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

Abstract

This invention provides a one-dimensional surface-shared oxide air electrode material, its preparation method, and its application, belonging to the technical field of air electrode materials. The novel one-dimensional surface-shared oxide air electrode material provided by this invention, which is non-stoichiometric, is A5B5O. 14 Type oxide, with the chemical formula Ba 5‑x Co 2.85 Fe 1.9 Ni 0.25 O 14‑δ Where 0 ≤ x ≤ 0.8. This invention modulates the oxygen vacancy concentration by changing the stoichiometric ratio of Ba at the A-site of the oxide, thereby improving its electrochemical performance in proton-conducting ceramic batteries. In Example 3 of this invention, Ba with x = 0.5... 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14‑δ When applied to proton-conducting ceramic batteries, it exhibits the highest measured electrochemical performance; at 700℃, in fuel cell mode, the measured polarization impedance is only 0.041 Ω·cm. 2 Its maximum power density reaches 2.101 W·cm³. ‑2 In electrolytic cell mode, after introducing humid air to the air electrode side, the current density reached 5.080 A·cm⁻¹ at an electrolytic voltage of 1.3V. ‑2 .

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of air electrode materials, and particularly relates to a one-dimensional face-sharing oxide air electrode material and a preparation method and application thereof. BACKGROUND

[0002] Solid oxide fuel cells (SOFC) can directly convert various chemical fuels, including hydrogen, methane, ethanol, natural gas, coal gas and biogas, into electricity, and have attracted extensive attention due to their high energy conversion efficiency and low environmental pollution characteristics. However, the traditional SOFC uses yttria-stabilized zirconia (YSZ) as the electrolyte, and its operation needs to be in a high temperature range, which leads to high operating costs and high requirements for battery component materials, limiting the commercialization of SOFC.

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

[0004] As a key component of PCC, the performance of air electrode material directly determines the overall performance and stability of the cell. Perovskite materials are considered to be ideal candidates for preparing 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 under high-temperature operating conditions, resulting in reduced catalytic activity and decreased cell performance, which limits the practical application range 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, thereby improving the overall performance of the cell. SUMMARY

[0005] The present application provides a one-dimensional face-sharing oxide air electrode material and a preparation method and application thereof. The one-dimensional face-sharing oxide air electrode material provided by the present application has high electrocatalytic activity and good chemical stability, significantly improving the electrochemical performance of the proton conductor ceramic cell prepared therefrom, including low polarization impedance and high power density.

[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0007] The application provides a one-dimensional face-sharing oxide air electrode material, a 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 , wherein 0 <= x <= 0.80, 0 <= delta < 0.3.

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

[0009] Preferably, the one-dimensional face-sharing oxide air electrode material is at least one of 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 .

[0010] The application further provides a preparation method of the one-dimensional face-sharing oxide air electrode material.

[0011] 1) according to a stoichiometric ratio, mixing water-soluble barium salt, water-soluble cobalt salt, water-soluble iron salt and water-soluble nickel salt with water, then adding a complexing agent, and sequentially performing ammonia water pH adjustment and heating stirring to obtain a precursor gel;

[0012] 2) sequentially performing drying, crushing and calcination on the precursor gel obtained in the step 1) to obtain the one-dimensional face-sharing oxide air electrode material.

[0013] Preferably, the ammonia water pH adjustment in the step 1) is to adjust the system pH value to 7-9; and the heating stirring temperature is 75-100 DEG C.

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

[0015] The application further provides an application of the one-dimensional face-sharing oxide air electrode material in a proton-conducting ceramic battery.

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

[0017] The application further provides a preparation method of the proton-conducting ceramic cell, comprising the following steps:

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

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

[0020] The one-dimensional face-sharing oxide air electrode material in the technical solution is coated on the BZCYYb electrolyte layer by a screen printing method to obtain the proton-conducting ceramic cell.

[0021] Preferably, the proton-conducting ceramic cell is kept at 1000℃ for 1-3h after preparation.

