Proton solid oxide and preparation method and application thereof

Abstract

The invention discloses a proton solid oxide and a preparation method and application thereof, and the proton solid oxide comprises a trigonal system ABO3 type La < 0.9 > Ba < 0.1 > Co < 0.7 > Ni < 0.2 > Ag < 0.1 > O < 3-delta >, a Ruddlesden-Popper type La < 0.9 > Ba < 0.1 > Co < 0.7 > Ni < 0.2 > Ag < 0.1 > O < 3-delta > and Ag nanoparticles. The proton solid oxide provided by the invention realizes a multi-phase coexistence structure, thermogravimetric analysis shows that the proton solid oxide meets the requirements of high catalytic activity and ion / electron transfer capability, and the structure not only improves the catalytic activity of the material, but also enhances the mechanical stability and thermal expansion resistance of the material, so that the proton solid oxide can be used for preparing a composite material. And the problems of unstable catalytic activity and high-temperature structure degradation caused by additional introduction of Ni-containing substances are avoided.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalytic materials, in particular to a proton solid oxide and a preparation method and application thereof. BACKGROUND

[0002] In recent years, the depletion of non-renewable energy and the irreversible damage to the environment caused by greenhouse gas emissions from the combustion of fossil fuels have made the efficient use of green energy an urgent demand in contemporary society. Hydrogen energy has attracted widespread attention due to its zero-pollution emission, high energy density and easy transportation. Common hydrogen production technologies include alkaline water electrolysis, proton exchange membrane electrolysis (PEM) and solid oxide electrolysis cell (SOEC). Among them, SOEC has higher electrolysis efficiency due to its higher working temperature, and does not require the use of noble metal catalysts, which makes SOEC a strong candidate technology for efficient and low-cost green hydrogen production. According to the type of ion transported in the electrolyte, SOEC can be divided into oxygen ion conductive SOEC (O-SOEC) and proton conductive SOEC (referred to as proton solid oxide electrolysis cell, P-SOEC). Proton conduction has a faster migration rate and lower activation energy than oxygen ion conduction. Therefore, P-SOEC can operate at a lower temperature (500-700℃) than O-SOEC (operating temperature higher than 800℃), which helps to develop electrolysis cells with excellent electrochemical performance and high stability.

[0003] However, the lower working temperature will cause the energy potential barrier of the oxygen evolution reaction (OER) at the anode of the proton solid oxide electrolysis cell (P-SOEC) to increase, thereby causing a significant increase in the polarization resistance (Rp). In addition, most of the early P-SOEC anodes are based on the improvement of anode materials for oxygen ion conductive SOEC (O-SOEC), such as Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF) and La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ (LSCF), which are excellent mixed ionic / electronic conductors (MIECs). According to the OER reaction equation at the anode of the P-SOEC, the anode based on MIECs limits the OER to the three-phase boundary (anode / electrolyte / air), which severely limits the effective reaction area and reduces the electrochemical performance. Therefore, it is crucial for the anode material to have proton / oxygen ion / electron conduction capability and high catalytic activity. SUMMARY

[0004] The present application aims to at least solve one of the above technical problems in the prior art. To this end, the present application aims to provide a proton solid oxide and a preparation method and application thereof.

[0005] To achieve the above-mentioned object, the technical solution adopted by the present application is:

[0006] In a first aspect of the present application, a proton solid oxide is provided, comprising a La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ , Ruddlesden-Popper type La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ and Ag nanoparticles.

[0007] In the LaCoO 3-δ The introduction of some alkaline earth metals Ba at the A site and transition metals at the B site can effectively improve the ion conductivity and catalytic activity of the anode. Doping Ag nanoparticles on the surface of the anode changes the surface activity of the anode, thereby further improving the catalytic activity. At the same time, it has high catalytic activity and good stability, thereby avoiding the sharp decline in battery performance, to meet the needs of stable operation and long service life of the proton solid oxide fuel cell. In the present application, the La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ (R-LBCNA) and Ruddlesden-Popper type La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ (RP-LBCNA) and doping of Ag nanoparticles not only improve the catalytic activity of the material, but also enhance the mechanical stability and thermal expansion resistance of the material.

