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CN113839054B - Reversible proton ceramic battery electrode material and preparation method and application thereof - Google Patents

Reversible proton ceramic battery electrode material and preparation method and application thereof Download PDF

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CN113839054B
CN113839054B CN202111040932.5A CN202111040932A CN113839054B CN 113839054 B CN113839054 B CN 113839054B CN 202111040932 A CN202111040932 A CN 202111040932A CN 113839054 B CN113839054 B CN 113839054B
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electrode material
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CN113839054A (en
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杨广明
刘左清
许琰
梁明壮
周嵬
邵宗平
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Nanjing Tech University
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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
    • 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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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • 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
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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
    • 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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Abstract

The invention relates to a high-performance proton ceramic fuel cell/electrolytic cell (PCFC/PCEC) reversible electrode material composition and a preparation method thereof, belonging to the technical field of solid oxide reversible cells. The electrode material has a two-phase structure consisting of a cubic structure and a honeycomb-like hexahedral structure. Compared with the air electrode of the traditional solid oxide fuel cell, the double-phase electrode has excellent proton conductivity and rapid hydration capability on the premise of having oxygen ion and electron conductivity. Thus allowing the electrode material to have excellent electrochemical properties in both PCFC and PCEC modes.

Description

Reversible proton ceramic battery electrode material and preparation method and application thereof
Technical Field
The invention relates to a high-performance reversible proton ceramic battery electrode material composition, a preparation method and application thereof, and belongs to the technical field of solid oxide reversible batteries.
Background
With the rapid development of the economy in China, the contradiction between supply and demand of energy and the environmental pollution problem caused by the low-efficiency utilization of energy are increasingly serious. The main energy sources at present are non-renewable fossil energy sources such as petroleum, coal and natural gas, and the inefficient combustion of these carbon-containing compounds is a major cause of atmospheric pollution. On the other hand, the turbulence and instability of the world also have a great influence on the supply of external energy. Therefore, developing a new energy system and improving the energy utilization rate are important to ensure the sustainable development of the economy and society of China and improve the energy safety of China.
Proton Ceramic Electrochemical Cell (PCEC) is a proton conductor based solid oxide cell that can be operated in a reversible manner, can utilize water electrolysis to generate hydrogen for storage of renewable energy sources, and then convert it back into electrical energy in a fuel cell mode. The application of PCECs demonstrates the uniqueness of combining dual functions of energy storage and distributed generation by integrating the PCEC and plant balancing into one system. In the last decade, as the development of solid state proton conductors and related electrochemical cells (fuel cells and electrolysers) has progressed significantly, PCECs represent a promising technology aimed at achieving low cost energy storage and conversion at low temperatures, attracting advantages such as high efficiency, longer system durability and cheaper materials. However, due to the slow electrode kinetics at moderate temperatures, the reduced lifetime of materials and interfaces, large scale deployment of PCECs remains difficult to achieve because of the severe limitations in developing highly active and stable electrodes.
In the prior art, research has been conducted to develop new oxygen electrode materials to alleviate these problems, which are the biggest causes of the degradation of the performance and the degradation of the efficiency of the existing PCEC. For example: CN110494595a discloses an anode material for use in an electrolytic water process, having as BaCo 1-x Ti x O 3-δ :Co 3 O 4 The structure shown, however, can only be applied to anode materials and does not have application in ORR processes. Currently, both the Water Oxidation Reaction (WOR) and the Oxygen Reduction Reaction (ORR) in Mixed Ion and Electron Conducting (MIEC) electrodes are severely limited to the three-phase boundary (TP) where ions, electrons and gases meetB) And (3) upper part. Thus, in PCEC systems, it is highly desirable to introduce proton conduction into the MIEC material to formulate a Triple Conductive Oxide (TCO), i.e., electrons, oxygen ions and protons, to extend TPB from the electrolyte/electrode interface into the electrode body. Despite these advantages, TCO candidate products have so far been few because of the difficulty in generating sufficient proton conduction defects under the preconditions of available readily hydratable oxygen, and despite the rapid development of PCEC technology, there are still some difficulties to be addressed, high performance, high stability and low cost remain the main focus of current development.
