CN117080468A - Self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material and preparation method and application thereof - Google Patents
Self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
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- 238000002360 preparation method Methods 0.000 title abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
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- 238000000034 method Methods 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 17
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
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- 230000002269 spontaneous effect Effects 0.000 claims description 4
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- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 3
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0054—Mixed oxides or hydroxides containing one rare earth metal, yttrium or scandium
-
- 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
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- 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
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- 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
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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- 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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Abstract
The invention provides a self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, and a preparation method and application thereof. The invention adjusts the mole ratio of Sr, nd and Fe in the raw materials to be 1-x:x:1-y, and self-assembles the iron-based perovskite SrFeO based on a one-step sol-gel method 3‑δ Simultaneously carrying out Nd doping and Fe site defect treatment on the Sr site so that the prepared composite cathode material simultaneously contains the orthorhombic perovskite phase Sr as a main phase 1‑ a Nd a FeO 3‑δ1 (P-SNF) and Ruddlesden-Popper (RP) perovskite phase Sr as second phase 3‑ b Nd b Fe 2 O 7‑δ2 And (RP-SNF), the advantages of the two-phase materials are cooperatively exerted, and meanwhile, the rapid oxygen transmission path existing at the heterogeneous interface of the two phases is combined, so that the oxygen reduction reaction activity of the cathode material is effectively improved, and the cathode material has better electrochemical performance.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, and a preparation method and application thereof.
Background
Solid Oxide Fuel Cells (SOFC) are a high-efficiency clean energy power generation technology for directly converting chemical energy into electric energy, and are attracting attention due to the characteristics of high energy conversion efficiency, cleanliness and no pollution. Conventional SOFCs operate at high temperatures (800-1000 ℃) with many problems, and efforts have been made to reduce the operating temperature of SOFCs to the mid-temperature range (600-800 ℃). However, the electrocatalytic activity of the oxygen reduction reaction of the SOFC cathode material is also drastically reduced due to the reduction of the working temperature, so that the polarization resistance of the cathode and the overall performance of the SOFC are adversely affected. Therefore, the development of a novel cathode material having good aerobic reduction catalytic activity in a medium temperature range has become an important research direction for solid oxide fuel cells.
SrFeO in various cathode materials of medium-temperature solid oxide fuel cells 3-δ The perovskite-based cathode material has a lower thermal expansion coefficient, and has better thermal matching property with the traditional electrolyte material, but has poorer oxygen reduction catalytic activity. At present, researchers mainly increase SrFeO by doping 3-δ Catalytic activity of the perovskite-based cathode material. For example, the number of the cells to be processed,the patent with publication number CN103682373A provides a stable cathode material of non-cobalt medium-temperature solid oxide fuel cell and application thereof, which is prepared by using SrFeO 3-δ Nd is doped at the A site and Cu is doped at the B site, so that the prepared single-phase cathode material has excellent oxygen reduction catalytic activity and greatly improved electrochemical performance. The patent publication No. CN109742414A provides a medium-temperature solid oxide fuel cell cathode material, a preparation method and application thereof, and the patent uses Ta with high and stable valence state 5+ And Mo (Mo) 6+ For SrFeO 3-δ Co-doping Ta and Mo to co-replace SrFeO 3-δ Thereby obtaining a single-phase cathode material with stable structure in a medium temperature region and good oxygen reduction catalytic activity. However, the above doping methods all produce cathode materials with single-phase structure, and the improvement effect on the oxygen reduction catalytic activity of the cathode materials is limited.
In view of the foregoing, there is a need for an improved two-phase heterostructure solid oxide fuel cell composite cathode material, and a method for preparing the same and applications thereof, to solve the above-mentioned problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, and a preparation method and application thereof. The invention uses the iron-based perovskite SrFeO 3-δ And simultaneously, the Sr site Nd doping and Fe site defect treatment are carried out, the self-assembly is carried out based on a one-step sol-gel method, the prepared composite cathode material simultaneously contains an orthogonal perovskite phase and an RP perovskite phase, and the advantages of the two-phase materials are cooperatively exerted, and meanwhile, the rapid oxygen transmission path existing at the heterogeneous interface of the two phases is combined, so that the oxygen reduction reaction activity of the cathode material is effectively improved.
