CN114665131B - H for representing oxygen electrode material 3 O + Method of transmissibility - Google Patents
H for representing oxygen electrode material 3 O + Method of transmissibility Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 115
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 115
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000007772 electrode material Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000446 fuel Substances 0.000 claims abstract description 38
- 238000012360 testing method Methods 0.000 claims abstract description 29
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 229920000557 Nafion® Polymers 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000005540 biological transmission Effects 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000007731 hot pressing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 10
- 229910021314 NaFeO 2 Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
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- 239000010410 layer Substances 0.000 abstract description 19
- 239000010406 cathode material Substances 0.000 abstract description 11
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- 239000007787 solid Substances 0.000 description 36
- 239000004020 conductor Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000003792 electrolyte Substances 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
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- 238000003795 desorption Methods 0.000 description 11
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- 230000032258 transport Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
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- 238000001354 calcination Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 8
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
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- 230000036961 partial effect Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
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- 238000001179 sorption measurement Methods 0.000 description 5
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- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 229910017135 Fe—O Inorganic materials 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- -1 oxygen ion Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 150000001450 anions Chemical group 0.000 description 1
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- 150000001768 cations Chemical group 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
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- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/409—Oxygen concentration cells
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
- G01N2013/003—Diffusion; diffusivity between liquids
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Inert Electrodes (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a method for characterizing H3O+ transmission of an oxygen electrode material. The method comprises the following steps: step 1, spraying the oxygen electrode material on one side of a Nafion film, and then performing hot pressing on the Nafion film on one side of the oxygen electrode material; spraying Pt/C electrodes on the outer side of the Nafion film to form a Pt/C | Nafion | cathode material | Nafion | Pt/C structure; and assembling carbon paper on two sides of the structure to form a proton exchange membrane fuel cell; and step 2, introducing hydrogen and air on two sides of the proton exchange membrane fuel cell to perform single cell testing, performing impedance testing under an open-circuit voltage, and calculating the H3O+ conductivity through the impedance. According to the method, the electronic insulation characteristic of the Nafion film is utilized, the electron transmission on two sides of an oxide layer is isolated, the interlayer transmission of H3O+ is realized, and the result is evaluated.
Description
Technical Field
The invention relates to a novel four-phase conductor proton conductor oxygen electrode material preparation and high-temperature in-situ characterization method, in particular to a proton conductor solid oxide fuel cell cathode material and optimization of a proton conductor solid oxide electrolytic cell oxygen electrode material.
Background
Due to the urgent demands for protecting the ecological environment and obtaining clean energy, the solid oxide fuel cell has received worldwide attention, on one hand, is clean and pollution-free in operation, and has the advantages of extremely high energy conversion efficiency and various fuel selectivities, and on the other hand, can be reversibly operated into a solid oxide electrolytic cell, and hydrogen can be obtained by electrolyzing water. Conventional solid oxide fuel cells/electrolysers have severely hampered their large-scale industrialization due to extremely high operating temperatures (800-1000 ℃). Therefore, in order to improve the stability of the fuel cell/electrolytic cell, reduce the material cost and promote the large-scale industrial application of the fuel cell/electrolytic cell, the operating temperature at medium-low temperature (400 to 700 ℃) is a trend of development thereof. As the operating temperature decreases, the advantages of the proton conductor over the oxygen ion conductor are demonstrated, the advantages of the proton conductor solid oxide fuel cell/electrolyzer are: protons have a smaller ionic radius and therefore have less activation energy during transport; as the temperature decreases, the proton mobility increases; for proton conductor solid oxide fuel cells, water is generated at the cathode, so that fuel gas is not diluted, and the recycling property of fuel is improved; for proton conductor solid oxide cells, the hydrogen electrode is capable of producing dry pure hydrogen gas without requiring subsequent processing to remove water vapor. Therefore, development of proton conductor fuel cell (electrolyzer) cathode (oxygen electrode) materials is a breakthrough direction in fuel cell research.
However, the existing proton conductor oxygen electrode material still has the problem of low oxygen reduction capability, proton conductivity and electron conductivity.
Disclosure of Invention
The invention provides a high-performance material Na which can be used as a cathode of a proton conductor solid oxide fuel cell and an oxygen electrode of the proton conductor solid oxide electrolytic cell simultaneously 0.3 Sr 0.7 Ti 0.1 Fe 0.9 O 3-δ (NSTF 0.3) and preparation method and application thereof.
The invention also provides a method for testing the H of the solid oxide material 3 O + The diffusion method of the (2) utilizes the electronic insulation property of the Nafion film to isolate the electronic transmission at the two sides of the oxide layer so as to realize H 3 O + And evaluate the results.