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

[0023] Figure 1 The XRD patterns of the one-dimensional face-sharing oxide air electrode materials prepared in Examples 1-4 of the application;

[0024] Figure 2 The comparison chart of the electrochemical performance tests of the proton-conducting ceramic cells prepared by using the corresponding one-dimensional face-sharing oxide air electrode materials prepared in Examples 1-4 as raw materials, wherein, Figure 2The corresponding one-dimensional face-shared oxide air electrode materials prepared in Examples 1-4 are referred to as Ba5, Ba 4.75 , 4.5 , 4.25 , Figure 2 In a, a is a graph of electrochemical impedance test results in fuel cell mode, Z' is the real part of impedance, and Z" is the imaginary part of impedance. Figure 2 In b, a is a graph of electrochemical impedance test results in electrolytic cell mode, Z' is the real part of impedance, and Z" is the imaginary part of impedance. Figure 2 In c, a is a graph of I-V-P curves in fuel cell mode. Figure 2 In d, a is a graph of I-V curves in electrolytic cell mode.

[0025] Figure 3 In Example 3, Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ The graph of long-term stability test results of the full cell (i.e., Ni-BZCYYb / BZCYYb / B 4.5 CFN) prepared using the raw material, wherein Figure 3 In a, two performance drops are gas fluctuations during the test. DETAILED DESCRIPTION

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

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

[0028] In the present application, the one-dimensional face-shared 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 the group consisting of Ba, Co, Fe and Ni.

[0029] The present application also provides a preparation method of the one-dimensional face-shared oxide air electrode material.

[0030] 1) mixing water-soluble barium salt, water-soluble cobalt salt, water-soluble iron salt, water-soluble nickel salt and water in a stoichiometric ratio, then adding a complexing agent, and sequentially adjusting pH with ammonia water and heating and stirring to obtain a precursor gel;

[0031] 2) sequentially drying, crushing and calcining the precursor gel obtained in step 1) to obtain the one-dimensional face-shared oxide air electrode material.

[0032] In the present application, the raw materials used are all conventional commercially available products in the art unless otherwise specified.

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

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

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

[0036] In the present application, the ammonia water is preferably used to adjust the pH of the system to 7-9. Adjusting the pH with ammonia water is conducive to the reaction and the formation of the one-dimensional face-shared oxide air electrode material. In the present application, the heating and stirring temperature is preferably 75-100°C, and more preferably 85-95°C; and the heating and stirring time is preferably 7-12h, and more preferably 8-10h. Heating and stirring is conducive to the uniform mixing of the components and the formation of the one-dimensional face-shared oxide air electrode material.

[0037] In the present application, the drying temperature is preferably 220-260 DEG C, more preferably 230-250 DEG C, and the drying time is preferably 4-8h, more preferably 6h. The present application gradually changes the precursor gel from a gel-like liquid into a fluffy black solid through drying. In the present application, the pulverizing method is preferably grinding.

[0038] In the present application, the calcining temperature is preferably 800-1000 DEG C, more preferably 900-950 DEG C, and the calcining time is preferably 4-7h, more preferably 5h. The present application removes residual organic matter and forms a one-dimensional face-sharing oxide air electrode material by controlling the calcining temperature and time within the above ranges.

[0039] The present application uses a sol-gel method to prepare a one-dimensional face-sharing oxide air electrode material with high electrocatalytic activity and good chemical stability.

[0040] The present application also provides the use of the one-dimensional face-sharing oxide air electrode material in a proton-conducting ceramic battery.

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

[0042] The present application also provides a preparation method of a proton-conducting ceramic battery, comprising the following steps:

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

[0044] A BZCYYb electrolyte layer is prepared on the surface of the anode support by a drop coating method, and after co-sintering, the one-dimensional face-sharing oxide air electrode material is coated on the BZCYYb electrolyte layer by a screen printing method, thereby obtaining a proton-conducting ceramic battery.

[0045] In the present application, the proton-conducting ceramic battery is preferably kept at 1000 DEG C for 1-3h after preparation. The present application optimizes the electrochemical performance of the prepared proton-conducting ceramic battery by keeping it at a certain temperature.

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

[0047] The application regulates the stoichiometric ratio of Ba element at A site in the one-dimensional face-shared oxide air electrode material, cooperatively controls the stoichiometric ratio of Co, Fe and Ni, so that the cathode prepared from the one-dimensional face-shared oxide air electrode material is easy to phase, the oxygen reduction reaction activity and stability are improved, and the electrochemical performance of the battery prepared from the one-dimensional face-shared oxide air electrode material is improved.

[0048] The technical solutions in the application will be described clearly and completely below in combination with the embodiments in the application. Obviously, the described embodiments are only some of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all the other embodiments obtained by those skilled in the art without creative work belong to the protection scope of the application.

