WO2024087266A1 - Bismuth ferrite-doped perovskite material, and preparation method therefor and use thereof - Google Patents

Bismuth ferrite-doped perovskite material, and preparation method therefor and use thereof Download PDF

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WO2024087266A1
WO2024087266A1 PCT/CN2022/131879 CN2022131879W WO2024087266A1 WO 2024087266 A1 WO2024087266 A1 WO 2024087266A1 CN 2022131879 W CN2022131879 W CN 2022131879W WO 2024087266 A1 WO2024087266 A1 WO 2024087266A1
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doped
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perovskite material
prbaco
prbaco2o5
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胡丁月
刘明
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浙江大学杭州国际科创中心
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/50—Fuel cells

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  • the present invention belongs to the technical field of perovskite materials, and in particular relates to a bismuth ferrite-doped perovskite material and a preparation method and application thereof.
  • Solid oxide fuel cell is a device that directly converts chemical energy in raw materials (hydrogen, oxygen, etc.) into electrical energy at an operating temperature of 500-1000°C. It has the advantages of high power generation efficiency, low environmental pollution, and easy construction. It can provide energy for large vehicles, ships, and distributed power stations, and is an important part of the hydrogen energy economy industry chain.
  • the existing oxygen ion conductor solid oxide fuel cell is a sandwich structure composed of two porous electrodes (cathode and anode) and a dense electrolyte.
  • the electrolyte in the O-SOFC system mostly uses acceptor-doped ZrO2 , CeO2 and LaGaO3 dense ceramics, the anode is a support body mechanically mixed with nickel oxide and electrolyte ceramic powder in a certain proportion, and the cathode is perovskite ceramic.
  • PrBaCo 2 O 5+ ⁇ is a typical double perovskite structure oxide, whose A-site elements are highly ordered. Pr 3+ and Ba 2+ occupy the A-site lattice in an orderly manner, forming layers alternately along the c-axis. The atomic layers are stacked in the order of [CoO 2 ][BaO][CoO 2 ][PrO ⁇ ]..., and the oxygen vacancies are completely concentrated in the rare earth ion Pr 3+ layer.
  • the special distribution of oxygen vacancies in the layered perovskite provides a channel for the rapid migration of oxygen ions in the material, which can greatly promote the diffusion of oxygen ions, and it can also provide more surface active sites for the reaction of oxygen molecules.
  • PBCO has a large thermal expansion coefficient (TEC).
  • TEC thermal expansion coefficient
  • the average thermal expansion coefficient of PBCO is 20* 10-6 ⁇ 26* 10-6 k -1 , which is about twice that of common electrolyte materials (10* 10-6 ⁇ 12* 10-6 k -1 ).
  • Such a huge TEC mismatch strain will inevitably cause the electrode to fall off from the electrolyte, seriously affecting the thermal cycle stability of the battery. Therefore, reducing the TEC of PBCO and adjusting the TEC matching have become one of the driving forces for the widespread application of PBCO.
  • the present invention provides a BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ -based perovskite material.
  • the introduction of BiFeO 3 reduces the concentration of Co element in PrBaCo 2 O 5+ ⁇ perovskite and reduces its thermal expansion coefficient, while also increasing the oxygen vacancy concentration in PrBaCo 2 O 5+ ⁇ perovskite.
  • a battery prepared by further using the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material has the advantages of small polarization resistance and high output power.
  • a BiFeO 3 doped PrBaCo 2 O 5+ ⁇ - based perovskite material has a general chemical formula of PrBaCo 2 O 5+ ⁇ -xBiFeO 3 , 0 ⁇ x ⁇ 0.15, and ⁇ is the number of oxygen defects.
  • the value range of x is 0.05 ⁇ x ⁇ 0.1.
  • x is within the above range, the thermal expansion coefficient and electrochemical performance of the perovskite material are better.
  • the BiFeO3 -doped PrBaCo2O5 + ⁇ - based perovskite material comprises Bi3+ and Fe3 + which replace the A position and B position of PrBaCo2O5 + ⁇ respectively, and BiFeO3 is introduced into the PrBaCo2O5 + ⁇ perovskite to form a composite structure of two perovskite phases;
  • Bi3 + can reduce the basicity of the original Ba2 + ions at the A position, and Bi3 + has high polarizability and multiple oxidation coordination chemical properties, and the lower Bi-O bond strength can make the perovskite oxide have a higher oxygen mobility;
  • Fe ions can be doped into the B position of PrBaCo2O5 + ⁇ , and the ionic radius of Fe3 + is larger than that of Co3 + , and doping can make the tolerance factor of PBCO close to 1, that is, the lattice distortion is reduced and the symmetry of the crystal structure is improved.