The invention also provides a method for detecting whether water vapor enters the bulk phase of the cathode material of the proton conductor solid oxide fuel cell in the working process, the target material of the method is a cathode, ag is an anode, and cathode electrons flow out and anode electrons flow out through directional current output and input, and the cathode electrons are identical to the electron transmission state in the actual working state, so that the replication of the cathode reaction is realized. Through synchrotron radiation test, the electronic structure change and the metal valence state change of the material are observed when the electrode reaction occurs, and finally the detection of the water vapor affinity condition is realized.
An oxide material having the molecular structural formula: na (Na) x Sr 1-x Ti 0.1 Fe 0.9 O 3-δ ，x＝0.05<x<0.5, delta represents oxygen vacancy content, and the main phase in the oxide is perovskite phase, and the oxide also contains an additional phase of beta-NaFeO 2 (NF)。
0≤δ≤1。
The preparation method of the oxide material is realized by a sol-gel method.
The preparation process of the sol-gel method comprises the following steps: adding tetrabutyl titanate and citric acid monohydrate into deionized water, heating and dissolving, mixing the tetrabutyl titanate and the citric acid monohydrate with sodium nitrate and ferric nitrate, dissolving, heating and stirring; adding ethylenediamine tetraacetic acid, then dropwise adding ammonia water until the pH value of the solution is between 7 and 8, and volatilizing water under the condition of heating and stirring to obtain a gel substance; and (3) drying the gel substance in an oven to obtain a cathode material precursor, and then placing the precursor in a muffle furnace for roasting to obtain the oxide material.
The total molar ratio of ethylenediamine tetraacetic acid and citric acid to metal ions (sodium, strontium, titanium and iron) is 2:0.5-1.5:0.5-1.5.
The roasting parameters are 950-1050 ℃ for 1-10h.
The use of the above-mentioned oxide materials in solid oxide fuel cells and/or solid oxide electrolysis cells.
In the solid oxide fuel cell, the electrolyte is BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3 。
In the solid oxide electrolytic cell, niO and BaZr are adopted as hydrogen electrode materials 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3 The mass ratio of NiO to BZTYYb in the composite hydrogen electrode is (3-5) (5-7).
H for representing oxygen electrode material 3 O + A method of transmissibility comprising the steps of:
step 1, spraying an oxygen electrode material on one side of a Nafion film, and hot-pressing the Nafion film on one side of the oxygen electrode material; spraying Pt/C electrodes on the outer sides of the Nafion films respectively to form a Pt/C|Nafion|cathode material|Nafion|Pt/C structure; respectively assembling carbon paper on two sides of the structure to form a proton exchange membrane fuel cell;
step 2, hydrogen and air are respectively introduced into two sides of the proton exchange membrane fuel cell to carry out single cell test, impedance test is carried out under open-circuit voltage, and H is calculated through impedance 3 O + Conductivity.
Oxygen electrode material loading was 0.025gcm -2 Pt loading of 0.1mgcm in Pt/C catalyst -2 。
The test temperature of the proton exchange membrane fuel cell is 60-80 ℃, and 1-5vol.% of water vapor is added at both sides of the anode and the cathode.
When the Pt/C electrode is sprayed, the mass ratio of Pt/C to solvent in the slurry is 0.1-5:100, wherein the solvent is an alcohol solvent.
When the oxygen electrode material is sprayed, the ratio of the oxygen electrode material to the solvent in the slurry is 0.5g of the oxygen electrode material: 5-20mL of solvent; the solvent is an alcohol solvent.
A method for detecting proton absorption capacity of a proton conductor solid oxide fuel cell cathode material in an operating state comprises the following steps:
step 1, spraying an oxygen electrode material on one side of an electrolyte, and coating silver on the other side of the electrolyte after calcination treatment;
step 2, connecting two sides of the electrolyte with a closed loop, respectively applying current under the low-temperature and high-temperature conditions, and simultaneously measuring the K-edge characteristic of Fe element under a fluorescence mode;
step 3, repeating the test of step 2 in the environment with water vapor;
if the valence state of Fe is increased under the condition of water vapor, the material phase is judged to be capable of absorbing protons.
In the step 1, the step of spraying oxygen electrode materials is as follows: preparing slurry containing oxygen electrode powder, and spraying the slurry on one side of an electrolyte; the concentration of the oxygen electrode powder in the slurry is 5-20wt%.
The slurry adopts alcohol solvents, ether solvents, benzene solvents or ester solvents.
In the step 1, the calcination condition is 1-5h at 800-1200 ℃; the electrolyte is BZTYYb.
In the step 2, the low temperature is room temperature, and the high temperature is 400-500 ℃.
In the step 2, the environment with water vapor is 1-5vol.% water vapor.
