Reversible proton ceramic battery and preparation method and application thereof
The preparation of reversible proton ceramic batteries through a combined process of dry pressure and spray coating solves the problem of slow electrode dynamics of PCEC at medium temperatures, and achieves high performance and stability in PCFC and PCEC modes, specifically manifested as high output power and current density.
Patent Information
- Application Number
- CN202410184551.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-02-19
- Publication Date
- 2025-05-23
AI Technical Summary
Existing proton ceramic electrochemical cells (PCECs) have slow electrode kinetics at medium temperatures and shorten the lifespan of materials and interfaces, making it difficult to achieve large-scale deployments.
Reversible proton ceramic batteries are prepared by a combination of dry pressure and spray coating. The anode blank is prepared by dry pressure, and electrolyte is sprayed on the anode blank to control the thickness of the electrolyte layer film and promote sintering between the electrolyte and the anode.
In PCFC and PCEC modes, the battery exhibits high performance and better stability, specifically manifested as obtaining a maximum output power of 1078mW cm-2 at 650°C and a maximum current density of -2035mA cm-2 at 1.3V.
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Figure CN120033283A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a reversible proton ceramic battery and a preparation method and application thereof, belonging to the technical field of solid oxide reversible batteries. Background Art
[0003] Protonic ceramic electrochemical cells (PCECs) are solid oxide cells based on proton conductors that can operate in a reversible manner to store renewable energy using water electrolysis to produce hydrogen, which can then be converted back into electricity in a fuel cell mode. The application of PCECs demonstrates the uniqueness of combining the dual functions of energy storage and distributed generation by integrating PCECs and balance of plant into one system. With the remarkable progress in the development of solid proton conductors and related electrochemical cells (fuel cells and electrolyzers) over the past decade, PCECs represent a promising technology that aims to achieve low-cost energy storage and conversion at low temperatures, attracting advantages such as high efficiency, longer system durability, and cheaper materials. However, large-scale deployment of PCECs remains elusive due to severe limitations in developing highly active and stable electrodes, owing to sluggish electrode kinetics and shortened lifetimes of materials and interfaces at moderate temperatures.
[0004] In the prior art, research has been conducted on the development of new oxygen electrode materials to alleviate these problems, which are the biggest reasons for the performance degradation and reduced efficiency of existing PCECs. Currently, both the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR) in mixed ionic and electronic conductive (MIEC) electrodes are strictly confined to the three-phase boundary (TPB) where ions, electrons and gases meet. Therefore, in PCEC systems, it is very necessary to introduce proton conduction into MIEC materials to formulate triple conductive oxides (TCOs), i.e., electrons, oxygen ions and protons, to extend the TPB from the electrolyte / electrode interface into the electrode body. Despite these advantages, there are few TCO candidate products to date due to the difficulty in producing sufficient proton conduction defects under the prerequisite of available hydrated oxygen. Although PCEC technology is developing rapidly, there are still some difficulties that need to be solved. High performance, high stability and low cost are still the main concerns of current research and development.
[0005] A reversible proton ceramic battery comprises a cathode, an electrolyte layer and an anode; the anode is obtained by a dry pressing process, and the electrolyte layer is obtained by spraying and calcining.
[0006] The chemical formula of the cathode material is Sr 3 (Co 0.8 Fe 0.1 Nb 0.1 ) 2 O7-δ , and it has a Ruddlesden-Popper layered structure.
[0007] The chemical formula of the electrolyte material in the electrolyte layer is BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , where δ represents the oxygen vacancy content.
[0008] The material of the anode is a composite anode composed of NiO and electrolyte, and the mass ratio of NiO to electrolyte is 6.5:3.5.
[0009] The preparation method of the above-mentioned reversible proton ceramic battery comprises the following steps:
[0010] Step 1, mixing NiO, electrolyte and pore-forming agent, forming by dry pressing and calcining to obtain an anode;
[0011] Step 2, spraying a slurry containing an electrolyte on the anode and performing a calcination treatment;
[0012] Step 3, spraying a slurry containing cathode material on the surface of the electrolyte layer, and then performing calcination treatment.
