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JP-7856961-B2 - Double perovskite material and its manufacturing method, and reversible proton ceramic electrochemical cell

JP7856961B2JP 7856961 B2JP7856961 B2JP 7856961B2JP-7856961-B2

Inventors

  • 劉 瑛
  • 陳 宇
  • 許 陽森

Assignees

  • 紫金鉱業新能源新材料科技（長沙）有限公司
  • 華南理工大学

Dates

Publication Date
20260512
Application Date
20240716
Priority Date
20230721

Claims (11)

  1. A double perovskite material characterized by having the general formula PrBa 1-x Cs x Co 2 O 6-δ , where δ is the oxygen vacancy content and the range of x is 0.01 to 0.15.
  2. The double perovskite material according to claim 1, characterized in that the range of x values is 0.05 to 0.125.
  3. The double perovskite material according to claim 1, characterized in that the double perovskite material has a tetragonal layered perovskite structure, wherein the lattice constants are 3.9045 ± 0.1 Å, 3.9045 ± 0.1 Å, and 7.6572 ± 0.1 Å.
  4. The double perovskite material according to claim 1, characterized in that its general formula is PrBa 0.9 Cs 0.1 Co 2 O 6-δ .
  5. A method for producing a double perovskite material according to any one of claims 1 to 4, characterized by comprising the steps of: (1) dissolving praseodymium nitrate, barium nitrate, cesium nitrate, and cobalt nitrate in water to obtain a mixture, then mixing the mixture with ethylenediaminetetraacetic acid, citric acid, and ammonia water, adjusting the pH to 7 to 8 to obtain a mixed solution; and (2) heating the mixed solution until it becomes gel-like, performing high-temperature treatment at 200 to 250°C to obtain a precursor, and calcining the precursor.
  6. The method for producing a double perovskite material according to claim 5, characterized in that in step (1), the molar ratio of the metal element, ethylenediaminetetraacetic acid, and citric acid is 0.5 to 1.5:0.5 to 1.5:1 to 2, wherein the metal element is the sum of Pr, Ba, Cs, and Co.
  7. A method for producing a double perovskite material according to claim 5, characterized in that in step (2), the heating temperature of the mixed solution is 80 to 100°C, and/or the time of the high-temperature treatment is 2 to 6 hours, and/or the firing temperature is 950 to 1050°C and the firing time is 2 to 4 hours.
  8. The use of a double perovskite material according to any one of claims 1 to 4, characterized in that it is used as an air electrode in a reversible proton ceramic electrochemical battery.
  9. A reversible proton ceramic electrochemical cell comprising sequentially connected anode support layers, an electrolyte, and an air electrode, wherein the air electrode is manufactured from the double perovskite material described in claim 1 .
  10. The reversible proton ceramic electrochemical battery according to claim 9, characterized in that the electrolyte material comprises BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , where δ is the oxygen vacancy content , and /or the anode support layer material comprises NiO and BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , where the mass ratio of NiO to BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ is 5.5 to 6.5:3.5 to 4.5, and/or the reversible proton ceramic electrochemical battery further comprises a transition layer, the transition layer being provided between the anode support layer and the electrolyte.
  11. The reversible proton ceramic electrochemical cell according to claim 10, characterized in that the transition layer contains NiO and BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3- δ , wherein the mass ratio of NiO to BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ is 5.5 to 6.5:3.5 to 4.5.

