One-dimensional surface shared oxide air electrode material and preparation method and application thereof

Abstract

The invention provides a one-dimensional surface shared oxide air electrode material and a preparation method and application thereof, and belongs to the technical field of air electrode materials, the non-stoichiometric novel one-dimensional surface shared oxide air electrode material provided by the invention is an A5B5O14 type oxide, the chemical formula of the material is Ba < 5-x > Co < 2.85 > Fe < 1.9 > Ni < 0.25 > O < 14-delta >, and x is greater than or equal to 0 and less than or equal to 0.8. The oxygen vacancy concentration is regulated and controlled by changing the stoichiometric ratio of the Ba element at the A site of the oxide, so that the electrochemical performance of the oxide when the oxide is used for the proton conduction type ceramic battery is improved. When Ba4. 5Co2. 85Fe1. 9Ni0. 25O14-delta with the value of x being 0.5 in an embodiment 3 of the invention is applied to a proton conduction type ceramic battery, the measured electrochemical performance is the highest, the measured polarization impedance is only 0.041 omega.cm < 2 > and the maximum power density reaches 2.101 W.cm <-2 > at 700 DEG C in a fuel battery mode, and the measured polarization impedance is only 0.041 omega.cm < 2 > and the maximum power density reaches 2.101 W.cm <-2 > in an electrolytic tank mode after wet air is introduced into one side of an air electrode under the electrolytic voltage of 1.3 V. And the current density reaches 5.080 A.cm <-2 >.

Description

Technical Field

[0001] The present invention relates to the technical field of air electrode materials, and in particular to a one-dimensional surface-shared oxide air electrode material and a preparation method and application thereof. Background Art

[0002] Solid oxide fuel cells (SOFCs) can directly convert a variety of chemical fuels, including hydrogen, methane, ethanol, natural gas, coal gas and biogas, into electrical energy, and have attracted widespread attention due to their high energy conversion rate and low environmental pollution. However, traditional SOFCs use yttria-stabilized zirconia (YSZ) as electrolytes, and their operation needs to be within a relatively high temperature range, which leads to high operating costs and high requirements for battery component materials, limiting the commercial promotion of SOFCs.

[0003] In order to promote the marketization of SOFC technology, the research focus has shifted to lowering its operating temperature to the medium temperature range (400℃ to 700℃). Proton conductor ceramic cell (PCC) is a proton-conducting solid oxide cell. Compared with traditional solid oxide fuel cells, PCC uses protons instead of oxygen ions as the main carriers. This change allows PCC to operate at a lower temperature, thereby reducing heat loss, and can maintain a high efficiency in the medium and low temperature working range. Functionally, it can achieve reversible operation of fuel cell mode and electrolytic cell mode, which is of great practical significance for realizing the full and comprehensive utilization of new energy.

[0004] As a key component of PCC, the performance of air electrode materials directly determines the overall performance and stability of the battery. Perovskite materials are considered to be ideal candidate materials for the preparation of high-performance air electrodes due to their unique electronic structure and excellent physical and chemical properties. However, traditional air electrode materials are prone to structural degradation and reduced catalytic activity under high-temperature operating environments, resulting in decreased battery performance, which limits the practical application scope of PCC. To address this issue, one of the core challenges is to develop air electrode materials with good catalytic activity and long-term stability, to achieve efficient oxygen reduction and oxygen evolution reactions in PCC, and thus improve the overall performance of the battery. Summary of the invention

[0005] The object of the present invention is to provide a one-dimensional surface shared oxide air electrode material and a preparation method and application thereof. The one-dimensional surface shared oxide air electrode material provided by the present invention has high electrocatalytic activity and good chemical stability, and significantly improves the electrochemical performance of the proton conductor ceramic battery prepared therefrom, including low polarization impedance and high power density.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a one-dimensional surface-shared oxide air electrode material, wherein the chemical general formula of the one-dimensional surface-shared oxide air electrode material is Ba 5-x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , where 0≤x≤0.80, 0≤δ<0.3.

[0008] Preferably, in the general chemical formula, 0≤x≤0.75.

