Proton ceramic battery nano-composite air electrode material based on single-double perovskite self-assembly and preparation method of proton ceramic battery nano-composite air electrode material

Abstract

The invention relates to a proton ceramic battery nano composite air electrode material based on single and double perovskite self-assembly and a preparation method thereof. A series of single perovskite Pr0.5 (Ba0. 5Sr0. 5) 0.5 Co < 0.8 > Fe < 0.2 > O < 3-delta > (PBSCF-SP) / double perovskite PrBa0. 5Sr0. 5Co < 1.5 > Fe < 0.5 > O < 6-delta > (PBSCF-DP) composite materials are developed through a self-assembly method and used for the air electrode of the proton ceramic battery, and the nominal composition of the composite materials is PrBa0. 5Sr0. 5Co < 1.5 > Fe < 0.5 > O < 6-delta > (PBSCF < x >, x = 0.43, 0.45 and 0.47). A series of self-assembled nano composite materials PBSCFx are subjected to phase structure and electrochemical performance analysis, and compared with a traditional double perovskite material PBSCF-DP, the PBSCF0.45 proton ceramic battery nano composite air electrode material has better oxygen evolution / oxygen reduction reaction (OER / ORR) activity.

Description

Technical Field

[0001] This invention relates to a nanocomposite air electrode material for proton ceramic batteries based on the self-assembly of single and double perovskites and its preparation method, and more specifically to a PrBa air electrode material for proton ceramic batteries prepared by the sol-gel method. 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ (PBSCF0.45) and its preparation method and applications belong to the field of solid oxide battery technology. Background Technology

[0002] With fossil fuels being increasingly depleted, the demand for energy is constantly rising. Recent research has focused on how to rationally and effectively utilize green energy, including renewable energy sources such as solar and wind power. Solid oxide batteries (SOCs), as a highly efficient green energy conversion and storage technology, have received widespread attention over the past decade.

[0003] However, current SOCs require relatively high operating temperatures (above 800°C) to achieve satisfactory battery performance. Simultaneously, high-temperature operation of SOCs leads to drawbacks such as excessive material costs, sealing difficulties, and insufficient long-term stability. Therefore, lowering the operating temperature of SOCs to the mid-to-low temperature range (400-650°C) can significantly reduce material and sealing costs and improve long-term battery stability. Simultaneously, reducing the operating temperature of SOCs has become a research hotspot and focus in the SOCs field in recent years. Compared to oxygen-ion conductor SOCs, proton ceramic batteries (PCCs) are more suitable for low-temperature operation due to their higher theoretical efficiency and lower ion activation energy. However, as the operating temperature decreases, PCCs do not show a significant advantage over SOCs, because the existing PCC air electrode materials lack sufficient electrochemical activity and stability at low temperatures. Therefore, designing and developing air electrode materials with higher oxygen evolution / oxygen reduction reaction (OER / ORR) performance at mid-to-low temperatures is key to the low-temperature development of PCCs.

[0004] Current research mainly focuses on the development of air electrode materials and the optimization of battery configurations to achieve efficient and stable operation of PCCs at medium and low temperatures. Research on PCC air electrode materials is largely based on the development of single perovskite oxides and their composites, which still suffer from shortcomings in electrochemical performance and stability. Summary of the Invention

[0005] The problem this invention aims to solve is to provide a single- and double perovskite self-assembled proton ceramic battery nanocomposite air electrode material, achieving better battery performance and stability. The single- and double perovskite composite air electrode material, its preparation method, and its applications provided in this invention exhibit better OER / ORR activity at low temperatures, enabling efficient and stable operation of proton ceramic batteries at medium and low temperatures.

[0006] A nanocomposite air electrode material for proton-ceramic batteries, consisting of single and double perovskite self-assembled structures, has the nominal chemical formula AA'B2O. 6-δ The molecular formula is: PrBa 0.5 Sr 0.5 Co 2-x Fe x O 6-δ , where δ represents the oxygen vacancy content.

[0007] x∈[0.43-0.47].

[0008] In one implementation, 0 ≤ δ ≤ 1.

[0009] In one embodiment, the molecular formula is: PrBa 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ .

[0010] A method for preparing a single- and double perovskite composite proton ceramic battery air electrode material includes the following steps: prepared by sol-gel method according to stoichiometry.