In order to achieve the above purpose, the invention provides a self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, wherein the molar ratio of Sr, nd, fe, O in the composite cathode material is 1-x, 1-y, 3-delta; the composite cathode material comprises a main phase and a second phase, wherein the main phase is an orthorhombic perovskite phase, and the chemical formula is Sr 1-a Nd a FeO 3-δ1 The second phase is RP type perovskite phase, and the chemical formula is Sr 3-b Nd b Fe 2 O 7-δ2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.1, a is more than 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.3, delta is more than or equal to 0 and less than or equal to 0.5, delta 1 is more than or equal to 0 and less than or equal to 0.5, and delta 2 is more than or equal to 0 and less than or equal to 1.
As a further improvement of the present invention, the mass ratio of the main phase and the secondary phase is 50-65:35-50.
The invention also provides a preparation method of the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, which comprises the following steps:
s1, configuring a Sr source, an Nd source and an Fe source according to a preset molar ratio;
s2, dissolving the Sr source, the Nd source and the Fe source which are configured in the step S1 in water to obtain a mixed solution; adding citric acid and ethylenediamine tetraacetic acid into the mixed solution, adjusting the pH value, stirring for reaction, and self-assembling to obtain a reactant;
s3, performing heating treatment on the reactant to obtain a precursor;
and S4, calcining the precursor to obtain the composite cathode material.
As a further improvement of the present invention, in step S1, the Sr source, nd source, and Fe source are strontium nitrate, neodymium nitrate, and ferric nitrate, respectively.
As a further improvement of the present invention, in step S2, the molar ratio of the ethylenediamine tetraacetic acid, citric acid and the metal cations in the mixed solution is 1:1.5:1.
As a further improvement of the present invention, in step S2, the manner of adjusting the pH value is: ammonia is added to adjust the pH value to be neutral.
As a further improvement of the invention, in the step S2, the stirring reaction time is 1-2 h.
As a further improvement of the present invention, in step S3, the heating treatment includes heating the reactant sufficiently until the solution evaporates, forming a gel-like substance; and heating the gel-like substance to spontaneous combustion, and continuously heating until the combustion reaction is finished to obtain a precursor.
As a further improvement of the present invention, in step S4, the calcination treatment includes pre-sintering the precursor at 500 to 700 ℃ for 3 to 5 hours to obtain a pre-sintered product; grinding the presintering product, and then calcining for 4-6 hours at 1100-1200 ℃.
The invention also provides application of the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material in preparation of a solid oxide fuel cell.
The beneficial effects of the invention are as follows:
the preparation method of the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material provided by the invention regulates and controls the stoichiometric ratio of raw materials, and performs self-assembly based on a one-step sol-gel method, so as to realize the self-assembly of the iron-based perovskite SrFeO 3-δ Simultaneously carrying out Nd doping and Fe site defect treatment on the Sr site, so that the prepared composite cathode material simultaneously contains the orthorhombic perovskite phase Sr as a main phase 1-a Nd a FeO 3-δ1 (P-SNF) and RP-type perovskite phase Sr as second phase 3- b Nd b Fe 2 O 7-δ2 (RP-SNF). Compared with a single-phase structure, the two-phase heterostructure formed in the composite cathode material provided by the invention not only can cooperatively play the advantages of the two-phase material, but also has a rapid oxygen transmission path at a perovskite heterogeneous interface, and can show faster oxygen surface exchange and diffusion kinetics, so that the oxygen reduction reaction activity is promoted.
Compared with the traditional solid-state mechanical mixed composite material mode, the self-assembled composite material has the advantages that by adopting the self-assembled synthesis mode, different components have more excellent chemical compatibility, more uniform component distribution is obtained, heterogeneous interfaces and three-phase interfaces are enlarged, good interface connection is realized, and the electrochemical performance is improved.
Drawings
FIG. 1 is an X-ray diffraction spectrum of the composite cathode materials prepared in examples 1 to 2 and the cathode material prepared in comparative example 1.
Fig. 2 is an SEM morphology of the composite cathode material prepared in example 1.
Fig. 3 is an HRTEM image of the composite cathode material prepared in example 1.
Fig. 4 is an ac impedance spectrum at 750 ℃ of the symmetrical batteries prepared in examples 1 to 2 and comparative example 1.
Fig. 5 is a graph showing discharge curves of the full cells prepared in examples 1 to 2 and comparative example 1 versus a power density curve.