Disclosure of Invention
The patent is developed for the triple conductive oxide electrode material, so that TCO obtains higher performance and better stability in PCFC and PCEC modes. The invention provides an electrode material of a high-performance proton conductor fuel cell/electrolytic cell, which has a double-phase structure formed by a cubic structure and a honeycomb hexahedral structure, and improves the performance of a proton conductor air electrode. The prepared air electrode has smaller polarization impedance, higher proton conductivity and the like, so that the cathode material can be applied to medium-low temperature proton conductor solid oxide fuel cells and has excellent performance. Meanwhile, the electrode has extremely high oxygen vacancy content, provides more sites for hydration reaction, and has good hydrophilicity and rapid hydration kinetics, so that the electrode also has excellent electrochemical performance in a proton conductor electrolytic cell.
A first object of the present invention is to provide:
a solid oxide air electrode material has a molecular formula of: ABO (anaerobic-anoxic-oxic) 3 Wherein the A-bit element is selected from any one or a plurality of Ba, sc, sm, pr; the B site element is selected from any one or more of Co, fe and Ti; and, the electrode material has a two-phase structure composed of a cubic structure and a honeycomb-like hexahedral structure.
In one embodiment, the a element is selected from Ba and Sc.
In one embodiment, the B-site element is selected from Co and Fe.
In one embodiment, formula Ba 0.75 Sr 0.75 Co 0.8 Fe 0.2 O 4-δ (BSCF-1.5) wherein delta represents the oxygen vacancy content.
A second object of the present invention is to provide:
the preparation method of the solid oxide air electrode material comprises the following steps: according to the stoichiometric ratio, the catalyst is prepared by a sol-gel method.
In one embodiment, barium nitrate, strontium nitrate, cobalt nitrate and ferric nitrate are prepared by a sol-gel method according to the stoichiometric ratio in the molecular formula.
In one embodiment, the method comprises the steps of: firstly, proper deionized water and Ba (NO) 3 ) 2 ，Sr(NO 3 ) 2 ， Co(NO 3 ) 2 ·6H 2 O，Fe(NO 3 ) 3 ·9H 2 Mixing O, heating, stirring and dissolving; after all the components are dissolved, ethylenediamine tetraacetic acid and citric acid monohydrate are added, then ammonia water is added dropwise until the pH value of the solution is between 7 and 8, and the water is volatilized under the condition of heating and stirring to obtain a gel substance; and (3) placing the gel substance in an oven for drying to obtain an electrode material precursor, and placing the precursor in a muffle furnace for roasting to obtain the required electrode material.
In one embodiment, the total molar ratio of ethylenediamine tetraacetic acid and citric acid monohydrate to Ba, sr, co, fe is from 1.5 to 2.5:0.5 to 1.5:0.5 to 1.5.
In one embodiment, the conditions of the drying process are 200-300 ℃ for 5-8 hours.
In one embodiment, the firing parameters are 950-1050 ℃ firing for 3-7 hours.
A third object of the present invention is to provide:
the use of the solid oxide air electrode material described above in a fuel cell.
In one embodiment, the use refers to use as a proton conductor cathode.
In one embodiment, the electrolyte is BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ 。
In one embodiment, the anode material is NiO or BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZTYYb).
In one embodiment, the mass ratio of NiO, electrolyte, and soluble starch in the composite anode is 6.5:3.5:1.
In one embodiment, the electrochemical performance of the electrode material is also evaluated in the described use.
In one embodiment, the use is to increase electron conductivity, proton conductivity, output power, or cell stability.
A fourth object of the present invention is to provide:
the use of the solid oxide air electrode material described above in proton ceramic electrolytic cells.
In one embodiment, the use refers to use as a proton conductor air electrode.
In one embodiment, the electrolyte is BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ 。
In one embodiment, the hydrogen electrode material is NiO or BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZTYYb).
In one embodiment, the mass ratio of NiO, electrolyte, and soluble starch in the composite electrode is 6.5:3.5:1.