[0008] In some embodiments of the present application, the proton solid oxide comprises 82-84wt% of La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ13-15.5 wt% Ruddlesden-Popper type La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ and 2-4 wt% Ag. In the present application, by optimizing the ratio of Co and Ni between different configurations of LBCNA, the problems of unstable catalytic activity and structural degradation at high temperature caused by the introduction of a third component are avoided.

[0009] In some embodiments of the present application, the proton solid oxide has a chemical formula of La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ wherein 3-δ is the number of combined oxygen atoms.

[0010] In some embodiments of the present application, the average diameter of the Ag nanoparticles is 5-15 nm, such as 8-12 nm. In the present application, the average diameter of the Ag nanoparticles is measured by high-resolution transmission electron microscopy (HR-TEM) and energy dispersive spectroscopy (EDS) mapping images, with 100 particles being counted.

[0011] In some embodiments of the present application, the proton solid oxide is spherical and / or spheroidal, with an average particle size of 40-80 nm, such as 50-70 nm. In the present application, the average particle size of the proton solid oxide is measured by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM), with 100 particles being counted.

[0012] In some embodiments of the present application, the Ag nanoparticles are anchored on the surface of the proton solid oxide.

[0013] In a second aspect of the present application, a preparation method of the proton solid oxide is provided, comprising the following steps:

[0014] S1: mixing and dissolving metal salts containing La, Ba, Co, Ni and Ag, and then performing a complexation reaction with a complexing agent to obtain a gel;

[0015] S2: grinding the gel and then sintering to obtain the proton solid oxide.

[0016] In some embodiments of the present application, the ratio of the total moles of the metal salts to the moles of the complexing agent is 1:(1.2-2.0), such as 1:(1.2-1.8) or 1:(1.3-1.7).

[0017] In some embodiments of the present application, the complexing agent comprises at least one of citric acid, EDTA.

[0018] In some embodiments of the present application, the reaction solvent of the complexing reaction comprises water; the reaction temperature of the complexing reaction is 50-80℃, such as 50-70℃, etc.

[0019] In some embodiments of the present application, the grinding comprises first heating the gel to 400-600℃ and holding for 0.5-1.5h, and then grinding after cooling.

[0020] In some embodiments of the present application, the calcination is performed at 700-1200℃, such as 750-1000℃, 750-900℃, etc.; the heating rate of the calcination is 8-15℃ / min -1 , such as 8-12℃ / min -1 ; the time of the calcination is 6-10h, such as 7-9h, etc.

[0021] In some embodiments of the present application, the metal salt comprises at least one of nitrate of metal, sulfate of metal, chloride of metal.

[0022] In some embodiments of the present application, the purity of the metal salt is above 98%.

[0023] In a third aspect of the present application, a solid oxide electrolysis cell anode is provided, comprising the protonic solid oxide.

[0024] In a fourth aspect of the present application, a solid oxide electrolysis cell is provided, comprising the solid oxide electrolysis cell anode, cathode and electrolyte.

[0025] In some embodiments of the present application, the cathode comprises any one of nickel-based material, cobalt-based material.

[0026] In some embodiments of the present application, the electrolyte comprises any one of proton-conducting ceramic material, oxide ion-conducting ceramic material.

[0027] The present application has the following beneficial effects:

[0028] The protonic solid oxide of the present application realizes a multiphase coexistence structure, and the thermogravimetric analysis shows that it meets the requirements of high catalytic activity and ion / electron transmission capability. This structure not only improves the catalytic activity of the material, but also enhances the mechanical stability and thermal expansion resistance of the material, avoiding the problems of unstable catalytic activity and high-temperature structural degradation caused by the additional introduction of Ni-containing substances.