[0011] The steps of the sol-gel method include:

[0012] Step 1: Weigh a certain mass of Pr(NO3)3·6H2O, Ba(NO3)2, Sr(NO3)2, Co(NO3)2·6H2O and Fe(NO3)3·9H2O according to the stoichiometric ratio, add an appropriate amount of deionized water and stir to dissolve, obtaining a clear solution; after complete dissolution, add ethylenediaminetetraacetic acid and citric acid monohydrate, then add ammonia water dropwise until the pH of the solution is between 7 and 8, and allow the water to evaporate under heating and stirring conditions to obtain a gel-like substance; place the gel-like substance in an oven at 180℃ for 5 hours to obtain the air electrode material precursor;

[0013] Step 2: Place the precursor obtained in Step 1 in a muffle furnace and calcine it in an air atmosphere to obtain the desired air electrode material.

[0014] In one embodiment, the molar ratio of total metal ions: ethylenediaminetetraacetic acid (EDTA): citric acid monohydrate (CA): ammonia is 1:0.5-1.5:1-3:3-20.

[0015] In one embodiment, the precursor is dried by calcining in an oven at 140-180°C for 5-10 hours.

[0016] In one embodiment, the calcination conditions are calcination at 950-1050°C for 5-10 hours in an air atmosphere, with a heating rate of 2-5°C / min.

[0017] The above-mentioned single and double perovskite nanocomposite air electrode materials are used in proton ceramic batteries.

[0018] The single- and double perovskite nanocomposite air electrode material of this invention has the following effects:

[0019] (1) This invention synthesizes PrBa via the sol-gel method. 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ (PBSCF0.45) is an air electrode material with uniform distribution of elements and a simple and efficient synthesis method.

[0020] (2) PrBa single- and double perovskite nanocomposite air electrode material prepared by sol-gel method 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ (PBSCF0.45). Symmetric cells using PBSCF0.45 as the air electrode exhibited excellent electrochemical performance with a low areal resistivity (ASR), demonstrating good OER / ORR activity. The ASR values ​​at 650℃, 600℃, 550℃, 500℃, and 450℃ were 0.126 Ωcm. 2 0.235Ωcm 2 0.550Ωcm 2 1.42Ωcm 2 and 5.40Ωcm 2 . Attached Figure Description

[0021] Figure 1 The images show the XRD patterns of five air electrode materials (PBSCF0.43, PBSCF0.45, PBSCF0.47, PBSCF-SP, and PBSCF-DP) after calcination at 1000℃ in air for 5 hours and then natural cooling to room temperature.

[0022] Figure 2The Arrhenius plot shows the ASR values ​​of three air electrode materials, PBSCF0.43, PBSCF0.45, and PBSCF0.47, as a function of temperature in a dry air atmosphere within the temperature range of 450-650℃.

[0023] Figure 3 The Arrhenius plot shows the ASR values ​​of three air electrode materials, PBSCF0.43, PBSCF0.45, and PBSCF0.47, as a function of temperature within a temperature range of 450-650℃ in a humid air atmosphere containing 5 vol.% water.

[0024] Figure 4 The Nyquist plots of the air electrode at 600°C and 650°C for a symmetric cell based on BZCYYb electrolyte and PBSCF0.45 electrode tested in a humid air atmosphere with 5 vol.% water.

[0025] Figure 5 A fuel cell with the structure PBSCF0.45|BZCYYb|Ni-BZCYYb fuel electrode supported was prepared using Ni-BZCYYb as the fuel electrode, BZCYYb as the electrolyte, and PBSCF0.45 as the air electrode. The IV and IP performance curves were obtained under the condition of hydrogen as fuel.

[0026] Figure 6 An electrolytic cell with the structure PBSCF0.45|BZCYYb|Ni-BZCYYb fuel electrode supported was prepared using Ni-BZCYYb as the fuel electrode, BZCYYb as the electrolyte, and PBSCF0.45 as the air electrode. The IV electrolysis performance curves obtained in the temperature range of 450-650℃ are shown.

[0027] Figure 7 The Nyquist plot of the air electrode of a symmetric cell based on BZCYYb electrolyte and PBSCF-SP electrode was tested in a humid air atmosphere with 5 vol.% water in a temperature range of 450-650 °C.

[0028] Figure 8 The Nyquist plots of the air electrode of a symmetric cell based on BZCYYb electrolyte and PBSCF-DP as electrode were tested in a humid air atmosphere with 5 vol.% water in the temperature range of 450-650 °C. Detailed Implementation

[0029] This invention relates to a nanocomposite air electrode material, PrBa, for proton ceramic batteries based on single- and double perovskite self-assembly. 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δThe preparation method utilizes the combination of the ordered cations of the double perovskite PBSCF-DP and the disordered cations of the single perovskite PBSCF-SP. Therefore, to further confirm the synergistic effect of the single- and double perovskite composite air electrode, we synthesized a self-assembled single- and double perovskite nanocomposite air electrode material, PrBa, using the sol-gel method. 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ The phase structure and electrochemical properties of self-assembled single- and double perovskite composite air electrode materials were investigated, and excellent OER / ORR activity and stability were obtained. These materials can be prepared by the sol-gel method according to the specified composition ratio.