In one embodiment, the electrochemical performance of the air electrode material is also evaluated in the described use.
In one embodiment, the use is to increase electron conductivity, hydration kinetics, output current, hydrogen production, and faraday efficiency.
Advantageous effects
The high-performance reversible solid oxide electrode material is prepared by a sol-gel method, and has the following effects:
(1) Simplicity of the synthesis method
The dual-phase electrode material with different unique phase structures is synthesized by a simple sol-gel one-step method: ba (Ba) 0.75 Sr 0.75 Co 0.8 Fe 0.2 O 4-δ (BSCF-1.5), the material has a cubic structure and a honeycomb-like hexagonal structure, and the synthesis method is simple and efficient.
(2) Material uniqueness
BSCF-1.5 is a unique dual phase material with both ORR and OER activity due to its ultra-high oxygen hole content and hydration properties.
The cubic phase improves the stability and electron conductivity of the material, and the honeycomb-like hexagonal phase has excellent proton transmission and ion phase diffusion capacity.
The dual-phase material has optimized ion and electron transmission paths in both electrolysis and fuel cell modes, and accelerates the reaction rate.
(3) Performance preference
BSCF-1.5 has a molecular weight of 1220mW cm at 650℃in fuel cell mode -2 High performance, and current density of-1333 mA cm at 1.3V voltage in electrolysis mode -2 。
Drawings
FIG. 1 is an XRD pattern for BSCF-1.5 at room temperature;
FIG. 2 is an XRD pattern of BSCF-1.5 after 100h treatment at 650 ℃;
FIG. 3 is an XPS characterization map; wherein (a) Co 2p of BSCF-1, BSCF-1.5 and BSCF-2 oxides 3/2 、Ba 3d 5/2 X-ray photoelectron spectroscopy, (b) Fe2p 3/2 X-ray photoelectron spectroscopy of (c).
FIG. 4 is electron conductivity of BSCF-1.5;
FIG. 5 is an Arrhenius plot of Dchem and kchem obtained from BSCF-1 and BSCF-1.5 oxides using a conductive relaxation process.
FIG. 6 is a graph of the output power performance of Ni-BZCYYb|BZCYb|BSCF-1.5 single cells over a temperature range of 500-650 ℃;
fig. 7 is an ECR curve of BSCF-1 oxide when air is changed from a dry state to pH2 o=0.03 atm.
FIG. 8 is sample N 2 Suction and release deviceA curve is attached;
FIG. 9 is an EIS curve for a 500-700℃symmetric cell oxygen reduction electrode. (a) BSCF-1, (b) BSCF-1.5, and (c) BSCF-2 oxygen reduction electrode;
FIG. 10 is a comparison of activation energy of BSCF-1.5 prepared by physical mixing and BSCF-1.5 prepared by one-step sol-gel.
FIG. 11 is the impedance of Ni-BZTYYb|BZTYYb|BSCF-1.5 single cell at 500-650℃temperature range;
FIG. 12 is a morphology graph of Ni-BZCYYb|BZCYb|BSCF-1.5 single cell after 2 hours of testing;
FIG. 13 is the impedance of a BSCF-1.5|BZCYYyb| BSCF-1.5 symmetric battery at a temperature in the range of 500-700 ℃;
FIG. 14 is the impedance stability of a BSCF-1.5|BZCYYyb| BSCF-1.5 symmetric cell at 550 ℃;
FIG. 15 is a graph showing the performance of a Ni-BZCYYb|BZCYb|BSCF-1.5 cell for electrolysis of water at a temperature in the range of 500-600 ℃;
FIG. 16 is the hydrogen yield of an Ni-BZCYYb|BZCYb|BSCF-1.5 cell at 600℃for electrolysis of various water partial pressures;
FIG. 17 is Faraday efficiencies of Ni-BZTYYb|BZTYYb|BSCF-1.5 cells at 600℃for electrolysis of different water partial pressures;
FIG. 18 is a graph of the performance of BSCF-1 and BSCF-2 in PCECCs mode.