[0009] Preferably, the one-dimensional surface-shared oxide air electrode material is Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.25 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ At least one of .

[0010] The present invention also provides a method for preparing the one-dimensional surface-shared oxide air electrode material described in the above technical solution, comprising the following steps:

[0011] 1) according to the stoichiometric ratio, a water-soluble barium salt, a water-soluble cobalt salt, a water-soluble iron salt and a water-soluble nickel salt are mixed with water, a complexing agent is added, ammonia water is used to adjust the pH, and heating and stirring are performed in sequence to obtain a precursor gel;

[0012] 2) The precursor gel obtained in step 1) is dried, crushed and calcined in sequence to obtain a one-dimensional surface-shared oxide air electrode material.

[0013] Preferably, in step 1), the pH value of the system is adjusted to 7-9 by using ammonia water; and the temperature of the heating and stirring is 75-100°C.

[0014] Preferably, the calcination temperature in step 2) is 800-1000° C., and the calcination time is 4-7 hours.

[0015] The present invention also provides the use of the one-dimensional surface-shared oxide air electrode material described in the above technical solution in a proton-conducting ceramic battery.

[0016] Preferably, the proton conducting ceramic battery uses NiO-BZCYYb as a fuel electrode and BZCYYb material as an electrolyte.

[0017] The present invention also provides a method for preparing a proton conductive ceramic battery, comprising the following steps:

[0018] The NiO-BZCYYb precursor is prepared by a tabletting method, and an anode support is obtained by calcination;

[0019] The BZCYYb electrolyte layer is prepared on the surface of the anode support by drop coating, and after co-sintering,

[0020] The one-dimensional surface-shared oxide air electrode material described in the above technical solution is coated on the BZCYYb electrolyte layer by screen printing to obtain a proton-conducting ceramic battery.

[0021] Preferably, the proton conductive ceramic battery is kept at 1000° C. for 1 to 3 hours after preparation.

[0022] The present invention provides a novel one-dimensional surface-shared oxide air electrode material with a non-stoichiometric ratio, which is A5B5O 14 Type oxide, its chemical formula is Ba 5-x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ (BCFN), wherein 0≤x≤0.8, 0≤δ<0.3. The present invention regulates the oxygen vacancy concentration by changing the stoichiometric ratio of the Ba element at the A position of the oxide, thereby improving its electrochemical performance when used in proton-conducting ceramic batteries. Compared with the prior art, the novel one-dimensional surface-shared oxide air electrode material with a non-stoichiometric ratio provided by the present invention has high electrocatalytic activity and good chemical stability. When used to prepare proton-conducting ceramic batteries (PCC), it improves the problems of insufficient performance and long-term stability of traditional perovskite cathode materials at medium temperatures, improves the long-term stability of the cathode and optimizes its electrocatalytic activity, thereby improving the electrochemical performance of PCC, including low polarization impedance and high power density. The PCC maintains structural stability and electrochemical activity in long-term tests. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 XRD diagram of the one-dimensional surface-shared oxide air electrode material prepared in Examples 1 to 4 of the present invention;

[0024] Figure 2 The electrochemical performance test comparison diagram of the proton conducting ceramic battery prepared using the corresponding one-dimensional surface shared oxide air electrode materials prepared in Examples 1 to 4 as raw materials, wherein: Figure 2The corresponding one-dimensional face-sharing oxide air electrode materials prepared in Examples 1 to 4 are respectively abbreviated as Ba5, Ba 4.75 , Ba 4.5 and Ba 4.25 . Figure 2 In Figure 2 , a is the electrochemical impedance test result graph in the fuel cell mode, Z' is the real part of the impedance, and Z” is the imaginary part of the impedance. Figure 2 In Figure 2 , b is the electrochemical impedance test result graph in the electrolytic cell mode, Z' is the real part of the impedance, and Z” is the imaginary part of the impedance. Figure 2 In Figure 2 , c is the I-V-P curve graph in the fuel cell mode. Figure 2 In Figure 2 , d is the I-V curve in the electrolytic cell mode.