Fig. 6 is an X-ray diffraction spectrum of the cathode material prepared in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, wherein the molar ratio of Sr, nd, fe, O in the composite cathode material is 1-x, x is 1-y, and 3-delta; the composite cathode material comprises a main phase and a second phase, wherein the main phase is an orthorhombic perovskite phase, and the chemical formula is Sr 1-a Nd a FeO 3-δ1 The second phase is RP type perovskite phase, and the chemical formula is Sr 3-b Nd b Fe 2 O 7-δ2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.1, a is more than 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.3, delta is more than or equal to 0 and less than or equal to 0.5, delta 1 is more than or equal to 0 and less than or equal to 0.5, and delta 2 is more than or equal to 0 and less than or equal to 1.
Preferably, the mass ratio of the main phase to the second phase is 50-65:35-50.
The invention also provides a preparation method of the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, which comprises the following steps:
s1, configuring a Sr source, an Nd source and an Fe source according to a preset molar ratio;
s2, dissolving the Sr source, the Nd source and the Fe source which are configured in the step S1 in water to obtain a mixed solution; adding citric acid and ethylenediamine tetraacetic acid into the mixed solution, adjusting the pH value, stirring for reaction, and self-assembling to obtain a reactant;
s3, performing heating treatment on the reactant to obtain a precursor;
and S4, calcining the precursor to obtain the composite cathode material.
In step S1, the Sr source, nd source, and Fe source are strontium nitrate, neodymium nitrate, and ferric nitrate, respectively; in some embodiments of the present invention, the Sr source, nd source, and Fe source are specifically Sr (NO 3 ) 2 、Nd(NO 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O; the mole ratio of corresponding Sr, nd and Fe in the Sr source, the Nd source and the Fe source is 1-x:x:1-y.
So arranged that the iron-based perovskite SrFeO can be prepared 3-δ Simultaneously carrying out Nd doping and Fe site defect treatment on the Sr site, so that the prepared composite cathode material simultaneously contains the orthorhombic perovskite phase Sr as a main phase 1-a Nd a FeO 3-δ1 (P-SNF) and RP-type perovskite phase Sr as second phase 3-b Nd b Fe 2 O 7-δ2 (RP-SNF) and thus exhibit faster oxygen surface exchange and diffusion kinetics to promote oxygen reduction reactivity with the rapid oxygen transport pathways present at the perovskite heterogeneous interface.
Preferably, in step S2, the molar ratio of the ethylenediamine tetraacetic acid, the citric acid and the metal cations in the mixed solution is 1:1.5:1; the pH value is adjusted by the following steps: ammonia water is added to adjust the pH value to be neutral; the stirring reaction time is 1-2 h.
In step S3, the heating treatment includes heating the reactant sufficiently until the solution evaporates, forming a gel-like mass; and heating the gel-like substance to spontaneous combustion, and continuously heating until the combustion reaction is finished to obtain a precursor.
In the step S4, the calcination treatment comprises the steps of placing the precursor at 500-700 ℃ for presintering for 3-5 hours to obtain a presintering product; grinding the presintering product, and then calcining for 4-6 hours at 1100-1200 ℃.
The invention also provides application of the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material in preparation of a solid oxide fuel cell.
The self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, the preparation method and the application thereof are specifically described below by combining specific examples.
Example 1
The embodiment provides a preparation method of a self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, which comprises the following steps:
s1, weighing Sr (NO) according to the mole ratio of 0.95:0.05:0.95 of Sr, nd and Fe 3 ) 2 、Nd(NO 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is used as Sr source, nd source and Fe source respectively.
S2, dissolving the Sr source, the Nd source and the Fe source weighed in the step S1 in deionized water, and stirring to obtain a clear mixed solution; and then adding citric acid and ethylenediamine tetraacetic acid into the mixed solution to make the molar ratio of the ethylenediamine tetraacetic acid, the citric acid and all metal cations in the mixed solution be 1:1.5:1, then adding ammonia water, adjusting the pH value of the solution to 7, stirring and reacting for 1.5h, and self-assembling to obtain a reactant.
S3, evaporating the reactant obtained in the step S2 in a water bath kettle at 80 ℃ to form a gel substance; and then placing the obtained gel-like substance on an electronic universal furnace for heating until spontaneous combustion occurs, continuously heating until the combustion reaction is finished, collecting black ash generated by combustion, and fully grinding to obtain a precursor.
S4, sintering the precursor obtained in the step S3 for 4 hours at 600 ℃ to remove residual organic matters, and obtaining a presintered product; and fully grinding the presintered product, and calcining at 1200 ℃ for 5 hours to obtain the composite cathode material.
The molar ratio of Sr, nd, fe, O in the composite cathode material is 0.95:0.05:0.95:3-delta, wherein delta is the content of oxygen vacancies, and the range of the oxygen vacancy content delta in the composite cathode material is more than or equal to 0 and less than or equal to 0.5 as measured by an iodine titration method.
