.
FIG. 5 shows LSFM-CeO 2 TEM image of the composite anode.
FIG. 6 is a nano-particulate CeO attached to LSFM 2 The scanned image of (a).
In FIG. 7, a and b are LSFM and LSFM-CeO, respectively 2 Impedance spectroscopy in hydrogen at 600-800 ℃ for half-cells that are electrodes; c and d are LSFM and LSFM-CeO respectively 2 And (4) analyzing a spectrogram of corresponding DRT of the half cell of the electrode.
In FIG. 8, a is LSFM and LSFM-CeO 2 Fitting impedance spectrogram of half cell at 600 deg.C; b is the corresponding DRT analysis spectrogram; c is the Rp value of the two half-cells at different temperatures; d is R at different temperatures of the two half-cells H And R L The value is obtained.
In FIG. 9, a and b are LSFM/BZCY/LSCF-SDC and LSFM-CeO, respectively 2 A BZCY/LSCF-SDC single cell has a maximum current density of 650-750 ℃ under hydrogen; c and d are LSFM/BZCY/LSCF-SDC and LSFM-CeO respectively 2 Maximum current density of/BZCY/LSCF-SDC cell 650-750 ℃ under ethane.
In FIG. 10, a and b are LSFM and LSFM-CeO, respectively 2 Product analysis in an ethane atmosphere for a single cell that was the anode.
In FIG. 11, a is LSFM and LSFM-CeO 2 Single cell as electrode 150mA cm in ethane atmosphere -2 Testing the long-term stability of 22h in a constant current mode; b is Ni/BZCY and LSFM-CeO 2 The Raman test of the anode surface after the BZCY long-term test; c is the appearance of the interface between the anode and the electrolyte after long-term test; d is the micro-topography of the anode interior after long-term testing.
Detailed Description
The present invention provides a proton conductor fuel cell and a method for manufacturing the same, and the present invention will be described in further detail below in order to make the objects, technical solutions, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a schematic diagram showing the results of a preferred embodiment of a proton conductor fuel cell according to the present invention, which includes a proton conductor electrolyte 10 and LSFM-CeO on both sides of the proton conductor electrolyte 10 2 A composite anode 20 and cathode 30; the LSFM-CeO 2 The composite anode 20 is coated with CeO on the surface 2 A perovskite precursor material of nanoparticles, the perovskite precursor material having the chemical formula La 0.5 Sr 0.5 Fe 0.9 Mo 0.1 O 3-δ 。
In this embodiment, LSFM is taken as oneThe perovskite parent material has excellent stability and catalytic performance, and CeO 2 Has good oxidation-reduction performance under high-temperature reducing atmosphere. CeO is added 2 Impregnating nano particles on porous anode LSFM to form LSFM-CeO 2 The composite anode material is used for proton conductor fuel cells, can obviously improve the discharge power of the cells, and effectively solves the problem of anode carbon deposition.
In some embodiments, the proton conductor electrolyte 10 is a solid state electrolyte material BZCY of the formula BaZr 0.2 Ce 0.7 Y 0.1 O 3-δ (ii) a The cathode 30 is a LSCF-SDC composite cathode, wherein LSCF has the chemical formula La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ The chemical formula of SDC is Sm 0.2 Ce 0.8 O 1.9 。
In some embodiments, the LSFM-CeO 2 The thickness of the composite anode is 15-20 mu m, and the CeO 2 The particle size of the nano particles is 20-50nm; the LSCF-SDC composite cathode is 15-20 mu m thick.
In some embodiments, there is also provided a method of making a proton conductor fuel cell, as shown in fig. 2, comprising the steps of:
s10, providing LSFM-CeO 2 A composite anode, said LSFM-CeO 2 The composite anode is coated with CeO on the surface 2 A perovskite precursor material of nanoparticles, the perovskite precursor material having the chemical formula La 0.5 Sr 0.5 Fe 0.9 Mo 0.1 O 3-δ ；
S20, subjecting the LSFM-CeO 2 The composite anode and cathode are arranged on both sides of proton conductor electrolyte, and the LSFM-CeO is connected with the composite anode and cathode through wires 2 And communicating the composite anode with the cathode to obtain the proton conductor fuel cell.
