CN114843564B - Cathode-anode co-doped solid oxide battery oxygen electrode material and preparation method thereof - Google Patents

Cathode-anode co-doped solid oxide battery oxygen electrode material and preparation method thereof Download PDF

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CN114843564B
CN114843564B CN202210316243.0A CN202210316243A CN114843564B CN 114843564 B CN114843564 B CN 114843564B CN 202210316243 A CN202210316243 A CN 202210316243A CN 114843564 B CN114843564 B CN 114843564B
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equal
electrode material
oxygen electrode
solid oxide
delta
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CN114843564A (en
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林彬
刘睿
杨权
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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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
    • 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
    • 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
    • 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
    • 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 belongs to the technical field of solid oxide batteries, and particularly relates to an oxygen electrode material of an anion-cation co-doped solid oxide battery and a preparation method thereof. The oxygen electrode material of the solid oxide battery is characterized in that the material comprises Sm0.5Sr0.5-xNaxFeO 3-delta-yFy, wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, and delta is more than or equal to 0 and less than or equal to 1. The invention carries out yin-yang co-doping on the conventional Sm0.5Sr0.5FeO3-delta, carries out Na element doping on the A-site Sr, and simultaneously carries out F doping on O to obtain the Sm0.5Sr0.5-xNaxFeO 3-delta-yFy material with more excellent performance. By co-doping of yin and yang, compared with the conventional Sm0.5Sr0.5FeO3-delta, the material of the invention improves the performance of an electric hammer, improves the power density of a battery, improves the conductivity, does not change the crystal structure, and does not change the chemical compatibility of the material with a conventional electrolyte such as YSZ.

