CN115241471B - Cathode material of solid oxide fuel cell and preparation method and application thereof - Google Patents
Cathode material of solid oxide fuel cell and preparation method and application thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 58
- 239000007787 solid Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 57
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005303 weighing Methods 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- 229960002303 citric acid monohydrate Drugs 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 16
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010416 ion conductor Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- 239000003792 electrolyte Substances 0.000 claims description 18
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 2
- 229940075630 samarium oxide Drugs 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 101100365571 Schizosaccharomyces pombe (strain 972 / ATCC 24843) sfc4 gene Proteins 0.000 description 49
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
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- 238000003825 pressing Methods 0.000 description 4
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- 229910000018 strontium carbonate Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
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- 239000011029 spinel Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
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- 238000012430 stability testing Methods 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a solid oxide fuel cell cathode material, the chemical formula of which is Sr 4FexCoyO13+δ, wherein 0< x <4, 2< y <6, δ is oxygen vacancy concentration, and 0< δ <1. The invention also discloses a preparation method of the solid oxide fuel cell cathode material, which comprises the following steps: weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water; sequentially dissolving in deionized water, heating and stirring to gel; drying to obtain a precursor; removing carbon from the precursor, and calcining the precursor under partial pressure of oxygen to obtain powder; grinding the powder to obtain Sr 4FexCoyO13+δ cathode material powder. The invention also discloses application of the catalyst in low-temperature oxygen ion conductor-based solid oxide fuel cells and low-temperature proton ceramic fuel cells. The solid oxide fuel cell cathode material prepared by the invention has excellent cell output performance.
Description
Technical Field
The invention belongs to a cathode material and a preparation method and application thereof, in particular to a solid oxide fuel cell cathode material and a preparation method and application thereof.
Background
Solid Oxide Fuel Cells (SOFC) are outstanding in developing clean energy sources due to the characteristics of high efficiency, no pollution, environmental friendliness and the like, are considered as one of the most potential energy conversion devices, and have important significance in relieving energy crisis, environmental pollution and the like. Although SOFCs exhibit desirable electrochemical performance at higher operating temperatures, excessive temperatures also present problems such as excessive sealing costs, electrode material sintering, and thermal expansion mismatch, which affect the life of the cell. Lowering the operating temperature is therefore a trend in SOFCs.
As the operating temperature decreases, particularly at an operating temperature below 600 ℃, the polarization resistance of the cathode material increases sharply, the catalytic activity decreases significantly, and the output power of the SOFC is affected, thereby limiting the practical application of the SOFC, so that development of the cathode material of the solid oxide fuel cell having high oxygen reduction activity and long-term stability at an operating temperature below 600 ℃ becomes a research hotspot.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention aims to provide a solid oxide fuel cell cathode material which is efficient and stable for a long time, and another aim of the invention is to provide a simple, efficient and low-cost preparation method of the solid oxide fuel cell cathode material, and further aim of the invention is to provide an application of the solid oxide fuel cell cathode material in a low-temperature oxygen ion conductor-based solid oxide fuel cell, and further aim of the invention is to provide an application of the solid oxide fuel cell cathode material in a low-temperature proton ceramic fuel cell.
The technical scheme is as follows: the chemical formula of the solid oxide fuel cell cathode material is Sr 4FexCoyO13+δ (SFC 4), wherein 0< x <4,2< y <6, and delta is oxygen vacancy concentration, and 0< delta <1.
Further, the average particle diameter of the cathode material is 300 to 500nm.
The preparation method of the solid oxide fuel cell cathode material comprises the following steps:
Step one, respectively weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water according to stoichiometric ratio;
sequentially dissolving the raw materials in deionized water, and heating and stirring until the raw materials are gel;
step three, placing the product obtained in the step two in an oven for drying to obtain a precursor;
Step four, placing the precursor obtained in the step three in a muffle furnace for decarbonizing treatment, and then calcining by oxygen partial pressure to obtain powder;
And fifthly, grinding the powder obtained in the step four to obtain Sr 4FexCoyO13+δ cathode material powder.
Further, in the first step, ethylenediamine tetraacetic acid: citric acid monohydrate: the molar ratio of the metal cations is 1:2:1-2, and the molar number of the metal cations is the sum of the molar numbers of strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate.