[0030] Example 1

[0031] PrBa nanocomposite air electrode material based on single and double perovskites 0.5 Sr 0.5 Co 2-x Fe x O 6-δ (PBSCFx) was prepared by the sol-gel method with PrBa 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ Taking (PBSCF0.45) as an example, the specific steps are as follows:

[0032] (1) According to PrBa 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ To prepare (PBSCF0.45), weigh out 8.7002 g of Pr(NO3)3·6H2O, 2.6134 g of Ba(NO3)2, 2.1163 g of Sr(NO3)2, 9.0219 g of Co(NO3)2·6H2O, and 3.6360 g of Fe(NO3)3·9H2O in a clean beaker. Add an appropriate amount of deionized water and stir on a heated stirring table to dissolve the solutions, obtaining a clear solution. Weigh out 23.379 g of ethylenediaminetetraacetic acid and 33.6224 g of citric acid monohydrate as complexing agents in a molar ratio of 1:2:1 for ethylenediaminetetraacetic acid:citric acid monohydrate:total metal ions. Dissolve these in deionized water.

[0033] (2) After adding the solution containing the complexing agent to the solution containing the metal ions, add an appropriate amount of ammonia water to make the pH of the solution reach between 7 and 8. Then stir under magnetic stirring until the water is completely evaporated to obtain a gel-like substance.

[0034] (3) The gel-like substance was placed in an oven and calcined at 180°C for 5 hours to obtain the corresponding precursor.

[0035] (4) The dried precursor was placed in a high-temperature muffle furnace and calcined at 1000℃ for 5h to obtain PBSCF0.45 air electrode powder.

[0036] The preparation process of PBSCF0.43 and PBSCF0.47 is similar to that of PBSCF0.45, the difference being the change in element ratio and the corresponding amount of raw materials added.

[0037] Comparative Example 1

[0038] Proton ceramic battery air electrode material Pr 0.5 (Ba 0.5 Sr 0.5 ) 0.5 Co 0.8 Fe 0.2 O 3-δ (PBSCF-SP), PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 6-δ (PBSCF-DP) was prepared by the sol-gel method with PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 6-δ Taking (PBSCF-DP) as an example, the specific steps are as follows: (1) According to PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 6-δ To prepare (PBSCF-DP), weigh out 8.7002 g of Pr(NO3)3·6H2O, 2.6134 g of Ba(NO3)2, 2.1163 g of Sr(NO3)2, 8.7309 g of Co(NO3)2·6H2O, and 4.0400 g of Fe(NO3)3·9H2O in a clean beaker. Add an appropriate amount of deionized water and stir on a heated stirring table to dissolve the solutions, obtaining a clear solution. Weigh out 23.379 g of ethylenediaminetetraacetic acid and 33.6224 g of citric acid monohydrate as complexing agents in a molar ratio of 1:2:1 for ethylenediaminetetraacetic acid:citric acid monohydrate:total metal ions. Dissolve these in deionized water.

[0039] (2) After adding the solution containing the complexing agent to the solution containing the metal ions, add an appropriate amount of ammonia water until the pH of the solution reaches between 7 and 8. Then, stir under magnetic stirring until the water is completely evaporated to obtain a gel-like substance.

[0040] (3) The gel-like substance was placed in an oven and calcined at 180°C for 5 hours to obtain the corresponding precursor.

[0041] (4) The dried precursor was placed in a high-temperature muffle furnace and calcined at 1000℃ for 5 hours to obtain PBSCF-DP air electrode powder.

[0042] The preparation process of PBSCF-SP is similar to that of PBSCF-DP, the difference being the change in the molecular ratio of the raw materials.

[0043] Preparation of symmetric cells

[0044] With PrBa 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ Taking (PBSCF0.45) electrode material as an example, the specific steps for the preparation and testing of symmetric cells are as follows:

[0045] (1) Weigh 1g of the air electrode powder PrBa obtained in Example 1. 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ (PBSCF0.45), 10 ml of isopropanol, 2 ml of ethylene glycol, and 0.8 ml of glycerol were poured into a high-energy ball mill and milled at 400 r / min for 30 min. The mixture was then transferred to a culture bottle with a dropper to obtain the corresponding air-electrode slurry.

