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CN119160946A - A spinel material, proton ceramic electrochemical cell and preparation method - Google Patents

A spinel material, proton ceramic electrochemical cell and preparation method Download PDF

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Publication number
CN119160946A
CN119160946A CN202411116225.3A CN202411116225A CN119160946A CN 119160946 A CN119160946 A CN 119160946A CN 202411116225 A CN202411116225 A CN 202411116225A CN 119160946 A CN119160946 A CN 119160946A
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spinel
mcco
spinel material
temperature
electrochemical cell
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陈宇
许阳森
刘瑛
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Zijin Mining New Energy And Materials Technology Changsha Co ltd
South China University of Technology SCUT
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Zijin Mining New Energy And Materials Technology Changsha Co ltd
South China University of Technology SCUT
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Abstract

The invention provides a spinel material, a proton ceramic electrochemical cell and a preparation method thereof. The expression of the spinel material is Mn 1‑xCsxCo2O4‑δ, wherein x is 0.01-0.15, and delta is oxygen vacancy content. The invention also provides a preparation method of the spinel material and a reversible proton ceramic electrochemical cell containing the spinel material. The Cs + doped spinel material has good stability, lower polarization impedance and higher ORR/OER activity, and the invention also provides a composite spinel material which is obtained by blending the spinel material and Co 3O4 according to different mass ratios so as to realize the highest electrochemical performance. The reversible proton ceramic electrochemical cell has good stability, electrocatalytic activity and electrochemical performance, and can be used for power generation in a fuel cell mode and synthesis of water and ethane chemical value-added products in an electrolysis mode.

Description

Spinel material, proton ceramic electrochemical cell and preparation method
Technical Field
The invention relates to the technical field of proton ceramic electrochemical cells, in particular to a spinel material, a proton ceramic electrochemical cell and a preparation method thereof.
Background
Ethylene (C 2H4) is one of the key raw material components in the chemical industry for the production of various polymers and high value added chemical products. Traditional ethylene production is obtained by high temperature pyrolysis of ethane (C 2H6), a process which is energy intensive and accompanied by significant carbon dioxide emissions. Recently, oxidative dehydrogenation of ethane to ethylene has been the most interesting because, in comparison with conventional steam cracking processes, oxidative dehydrogenation of ethane can be spontaneously reacted without high temperature and fuel consumption. However, in the ethane oxidative dehydrogenation process, ethane may be deeply oxidized into hydrocarbons other than ethylene. In contrast, the use of a non-oxidative Ethane Dehydrogenation (EDH) process can avoid most of the problems associated with oxidative dehydrogenation. And the non-oxidative ethane dehydrogenation process may be suitable for converting natural gas containing ethane, such as combustion gas, shale gas field gas, and refinery off gas in geographically severe areas. The proton ceramic electrochemical cell (Protonic ceramic electrochemical cells, PCEC) can directly convert chemical fuel into electric energy in a fuel cell mode, and can generate chemical value-added products by electrolyzing water or light alkane (such as methane, ethane and propane) in an electrolysis mode, so that the proton ceramic electrochemical cell is clean, environment-friendly and efficient energy conversion/storage equipment. The PCEC may operate at relatively low temperatures due to the high proton conductivity and low barrier to proton transfer of the proton conductor electrolyte. Unlike conventional oxygen ion ceramic electrochemical cells, PCECs avoid most of the problems of poor stability, difficult sealing, and high cost. For the electrocatalytic non-oxidative direct dehydrogenation of ethane, the lower operating temperatures may avoid some of the associated problems, including thermal cracking of C 2H6 and low selectivity of C 2H4. As the PCEC operating temperature decreases, slow electrode reaction kinetics of Oxygen Reduction Reactions (ORR), oxygen Evolution Reactions (OER), and non-oxidative Ethane Dehydrogenation (EDH) severely affect the electrochemical performance of the PCEC. Therefore, developing efficient electrodes for three reactions, oxygen Reduction Reaction (ORR) in fuel cell mode, oxygen Evolution Reaction (OER) in electrolytic cell mode, and non-oxidative dehydrogenation of ethane, presents a significant challenge.
The use of highly active and durable electrode materials, especially at low temperatures, is critical to the development of the PCEC. Several strategies such as surface modification, construction of heterostructures and cation doping have been proposed to design electrode materials with high catalytic activity and stability for Oxygen Reduction Reactions (ORR), oxygen Evolution Reactions (OER) and ethane non-oxidative dehydrogenation reactions (EDH). It is notable that the materials currently designed for ORR/OER/EDH electrodes are mostly associated with perovskite or perovskite-related oxides. Spinel oxides are of less concern than the widely studied perovskite electrodes. Spinel oxides are widely used as coatings for solid oxide fuel cell interconnects due to good thermal compatibility with other cell components. Although in recent years researchers have achieved good electrochemical performance with spinel oxide as the cathode of solid oxide fuel cells, and are comparable to some classical perovskite-based electrodes. This demonstrates the effectiveness of using spinel oxide as the oxygen electrode and expands the range of PCEC oxygen electrode options. However, the electrocatalytic activity of these spinel electrodes on oxygen evolution reactions and ethane non-oxidative dehydrogenation reactions has not been reported.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-efficiency spinel electrode material, a preparation method thereof and a reversible proton ceramic electrochemical cell which can be used for generating electricity, electrolyzing water/ethane to synthesize chemical value-added products. The novel spinel-based composite material provided by the invention has good electrochemical stability, and simultaneously has higher electrocatalytic activity on oxygen reduction reaction, oxygen precipitation reaction and ethane non-oxidative dehydrogenation reaction. The reversible proton ceramic electrochemical cell provided by the invention can be simultaneously suitable for conversion of chemical energy and electric energy and conversion of ethane into ethylene in an electrochemical mode.
In a first aspect, the invention provides a (Cs + doped) spinel material, wherein the expression of the spinel material is Mn 1-xCsxCo2O4-δ, x is 0.01-0.15, and delta is oxygen vacancy content. The Cs + doped spinel material has good stability, lower polarization impedance and higher ORR/OER activity. Preferably, the expression of the spinel material is Mn 1-xCsxCo2O4-δ, wherein x is 0.05-0.125, delta is oxygen vacancy content, preferably Mn 0.9Cs0.1Co2O4-δ, and delta is oxygen vacancy content.