In the second step, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, heated and stirred to obtain a metal nitrate solution, ethylenediamine tetraacetic acid is dissolved in ammonia water, ammonia water dissolved with ethylenediamine tetraacetic acid and citric acid monohydrate are added into the metal nitrate solution, and the heating and stirring are continued until the metal nitrate solution is gel. The heating temperature is 80-100 ℃, and the stirring speed is 200-300 r.min -1. Heating to a temperature below 80 ℃ retards the gel formation rate; the heating temperature is higher than 100 ℃, so that the stirring time is shortened, and the gel is easy to foam at high temperature. The stirring speed is lower than 200 r.min -1, which can influence the complexing uniformity of metal ions; stirring speeds above 300 r.min -1 can lead to splashing of the solution.
Further, in the third step, the drying temperature is 200-300 ℃ and the drying time is 200-300 min. The drying temperature is lower than 200 ℃, which can lead to insufficient carbonization of organic matters in the gel; the drying temperature is higher than 300 ℃, which can lead to the combustion of the carbon skeleton.
Further, in the fifth step, the ground materials are sieved by a 200-400-mesh sieve.
The application of the solid oxide fuel cell cathode material in the low-temperature oxygen ion conductor-based solid oxide fuel cell takes Sr 4FexCoyO13+δ as a cathode, samarium oxide doped cerium oxide as an electrolyte and a mixture of NiO and SDC as an anode.
The application of the solid oxide fuel cell cathode material in the low-temperature proton ceramic fuel cell takes Sr 4FexCoyO13+δ as a cathode, baZr 0.1Ce0.7Y0.1Yb0.1O3-δ as an electrolyte and a mixture of NiO and BZCYYb as an anode.
The preparation principle is as follows: the Sr 4FexCoyO13+δ material consists of nano-scale single perovskite phase Sr (Co, fe) O 3, spinel phase (Co, fe) 3O4, cobalt oxide CoO, and strontium carbonate SrCO 3. The single perovskite phase has excellent conductivity and better oxygen reduction activity, the spinel phase has low conductivity but high oxygen reduction catalytic activity, and the existence of the strontium carbonate and the cobalt oxide reduces the thermal expansion coefficient and ensures long-time operation stability. By the self-assembly mixing of the nanoscale catalyst of the system and the influence of a synergistic effect, the battery prepared from the material is promoted to have excellent output power and long-time stability, has stable structure in a low temperature range, and can show good ORR catalytic activity when applied to O-SOFC and PCFC.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable characteristics:
1. The prepared solid oxide fuel cell cathode material has excellent cell output performance, the output power of the prepared low-temperature proton ceramic fuel cell reaches 645mW cm -2 at 550 ℃, and the output power of the prepared oxygen ion conductor-based fuel cell reaches 1250mW cm -2 at 600 ℃;
2. The prepared cathode material of the solid oxide fuel cell has excellent long-time thermochemical stability, the proton-based symmetrical cell and the proton ceramic fuel cell can respectively and continuously work for 1000h and 3100h at 550 ℃, the impedance and the output power of the proton-based symmetrical cell are not obviously attenuated, the prepared oxygen ion-based symmetrical cell can continuously work for 1000h at 550 ℃, the impedance of the oxygen ion-based symmetrical cell is not obviously attenuated, and the oxygen ion-based symmetrical cell has good heat stability;
3. the prepared cathode material has wide application range and certain proton conductivity, so that the material can be used as an O-SOFC cathode and is also suitable for PCFC;
4. The cathode material is synthesized by a simple sol-gel one-step method, the preparation method is simple and efficient, the raw material cost is low, and the method is suitable for industrial mass production;
5. the average particle size of the cathode material SFC4 is on the nanometer scale, so that the effective three-phase line length inside the structure is increased, and the electrochemical reaction range is wider;
6. The partial pressure of oxygen is adopted for calcination, namely, the oxygen gradually decreases along with the calcination in a closed environment, so that carbonate can be generated, and the cathode material can keep stable working for a long time;
7. when the cathode material SFC4 is prepared, a layered perovskite phase is generated, and the structure has good chemical flexibility, higher conductivity and strong structural stability, so that the cathode material can keep stable working for a long time.