Advantageous effects
(1) Through the test of a proton exchange membrane fuel cell, NSTF0.3 oxide is taken as an intermediate layer to obtain excellent performance, and the performance reaches 126mW/cm at 70 DEG C 2 And has H 3 O + The conductivity was 0.022S/cm.
(2) The solid oxide fuel cell cathode/solid oxide electrolytic cell oxygen electrode material NSTF0.3 prepared by adopting a sol-gel method. The battery has higher output performance, and the output power of a single battery prepared by taking Ni-BZCYb as an anode support respectively reaches 1118mW cm under the optimal water vapor at 650 ℃,600 ℃,550 ℃,500 ℃,450 ℃ and 400 DEG C -2 ，807mW cm -2 ，605mW cm -2 ，427mW cm -2 ，268mW cm -2 ，143mW cm -2 。
(3) Through a proton exchange membrane fuel cell test method, the fact that H3O+ transmission exists between NSTFx two phases is found, and improvement of cathode proton transmission capacity is achieved.
(4) For proton conductor solid oxide fuel cells, cathode water vapor generation will dilute the air to reduce the oxygen partial pressure, which is detrimental to the surface diffusion of oxygen, and the highest cathode performance is sought by controlling the surface water vapor concentration.
(5) Through a surface oxygen active substance SrCoO 3-δ The surface oxygen activity is strengthened, and the proton conductor material with both proton transmission and high oxygen activity is obtained;
(6) In the electrolysis mode, a solid oxide electrolytic cell using NSTFx as an oxygen electrode is found to have excellent performance, so that the excellent proton transmission capability of the solid oxide electrolytic cell can be used as an oxygen electrode material of the solid oxide electrolytic cell.
Drawings
FIG. 1 is an XRD refinement of NSTFx at room temperature;
FIG. 2 is an SEM and FIB-TEM image of NSTF 0.3;
FIG. 3 shows the performance of a proton exchange membrane fuel cell with an oxide as an intermediate layer and H of each material 3 O + Conductivity of the material;
FIG. 4 is an SEM image of a proton exchange membrane fuel cell oxide layer;
FIG. 5 is a drawing showing the removal of water from NSTF0.3 and a comparative material at 250℃and 500℃after water treatment, respectively;
FIG. 6 is a graph of NSTF0.3 versus NSTF0 cathode material high temperature in situ synchrotron radiation data and field device map;
FIG. 7 is a cathode material active site distribution at 600 ℃;
FIG. 8 is a graph of the resistance of the cathode material at various temperatures at 5% moisture;
fig. 9 is a graph of the performance of cathode NSTF0.3 under different cathode atmospheres;
fig. 10 is a graph of impedance and optimal cell performance of cathode NSTF0.3 after SC impregnation, a cross-sectional view of a single cell, and a morphology of cathode channels after SC impregnation.
FIG. 11 is an I-V graph of a solid oxide cell at 600 degrees at different water partial pressures on the oxygen electrode side.
FIG. 12 is a graph showing the change in Faraday efficiency with current density at 500 and 550℃with a water partial pressure of 80% at the oxygen electrode side of the solid oxide electrolytic cell.
Fig. 13 is a schematic view of the technical concept of the present patent.
Detailed Description
The invention relates to a series of design optimization strategies for proton conductor oxygen electrode materials, which are specific to iron-based perovskite SrTi 0.1 Fe 0.9 O 3-δ A-site Na doping is carried out to prepare the molecular formula Na x Sr 1-x Ti 0.1 Fe 0.9 O 3-δ (NSTFx, x= 0,0.1,0.2,0.3 and 0.4), wherein δ represents the oxygen vacancy content, belongs to the field of solid oxide fuel cell cathodes and solid oxide electrolysis cell oxygen electrode materials. The performance of the single cell is improved by carrying out three optimization strategies of ion doping, surface water vapor partial pressure regulation and control and oxygen active material impregnation on the material. The best performance is achieved by the preparation of NSTF0.3, which is composed of a main phase perovskite phase and an additional phase beta-NaFeO 2 (NF) a composite oxygen electrode material. And we have found a novel proton transport form, H 3 O + Such a four-phase conductivity (H 3 O + /H + /O 2- /e - ) The performance of the oxygen electrode is greatly improved, and an optimization thought is provided for the design of the proton conductor solid oxide fuel cell cathode and the solid oxide electrolytic cell oxygen electrode material. Meanwhile, the material is characterized by adopting high-temperature in-situ synchrotron radiation, and the structural change of the electrode of the material in the working environment is analyzed.