[0013] In step 1, the pore former is starch, and the weight ratio between the pore former and the electrolyte is 2-6:1.
[0014] In step 2, the electrolyte-containing slurry includes electrolyte powder and solvent in a ratio of 1g:10-20ml, and the solvent is an alcohol solvent; the temperature of the calcination process is 1400-1500°C, and the time is 1-10h.
[0015] In step 3, the slurry containing the cathode material includes cathode active material powder and solvent in a ratio of 1g:5-20ml, and the solvent is an alcohol solvent; the temperature of the calcination process is 900-1100°C and the time is 1-5h.
[0016] The preparation method of the electrolyte comprises the following steps: adding barium salt, cerium salt, zirconium salt, yttrium salt and ytterbium salt into water according to a stoichiometric ratio, adding a complexing agent and a pH regulator, preparing a gel by a sol-gel method, drying to obtain a precursor, and calcining to obtain the electrolyte.
[0017] The complexing agent is ethylenediaminetetraacetic acid and citric acid, the pH regulator is ammonia water, and the pH of the system is adjusted to 6-7 after the pH regulator is added; the calcination parameters are calcination at 900-1100°C for 5-10h, and the heating rate is 2-5°C / min.
[0018] The barium salt, the cerium salt, the zirconium salt, the yttrium salt and the ytterbium salt are barium nitrate, cerium nitrate, zirconium nitrate, yttrium nitrate and ytterbium nitrate respectively.
[0019] The method for preparing the cathode active material powder comprises the following steps:
[0020] Strontium salt, niobium salt, cobalt salt and iron salt are taken according to the stoichiometric ratio, niobium salt and the first complexing agent are first added into water, and then strontium salt, cobalt salt and iron salt are added, and after they are dissolved, the second complexing agent is added, and then a pH regulator is added to adjust the pH of the system to 7-8, and a gel is prepared by a sol-gel method, and a precursor is obtained after drying, and then calcined to obtain the product.
[0021] The first complexing agent is citric acid, the second complexing agent is ethylenediaminetetraacetic acid, and the pH regulator is ammonia water; the calcination parameters are calcination at 900-1100° C. for 5-10 hours, and a heating rate of 2-5° C. / min.
[0022] The strontium salt, niobium salt, cobalt salt and iron salt are strontium nitrate, niobium oxalate, cobalt nitrate and iron nitrate respectively.
[0023] The above-mentioned reversible proton ceramic battery is used in fuel cells and electrolytic cells. Summary of the invention
[0024] This patent is aimed at the preparation of triple conductive oxide electrode materials and adopts a battery preparation process. This preparation method can achieve high performance and better stability in both PCFC and PCEC modes for reversible proton ceramic batteries. The present invention adopts a combination of dry pressing and spraying in the preparation of anodes and electrolytes. The anode blank is prepared by dry pressing, and the electrolyte is sprayed on the anode blank. This preparation method is easy to control the thickness of the electrolyte layer film and can promote the sintering between the electrolyte and the anode.
[0025] .The present invention adopts a high-performance electrode material for proton conductor fuel cells / electrolyzers, which has a layered structure of cubic perovskite layers and rock salt layers to improve the performance of proton conductor air electrodes. The prepared air electrode has a smaller polarization impedance, higher proton conductivity, etc., so that the cathode material can be applied to medium and low temperature proton conductor solid oxide fuel cells and has excellent performance. At the same time, the electrode has an extremely high oxygen vacancy content, providing more sites for hydration reactions, and good hydrophilicity and fast hydration kinetics, so that it also has excellent electrochemical performance in proton conductor electrolyzers.
[0026] Beneficial Effects
[0027] The present invention relates to a high-performance reversible proton ceramic battery and a preparation method and use thereof. In the preparation of the anode and the electrolyte, a process combining dry pressing and spraying is adopted. The anode blank is prepared by dry pressing, and the electrolyte is sprayed on the anode blank. Such a preparation method has the following effects: the thickness of the electrolyte layer film can be controlled, and the sintering between the electrolyte and the anode can be promoted. Studies have found that electrolyte layers of different thicknesses have a great influence on the impedance and performance of a single cell. Batteries with electrolyte layers of appropriate thickness exhibit excellent electrochemical performance and stability in the reversible FC / EC working mode.