[0025] Figure 3 is the long-term stability test result graph of the all-cell (i.e., Ni-BZCYYb丨BZCYYb丨B 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ prepared using as raw materials, where 4.5 CFN). Among them, Figure 3 the two performance drops in Figure 3 are due to gas fluctuations during the test. Detailed implementation manners

[0026] The present invention provides a one-dimensional face-sharing oxide air electrode material, and the chemical general formula of the one-dimensional face-sharing oxide air electrode material is Ba 5-x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , where 0 ≤ x ≤ 0.80 and 0 ≤ δ < 0.3.

[0027] In the present invention, it is preferred that 0 ≤ x ≤ 0.75 in the chemical general formula.

[0028] In the present invention, the one-dimensional face-sharing oxide air electrode material is preferably Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.25 Co 2.85 Fe1.9 Ni 0.25 O 14-δ At least one of .

[0029] The present invention also provides a method for preparing the one-dimensional surface-shared oxide air electrode material described in the above technical solution, comprising the following steps:

[0030] 1) according to the stoichiometric ratio, a water-soluble barium salt, a water-soluble cobalt salt, a water-soluble iron salt, a water-soluble nickel salt and water are mixed, a complexing agent is added, ammonia water is used to adjust the pH, and heating and stirring are performed in sequence to obtain a precursor gel;

[0031] 2) The precursor gel obtained in step 1) is dried, crushed and calcined in sequence to obtain a one-dimensional surface-shared oxide air electrode material.

[0032] In the present invention, unless otherwise specified, the raw materials used are conventional commercial products in the art.

[0033] In the present invention, the water-soluble barium salt is preferably at least one of barium nitrate, barium carbonate, and barium acetate; the water-soluble cobalt salt is preferably at least one of cobalt nitrate hexahydrate, cobalt carbonate, and cobalt acetate; the water-soluble iron salt is preferably at least one of iron nitrate nonahydrate, iron carbonate, and iron acetate; the water-soluble nickel salt is preferably at least one of nickel nitrate hexahydrate, nickel carbonate, and nickel acetate.

[0034] In the present invention, the complexing agent is preferably one or more of acetic acid, citric acid monohydrate, and ethylenediaminetetraacetic acid; more preferably citric acid monohydrate and ethylenediaminetetraacetic acid.

[0035] In the present invention, the ratio of the total molar number of metal ions in the water-soluble barium salt, water-soluble cobalt salt, water-soluble iron salt and water-soluble nickel salt to the molar number of citric acid monohydrate and ethylenediaminetetraacetic acid is 1:(0.5-4):(0.5-4), more preferably 1:(1-2):(1-2). The present invention controls the ratio of the total molar number of metal ions to the molar number of citric acid monohydrate and ethylenediaminetetraacetic acid within the above range, which is conducive to the formation of a one-dimensional surface-shared oxide air electrode material with high comprehensive performance.

[0036] In the present invention, the ammonia water is preferably used to adjust the pH value of the system to 7 to 9. The present invention uses ammonia water to adjust the pH to promote the reaction, which is conducive to the formation of a one-dimensional surface-shared oxide air electrode material. In the present invention, the temperature of the heating and stirring is preferably 75 to 100°C, more preferably 85 to 95°C; the heating and stirring time is preferably 7 to 12h, more preferably 8 to 10h. The present invention uses heating and stirring to fully mix the components, which is conducive to the formation of a one-dimensional surface-shared oxide air electrode material.

[0037] In the present invention, the drying temperature is preferably 220-260°C, more preferably 230-250°C, and the drying time is preferably 4-8h, more preferably 6h. In the present invention, the precursor gel is gradually transformed from a gel-like liquid into a fluffy black solid by drying. In the present invention, the pulverization method is preferably grinding.

[0038] In the present invention, the calcination temperature is preferably 800-1000°C, more preferably 900-950°C; the calcination time is preferably 4-7h, more preferably 5h. The present invention controls the calcination temperature and time within the above ranges to remove residual organic matter and form a one-dimensional surface-shared oxide air electrode material.