[0029] The protonic solid oxide of the present application does not produce impurities at high temperature (800℃-1000℃), and has high-temperature stability.

[0030] The proton solid oxide of the present application has significant advantages in catalytic activity, proton conduction ability and high-temperature stability. Specifically, the polarization resistance (ASR) of the material of the present application at 600℃ is only 0.15 Ω·cm 2 ; it exhibits excellent proton conduction ability at 500℃, and the ASR does not increase significantly within 100 hours in an air / water vapor atmosphere at 800℃, indicating that it has good long-term stability. In addition, the current density of the material of the present application at 600℃ under a voltage of 1.3V can reach 1.8 A·cm -2 . These advantages are mainly due to the introduction of a multiphase coexistence structure and the doping of Ag nanoparticles, which improve the catalytic activity and stability of the material.

[0031] The proton solid oxide of the present application can be widely used in the manufacture of proton solid oxide fuel cells, and the air electrode prepared therefrom has high catalytic activity and good high-temperature stability, which is beneficial to improve the operation stability and service life of the proton solid oxide fuel cell. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 Figure 1 is the XRD pattern of the proton solid oxide LBCNA-800, LBCNA-900 and LBCNA-1000 powders prepared in Examples 1-3 of the present application; wherein (a) is a summary figure; (b)-(d) correspond to the XRD patterns of LBCNA-800, LBCNA-900 and LBCNA-1000 powders, respectively.

[0033] Figure 2 Figure 2 is the SEM image and particle size distribution statistics (d) of the proton solid oxide LBCNA-800 (a), LBCNA-900 (b) and LBCNA-1000 (c) prepared in Examples 1-3 of the present application.

[0034] Figure 3 Figure 3 is the XPS spectrum of O 1s (a) and Ag 3d (b) of the proton solid oxide LBCNA-800, LBCNA-900 and LBCNA-1000 prepared in Examples 1-3 of the present application, and the fitting results (c).

[0035] Figure 4 Figure 4 is the high-resolution transmission electron microscopy image (a)-(e) and the energy spectrum analysis element distribution map (f) of La, Ba, Co, Ni, Ag and O of the proton solid oxide LBCNA-900 prepared in Example 2 of the present application.

[0036] Figure 5TGA graph (a), calculated results of the concentration of hydrated proton defects (b), FT-IR spectrum (c) of the proton solid oxide LBCNA-900 prepared in Example 2 of the present application.

[0037] Figure 6 Polarization resistance of the proton solid oxide LBCNA-800, LBCNA-900 and LBCNA-1000 prepared in Examples 1-3 of the present application as air electrode of symmetric cell as a function of temperature (a), comparison of polarization resistance of different samples (b), comparison of area specific resistance (ASR) of LBCNA-900 with other reported advanced anodes (c), stability of ASR of LBCNA-900 electrode in 600℃ humid air (d), electrochemical impedance spectroscopy (EIS) of LBCNA-900 before and after stability test (e).

[0038] Figure 7 Current-voltage (I-V) curve of the proton solid oxide LBCNA-900 prepared in Example 2 of the present application as air electrode of full cell at 600-700℃ (a), comparison of current density of LBCNA-900 of the present application with other advanced anodes at 1.3V (b), electrochemical impedance spectroscopy (EIS) of P-SOEC using LBCNA-900 anode at 600-700℃ (c), Arrhenius plot of R o and R p (d), and distribution of relaxation of impedance (DRT) plot of EIS at 700℃, 650℃ and 600℃ (e). DETAILED DESCRIPTION

[0039] The present application will be further described in details by specific examples. The raw materials, reagents or devices used in the examples and comparative examples are commercially available or can be obtained by prior art methods unless otherwise specified. The test or test method is the conventional method in the art unless otherwise specified.