The preparation method of the proton conductor fuel cell provided by the embodiment is simple and easy to implement, and the prepared proton conductor fuel cell has better discharge power and can effectively solve the problem of carbon deposition on the anode of the cell.
In some embodiments, LSFM-CeO 2 The preparation of the composite anode comprises the following steps:
firstly, preparing LSFM anode powder by a citric acid combustion method, dissolving lanthanum nitrate, strontium nitrate, ferric nitrate and ammonium molybdate in dilute nitric acid heated to 80-100 ℃ to prepare mixed metal ion solution; adding citric acid serving as a complexing agent into the mixed metal ion solution, stirring, and then adding ammonia water to adjust the pH value of the mixed metal ion solution to 7-7.5; heating the mixed metal ion solution at 80-100 ℃ to continuously evaporate water in the mixed metal ion solution to obtain wet gel; continuously heating the wet gel to obtain dry gel; continuously heating the xerogel, and performing self-propagating combustion when the gel reaches a combustion point to obtain uniformly dispersed LSFM precursor powder; calcining the LSFM precursor powder to obtain LSFM anode powder with a pure phase; adding polyethylene glycol and alcohol into the LSFM anode powder, and grinding and mixing to obtain anode slurry; coating the anode slurry on one side of a proton conductor electrolyte and carrying out primary calcination treatment to prepare an LSFM porous anode on one side of the proton conductor electrolyte; weighing a certain amount of cerous nitrate medicine, dissolving the cerous nitrate medicine in deionized water, adding glycine serving as a complexing agent, and mixing to obtain Ce (NO) 3 ) 3 Impregnating liquid; subjecting the Ce (NO) to vacuum 3 ) 3 Impregnating the LSFM porous anode with impregnation liquid, and performing secondary calcination treatment in air atmosphere to obtain Ce (NO) impregnated in the LSFM porous anode 3 ) 3 Decomposed into CeO 2 And attaching the composite anode material to the LSFM porous anode to prepare the composite anode material LSFM-CeO 2 Said LSFM-CeO 2 The composite anode is coated with CeO on the surface 2 A perovskite precursor material of nanoparticles, the perovskite precursor material having the chemical formula La 0.5 Sr 0.5 Fe 0.9 Mo 0.1 O 3-δ 。
In the embodiment, the temperature of the calcination pretreatment is 1000-1200 ℃, and the time is 4-6h; the temperature of the first calcination treatment is 1000-1200 ℃, and the time is 1-3h; the temperature of the second calcination treatment is 700-900 ℃, and the time is 1-3h.
In some embodiments, the BZCY and SDC precursor powders are prepared using a citric acid combustion process; weighing the required raw materials according to the stoichiometric ratio, preparing the weighed various reagents into nitrate solution, and clarifying the nitrate solution according to the molar ratio of metal ions in the mixed solution of 1:1.5 adding citric acid as complexing agent; adding ammonia water after stirring to adjust the pH value of the solution to 7-7.5; after the solution is stirred for 6 hours, heating the solution to evaporate water in the mixed solution to obtain wet gel; continuously heating the wet gel to obtain dry gel; continuously heating the xerogel, and performing self-propagating combustion on the gel to obtain uniformly dispersed nano precursor powder; and (3) respectively placing the BZCY powder and the SDC powder in muffle furnaces at 1000 ℃ and 600 ℃ to calcine for 5h and 3h to obtain the BZCY powder and the SDC powder with pure phases. Adding 1 percent of NiO powder serving as a sintering aid into BZCY, dissolving the NiO powder serving as the sintering aid into an appropriate amount of absolute ethyl alcohol, placing the mixture into a planetary ball mill for ball milling for 24 hours, placing the mixed solution into an oven for drying, and then grinding to obtain uniformly mixed BZCY powder.