[0049] Embodiment 1

[0050] The one-dimensional face-shared oxide air electrode material has a chemical general formula of Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ , wherein x is 0, 0≤δ<0.3.

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

[0052] 1) Ba(NO3)2, Co(NO3)2.6H2O, Fe(NO3)3.9H2O, Ni(NO3)2.6H2O are weighed according to the stoichiometric ratio of Ba:Co:Fe:Ni=1:0.57:0.38:0.05, added into deionized water and mixed uniformly, complexing agents citric acid monohydrate and ethylenediaminetetraacetic acid are added into the solution according to the ratio of total moles of metal ions: moles of citric acid: moles of EDTA=1:1.5:1, ammonia water is added to adjust the pH value of the solution to 7, and finally heated to 90℃ and magnetically stirred for 10h to obtain Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ a precursor gel;

[0053] 2) The precursor gel obtained in the step 1) is dried in a 240℃ oven for 6h, and the gel-like liquid gradually changes into a fluffy black solid. The black solid is ground into powder in a mortar to obtain Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ a precursor powder;

[0054] The black precursor powder sample is placed in a 100 mL corundum crucible, and heated at 900-950 °C for 5 h to remove residual organic matter and form one-dimensional face-shared oxide crystals. The obtained solid powder substance is Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ one-dimensional face-shared oxide air electrode material.

[0055] Example 2:

[0056] one-dimensional face-shared oxide air electrode material, with a general chemical formula of Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ wherein x is 0.25, and 0≤δ<0.3.

[0057] The preparation method of the one-dimensional face-shared oxide air electrode material, comprising the following steps:

[0058] 1) Ba(NO3)2, Co(NO3)2.6H2O, Fe(NO3)3.9H2O, Ni(NO3)2.6H2O are weighed according to the stoichiometric ratio of Ba:Co:Fe:Ni=0.95:0.57:0.38:0.05, and then mixed uniformly in deionized water. Complexing agents citric acid monohydrate and ethylenediaminetetraacetic acid are added to the solution according to the ratio of total moles of metal ions: moles of citric acid: moles of EDTA = 1:1.5:1. Ammonia water is added to adjust the pH value of the solution to 7. Finally, the solution is heated to 90 °C and magnetically stirred for 10 h 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) is placed in a 240 °C oven and dried for 6 h. The gel-like liquid gradually changes into a fluffy black solid. The black solid is 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 prepared black precursor powder sample is placed in a 100 mL corundum crucible, and heated at 900-950 °C for 5 h to remove residual organic matter and form one-dimensional face-shared oxide crystals. The obtained solid powder substance is Ba 4.75 Co 2.85 Fe 1.9 Ni 0.25O 14-δ One-dimensional face-shared oxide air electrode material.

[0061] Example 3:

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

[0063] The preparation method of the one-dimensional face-shared oxide air electrode material, comprising the steps of:

[0064] 1) The barium nitrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate, and nickel nitrate hexahydrate are weighed according to the stoichiometric ratio of Ba:Co:Fe:Ni=0.9:0.57:0.38:0.05, and then mixed uniformly in deionized water; the complexing agent citric acid monohydrate, ethylenediaminetetraacetic acid, and ammonia water are added to the solution according to the ratio of the total number of moles of metal ions: the number of moles of citric acid: the number of moles of EDTA=1:1.5:1, and the pH value of the solution is adjusted to 7; finally, the solution is heated to 90°C and magnetically stirred for 10h 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) is placed in a 240°C oven and dried for 6h, and the gel-like liquid gradually changes into a fluffy black solid; the black solid is 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 is placed in a 100mL corundum crucible and heat-treated at 900-950°C for 5h to remove residual organic matter and form one-dimensional face-shared oxide crystals; the obtained solid powder material is Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ one-dimensional face-shared oxide air electrode material.

[0067] Example 4:

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

[0069] The preparation method of the one-dimensional face-shared oxide air electrode material is as follows:

[0070] 1) Ba(NO3)2, Co(NO3)2.6H2O, Fe(NO3)3.9H2O, Ni(NO3)2.6H2O are weighed according to the stoichiometric ratio of Ba:Co:Fe:Ni=0.85:0.57:0.38:0.05, and then mixed uniformly in deionized water. Complexing agents citric acid monohydrate, ethylenediaminetetraacetic acid, and ammonia water are added to the solution according to the ratio of total moles of metal ions: moles of citric acid: moles of EDTA = 1:1.5:1, and the pH value of the solution is adjusted to 7. Finally, the solution is heated to 90°C and magnetically stirred for 10h to obtain Ba 4.25 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ a precursor gel.