[0040] Example 1

[0041] In this example, a proton solid oxide is prepared by the following process:

[0042] S1: Sol-gel reaction: nitrate salts of La, Ba, Co, Ni and Ag with purity greater than 98% are dissolved in deionized water to obtain a mixed solution of metal nitrates, and a complexation reaction is carried out with citric acid under heating until a gel is formed; wherein the molar ratio of La, Ba, Co, Ni and Ag in the mixed solution of metal nitrates is 0.9:0.1:0.7:0.2:0.1; the sol-gel reaction is carried out at a temperature of 60℃, and the molar ratio of citric acid:LBCNA is 1.5:1.

[0043] S2: grinding: the gel was placed in a muffle furnace, heated to 500°C, and kept for 1 h, and taken out after cooling and grinding to obtain the precursor;

[0044] S3: high-temperature sintering: the precursor was placed in a crucible boat, heated to 800°C at a rate of 10°C / min in an air atmosphere, and kept for 8 h to obtain LBCNA-800 proton solid oxide. -1

[0045] Example 2

[0046] A proton solid oxide was prepared in this example, and the preparation method was carried out according to Example 1, and the difference from Example 1 was only that the calcination temperature was 900°C, and LBCNA-900 proton solid oxide was obtained.

[0047] Example 3

[0048] A proton solid oxide was prepared in this example, and the preparation method was carried out according to Example 1, and the difference from Example 1 was only that the calcination temperature was 1000°C, and LBCNA-1000 proton solid oxide was obtained.

[0049] Example 4

[0050] A symmetric battery was prepared in this example, and the specific process was as follows:

[0051] BaCO3, ZrO2, CeO2, Y2O3 and Yb2O3 were mixed according to the stoichiometric ratio, ball milled and calcined at 1100°C for 10 hours to prepare BeCe 0.4 Zr 0.4 Y 0.1 Yb 0.1 O 3-δ (BZCYYb4411) powder. Then, the BZCYYb4411 powder was mixed with 1% NiO, pressed into a sheet and sintered at 1550°C for 8 hours to obtain a dense electrolyte sheet. Then, the LBCNA oxide prepared in Examples 1-3 was mixed with terpineol at a weight ratio of 1:1.5 and ball milled to prepare an electrode slurry, and coated on both sides of the electrolyte sheet by screen printing to form a symmetric battery. In addition, in order to prepare a symmetric battery, NiO, BZCYYb4411 and starch were mixed at a weight ratio of 6:4:1 and pressed into a sheet, and then co-sintered at 1500°C for 8 hours. The sheet was coated with LBCNA anode on both sides, and Ag was coated on one side as a current collector to complete the preparation of the symmetric battery.

[0052] Example 5

[0053] A full battery was prepared in this example, and the specific process was as follows:​

[0054] The BZCYYb4411 powder was mixed with 1% NiO, pressed into a pellet and sintered at 1550°C for 8 hours to obtain a dense electrolyte pellet. Then, the LBCNA-900 oxide prepared in Example 2 was mixed with terpineol in a weight ratio of 1:1.5 and ball-milled to prepare an electrode slurry, which was coated on both sides of the electrolyte pellet by screen printing to form a symmetric cell. To prepare a full cell, the NiO-BZCYYb4411 was used as a cathode support material, and the BZCYYb4411 electrolyte slurry was coated on the cathode support material by spin coating, followed by co-sintering at 1500°C for 8 hours. One side of the sintered pellet was polished and coated with Ag as a current collector, and the other side was coated with the LBCNA-900 anode material to complete the preparation of the full cell.

[0055] Test Example 1

[0056] The proton solid oxides prepared in the examples were characterized in this test example, and the specific process was as follows:

[0057] The proton solid oxides LBCNA-800, LBCNA-900, LBCNA-1000 powders prepared in Examples 1-3 were tested by in-situ X-ray diffraction, and the results of X-ray diffraction are shown in Figure 1 .