The preparation method of the LSCF-SDC composite cathode comprises the following steps: mixing LSCF and SDC in a mass ratio of 6:4, dissolving the powder mixed according to the proportion of 1.5:2, adding polyethylene glycol, placing in a planetary ball mill for ball milling for 24 hours, fully mixing, drying and grinding to obtain precipitated thick and uniform cathode slurry; and (3) coating uniform cathode slurry on one side of the proton conductor electrolyte by a screen printing method in the center of a circle with the radius of 5mm, and calcining in a muffle furnace at 1100 ℃ for 2h to obtain the LSCF-SDC composite cathode.
The following examples illustrate the LSFM-CeO prepared by the present invention 2 The performance of the composite anode and proton conductor fuel cell is further explained:
example 1
Preparation of proton conductor fuel cell:
s1) preparing SDC precursor powder, BZCY precursor powder, LSFM anode precursor powder and LSCF cathode precursor powder by a citric acid combustion method; dissolving required salts into dilute nitric acid according to a stoichiometric ratio to prepare a mixed metal ion solution; adding citric acid serving as a complexing agent into the mixed metal ion solution, wherein the ratio of the citric acid to the total metal ions is 1.5:1; adding ammonia water after stirring to adjust the pH value of the solution to 7-7.5; after the solution is stirred for 6 hours, heating the solution to evaporate water in the mixed solution to obtain wet gel; continuously heating the wet gel to obtain dry gel; continuously heating the xerogel, and performing self-propagating combustion on the gel to obtain uniformly dispersed nano precursor powder;
s2) calcining the SDC precursor powder, the BZCY precursor powder, the LSFM anode precursor powder and the LSCF cathode precursor powder at 600 ℃, 1000 ℃ and 1000 ℃ for 3h, 5h and 5h respectively to obtain various pure-phase powders:
s3) adding NiO powder with the volume ratio of 1% into the BZCY powder by adopting a solid phase method, uniformly mixing on a planetary ball mill, drying and grinding to obtain uniform BZCY electrolyte powder;
and S4) pressing the BZCY electrolyte powder into a shape by adopting a dry pressing method, and sintering at the high temperature of 1400 ℃ to obtain a compact electrolyte layer. Grinding the electrolyte layer to a thickness of 300 μm on a grinding and polishing machine;
s5) dissolving the anode LSFM powder with pure phase in absolute ethyl alcohol, wherein the cathode is formed by mixing LSCF and SDC according to the mass ratio of 6:4, dissolving the powder mixed according to the proportion of 1.5:2, adding polyethylene glycol according to the mass ratio, respectively placing the mixture in a planetary ball mill for ball milling for 24 hours, fully mixing, drying and grinding to obtain precipitated thick and uniform cathode and anode slurry; coating uniform cathode and anode on the center of the electrolyte by a screen printing method in a circle with the radius of 5mm at two sides, and calcining for 2h in a muffle furnace at 1100 ℃ to obtain a porous LSCF-SDC cathode and an LSFM anode;
s6) impregnation of Ce (NO) onto the anode by impregnation 3 ) 3 Calcining the solution at 850 ℃ for 3 hours to obtain CeO 2 Nanoparticles to obtain LSFM-CeO 2 Compounding an anode; a proton conductor fuel cell is obtained.
Example 3
For the LSFM-CeO in example 1 2 The composite anode performance was tested and compared to the LSFM anode:
to makeFor example, a solid electrolyte is prepared by a dry pressing method, and a cathode and an anode are prepared by a screen printing method. If a reaction occurs between the materials in contact with each other to form other substances, the substances may hinder the conductivity of the materials and the catalytic activity of the reaction, directly affect the stability of the battery, and cause the degradation or damage of the battery. As shown in FIG. 3 (a), LSFM was stable in operation in a reducing atmosphere and after impregnation CeO appeared in the material 2 Indicating that the impregnation of the anode has been successful. Fig. 3 (b) shows LSFM, BZCY materials and their blends at 1: after the mixed powder with the volume ratio of 1 is ground, sintering is carried out at the electrolyte sintering temperature of 1400 ℃, the chemical compatibility among materials can be seen to be good, LSFM and BZCY do not have any reaction at high temperature, and no new phase is generated.