Drawings
FIG. 1 is an XRD pattern of an SFC4 cathode material of the present invention;
FIG. 2 is a graph of the impedance of the oxygen ion-based symmetric cell SFC4|SDC|SFC4 of the present invention at 550 ℃;
FIG. 3 is a graph of the long term stability of the oxygen ion-based symmetric cell SFC4|SDC|SFC4 of the present invention at 550 ℃;
FIG. 4 is a graph of the power output performance of the oxygen-ion-based fuel cell SFC4|SDC|NiO-SDC of the present invention at temperatures of 400 ℃, 500 ℃ and 600 ℃;
FIG. 5 is an SEM of a cross-section of an oxygen-ion-based fuel cell SFC4|SDC|NiO-SDC of the present invention;
FIG. 6 is a graph of the impedance of the proton-based symmetric cell SFC4| BZCYYb |SFC4 of the present invention at 550 ℃;
FIG. 7 is a graph of the long term stability of the proton-based symmetrical cell SFC4| BZCYYb |SFC4 of the present invention at 550 ℃;
FIG. 8 is a graph of the power output performance of the proton ceramic fuel cell SFC4| BZCYYb |NiO-BZCYYb of the present invention at temperatures of 350, 450, and 550 ℃;
FIG. 9 is an SEM image of a cross section of a proton ceramic fuel cell SFC4| BZCYYb |NiO-BZCYYb of the present invention;
Fig. 10 is a graph of the long term stability of the proton ceramic fuel cell sfc4| BZCYYb |nio-BZCYYb of the invention at 550 ℃.
Detailed Description
In each of the examples below, the decarbonization treatment was calcination of the precursor in a muffle furnace at 700 ℃ for 5 hours. The mole number of the metal cations is the sum of mole numbers of strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate.
Example 1
A preparation method of a solid oxide fuel cell cathode material comprises the following steps:
a. Respectively weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water according to the stoichiometric ratio, and ethylenediamine tetraacetic acid: citric acid monohydrate: the molar ratio of the metal cations is 1:2:1;
b. Firstly, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, heating and stirring are carried out at the temperature of 80 ℃ and the rotating speed of 300 r.min -1 to obtain a metal nitrate solution, deionized water and ammonia water are added into ethylenediamine tetraacetic acid, ammonia water dissolved with ethylenediamine tetraacetic acid and citric acid monohydrate are added into the metal nitrate solution, and heating and stirring are carried out continuously at the temperature of 80 ℃ and the rotating speed of 300 r.min -1 until the solution becomes gel;
c. c, placing the gel obtained in the step b in a baking oven at 200 ℃ for baking for 300min to obtain a precursor;
d. C, placing the precursor obtained in the step c in a muffle furnace for decarbonizing treatment, and then calcining with oxygen partial pressure to obtain powder;
e. Grinding the powder obtained in the step four, and sieving with a 200-mesh sieve to obtain Sr 4Fe0.5Co5.5O13+δ (SFC 4) cathode material powder, wherein the average particle size of the powder is 300nm.
Example 2
A preparation method of a solid oxide fuel cell cathode material comprises the following steps:
a. Respectively weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water according to the stoichiometric ratio, and ethylenediamine tetraacetic acid: citric acid monohydrate: the molar ratio of the metal cations is 1:2:2;
b. Firstly, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, heating and stirring are carried out at the temperature of 100 ℃ and the rotating speed of 200 r.min -1 to obtain a metal nitrate solution, deionized water and ammonia water are added into ethylenediamine tetraacetic acid, ammonia water dissolved with ethylenediamine tetraacetic acid and citric acid monohydrate are added into the metal nitrate solution, and heating and stirring are carried out continuously at the temperature of 100 ℃ and the rotating speed of 200 r.min -1 until the solution becomes gel;
c. C, placing the gel obtained in the step b in a baking oven at 300 ℃ for baking for 200min to obtain a precursor;
d. C, placing the precursor obtained in the step c in a muffle furnace for decarbonizing treatment, and then calcining with oxygen partial pressure to obtain powder;
e. Grinding the powder obtained in the step four, and sieving with a 400-mesh sieve to obtain Sr 4Fe3.5Co2.5O13+δ (SFC 4) cathode material powder, wherein the average particle size of the powder is 500nm.