Detailed Description
The invention provides an air electrode material Ba of a high-performance proton conductor fuel cell/electrolytic cell 0.75 Sr 0.75 Co 0.8 Fe 0.2 O 4-δ (BSCF-1.5), a preparation method and application thereof, wherein delta represents oxygen vacancy content, and belongs to the technical field of reversible solid oxide batteries. One-step synthesis of two-phase electrode BSCF-1.5 by sol-gel method, wherein the two-phase composition is Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF-1) and BaSrCo 0.8 Fe 0.2 O 4-δ (BSCF-2). The BSCF-1 provides higher electronic conductivity, wherein high-content Co can better keep proton conductivity of a double perovskite structure of a parent material, and the material has excellent conductivity and catalytic activity; and Fe elementThe element can also improve the conductivity and catalytic activity of the parent material, and on the other hand, the structure and electrochemical stability of the material are further improved due to the relatively large ionic radius. While BSCF-2 provides a large amount of oxygen vacancy content due to the honeycomb-like hexagonal structure, a high proportion of Ba, sr content significantly increases the hydrophilicity of the material, so BSCF-2 provides more hydration reaction sites, and rapid proton diffusion and transport capacity.
The synergistic effect of BSCF-1 and BSCF-2 provides good reversible assurance for BSCF-1.5, resulting in excellent performance in both proton ceramic fuel cell and electrolyser applications. In PCFC mode, the corresponding single cell is capable of achieving 1218mW cm at 650 DEG C -2 Maximum output power of (2); electrolysis of H in PCEC mode at 600 DEG C 2 O, at 1.3V, gives-1.33A cm -2 Is a maximum current density of (c). The invention develops a high-performance reversible electrode material and a preparation method thereof, and greatly improves the electrochemical performance of proton ceramic fuel cells and electrolytic cells.
Example 1 Low temperature proton ceramic Fuel cell/electrolytic cell air electrode Material Ba 0.75 Sr 0.75 Co 0.8 Fe 0.2 O 4-δ Is prepared from
(1) 9.8007g of barium nitrate, 7.9362g of strontium nitrate, 11.6412g of cobalt nitrate and 4.04g of ferric nitrate are weighed and dissolved by adding a small amount of deionized water. According to ethylenediamine tetraacetic acid: citric acid monohydrate: 11.7g of ethylenediamine tetraacetic acid and 16.8g of hydrated citric acid are weighed according to the molar ratio of 1:2:1, and are dissolved in deionized water as complexing agents.
(2) Adding the solution dissolved with the complexing agent into the solution dissolved with the metal ions, then dripping a proper amount of ammonia water until the pH value of the solution reaches 7-8, and stirring under the condition of magnetic stirring to completely evaporate water to obtain a gel substance.
(3) The gel-like mass was placed in an oven and calcined at 250 ℃ for 5 hours to give the desired foam-like precursor.
(4) And (3) placing the precursor in a high-temperature muffle furnace, and calcining for 5 hours at the temperature of 1000 ℃ to obtain the required cathode powder.
Example 2 preparation of symmetrical cells
(1) 1g of the cathode powder Ba obtained in example 1 was weighed out 0.75 Sr 0.75 Co 0.8 Fe 0.2 O 4-δ 10ml of isopropanol, 2ml of ethylene glycol and 0.8ml of glycerol are poured into a high-energy ball mill, ball-milled for 30min under the condition of 400r/min, and then transferred to a strain bottle by a straw to obtain the required cathode slurry.
(2) And (3) placing the prepared BZCYb electrolyte on a heating table to preheat at 200 ℃, uniformly spraying the prepared cathode slurry on two sides of the electrolyte by using a spray gun under the pushing of inert gas, placing the sprayed electrolyte in a high-temperature muffle furnace to calcine for 2 hours at 1000 ℃ after the liquid is completely volatilized, and obtaining the required symmetrical battery for testing the polarization impedance of the cathode material at the temperature range of 500-700 ℃. Wherein the polarization impedance of the cell at 700 ℃ is 0.04 Ω cm 2 。
Example 3 preparation of Single cell
(1) 1g of the cathode powder Ba obtained in example 1 was weighed out 0.75 Sr 0.75 Co 0.8 Fe 0.2 O 4-δ 10ml of isopropanol, 2ml of ethylene glycol and 0.8ml of glycerol are poured into a high-energy ball mill, ball-milled for 30min under the condition of 400r/min, and then transferred to a strain bottle by a straw to obtain the required cathode slurry.
