An anode material, a preparation method and application thereof

Abstract

The application discloses an anode material and a preparation method and application thereof, and belongs to the field of solid oxide batteries. 2‑x Ba x Ni 1‑y N y O 4+δ and BaCO3, wherein 0 < x < 0.5, 0 < y < 0.6, 0 < delta < 0.5, M is one or more than two of Pr, Sm, La, Ce, Nd, Gd and Y, and N is one or more than two of Fe, Cu, Zn, Ti, Mn, Cr, Sc and V. The solid oxide electrolysis cell anode material does not contain Co element, has a small difference in thermal expansion coefficient with electrolyte material, and is good in material thermal stability. In addition, the anode material has excellent oxygen evolution reaction (ORR) activity, and the polarization resistance is not higher than 0.1 ohm cm 2 at 600 DEG C.

Description

Technical Field

[0001] This invention belongs to the field of solid oxide batteries, specifically relating to an anode material, its preparation method, and its application. Background Technology

[0002] Solid oxide electrolyzers (SOECs) are all-solid-state electrochemical devices that can couple renewable energy power and industrial waste heat to electrolyze water vapor to produce "green hydrogen." With system efficiencies exceeding 90%, they are considered the most efficient water electrolysis technology. Cost, performance, and stability are key indicators determining the practical application of this technology. Due to the sluggish oxygen evolution reaction kinetics, the anode material is a major factor limiting SOEC performance. Researchers have developed several highly active perovskite-structured anode materials such as (La,Sr)CoO3, (Sm,Sr)CoO3, and (Ba,Sr)(Co,Fe)O3. However, these high-performance anode materials generally contain Co, and the thermal reduction of Co (Co... 4+ →Co 3+ Co 3+ →Co 2+ This leads to a decrease in the thermal stability of the material, and the coefficient of thermal expansion of Co-containing materials is generally as high as 20*10. -6 K -1 The coefficient of thermal expansion is much higher than that of the electrolyte material used, making it easy for anode / electrolyte interface delamination to occur during heating and cooling cycles. Therefore, there is an urgent need in this field to develop an anode material that is free of Co and has excellent performance and good stability. Summary of the Invention

[0003] To address the problems existing in the prior art, this invention provides an anode material, its preparation method, and its applications. This anode material is free of Co and exhibits excellent electrochemical performance and stability.

[0004] This invention provides an anode material, the anode material being composed of M 2-x Ba x Ni 1-y N y O 4+δ The anode material is composed of BaCO3, wherein 0 < x ≤ 0.5, 0 ≤ y ≤ 0.6, 0 ≤ δ ≤ 0.5, M is one or more of Pr, Sm, La, Ce, Nd, Gd, and Y, and N is one or more of Fe, Cu, Zn, Ti, Mn, Cr, Sc, and V; in the anode material, the BaCO3 nanoparticles are distributed in M 2- x Ba x Ni 1-y N y O 4+δOn the surface of micron-sized particles, BaCO3 has a particle size of 5–50 nm, M 2-x Ba x Ni 1-y N y O 4+δ The particle size is 1–2 μm.

[0005] Furthermore, the M 2-x Ba x Ni 1-y N y O 4+δ In this context, M represents one or more of Pr, Sm, La, and Nd.

[0006] Furthermore, the M 2-x Ba x Ni 1-y N y O 4+δ In this context, N is one or more of Fe, Cu, Zn, Ti, Mn, and Sc.

[0007] Furthermore, the M 2-x Ba x Ni 1-y N y O 4+δ In the equation, 0.1≤x≤0.5, 0.1≤y≤0.5.

[0008] The present invention also provides a method for preparing an anode material, comprising the following steps: taking M 2-x Ba x Ni 1-y N y O 4+δ After being mixed with BaCO3, the mixture is sintered, and then electrolyzed in a N2-O2 mixed atmosphere at a voltage of 1.5–1.8V for 0.5–50 hours to obtain the anode material.

[0009] Furthermore, the volume content of O2 in the N2-O2 atmosphere is 0.05 to 0.2%.

[0010] Furthermore, the sintering temperature is 900–1000°C, and the time is 2–10 hours.

[0011] This invention also provides an application of an anode material, used in a solid oxide electrolytic cell for the electrolysis of water vapor to produce hydrogen or for the co-electrolysis of carbon dioxide and water vapor.