Example 3
A preparation method of a solid oxide fuel cell cathode material comprises the following steps:
a. Respectively weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water according to the stoichiometric ratio, and ethylenediamine tetraacetic acid: citric acid monohydrate: the molar ratio of the metal cations is 1:2:1.5;
b. firstly, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, heating and stirring are carried out at the temperature of 95 ℃ and the rotating speed of 230 r.min -1 to obtain a metal nitrate solution, deionized water and ammonia water are added into ethylenediamine tetraacetic acid, ammonia water dissolved with ethylenediamine tetraacetic acid and citric acid monohydrate are added into the metal nitrate solution, and heating and stirring are continuously carried out at the temperature of 95 ℃ and the rotating speed of 230 r.min -1 until the solution becomes gel;
c. C, placing the gel obtained in the step b in a 220 ℃ oven to be dried for 230min to obtain a precursor;
d. C, placing the precursor obtained in the step c in a muffle furnace for decarbonizing treatment, and then calcining with oxygen partial pressure to obtain powder;
e. Grinding the powder obtained in the step four, and sieving with a 300-mesh sieve to obtain Sr 4Fe3Co5O13+δ (SFC 4) cathode material powder, wherein the average particle size of the powder is 350nm.
Example 4
A preparation method of a solid oxide fuel cell cathode material comprises the following steps:
a. Respectively weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water according to the stoichiometric ratio, and ethylenediamine tetraacetic acid: citric acid monohydrate: the molar ratio of the metal cations is 1:2:1;
b. Firstly, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, heating and stirring are carried out at the temperature of 90 ℃ and the rotating speed of 300 r.min -1 to obtain a metal nitrate solution, meanwhile, deionized water and ammonia water are added into ethylenediamine tetraacetic acid, ammonia water dissolved with ethylenediamine tetraacetic acid and citric acid monohydrate are added into the metal nitrate solution, and heating and stirring are continuously carried out at the temperature of 90 ℃ and the rotating speed of 300 r.min -1 until the solution becomes gel;
c. c, placing the gel obtained in the step b in a 250 ℃ oven to be dried for 250min to obtain a precursor;
d. C, placing the precursor obtained in the step c in a muffle furnace for decarbonizing treatment, and then calcining with oxygen partial pressure to obtain powder;
e. Grinding the powder obtained in the step four, and sieving with a 300-mesh sieve to obtain Sr 4Fe3Co4O13+δ (SFC 4) cathode material powder, wherein the average particle size of the powder is 400nm.
The SFC4 cathode material synthesized in this example was subjected to X-ray diffraction (XRD) characterization, and the results are shown in fig. 1. As can be seen from the results in fig. 1, the SFC4 cathode material is composed of a nano-sized single perovskite phase Sr (Co, fe) O 3, a spinel phase (Co, fe) 3O4, cobalt oxide CoO, and strontium carbonate SrCO 3. The Pmcn phase in fig. 1 is a space group of strontium carbonate, accounting for 4.1% of the material. The carbonate can improve the oxygen activating performance and stability of the electrode material, which is one of the important reasons that the single cell prepared by the material can have higher output performance and long-time stability. In addition, the single perovskite phase has good conductivity, and the layered perovskite phase has higher conductivity and long-time performance stability, which is the root cause that the single cell prepared from the material can have higher output performance and long-time stability.
Comparative example 1
The remaining steps of this comparative example are the same as in example 4, except that: the temperature in step b was replaced with 70 ℃. The result shows that: the gel formation rate is greatly reduced.
Comparative example 2
The remaining steps of this comparative example are the same as in example 4, except that: the temperature in step b was replaced with 110 ℃. The result shows that: the stirring time is shortened, and the gel is easy to foam at high temperature.
Comparative example 3
The remaining steps of this comparative example are the same as in example 4, except that: the temperature of the oven in step c was replaced with 180 ℃. The result shows that: the organic matter in the gel is not carbonized enough.