(2) And (3) placing the prepared dry-pressed battery piece on a heating table for preheating at 200 ℃, uniformly spraying the prepared cathode slurry on the electrolyte surface of the dry-pressed piece by using a spray gun under the pushing of inert gas, placing the sprayed dry-pressed battery piece in a high-temperature muffle furnace for calcining at 1000 ℃ for 2 hours after the liquid is completely volatilized, and obtaining the required symmetrical battery for testing the polarization impedance of the cathode material at the temperature of 500-650 ℃.
Characterization of results
XRD characterization
FIG. 1 shows Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF-1)，Ba 0.75 Sr 0.75 Co 0.8 Fe 0.2 O 4-δ (BSCF-1.5) andBaSrCo 0.8 Fe 0.2 O 4-δ (BSCF-2) powder X-ray diffraction (XRD) pattern. It is known from this that both BSCF-1 and BSCF-2 powders obtained a single phase and no detectable impurities were observed, indicating that pure phase powders were successfully prepared. By XRD refinement it is possible to obtain that BSCF-1 is a cubic perovskite and BSCF-2 is a unique hexagonal structure consisting of a cellular network, from which it can be seen from the X-ray diffraction pattern that the peak position of BSCF-1.5 is exactly the superposition of BSCF-1 and BSCF-2, thus indicating that BSCF-1.5 synthesized by a simple sol-gel process is a biphasic material.
FIG. 2 is an XRD pattern for BSCF-1.5 calcined at 650℃ for 100 hours, from which it can be seen that BSCF-1.5 maintains a good biphasic composition with no other impurity phases formed and both phases maintain a stable phase structure.
XPS characterization
As shown in FIG. 3, three samples were Co of BSCF-2 at room temperature 3+ At least 77.3% of Co, and BSCF-1, BSCF-1.5 3+ The content was 60.8% and 63%, respectively. On the other hand, the Fe2p spectrum of the sample in the figure can be divided into three bands corresponding to Fe respectively 2+ ，Fe 3+ And Fe (Fe) 4+ . Fe in BSCF-1, BSCF-1.5 and BSCF-2 2+ The contents of (2) are 70%,61.8% and 56.9%, respectively, fe 3+ The contents of (2) are 23.4%,25% and 16.1%, respectively, fe 4+ The content of (2) was 6.6%,13.2% and 27%, respectively. It is apparent that the average valence of the B site in BSCF-1.5 is intermediate between the BSCF-1 and BSCF-2 samples, resulting in an oxygen vacancy concentration at room temperature that is also intermediate.
3. Conductivity characterization
FIG. 4 is a graph of the conductivity of BSCF-1.5 composites and the conductivities of conventional BSCF-1 and BSCF-2 measured in air between 300℃and 800 ℃. The conductivity of BSCF-1.5 is between 5 and 32Scm -1 Between which the conductivity of BSCF-1.5 is slightly lower than that of BSCF-1 (21-75 Scm -1 ) But higher than BSCF-2 (0.1-3 Scm) -1 ). The conductivities of BSCF-1 and BSCF-1.5 meet the basic requirements of PCFC cathodes.
4. Oxygen diffusivity characterization
FIG. 5 by using density>97% ceramic sample measurement oxygen surface cross-sectionThe coefficient of exchange (kchem) and the oxygen volumetric diffusion coefficient (Dchem), BSCF-1.5 also showed extremely high oxygen diffusivities. At each temperature, the Dchem and kchem of BSCF-1.5 are much higher than BSCF-1, with the Dchem and kchem values of BSCF-1.5 being 2.51X10 for example at 700 ℃ -3 And 4.69×10 -3 However, BSCF-1 is 2.27X10 respectively -4 And 4.88×10 -4 . Dchem and kchem increased by about 8.24 and 8.61 times, respectively. These Dchem and kchem values are the highest values of perovskite oxides currently known and are comparable to those of BSCF and other MIECs. The enhancement of oxygen ion conductivity gives the electrode good charge transfer capability in ORR.