[0039] The invention utilizes a sol-gel method to prepare a one-dimensional surface-shared oxide air electrode material with high electrocatalytic activity and good chemical stability.

[0040] The present invention also provides the use of the one-dimensional surface-shared oxide air electrode material described in the above technical solution in a proton-conducting ceramic battery.

[0041] In the present invention, the proton conductive ceramic battery preferably uses NiO-BZCYYb as a fuel electrode and uses BZCYYb material as an electrolyte.

[0042] The present invention also provides a method for preparing a proton conductive ceramic battery, comprising the following steps:

[0043] The NiO-BZCYYb precursor is prepared by a tabletting method, and an anode support is obtained by calcination;

[0044] A BZCYYb electrolyte layer is prepared on the surface of the anode support by a drop coating method. After co-sintering, the one-dimensional surface shared oxide air electrode material described in the above technical solution is coated on the BZCYYb electrolyte layer by a screen printing method to obtain a proton conductive ceramic battery.

[0045] In the present invention, the proton conductive ceramic battery is preferably kept at 1000° C. for 1 to 3 hours after preparation. The present invention optimizes the electrochemical performance of the prepared proton conductive ceramic battery by keeping the temperature.

[0046] In the present invention, during use of the proton conducting ceramic battery, preferably, fuel gas is introduced into the fuel electrode side, and air is introduced into the air electrode side; the fuel gas is preferably hydrogen.

[0047] The present invention adjusts the stoichiometric ratio of the Ba element at the A position in the one-dimensional surface-shared oxide air electrode material and coordinately controls the stoichiometric ratio of Co, Fe and Ni, so that the cathode prepared from the one-dimensional surface-shared oxide air electrode material is easy to form a phase, the activity and stability of the oxygen reduction reaction are improved, and thus the electrochemical performance of the battery prepared from the one-dimensional surface-shared oxide air electrode material is improved.

[0048] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0049] Example 1

[0050] One-dimensional surface-shared oxide air electrode material, with the general chemical formula of Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , where x is 0, 0≤δ<0.3.

[0051] The preparation method of the above-mentioned one-dimensional surface shared oxide air electrode material comprises the following steps:

[0052] 1) Weigh barium nitrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate, and nickel nitrate hexahydrate according to the stoichiometric ratio of Ba: Co: Fe: Ni = 1: 0.57: 0.38: 0.05, add them to deionized water and mix them evenly, add complexing agents citric acid monohydrate and ethylenediaminetetraacetic acid to the solution according to the ratio of total molar number of metal ions: molar number of citric acid: molar number of EDTA = 1: 1.5: 1, then add ammonia water to adjust the pH value of the solution to 7, and finally heat to 90 ° C and stir magnetically for 10 hours to obtain Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Precursor gel;

[0053] 2) The precursor gel obtained in step 1) was placed in an oven at 240°C and dried for 6 hours, and the gel-like liquid gradually turned into a fluffy black solid. The black solid was ground into powder in a mortar to obtain Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Precursor powder;

[0054] The black precursor powder sample was placed in a 100 mL corundum crucible and kept at 900-950°C for 5 h to remove the residual organic matter and form a one-dimensional surface-shared oxide crystal. The solid powder obtained was Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ One-dimensional surface-shared oxide air electrode materials.

[0055] Embodiment 2:

[0056] One-dimensional surface-shared oxide air electrode material, with the general chemical formula of Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , where x is 0.25, 0≤δ<0.3.

[0057] The preparation method of the above-mentioned one-dimensional surface shared oxide air electrode material comprises the following steps:

[0058] 1) Weigh barium nitrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate, and nickel nitrate hexahydrate according to the stoichiometric ratio of Ba: Co: Fe: Ni = 0.95: 0.57: 0.38: 0.05, add them to deionized water and mix them evenly, add complexing agents citric acid monohydrate and ethylenediaminetetraacetic acid to the solution according to the ratio of total molar number of metal ions: molar number of citric acid: molar number of EDTA = 1: 1.5: 1, then add ammonia water to adjust the pH value of the solution to 7, and finally heat to 90 ° C and stir magnetically for 10 hours to obtain Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Precursor gel;

[0059] 2) The precursor gel obtained in step 1) was placed in an oven at 240° C. and dried for 6 h. The gel-like liquid gradually turned into a fluffy black solid. The black solid was ground into powder in a mortar to obtain Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Precursor powder;

[0060] The obtained black precursor powder sample was placed in a 100 mL corundum crucible and kept at 900-950 ° C for 5 h to remove the residual organic matter and form a one-dimensional surface-shared oxide crystal. After cooling to room temperature, the obtained solid powdery substance was Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25O 14-δ One-dimensional surface-shared oxide air electrode materials.