[0046] (2) The prepared BZCYYb electrolyte sheet was placed on a heating table and preheated at 150°C. The air electrode slurry was uniformly sprayed onto both sides of the electrolyte sheet using a spray gun under the push of inert gas. After the liquid evaporated completely, the sprayed electrolyte sheet was placed in a high-temperature muffle furnace and calcined at 1000°C for 2 hours to obtain the corresponding symmetrical battery, which was used to test the polarization impedance of the air electrode material in the temperature range of 450-650°C.

[0047] Preparation of single cells

[0048] With PrBa 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ Taking (PBSCF0.45) air electrode material as an example, the specific steps for the preparation and testing of a single cell are as follows:

[0049] (1) Weigh 1g of the air electrode powder PrBa obtained in Example 1. 0.5 Sr 0.5 Co1.55 Fe 0.45 O 6-δ (PBSCF0.45), 10 ml of isopropanol, 2 ml of ethylene glycol, and 0.8 ml of glycerol were poured into a high-energy ball mill and milled at 400 r / min for 30 min. The mixture was then transferred to a culture bottle with a dropper to obtain the corresponding air-electrode slurry.

[0050] (2) The prepared Ni-BZCYYb dry-pressed battery cell was placed on a heating table and preheated at 150°C. The air electrode slurry was uniformly sprayed onto the electrolyte surface of the dry-pressed battery cell under the push of inert gas using a spray gun. After the liquid evaporated completely, the sprayed dry-pressed battery cell was placed in a high-temperature muffle furnace and calcined at 1000°C for 2 hours to obtain the corresponding single cell, which was used to test the performance of the air electrode material in fuel cells and electrolyzers in the temperature range of 450-650°C.

[0051] 1. XRD characterization

[0052] Figure 1 The images show the XRD patterns of five oxides (PBSCF0.43, PBSCF0.45, PBSCF0.47, PBSCF-SP, and PBSCF-DP) prepared in Example 1 and Comparative Example 1, calcined at 1000°C in air for 5 hours and then naturally cooled to room temperature. Compared to PBSCF-SP and PBSCF-DP, the peaks of PBSCF0.43, PBSCF0.45, and PBSCF0.47 near 33° are wider, indicating that the peaks of these three air electrode materials are the overlap of single- and double perovskite two-phase peaks. Furthermore, since the atomic radius of Fe is slightly larger than that of Co, the peak shifts to the left as the Fe / Co ratio increases.

[0053] 2. Performance Analysis of Symmetrical Cells

[0054] The electrochemical activity of PBSCF0.45 was first evaluated using electrochemical impedance spectroscopy (EIS). The EIS of the PBSCF0.45|BZCYYb|PBSCF0.45 symmetric cell was tested in the temperature range of 450-650℃ in a humid air atmosphere containing 5 vol.% water. The difference between the real axis intercepts of the high and low frequencies of the EIS was represented by the areal resistivity (ASR) of the electrode. A smaller ASR value at the air electrode indicated higher OER / ORR catalytic activity.

[0055] Figure 2The Arrhenius curves of the PBSCFx (x=0.43,0.45,0.47) air electrodes in dry air atmosphere within the range of 450-650℃ are shown. Among the listed air electrodes, PBSCF0.45 obtained the lowest ASR value, therefore PBSCF0.45 has better OER / ORR activity in dry air atmosphere.

[0056] Figure 3 The Arrhenius curves for the air electrodes of PBSCFx (x = 0.43, 0.45, 0.47) in a humid air atmosphere containing 5 vol.% water within the range of 450-650℃ are shown. Among the listed air electrodes, PBSCF0.45 obtained the lowest ASR value, therefore PBSCF0.45 has superior OER / ORR activity in a humid air atmosphere containing 5 vol.% water.

[0057] Figure 4 This is the Nyquist plot of the PBSCF0.45 air electrode in a symmetrical cell based on BZCYYb electrolyte and using PBSCF0.45 as the electrode, tested at 650℃ and 600℃. The EIS plots are also shown at 650℃ and 600℃, under open-circuit voltage test conditions in a humid air atmosphere containing 5 vol.% water. The EIS plots show that the impedance of PBSCF0.45 is lowest at both 650℃ and 600℃, at 0.126 Ωcm. 2 0.235Ωcm 2 .