According to the invention, cs can be used as an A-site dopant to effectively improve the content of oxygen vacancies of spinel oxide MnCo 2O4 (MCO) and improve the conductivity thereof, so that the electrocatalytic activity is improved, namely Mn 0.9Cs0.1Co2O4-δ(MCCO).Co3O4 (CO) nano particles have a lower melting point (about 895 o C), the interface between an electrode and an electrolyte can be optimized, and meanwhile, the catalyst has good catalytic activity on oxidation-reduction reaction. The invention designs and prepares a novel spinel based composite material Mn 0.9Cs0.1Co2O4-δ(MCCO)-Co3O4 (CO) (MCCO-CO with the mass ratio of preferably 8:2) which is used as a three-functional electrode of a proton ceramic electrochemical cell to evaluate the electrocatalytic activity, the water splitting capacity and the ethylene electrochemical student capacity at the intermediate temperature. The spinel-based electrode material with high catalytic activity and stability is designed and realized, and is applied to PCEC, so that a new electrode design field is provided for reversible oxygen reduction/precipitation on PCEC and ethylene electrochemical production.
In a second aspect, the invention also provides a method for preparing the spinel material, which is characterized by comprising the following steps.
1) According to the stoichiometric ratio, mixing manganese acetate, cesium nitrate, cobalt nitrate and water, and adding a complexing agent to obtain a mixed solution.
2) Ammonia water is added into the mixed solution, the pH value is regulated, and the mixed solution is heated under the stirring condition, so that a gel-like substance is obtained.
3) And drying the gel-like substance at high temperature to obtain a precursor.
4) And calcining the precursor to obtain the spinel material.
Preferably, in the step 1), the complexing agent is ethylenediamine tetraacetic acid and citric acid monohydrate, preferably, citric acid is added according to 1.5+/-0.2 times of the molar amount of metal ions, ethylenediamine tetraacetic acid is added according to 1+/-0.2 times of the molar amount of metal ions, wherein the metal elements are the sum of Mn, cs and Co, and more preferably, the molar ratio of the metal elements, ethylenediamine tetraacetic acid and citric acid monohydrate is 0.9-1.1:0.9-1.1:1.4-1.6, preferably 1:1:1.5.
Preferably, in the step 2), the pH value is adjusted to 7-8, and/or the heating temperature is 100-180 ℃, preferably, the heating temperature is 120-170 ℃, preferably, the treatment is 5 h at 150 ℃.
Preferably, in the step 3), the high-temperature drying is performed at a temperature of 250-300 ℃ for 1.5-7 hours. Preferably, the high-temperature drying temperature is 280-320 ℃ and the time is 2-6 hours, and the porous precursor is obtained by drying the porous precursor in a blast drying oven at 300 ℃ for 2 hours.
Preferably, in the step 4), the calcination temperature is 900-1000 ℃ and the time is 2-4 hours. Calcination is preferably carried out at 950℃for 3 hours, giving the desired electrode material powder Mn 0.9Cs0.1Co2O4-δ (designated as MCCO).
In the invention, the preparation process of the spinel material is successfully optimized by precisely controlling the proportion of the complexing agent, the pH value, the heating temperature and time and the calcining condition. The ethylenediamine tetraacetic acid and the citric acid are used as complexing agents, so that the uniform dispersion of metal ions is ensured, and particle aggregation is avoided, so that the Mn 0.9Cs0.1Co2O4-δ spinel material with excellent conductivity and catalytic activity is produced. Meanwhile, the prepared material powder presents ideal nanoscale particles through high-temperature drying and calcination at proper temperature, and the presented high specific surface area can further improve the electrocatalytic activity of the material.
In a second aspect, the invention provides a composite spinel material, which comprises the spinel material or the spinel material obtained by the preparation method, and preferably further comprises a spinel oxide material, wherein the expression of the spinel oxide material is Co 3O4.
In the present invention, the spinel oxide material is obtained by blending a raw material comprising the spinel material and the spinel oxide material. The spinel material and Co 3O4 are blended according to a certain mass ratio to realize the composite spinel material with the highest electrochemical performance.
Preferably, the preparation method of the spinel oxide material comprises the following steps.
1) Dissolving cobalt nitrate in deionized water, adding ethylenediamine tetraacetic acid and citric acid monohydrate as complexing agents into the solution, wherein the molar ratio of the citric acid monohydrate to the ethylenediamine tetraacetic acid to the metal cations is 1.5:1:1, then pouring ammonia into the solution, and adjusting the pH value to 7-8 to obtain a mixed solution.
2) Heating the mixed solution to gel state, treating at high temperature to obtain a precursor, and calcining the precursor to obtain the spinel oxide material (Co 3O4).
Preferably, in the step 1), the molar ratio of the metal element, the ethylenediamine tetraacetic acid and the citric acid monohydrate is 1:1:1.5, wherein the metal element is the sum of Co.
Preferably, in step 2), the mixed solution is heated to 100-180 ℃.
Preferably, in the step 2), the temperature of the high-temperature treatment is 250-300 ℃ and the time is 5-7 h.
Preferably, in the step 2), the calcination temperature is 900-1000 ℃ and the time is 2-4 hours.
Preferably, the composite spinel material comprises Mn 0.9Cs0.1Co2O4-δ and Co 3O4, wherein the mass ratio of Mn 0.9Cs0.1Co2O4-δ to Co 3O4 is 7-9:3-1.
According to the preferred scheme of the invention, the composite spinel material Mn 0.9Cs0.1Co2O4-δ and Co 3O4 are compounded according to a specific mass ratio, so that the electrochemical performance of the material is obviously improved, and the comprehensive performance of the composite material is optimized.
In a third aspect, the invention provides a reversible anode-supported proton ceramic electrochemical cell comprising a fuel electrode, an electrolyte and an air electrode arranged in sequence, preferably further comprising a transition layer between the fuel electrode and the electrolyte, the material of the air electrode comprising the spinel material described above and/or the composite spinel material described above and/or MnCo 2O4.
The reversible proton ceramic electrochemical cell provided by the invention has good stability, electrocatalytic activity and electrochemical performance, and can be used for power generation in a fuel cell mode and synthesis of water and ethane chemical value-added products in an electrolysis mode.
In the present invention, the air electrode may also be denoted as an air electrode & positive electrode, and the same electrode may have different expressions in different modes. Such as an air electrode when water is electrolyzed and a positive electrode when ethane is electrolyzed. The fuel electrode may also be denoted as anode.
Preferably, the material of the electrolyte comprises BaZr 0.1Ce0.7Y0.1Yb0.1O3-δ, wherein δ is the oxygen vacancy content.
Preferably, the material of the fuel electrode comprises NiO and BaZr 0.1Ce0.7Y0.1Yb0.1O3-δ, wherein the mass ratio of NiO to BaZr 0.1Ce0.7Y0.1Yb0.1O3-δ is 5-7:3-5, and preferably 6:4.