[0012] Furthermore, the anode material is suitable for use as the anode of solid oxide electrolytic cells of the flat plate type, tubular type, flat tube type, etc.

[0013] Beneficial effects of the present invention

[0014] (1) The anode material of the present invention, under a N2-O2 mixed atmosphere and an electrolysis voltage of 1.3-1.8V, forms micron-sized M particles after electrolysis operation for 0.5-50 hours. 2-x Ba x Ni 1-y N y O 4+δ The surface is distributed with BaCO3 nanoparticles. The nano-BaCO3 increases the density of active sites in the electrode and improves the performance of the anode. The anode structure can be obtained directly on the electrolytic cell operating device without additional preparation process, resulting in low preparation cost.

[0015] (2) The anode material of this invention does not contain Co, which improves the thermal reduction stability of the material. Its coefficient of thermal expansion is similar to that of the electrolyte material, thus improving the structural stability of the material in a water vapor atmosphere. M... 2-x Ba x Ni 1-y N y O 4+δ By appropriately doping the nitrogen element at the B site, the catalytic activity and electronic conductivity of the anode were improved. Appropriate doping of the nitrogen element at the A site increased the surface oxygen vacancy concentration, thereby increasing the oxygen ion and proton conductivity of the material. This appropriate doping of components simultaneously improved the electron, oxygen ion, and proton conductivity of the material, increased the number of reactive sites, and resulted in excellent electrochemical performance and stability. The anode material exhibits excellent oxygen evolution reaction (ORR) activity.

[0016] (3) The anode material of the present invention is applicable to the anodes of solid oxide electrolytic cells such as flat plate type, tubular type, and flat tube type, and has a wide range of applications. Attached Figure Description

[0017] Figure 1 Y prepared in Example 1 1.6 Ba 0.39 Ni 0.6 Fe 0.4 O 4.2 -BaCO3 anode SEM. Detailed Implementation

[0018] The following non-limiting embodiments are intended to enable those skilled in the art to more fully understand the present invention, but do not limit the invention in any way.

[0019] In all comparative examples and embodiments of the present invention, the cathode of the membrane electrode is NiO and BaZr. 0.1 Ce 0.7 Y 0.2 The O3 complex, with a mass ratio of 5:5, has a cathode thickness of approximately 0.6 mm and uses BaZr as the electrolyte. 0.1 Ce0.7 Y 0.2 O3, with a thickness of 15 micrometers.

[0020] Comparative Example 1

[0021] An anode material Y 1.6 Ba 0.4 Ni 0.6 Fe 0.4 O 4.2 The preparation process of the anode material is described as follows: 0.008 mol of Y2O3, 0.004 mol of BaCO3, 0.006 mol of NiO, and 0.004 mol of FeO oxide powders were mixed and ground with anhydrous ethanol in a ball mill jar for 24 h. After drying, the powder material was sintered at 1100 °C for 5 h in a high-temperature furnace to obtain a phase-forming powder material. The powder material was then ball-milled for 24 h, dried, and used as an anode for later use.

[0022] 0.5g of the above-mentioned anode powder was weighed and mixed with 0.5g of electrode binder (6% ethyl cellulose in terpineol) and ground to prepare an anode electrode slurry. The anode slurry was coated on the surface of the electrolyte in the fuel electrode-electrolyte dual-use electrode, and the electrode was fired at 950°C for 2 hours to obtain a complete membrane electrode. Electrochemical tests were then performed.

[0023] The TEC of the anode material is 10.5–12.6 × 10⁻⁶. -6 K -1 Electrochemical tests showed that the anodic polarization resistance was 0.38 Ω·cm at 600℃. 2 At 600℃ and 1.3V, the current density for electrolyzing water vapor is only 0.35 A·cm⁻¹. -2 .