The design concept of the materials is as follows: NSTFx adopts a parent material Sr 0.9 Ti 0.1 Fe 0.9 O 3-δ The catalyst has certain oxygen activating capacity and is applied to oxygen ion solid oxide fuel cells, but is not optimized and applied to the fields of proton conductor solid oxide fuel cells and proton conductor solid oxide electrolytic cells. The invention is found to be low in costThe Na element A is doped, so that the function is enhanced in proton absorption and transmission; and by a second phase of beta-NaFeO which is eluted at high Wen Chengxiang 2 (NF) enhancing proton absorption while desirably providing two-phase interlayer ion transport; and meanwhile, the second phase can provide dispersed oxygen and water vapor active sites under specific water vapor, so that the active sites are utilized to the maximum extent. The special characteristics of the proton conductor electrode are continuously made up by the modification of the multiphase material, and the excellent proton conductor electrode material is obtained.
Example 1 Low temperature proton conductor oxygen electrode Material Na x Sr 1-x Ti 0.1 Fe 0.9 O 3-δ (x= 0,0.1,0.2,0.3 and 0.4)
(1) 1.7015g of tetrabutyl titanate and 42g of citric acid monohydrate are weighed, 50mL of deionized water is added, and the mixture is heated, stirred and dissolved to be a clear solution;
(2) 0.4250g, 0.8499g, 1.2749g and 1.6999g of sodium nitrate (sodium nitrate is not added when x is 0), 7.4071g of strontium nitrate and 18.18g of ferric nitrate are respectively weighed into a clear solution, heated and stirred until dissolved;
(3) Weighing 29g of ethylenediamine tetraacetic acid as a complexing agent, adding a solution dissolved with metal ions, dropwise adding a proper amount of ammonia water until the pH value of the solution reaches 7-8, and stirring under the condition of magnetic stirring until the water is completely evaporated to obtain a gel substance;
(4) Calcining the gel material in an oven at 180 ℃ for 5 hours to obtain a required foam-like precursor;
(5) 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 oxygen electrode powder.
Example 2 comparative material beta-NaFeO 2 Is prepared from
(1) 4.2495g of sodium nitrate and 20.2g of ferric nitrate are respectively weighed and put into deionized water for stirring until the sodium nitrate and the ferric nitrate are dissolved;
(2) Weighing 29g of ethylenediamine tetraacetic acid and 42g of citric acid monohydrate as complexing agents, adding a solution dissolved with metal ions, dropwise adding 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) Calcining the gel material in an oven at 180 ℃ for 5 hours to obtain a required 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 oxygen electrode powder.
Characterization of materials
XRD characterization
The a region of fig. 1 is the XRD pattern of the NSTFx-series cathode material at room temperature, and it can be seen from the figure that NSTF0 presents a cubic perovskite single-phase material when not doped with Na element, NSTF0.1 can still maintain a pure cubic perovskite phase by a little Na doping, but when Na ratio exceeds 0.2, there is a second phase which is desolventized from the matrix and eluted, by XRD verification, is NF phase, and the relative peak intensity of the second phase increases with increasing Na doping ratio.
The b, c, d, e, f region of fig. 1 is the XRD trimming result of NSTF0-NSTF0.4, respectively, and the proportion of NF phase increases by increasing the doping proportion of Na.
The matrix single-phase cubic perovskite is subjected to Na doping to remove the second phase, so that a composite oxygen electrode material is formed, and the proton absorption capacity of the oxygen electrode material is enhanced by adding the second phase, so that interlayer proton species transmission is formed.
2. Powder morphology characterization analysis
Figure 2, panel a, is an SEM image of NSTF0.3 with the second phase NF nano-platelets overlying the perovskite macroparticles.
Fig. 2 b, c, and d are FIB-TEM images, and it was found that the nano-scale NF phase was embedded in the perovskite phase, instead of having the NF phase on the surface and near the inner surface of the perovskite.
FIG. 2 e is an elemental mapping analysis of FIB-SEM, verifying NF phase formation at the surface and bulk surface.
Proton exchange membrane cell testing with oxide as ion transport layer
(1) Pouring 0.5g of oxygen electrode powder and 10mL of isopropanol into a high-energy ball mill, ball milling for 30min under the condition of 400r/min, and transferring the mixture to a strain bottle by using a straw to obtain the required oxygen electrode slurry;
(2) Adding commercial Pt/C and isopropanol into a strain bottle in a mass ratio of 1:99, and uniformly dispersing by using ultrasonic;
(3) Spraying oxygen electrode material with thermal spraying machine (Siansonic UC 320), spraying 2mL of slurry at 75deg.C on commercial Nafion film (Dupont, USA) with effective area of 4cm 2 ；
(4) Covering the oxide layer with another Nafion film and pressing the film into a (Nafion|oxide layer|Nafion) sandwich structure by a hot press;
(5) Pt/C slurry (6 mg 20% Pt/C, 40mg Nafion and 2mL isopropyl alcohol ultrasonic mixed) was sprayed on both sides of the three-layer film by a thermal spraying machine so that the Pt load on both sides was 0.1mg cm -2 ；
(6) Finally, sealing the edges of the proton exchange membrane fuel cell by using polytetrafluoroethylene, wherein carbon paper is used as an electronic current collector and a gas diffusion layer on two sides of the proton exchange membrane fuel cell, and solid oxide is used as an intermediate interlayer;
(7) The single cell test is performed by passing high purity hydrogen and high purity air through both sides, and the impedance test is performed under open circuit voltage.