[0061] Embodiment 3:

[0062] One-dimensional surface-shared oxide air electrode material, with the general chemical formula of Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , where x is 0.5, 0≤δ<0.3.

[0063] The preparation method of the above-mentioned one-dimensional surface shared oxide air electrode material comprises the following steps:

[0064] 1) Weigh barium nitrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate, and nickel nitrate hexahydrate according to the stoichiometric ratio of Ba: Co: Fe: Ni = 0.9: 0.57: 0.38: 0.05, add them to deionized water and mix them evenly, add complexing agents citric acid monohydrate and ethylenediaminetetraacetic acid to the solution according to the ratio of total molar number of metal ions: molar number of citric acid: molar number of EDTA = 1: 1.5: 1, and then add ammonia water to adjust the pH value of the solution to 7, and finally heat to 90 ° C and stir magnetically for 10 hours to obtain Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Precursor gel;

[0065] 2) The precursor gel obtained in step 1) was placed in an oven at 240° C. and dried for 6 h. The gel-like liquid gradually turned into a fluffy black solid. The black solid was ground into powder in a mortar to obtain Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Precursor powder;

[0066] The black precursor powder sample was placed in a 100 mL corundum crucible and kept at 900-950° C. for 5 h to remove the residual organic matter and form a one-dimensional surface-shared oxide crystal. The solid powder obtained was BaO2. 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ One-dimensional surface-shared oxide air electrode materials.

[0067] Embodiment 4:

[0068] One-dimensional surface-shared oxide air electrode material, with the general chemical formula of Ba 4.25 Co2.85 Fe 1.9 Ni 0.25 O 14-δ , where x is 0.75, 0≤δ<0.3.

[0069] The preparation method of the above-mentioned one-dimensional surface shared oxide air electrode material comprises the following steps:

[0070] 1) Weigh barium nitrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate, and nickel nitrate hexahydrate according to the stoichiometric ratio of Ba: Co: Fe: Ni = 0.85: 0.57: 0.38: 0.05, add to deionized water and mix evenly. Add complexing agents citric acid monohydrate and ethylenediaminetetraacetic acid to the solution according to the ratio of total molar number of metal ions: molar number of citric acid: molar number of EDTA = 1: 1.5: 1, and then add ammonia water to adjust the pH value of the solution to 7, and finally heat to 90 ° C and stir magnetically for 10 hours to obtain Ba 4.25 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Precursor gel.

[0071] 2) The precursor gel obtained in step 1) was placed in an oven at 240° C. and dried for 6 h, and the gel-like liquid gradually turned into a fluffy black solid; the black solid was ground into powder in a mortar to obtain Ba 4.25 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Precursor powder;

[0072] The obtained black precursor powder sample was placed in a 100 mL corundum crucible and kept at 900-950 ° C for 5 h to remove the residual organic matter and form a one-dimensional surface-shared oxide crystal. After cooling to room temperature, the obtained solid powdery substance was Ba 4.25 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ One-dimensional surface-shared oxide air electrode materials.

[0073] The one-dimensional surface shared oxide air electrode materials prepared in Examples 1 to 4 were subjected to XRD analysis and testing, and the XRD patterns of the one-dimensional surface shared oxide air electrode materials prepared in Examples 1 to 4 were as follows: Figure 1 As shown by Figure 1 It can be seen that the four novel one-dimensional surface-shared oxide materials (ie, one-dimensional surface-shared oxide air electrode materials) prepared in Examples 1 to 4 do not have any impurity phase.