Comparative example 4
The remaining steps of this comparative example are the same as in example 4, except that: the temperature of the oven in step c was replaced with 320 ℃. The result shows that: the carbon skeleton is excessively burned.
Example 5
Using the SFC4 cathode material of example 4, an SFC4|sdc|sfc4 oxy-ion symmetric cell was prepared as follows:
(1) Weighing 10ml of isopropanol, 2ml of glycol and 0.6ml of glycerol, weighing 1gSFC to 4 cathode powder, and placing the cathode powder on a planetary ball mill for ball milling, wherein the rotation speed of the ball mill is 400r min -1, and the ball milling time is 2 hours, so as to prepare cathode powder slurry;
(2) 0.5g of SDC electrolyte powder was weighed and pressed into 15mm round pieces by a tablet press, and the round pieces were placed in a high temperature furnace at about 1400 ℃ to be calcined for 5 hours, thereby obtaining electrolyte sheets.
(3) Uniformly spraying the slurry on two sides of an electrolyte sheet by using a spray gun, and placing the slurry in a muffle furnace at about 800 ℃ for calcining for 2 hours to prepare a symmetrical battery;
(4) And brushing current collecting layers on two sides of the oxygen ion group symmetrical battery, and connecting silver wires.
The sfc4|sdc|sfc4 oxy-symmetric cells prepared in this example were tested for electrochemical impedance in an air atmosphere at 550 c and the results are shown in fig. 2. As can be seen from the results in FIG. 2, the SFC4|SDC|SFC4 oxyanion symmetrical cell has a resistance of 0.04 Ω cm 2 at a test temperature of 550 ℃.
The sfc4|sdc|sfc4 oxy-symmetric cells prepared in this example were tested for thermochemical stability and the results are shown in fig. 3. As can be seen from the results in fig. 3, the oxygen ion-based symmetric cell prepared from the SFC4 cathode material can be operated continuously for 1000 hours at a test temperature of 550 c without a significant increase in the impedance.
Example 6
Using the SFC4 cathode material of example 4, an sfc4|sdc|nio-SDC oxy-fuel cell was prepared as follows:
(1) Weighing 10ml of isopropanol, 2ml of ethylene glycol and 0.6ml of glycerol, weighing 1g of SFC4 cathode powder, and placing the powder on a planetary ball mill for ball milling, wherein the rotation speed of the ball mill is 400r min -1, and the ball milling time is 2 hours to prepare cathode powder slurry;
(2) 7g of NiO powder, 3g of SDC powder and 0.7g of PVB are weighed, placed in a mortar, and poured with a proper amount of alcohol, ground until the alcohol is completely volatilized, placed in an oven for drying, and placed in the mortar for grinding into NiO-SDC anode powder.
(3) Weighing 0.35g of NiO-SDC anode powder, pressing the powder into 15mm wafers by a tablet press, weighing 0.015g of SDC electrolyte powder, uniformly sieving the powder on one side surface of the anode powder wafer by a 300-mesh sieve, continuously pressing, and calcining the pressed wafer in a high-temperature furnace at 1400 ℃ for 5 hours to prepare the half-cell.
(4) Uniformly spraying the cathode powder slurry on one side of an electrolyte of a half cell by using a spray gun, and placing the half cell in a muffle furnace at 800 ℃ for calcining for 2 hours to prepare an oxygen ion-based fuel cell;
(5) And brushing a current collecting layer on the cathode side of the oxygen ion-based fuel cell, connecting silver wires on two sides, and packaging on a quartz glass tube.
The oxygen ion group fuel cell prepared in this embodiment is subjected to output performance test, and the specific method is as follows: the test was conducted at 400 c, 500 c and 600 c using dry H 2 as fuel and air as oxidant, using a digital source meter (Keithley 2440) at 50 c intervals, resulting in a maximum power density of 1250mW cm -2 at 600 c, as shown in fig. 4.
Fig. 5 shows an SEM image of an oxygen-ion-based fuel cell prepared in this example, comprising the cross-sectional image shape of an SFC4 porous cathode, a dense SDC electrolyte, and a NiO-SDC composite anode. As can be seen from fig. 5, the adhesion between the SFC4 cathode (thickness about 25 μm) and the SDC electrolyte (thickness about 20 μm) was very tight, thereby proving the reliability of the oxygen-ion-based fuel cell performance test results.