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

[0072] The prepared black precursor powder sample is placed in a 100mL corundum crucible and heat-treated at 900-950°C for 5h to remove residual organic matter and form one-dimensional face-shared oxide crystals. The obtained solid powder material is Ba 4.25 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ a one-dimensional face-shared oxide air electrode material.

[0073] The one-dimensional face-shared oxide air electrode materials prepared in Examples 1-4 are subjected to XRD analysis and testing, and the XRD patterns of the one-dimensional face-shared oxide air electrode materials prepared in Examples 1-4 are shown in FIG. 1. Figure 1 As can be seen from FIG. 1, none of the four new one-dimensional face-shared oxide materials (i.e., one-dimensional face-shared oxide air electrode materials) prepared in Examples 1-4 has any impurity phase. Figure 1

[0074] Example 5 ​

[0075] Application of one-dimensional face-shared oxide air electrode material in preparation of proton-conducting ceramic battery

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

[0077] The one-dimensional face-shared oxide air electrode material Ba 5- x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ (0≤x≤0.75, 0≤δ<0.3) as an air electrode, the slurry obtained by mixing and stirring the one-dimensional face-shared oxide air electrode material, a binder and an organic solvent is coated on the electrolyte side of the fuel electrode-electrolyte support body, and a proton-conducting ceramic battery is prepared.

[0078] The fuel electrode-electrolyte support body is prepared by using 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 min to form a fuel electrode embryo, the pre-sintered NiO-BZCYYb fuel electrode is obtained by pre-sintering at 1150 DEG C for 2.5 h; the electrolyte powder is mixed with an organic solvent and ball milled, and then drop-coated on the pre-sintered NiO-BZCYYb fuel electrode to uniformly disperse, and the electrolyte-fuel electrode support body is formed by co-sintering at 1450 DEG C for 5 h.

[0079] Subsequently, the one-dimensional face-shared oxide air electrode material prepared in each of Examples 1 to 4 is mixed with a binder and screen printed on the surface of the electrolyte, and then sintered at 1000 DEG C in air for 2 h to obtain a full cell, i.e., a proton ceramic battery.

[0080] The one-dimensional face-shared oxide air electrode material Ba 5- x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ (0≤x≤0.75, 0≤δ<0.3) as raw materials, the proton-conducting ceramic battery is loaded into a test furnace, air is introduced on the air electrode side, hydrogen is introduced on the fuel electrode side, the furnace temperature is raised to 800 DEG C, and an electrochemical workstation is connected to perform cyclic voltammetry scanning for 80 to 200 cycles to fully reduce the battery, the scanning speed is 5 to 20 mV·s -1 , and the scanning range is 0.2 to 1.2 V. After reduction, the furnace temperature is reduced to 700 DEG C for electrochemical performance testing. In the fuel cell mode, electrochemical impedance spectroscopy testing is performed, the applied perturbation is 20 mV, and the test frequency range is 0.1 to 105 Hz; Volt-ampere characteristic curve test was performed at a scan rate of 5 mV·s. -1 The scanning range was 1.2–0.2 V. In electrolytic cell mode, humid air (containing 3% water) was introduced through the air electrode side for electrochemical impedance spectroscopy (EIS) testing. The applied perturbation was 20 mV, the applied bias voltage was 1.1 V, and the test frequency range was 0.1–10 mV. 5 Hz; Volt-ampere characteristic curve test was performed at a scan rate of 5 mV·s. -1 The scanning range is 0.9 to 1.5 V.

[0081] The one-dimensional surface-shared 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-conducting ceramic battery prepared from the raw material was loaded into the test furnace, and the reduction process was the same as above. After complete reduction, the furnace temperature was lowered to 600℃ for long-term stability testing, with an applied current density of -400 mA / cm². 2 The test lasted for 230 hours.