[0028] The high-performance reversible solid oxide electrode material of the present invention is prepared by a sol-gel method and has the following effects: a layered electrode material is synthesized by a simple sol-gel one-step method: Sr 3 (Co 0.8 Fe 0.1 Nb 0.1 ) 2 O 7-δ The method is simple and efficient. There are many different oxygen ion transport pathways in the unique rock salt layered structure of RP, which makes it have high oxygen permeability and ion conductivity. As a unique layered perovskite material with both ORR and OER activity, SCFN-RP has ultra-high oxygen vacancy content and hydration performance. It can optimize the ion and electron transport pathways and accelerate the reaction rate in both electrolysis and fuel cell modes. The reversible proton ceramic battery prepared by the above process has a power of 1078mW cm at 650℃ in fuel cell mode. -2 Peak power density, and the current density at 1.3V in electrolysis mode is -2035mAcm -2 . BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Figure 1 It is the XRD refinement pattern of SCFN-RP and comparative materials at room temperature;
[0030] Figure 2 The SEM and FIB-TEM images of the cross section of the Ni-BZCYYb|BZCYYb|SCFN-RP single cell;
[0031] Figure 3 It is the output power performance curve of Ni-BZCYYb|BZCYYb|SCFN-RP and Ni-BZCYYb|BZCYYb|SCFN single cells in the temperature range of 450-650℃;
[0032] Figure 4It is the EIS curve of 500-700℃ symmetric battery oxygen reduction electrode; (A) SCFN-RP, (B) SCFN, (C) SCFN-RP-5% water vapor condition, (D) SCFN-5% water vapor condition;
[0033] Figure 5 is the impedance stability of the SCFN-RP|BZCYYb|SCFN-RP symmetric cell at 600°C;
[0034] Figure 6 It is the thermal stability of SCFN-RP|BZCYYb|SCFN-RP and SCFN|BZCYYb|SCFN symmetric cells;
[0035] Figure 7 1 is a diagram of water desorption at elevated temperature of SCFN-RP material and comparative material;
[0036] Figure 8 is the thermogravimetric diagram of SCFN-RP material and comparison material; Fig. 9 It is the performance curve of Ni-BZCYYb|BZCYYb|SCFN-RP electrolytic cell for electrolyzing water in the temperature range of 450-650℃. DETAILED DESCRIPTION
[0037] The present invention relates to a high-performance reversible proton ceramic battery and a preparation method and use thereof. A process combining dry pressing and spraying is adopted in the preparation of the anode and the electrolyte. The anode blank is prepared by dry pressing, and the electrolyte is sprayed on the anode blank. Such a preparation method can prepare a thinner electrolyte layer and promote the sintering between the electrolyte and the anode.
[0038] In some other embodiments, the present invention uses a high-performance proton conductor fuel cell / electrolyzer air electrode material, which has a general composition formula A n+1 B n O 3n+1 , molecular formula: Sr 3 (Co 0.8 Fe 0.1 Nb 0.1 ) 2 O 7-δ(SCFN-RP), where δ represents the oxygen vacancy content. Sr3(Co0.8Fe0.1Nb0.1)2O7-δ with a layered structure was synthesized in one step by adjusting the element ratio according to the sol-gel method. Ruddlesden-Popper (RP), as a layered perovskite, has the general formula An+1BnO3n+1, which consists of n repeated cubic perovskite layers alternating with rock salt layers. Compared with single perovskite, there are many different oxygen ion transport pathways in the unique rock salt layered structure of RP, which gives it higher oxygen permeability and ion conductivity. The layered structure of SCFN-RP provides a large amount of oxygen vacancy content and hydration reaction sites, which makes it have fast proton diffusion and transport capabilities, so that it can achieve excellent performance in both proton ceramic fuel cells and electrolyzer applications. In PCFC mode, the corresponding single cell can obtain 1078mW cm at 650℃. -2 The maximum output power of H electrolysis in PCEC mode at 600℃ 2 O, at 1.3V, can get -2035mA cm -2 The invention develops a high-performance reversible electrode material and a preparation method, which greatly improves the electrochemical performance of proton ceramic fuel cells and electrolytic cells.