Example 7
Using the SFC4 cathode material of example 4, an SFC4| BZCYYb |sfc4 proton-based symmetric cell was prepared as follows:
(1) Weighing 10ml of isopropanol, 2ml of ethylene glycol and 0.6ml of glycerol, weighing 1g of SFC4 cathode powder, and placing the powder on a planetary ball mill for ball milling, wherein the rotation speed of the ball mill is 400r min -1, and the ball milling time is 2 hours to prepare cathode powder slurry;
(2) About 0.5g of BZCYYb electrolyte powder was weighed, pressed into a 15mm diameter disc by a tablet press, and placed in a high-temperature furnace at about 1450 ℃ for calcination for 5 hours to prepare an electrolyte sheet.
(3) Uniformly spraying the slurry on two sides of an electrolyte sheet by using a spray gun, and placing the slurry in a muffle furnace at about 800 ℃ for calcining for 2 hours to prepare a symmetrical battery;
(4) And brushing current collecting layers on two sides of the proton-based symmetrical battery, and connecting silver wires.
The sfc4| BZCYYb |sfc4 proton-based symmetrical battery prepared in this example was subjected to electrochemical impedance test in a wet air (3%H 2 O) atmosphere at 550 c, and the results are shown in fig. 6. As can be seen from the results in fig. 6, the resistance of the symmetric cell prepared from the SFC4 cathode material was 0.774 Ω cm 2 at a test temperature of 550 ℃.
The results of thermochemical stability testing of the SFC4| BZCYYb |SFC4 proton-based symmetrical cells prepared in this example are shown in FIG. 7. From the results in FIG. 7, it is understood that the SFC4| BZCYYb |SFC4 mass-based symmetrical cell can be operated continuously for 1000 hours at a test temperature of 550℃and its impedance is increased at a rate of 4/10000. OMEGA cm 2/h.
Example 8
The preparation method of the SFC4| BZCYYb |SFC4 proton ceramic fuel cell in the embodiment comprises the following specific steps:
(1) Weighing 10ml of isopropanol, 2ml of ethylene glycol and 0.6ml of glycerol, weighing 1g of SFC4 cathode powder, and placing the powder on a planetary ball mill for ball milling, wherein the rotation speed of the ball mill is 400r min -1, and the ball milling time is 2 hours to prepare cathode powder slurry;
(2) Weighing 6g of NiO powder, 4g BZCYYb g of powder and 1g of starch, placing into a ball milling tank, pouring a proper amount of alcohol, placing into a planetary ball mill, ball milling for 40min at the rotating speed of 400r min -1, pouring the ball-milled slurry into a mortar for grinding until the alcohol is completely volatilized, placing into an oven for drying, and placing into the mortar for grinding into NiO-BZCYYb anode powder.
(3) Weighing 0.35g of NiO-BZCYYb anode powder, pressing the powder into 15mm wafers by a tablet press, weighing 0.015g of BZCYYb electrolyte powder, uniformly sieving the powder on one side surface of the anode powder wafer by a 300-mesh sieve, continuously pressing, and calcining the pressed wafer in a high-temperature furnace at 1450 ℃ for 10 hours to prepare the half-cell.
(4) Uniformly spraying the cathode powder slurry on one side of an electrolyte of a half cell by using a spray gun, and placing the half cell in a muffle furnace at 800 ℃ for calcining for 2 hours to prepare the proton ceramic fuel cell;
(5) And brushing a current collecting layer on the cathode side of the single cell, connecting silver wires on two sides, and packaging on a quartz glass tube.
The proton ceramic fuel cell prepared in this embodiment is tested for output performance, and the specific method is as follows: wet H 2(3％H2 O) and air as the oxidant were tested using a digital source meter (Keithley 2440) at temperatures of 350 ℃, 450 ℃ and 550 ℃, respectively, resulting in a maximum power density of 645mW cm -2 at 550 ℃ as shown in fig. 8.