The composite cathode material prepared in this example was subjected to X-ray diffraction analysis and morphology characterization, and the results are shown in fig. 1-3, respectively.
FIG. 1 is an X-ray diffraction pattern of a composite cathode material. In FIG. 1, the diffraction spectrum corresponding to SNF0.05 is that of the composite cathode material prepared in this example, and as can be seen from FIG. 1, the composite cathode material prepared in this example is a two-phase mixture comprising a main phase orthorhombic perovskite phase Sr 0.95 Nd 0.05 FeO 3-δ1 (P-SNF) and a second phase RP-type perovskite phase Sr 2.85 Nd 0.15 Fe 2 O 7-δ1 (RP-SNF). By analyzing the XRD data using the jack software, it can be derived that: in this example, the mass ratio of the primary phase P-SNF to the secondary phase RP-SNF was 63.4:36.6.
Fig. 2 is an SEM morphology of the surface of the composite cathode material, and as can be seen from fig. 2, the second phase RP-SNF covers the perovskite macroparticles in nano-platelets.
Fig. 3 is an HRTEM image of the surface of the composite cathode material. From FIG. 3, it can be seen that the 400 crystal plane of the P-SNF phase having a lattice spacing of 0.272nm and the 105 crystal plane of the RP-SNF phase having a lattice spacing of 0.278nm are closely connected to form a hetero interface.
The embodiment also provides application of the composite cathode material in battery preparation, and specifically comprises preparation of a symmetrical battery and preparation of a full battery.
The preparation of the symmetrical battery comprises the following steps:
mixing the prepared cathode material with a binder to obtain cathode slurry, wherein the binder is a mixture of 92% terpineol and 8% ethylcellulose;
coating cathode slurry on both sides of electrolyte, oven drying at 80deg.C for 1 hr, and then drying at 80deg.CSintering at 1000 deg.c for 2 hr to obtain symmetrical cell with La as electrolyte 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (LSGM)。
The preparation of the full cell comprises the following steps:
ce is prepared from 0.8 Sm 0.2 O 3-δ Mixing (SDC) powder with binder, grinding to form uniform slurry, applying the slurry on one side of LSGM electrolyte by screen printing method, oven drying, calcining at 1300 deg.C for 2 hr, and using as buffer layer of full cell.
Mixing NiO and SDC uniformly in a ratio of 7:3 to obtain anode powder, adding a binder, fully grinding into uniform slurry, uniformly coating the slurry on the surface of a buffer layer by screen printing, drying and calcining at 1250 ℃ for 4 hours.
The composite cathode material prepared in this example was mixed with a binder and then sufficiently ground into a uniform slurry, which was applied to the other surface of the LSGM electrolyte by screen printing, and calcined at 950 ℃ for 2 hours to prepare a full cell.
Example 2
Embodiment 2 provides a method for preparing a self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, which is different from embodiment 1 only in that the molar ratio of Sr, nd, fe in step S1 is modified to 0.9:0.1:0.9, and other steps and parameters are the same as those in embodiment 1, and are not described herein.
The X-ray diffraction spectrum of the composite cathode material prepared in this example is shown as SNF0.1 in fig. 1. As can be seen from FIG. 1, the composite cathode material prepared in this example is also a two-phase mixture comprising a main phase of orthorhombic perovskite phase Sr 0.9 Nd 0.1 FeO 3-δ1 (P-SNF) and a second phase RP perovskite phase Sr 2.7 Nd 0.3 Fe 2 O 7-δ1 (RP-SNF). By analyzing the XRD data using the jack software, it can be derived that: in this example, the mass ratio of the primary phase P-SNF to the secondary phase RP-SNF was 50.3:49.7.
The prepared composite cathode material is applied to the preparation of symmetrical batteries and full batteries, and the preparation methods of the corresponding symmetrical batteries and full batteries are the same as those described in the embodiment 1, and are not repeated here.
Comparative example 1
The comparative example provides a method for preparing a cathode material of a solid oxide fuel cell, which is different from example 1 only in that no Nd source is added in step S1, and the molar ratio of Sr to Fe is controlled to be 1:1, which corresponds to not performing Sr Nd doping or Fe site defect treatment, and other steps and parameters are the same as those of example 1, and are not repeated here.
The X-ray diffraction spectrum of the cathode material prepared in this example is shown as SF in fig. 1. As can be seen from FIG. 1, the cathode material prepared in comparative example 1 contains only a single phase SrFeO 3-δ The two-phase heterostructures of example 1 and example 2 are absent.