Description

Cathode-anode co-doped solid oxide battery oxygen electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of solid oxide batteries, and particularly relates to an oxygen electrode material of a solid oxide battery and a preparation method thereof.
Background
The solid oxide fuel cell (SolidOxideFuelCells, SOFC) is used as a novel power generation technology, and directly promotes the electrochemical reaction of fuel gas (H2, CO, NH3 and CH 4) and oxidizing gas (O2 and air) to directly convert chemical energy into electric energy when in operation, has no combustion and mechanical movement, and has the characteristics of high efficiency, greenness, no pollution and the like. Can remarkably relieve the problems of large energy loss, ecological environment damage and the like when traditional fuels such as coal, petroleum and the like are combusted. Currently, the main structure of a solid oxide fuel cell includes an anode layer, an electrolyte layer, a cathode layer, and the like. Wherein Sm is 0.5 Sr 0.5 FeO 3-δ (hereinafter referred to as SSF) is often used as a common electrode material for oxygen electrodes of batteries, but it has problems of low electrical properties and low power. If SSF is co-doped with sodium fluoride, sm is obtained 0.5 Sr 0.5-x Na x FeO 3-δ-yFy (hereinafter referred to as SSNFF), will be able to, on the basis of the chemical compatibility no longer being affected,the performance of the battery is effectively improved.
Disclosure of Invention
Aiming at the poor performance of the existing SSF, the invention provides a high-performance solid oxide battery oxygen electrode material. The technical scheme provided by the invention is as follows.
A solid oxide battery electrode material for use in a battery oxygen electrode, the electrode material comprising
The molecular formula of the electrode material is as follows: sm (Sm) 0.5 Sr 0.5-x Na x FeO 3-δ-yFy 。
Wherein x is more than or equal to 0 and less than or equal to 0.05, and y is more than or equal to 0 and less than or equal to 0.05.
Further, as a preferable embodiment of the electrode material, the x=0.05, and y=0.05.
The preparation method of the material is as follows.
1) Preparation of the Sm 0.5 Sr 0.5-x Na x FeO 3-δ-yFy A solution.
2) Heat treating the solution to produce the precursor powder.
3) And heat treating the powder obtained in the step 2) to obtain the functional layer powder.
4) Grinding the powder obtained in the step 3) and a terpineol mixed solvent containing PVB to prepare the uniformly mixed electrode slurry.
Further, the step 1) includes the following steps.
a) Sm is to 2 O 3 、Sr(NO 3 ) 2 、Fe(NO 3 )3、NaNO 3 And NH 4 F was dissolved in 100ml deionized water and mixed well.
b) Adding concentrated nitric acid and citric acid into the mixed solution obtained in the step a).
c) Adjusting the pH of the mixture obtained in step b) to 7-8 by using ammonia water, and carrying out water bath at 50-100 ℃.
Further, the concentrated nitric acid was 30ml.
Further, the molar ratio of metal ions in the functional layer material of the citric acid is 1.1:1.
further, the step 2) includes: and (3) placing the solution obtained in the step (1) in an evaporation dish, heating to form sol, and finally burning.
Further, the step 3) includes.
a) Grinding the precursor powder.
b) Preserving the powder obtained in step a) at 1000 ℃ for 3h.
Further, in the step 4), the mass fraction of PVB is 10%, and the mass ratio of the addition mass of the terpineol mixed solvent containing PVB to the mass ratio of the electrode powder is 3:2.
compared with the prior art, the invention has the following advantages and technical effects.
1) The SSNFF electrode material of the invention has excellent solid oxide fuel cell performance, higher power output density and excellent cycle performance on the basis of not changing the chemical compatibility of the electrode and electrolyte.
2) The solid oxide fuel cell of SSNFF and the like is relatively simple in preparation method and suitable for mass production.
Drawings
Fig. 1, 7 are performance curves measured using SSF, ssNFF, respectively, as oxygen electrode for a conventional fuel cell.
Figure 2 is an XRD pattern for the material of the invention and SSF.
Fig. 3 is an XRD pattern of the material of the present invention after mixing with SSF and electrolyte material YSZ.
Fig. 4 is an XRD pattern of the inventive material after mixing with SSF and transition layer material SNDC.
FIG. 5 is a graph of the conductivity of the material of the present invention versus SSF.
FIG. 6 shows Arrhenius behavior of the material of the invention versus the electrical conductivity of SSF.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the detailed description and the accompanying drawings.
Example one implementation.
And synthesizing SSF functional layer powder by adopting a sol-gel method. According to Sm 0.5 Sr 0.5 FeO 3-δ Stoichiometric formulation ofIn which x=0.05, y=0.05, sm 2 O 3 、Sr(NO 3 ) 2 And Fe (NO) 3 ) 3 in 100ml deionized water, adding about 30ml concentrated nitric acid and continuously stirring, adding citric acid in a molar ratio of metal ions to citric acid of 1:1.1, continuously stirring to form a uniform solution, and regulating the pH value of the solution to 7-8 by ammonia water. The solution was then heated in an evaporation pan to form a gel until the self-ignition formed a fluffy SDC precursor powder. Grinding the powder, and roasting in a high temperature furnace at 1000 ℃ for 3 hours to fully decompose the organic matters. Mixing calcined powder with terpineol containing 10% PVB at a ratio of 2:3, grinding after mixing the components in proportion to obtain the uniformly mixed electrode slurry. The obtained electrode slurry was spin-coated on a battery using Ni-YSZ as an anode, YSZ as an electrolyte, and coated with an SNDC transition layer, heated and calcined in a sintering furnace, and the obtained complete battery was taken out and measured to have a maximum power density of 679.20mw·cm2 at 800 ℃, a maximum conductivity of 105.05s·cm-1 at 700 ℃, and an activation energy of 0.170eV. The XRD pattern was obtained by X-ray diffraction measurement using electrode powder before the electrode slurry was prepared.
Example two was implemented.
And synthesizing SSNFF functional layer powder by adopting a sol-gel method. According to Sm 0.5 Sr 0.5-x Na x FeO 3-δ-yFy Stoichiometric formulation, where x=0.05, y=0.05, sm 2 O 3 、Sr(NO 3 ) 2 、Fe(NO 3 )3、NaNO 3 And NH 4 F is dissolved in 100ml deionized water, about 30ml concentrated nitric acid is added and stirred continuously, and citric acid is added and stirred continuously in the molar ratio of metal ions to citric acid of 1:1.1, so that a uniform solution is formed, and the pH value of the solution is regulated to 7-8 by ammonia water. The solution was then heated in an evaporation pan to form a gel until the self-ignition formed a fluffy SDC precursor powder. Grinding the powder, and roasting in a high temperature furnace at 1000 ℃ for 3 hours to fully decompose the organic matters. Mixing calcined powder with terpineol containing 10% PVB at a ratio of 2:3, grinding after mixing the components in proportion to obtain the uniformly mixed electrode slurry. The obtained electrode slurry was spin-coated on a battery using Ni-YSZ as an anode, YSZ as an electrolyte, and coated with an SNDC transition layer, heated and calcined in a sintering furnace, and the obtained complete battery was taken out and measured to have a maximum power density of 876.52mw·cm2 at 800 ℃, a maximum conductivity of 111.64s·cm-1 at 600 ℃, and an activation energy of 0.164eV. The XRD pattern was obtained by X-ray diffraction measurement using electrode powder before the electrode slurry was prepared.
According to comparative analysis, the power density of the fuel cell can be effectively improved by carrying out sodium fluoride co-doping on the SSF, and meanwhile, the conductivity maximum value exists at 600 ℃ and the undoped SSF only exists at 700 ℃, so that the SSNFF is more suitable for working at low temperature, and the electrical property of the fuel cell working at low temperature can be effectively improved by carrying out sodium fluoride co-doping.
As is clear from comparison of XRD patterns, sodium fluoride co-doping of SSF does not generate other crystal phases, peak positions are not shifted, and lattice distortion is not generated. The XRD pattern measured for SSNFF after mixing with electrolyte material YSZ is consistent with the change in XRD pattern measured after mixing SSF with YSZ, all producing peak positions for SrZrO3 material. However, in the practical application process, a transition layer SNDC exists between the oxygen electrode and the electrolyte, and no new crystal phase is generated after the SSNFF and the SNDC are mixed, which indicates that the chemical compatibility between the oxygen electrode and the electrolyte is good.
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 above embodiments, one skilled in the art may make modifications and equivalents to the specific embodiments of the present invention, and any modifications and equivalents thereof without departing from the spirit and scope of the present invention are within the scope of the claims of the present invention.