[0074] Example 5

[0075] Application of one-dimensional surface-shared oxide air electrode materials in the preparation of proton-conducting ceramic batteries;

[0076] The preparation method of the proton ceramic battery comprises the following steps:

[0077] The corresponding one-dimensional surface-shared oxide air electrode materials Ba prepared in Examples 1 to 4 are respectively 5- x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ (wherein 0≤x≤0.75, 0≤δ<0.3) is an air electrode, and a slurry obtained by mixing and stirring a one-dimensional surface-shared oxide air electrode material, a binder and an organic solvent is coated on the electrolyte side of a fuel electrode-electrolyte support to prepare a proton-conducting ceramic battery;

[0078] The fuel electrode-electrolyte support is prepared by a co-pressing method, and the specific process is as follows: 0.4 g of dry and uniform fuel electrode powder is placed in a cylindrical mold, a pressure of 6 MPa is applied and the pressure is maintained for 1 minute to form a fuel electrode embryo, and the mixture is pre-fired at 1150°C for 2.5 hours to obtain a pre-fired NiO-BZCYYb fuel electrode; the electrolyte powder is mixed with an organic solvent, ball-milled, and then dripped on the pre-fired NiO-BZCYYb fuel electrode to make it uniformly dispersed, and co-sintered at 1450°C for 5 hours to form an electrolyte-fuel electrode support;

[0079] Subsequently, the corresponding one-dimensional surface-shared oxide air electrode materials prepared in Examples 1 to 4 were mixed with a binder and screen-printed onto the electrolyte surface, followed by sintering at 1000° C. for 2 h in air to obtain a full cell, i.e., a proton ceramic cell.

[0080] The corresponding one-dimensional surface-shared oxide air electrode materials Ba prepared in Examples 1-4 are 5- x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ The proton-conducting ceramic battery prepared as raw materials (where 0≤x≤0.75, 0≤δ<0.3) was loaded into the test furnace, air was introduced into the air electrode side, hydrogen was introduced into the fuel electrode side, the furnace temperature was raised to 800°C, and the electrochemical workstation was connected to perform cyclic voltammetry scanning for 80 to 200 cycles to fully reduce the battery, and the scanning speed was 5 to 20 mV·s -1 , the scanning range is 0.2~1.2V, and after reduction, the furnace temperature is lowered to 700℃ for electrochemical performance test. In the fuel cell mode, the electrochemical impedance spectroscopy test is carried out, the added perturbation is 20mV, and the test frequency range is 0.1~105 Hz; perform volt-ampere characteristic curve test with a scan rate of 5mV·s -1 , the scanning range is 1.2~0.2V. In the electrolytic cell mode, humid air (wherein the water content is 3%) is introduced into the air electrode side, and the electrochemical impedance spectroscopy test is performed. The applied perturbation is 20mV, the applied bias is 1.1V, and the test frequency range is 0.1~10 5 Hz; perform volt-ampere characteristic curve test with a scan rate of 5mV·s -1 , the scanning range is 0.9~1.5V.

[0081] The one-dimensional surface-sharing oxide air electrode material Ba prepared in Example 3 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ The proton conductive ceramic battery prepared as raw material was loaded into the test furnace and the reduction process was the same as above. After full reduction, the furnace temperature was lowered to 600℃ for long-term stability test, and the applied current density was -400mA / cm 2 , the test duration is 230h.

[0082] The electrochemical performance of the proton conducting ceramic battery prepared by using the corresponding one-dimensional surface shared oxide air electrode materials prepared in Examples 1 to 4 as raw materials at a working temperature of 700° C. was compared according to the above method, and a comparison diagram of the electrochemical performance test of the proton conducting ceramic battery prepared by using the corresponding one-dimensional surface shared oxide air electrode materials prepared in Examples 1 to 4 as raw materials was obtained. Figure 2 As shown. Figure 2 It can be found that relative to the stoichiometric ratio of Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ Oxide materials, when x is 0.5, that is, Ba in Example 3 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ The full battery prepared as raw material has the highest power density and the lowest battery impedance, with a polarization impedance of only 0.041Ω·cm 2 , the maximum power density reaches 2.101W·cm -2 This indicates that the electrocatalytic activity of the oxide material can be improved by adjusting the stoichiometric ratio of the Ba element, thereby improving its electrochemical performance when used in proton-conducting ceramic batteries. 2 The current density constant current output is recorded, and the voltage changes at different times are obtained. 4.5 Co2.85 Fe 1.9 Ni 0.25 O 14-δ The long-term stability test results of the full battery prepared as raw materials are shown in the figure Figure 3 As shown. Figure 3 It can be seen that in Example 3, Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ The full battery prepared as raw materials can output stably for a long time.