Preferably, the transition layer comprises NiO and BaZr 0.1Ce0.7Y0.1Yb0.1O3-δ, wherein the mass ratio of NiO to BaZr 0.1Ce0.7Y0.1Yb0.1O3-δ is 6:4.
According to the preferred scheme of the invention, the materials are used in the electrolyte, the fuel electrode and the transition layer and are compounded in a certain mass ratio, so that the overall performance of the proton ceramic electrochemical cell is remarkably improved, and excellent electrochemical performance and cycle stability are shown.
In a fourth aspect, the present invention provides a method for preparing the proton ceramic electrochemical cell, comprising the steps of.
1) And carrying out tape casting treatment on the electrolyte slurry, the transition layer slurry and the fuel electrode slurry, drying, degreasing, and then carrying out high-temperature calcination to obtain the anode-supported half-cell.
2) Brushing the slurry of the air electrode on the electrolyte surface of the half cell, and calcining at high temperature to obtain the proton ceramic electrochemical cell supported by the reversible anode.
Preferably, in the step 1), the degreasing treatment is performed at a temperature of 550-750 ℃, and/or in the step 1), the high-temperature calcination is performed at a temperature of 1425-1525 ℃, and/or in the step 2), the high-temperature calcination is performed at a temperature of 900-1000 ℃.
Preferably, the degreasing treatment is performed at 550-750 ℃ for 1.5-3.5 hours.
Preferably, in step 1), the high-temperature calcination temperature is 1425-1525 ℃ and the time is 5-7 h.
Preferably, in step 1), the drying is natural drying for 22-25 hours.
Preferably, in the step 2), the high-temperature calcination temperature is 900-1000 ℃ and the time is 5-15 min.
Preferably, the slurry of the electrolyte is obtained by ball milling BZCYYb1711 powder, a dispersing agent and absolute ethyl alcohol.
Preferably, the slurry of the transition layer is prepared by blending BZCYYb1711 powder, nano nickel oxide, graphite, a dispersing agent, absolute ethyl alcohol and butyl acetate and ball milling for 20-30 hours.
Preferably, the slurry of the fuel electrode is obtained by blending BZCYYb1711, nickel oxide, graphite, a dispersing agent, absolute ethyl alcohol and butyl acetate and ball milling for 20-30 hours.
Preferably, the air electrode and positive electrode slurry is obtained by blending Mn 0.9Cs0.1Co2O4-δ、Co3O4 spinel oxide with terpineol, and the preferred slurry composition is Mn 0.9Cs0.1Co2O4-δ of 0.8 g, co 3O4 of 0.2 g and terpineol of 0.15-0.25 g.
In the embodiment of the invention, the thickness of the electrolyte layer in the NiO-BZCYYb1711 anode support half cell is 8-10 mu m, the thickness of the anode support layer is 550-650 mu m, and the thickness of the Ni-BZCYYb 1711 transition layer is 17-23 mu m.
In a fifth aspect, the present invention also provides the use of a reversible anode-supported proton ceramic electrochemical cell as described above for the synthesis of chemical value-added products including power generation, electrolysis of water/ethane.
The invention has the advantages that the novel spinel material doped with Cs is prepared by doping elements at A site on the basis of the traditional spinel oxide MnCo 2O4 and blending with Co 3O4 spinel oxide. The mass ratio of the anode to the anode material MnCo2O4(MCO),Mn0.9Cs0.1Co2O4-δ(MCCO)、Mn0.9Cs0.1Co2O4-δ-Co3O4(MCCO-CO, of the anode-supported proton ceramic electrochemical cell prepared by adopting the combustion method is 8:2). The spinel electrode composited by the anode-supported proton ceramic electrochemical cell has lower polarization impedance and higher electrocatalytic activity. The polarization resistance of the NiO-BZCYYb 1711I transition layer (NiO-BZCYYb 1711) I BZCYYb I MCCO-CO at 700 ℃,650 ℃,600 ℃,550 ℃ and 500 ℃ of the anode-supported proton ceramic electrochemical cell prepared by the invention is 0.076 Ω cm 2,0.176 Ω cm2,0.382 Ω cm2,0.984 Ω cm2 and 2.940 Ω cm 2 respectively, and the highest power density is 1.73W cm -2, 1.34 W cm-2, 0.97 W cm-2, 0.62 W cm-2 and 0.28W cm -2. After the humidified air was introduced at the air electrode side, the proton ceramic electrochemical cell was operated in an electrolysis mode with current densities of-3.93A cm -2,-2.48 A cm-2,-1.45 A cm-2,-0.56 A cm-2 and-0.24A cm -2 at voltages of 700 ℃,650 ℃,600 ℃,550 ℃ and 500 ℃, 1.3V, respectively. The anode-supported proton ceramic electrochemical cell of the invention has excellent stability, oxygen ion exchange kinetics, electrocatalytic activity and electrochemical properties.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is an XRD pattern of the electrode material Mn 0.9Cs0.1Co2O4-δ (MCCO) provided in the example of the present invention after calcination at 950 ℃ for 3 hours.
Fig. 2 is an XRD pattern of an air electrode material Mn 0.9Cs0.1Co2O4-δ (MCCO) provided in an embodiment of the present invention after co-firing 10min with an anode-supported half-cell electrolyte BZCYYb1711 in a high temperature muffle furnace at 950 ℃.
Fig. 3 is an XRD pattern of the electrode material Mn 0.9Cs0.1Co2O4-δ (MCCO) provided in the example of the present invention after 10h of treatment with 30% water at 600 ℃.
Fig. 4 is a chart showing conductivity test at 300-800 ℃ of spinel electrode materials MnCo 2O4 (MCO) and Mn 0.9Cs0.1Co2O4-δ (MCCO) provided in the embodiment of the present invention.
Fig. 5 is an X-ray photoelectron spectrum (XPS) of air electrode materials MCCO and MCO provided in an embodiment of the present invention, wherein the left panel is Co 2p and the right panel is Mn 2p.
Fig. 6 is an O1s X ray photoelectron spectrum of the air electrode materials MCCO (left panel) and MCO (right panel) provided by the embodiment of the present invention.
Fig. 7 is an elemental distribution diagram of a spinel electrode material according to the present invention.
Fig. 8 is an area specific impedance diagram of the symmetric battery MCCO-CO composite spinel material (a), MCCO spinel material (b), MCO spinel material (c) as an electrode, BZCYYb1711 as an electrolyte support under humidified air (3% H 2 O) according to an embodiment of the present invention.