FIG. 3 a is a schematic diagram of a proton exchange membrane, in which a proton exchange membrane cell using an oxide as a proton species diffusion layer is designed to study the presence of H between oxide layers while isolating the electron conductivity of the oxide 3 O + Is a diffusion of (a). Due to the electronic insulation characteristic of the Nafion film, the electron transmission at the two sides of the oxide layer is isolated, and the electronic insulation requirement of the electrolyte in the proton exchange membrane battery is realized. At the same time, protons are in Nafion membrane as H 3 O + In the form of (a) the proton transport in the oxide phase is hardly achieved at low temperatures, the surface proton diffusion is the best choice, H 3 O + Is the largest possible for its proton transport. Due to the water absorption capacity of the oxide, protons will take water as a transmission medium on the surface to realize H 3 O + And there is a difference in proton transport capacity due to the difference in water adsorption capacity thereof.
B, c, d, e of FIG. 3 is a proton exchange membrane single-electrode with various oxides as intermediate layersCell performance diagram, through single cell test, shows that the performance of proton exchange membrane cell without oxide intermediate layer is far greater than that of other proton exchange membrane single cells with oxide intermediate layer, which is 291mW/cm 2 With NSTF0.3, NSTF0 and beta-NaFeO 2 The performances of single cells of the proton exchange membrane serving as the middle layer are respectively 126mW/cm 2 、5mW/cm 2 And 13.5mW/cm 2 From the results, it can be seen that almost no H exists at the single-phase perovskite phase and grain boundary 3 O + Conduction of the same beta-NaFeO 2 H at bulk phase and grain boundaries 3 O + Conduction is also weak, however, when two phases are compounded, there is excellent H between the two phases 3 O + Conduction.
FIG. 3 is a graph f of ohmic resistance of each PEM cell tested at open circuit voltage, as can be seen, NSTF0.3 has the best H 3 O + Conduction.
The g-plot of FIG. 3 is H calculated from the impedance 3 O + Conductivity, NSTF0.3 existence of H far exceeding that of other two single-phase materials between two phases 3 O + Conduction.
Fig. 4 is a cross-sectional view of an oxide layer of each proton exchange membrane cell with oxide as an intermediate layer, we can obtain a cross-sectional view with a relatively good morphology by placing in liquid nitrogen for 30s and then shooting the cross-section with a blade shear, and by SEM images, we can calculate the ionic conductivity by measuring the thickness of the NF, NSTF0, NSTF0.3 oxide layers, which are 23.8 microns, 48 microns and 65.2 microns, respectively.
Influence of the presence of moisture on oxygen transport
The influence of the material on oxygen transmission in the presence of water vapor is examined through a temperature programming desorption experiment of water and oxygen.
FIG. 5, panel a, shows that a powder sample was subjected to 250℃and 20vol.% H 2 O-80vol.% air for 3 hours, then quenched to room temperature, and the sample subjected to H 2 And (3) performing temperature programming desorption experiments on O. We found that NSTF0.3 possessed the largest and sharp desorption peaks, demonstrating its large amount of water vapor stored at the two-phase interface, and rapid interlayer water vapor transport capacity.
FIG. 5 b shows the powder sample passing 500℃20vol% H 2 O-80vol% air for 3 hours, then quenched to room temperature, and the sample subjected to H 2 And (3) performing temperature programming desorption experiments on O. With the increase of NF phase of the second phase, the capability of the material for storing water vapor is stronger, and the water vapor still exists at the interface of the two phases under the condition of 500 ℃ and accords with the water vapor absorption condition which can occur in the operating temperature range of the battery.
FIG. 5 c is a graph of the powder sample passing 250℃and 20vol% H 2 O-80vol% air for 3 hours, then quenched to room temperature, and then O is applied to the sample 2 Is a programmed temperature desorption experiment. We have found that NSTF0.3 also has an O at 271 ℃ 2 And the desorption peak of the (2) indicates that the water vapor and the oxygen are desorbed simultaneously, and the two species have different adsorption sites.
FIG. 5 d is a graph of the powder sample passing 250℃and 20vol% H 2 O-80vol% air for 3 hours, then quenched to room temperature, and then O is applied to the sample 2 Is directly carried out O without water vapor treatment 2 Is compared with the temperature programming desorption experiment. We found that NSTF0 was shifted back in desorption temperature after water vapor treatment, indicating that water vapor absorption affected desorption of oxygen and that two species had competitive adsorption.