The prepared composite cathode material is also applied to the preparation of symmetrical batteries and full batteries, and the preparation methods of the corresponding symmetrical batteries and full batteries are the same as those described in the embodiment 1, and are not repeated here.
For the electrochemical properties of the cathode materials prepared in comparative examples 1 to 2 and comparative example 1, the symmetrical cells and the full cells prepared in examples 1 to 2 and comparative example 1 were examined, and the results are shown in fig. 4 and 5.
Among them, fig. 4 is an ac impedance spectrum at 750 ℃ of the symmetrical batteries prepared in examples 1 to 2 and comparative example 1. Fig. 5 is a graph showing the discharge curves of the full cells prepared in examples 1 to 2 and comparative example 1, versus the power density curve.
As can be seen from FIG. 4, the polarization impedance of the single-phase SF cathode symmetric cell prepared in comparative example 1 was 0.5852 Ω -cm 2 The polarization resistance of the two-phase composite SNF0.05 cathode symmetric cell prepared in example 1 was 0.1812 Ω cm 2 The polarization resistance of the two-phase composite SNF0.1 cathode symmetric cell prepared in example 2 was 0.2986 Ω cm 2 The composite cathode materials prepared in examples 1-2 were shown to have significantly lower polarization resistance than the single-phase cathode material prepared in comparative example 1, and the polarization resistance corresponding to the doped amount of Nd in example 1 was lower than that corresponding to the doped amount of Nd in example 2 of 0.1 at a doped amount of Nd of 0.05. Namely, the complex prepared by the inventionThe oxygen reduction reaction activity of the cathode material was significantly increased compared to the single-phase cathode material prepared in comparative example 1, and the Nd doping amount was 0.05, which was higher than that of comparative example 1, if the Nd doping amount was further increased to 0.1, the oxygen reduction activity was rather decreased, but was still better than that of comparative example 1.
As can be seen from FIG. 5, the single-phase SF cathode full cell prepared in comparative example 1 has a maximum power density of 324 mW.cm -2 Whereas the maximum power density of the two-phase composite SNF0.05 cathode material full cell prepared in example 1 was significantly increased to 595mw·cm relative to comparative example 1 -2 The maximum power density of the two-phase composite SNF0.1 cathode material full cell prepared in example 2 was raised to 487mw·cm relative to comparative example 1 -2 The full cells prepared based on the composite cathode materials prepared in examples 1-2 were shown to have a greater power density than the full cells prepared based on the single-phase cathode material prepared in comparative example 1, demonstrating that the solid oxide fuel cell composite cathode material of the two-phase heterostructure has better electrochemical performance than the single-phase cathode material, and the maximum power density corresponding to the doped amount of Nd of 0.05 in example 1 is higher than the maximum power density corresponding to the doped amount of Nd of 0.1 in example 2.
Comparative example 2
The comparative example provides a method for preparing a cathode material of a solid oxide fuel cell, which is different from example 1 only in that the molar ratio of Sr, nd, and Fe in step S1 is modified to 0.95:0.05:1, which is equivalent to not performing Fe site defect treatment, and other steps and parameters are the same as those of example 1, and are not repeated here.
The solid oxide fuel cell cathode material prepared in this comparative example was subjected to X-ray diffraction analysis, and the results are shown in fig. 6. As can be seen from FIG. 6, the cathode material contains only the orthorhombic perovskite phase Sr 0.95 Nd 0.05 FeO 3-δ No second phase was generated, indicating that for iron-based perovskite SrFeO alone 3-δ The composite cathode material containing both the orthorhombic perovskite phase and the RP perovskite phase cannot be obtained by performing the Sr-site Nd doping without performing the Fe-site defect treatment.