[0039] Example 1 Low temperature proton conductor solid oxide fuel cell electrolyte material Ba(Zr 0.1 Ce 0.7 Y 0.1 Yb 0.1 ) 3-δ Preparation (1) Weigh 13.067 g of barium nitrate, 2.1466 g of cerium nitrate, 15.1977 g of zirconium nitrate, 1.916 g of yttrium nitrate, and 2.2457 g of ytterbium nitrate into a clear solution, heat and stir until dissolved;
[0040] (3) 29 g of ethylenediaminetetraacetic acid and 42 g of citric acid monohydrate as a complexing agent are added to the solution containing metal ions, and then an appropriate amount of ammonia water is added dropwise to make the pH of the solution reach between 7 and 8. The solution is then stirred under magnetic stirring until the water is completely evaporated to obtain a gel-like substance;
[0041] (4) placing the gel-like substance in an oven at 180° C. and calcining it for 5 h to obtain the desired foam precursor;
[0042] (5) The precursor is placed in a high-temperature muffle furnace and calcined at 1000°C for 5 hours to obtain an electrolyte material powder.
[0043] Example 2 Preparation of air electrode material Sr by EDTA-CA combined complexation method 3 (Co 0.8 Fe0.1 Nb 0.1 ) 2 O 7-δ And comparison material SrCo 0.8 Fe 0.1 Nb 0.1 O 3-δ (SCFN)
[0044] (1) The material prepared by the EDTA-CA combined complexation method has the advantages of nano-scale particle size and uniform element distribution, while niobium oxalate is insoluble under neutral conditions. Here, 2.1522 g of niobium oxalate was weighed, 50 mL of deionized water and 42 g of citric acid monohydrate were added to adjust the pH, and the niobium oxalate was dissolved by heating and stirring to obtain a clear solution;
[0045] (2) Weigh 12.6978 g of strontium nitrate, 9.3130 g of cobalt nitrate, and 1.616 g of iron nitrate and add them to the clear niobium oxalate solution and continue heating and stirring until dissolved;
[0046] (3) 29 g of ethylenediaminetetraacetic acid was weighed as a complexing agent and added to the solution containing the metal ions, and then an appropriate amount of ammonia water was added dropwise until the pH of the solution reached between 7 and 8, and then the solution was stirred under magnetic stirring until the water was completely evaporated to obtain a gel-like substance;
[0047] (4) placing the gel-like substance in an oven at 180° C. and calcining it for 5 h to obtain the desired foam precursor;
[0048] (5) placing the precursor in a high-temperature muffle furnace and calcining it at 1000° C. for 5 h to obtain the desired cathode powder;
[0049] (6) Comparative material SrCo 0.8 Fe 0.1 Nb 0.1 O 3-δ The preparation process of Sr 3 (Co 0.8 Fe 0.1 Nb 0.1 ) 2 O 7-δ Similarly, only the ratio of elements needs to be changed. Weigh 10.5818g of strontium nitrate, 2.6902g of niobium oxalate, 11.6412g of cobalt nitrate, and 2.02g of iron nitrate.
[0050] Example 3 Symmetrical battery preparation
[0051] (1) Weigh 2 g of the cathode powder SCFN-RP prepared in Example 2, 10 ml of isopropanol, 2 ml of ethylene glycol, and 0.8 ml of propylene glycol, and pour them into a high-energy ball mill. After ball milling at 400 r / min for 30 min, transfer the mixture to a culture bottle with a pipette to obtain the desired cathode slurry.
[0052] (2) The prepared BZCYYb electrolyte was placed on a heating table and preheated at 200°C. The prepared cathode slurry was evenly sprayed on both sides of the electrolyte using a spray gun under the push of inert gas. After the liquid evaporated completely, the sprayed electrolyte was placed in a high-temperature muffle furnace and calcined at 1000°C for 2h to obtain the required symmetrical battery, which was used to test the polarization impedance of the cathode material in the temperature range of 500-700°C.