FIG. 4 is an SEM image of the surface and cross section of the impregnated composite anode, and it can be seen from the microstructure that after impregnation, the porous anode LSFM surface has obvious attachments which are nanoparticles with the size of 20-50nm and are uniformly distributed on the anode surface, and the particles may be CeO formed after the impregnation liquid is calcined 2 And (3) nanoparticles.
FIG. 5 is a TEM image of an LSFM-CeO2 composite anode. As can be seen from the macroscopic picture, the anodic LSFM presents a rough surface with a lattice spacing of 0.276nm as measured by High Resolution Transmission Electron Microscopy (HRTEM), corresponding to (La) in Jade 0.5 Sr 0.5 )FeO 3 The (110) surface of the phase (PDF # 82-1962). And CeO 2 The particles exhibited a smooth surface with interplanar spacings measured at 0.271nm, corresponding to the Jade CeO 2 The (200) surface of the phase (PDF # 89-8436). This indicates that CeO 2 The nanoparticles tend to be in (La) 0.5 Sr 0.5 )FeO 3 The (110) crystal plane of the phase grows. And carrying out line scanning on the nanoparticles on the surface of the material. TEM-EDS results are shown in FIG. 6, and it can be seen that the particles consist essentially of Ce and O (Ce: O =33%: 66%), indicating that the attachment on the anode surface is CeO 2 Nanoparticles, this corresponds to CeO shown in XRD spectrum 2 The peaks are consistent, further demonstrating that CeO 2 Successfully impregnated on the surface of the porous anode.
For better understanding, ceO was impregnated at the anode 2 The electrochemical performance of the battery is influenced, and LSFM/BZCY/LSFM and LSFM-CeO are prepared 2 /BZCY/LSFM-CeO 2 Half-cell, tested for electrochemical impedance spectroscopy at operating temperature of 600-800 ℃ under open circuit voltage conditions in a hydrogen atmosphere. The test results are shown in FIGS. 7 (a) and (b). To further reveal the kinetic effect of impregnation on catalytic activity, LSFM and LSFM-CeO were analyzed at 600-800 ℃ by the relaxation time Distribution (DRT) method 2 The impedance spectrum of (c) is shown in FIGS. 7 (c) and (d). Through DRT analysis, three time constants are found to appear in the half-cell operation process, so that the impedance diagram is fitted with the corresponding equivalent circuits L1R1 (R2// CPE 1) (R3// CPE 2) (R4// CPE 3). And R2, R3 and R4 represent high frequency, intermediate frequency and low frequency polarization resistances R, respectively H 、R M And R L . CPE1, CPE2, CPE3 are constant phase angle elements. As can be seen from both the impedance spectrum and the DRT spectrum, the impedance decreases significantly with increasing temperature, and the decrease in the area in the DRT also represents the decrease in impedance. This is because as the temperature increases, the energy of the reaction increases, and both the molecules and ions move faster, thereby reducing the overall impedance.