[0024] Comparative Example 2

[0025] A type of Y 1.6 Ba 0.4 Ni 0.6 Fe 0.4 O 4.2 An anode composed of Y₂O₃ and BaCO₃ (molar ratio 1:0.01) was prepared. The anode preparation process is described as follows: 0.008 mol Y₂O₃, 0.004 mol BaCO₃, 0.006 mol NiO, and 0.004 mol FeO oxide powders were mixed and ground with anhydrous ethanol in a ball mill for 24 h. After drying, the mixture was sintered at 1100℃ for 5 h in a high-temperature furnace to obtain a phase-forming powder material. The powder material was then ball-milled for 24 h, dried, and set aside for later use. 0.5 mol Y₂O₃ was weighed... 1.6 Ba 0.4 Ni 0.6 Fe 0.4 O 4.2An anode electrode slurry was prepared by mixing and grinding 0.005 mol of purchased nano-BaCO3 (particle size 5-10 nm) and 0.5 g of electrode binder (6% ethyl cellulose in terpineol). The anode slurry was coated onto the surface of the electrolyte in a fuel electrode-electrolyte hybrid, and the electrode was fired at 950 °C for 2 hours to obtain a complete membrane electrode. Electrochemical tests were then performed.

[0026] Test results show that the anodic polarization resistance is 0.42 Ω·cm at 600℃. 2 At 600℃ and 1.3V, the current density for electrolyzing water vapor reaches 0.32 A·cm⁻¹. -2 .

[0027] Example 1

[0028] A type of Y 1.6 Ba 0.39 Ni 0.6 Fe 0.4 O 4.2 An anode material composed of Y₂O₃ and BaCO₃ (molar ratio 1:0.01) was prepared. The anode preparation process is described as follows: 0.008 mol of Y₂O₃, 0.004 mol of BaCO₃, 0.006 mol of NiO, and 0.004 mol of FeO oxide powders were mixed and ground with anhydrous ethanol in a ball mill for 24 hours. After drying, the mixture was sintered at 1100℃ for 5 hours in a high-temperature furnace to obtain a phase-forming powder material. This powder material was then ball-milled for 24 hours and dried for later use. 0.5 g of the above powder material was weighed and mixed with 0.5 g of electrode binder (6% ethyl cellulose in terpineol) and ground to prepare an anode electrode slurry. The anode slurry was coated onto the surface of the electrolyte in a fuel electrode-electrolyte hybrid, and then fired at 950℃ for 2 hours to obtain a complete membrane electrode.

[0029] The membrane electrode was electrolyzed at 1.5V for 1 hour. The cathode atmosphere was 50% vol H2-50% vol H2O, and the anode atmosphere was 10% vol O2-90% vol N2. The microstructure of the anode is shown in the attached figure. Figure 1 As shown in the SEM image, Y 1.6 Ba 0.39 Ni 0.6 Fe 0.4 O 4.2 The particle size is 1 micrometer, and the surface BaCO3 particles have a size of 20-30 nanometers.

[0030] After the membrane electrode is treated at 1.5V, Y 1.6 Ba 0.39 Ni 0.6 Fe 0.4 O 4.2 Ba segregation occurred, forming BaCO3, with the anode composition being Y.1.6 Ba 0.39 Ni 0.6 Fe 0.4 O 4.2 And BaCO3.

[0031] The TEC of the anode material is 10.5–12.6 × 10⁻⁶. -6 K -1 Electrochemical tests showed that the anodic polarization resistance was 0.23 Ω·cm at 600℃. 2 Electrochemical tests showed that at 600℃ and 1.3V, the current density for electrolyzing water vapor reached 0.78 A·cm⁻¹. -2 .

[0032] Example 2

[0033] A type of La 1.6 Ba 0.39 Ni 0.6 Fe 0.4 O 4.2 An anode composed of a composite of La₂O₃ and BaCO₃ (molar ratio 1:0.01) was prepared. The anode preparation process is described as follows: 0.008 mol of La₂O₃, 0.004 mol of BaCO₃, 0.006 mol of NiO, and 0.004 mol of FeO oxide powders were mixed and ground with anhydrous ethanol in a ball mill for 24 h. After drying, the powder was sintered at 1100 °C for 5 h in a high-temperature furnace to obtain a phase-forming powder material. The powder material was then ball-milled for 24 h and dried for later use. 0.5 g of the above powder material was weighed and mixed with 0.5 g of electrode binder (6% ethyl cellulose in terpineol) and ground to prepare an anode electrode slurry. The anode slurry was coated onto the surface of the electrolyte in the fuel electrode-electrolyte hybrid and fired at 950 °C for 2 hours to obtain a complete membrane electrode. The membrane electrode was electrolyzed at 1.8V for 5 hours, with a cathode atmosphere of 50% vol H2-50% vol H2O and an anode atmosphere of 5% vol O2-95% vol N2, and then electrochemical tests were performed.