[0053] Example 4 Preparation of dry pressed anode blank
[0054] (1) Weigh 3.5 g of the electrolyte powder BZCYYb prepared in Example 1, 6.5 g of nano-NiO powder and 1 g of soluble starch and add them to a high-energy ball mill. After ball milling at 400 r / min for 30 min, mix them evenly and transfer them to a mortar for stirring and grinding to obtain anode powder.
[0055] (2) Weigh 0.35 g of the prepared anode powder and dry press it in a tableting mold at a pressure of 2 MPa to obtain an anode blank.
[0056] Example 5 Preparation of single cell
[0057] (1) Pour 1 g of the electrolyte powder BZCYYYb prepared in Example 1 and 15 ml of ethanol into a high-energy ball mill. After ball milling at 400 r / min for 30 min, transfer the mixture to a culture bottle with a pipette to obtain the desired electrolyte spray solution.
[0058] (2) The prepared dry-pressed anode blank is placed on a heating table and preheated at 80°C. The prepared electrolyte spray liquid is evenly sprayed on the surface of the dry-pressed tablet using a spray gun under the push of inert gas. After the liquid evaporates completely, the weight increases by about 0.006g. The sprayed blank is then dry-pressed in a tablet pressing mold at a pressure of 4Mpa, and the sprayed dry-pressed battery is placed in a high-temperature muffle furnace at 1450°C-5h to obtain the required half-cell.
[0059] (3) Take 1 g of the cathode powder SCFN-RP prepared in Example 1, 10 ml of isopropanol, 2 ml of ethylene glycol, and 0.8 ml of propylene glycol, pour them into a high-energy ball mill, ball mill at 400 r / min for 30 min, and transfer them to the culture bottle with a pipette to obtain the required cathode slurry.
[0060] (4) The prepared dry-pressed battery sheet is placed on a heating table and preheated at 200°C. The prepared cathode slurry is evenly sprayed on the electrolyte surface of the dry-pressed sheet using a spray gun under the push of inert gas. After the liquid evaporates completely, the sprayed dry-pressed battery is placed in a high-temperature muffle furnace and calcined at 1000°C for 2 hours to obtain the required single cell, which is used for single cell performance testing of cathode materials in the temperature range of 400 to 650°C.
[0061] Characterization results
[0062] 1. XRD characterization
[0063] Figure 1 Figure D is the XRD refinement diagram of the comparison material SCFN. According to the refinement results, it can be seen that SCFN-RP is a tetragonal perovskite structure with a space group of I4-mmm and a lattice parameter of SCFN is a cubic perovskite structure with a space group of P4-mmm and a lattice parameter of
[0064] 2. Morphological Characterization and Analysis
[0065] Figure 2 Figure A is a cross-sectional SEM image of Ni-BZCYYb|BZCYYb|SCFN-RP, showing that the anode and electrolyte are well sintered and the thickness of the electrolyte film is controllable. The thickness of the sprayed electrolyte in the figure is about 8 microns thinner than the electrolyte layer using the traditional dry pressing method.
[0066] Figure 2 Figure E is the element mapping analysis of FIB-SEM, which verifies that each element phase is evenly distributed on the surface and bulk surface.
[0067] 3. Output power characterization
[0068] Figure 3 The typical IV and IP curves of the output power of Ni-BZCYYb|BZCYYb|SCFN-RP single cell in the temperature range of 450-650°C. The power density of the SCFN-RP cathode single cell increases monotonically with increasing temperature, following the same pattern as other PCFCs, and is 1078, 821, 536, and 304 mW cm at 650 to 500°C. -2 , which is significantly improved compared with the comparative material SCFN. At 650℃, 550℃ and 500℃, the open circuit voltage (OCV) of SCFN-RP is 1.059V, 1.098V and 1.078V, which is close to the theoretical OCV value at this temperature, showing good single cell sealing and negligible electrolyte electron leakage.