  • BiFeO 3 reduces the concentration of Co element in PrBaCo 2 O 5+ ⁇ perovskite and reduces its thermal expansion coefficient. It also increases the oxygen vacancy concentration in PrBaCo 2 O 5+ ⁇ perovskite and improves the oxygen transport performance of the material at the battery operating temperature.
  • the present invention also provides a method for preparing the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material, comprising the following steps:
  • the precursor powder is ball-milled, dried, pressed into tablets, and further sintered to prepare the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material.
  • the praseodymium source is Pr 6 O 11
  • the barium source is BaCO 3
  • the cobalt source is Co 3 O 4
  • the iron source is Fe 2 O 3
  • the bismuth source is Bi 2 O 3 .
  • the praseodymium source, barium source, cobalt source, iron source and bismuth source are ball-milled and mixed and then dried to be fully mixed, and the ball-milling time is 10-14 hours.
  • the parameters of high temperature calcination are: air atmosphere, 800-1000° C., 10-14 h.
  • the ball milling parameter is 10-14h.
  • isopropyl alcohol is selected as the ball milling dispersant.
  • the sintering parameters are: air atmosphere, 1000-1100° C., 10-14 h.
  • the method of the present invention adopts two-step sintering.
  • the first step of sintering is to generate a pre-product and reduce the chemical potential energy required for the first step of sintering.
  • the second step of sintering is to obtain a dense ceramic material.
  • the present invention also provides the application of the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material in a solid oxide fuel cell.
  • the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material is used as a cathode material to prepare a solid oxide fuel cell.
  • the single cell prepared using the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material has a non-ohmic resistance of 0.19 ⁇ cm 2 at 600°C and a maximum power density of 592 ⁇ 64mW ⁇ cm -2 .
  • the present invention has the following beneficial effects:
  • the preparation method of the BiFeO3- doped PrBaCo2O5 + ⁇ - based perovskite material provided by the present invention is simple, has low production cost, is environmentally friendly, is suitable for large-scale preparation, reduces 1-2 steps compared with the sol-gel method, and no waste liquid contaminated by any heavy metals is generated during the reaction process.
  • the prepared BiFeO3- doped PrBaCo2O5 + ⁇ - based perovskite material has a simple crystal structure and high purity, and no impurities or other phases except perovskite are generated during the reaction process.
  • BiFeO 3 reduces the concentration of Co element in PrBaCo 2 O 5+ ⁇ perovskite and its thermal expansion coefficient. It also increases the oxygen vacancy concentration in PrBaCo 2 O 5+ ⁇ perovskite and improves the oxygen transport performance of the material at the battery operating temperature.
  • the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material provided by the present invention has a moderate thermal expansion coefficient of 18.04*10 -6 k -1 , which is lower than that of undoped modified PrBaCo 2 O 5+ ⁇ , and is easy to match with the electrolyte material Sm 0.20 Ce 0.80 O 1.95.
  • the cathode coating of the solid oxide fuel cell is not easy to fall off at the operating temperature (>500°C), and the electrochemical performance is excellent, the polarization resistance is small, and the output power is high.
  • FIG1 is an X-ray diffraction diagram of PrBaCo 2 O 5+ ⁇ -0.05BiFeO 3 prepared in Example 1, PrBaCo 2 O 5+ ⁇ -0.1BiFeO 3 prepared in Example 2, and PrBaCo 2 O 5+ ⁇ .
  • FIG. 2 is a scanning electron microscope image of PrBaCo 2 O 5+ ⁇ -0.1BiFeO 3 prepared in Example 2.
  • FIG3 is a graph showing the electrochemical performance of an oxygen ion conductor high temperature solid fuel cell prepared from PrBaCo2O5 + ⁇ - 0.1BiFeO3 prepared in Example 2, wherein A is the ohmic impedance graph of a single cell at 500-650°C, and B is the output power curve of a single cell at 500-650°C.