[0034] Electrochemical test results show that the anodic polarization resistance is 0.18 Ω·cm at 600℃. 2 At 600℃ and 1.3V, the current density for electrolyzing water vapor reaches 0.98 A·cm⁻¹. -2 .

[0035] Example 3

[0036] A type of La 1.6 B 0.38 Ni 0.4 Fe 0.6 O 4.2An anode composed of a composite of La₂O₃ and BaCO₃ (molar ratio 1:0.02) was prepared. The anode preparation process is described as follows: 0.008 mol of La₂O₃, 0.004 mol of BaCO₃, 0.004 mol of NiO, and 0.006 mol of FeO oxide powders were mixed and ground with anhydrous ethanol in a ball mill for 24 h. After drying, the powder was sintered at 1100 °C for 5 h in a high-temperature furnace to obtain a phase-forming powder material. The powder material was then ball-milled for 24 h and dried for later use. 0.5 g of the above powder material was weighed and mixed with 0.5 g of electrode binder (6% ethyl cellulose in terpineol) and ground to prepare an anode electrode slurry. The anode slurry was coated onto the surface of the electrolyte in the fuel electrode-electrolyte hybrid and fired at 950 °C for 2 hours to obtain a complete membrane electrode.

[0037] The membrane electrode was electrolyzed at 1.8V for 5 hours, with a cathode atmosphere of 50% vol H2-50% vol H2O and an anode atmosphere of 5% vol O2-95% vol N2, and then electrochemical tests were performed.

[0038] Electrochemical test results show that the anodic polarization resistance is 0.25 Ω·cm at 600℃. 2 At 600℃ and 1.3V, the current density for electrolyzing water vapor reaches 0.68 A·cm⁻¹. -2 .

[0039] Example 4

[0040] A type of La 1.6 Ba 0.38 Ni 0.6 Mn 0.35 Sc 0.05 O 4.25 The anode was prepared by combining it with BaCO3 (molar ratio 1:0.02). The anode preparation process is described as follows: 0.008 mol of La2O3, 0.004 mol of BaCO3, 0.006 mol of NiO, 0.0035 mol of MnO, and 0.00025 mol of Sc2O3 oxide powders were mixed and ground with anhydrous ethanol in a ball mill for 24 h. After drying, the powder was sintered at 1100 °C for 5 h in a high-temperature furnace to obtain a phase-forming powder material. The powder material was then ball-milled for 24 h and dried for later use. 0.5 g of the above powder material was weighed and mixed with 0.5 g of electrode binder (6% ethyl cellulose in terpineol) and ground to prepare an anode electrode slurry. The anode slurry was coated on the surface of the electrolyte in the fuel electrode-electrolyte hybrid and fired at 1000 °C for 2 hours to obtain a complete membrane electrode. The membrane electrode was electrolyzed at 1.8V for 5 hours, with a cathode atmosphere of 50% vol H2-50% vol H2O and an anode atmosphere of 5% vol O2-95% vol N2, and then electrochemical tests were performed.

[0041] Electrochemical test results show that the anodic polarization resistance is 0.14 Ω·cm at 600℃. 2 At 600℃ and 1.3V, the current density for electrolyzing water vapor reaches 1.1 A·cm⁻¹. -2 .

[0042] Example 5

[0043] A type of La 1.6 Ba 0.38 Ni 0.6 Mn 0.35 Sc 0.05 O 4.25 An anode composed of a composite of La₂O₃ and BaCO₃ (molar ratio 1:0.02) was prepared. The anode preparation process is described as follows: 0.008 mol of La₂O₃, 0.004 mol of BaCO₃, 0.006 mol of NiO, 0.0035 mol of MnO, and 0.00025 mol of Sc₂O₃ oxide powders were mixed and ground with anhydrous ethanol in a ball mill for 24 h. After drying, the powder was sintered at 1100 °C for 5 h in a high-temperature furnace to obtain a phase-forming powder material. The powder material was then ball-milled for 24 h and dried for later use. 0.5 g of the above powder material was weighed and mixed with 0.5 g of electrode binder (6% ethyl cellulose in terpineol) and ground to prepare an anode electrode slurry. The anode slurry was coated onto the surface of the electrolyte in the fuel electrode-electrolyte hybrid and fired at 1000 °C for 2 hours to obtain a complete membrane electrode. The membrane electrode was electrolyzed at 1.1V for 5 hours, with a cathode atmosphere of 50% vol H2-50% vol H2O and an anode atmosphere of 5% vol O2-95% vol N2, and then electrochemical tests were performed.