Fig. 9 shows an SEM image of a proton ceramic fuel cell prepared in this example, comprising a SFC4 porous cathode, a dense BZCYYb electrolyte, and a NiO-BZCYYb composite anode in cross-sectional image shape. It is evident from the figure that the adhesion between the SFC4 cathode (thickness about 30 μm) and BZCYYb electrolyte (thickness about 25 μm) is still very tight, which also demonstrates the reliability of the proton ceramic fuel cell performance test results.
The proton ceramic fuel cell prepared in the embodiment is subjected to thermochemical stability test, and the specific method comprises the following steps: stability testing was performed using dry H 2 as the fuel and air as the oxidant at 550 ℃ using a digital source meter (Keithley 2440) and as shown in fig. 10, stable operation was continued for 3100H at 550 ℃ test temperature.
Claims (9)
1. The application of the cathode material of the solid oxide fuel cell in the low-temperature oxygen ion conductor-based solid oxide fuel cell is characterized in that: sr 4FexCoyO13+δ is used as a cathode, samarium oxide doped cerium oxide is used as an electrolyte, and a mixture of NiO and SDC is used as an anode; the chemical formula of the solid oxide fuel cell cathode material is Sr 4FexCoyO13+δ, wherein 0< x <4,2< y <6, delta is oxygen vacancy concentration, and 0< delta <1.
2. The use of a solid oxide fuel cell cathode material according to claim 1 in a low temperature oxygen ion conductor based solid oxide fuel cell, characterized in that: the average particle size of the cathode material is 300-500 nm.
3. The use of a solid oxide fuel cell cathode material according to claim 1 in a low temperature oxygen ion conductor based solid oxide fuel cell, wherein the method for preparing the solid oxide fuel cell cathode material comprises the steps of:
Step one, respectively weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water according to stoichiometric ratio;
sequentially dissolving the raw materials in deionized water, and heating and stirring until the raw materials are gel;
Step three, drying the product obtained in the step two to obtain a precursor;
step four, carrying out carbon removal treatment on the precursor obtained in the step three, and then carrying out oxygen partial pressure calcination to obtain powder;
And fifthly, grinding the powder obtained in the step four to obtain Sr 4FexCoyO13+δ cathode material powder.
4. Use of a solid oxide fuel cell cathode material according to claim 3 in a low temperature oxygen ion conductor based solid oxide fuel cell, characterized in that: in the first step, ethylenediamine tetraacetic acid: citric acid monohydrate: the molar ratio of the metal cations is 1:2:1-2, and the molar number of the metal cations is the sum of the molar numbers of strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate.
5. Use of a solid oxide fuel cell cathode material according to claim 3 in a low temperature oxygen ion conductor based solid oxide fuel cell, characterized in that: in the second step, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are firstly dissolved in deionized water, heated and stirred to obtain a metal nitrate solution, then ethylenediamine tetraacetic acid is dissolved in ammonia water, the ammonia water dissolved with ethylenediamine tetraacetic acid and citric acid monohydrate are added into the metal nitrate solution, and the heating and stirring are continued until the metal nitrate solution is gel.
6. Use of a solid oxide fuel cell cathode material according to claim 3 in a low temperature oxygen ion conductor based solid oxide fuel cell, characterized in that: in the second step, the heating temperature is 80-100 ℃, and the stirring speed is 200-300 r.min -1.
7. Use of a solid oxide fuel cell cathode material according to claim 3 in a low temperature oxygen ion conductor based solid oxide fuel cell, characterized in that: in the third step, the drying temperature is 200-300 ℃ and the drying time is 200-300 min.
8. Use of a solid oxide fuel cell cathode material according to claim 3 in a low temperature oxygen ion conductor based solid oxide fuel cell, characterized in that: in the fifth step, the grinding is followed by sieving with a 200-400 mesh sieve.
9. The application of the solid oxide fuel cell cathode material in the low-temperature proton ceramic fuel cell is characterized in that: sr 4FexCoyO13+δ was used as a cathode, baZr 0.1Ce0.7Y0.1Yb0.1O3-δ was used as an electrolyte, and a mixture of NiO and BZCYYb was used as an anode; the chemical formula of the solid oxide fuel cell cathode material is Sr 4FexCoyO13+δ, wherein 0< x <4,2< y <6, delta is oxygen vacancy concentration, and 0< delta <1.
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