It can be seen that NSTF0.3 material may be able to effectively avoid H 2 Impact on oxygen transport properties of materials in the presence of O. Testing of changes in electronic structure of proton conductor solid oxide fuel cell cathode materials under operating conditions
And adopting a high-temperature proton conductor oxygen electrode in-situ synchrotron radiation test:
(1) 1g of the oxygen electrode powder NSTF0.3 obtained in example 1, 10ml of isopropanol, 2ml of ethylene glycol and 0.8ml of glycerol are weighed, poured into a high-energy ball mill, ball-milled for 30min under the condition of 400r/min, and transferred to a strain bottle by a straw to obtain the required oxygen electrode slurry.
(2) Grinding the edge of a BZTYYb electrolyte sheet into a circular sheet with the diameter of 1cm, placing the circular sheet on a heating table for preheating at 200 ℃, using a spray gun to uniformly spray the prepared oxygen electrode slurry on one side surface of the electrolyte under the pushing of inert gas, and placing the sprayed half-cell in a high-temperature muffle furnace for calcining for 2 hours at 1000 ℃ after the liquid is completely volatilized;
(3) Coating silver paste on the other side of the BZCYb battery, and connecting silver wires on the two sides to lead out to form a (NSTF 0.3|BZCYYb|Ag) battery structure;
(4) Placing the battery in a high-temperature in-situ synchrotron radiation device, and connecting an oxygen electrode side wire and an Ag electrode side wire with an electrochemical workstation for testing;
(5) Applying current at room temperature and high temperature of 450 ℃ on both sides, and introducing dry air and humid air (3 vol.% H) into the cavity of the high temperature device 2 O) oxygen reduction reaction occurs on the oxygen electrode material side, synchrotron radiation test is carried out on the oxygen electrode surface, and the test condition fluorescence mode tests the Fe element K-edge; the target material is used as a cathode, ag is used as an anode, and cathode electrons and anode electrons flow out through directional current output and input, so that the replication of cathode reaction is realized, wherein the electron transport state is the same as the actual working state. Through the synchrotron radiation test, the electron structure change and the metal valence state change of the material are observed when the electrode reaction occurs, the K-edge test of Fe is often used for observing the valence state and the electron structure of Fe ions, the high-energy shift of the peak position is the valence state rise, the height of the diffraction peak in the R space represents the change of the coordination number of anions/cations bonded with the Fe ions, the coordination number change of Fe-O is here, and the peak shift is the coordination number increase of Fe-O.
Figures a and b of fig. 6 are graphs of synchrotron radiation of NSTF0 material at room temperature and high temperature in situ. After the temperature is raised, the valence state of Fe is reduced due to the generation of oxygen vacancies, and the valence state of Fe is improved after water is introduced, but the b diagram shows that the coordination peak of Fe-O is weakened along with the temperature rise, the loss of coordination bonds caused by the temperature rise desorption of lattice oxygen is not obviously raised along with the increase of water vapor, which indicates that in the actual process of the NSTF0 cathode, the water vapor does not enter the bulk phase, and the water vapor is very likely to be in competitive adsorption with oxygen.
Fig. 6 c and d are graphs of synchrotron radiation of NSTF0.3 material at room temperature and high temperature in situ. After the temperature is raised, the valence state of Fe is reduced due to oxygenThe generation of vacancies causes that the valence state of Fe is obviously improved after water is introduced, and d diagram shows that the coordination peak of Fe-O is weakened along with the temperature rise, the loss of coordination bonds caused by the temperature rise desorption of lattice oxygen is obviously improved along with the increase of water vapor, which indicates that in the actual process of NSTF0.3 cathode, the water vapor has a severe hydration reaction on the surface, and oxygen vacancies are filled, so that the valence state of surrounding Fe is improved. Proved by the extremely hydrophilic property of NSTF0.3 to water vapor, is beneficial to H 3 O + Is formed and adsorbed on the surface of the substrate.
ASR testing in a vapor-bearing condition
(1) 1g of the oxygen electrode powder NSTF0.3 obtained in example 1, 10ml of isopropanol, 2ml of ethylene glycol and 0.8ml of glycerol are weighed, poured into a high-energy ball mill, ball-milled for 30min under the condition of 400r/min, and transferred to a strain bottle by a straw to obtain the required oxygen electrode slurry.
(2) And placing the prepared BZTYYb and SDC electrolyte on a heating table to preheat at 200 ℃, uniformly spraying the prepared oxygen electrode 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 at 1000 ℃ for 2 hours after the liquid volatilizes completely, and obtaining the required symmetrical battery for testing the polarization impedance of the oxygen electrode material at the temperature of 500-700 ℃.