Fig. 9 shows electrochemical stability of the symmetric cell MCCO-CO, MCCO and MCO as electrodes, BZCYYb1711 as electrolyte support under humidified air (3% H 2 O) according to the embodiment of the present invention.
FIG. 10 is an infrared spectrum of MCO, MCCO and MCCO-CO spinel oxide provided by the embodiment of the invention after 50 h of treatment under air containing 30% water vapor at 600 ℃.
Fig. 11 is a graph of the highest power density of a single cell (Ni-BZCYYb 1711|transition layer Ni-BZCYYb1711|| BZCYYb |mcco-CO/MCCO/MCO) prepared by using MCCO-CO (a), MCCO (b), and MCO (C) as an air electrode in the embodiment of the present invention under a fuel cell mode (humidified hydrogen is introduced into the anode side, and ambient air is introduced into the oxygen electrode side) under a fuel electrode support.
Fig. 12 is a current density diagram corresponding to 1.3V when an embodiment of the present invention uses MCCO-CO (a), MCCO (b), and MCO (C) as air electrodes, and Ni-BZCYYb 1711 is a single cell (Ni-BZCYYb 1711 i transition layer Ni-BZCYYb 1711 i BZCYYb i MCCO-CO/MCCO/MCO) prepared by fuel electrode support, and tested in an electrolysis mode (humidified hydrogen is introduced into the anode side and humidified air is introduced into the oxygen electrode side) within a range of 700-500 ℃.
Fig. 13 is a graph showing operation stability of a single cell (Ni-BZCYYb 1711 transition layer Ni-BZCYYb1711 BZCYYb MCCO-CO/MCCO/MCO) in a 650 ℃ test mode (a) and in a cell mode (b) of an MCCO-CO air electrode and a Ni-BZCYYb1711 single cell (Ni-BZCYYb 1711 transition layer Ni-BZCYYb1711 MCCO/MCO) prepared by anode support according to an embodiment of the present invention.
Fig. 14 is a graph showing the cycling stability of a single cell (Ni-BZCYYb 1711|transition layer Ni-BZCYYb1711| BZCYYb1711 |mcco-CO/MCCO/MCO) tested at 650 ℃ with MCCO-CO as an air electrode and Ni-BZCYYb1711 as a fuel electrode support according to an embodiment of the present invention.
Fig. 15 is a graph showing the faraday efficiency of a single cell (Ni-BZCYYb 1711 transition layer Ni-BZCYYb1711 BZCYYb1711 MCCO-CO/MCCO/MCO) prepared by using MCCO-CO as an air electrode and Ni-BZCYYb1711 as an anode support layer according to the change of the applied current density.
Fig. 16 is a graph showing the variation of hydrogen production rate of a single cell prepared by using MCCO-CO as an air electrode and Ni-BZCYYb1711 as an anode support layer according to the current density applied in the embodiment of the present invention.
FIG. 17 shows the relationship between current density and voltage for a single cell prepared from MCO, MCCO and MCCO-CO as the positive electrode and Ni-BZCYYb1711 as the anode support layer in the electrochemical ethane non-oxidative dehydrogenation process according to the embodiment of the present invention.
FIG. 18 is an electrochemical impedance spectrum of a single cell prepared by using MCO, MCCO and MCCO-CO as positive electrodes and Ni-BZCYYb1711 as an anode supporting layer in the non-oxidative dehydrogenation process of electrochemical ethane.
FIG. 19 shows electrochemical stability of a single cell prepared from MCO, MCCO and MCCO-CO as positive electrodes and Ni-BZCYYb1711 as anode support layer in the electrochemical ethane non-oxidative dehydrogenation process according to the embodiment of the present invention.
FIG. 20 shows the conversion of ethane and the selectivity of ethylene in the electrochemical non-oxidative dehydrogenation of ethane using a single cell prepared by using MCO, MCCO and MCCO-CO as the positive electrode and Ni-BZCYYb1711 as the anode support layer according to the embodiment of the present invention.
Fig. 21 shows the hydrogen generation rate (a) and the corresponding faraday efficiency (b) of a single cell prepared by using MCO, MCCO and MCCO-CO as the positive electrode and Ni-BZCYYb1711 as the anode support layer for the negative electrode side in the electrochemical ethane non-oxidative dehydrogenation process according to the embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods. The examples are not intended to identify the particular technology or conditions, and are either conventional or are carried out according to the technology or conditions described in the literature in this field or are carried out according to the product specifications. The reagents and instruments used, etc. are not identified to the manufacturer and are conventional products available for purchase by regular vendors.
The invention relates to preparation and characterization of an air electrode and anode material doped with metal cations Cs +, wherein the molecular formula of the air electrode and anode material is Mn 0.9Cs0.1Co2O4-δ (MCCO). The oxygen reduction/precipitation reaction of the anode-supported proton ceramic electrochemical cell and the electrocatalytic activity and stability of ethane non-oxidative dehydrogenation are improved by doping Cs ions at A site in spinel material MnCo 2O4. Mn 0.9Cs0.1Co2O4-δ (MCCO) electrodes can be further enhanced in catalytic activity by physical mixing of Mn 0.9Cs0.1Co2O4-δ (MCCO) with Co 3O4 spinel oxide. At 700 ℃, the maximum output power of a single cell with the composition of Ni-BZCYYb 1711|transition layer Ni-BZCYYb1711| BZCYYb1711|MCCO-CO in a fuel cell mode reaches 1.73W cm -2, and the polarization resistance of the cell is only 0.038 Ω cm 2. When air containing 3% moisture was introduced to the air electrode side, a current density of-3.93A cm -2 was obtained at a voltage of 1.3V at 700 ℃. According to the invention, polarization impedance of the MnCo 2O4 air electrode can be obviously reduced by doping Cs, and electrocatalytic activity of the MnCo 2O4 air electrode can be improved. Meanwhile, a composite spinel electrode composed of Mn 0.9Cs0.1Co2O4-δ (MCCO) and Co 3O4 spinel oxide in a mass ratio of 8:2 shows the highest electrochemical performance.
In addition, the current research on the cycle stability of the proton ceramic electrochemical cell supported by the medium-low temperature anode is less, the characterization method for the stability of the proton ceramic electrochemical cell is extremely rare, and the invention also provides a characterization test means for the purpose of characterizing the cycle stability of the proton ceramic electrochemical cell related to the invention. The method comprises the main steps of brushing electrode materials on an electrolyte membrane of a proton ceramic electrochemical cell supported by an anode, introducing hydrogen containing 3% of water vapor into the anode side, and introducing air containing 3% of water vapor into the air electrode side. And (3) carrying out a cycle stability test on the single cell, namely, alternately and circularly operating the proton ceramic electrochemical cell supported by the anode in a fuel cell mode and an electrolytic cell mode respectively by applying a current of +/-0.5A cm -2, so as to evaluate the electrochemical stability of the electrode.