Claims (4)

1. A novel oxygen electrode material for solid oxide cell is characterized by that its main body is Sm 0.5 Sr 0.5-x Na x FeO 3-δ-y F y ：
Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, and delta is more than or equal to 0 and less than or equal to 1.
2. The method for producing an oxygen electrode material according to claim 1, characterized in that: the solid oxide battery oxygen electrode material is prepared by adopting a sol-gel method and comprises the following steps:
(1) Preparing corresponding metal salt according to the metal elements in the chemical composition molecular formula of the oxygen electrode material and the stoichiometric ratio, adding deionized water, acid, alkali and complexing agent, uniformly mixing, and heating to form gel;
(2) Heating and calcining the gel to form powder;
(3) Calcining the collected powder at 1000 ℃;
(4) The powder obtained by calcination is ground and dried.
3. The method for producing an oxygen electrode material according to claim 2, characterized in that: in the step (1), the complexing agent comprises citric acid.
4. The method for producing an oxygen electrode material according to claim 2, characterized in that: in the step (2), the calcining temperature is 1000 ℃, and the heat is preserved for 3 hours.
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO973363D0 (en) * 1996-07-22 1997-07-21 Sankyo Co Neuraminic acid derivatives, their preparation and medical uses
WO1998049738A1 (en) * 1997-04-30 1998-11-05 The Dow Chemical Company Electrode structure for solid state electrochemical devices
CN1309820A (en) * 1998-06-12 2001-08-22 朱斌 Fuel cell
EP1760817A1 (en) * 2005-08-31 2007-03-07 Technical University of Denmark Reversible solid oxide fuell cell stack and method for preparing same
JP2009134980A (en) * 2007-11-30 2009-06-18 Dainippon Printing Co Ltd Manufacturing method of solid oxide fuel cell
JP2009152014A (en) * 2007-12-19 2009-07-09 Tokyo Institute Of Technology Solid oxide cell
CN104169057A (en) * 2011-12-23 2014-11-26 法商圣高拜欧洲实验及研究中心 Process for the manufacture of a mesoporous product
CN108470918A (en) * 2018-03-12 2018-08-31 北京科技大学 A kind of anion doped La of F0.8Sr0.2MnFxO3-x-δCathode material and preparation method thereof
WO2018232133A1 (en) * 2017-06-15 2018-12-20 North Carolina State University Oxygen carrying materials with surface modification for redox-based catalysis and methods of making and uses thereof
CN109742414A (en) * 2019-01-09 2019-05-10 渤海大学 A kind of intermediate temperature solid oxide fuel cell cathode material and the preparation method and application thereof
CN112670525A (en) * 2020-12-01 2021-04-16 全球能源互联网研究院有限公司 Solid oxide fuel cell electrode material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014154225A (en) * 2013-02-05 2014-08-25 Sony Corp Electrode material, electrode, and battery

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO973363D0 (en) * 1996-07-22 1997-07-21 Sankyo Co Neuraminic acid derivatives, their preparation and medical uses
WO1998049738A1 (en) * 1997-04-30 1998-11-05 The Dow Chemical Company Electrode structure for solid state electrochemical devices
CN1309820A (en) * 1998-06-12 2001-08-22 朱斌 Fuel cell
EP1760817A1 (en) * 2005-08-31 2007-03-07 Technical University of Denmark Reversible solid oxide fuell cell stack and method for preparing same
JP2009134980A (en) * 2007-11-30 2009-06-18 Dainippon Printing Co Ltd Manufacturing method of solid oxide fuel cell
JP2009152014A (en) * 2007-12-19 2009-07-09 Tokyo Institute Of Technology Solid oxide cell
CN104169057A (en) * 2011-12-23 2014-11-26 法商圣高拜欧洲实验及研究中心 Process for the manufacture of a mesoporous product
WO2018232133A1 (en) * 2017-06-15 2018-12-20 North Carolina State University Oxygen carrying materials with surface modification for redox-based catalysis and methods of making and uses thereof
CN108470918A (en) * 2018-03-12 2018-08-31 北京科技大学 A kind of anion doped La of F0.8Sr0.2MnFxO3-x-δCathode material and preparation method thereof
CN109742414A (en) * 2019-01-09 2019-05-10 渤海大学 A kind of intermediate temperature solid oxide fuel cell cathode material and the preparation method and application thereof
CN112670525A (en) * 2020-12-01 2021-04-16 全球能源互联网研究院有限公司 Solid oxide fuel cell electrode material

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