  • the preparation method of PrBaCo 2 O 5+ ⁇ -0.05BiFeO 3 (PBCO-0.05BFO) in this embodiment specifically includes the following steps:
  • the precursor powder obtained in step (1) is ball-milled with 15 mL of isopropanol and 30 g of zirconium oxide balls in a ball mill for 12 hours, and the turbid mixed solution obtained by ball milling is dried in an oven at 100° C. for 3 hours to obtain a dry powder; the dried powder is then pressed into a disc with a diameter of 10 mm and a thickness of 1 mm using a uniaxial tablet press, and then sintered in an air atmosphere at 1000° C. for 12 hours, with the heating and cooling rates during the sintering process being 5° C./min, to obtain the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material.
  • the preparation method of PrBaCo 2 O 5+ ⁇ -0.1BiFeO 3 (PBCO-0.1BFO) in this embodiment specifically includes the following steps:
  • the precursor powder obtained in step (1) is ball-milled with 15 mL of isopropanol and 30 g of zirconium oxide balls in a ball mill for 12 hours, and the turbid mixed solution obtained by ball milling is dried in an oven at 100° C. for 3 hours to obtain a dry powder; the dried powder is then pressed into a disc with a diameter of 10 mm and a thickness of 1 mm using a uniaxial tablet press, and then sintered in an air atmosphere at 1100° C. for 12 hours, with the heating and cooling rates during the sintering process being 5° C./min, to obtain the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material.
  • the preparation method of PrBaCo 2 O 5+ ⁇ -0.1BiFeO 3 (PBCO-0.1BFO) in this embodiment specifically includes the following steps:
  • the precursor powder obtained in step (1) is ball-milled with 15 mL of isopropanol and 30 g of zirconium oxide balls in a ball mill for 14 hours, and the turbid mixed solution obtained by ball milling is dried in an oven at 100° C. for 3 hours to obtain a dry powder; the dried powder is then pressed into a disc with a diameter of 10 mm and a thickness of 1 mm using a uniaxial tablet press, and then sintered in an air atmosphere at 1100° C. for 14 hours, with the heating and cooling rates during the sintering process being 5° C./min, to obtain the BiFeO 3 -doped PrBaCo 2 O 5+ ⁇ - based perovskite material.
  • Figure 1 is the X-ray diffraction diagram of PrBaCo 2 O 5+ ⁇ -0.05BiFeO 3 prepared in Example 1, PrBaCo 2 O 5+ ⁇ -0.1BiFeO 3 and PrBaCo 2 O 5+ ⁇ prepared in Example 2.
  • BiFeO 3 doping the crystal structure does not change significantly compared with undoped PrBaCo 2 O 5+ ⁇ , and both are orthorhombic double perovskite structures (space point group is Pmmm).
  • space point group is Pmmm.
  • FIG2 is a scanning electron microscope image of PrBaCo 2 O 5+ ⁇ -0.1BiFeO 3 prepared in Example 2.
  • the SEM result shows that the PrBaCo 2 O 5+ ⁇ -0.1BiFeO 3 sample forms uniform grains after the second sintering, and the average grain size is 1 ⁇ m.
  • An anode precursor disc was prepared using Sm 0.20 Ce 0.80 O 1.95 (SDC), 6 g NiO powder and 1.5 g potato starch as raw materials; a blank electrolyte solution was prepared by mixing methyl ethyl ketone, ethanol, triethanolamine, polyethylene oxide polypropylene oxide monobutyl ether, toluyl butyl phthalate and polyvinyl butyral to prepare an electrolyte-anode single cell substrate;
  • the BiFeO3- doped PrBaCo2O5 + ⁇ - based perovskite materials prepared in Example 1 and Example 2 were fully stirred and mixed with the cathode slurry binder V600 to obtain two cathode slurries.
  • the two cathode slurries were uniformly coated on the surface of the electrolyte-anode single cell base electrolyte layer, dried at room temperature, and placed in a muffle furnace for calcination at 950°C for 1 hour.
  • the heating and cooling rates during the calcination process were 1.8°C/min and 3°C/min, respectively.
  • the single cell 1 to be tested and the single cell 2 to be tested were obtained, respectively.