In the following examples, the comparative sample MCO, which has the composition MnCo 2O4, was prepared in the same manner as in the examples.
Example 1
The embodiment provides an anode-supported proton ceramic electrochemical cell air electrode material MnCo 2O4, which is prepared by the following specific steps:
1) Manganese acetate and cobalt nitrate were added sequentially to deionized water solution at a stoichiometric ratio of MnCo 2O4 (MCO). Subsequently, citric acid was added in an amount 1.5 times the molar amount of the metal ion, and ethylenediamine tetraacetic acid was added in an amount 1 times the molar amount of the metal ion.
2) Adding complexing agent into the solution dissolved with metal ions, adding ammonia water, adjusting the pH value to 7-8, and then heating and stirring under the condition of magnetic stirring until water is evaporated to dryness to obtain a gel-like substance.
3) The gel-like mass was dried in a forced air drying oven at 300 ℃ for 2 hours to give a fluffy porous precursor.
4) The precursor was calcined in a high temperature muffle furnace at 950 ℃ for 3 hours to obtain the desired electrode material powder MnCo 2O4 (noted MCO).
Example 2
The embodiment provides a preparation method of an anode-supported proton ceramic electrochemical cell air electrode material Mn 0.9Cs0.1Co2O4-δ, which comprises the following specific steps.
1) Manganese acetate, cesium nitrate and cobalt nitrate were added sequentially in stoichiometric ratios to a deionized water solution in stoichiometric ratios of Mn 0.9Cs0.1Co2O4-δ (MCCO). Subsequently, citric acid was added in an amount 1.5 times the molar amount of the metal ion, and ethylenediamine tetraacetic acid was added in an amount 1 times the molar amount of the metal ion.
2) Adding complexing agent into the solution dissolved with metal ions, adding ammonia water, adjusting the pH value to 7-8, and then heating and stirring under the condition of magnetic stirring until water is evaporated to dryness to obtain a gel-like substance.
3) The gel-like mass was dried in a forced air drying oven at 300 ℃ for 2 hours to give a fluffy porous precursor.
4) The precursor was calcined in a high temperature muffle furnace at 950 ℃ for 3 hours to obtain the desired electrode material powder Mn 0.9Cs0.1Co2O4-δ (noted MCCO).
Example 3
The embodiment provides a preparation method of an anode-supported proton ceramic electrochemical cell electrode material Co 3O4, which comprises the following specific steps.
1) Cobalt nitrate was added to the deionized water solution in a stoichiometric ratio of Co 3O4 (CO). Subsequently, citric acid was added in an amount 1.5 times the molar amount of the metal ion, and ethylenediamine tetraacetic acid was added in an amount 1 times the molar amount of the metal ion.
2) Adding complexing agent into the solution dissolved with metal ions, adding ammonia water, adjusting the pH value to 7-8, and then heating and stirring under the condition of magnetic stirring until water is evaporated to dryness to obtain a gel-like substance.
3) The gel-like mass was dried in a forced air drying oven at 300 ℃ for 2 hours to give a fluffy porous precursor.
4) The precursor was calcined in a high temperature muffle furnace at 950 ℃ for 3 hours to obtain the desired electrode material powder Co 3O4 (noted as Co).
Example 4
This example provides a reversible anode-supported proton ceramic electrochemical cell using a MnCo 2O4 (MCO) or Mn 0.9Cs0.1Co2O4-δ (MCCO) or Mn 0.9Cs0.1Co2O4-δ-Co3O4 (MCCO-CO, mass ratio of 8:2) composite spinel oxide as the air electrode of the cell to prepare a Ni-BZCYYb 1711|transition layer Ni-BZCYYb1711| BZCYYb 1711|mco/MCCO-CO, comprising the following steps.
(1) The preparation of electrolyte layer slurry comprises the steps of uniformly mixing 6g of BZCYb 1711 powder, 0.2g of fish oil dispersant, 1.6g of absolute ethyl alcohol and 1.6g of butyl acetate to obtain BZCYYb1711 electrolyte layer slurry, preparing transition layer slurry, uniformly mixing 2.4g of BZCYb 1711 powder, 3.6g of nano nickel oxide, 0.6g of graphite, 0.2g of fish oil dispersant, 1.5g of absolute ethyl alcohol and 1.5g of butyl acetate to obtain Ni-BZCYYb 1711 transition layer slurry, preparing anode support layer slurry, uniformly mixing 20g BZCYYb1711,30g nickel oxide, 3.0g of graphite, 2.0g of fish oil dispersant, 6.0g of absolute ethyl alcohol and 6.0g of butyl acetate to obtain anode slurry, and respectively placing the slurries on a roller ball mill for 20-30 hours.
(2) Sequentially casting the electrolyte slurry, the transition layer slurry and the anode slurry which are subjected to ball milling and blending on a polyethylene terephthalate release film, then placing the co-cast electrolyte layer-transition layer-anode support layer film in air for naturally drying 16 h, then cutting the film into a plurality of thin sheets with the diameter of 15 mm by adopting a forming die with the diameter of 15 mm, placing the thin sheets in a muffle furnace for degreasing treatment of 2h at 600 ℃, and finally placing the degreased thin sheets in the muffle furnace for calcining 5h at 1450 ℃ to obtain the required anode-supported half cell, wherein the prepared anode-supported half cell comprises a BZCYYb1711 electrolyte layer (with the thickness of 6-8 mu m), a Ni-BZCYYb1711 transition layer (with the thickness of 30-40 mu m) and a Ni-BZCYYb1711 anode support layer (with the thickness of 500-600 mu m).
(3) The air electrode powder MnCo 2O4 prepared in example 1 of 1g was weighed and mixed uniformly with 0.3g terpineol and 0.04g ethylcellulose for 1.5 hours to obtain the desired spinel electrode slurry.
(4) The air electrode powder Mn 0.9Cs0.1Co2O4-δ prepared in example 2 of 1 g was weighed and mixed uniformly with 0.3g terpineol and 0.04g ethylcellulose for 1.5 hours to obtain the desired spinel electrode slurry.
(5) The air electrode powder prepared in example 1 of 0.8 g and the electrode powder prepared in example 4 of 0.2 g were weighed and uniformly mixed with 0.3g of terpineol and 0.04g of ethylcellulose for 1.5 hours to obtain the desired spinel electrode slurry.