Description

This invention relates to the field of reversible proton ceramic electrochemical batteries, and more particularly to double perovskite materials, methods for producing the same, and reversible proton ceramic electrochemical batteries. The finite nature of fossil fuel storage and the intensification of greenhouse gas emissions create a strong need to find clean and pollution-free energy conversion devices to mitigate the current energy and environmental crises. Reversible proton ceramic electrochemical cell (R-PCEC) technology can be one effective means of solving these problems. When operating in fuel cell mode, a reversible proton ceramic electrochemical cell can convert chemical energy into electrical energy, and when operating in electrolysis mode, it can convert electrical energy into chemical energy. Furthermore, because R-PCEC, based on a proton-conducting electrolyte, has relatively high proton conductivity, it can operate at medium to low temperatures (400-700°C). The relatively low operating temperature of R-PCEC is advantageous not only for extending the lifespan of the cell itself but also for reducing manufacturing costs. However, as the operating temperature of the R-PCEC decreases, the reaction kinetics of the air electrode also slow down, significantly degrading the electrochemical performance of the R-PCEC. Therefore, designing an air electrode material that possesses high catalytic activity in the oxygen reduction (ORR)/oxygen evolution (OER) reaction and sufficient chemical stability under operating conditions at medium to low temperatures is one of the most critical challenges facing the R-PCEC. In recent years, researchers have designed many air electrode materials, but most of them exhibit moderate electrochemical performance in R-PCEC. PrBaCo₂O₆ -δ (PBC), a double perovskite material, possesses excellent electrical conductivity, oxygen ion conductivity, oxygen surface exchange coefficient, and oxygen ion diffusion dynamics, exhibiting superior electrochemical performance as an air electrode for solid oxide fuel cells (SOFCs). Cesium (Cs) is sometimes used in the design of perovskite solar cell materials because Cs doping enhances the thermal stability and moisture resistance of the material's crystal structure. According to density functional theory (DFT) calculations, the main reason for the improved ORR activity of air electrodes after Cs doping is the shift of electron pairs due to the polarization distribution of Lewis acid strength at the A and B sites, which further reduces the oxygen vacancy formation energy of the oxide. Currently, there are few reports on the application of air electrodes designed by Cs doping at site A to R-PCEC. This is a refined XRD pattern obtained after firing the air electrode material PrBa 0.9 Cs 0.1 Co 2 O 6-δ (PBCsC) according to Example 1 of the present invention at 1000°C for 2 hours.This is an XRD pattern obtained after simultaneously firing the air electrode material PrBa 0.9 Cs 0.1 Co 2 O 6-δ (PBCsC) and the electrolyte BZCYYb powder in a high-temperature muffle furnace at 950°C for 2 hours, according to Example 1 of the present invention.This is the XRD pattern of the air electrode material PrBa 0.9 Cs 0.1 Co 2 O 6-δ (PBCsC) according to Example 1 of the present invention after being treated with 30% water at 600°C for 10 hours.This is a high-temperature in situ XRD pattern obtained after firing the air electrode material PrBa 0.9 Cs 0.1 Co 2 O 6-δ (PBCsC) according to Example 1 of the present invention at 1000°C for 2 hours.These are the X-ray photoelectron spectra (XPS) of the air electrode materials PBCsC and PBC according to Example 1 of the present invention, where a is Pr 3d and b is Co 2p.These are the O 1s X-ray photoelectron spectra of the air electrode materials PBCsC(6a) and PBC(6b) according to Example 1 of the present invention.This is an evaluation diagram of the relaxation characteristics of the air electrode materials PBCsC and PBC according to Example 1 of the present invention.This figure shows the area specific impedance (8a) and impedance stability (8b) of a symmetric battery according to Example 1 of the present invention (where PBCsC is the electrode and BZCYYb1711 is the electrolyte support) in humid air (3% H₂O ).This figure shows the electrochemical stability of a symmetrical battery according to Example 1 of the present invention (where PBCsC and PBC are electrodes and BZCYYB1711 is the electrolyte support) in humid air (3% H₂O ).This is the infrared spectrum obtained after treating PBCsC and PBC oxide according to Example 1 of the present invention at 600°C with air containing 30% water vapor for 50 hours.This figure shows the maximum power density when a single cell (Ni-BZCYYB1711||transition layer Ni-BZCYYB1711||BZCYYB1711||PBCsC) manufactured using PBCsC as the air electrode in Embodiment 2 of the present invention is measured in FC mode (humidified hydrogen gas is supplied to the anode side and air is supplied to t