[0058] It can be seen that the LBCNA powders are pure phases at 800°C-1000°C. The proton solid oxides prepared in the examples show similar compositions composed of three phases, wherein LBCNA-800 contains 83.5wt% R-LBCNA, 13.1wt% RP-LBCNA and 3.4wt% Ag; LBCNA-900 contains 82.9wt% R-LBCNA, 14.3wt% RP-LBCNA and 2.8wt% Ag; and LBCNA-1000 contains 82.3wt% R-LBCNA, 15.2wt% RP-LBCNA and 2.5wt% Ag. The three-phase composition is very consistent with La 1.52 Ba 0.48 NiO4(I4 / mmm, PDF #48-0123) and Ag metal very consistent with Figure 1 (a) in the middle.

[0059] Figure 2 are scanning electron microscope (SEM) images and particle size distribution statistics of the proton solid oxides LBCNA-800, LBCNA-900, LBCNA-1000 prepared in Examples 1-3.

[0060] The results show that the oxide particles are uniform spherical, the average particle size is about 60-80 nm, the specific surface area is moderate, which is beneficial to expose more active sites, improve the electrocatalytic performance, and lead to excellent electrochemical performance.

[0061] Figure 3 are XPS spectra of O 1s (a), Ag 3d (b) and their fitting results (c) of the proton solid oxides LBCNA-800, LBCNA-900 and LBCNA-1000 prepared in Examples 1-3, from which it can be seen that LBCNA-900 has a higher O concentration, which can provide more sites for the migration of O 2- and protons, thereby achieving better catalytic activity, and the interionic charge transfer between Co and Ni cations, thereby more effectively oxidizing oxygen species and accelerating the charge transfer process, improving the catalytic efficiency.

[0062] Figure 4 are high-resolution transmission electron microscopy images and energy dispersive spectroscopy element distribution maps of La, Ba, Co, Ni, Ag and O of the multiphase coexisting proton solid oxide LBCNA-900 prepared in Example 2, the EDS mapping images show that La, Ba, Co, Ni and O elements are uniformly distributed in the whole particle, and Ag nanoparticles (~10 nm) are anchored on the surface of the oxide. It is shown that La, Ba, Co, Ni and O are uniformly distributed in the particle interior, while Ag nanoparticles (~10 nm) are anchored on the surface to form a heterojunction structure. The X-ray photoelectron spectroscopy (XPS) spectra of oxygen 1s (O 1s) of the three proton solid oxides LBCNA-800, LBCNA-900 and LBCNA-1000 are shown. Through XPS analysis, the O 1s spectrum is decomposed into four oxygen species, which correspond to lattice oxygen (O lat ) located at about 528.8 eV, adsorbed oxygen (O ad ) located at about 529.8 eV, hydroxylated oxygen species (O OH- ) located at about 531.2 eV and adsorbed surface water (O H2O ) located at about 532.7 eV. Among them, the ratio of O ad and O lat of LBCNA-900 is 35.38%, which is higher than that of LBCNA-800 and LBCNA-1000, indicating that it has a higher oxygen vacancy concentration, which provides more active sites for the migration of oxygen ions and protons, thereby improving the catalytic activity of the electrode. Figure 4(b) is the silver 3d (Ag 3d) XPS spectrum, showing the valence state of silver (Ag) in LBCNA-800, LBCNA-900 and LBCNA-1000. The XPS peak of Ag 3d is located at about 368.3 / 374.3 eV, indicating that silver mainly exists in the form of elemental silver (Ag 0 ). The presence of Ag 0 in LBCNA-900 indicates the successful precipitation of silver nanoparticles on the surface of the material, which helps to improve the catalytic activity and stability of the electrode, because silver nanoparticles can act as active sites to promote the progress of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Figure 4 (c) and Figure 4 (d) respectively show the XPS fitting results of O1s and Ag 3d. Through accurate XPS fitting analysis, the relative content of different oxygen species and silver valence states can be more accurately determined. For example, the higher O ad / O lat ratio and the presence of Ag 0 in LBCNA-900 further confirm its advantages in catalytic activity and stability. These results show that LBCNA-900 oxides have significant advantages in surface chemical properties, which provide strong support for their efficient application in proton solid oxide electrolysis cells (P-SOEC).