(6) The prepared air electrode slurry is brushed on an electrolyte membrane of a half cell, then placed in a 70 ℃ oven, and after the cathode slurry is dried, the assembled full cell is calcined in a high temperature muffle furnace at 950 ℃ for 10min for electrochemical performance testing of the fuel cell, the electrolytic cell and the ethane electrolysis mode.
The characterization results of the above embodiments of the present invention are as follows.
1. XRD characterization
Fig. 1 is an XRD refinement after calcination of Mn 0.9Cs0.1Co2O4-δ (MCCO) powder at 950 ℃ for 3h, indicating that the synthesized MCCO shows a single spinel phase structure. At the same time, the XRD refinement result shows that the spatial group configuration of the synthesized MCCO is Fd-3m, and the lattice parameter thereof is a=b=c= 8.2492 a (refinement parameter: gof=1.03).
Fig. 2 shows the chemical compatibility of the synthesized air electrode material MCCO with the electrolyte membrane of a proton ceramic electrochemical cell. As can be seen from the figure, the MCCO and BZCYYb1711 electrolyte membrane did not react chemically with the electrolyte membrane before the powder was calcined at a high temperature of 950 ℃ in the muffle furnace for 10: 10min ℃, indicating that the MCCO spinel material has good chemical compatibility with the BZCYYb1711 electrolyte membrane.
Fig. 3 is an XRD image of Mn 0.9Cs0.1Co2O4-δ (MCCO) powder after treatment for 10 hours in air at 600 ℃ with 30% moisture, wherein the main peaks of the XRD image of the treated MCCO are significantly shifted to lower angles, possibly due to swelling of the lattice by moisture entering the lattice.
FIG. 4 is a conductivity test of MnCo 2O4 (MCO) and Mn 0.9Cs0.1Co2O4-δ (MCCO) spinel materials at 300-800 o C. It can be seen from the figure that the conductivity of MCO and MCCO powder increases with increasing temperature, while MCCO exhibits a higher conductivity. Higher conductivity favors charge transfer and thus increases the reaction rate.
2. X-ray photoelectron spectroscopy (XPS) characterization
According to fitting data, after Cs partially replaces the A-site Mn element in MCO, the high valence state ratio of Co and Mn is further improved in order to maintain the electric neutrality of the material. As shown in fig. 5 (left), the content of Co 4+ in MCO was 31.6%, while the content of Co 4+ in MCCO was increased to 39.9%. Similar trends in Mn also occur, as shown in fig. 5 (right). In MCO, the contents of Mn 3+ and Mn 4+ were 36.6% and 25.3%, respectively, whereas in MCCO, these contents were raised to 41.5% and 29.3%, respectively. XPS results indicate that incorporation of Cs in MCO results in an increase in the high valence cation content of Co and Mn.
The corresponding O1s XPS fitting data for MCCO and MCO are shown in fig. 6. Wherein the O1s of MCCO (left) and MCO (right) can be separated into four distinct peaks, including lattice oxygen (O lat), high oxygen oxide (O -/O2 2-), adsorbed oxygen (O ads) and oxygen in the hydroxyl environment (OH -). Wherein the ratio of O -/O2 2 to O lat reflects the oxygen vacancy content, and the ratio of MCCO to MCO is 0.61 and 0.41, respectively. Furthermore, the O -/O2 2- duty cycle in the oxide is generally believed to play a critical role in the ORR process.
3. Element distribution diagram
FIG. 7 is an elemental profile of the novel spinel oxide Mn 0.9Cs0.1Co2O4-δ (MCCO) prepared. As can be seen from the figure, the Mn, cs, co and O elements are uniformly distributed, and no aggregation and precipitation of elements are observed, indicating that Cs successfully enters the lattice of MnCo 2O4 (MCO) spinel oxide.
4. Electrochemical impedance and stability studies
The electrocatalytic activity of MCO, MCCO and MCCO-CO air electrodes was studied by measuring for the first time the area specific resistance of BZCYYb1711 supported symmetric cells in 700-500 ℃ humid air (3% H 2 O). As shown in fig. 8 (a), the specific surface resistance values of the MCCO-CO air electrodes reached 0.076, 0.176, 0.382, 0.984 and 2.940 Ω cm 2 at 700, 650, 600, 550 and 500 ℃, respectively. Fig. 8 (b) shows the electrocatalytic activity of the MCCO air electrode. Under the same test conditions, the specific surface resistance values of the MCCO air electrodes reached 0.119, 0.231, 0.572, 1.588 and 4.382 Ω cm 2 at 700, 650, 600, 550 and 500 ℃, respectively. FIG. 8C shows the area specific resistance values of the MCO air electrodes reaching 0.157, 0.295, 0.869, 2.649 and 6.153 Ω cm 2 at 700, 650, 600, 550 and 500 ℃. Compared with the MCO and MCCO air electrodes, the MCCO-CO air electrode has higher electrocatalytic activity.
FIG. 9 shows the stability of MCO, MCCO and MCCO-CO in humid air (3% H 2 O). The specific surface resistance values of the air electrodes with MCO, MCCO and MCCO-CO all exhibit good stability and electrocatalytic activity when exposed to humid air.
7. Fourier Transform Infrared (FTIR) characterization
Fig. 10 shows fourier transform infrared spectra of MCO, MCCO and MCCO-CO spinel oxide after 50 h in humid air containing 30% water vapor at 600 ℃. The hydroxyl signal value in the oxide can be identified by FTIR measurement, and the characteristic peak appears in the range of 3400-3800 cm -1. The test results show that the hydroxyl peak of the 30% water vapor treated MCCO-CO is slightly higher than that of the MCCO and the MCO oxide, and the MCCO-CO shows better hydration behavior.
8. Electrochemical performance test
Electrochemical power density testing was performed in the fuel cell mode (FC mode) and current density testing was performed in the electrolysis mode (EC mode) using the cells prepared in example 4. Fig. 11 shows a test of a full cell comprising MCCO-CO, MCCO and MCO as air electrodes according to the present invention under the conditions that humidified hydrogen was introduced into the anode side and the atmosphere of the air electrode side was air in the fuel cell mode. Fig. 11 (a) shows that the power densities of the MCCO-CO single cells tested in the range of 700 to 500 ℃ are 1.73W cm -2,1.34 W cm-2, 0.97 W cm-2, 0.62 W cm-2 and 0.28 to W cm -2, respectively. Fig. 11 (b) shows that the MCCO cells have power densities of 1.19W cm -2,0.87 W cm-2, 0.58 W cm-2, 0.37 W cm-2 and 0.20W cm -2, respectively, measured in the range of 700-500 ℃. Fig. 11C shows that the MCO cells have power densities of 0.86W cm -2,0.52 W cm-2, 0.31 W cm-2, 0.20 W cm-2 and 0.11W cm -2, respectively, tested at 700-500 ℃.