To sum up, the present inventionThe invention provides a self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material, and a preparation method and application thereof. The invention adjusts the mole ratio of Sr, nd and Fe in the raw materials to be 1-x:x:1-y, and self-assembles the iron-based perovskite SrFeO based on a one-step sol-gel method 3-δ Simultaneously carrying out Nd doping and Fe site defect treatment on the Sr site, so that the prepared composite cathode material simultaneously contains the orthorhombic perovskite phase Sr as a main phase 1-a Nd a FeO 3-δ1 (P-SNF) and RP-type perovskite phase Sr as second phase 3-b Nd b Fe 2 O 7-δ2 And (RP-SNF) combines a rapid oxygen transmission path existing at a two-phase heterogeneous interface while cooperatively playing the advantages of the two-phase material, so that the oxygen reduction reaction activity of the cathode material is effectively improved, and the cathode material has better electrochemical performance.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material is characterized in that: the molar ratio of Sr, nd, fe, O in the composite cathode material is 1-x, x is 1-y, and 3-delta; the composite cathode material comprises a main phase and a second phase, wherein the main phase is an orthorhombic perovskite phase, and the chemical formula is Sr 1-a Nd a FeO 3-δ1 The second phase is RP type perovskite phase, and the chemical formula is Sr 3-b Nd b Fe 2 O 7-δ2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.1, a is more than 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.3, delta is more than or equal to 0 and less than or equal to 0.5, delta 1 is more than or equal to 0 and less than or equal to 0.5, and delta 2 is more than or equal to 0 and less than or equal to 1.
2. The self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material of claim 1, wherein: the mass ratio of the main phase to the second phase is 50-65:35-50.
3. A method for preparing the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material of claim 1 or 2, comprising the steps of:
s1, configuring a Sr source, an Nd source and an Fe source according to a preset molar ratio;
s2, dissolving the Sr source, the Nd source and the Fe source which are configured in the step S1 in water to obtain a mixed solution; adding citric acid and ethylenediamine tetraacetic acid into the mixed solution, adjusting the pH value, stirring for reaction, and self-assembling to obtain a reactant;
s3, performing heating treatment on the reactant to obtain a precursor;
and S4, calcining the precursor to obtain the composite cathode material.
4. The method for preparing the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material according to claim 3, wherein the method comprises the following steps: in step S1, the Sr source, nd source, and Fe source are strontium nitrate, neodymium nitrate, and ferric nitrate, respectively.
5. The method for preparing the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material according to claim 3, wherein the method comprises the following steps: in step S2, the molar ratio of the ethylenediamine tetraacetic acid, the citric acid and the metal cations in the mixed solution is 1:1.5:1.
6. The method for preparing the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material according to claim 3, wherein the method comprises the following steps: in step S2, the pH adjustment means is as follows: ammonia is added to adjust the pH value to be neutral.
7. The method for preparing the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material according to claim 3, wherein the method comprises the following steps: in the step S2, the stirring reaction time is 1-2 h.
8. The method for preparing the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material according to claim 3, wherein the method comprises the following steps: in step S3, the heating treatment includes heating the reactant sufficiently until the solution evaporates, forming a gel-like mass; and heating the gel-like substance to spontaneous combustion, and continuously heating until the combustion reaction is finished to obtain a precursor.
9. The method for preparing the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material according to claim 3, wherein the method comprises the following steps: in the step S4, the calcination treatment comprises the steps of placing the precursor at 500-700 ℃ for presintering for 3-5 hours to obtain a presintering product; grinding the presintering product, and then calcining for 4-6 hours at 1100-1200 ℃.
10. Use of the self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material of claim 1 or 2, characterized in that: the composite cathode material is used for preparing a solid oxide fuel cell.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040081893A1 (en) * | 2000-11-14 | 2004-04-29 | Hansen Jesper Romer | Conductive material comprising at least two phases |
| CN103682373A (en) * | 2013-12-23 | 2014-03-26 | 上海交通大学 | Non-cobalt IT-SOFC (Intermediate-Temperature Solid Oxide Fuel Cell) stable anode material and application thereof |
| CN114420943A (en) * | 2022-01-13 | 2022-04-29 | 上海交通大学 | Heterogeneous interface composite electrode material and preparation method and application thereof |
| CN115321611A (en) * | 2022-09-05 | 2022-11-11 | 天津大学 | RP phase oxide prepared by Ba-doped one-step method and capable of precipitating nanoparticles in situ and application of RP phase oxide |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040081893A1 (en) * | 2000-11-14 | 2004-04-29 | Hansen Jesper Romer | Conductive material comprising at least two phases |
| CN103682373A (en) * | 2013-12-23 | 2014-03-26 | 上海交通大学 | Non-cobalt IT-SOFC (Intermediate-Temperature Solid Oxide Fuel Cell) stable anode material and application thereof |
| CN114420943A (en) * | 2022-01-13 | 2022-04-29 | 上海交通大学 | Heterogeneous interface composite electrode material and preparation method and application thereof |
| CN115321611A (en) * | 2022-09-05 | 2022-11-11 | 天津大学 | RP phase oxide prepared by Ba-doped one-step method and capable of precipitating nanoparticles in situ and application of RP phase oxide |
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