[0063] Figure 5 is the thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR) test results of LBCNA-900 oxides prepared in Example 2. Among them, Figure 5 the TGA curve in (a) shows that the mass loss of the material is less than 2% in the test temperature range of 50 to 800℃, which is measured at a heating rate of 10℃ / min in a nitrogen atmosphere (flow rate 50mL / min), fully demonstrating the excellent thermal stability of LBCNA-900 oxides. Figure 5 The TGA curve in (b) shows that under the same heating rate but in an air atmosphere (flow rate 50mL / min), the material has a significant mass change in the range of 200 to 400℃, which is mainly due to the volatilization of water and organic residues inside the material. This phenomenon further confirms the stability of the material at high temperatures, indicating that it can effectively remove impurities and maintain structural stability. While Figure 5 the FT-IR spectrum in (c) presents a clear -OH stretching vibration peak at 3500cm -1 , which is prepared by KBr pressing method at room temperature, with a scanning range of 400-4000cm -1 and a resolution of 4cm -1The appearance of the peak obtained under the test condition of 32 scans powerfully proves that LBCNA-900 oxide has excellent hydration capacity, which is extremely important for promoting proton conduction, and provides strong support for the application of the material in related fields.

[0064] Test Example 2

[0065] In this test example, the performance of the proton solid oxide cell prepared in the example is tested, and the specific process is as follows:

[0066] Electrochemical performance test method of symmetrical cell air electrode:

[0067] The electrochemical performance test of the symmetrical cell air electrode is carried out by using Gamry Reference 3000 electrochemical workstation. The test is carried out in air atmosphere, and the temperature range is set to 550-700℃. The frequency range of electrochemical impedance spectrum (EIS) test is 0.01Hz-100kHz. By analyzing the impedance characteristics of high frequency region (HF), intermediate frequency region (IF) and low frequency region (LF), the efficiency of oxygen ion transport, surface charge exchange and ion diffusion, gas diffusion and adsorption-desorption process is evaluated, and the electrochemical process in different frequency bands is determined by using relaxation time distribution (DRT) analysis to further analyze the EIS data. The phase structure of the electrode powder is analyzed by using Rigaku Ultima IV XRD, and the XRD data is refined to obtain detailed crystallographic information; and the microstructure and element distribution of the sample are observed by using HITACHI SU8010 SEM, and the micro-morphology of the electrode is analyzed.

[0068] Full cell electrochemical performance test method:

[0069] The electrochemical performance of the full cells was tested using a Gamry Reference 3000 electrochemical workstation. The tests were conducted in an air atmosphere, with a temperature range set between 550 and 700°C. The frequency range for the electrochemical impedance spectroscopy (EIS) tests was 0.01 Hz to 100 kHz. By analyzing the impedance characteristics in the high frequency (HF), intermediate frequency (IF), and low frequency (LF) regions, the efficiency of oxygen ion transport, surface charge exchange and ion diffusion, gas diffusion and adsorption-desorption processes was evaluated. The relaxation time distribution (DRT) analysis was further used to analyze the EIS data and determine the electrochemical processes in different frequency bands. The current-voltage (I-V) curve tests were conducted in fuel cell mode, recording the voltage response at different current densities and calculating the power density to evaluate the maximum power output of the cell. In addition, long-term stability tests were also conducted to monitor the change in voltage over time and evaluate the long-term stability of the cell. Rigaku Ultima IV XRD was used to analyze the phase structure of the electrode powder, and the XRD data was refined to obtain detailed crystallographic information. HITACHI SU8010 SEM was used to observe the microstructure and element distribution of the samples, and the micro-morphology of the electrode was analyzed.