(3) 6.3489g of strontium nitrate, 8.7309g of cobalt nitrate and 6.7563g of glycine are weighed, 100mL of deionized water is used for dissolving the solution to a clear solution, and 20mL of solution and 5mL of absolute ethyl alcohol are measured to form an impregnating solution;
(4) Dropping the soaking solution into the cathode skeleton with a dropper for 3 times at 400 deg.c for 30min and 700 deg.c for 2 hr. The required symmetrical battery is prepared and used for testing the polarization impedance of the oxygen electrode material at the temperature range of 500-700 ℃.
Figure 7, panel a, is an electrode polarization ASR plot of the respective electrode materials of an SDC supported symmetric cell under dry air, evaluating the ORR activity of the respective materials in the absence of proton carrier. Under these conditions, the single phase STF electrode produced the lowest ASR and the ASR increased with increasing Na content in the NSTFx nanocomposite electrode untilASR begins to decrease after x reaches 0.2. Panel b of FIG. 7 shows DRT analysis of dry air at 600℃and DRT spectra show three different peaks corresponding to three different electrocatalytic processes. The high band small peak around 1000Hz may be related to the charge transfer process at the electrode/electrolyte interface. Peaks occurring in the frequency range of 100-300Hz are likely to be associated with ion diffusion within the porous oxygen electrode body. Finally, we attribute the large peak in the frequency range from 1-100Hz to O 2 Adsorption/desorption, dissociation, surface O 2- Diffusion and O 2 The co-action of gas diffusion. The size and shape of the high and medium frequency peaks are similar for all samples. However, the size and position of the low band peaks shift significantly with Na content, indicating that incorporation of Na (and/or formation of ORR inactive NF second phases) may adversely affect oxygen ion surface transport and reaction of surface active oxygen species. As the Na doping amount increases, the low-band peak increases (until x=0.2) and then decreases while its position is continuously shifted toward low frequency. In the c-h plots of fig. 7, the low frequency peaks in the DRT pattern are most affected, and it can be concluded that adsorbed water can negatively affect the oxygen adsorption and surface reaction process. The i-plot of fig. 7 shows that the comparison of ASR with different vapors and ASR with dry air for an SDC symmetric cell increases with increasing water vapor content, and for most electrode composites the increase in relative ASR is typically between 1.5-2.5 times. However, the ASR increase at low water vapor content for NSTF0.3 electrode is significantly less, at 2.5vol.% H 2 O is relatively increased by 1.17 times, at 5vol.% H 2 The relative increase in O was 1.23 times. This suggests that NSTF0.3 electrode can achieve an optimal balance between ORR activity provided by NSTF phase and water absorption capacity provided by NF phase, thereby minimizing competition between oxygen and water adsorbate under low partial pressure of water vapor, a finding also consistent with H 2 The results for O-TPD are consistent.
Proton conductor performance test
Preparation of single cell and electrolytic cell
(1) 1g of the powder NSTF0.3 obtained in example 1, 10ml of isopropanol, 2ml of ethylene glycol and 0.8ml of glycerol were weighed, poured into a high-energy ball mill, ball-milled for 30min at 400r/min, and transferred to a strain bottle by a straw to obtain the required oxygen electrode slurry.
(2) And (3) placing the prepared dry-pressed battery piece on a heating table for preheating at 200 ℃, uniformly spraying the prepared oxygen electrode slurry on the electrolyte surface of the dry-pressed battery 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 volatilizes completely, and obtaining the required single battery which is used for testing the performances of the single battery and an electrolytic cell of the oxygen electrode material within the temperature range of 400-650 ℃.
(3) Dropping the soaking solution into the cathode skeleton with a dropper for 3 times at 400 deg.c for 30min and 700 deg.c for 2 hr. The required symmetrical battery is prepared and used for testing the single cell performance of the oxygen electrode material at the temperature of 400-600 ℃. Preparation method of impregnating solution comprises mixing strontium nitrate, cobalt nitrate and glycine according to 0.3mol L -1 ,0.3mol L -1 And 0.9mol L -1 Is dissolved in 100mL of deionized water, and 20mL of the ionic solution is mixed with 5mL of absolute ethanol.
FIG. 8 is a graph of the impedance of oxygen electrode material at various temperatures at 5% moisture, in which case ORR and hydration reactions occur simultaneously, with proton carriers acting electrochemically. Under these conditions, the single phase STF electrode produced the greatest ASR, with a significant decrease in ASR for the series of NSTFx cathodes, and the minimum ASR for NSTF0.3.