FIGS. 8 (a) and (b) are graphs showing the results of the reaction at 600 ℃ with LSFM and LSFM-CeO 2 The impedance spectrum of the electrode half cell and the DRT analysis chart are shown. At the same temperature, LSFM-CeO 2 /BZCY/LSFM-CeO 2 The impedance of the half cell is much smaller than that of the cell with LSFM as anode material, and this information is also reflected in the DRT analysis. The processes P1, P2 and P3 in the high frequency, intermediate frequency and low frequency regions in the diagram b represent the ion conduction process at the three-phase interface between the electrode and the electrolyte, the transfer process of charges between the electrode and the electrolyte interface and the adsorption, dissociation and diffusion processes of the ethane fuel gas inside the porous electrode, respectively. Thus, high, medium and low frequency polarization resistances R H 、R M And R L Corresponding to the P1, P2 and P3 processes, respectively. It can be seen that the main impedance of both cells is concentrated in the P3 region, i.e. the process of adsorption, dissociation and diffusion of the gas is the controlling step of the overall reaction process. The impedance of the two half batteries in the P2 interval is basically equal, and the impedance of the LSFM in the P1 intervalSlightly larger anti-LSFM-CeO 2 While the impedance of LSFM in the P3 interval is much larger than LSFM-CeO 2 Note that CeO was impregnated 2 Then, the processes of adsorption, dissociation and diffusion of ethane gas are greatly improved, thereby improving the electrocatalytic activity. FIG. 8 (c) shows R P Resistance at different temperatures, R P The difference value between the intercept of the high-frequency end and the intercept of the low-frequency end and the X axis also represents the polarization resistance of the whole electrode, and the RP is a main factor for evaluating the catalytic activity. LSFM-CeO at different temperatures 2 R of (A) to (B) P The values are all less than LSFM, further illustrating LSFM-CeO 2 The material has improved catalytic activity for ethane materials. FIG. 8 (d) shows two material half cells at different temperatures R H And R L The process of variation of (c). From 600-800 ℃, RL is always the main rate-limiting step in the anode reaction process, R H Also one of the main factors affecting the anodic process, LSFM-CeO 2 In the material R H And R L Further reveals impregnated CeO 2 The nanoparticles enhance catalytic activity for ethane conversion by improving ion diffusion processes at the three-phase interface of the anodic reaction and adsorption, dissociation and diffusion processes of gases at the porous anode.
The discharge power density curve and polarization curve at a temperature of 650-750 c of LSFM/BZCY/LSCF unit cells and LSFM-CeO2/BZCY/LSCF unit cells using hydrogen and ethane as fuel were tested as shown in fig. 9. Under a hydrogen atmosphere, the maximum discharge power densities at 650, 700 and 750 ℃ of a single cell using LSFM as an anode catalyst were 122, 183 and 253mW.cm, respectively -2 . And using LSFM-CeO 2 The maximum discharge power densities for the anode material cells at 650, 700 and 750 ℃ were 142, 210 and 291mW.cm, respectively -2 . When ethane was used as the fuel gas, the maximum power densities of the LSFM/BZCY/LSCF cells were 24, 56, and 140mW.cm at 650, 700, and 750 deg.C, respectively -2 . And LSFM-CeO 2 The maximum power densities of the/BZCY/LSCF cells were 39, 90 and 190mW.cm at 650, 700 and 750 ℃ respectively -2 . It is evident that under either hydrogen or ethane atmosphere, LSFM-CeO was used 2 Single cell performance as anodeIs far higher than the single cell performance of taking LSFM as the anode catalyst. LSFM-CeO at 750 deg.C under hydrogen and ethane atmosphere 2 the/BZCY/LSCF single cell is 38 and 50mW/cm higher than the LSFM/BZCY/LSCF single cell respectively -2 。
The product after ethane conversion was passed to a Gas Chromatograph (GC) and the composition of the anode product after the reaction was analyzed. And (5) carrying out calibration analysis on the content of the product by adopting an internal standard method. Firstly, calibrating a gas chromatograph, introducing mixed gas with a standard volume into the gas chromatograph, comparing the mixed gas with an internal standard gas nitrogen, obtaining a correction factor according to the peak area of the mixed gas on the chromatograph and the linear relation between the mixed gas and the peak area of the nitrogen, and then calculating the content of the gas component to be tested according to a standard curve. During the product detection process, the battery is subjected to a constant voltage discharge test at the same time under the maximum discharge power. The test batteries are LSFM/BZCY/LSCF single battery and LSFM-CeO respectively 2 The test temperature of the/BZCY/LSCF single cell is 650-750 ℃, the working gas is ethane, and the test result is shown in figure 10. At 750 c, the test product had methane, propane, ethylene and propylene, no propane was produced at 700 c and no propane and propylene were present in the product at 650 c.