[0082] The electrochemical performance of proton-conducting ceramic batteries prepared using the corresponding one-dimensional shared oxide air electrode materials prepared in Examples 1-4 as raw materials was compared at an operating temperature of 700°C according to the above method. The comparison graph of the electrochemical performance tests of the proton-conducting ceramic batteries prepared using the corresponding one-dimensional shared oxide air electrode materials prepared in Examples 1-4 as raw materials is shown below. Figure 2 As shown. By Figure 2 It can be observed that, relative to the stoichiometric ratio of Ba5Co 2.85 Fe 1.9 Ni 0.25 O 14-δ For oxide materials, when x is 0.5, i.e. Ba in Example 3 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ The full cell prepared using this raw material has the highest power density and the lowest battery impedance, with a polarization impedance of only 0.041 Ω·cm. 2 The maximum power density reaches 2.101 W·cm³. -2 This indicates that adjusting the stoichiometry of Ba can improve the electrocatalytic activity of this oxide material, thereby enhancing its electrochemical performance in proton-conductive ceramic batteries. At an operating temperature of 600℃, with a current of -400 mA / cm²... 2 The constant current output of the current density was recorded at different times to obtain the Ba in Example 3. 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 following figure: Figure 3 Figure 3 It can be seen from the figure that the Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ The full battery prepared as raw materials can stably output for a long time.

[0083] In summary, the Ba 4.5 Co 2.85 Fe 1.9 Ni 0.25 O 14-δ When applied to a proton-conducting ceramic battery, the highest electrochemical performance was measured, and in fuel cell mode at 700℃, the measured polarization resistance was only 0.041Ω·cm 2 , and the maximum power density reached 2.101W·cm -2 , while in electrolytic cell mode, after wet air was introduced into the air electrode side, the current density reached 5.080A·cm -2 at an electrolytic voltage of 1.3V. It can be seen that the new one-dimensional face-sharing oxide air electrode material with a non-stoichiometric ratio has great potential in PCC applications. The new one-dimensional face-sharing oxide (i.e., one-dimensional face-sharing oxide air electrode material) prepared by adjusting the stoichiometric ratio of the A-site Ba element in the present embodiment improves the electrochemical performance of the battery by making the prepared cathode easy to phase, improving the oxygen reduction reaction activity and stability.

[0084] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, several improvements and refinements can be made, and these improvements and refinements should also be considered within the scope of protection of the present application.​

Claims

1. A one-dimensional face-shared oxide air electrode material, characterized in that, The one-dimensional face-shared oxide air electrode material has a chemical general formula of Ba 5-x Co 2.85 Fe 1.9 Ni 0.25 O 14-δ wherein 0 < x < 0.75, 0 < δ < 0.

3.

2. The one-dimensional face-shared oxide air electrode material of claim 1, wherein, The one-dimensional face-shared oxide air electrode material is 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 3. A method of producing the one-dimensional face-shared oxide air electrode material of claim 1 or 2, characterized in that, The method comprises the following steps: 1) mixing water-soluble barium salt, water-soluble cobalt salt, water-soluble iron salt and water-soluble nickel salt with water in a stoichiometric ratio, then adding a complexing agent, and sequentially adjusting the pH with ammonia water and heating and stirring to obtain a precursor gel; 2) sequentially drying, crushing and calcining the precursor gel obtained in step 1) to obtain a one-dimensional face-shared oxide air electrode material.

4. The production method according to claim 3, characterized by, In step 1), the ammonia water is used to adjust the pH of the system to 7-9, and the heating and stirring is performed at a temperature of 75-100 ℃.

5. The preparation method according to claim 3, characterized in that, In step 2), the calcination is performed at a temperature of 800-1000 ℃ for 4-7 h.

6. The one-dimensional face-shared oxide air electrode material according to claim 1 or 2 is used in a proton-conducting ceramic battery.

7. Use according to claim 6, characterized in that, The proton-conducting ceramic battery uses NiO-BZCYYb as a fuel electrode and BZCYYb material as an electrolyte.

8. A method of making a proton-conducting ceramic battery, characterized by, The method comprises the following steps: An anode support is prepared by tabletting NiO-BZCYYb precursor and calcining; A BZCYYb electrolyte layer is prepared on the surface of the anode support by a drop-coating method, and after co-sintering, the one-dimensional face-shared oxide air electrode material according to claim 1 or 2 is coated on the BZCYYb electrolyte layer by a screen printing method to obtain a proton-conducting ceramic battery.

9. The production method according to claim 8, characterized by, After preparation, the proton-conducting ceramic battery is kept at 1000 ℃ for 1-3 h.

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