FIG. 9 is a graph showing the performance of oxygen electrode material NSTF0.3 in different oxygen electrode atmospheres, NSTF0.3 obtaining 97mW cm in a temperature range of 400-650℃under static air, respectively -2 To 770mW cm -2 Is provided. After flowing air, 143mW cm was obtained at a temperature in the range of 400-650 DEG C -2 To 1116mW cm -2 It can be seen that optimum performance is achieved when the moisture content in the cathode cavity is controlled to a certain extent.
FIG. 10 a is a graph showing the impedance and optimal cell performance of an oxygen electrode material NSTF0.3 impregnated with SC, where NSTF0.3@SC single cell has a PPD of 966mW cm at 600 ℃ -2 Optimum air flowThe speed is 550mL min -1 Whereas standard NSTF0.3 cells had an optimal air flow rate of 400mL min -1 The PPD at this time was 807mW cm -2 . And b, an oxygen electrode pore canal morphology chart. The higher optimal air flow rate that the SC-impregnated cells can withstand also indicates that the three-phase oxygen electrode has better water absorption capacity than the two-phase NSTF0.3. On a bzcybb electrolyte, humid air (5 vol.% H 2 Both nstf0.3@sc in O) and ASR of the symmetric cell in dry air on SDC electrolyte showed that impregnation of SC catalyst significantly improved ORR activity.
Fig. 11 is a graph of the electrolytic performance of oxygen electrode material NSTF0.3 under different oxygen electrode atmospheres. At 600 ℃, when the oxygen electrode side air water partial pressure was increased from 10vol.% to 80vol.%, the cell was at a power density of 1.28V from-1.22A cm -2 Rise to-1.42A cm -2 This is because both the ohmic resistance and the polarization resistance of the electrolytic cell decrease with an increase in the oxygen electrode side humidity.
FIG. 12 shows Faraday efficiencies at different temperatures and different current densities for solid oxide cells with NSTF0.3 as the oxygen electrode, BZTYYb as the electrolyte, and NiO+BZTYYb as the hydrogen electrode. As the current density increases, the faraday efficiency increases rapidly and then gradually decreases. At a current density of-0.5A cm -2 The Faraday efficiency is as high as 98%, and the hydrogen yield is higher than 3.3mL min -1 cm -2 A great advantage of NSTF0.3 as a solid oxide cell oxygen electrode was demonstrated.
Claims (8)
1. H for representing oxygen electrode material 3 O + A method of transmissibility comprising the steps of:
step 1, spraying an oxygen electrode material on one side of a Nafion film, and hot-pressing the Nafion film on one side of the oxygen electrode material; spraying Pt/C electrodes on the outer sides of the Nafion films respectively to form a Pt/C|Nafion|oxygen electrode material|Nafion|Pt/C structure; respectively assembling carbon paper on two sides of the structure to form a proton exchange membrane fuel cell;
step 2, hydrogen and air are respectively introduced into two sides of the proton exchange membrane fuel cell to test single cellsImpedance test under open circuit voltage and calculation of H by impedance 3 O + Conductivity of the material;
the molecular structural formula of the oxygen electrode material is as follows: na (Na) x Sr 1-x Ti 0.1 Fe 0.9 O 3-δ ，0.2<x<0.4, delta is more than or equal to 0 and less than or equal to 1; delta represents the oxygen vacancy content and the oxide is composed of a main phase perovskite phase and an additional phase beta-NaFeO 2 Composition is prepared.
2. The method for characterizing H of an oxygen electrode material according to claim 1 3 O + A method for transporting an oxygen electrode material, characterized in that the oxygen electrode material is supported in an amount of 0.025 g/cm -2 。
3. The method for characterizing H of an oxygen electrode material according to claim 1 3 O + The transmissibility method is characterized in that the testing temperature of the proton exchange membrane fuel cell is 60-80 ℃.
4. The method for characterizing H of an oxygen electrode material according to claim 1 3 O + The transmission method is characterized in that 1-5vol.% of water vapor is simultaneously added to both sides of the anode and cathode of the proton exchange membrane fuel cell.
5. The method for characterizing H of an oxygen electrode material according to claim 1 3 O + The transmissibility method is characterized in that when the Pt/C electrode is sprayed, the mass ratio of Pt/C to solvent in the slurry is 0.1-5:100.
6. the method of characterizing H of an oxygen electrode material according to claim 5 3 O + A method of transmissibility, characterized in that said solvent is an alcoholic solvent.
7. The method for characterizing H of an oxygen electrode material according to claim 1 3 O + The transmissibility method is characterized in that when the oxygen electrode material is sprayed, the ratio of the oxygen electrode material to the solvent in the slurry is 0.5g of the oxygen electrode material: 5-20mL of solvent.
8. The method for characterizing H of an oxygen electrode material according to claim 7 3 O + A method of transmissibility, characterized in that said solvent is an alcoholic solvent.
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| CN114649527A (en) | 2022-06-21 |
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