[0044] Electrochemical test results show that the anodic polarization resistance is 0.24 Ω·cm at 600℃. 2 At 600℃ and 1.3V, the current density for electrolyzing water vapor reaches 0.82 A·cm⁻¹. -2 .

[0045] Example 6

[0046] A type of Sm 1.6 Ba 0.37 Ni 0.6 Ti 0.4 O 4.25An anode composed of Sm₂O₃ and BaCO₃ (molar ratio 1:0.03) was prepared. The anode preparation process is described as follows: 0.008 mol of Sm₂O₃, 0.004 mol of BaCO₃, 0.006 mol of NiO, and 0.0004 mol of TiO₂ oxide powder were mixed and ground with anhydrous ethanol in a ball mill for 24 h. After drying, the powder was sintered at 1100 °C for 5 h in a high-temperature furnace to obtain a phase-forming powder material. The powder material was then ball-milled for 24 h, dried, and used as the anode. 0.5 g of the above powder material was weighed and mixed with 0.5 g of electrode binder (6% ethyl cellulose in terpineol) and ground to prepare an anode electrode slurry. The anode slurry was coated on the surface of the electrolyte in the fuel electrode-electrolyte hybrid and fired at 1000 °C for 2 hours to obtain a complete membrane electrode. The membrane electrode was electrolyzed at 1.5V for 50 hours, with a cathode atmosphere of 50% vol H2-50% vol H2O and an anode atmosphere of 5% vol O2-95% vol N2, and then electrochemical tests were performed.

[0047] Electrochemical test results show that the anodic polarization resistance is 0.12 Ω·cm at 600℃. 2 At 600℃ and 1.3V, the current density for electrolyzing water vapor reaches 1.15 A·cm⁻¹. -2 .

Claims

1. A method for preparing an anode material, characterized in that: Includes the following steps: M2 will be formed x Ba x Ni1 y N y O 4+δ The raw materials are mixed with BaCO3 in a certain proportion, sintered, and then subjected to N2. In an O2 mixed atmosphere, the electrolysis voltage is 1.5 to 1.8 V, and the voltage is operated for 0.5 to 50 hours to obtain the anode material; The anode material is made of M2 x Ba x Ni1 y N y O 4+δ The anode material is composed of BaCO3, wherein 0 < x ≤ 0.5, 0 ≤ y ≤ 0.6, 0 ≤ δ ≤ 0.5, M is one or more of Pr, Sm, La, Ce, Nd, Gd, and Y, and N is one or more of Fe, Cu, Zn, Ti, Mn, Cr, Sc, and V; in the anode material, the BaCO3 nanoparticles are distributed in M2. x Ba x Ni1 y N y O 4+δ On the surface of micron-sized particles, BaCO3 has a particle size of 5–50 nm, M2 x Ba x Ni1 y N y O 4+δ The particle size is 1–2 μm.

2. The method for preparing the anode material according to claim 1, characterized in that: The M2 x Ba x Ni1 y N y O 4+δ In this context, M represents one or more of Pr, Sm, La, and Nd.

3. The method for preparing the anode material according to claim 1, characterized in that: The M2 x Ba x Ni1 y N y O 4+δ In this context, N is one or more of Fe, Cu, Zn, Ti, Mn, and Sc.

4. The method for preparing the anode material according to claim 1, characterized in that: The M2 x Ba x Ni1 y N y O 4+δ In the equation, 0.1≤x≤0.5, 0.1≤y≤0.

5.

5. The method for preparing the anode material according to claim 1, characterized in that: The N2 The volume content of O2 in the O2 atmosphere is 0.05 to 0.2%.

6. The method for preparing the anode material according to claim 1, characterized in that: The sintering temperature is 900–1000℃, and the time is 2–10 hours.

7. Claim 1 The application of the anode material prepared by any one of the preparation methods described in any 6, characterized in that: It is used in solid oxide electrolysis cells for hydrogen production by electrolyzing water vapor or for co-electrolysis of carbon dioxide and water vapor.

8. The application according to claim 7, characterized in that: The anode material is suitable for use as an anode in flat plate, tubular, or flat tube type solid oxide electrolytic cells.

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