And substituting a formula according to the peak area relationship of ethylene and ethane on the FID2 and the relationship of the area of a nitrogen peak, the area of an ethane peak and the area of an ethylene peak on the TCD, and calculating the conversion rate of ethane and the selectivity of ethylene. As shown, the ethane conversion of the LSFM-/BZCY/LSCF single cell at the operating temperature of 650-750 ℃ is 20.2%, 28.7% and 38.9%, respectively, and the selectivity to ethylene is 98.6%, 97.5% and 94.4. Ethylene yields of 19.9%, 28.0% and 36.7% were further determined from ethane conversion and ethylene selectivity. While the ethane conversion at the operating temperature of 650-750 ℃ of the LSFM-CeO2/BZCY/LSCF single cell was 26.4%, 30.3% and 39.7%, respectively, and the ethylene selectivity was 98.7%, 97.0% and 93.4%, respectively, it was further found that the ethylene yields at the different temperatures were 26.1%, 29.4% and 37.1%, respectively.
LSFM-CeO 2 The ethane conversion and ethylene yield of the anode at different temperatures were higher than that of the LSFM anode. This is because CeO 2 The increased active sites of the particles increase the catalytic activity of the anode material towards ethane, which in turn increases ethane conversion and ethylene yield. And the improvement of the ethylene yield is of great significance industrially.
To compare CeO 2 The influence on the long-term stability of the SOFC single cell in the working environment before and after impregnation is tested by LSFM/BZCY/LSCF single cell and LSFM-CeO 2 Long-term stability of/BZCY/LSCF cells in a working environment of an ethane atmosphere at 750 ℃. The test adopts a constant current mode, the current density is 150mA/cm < -2 >, the test time is 22h, and the voltage change condition under the constant current condition is observed, so that the stability of the battery is evaluated. The test results are shown in FIG. 11 (a).
As can be seen from the test results, the voltage value of the LSFM/BZCY/LSCF single cell continuously decays during the discharge, and 22h decays by 3.88 percent, while the LSFM-CeO 2 The voltage of the/BZCY/LSCF single cell is attenuated by 0.49 percent, and basically keeps a stable state with only a small amount of attenuation. Therefore, LSFM-CeO 2 The anode has better long-term stability in ethane operation than LSFM anode, and is impregnated with CeO 2 The stability of the cell in ethane can be improved. This is probably because CeO is impregnated in an appropriate ratio 2 Effectively improves the structure of the anode and the attached CeO 2 Greatly expands the area of the anode three-phase interface and increases a large number of reaction active sites. Further, ceO 2 The anode has good electronic conductivity and high ionic conductivity, so that the ion transfer rate and the electron transfer rate in the anode are increased, and the electrochemical reaction rate of the anode is further improved.
11 (b) in the figure shows a Ni-based anode cell and LSFM-CeO 2 And after the anode battery is tested under ethane for a long time, the Raman analysis result of the battery surface is obtained. It can be seen that the Ni-based anode has two distinct carbon characteristic peaks in the D band and G band, while LSFM-CeO 2 The anode had no distinct peak characteristic of carbon and therefore no carbon deposition. This indicates that LSFM-CeO 2 The anode has a certain carbon deposit resistance due to CeO 2 In CeO 2 Loss of a significant amount of oxygen to form a large number of oxygen vacancies, resulting in non-stoichiometric CeO 2 And generates a large amount of lattice oxygenSo that CeO 2 Has high oxygen storage capacity and oxygen mobility, and carbon is deposited on CeO 2 Surface, may be formed by a chemical reaction from CeO 2 The lattice oxygen of (2) promotes the elimination of carbon. The LSFM-CeO after the test is shown in FIG. 11 (c) 2 After long-term test, the interface diagram of the connection of the anode and the BZCY shows that the electrolyte and the anode are still tightly combined without obvious layering, which indicates that the battery structure is stable. Meanwhile, the enlarged cross-sectional view of the anode surface after the long-term test is shown in FIG. 11 (d), and no significant carbon nanotubes are found inside the anode, which further illustrates the impregnation of CeO on the anode LSFM, which is the anode 2 Has certain carbon deposition resistance.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (2)