[0069] 4. Electrochemical impedance spectroscopy
[0070] Figure 4 The A and B areas in the figure show the electrochemical impedance spectra of SCFN-RP and SCFN in dry air, respectively. The C and D areas show the electrochemical impedance spectra of SCFN-RP and SCFN in 5% water vapor, respectively. The impedance of SCFN-RP in dry air is 0.055, 0.1481, 0.4297, 1.1872 and 5.0422Ωcm 2 The impedance under 5% water vapor conditions is 0.0706, 0.1674, 0.398, 1.027 and 2.6652Ωcm 2 At 700, 650, 600, 550 and 500 ° C respectively. After passing water, the reduction in the low temperature section is very obvious and is less than the control sample SCFN. For a single cell with SCFN-RP as the cathode, the polarization impedance accounts for only 10% to 20% of the total ASR of the single cell, while the ohmic impedance is determined by the thickness of the BZCYYb electrolyte and the battery preparation process. The ohmic impedance becomes the main resistance during operation. At the same time, it can be seen that the polarization impedance is significantly lower than the polarization impedance of the current mainstream proton ceramic fuel cell cathode.
[0071] 5. Impedance Characterization
[0072] Figure 5 This is the impedance stability of the SCFN-RP|BZCYYb|SCFN-RP symmetric battery at 600℃; after 400h of symmetric battery stability test, the impedance did not increase significantly, indicating that SCFN-RP has good electrochemical stability.
[0073] Figure 6 To characterize the thermal cycling stability of the SCFN-RP|BZCYYb|SCFN-RP symmetric battery, the SCFN-RP symmetric battery was subjected to 99 thermal cycles between 300℃-600℃ for 150 hours. It can be seen from the figure that its impedance did not increase significantly, and compared with the comparison material SCFN, it shows that the SCFN-RP electrode and the BZCYYb electrolyte have good thermal matching.
[0074] 6. Temperature-Programmed Desorption of Water (H 2 O-TPD) Characterization
[0075] Figure 5 The powder samples of SCFN-RP and the comparative material SCFN were heated at 250℃ and 20vol.%H 2 O-80 vol.% air for 3 hours, then quenched to room temperature, and then the sample was subjected to H 2 Programmed temperature desorption experiment of O. We found that SCFN-RP has the largest and sharpest desorption peak, indicating that the layered perovskite of SCFN-RP has more oxygen vacancies for water adsorption.
[0076] 7. Thermogravimetric (TGA) characterization
[0077] Figure 8 This is the thermogravimetric diagram of SCFN-RP and the comparison material SCFN. As the temperature rises, the high-temperature thermal reduction of cobalt ions in the material causes oxygen ions to escape from the lattice to form oxygen vacancies, and the quality of the material decreases. It can be seen from the figure that as the temperature rises, the weight of SCFN-RP decreases more than that of SCFN, which indicates that the SCFN-RP material has more oxygen vacancies than the comparison material.
[0078] 8. Characterization of electrolytic performance
[0079] Fig. 9 The performance curve of water electrolysis of Ni-BZCYYb|BZCYYb|SCFN-RP electrolytic cell in the temperature range of 450-650℃; the current density corresponding to SCFN-RP at a voltage of 1.3V is -2035, -1285, -714, 464mA cm -2 650, 600, 550 and 500 °C, respectively. The excellent electrolytic performance is mainly attributed to the high oxygen vacancies and fast hydration reaction, as well as the excellent water storage capacity of SCFN-RP.
[0080] In summary, it can be seen that the reversible proton ceramic battery prepared by the combination of dry pressing and spraying can control the thickness of the electrolyte layer compared with the traditional solid oxide fuel cell, which is convenient for preparing the electrolyte layer of suitable thickness. The air electrode material SCFN-RP, on the premise of having oxygen ion and electron conductivity, also has excellent proton conductivity and rapid hydration ability, so it has excellent electrochemical performance in both PCFC and PCEC modes. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ When the hydrogen electrode is composed of 65% NiO and 35% BZCYYb, the corresponding single cell can obtain 1078mW cm at 650℃ in PCFC mode. -2 The maximum output power of H electrolysis in PCEC mode at 650℃ 2 O, at 1.3V, can get -2035mA cm -2 The invention relates to a high-performance reversible proton ceramic battery and a preparation method thereof, which greatly improves the electrochemical performance of a proton ceramic fuel cell and an electrolytic cell.