  • the anode surface of the single cell to be tested was encapsulated in a solid fuel cell test system, the temperature was raised to 500-650°C, hydrogen was passed through the anode (flow rate 200mL/min), and dry air was passed through the cathode (flow rate 100mL/min), to complete the test of the non-ohmic resistance and maximum output power of the single cell;
  • the test results of the single cell 2 prepared from PrBaCo2O5 + ⁇ - 0.1BiFeO3 in Example 2 are shown in A and B in Figure 3, respectively, and the non-ohmic impedance values measured at 650°C, 600°C, 550°C, and 500°C are 0.146 ⁇ cm2 , 0.205 ⁇ cm2 , 0.240 ⁇ cm2 , and 0.453 ⁇ cm2, respectively, and the peak output powers measured are 868mW ⁇ cm -2 , 677mW ⁇ cm -2 , 428mW ⁇ cm- 2 , and 226mW ⁇ cm -2

Abstract

A bismuth ferrite-doped perovskite material, and a preparation method therefor and a use thereof, relating to the technical field of perovskite materials. The chemical general formula of a BiFeO3-doped PrBaCo2O5+ δ-based perovskite material is PrBaCo2O5+ δ-xBiFeO3, wherein 0<x≤0.15, and δ is the number of oxygen defects. The preparation method comprises: weighing a praseodymium source, a barium source, a cobalt source, an iron source, and a bismuth source according to a stoichiometric ratio in the general formula, fully mixing same, calcining at a high temperature to obtain precursor powder, performing ball milling and drying, then tableting, and sintering again to prepare a BiFeO3-doped PrBaCo2O5+ δ-based perovskite material. The addition of BiFeO3 reduces the concentration of Co in PrBaCo2O5+ δ perovskite, reduces the thermal expansion coefficient thereof, also increases the oxygen vacancy concentration in the PrBaCo2O5+ δ perovskite, and improves the oxygen transmission performance of the material at the operating temperature of batteries.

Description

一种铁酸铋掺杂的钙钛矿材料及其制备方法和应用A bismuth ferrite-doped perovskite material and its preparation method and application 技术领域Technical Field
本发明属于钙钛矿材料技术领域，具体涉及一种铁酸铋掺杂的钙钛矿材料及其制备方法和应用。The present invention belongs to the technical field of perovskite materials, and in particular relates to a bismuth ferrite-doped perovskite material and a preparation method and application thereof.
背景技术Background technique
固态氧化物燃料电池(SOFC)是一种在500-1000℃的工作温度下把原料(氢气，氧气等)中的化学能直接转化为电能的装置，具有发电效率高、环境污染小、易于建设等优点，可为大型车辆、舰艇以及分布式电站供能，是氢能经济产业链中重要的组成部分。Solid oxide fuel cell (SOFC) is a device that directly converts chemical energy in raw materials (hydrogen, oxygen, etc.) into electrical energy at an operating temperature of 500-1000°C. It has the advantages of high power generation efficiency, low environmental pollution, and easy construction. It can provide energy for large vehicles, ships, and distributed power stations, and is an important part of the hydrogen energy economy industry chain.
现有的氧离子导体固体氧化物燃料电池(O-SOFC)是由两个多孔电极(阴极和阳极)与致密的电解质结合成的三明治结构，O-SOFC系统中电解质多采用受体掺杂的ZrO 2、CeO 2以及LaGaO 3致密陶瓷，阳极为氧化镍和电解质陶瓷粉末以一定比例机械混合的支撑体，阴极为钙钛矿陶瓷。 The existing oxygen ion conductor solid oxide fuel cell (O-SOFC) is a sandwich structure composed of two porous electrodes (cathode and anode) and a dense electrolyte. The electrolyte in the O-SOFC system mostly uses acceptor-doped ZrO2 , CeO2 and LaGaO3 dense ceramics, the anode is a support body mechanically mixed with nickel oxide and electrolyte ceramic powder in a certain proportion, and the cathode is perovskite ceramic.
PrBaCo 2O 5+δ(PBCO)是一种典型双钙钛矿结构氧化物，其A位元素是高度有序化的，Pr 3+和Ba 2+有序化地占据A位晶格，沿c轴交替形成层，原子层按[CoO 2][BaO][CoO 2][PrO δ]…的顺序堆叠，氧空位完全集中在稀土离子Pr 3+层。与单个A位无序的钙钛矿材料相比，分层钙钛矿中氧空位的特殊分布为氧离子在材料中的快速迁移提供了通道，可以极大地促进氧离子的扩散，且它还可以为氧分子的反应提供更多的表面活性位点。 PrBaCo 2 O 5+δ (PBCO) is a typical double perovskite structure oxide, whose A-site elements are highly ordered. Pr 3+ and Ba 2+ occupy the A-site lattice in an orderly manner, forming layers alternately along the c-axis. The atomic layers are stacked in the order of [CoO 2 ][BaO][CoO 2 ][PrO δ ]…, and the oxygen vacancies are completely concentrated in the rare earth ion Pr 3+ layer. Compared with the single A-site disordered perovskite material, the special distribution of oxygen vacancies in the layered perovskite provides a channel for the rapid migration of oxygen ions in the material, which can greatly promote the diffusion of oxygen ions, and it can also provide more surface active sites for the reaction of oxygen molecules.