Fig. 12 is an I-V graph of a single cell (Ni-BZCYYb 1711 BZCYYb1711 PBCsC) prepared by fuel electrode support tested in EC mode (humidified hydrogen is introduced into the anode side and humidified air is introduced into the oxygen electrode side) at 700-500 ℃ with MCCO-CO, MCCO and MCO as air electrodes and Ni-BZCYYb 1711 as fuel electrode support according to the present invention. FIG. 12 (a) shows the electrolysis performance of the MCCO-CO air electrode, with current densities of-3.93A cm -2,-2.48 A cm-2,-1.45 A cm-2,-0.56 A cm-2, and-0.24A cm -2, respectively, at 700,650,600,550 and 500 ℃ under 1.3V voltage conditions. Fig. 12 (b) shows the electrolysis performance of the MCCO air electrode with current densities of-2.56A cm -2,-1.51 A cm-2,-0.83 A cm-2,-0.37 A cm-2 and-0.14A cm -2 at voltages of 1.3V at 700,650,600,550 and 500 ℃, respectively. FIG. 12C shows the electrolysis performance of the MCO air electrode, with current densities of-1.77A cm -2,-1.03 A cm-2,-0.53 A cm-2,-0.27 A cm-2, and-0.12A cm -2, respectively, at 700,650,600,550 and 500 ℃ under 1.3V voltage conditions. The electrolytic cell of the MCCO-CO air electrode also exhibits more excellent electrolytic performance.
9. Single cell stability and cycling test
Fig. 13 (a) shows the long term stability of a cell with a MCCO-CO air electrode having a current density of 0.5A cm -2 at 650 ℃ and operating in fuel cell mode for 223 hours. Furthermore, the tolerance of the air electrode to steam is critical to the stability of the cell due to the presence of humid air in the air electrode chamber of the proton ceramic electrochemical cell. Fig. 13 (b) shows that the full cell of the MCCO-CO air electrode shows good stability in the electrolysis mode using humid air (3% H 2 O) as oxidant, stably operating 209H at-0.5A cm -2 and 650 ℃. Cycling experiments were performed for FC and EC dual mode switching every 2: 2h at temperatures of ± 0.5A cm -2 and 650 ℃ (fig. 14). The cell with the MCCO-CO air electrode exhibited good stability during the reversible operation of 208 h.
10. Faraday efficiency (FARADAIC EFFICIENCY) and hydrogen production rate test
Faraday efficiency is critical to hydrogen production in the electrochemical process of proton conductor solid oxide fuel in the reversible mode and is defined as the ratio of the actual H 2 rate (detected by the gas chromatography device) to the theoretical H 2 rate (calculated from the applied current). Fig. 15 and 16 show faraday efficiencies and hydrogen generation rates at different current densities and 600 ℃ humid air (30% steam concentration). The faraday efficiency drops from 83.4% to 67.2% and 53.6% when the cell is applied at different current densities of-0.5, -0.75 and-1.0A cm -2 (fig. 15). Further, at-0.5, -0.75, and-1.0A cm -2 current densities, the corresponding H 2 production rates rose from 2.91 to 3.51 and 3.73 as shown in fig. 16.
10. Electrochemical ethane non-oxidative dehydrogenation test
FIG. 17 shows the relationship between current density and voltage across a cell when the cathode of the cell was subjected to non-oxidative dehydrogenation of ethane at 700 o C. Compared with MCO and MCCO, the MCCO-CO anode has higher current density, and the increased current density is beneficial to accelerating the progress of the ethane non-oxidative dehydrogenation reaction. Fig. 18 is an electrochemical impedance spectrum of a single cell with MCO, MCCO and MCCO-CO as positive electrodes in the electrochemical ethane non-oxidative dehydrogenation process according to the present invention. The decrease of the polarization resistance value is related to the difference of the positive electrode and the potential, and the improvement of the applied voltage can enhance the reaction kinetics of ethane non-oxidative dehydrogenation. Fig. 19 shows electrochemical stability of MCO, MCCO and MCCO-CO as positive electrode cells according to the present invention for use in electrochemical ethane non-oxidative dehydrogenation processes. At different voltages, these single cells all exhibit good electrochemical stability. FIG. 20 shows the conversion of ethane and the selectivity of ethylene in the electrochemical non-oxidative dehydrogenation of ethane using a single cell prepared by using MCO, MCCO and MCCO-CO as the positive electrode and Ni-BZCYYb1711 as the anode support layer according to the present invention. Among them, the ethane conversion rate and ethylene selectivity of the MCCO-CO unit cell were 40.3% and 94% higher than those of the MCCO and MCO unit cells. Fig. 21 shows the hydrogen generation rate (a) and the corresponding faraday efficiency (b) of a single cell prepared by using MCO, MCCO and MCCO-CO as the positive electrode and Ni-BZCYYb1711 as the anode support layer for the negative electrode side in the electrochemical ethane non-oxidative dehydrogenation process according to the present invention. When the applied potential was increased from 1.3V to 1.5V, the corresponding H 2 production rate on the negative side of the MCCO-CO cell increased from 2.8 mL min -1cm-2 to 4.65 mL min -1cm-2, and FE decreased from 97% to 80%.
It should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the technical solution described in the above-mentioned embodiments may be modified or some technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the spirit and scope of the technical solution of the embodiments of the present invention.