FIG. 6 shows ECR curves of BSCF-1 oxide at air change pH2 O=0.03 atm from dry state, where the same differences remain for Dchem and kchem values of BSCF-1.5 and BSCF-1 at 500℃, but the impedance test shows a decrease in the difference, indicating that the effect of water adsorption on impedance is not negligible with decreasing temperature. FIG. 7 shows sample N 2 The adsorption and desorption curves show that the specific surface areas of BSCF-1, BSCF-1.5 and BSCF-2 are sequentially increased, but the BSCF-1.5 has the highest specific surface area after 2 hours of wet air treatment.
5. Output power characterization
FIG. 8 is a typical I-V and I-P curves for the output power of a Ni-BZTYYb|BZTYYb|BSCF-1.5 single cell over a temperature range of 500-650 ℃. The power density of the BSCF-1.5 cathode cell increases monotonically with increasing temperature, as in other PCFC modes, 1220, 850, 610 and 410mW cm at 650 to 500 ℃ -2 . The BSCF-1.5 Open Circuit Voltages (OCV) at 650 ℃,550 ℃ and 500 ℃ were 1.036V,1.070V and 1.097V, approaching the theoretical OCV values at these temperatures, showing good cell sealability and negligible electrolyte electron leakage.
6. Electrochemical impedance analysis
The electrochemical impedance spectra of BSCF-1, BSCF-1.5 and BSCF-2 under humid air conditions are shown in the regions a, b, c, respectively, of FIG. 9. The impedance of BSCF-1.5 was 0.04,0.082,0.24,0.75 and 2.8 Ω cm at 700, 650, 600, 550 and 500 ℃, respectively. Significantly smaller than the samples BSCF-1 and BSCF-2. For a cell with BSCF-1.5 as the cathode, the polarization resistance is only 10% to 20% of the total ASR of the cell, while the ohmic resistance is determined by the thickness of the bzcyybb electrolyte and the cell preparation process. Ohmic resistance becomes the main resistance during operation. Meanwhile, the polarization impedance is obviously lower than that of the cathode of the current mainstream proton ceramic fuel cell, and the cathode has certain commercial application prospect.
7. Testing of activation energy
FIG. 10 compares the difference between the physical mixing prepared BSCF-1.5 and the one-step sol-gel preparation to prepare BSCF-1.5 (PM) powder by physically mixing BSCF-1 and BSCF-2 in a molar ratio of 1:1. The symmetrical cell with BSCF-1.5 as electrode prepared in one step has lower activation energy under the same conditions. The main reason is that the one-step method is more uniform in mixing and smaller in particle size, and is beneficial to the electrochemical reaction.
FIG. 11 shows the cross-sectional image shape of a single cell containing a Ni-BZTYYb composite anode, a dense BZTYYb electrolyte and a porous BSCF-1.5 cathode after performance testing. It is apparent from the figure that the adhesion between the BSCF-1.5 cathode and the BCZYYb electrolyte is still very tight, which also demonstrates the reliability of the cell performance test results.
8. Impedance characterization
FIG. 13 is a graph showing the impedance of a BSCF-1.5|BZCYYYb|BSCF-1.5 symmetric cell at temperatures ranging from 500 to 700℃, where it is seen that the polarization impedance of BSCF-1.5 is 0.04,0.082,0.24,0.75 and 2.8 Ω cm at 700, 650, 600, 550 and 500℃ -2 。
FIG. 14 is the impedance stability of a BSCF-1.5|BZCYYyb| BSCF-1.5 symmetric cell at 550 ℃; through the 420h symmetrical cell stability test, the impedance is not obviously increased, which proves that the BSCF-1.5 has good electrochemical stability.