Claims
1. A reversible proton ceramic battery, characterized in that: It comprises a cathode, an electrolyte layer and an anode; the anode is obtained by dry pressing, and the electrolyte layer is obtained by spraying and calcining.
2. The reversible proton ceramic battery according to claim 1, characterized in that: The chemical formula of the cathode material is Sr3(Co 0.8 Fe 0.1 Nb 0.1 )2O 7-δ , δ is the oxygen vacancy content, and it has a Ruddlesden-Popper perovskite layered structure.
3. The reversible proton ceramic battery according to claim 1, characterized in that: The chemical formula of the electrolyte material in the electrolyte layer is BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , where δ represents the oxygen vacancy content.
4. The reversible proton ceramic battery according to claim 1, characterized in that: The material of the anode is a composite anode composed of NiO and electrolyte, and the mass ratio of NiO to electrolyte is 4-7:2-5.
5. The method for preparing the reversible proton ceramic battery according to claim 1, characterized in that: The steps include: Step 1, mixing NiO, electrolyte and pore-forming agent, forming by dry pressing and calcining to obtain an anode; Step 2, spraying a slurry containing an electrolyte on the anode and performing a calcination treatment; Step 3, spraying a slurry containing cathode material on the surface of the electrolyte layer, and then performing calcination treatment.
6. The method for preparing a reversible proton ceramic battery according to claim 5, characterized in that: In step 1, the pore former is starch, and the weight ratio between the pore former and the electrolyte is 2-6:
1.
7. The method for preparing a reversible proton ceramic battery according to claim 5, characterized in that: In step 2, the electrolyte slurry includes electrolyte powder and solvent in a ratio of 1g:10-20ml, and the solvent is an alcohol solvent; the temperature of the calcination process is 1400-1500°C and the time is 1-10h; In step 3, the slurry containing the cathode material includes cathode active material powder and solvent in a ratio of 1g:5-20ml, and the solvent is an alcohol solvent; the temperature of the calcination process is 900-1100°C and the time is 1-5h.
8. The method for preparing a reversible proton ceramic battery according to claim 5, characterized in that: The preparation method of the electrolyte comprises the following steps: adding barium salt, cerium salt, zirconium salt, yttrium salt and ytterbium salt into water according to a stoichiometric ratio, adding a complexing agent and a pH regulator, preparing a gel by a sol-gel method, drying to obtain a precursor, and calcining to obtain; The complexing agent is ethylenediaminetetraacetic acid and citric acid, the pH regulator is ammonia water, and the pH of the system is adjusted to 6-7 after the pH regulator is added; the calcination parameters are calcination at 900-1100°C for 5-10h, and the heating rate is 2-5°C / min; The barium salt, the cerium salt, the zirconium salt, the yttrium salt and the ytterbium salt are barium nitrate, cerium nitrate, zirconium nitrate, yttrium nitrate and ytterbium nitrate respectively.
9. The method for preparing a reversible proton ceramic battery according to claim 5, characterized in that: The preparation method of the cathode active material and the comparative material powder comprises the following steps: Strontium salt, niobium salt, cobalt salt and iron salt are taken according to the stoichiometric ratio, niobium salt and the first complexing agent are first added into water, and then strontium salt, cobalt salt and iron salt are added, and after they are dissolved, the second complexing agent is added, and then a pH regulator is added to adjust the pH of the system to 7-8, and a gel is prepared by a sol-gel method, and a precursor is obtained after drying, and then calcined to obtain the product. The first complexing agent is citric acid, the second complexing agent is ethylenediaminetetraacetic acid, and the pH regulator is ammonia water; the calcination parameters are calcination at 900-1100° C. for 5-10 hours, and a heating rate of 2-5° C. / min. The strontium salt, niobium salt, cobalt salt and iron salt are strontium nitrate, niobium oxalate, cobalt nitrate and iron nitrate respectively.
10. Use of the reversible proton ceramic battery according to claim 1 in fuel cells and electrolytic cells.