1. A method of making a proton conductor fuel cell, comprising the steps of:
providing LSFM-CeO 2 Composite anode of said LSFM-CeO 2 The composite anode is coated with CeO on the surface 2 A perovskite precursor material of nanoparticles, the perovskite precursor material having the chemical formula La 0.5 Sr 0.5 Fe 0.9 Mo 0.1 O 3-δ ；
Subjecting the LSFM-CeO 2 The composite anode and cathode are arranged on both sides of proton conductor electrolyte, and the LSFM-CeO is connected with the composite anode and cathode through wires 2 Communicating the composite anode with the cathode to prepare the proton conductor fuel cell;
wherein the CeO 2 The particle size of the nano particles is 20-50nm;
the material of the proton conductor electrolyte is BaZr 0.2 Ce 0.7 Y 0.1 O 3-δ ；
The cathode is an LSCF-SDC composite cathode, wherein the chemical formula of the LSCF is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ The chemical formula of SDC is Sm 0.2 Ce 0.8 O 1.9 ；
The LSFM-CeO 2 The thickness of the composite anode is 15-20 μm, and the thickness of the LSCF-SDC composite cathode is 15-20 μm;
the composite anode material LSFM-CeO 2 The preparation method comprises the following steps:
dissolving lanthanum nitrate, strontium nitrate, ferric nitrate and ammonium molybdate in dilute nitric acid heated to 80-100 ℃ to prepare mixed metal ion solution;
adding citric acid serving as a complexing agent into the mixed metal ion solution, stirring, and adding ammonia water to adjust the mixed metal ion solution to be alkaline;
heating the mixed metal ion solution at 80-100 ℃ to continuously evaporate water in the mixed metal ion solution to obtain wet gel; continuously heating the wet gel to obtain dry gel; continuously heating the xerogel, and performing self-propagating combustion on the gel when the gel reaches an ignition point to obtain uniformly dispersed LSFM precursor powder;
calcining the LSFM precursor powder to obtain LSFM anode powder with a pure phase;
adding polyethylene glycol and alcohol into the LSFM anode powder, and grinding and mixing to obtain anode slurry;
coating the anode slurry on one side of a proton conductor electrolyte and carrying out primary calcination treatment to prepare an LSFM porous anode on one side of the proton conductor electrolyte;
weighing a certain amount of cerous nitrate medicine, dissolving the cerous nitrate medicine in deionized water, adding glycine serving as a complexing agent, and mixing to obtain Ce (NO) 3 ) 3 Impregnating liquid;
the Ce (NO) is vacuumized 3 ) 3 Impregnating the LSFM porous anode with impregnation liquid, and performing secondary calcination treatment in air atmosphere to obtain Ce (NO) impregnated in the LSFM porous anode 3 ) 3 Decomposed into CeO 2 And attaching the composite anode material to the LSFM porous anode to prepare the composite anode material LSFM-CeO 2 ；
The preparation of the composite cathode material LSCF-SDC comprises the following steps:
mixing LSCF and SDC in a mass ratio of 6:4, dissolving the powder mixed according to the proportion of 1.5:2, adding polyethylene glycol according to the mass ratio, placing the mixture in a planetary ball mill for ball milling for 24 hours, fully mixing, drying and grinding to obtain cathode slurry; coating uniform cathode slurry on one side of a proton conductor electrolyte by a screen printing method, wherein the center of the cathode slurry is a circle with the radius of 5mm, and placing the cathode slurry in a muffle furnace at 1100 ℃ for calcining for 2h to obtain an LSCF-SDC composite cathode;
the temperature of the calcination pretreatment is 1000-1200 ℃, and the time is 4-6h; and/or the temperature of the first calcination treatment is 1000-1200 ℃, and the time is 1-3h; and/or the temperature of the second calcination treatment is 700-900 ℃ and the time is 1-3h.
2. The method for producing a proton conductor fuel cell according to claim 1, wherein in the step of adding citric acid as a complexing agent to the mixed metal ion solution and adjusting the mixed metal ion solution to be alkaline by adding ammonia water after stirring, the molar ratio of citric acid to the total metal in the mixed metal ion solution is 1.5:1, adding ammonia water to adjust the pH value of the mixed metal ion solution to 7-7.5 after stirring.
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