9. Characterization of electrolytic Properties
FIG. 15 is a graph showing the performance of a Ni-BZCYYb|BZCYb|BSCF-1.5 cell for electrolysis of water at a temperature in the range of 500-600 ℃; BSCF-1.5 corresponds to a current density of-1333, -844, -466mA cm at a voltage of 1.3 V -2 600, 550 and 500 c, respectively. The excellent electrolysis performance is mainly due to high oxygen vacancies and rapid hydration reactions, and the excellent water storage of BSCF-1.5Sex.
FIG. 14 is the hydrogen yield of an Ni-BZCYYb|BZCYb|BSCF-1.5 cell at 600℃for electrolysis of various water partial pressures; the hydrogen yield of 10%, 20% and 30% different water partial pressures is tested under the condition of 600 ℃, and the current density is changed to find that the hydrogen yield is increased along with the increase of the current density, the water partial pressure is in direct proportion to the hydrogen yield at the same current density, and the hydrogen yield is close to a theoretical value when the water partial pressure is 30% according to the conventional test conclusion.
FIG. 16 is Faraday efficiencies of Ni-BZTYYb|BZTYYb|BSCF-1.5 cells at 600℃for electrolysis of different water partial pressures; the figure shows that the Faraday efficiency under the 30% moisture pressure condition is close to 100%, which shows that the electrode material and the whole preparation process of the electrolytic cell are excellent, and the air electrode also has excellent electrochemical performance.
FIG. 18 is a graph of the performance of BSCF-1 and BSCF-2 in PCECS mode, it can be seen that the BSCF-1.5 material exhibits better Faraday efficiency and current density relative to the BSCF-1 and BSCF-2 materials.
In summary, it can be seen that the dual-phase electrode has excellent proton conductivity and rapid hydration capability compared with the conventional air electrode of the solid oxide fuel cell under the premise of having oxygen ion and electron conductivity. Thus allowing BSCF-1.5 to have excellent electrochemical performance in both PCFC and PCEC modes. In the presence of proton conductor electrolyte BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZTYYb) and hydrogen electrode composed of 65% by mass of NiO and 35% by mass of BZTYYb, the corresponding single cell was capable of obtaining 1218mW cm in PCFC mode at 650 DEG C -2 Maximum output power of (2); electrolysis of H in PCEC mode at 600 DEG C 2 O, at 1.3V, gives-1.33A cm -2 Is a maximum current density of (c). The invention develops a high-performance reversible electrode material and a preparation method thereof, and greatly improves the electrochemical performance of proton ceramic fuel cells and electrolytic cells.

Claims (2)

1. Use of solid oxide air electrode material in proton ceramic electrolytic cell and fuel cellThe solid oxide air electrode material is characterized in that the molecular formula is Ba 0.75 Sr 0.75 Co 0.8 Fe 0.2 O 4-δ The electrode material has a biphase structure consisting of a cubic structure and a honeycomb-like hexagonal structure;
the preparation method of the solid oxide air electrode material comprises the following steps: according to the stoichiometric ratio, a proper amount of deionized water and Ba (NO) 3 ) 2 ，Sr(NO 3 ) 2 ，Co(NO 3 ) 2 ·6H 2 O，Fe(NO 3 ) 3 ·9H 2 Mixing O, heating, stirring and dissolving; after all the components are dissolved, ethylenediamine tetraacetic acid and citric acid monohydrate are added, then ammonia water is added dropwise until the pH value of the solution is between 7 and 8, and the water is volatilized under the condition of heating and stirring to obtain a gel substance; drying the gel substance in a drying oven to obtain an electrode material precursor, and then placing the precursor in a muffle furnace for roasting to obtain a required electrode material;
roasting for 3-7h at 950-1050 ℃;
the total molar ratio of ethylenediamine tetraacetic acid and citric acid monohydrate to Ba, sr, co, fe is 1.5-2.5:0.5-1.5:0.5-1.5.
2. Use according to claim 1, characterized in that the conditions of the drying process are 200-300 ℃ for 5-8 hours.
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