[0058] 3. Fuel Cell Performance Testing

[0059] Figure 5 These are the IV and IP curves of a fuel cell. A fuel cell with a structure of PBSCF0.45|BZCYYb|Ni-BZCYYb fuel electrode supported by Ni-BZCYYb as the fuel electrode, BZCYYb as the electrolyte, and PBSCF0.45 as the air electrode was prepared. The IV and IP curves of the fuel cell were obtained under hydrogen fuel conditions. In the temperature range of 450-650℃, the single cell with PBSCF0.45 as the air electrode showed excellent power output, with peak power densities of 0.824 W / cm² at 650℃, 600℃, 550℃, 500℃, and 450℃. -2 0.621W cm -2 0.486W cm -2 0.348W cm -2 and 0.244Wcm -2 .

[0060] 4. Electrolytic Cell Performance Testing

[0061] Figure 6 This is the IV curve of the electrolytic cell. An electrolytic cell with the structure PBSCF0.45|BZCYYb|Ni-BZCYYb fuel electrode supported was prepared using Ni-BZCYYb as the fuel electrode, BZCYYb as the electrolyte, and PBSCF0.45 as the air electrode. Within the temperature range of 450-650℃, the electrolytic cell with PBSCF0.45 as the air electrode exhibited excellent current output, with current densities of -1.39 A cm⁻¹ at 650℃, 600℃, 550℃, 500℃, and 450℃ at 1.3V. -2 -0.978A cm -2 -0.699A cm -2 -0.552Acm -2 and -0.397Acm -2 .

[0062] 5. Comparative correlation test

[0063] Figure 7 Nyquist plots of a symmetric cell based on BZCYYb electrolyte and PBSCF-SP as electrode, tested at 650–450 °C. The figure shows the EIS plots of the PBSCF-SP air electrode material under open-circuit voltage testing conditions in a humid air atmosphere containing 5 vol.% water. At 650 °C, the ASR value of the symmetric cell based on the PBSCF-SP air electrode is 0.217 Ωcm. 2 .

[0064] Figure 8 Nyquist plots of a symmetric cell based on BZCYYb electrolyte and PBSCF-DP as electrode, tested at 650-450℃. The figure shows the EIS plots of the PBSCF-DP air electrode material under open-circuit voltage test conditions in a humid air atmosphere containing 5 vol.% water. At 650℃, the ASR value of the symmetric cell based on the PBSCF-DP air electrode is 0.225 Ωcm. 2 .

Claims

1. A proton ceramic battery air electrode material, characterized in that, Its nominal chemical formula is AA'B2O 6-δ The molecular formula is: PrBa 0.5 Sr 0.5 Co 2-x Fe x O 6-δ , where δ represents the oxygen vacancy content.

2. The proton ceramic battery air electrode material according to claim 1, characterized in that, x∈[0.43-0.47]。 3. The proton ceramic battery air electrode material according to claim 1, characterized in that, 0≤δ≤1.

4. The proton ceramic battery air electrode material according to claim 1, characterized in that, The nominal molecular formula is: PrBa 0.5 Sr 0.5 Co 1.55 Fe 0.45 O 6-δ .

5. The method for preparing the air electrode material according to claim 1, characterized in that, The process includes the following steps: prepared by sol-gel method according to stoichiometry.

6. The preparation method according to claim 5, characterized in that, Step 1, characterized by comprising the following steps: Step 1, according to PrBa 0.5 Sr 0.5 Co 2-x Fe x O 6-δ To prepare a stoichiometric solution for (PBSCFx), weigh out a certain mass of Pr(NO3)3·6H2O, Ba(NO3)2, Sr(NO3)2, Co(NO3)2·6H2O, and Fe(NO3)3·9H2O. Add an appropriate amount of deionized water and stir to dissolve, obtaining a clear solution. After complete dissolution, add ethylenediaminetetraacetic acid and citric acid monohydrate, then add ammonia dropwise until the pH of the solution is between 7 and 8. Under heating and stirring conditions, allow the water to evaporate to obtain a gel-like substance. Place the gel-like substance in an oven and calcine to obtain an air electrode material precursor. In step 2, place the precursor obtained in step 1 in a muffle furnace and calcine it in an air atmosphere to obtain the desired air electrode material.

7. The preparation method according to claim 6, characterized in that, The molar ratio of total metal ions: ethylenediaminetetraacetic acid: citric acid monohydrate: ammonia is 1:0.5-1.5:1-3:3-20.

8. The preparation method according to claim 6, characterized in that, The drying conditions are calcination at 140-180℃ for 5-10 hours.

9. The preparation method according to claim 6, characterized in that, The calcination conditions are: calcination at 950-1050℃ for 5-10 hours in air atmosphere, with a heating rate of 2-5℃ / min.

10. Use of the nanocomposite air electrode material of claim 1 in a proton ceramic battery.

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