[0070] Figure 6 Figure 1 shows the electrochemical performance test results of the proton solid oxides LBCNA-800, LBCNA-900, and LBCNA-1000 prepared in Examples 1-3 as air electrodes of symmetric cells.

[0071] Figure 6 Figure 2 shows the polarization resistance (ASR) curves of LBCNA-800, LBCNA-900, and LBCNA-1000 as air electrodes of symmetric cells as a function of temperature. Figure 6 Figure 1(a) shows the polarization resistance (ASR) curves of the proton solid oxides LBCNA-800, LBCNA-900, and LBCNA-1000 as air electrodes of symmetric cells as a function of temperature. At 600°C, LBCNA-900 exhibits the lowest ASR value of about 0.10 Ω·cm 2 , which is significantly lower than the 0.46 Ω·cm 2 of LBCNA-800 and the 0.93 Ω·cm 2 of LBCNA-1000, indicating its excellent electrochemical performance and high catalytic activity at this temperature. Figure 3 Figure 1(b) is a comparison of the polarization resistance of different samples, and at 600°C, LBCNA-900 has the lowest ASR value, further confirming its advantage in electrochemical performance. Figure 6(c) The ASR of LBCNA-900 was compared with other reported advanced anode materials. The results showed that the ASR value of LBCNA-900 at 600 °C was significantly lower than that of other materials, such as Ba(Co). 0.4 Fe 0.4 Zr 0.1 Y 0.1 ) 0.95 Ni 0.05 F 0.1 O 2.9-δ (BCFZYNF, 0.17Ω·cm) 2 ), La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ (LSCF, 0.27Ω·cm) 2 ) and Pr 0.2 Ba 0.2 Sr 0.2 La 0.2 Ca 0.2 CoO 3-δ (PBSLCC, 0.26Ω·cm) 2 This indicates that LBCNA-900 performs better in reducing polarization resistance. Figure 6 The middle (d) graph shows the stability of the ASR of the LBCNA-900 electrode in humid air at 600℃. The test lasted for 50 hours. During this period, the ASR value of LBCNA-900 did not increase significantly and remained at a low level, which fully demonstrates the long-term stability of the material in high temperature and humid environment. Figure 6 Image (e) shows the electrochemical impedance spectroscopy (EIS) spectra of LBCNA-900 before and after the stability test. The results show that the EIS curves before and after the stability test are basically identical, indicating that the electrochemical performance of the LBCNA-900 electrode did not decrease significantly after 50 hours of stability testing, further confirming its good stability. Overall, the above results demonstrate that LBCNA-900 oxide exhibits significant advantages in both electrochemical performance and stability as an air electrode for symmetrical cells. Its low polarization resistance and good high-temperature and moisture stability make it a highly promising high-performance electrode material suitable for electrochemical applications such as proton solid oxide electrolyzers (P-SOEC).