[0083] In summary, the Ba in Example 3 of the present invention with a value of x of 0.5 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ When applied to proton-conducting ceramic batteries, the measured electrochemical performance is the highest. At 700°C, in fuel cell mode, the measured polarization impedance is only 0.041Ω·cm 2 , its maximum power density reaches 2.101W·cm -2 In the electrolytic cell mode, after the humid air was introduced into one side of the air electrode, the current density reached 5.080A·cm at an electrolysis voltage of 1.3V. -2 . It can be seen that the new non-stoichiometric one-dimensional surface-shared oxide air electrode material shows great potential in PCC applications. The embodiment of the present invention prepares a new one-dimensional surface-shared oxide (i.e., one-dimensional surface-shared oxide air electrode material) by adjusting the stoichiometric ratio of the Ba element at the A position, so that the cathode prepared by it is easy to form a phase, the activity and stability of the oxygen reduction reaction are improved, and thus the electrochemical performance of the battery is improved.

[0084] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A one-dimensional surface-shared oxide air electrode material, characterized in that: The chemical formula of the one-dimensional surface-shared oxide air electrode material is Ba 5-x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , where 0≤x≤0.80, 0≤δ<0.

3.

2. The one-dimensional surface-shared oxide air electrode material according to claim 1, characterized in that: In the general chemical formula, 0≤x≤0.

75.

3. The one-dimensional surface-shared oxide air electrode material according to claim 1 or 2, characterized in that: The one-dimensional surface shared oxide air electrode material is Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , Ba 4.25 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ At least one of .

4. A method for preparing the one-dimensional surface-shared oxide air electrode material according to any one of claims 1 to 3, characterized in that: The following steps are involved: 1) according to the stoichiometric ratio, a water-soluble barium salt, a water-soluble cobalt salt, a water-soluble iron salt and a water-soluble nickel salt are mixed with water, a complexing agent is added, ammonia water is used to adjust the pH, and heating and stirring are performed in sequence to obtain a precursor gel; 2) The precursor gel obtained in step 1) is dried, crushed and calcined in sequence to obtain a one-dimensional surface-shared oxide air electrode material.

5. The preparation method according to claim 4, characterized in that: In the step 1), the pH value of the system is adjusted to 7-9 by using ammonia water; and the temperature of the heating and stirring is 75-100°C.

6. The preparation method according to claim 4, characterized in that: The calcination temperature in step 2) is 800-1000° C., and the calcination time is 4-7 hours.

7. Use of the one-dimensional surface-shared oxide air electrode material according to any one of claims 1 to 3 in a proton-conducting ceramic battery.

8. The use according to claim 7, characterized in that: The proton conductive ceramic battery uses NiO-BZCYYb as a fuel electrode and BZCYYb material as an electrolyte.

9. A method for preparing a proton conductive ceramic battery, characterized in that: The following steps are involved: The NiO-BZCYYb precursor is prepared by a tabletting method, and an anode support is obtained by calcination; A BZCYYb electrolyte layer is prepared on the surface of the anode support by a drop coating method. After co-sintering, the one-dimensional surface shared oxide air electrode material according to any one of claims 1 to 3 is coated on the BZCYYb electrolyte layer by a screen printing method to obtain a proton conducting ceramic battery.

10. The preparation method according to claim 9, characterized in that: After the proton conductive ceramic battery is prepared, it is kept at 1000° C. for 1 to 3 hours.

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