Claims (10)

1.一种尖晶石材料，其特征在于，所述尖晶石材料的表达式为Mn1-xCsxCo2O4-δ；其中，x为0.01~0.15，δ为氧空位含量。1. A spinel material, characterized in that the expression of the spinel material is Mn 1-x Cs x Co 2 O 4-δ ; wherein x is 0.01-0.15, and δ is the oxygen vacancy content. 2.根据权利要求1所述的尖晶石材料，其特征在于，表达式为Mn1-xCsxCo2O4-δ；其中，x为0.05~0.125，δ为氧空位含量；优选为Mn0.9Cs0.1Co2O4-δ，δ为氧空位含量。2. The spinel material according to claim 1, characterized in that the expression is Mn 1-x Cs x Co 2 O 4-δ ; wherein x is 0.05-0.125, and δ is the oxygen vacancy content; preferably Mn 0.9 Cs 0.1 Co 2 O 4-δ , and δ is the oxygen vacancy content. 3.权利要求1或2所述的尖晶石材料的制备方法，其特征在于，包括：3. The method for preparing the spinel material according to claim 1 or 2, characterized in that it comprises: 1）按照化学计量比，将乙酸锰、硝酸铯、硝酸钴和水混合，加入络合剂，得到混合溶液；1) mixing manganese acetate, cesium nitrate, cobalt nitrate and water according to a stoichiometric ratio, and adding a complexing agent to obtain a mixed solution; 2）向所述混合溶液中加入氨水，调节pH值，在搅拌的条件下加热，得到凝胶状物质；2) adding aqueous ammonia to the mixed solution, adjusting the pH value, and heating under stirring to obtain a gel-like substance; 3）将所述凝胶状物质进行高温干燥，得到前驱体；3) drying the gel-like substance at high temperature to obtain a precursor; 4）将所述前驱体进行煅烧，得到尖晶石材料。4) calcining the precursor to obtain a spinel material. 4.根据权利要求3所述的尖晶石材料的制备方法，其特征在于，步骤1）中，所述络合剂为乙二胺四乙酸和一水合柠檬酸；4. The method for preparing the spinel material according to claim 3, characterized in that in step 1), the complexing agent is ethylenediaminetetraacetic acid and citric acid monohydrate; 和/或，步骤2）中，调节pH值至7~8；和/或，所述加热的温度为100~180 ℃；and/or, in step 2), adjusting the pH value to 7-8; and/or, the heating temperature is 100-180°C; 和/或，步骤3）中，所述高温干燥的温度为250~300 ℃；And/or, in step 3), the high temperature drying temperature is 250-300°C; 和/或，步骤4）中，所述煅烧的温度为900~1000 ℃，时间为2~4 h。And/or, in step 4), the calcination temperature is 900-1000°C and the time is 2-4 h. 5.一种复合尖晶石材料，其特征在于，所述复合尖晶石材料包含权利要求1或2所述的尖晶石材料或权利要求3或4所述制备方法得到的尖晶石材料；所述复合尖晶石材料优选还含有尖晶石氧化物材料，所述尖晶石氧化物材料的表达式为Co3O4。5. A composite spinel material, characterized in that the composite spinel material comprises the spinel material according to claim 1 or 2 or the spinel material obtained by the preparation method according to claim 3 or 4; the composite spinel material preferably further comprises a spinel oxide material, and the expression of the spinel oxide material is Co3O4 . 6.根据权利要求5所述的复合尖晶石材料，其特征在于，所述复合尖晶石材料包含Mn0.9Cs0.1Co2O4-δ和Co3O4，其中，Mn0.9Cs0.1Co2O4-δ和Co3O4的质量比为7~9：3~1。6 . The composite spinel material according to claim 5 , characterized in that the composite spinel material comprises Mn 0.9 Cs 0.1 Co 2 O 4-δ and Co 3 O 4 , wherein the mass ratio of Mn 0.9 Cs 0.1 Co 2 O 4-δ to Co 3 O 4 is 7-9:3-1. 7.一种可逆阳极支撑的质子陶瓷电化学电池，其特征在于，包括依次设置的燃料电极、电解质和空气电极，优选还包括位于所述燃料电极和所述电解质之间的过渡层；所述空气电极的材料包含权利要求1或2所述的尖晶石材料和/或权利要求5或6所述的复合尖晶石材料和/或MnCo2O4。7. A reversible anode-supported protonic ceramic electrochemical cell, characterized in that it comprises a fuel electrode, an electrolyte and an air electrode arranged in sequence, and preferably further comprises a transition layer located between the fuel electrode and the electrolyte; the material of the air electrode comprises the spinel material according to claim 1 or 2 and/or the composite spinel material according to claim 5 or 6 and/ or MnCo2O4 . 8.根据权利要求7所述的质子陶瓷电化学电池，其特征在于，所述电解质的材料包含BaZr0.1Ce0.7Y0.1Yb0.1O3-δ，其中，δ为氧空位含量；和/或，所述燃料电极的材料包含NiO和BaZr0.1Ce0.7Y0.1Yb0.1O3-δ；其中，NiO和BaZr0.1Ce0.7Y0.1Yb0.1O3-δ的质量比5~7:3~5；和/或，所述过渡层包含NiO和BaZr0.1Ce0.7Y0.1Yb0.1O3-δ；其中，NiO和BaZr0.1Ce0.7Y0.1Yb0.1O3-δ的质量比为5~7：3~5。8. The protonic ceramic electrochemical cell according to claim 7, characterized in that the material of the electrolyte comprises BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , wherein δ is the oxygen vacancy content; and/or the material of the fuel electrode comprises NiO and BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ ; wherein the mass ratio of NiO to BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ is 5~7:3~5; and/or the transition layer comprises NiO and BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ ; wherein the mass ratio of NiO to BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ is 5~7:3~5. 9.权利要求7或8所述质子陶瓷电化学电池的制备方法，其特征在于，包括以下步骤：9. The method for preparing the proton ceramic electrochemical cell according to claim 7 or 8, characterized in that it comprises the following steps: 1）将电解质的浆料、过渡层的浆料和燃料电极的浆料进行流延处理，干燥后进行脱脂处理，然后进行高温煅烧，得到阳极支撑的半电池；1) The electrolyte slurry, the transition layer slurry and the fuel electrode slurry are subjected to tape casting, degreased after drying, and then calcined at high temperature to obtain an anode-supported half-cell; 2）将空气电极的浆料刷涂在所述半电池的电解质表面，进行高温煅烧，得到可逆阳极支撑的质子陶瓷电化学电池。2) The air electrode slurry is brushed onto the electrolyte surface of the half-cell and calcined at high temperature to obtain a reversible anode-supported proton ceramic electrochemical cell. 10.根据权利要求9所述的质子陶瓷电化学电池的制备方法，其特征在于，步骤1）中，所述脱脂处理的温度为550~750 ℃；和/或，步骤1）中，所述高温煅烧的温度为1425~1525 ℃；和/或，步骤2）中，所述高温煅烧的温度为900~1000 ℃。10. The method for preparing a protonic ceramic electrochemical cell according to claim 9, characterized in that, in step 1), the temperature of the degreasing treatment is 550-750°C; and/or, in step 1), the temperature of the high-temperature calcination is 1425-1525°C; and/or, in step 2), the temperature of the high-temperature calcination is 900-1000°C.
CN202411116225.3A 2024-08-14 2024-08-14 A spinel material, proton ceramic electrochemical cell and preparation method Pending CN119160946A (en)

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