[0072] Figure 7 The electrochemical performance of a full cell (Ni-BZCYYb electrolyte support) using LBCNA-900 oxide prepared in Example 2 of this invention as an air electrode is shown. Figure 7Figure 1 (a) shows the current-voltage (I-V) curves of proton solid oxide LBCNA-900 as a full-cell air electrode at 600-700°C, where the LBCNA-900 electrode exhibits a higher current density of 1.8 A-cm -2 at 600°C, indicating its excellent electrochemical performance. Figure 7 Figure 1 (b) is a plot of current density, where the current density of LBCNA-900 is significantly higher than other advanced anode materials such as PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ at 1.3 V, further confirming the advantage of LBCNA-900 in electrochemical performance. -2 ), PrNi 0.5 Co 0.5 O 3-δ at 1.3 V, further confirming the advantage of LBCNA-900 in electrochemical performance. -2 ), and Ba(Co 0.4 Fe 0.4 Zr 0.1 Y 0.1 ) 0.95 Ni 0.05 F 0.1 O 2.9-δ at 1.3 V, further confirming the advantage of LBCNA-900 in electrochemical performance. -2 Figure 7 Figure 1 (c) shows the electrochemical impedance spectroscopy (EIS) of a proton solid oxide electrolysis cell (P-SOEC) using LBCNA-900 anode at 600-700°C, where the impedance values of LBCNA-900 electrode at different frequencies are lower, especially in the intermediate frequency region (IF), indicating that it exhibits lower resistance in the charge transfer and ion diffusion processes. Figure 7 Figure 1 (d) shows the Arrhenius plot of Ro (ohmic resistance) and Rp (polarization resistance), where the Rp activation energy of LBCNA-900 is 0.92 eV, which is significantly lower than other typical anode materials such as La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ (LSCF, 1.40 eV), BaCo 0.7 (Ce 0.8 Y 0.2 ) 0.3 O 3-δ (BCCY, 1.13 eV), and La 0.7 Ca 0.3 Co​0.8 Ni 0.2 O 3-δ (LCCN7382, 1.14eV), the lower activation energy indicates that LBCNA-900 needs to overcome smaller energy barrier in electrochemical reaction, and the reaction rate is faster. Figure 7 The DRT analysis results show that the impedance relaxation distribution of LBCNA-900 electrode at different temperatures is relatively concentrated, and mainly concentrated in the intermediate frequency region (IF), indicating that it has fast kinetics in the process of charge transfer and ion diffusion. Overall, the above results show that the proton solid oxide of the application as an air electrode of the full cell has significant advantages in electrochemical performance and kinetics, making it a highly potential high-performance electrode material.

[0073] The above examples are the preferred embodiments of the application, but the embodiments of the application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the application shall be equivalent replacement methods and shall be within the scope of protection of the application.

Claims

1. A proton-containing solid oxide, characterized in that: Including trigonal ABO3 type La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ Ruddlesden-Popper type La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ And Ag nanoparticles.

2. The proton-containing solid oxide according to claim 1, characterized in that: The proton solid oxide comprises 82-84 wt% trigonal ABO3 type La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ , 13-15.5wt% Ruddlesden-Popper type La 0.9 Ba 0.1 Co 0.7 Ni 0.2 Ag 0.1 O 3-δ And 2-4 wt% Ag.

3. The proton-containing solid oxide according to claim 1, characterized in that: The Ag nanoparticles have an average diameter of 5-15 nm.

4. The proton-containing solid oxide according to claim 1, characterized in that: The proton solid oxide is spherical and / or near-spherical, with an average particle size of 40-80 nm.

5. The proton-containing solid oxide according to claim 1, characterized in that: The Ag nanoparticles are anchored to the surface of a proton-containing solid oxide.

6. A method for preparing a proton solid oxide according to any one of claims 1-5, characterized in that: Includes the following steps: S1: After dissolving a metal salt containing La, Ba, Co, Ni and Ag, a complexing agent is reacted with the solution to obtain a gel. S2: The gel is ground and then sintered to obtain the proton solid oxide.

7. The method for preparing proton solid oxide according to claim 6, characterized in that: The grinding process involves first heating the gel to 400-600℃ and then holding it at that temperature for 0.5-1.5 hours, followed by cooling and grinding.

8. The method for preparing proton solid oxide according to claim 6, characterized in that: The calcination is carried out at 700-1200℃; preferably, the heating rate of the calcination is 8-15℃ / min. -1 Preferably, the calcination time is 6-10 hours.

9. An anode for a solid oxide electrolytic cell, characterized in that: Includes the proton solid oxide according to any one of claims 1-5.

10. A solid oxide electrolytic cell, characterized in that: It includes the solid oxide electrolytic cell anode, cathode, and electrolyte as described in claim 9.

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