但是PBCO又具有较大的热膨胀系数(TEC)，在室温至1000℃的范围内，PBCO的平均热膨胀系数为20*10 -6～26*10 -6k -1,，约为常见电解质材料(10*10 -6～12*10 -6k -1)的2倍，如此巨大的TEC失配应变必然导致电极从电解液中脱落，严重影响电池热循环稳定性。因此，降低PBCO的TEC，调整TEC匹配成为推动PBCO广泛应用的动力之一。 However, PBCO has a large thermal expansion coefficient (TEC). In the range of room temperature to 1000℃, the average thermal expansion coefficient of PBCO is 20* 10-6 ~ 26* 10-6 k -1 , which is about twice that of common electrolyte materials (10* 10-6 ~ 12* 10-6 k -1 ). Such a huge TEC mismatch strain will inevitably cause the electrode to fall off from the electrolyte, seriously affecting the thermal cycle stability of the battery. Therefore, reducing the TEC of PBCO and adjusting the TEC matching have become one of the driving forces for the widespread application of PBCO.
现有技术中，有研究表明微量Mo元素掺杂可以有效地降低PrBaCo 2O 5+δ的热膨胀系数，提高其电化学性能(杨剑等.Mo掺杂PrBaCo 2O 5+δ固体氧化物燃料电池阴极材料的性能研究[J].燕山大学学报,2020,44(5):6.)，另外还有很多的其他大量工作尝试分别在A位和B位对PBCO进行掺杂改性，力图调控PBCO的物理及电化学性能，虽然已经取得了一定的成果，但在PBCO的A位和B位同时掺杂，特别是在A位掺杂Bi 3+还未见发表。 In the prior art, studies have shown that trace Mo doping can effectively reduce the thermal expansion coefficient of PrBaCo 2 O 5+δ and improve its electrochemical performance (Yang Jian et al. Performance study of Mo-doped PrBaCo 2 O 5+δ solid oxide fuel cell cathode materials [J]. Journal of Yanshan University, 2020, 44(5): 6.). In addition, there are many other large-scale works attempting to dope and modify PBCO at the A and B positions, respectively, in an effort to regulate the physical and electrochemical properties of PBCO. Although certain results have been achieved, the simultaneous doping of PBCO at the A and B positions, especially the doping of Bi 3+ at the A position, has not been published.
发明内容Summary of the invention
为了解决现有技术中PrBaCo 2O 5+δ材料热膨胀系数较高影响电池电化学性能的问题，本发明提供了一种BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料，BiFeO 3的引入降低了PrBaCo 2O 5+δ钙钛矿中Co元素的浓度，降低了其热膨胀系数，同时也增加了PrBaCo 2O 5+δ钙钛矿中的氧空位浓度，进一步利用该BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料制备得到的电池具有极化电阻小、输出功率高的优点。 In order to solve the problem in the prior art that the high thermal expansion coefficient of PrBaCo 2 O 5+δ materials affects the electrochemical performance of batteries, the present invention provides a BiFeO 3 -doped PrBaCo 2 O 5+δ -based perovskite material. The introduction of BiFeO 3 reduces the concentration of Co element in PrBaCo 2 O 5+δ perovskite and reduces its thermal expansion coefficient, while also increasing the oxygen vacancy concentration in PrBaCo 2 O 5+δ perovskite. A battery prepared by further using the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material has the advantages of small polarization resistance and high output power.
具体采用的技术方案如下：The specific technical solutions adopted are as follows:
一种BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料，化学通式为PrBaCo 2O 5+δ-xBiFeO 3，0＜x≤0.15，δ为氧缺陷数。 A BiFeO 3 doped PrBaCo 2 O 5+δ- based perovskite material has a general chemical formula of PrBaCo 2 O 5+δ -xBiFeO 3 , 0＜x≤0.15, and δ is the number of oxygen defects.
优选的，x的取值范围为0.05≤x≤0.1，当x在上述范围下，该钙钛矿材料的热膨胀系数、电化学性能更好。Preferably, the value range of x is 0.05≤x≤0.1. When x is within the above range, the thermal expansion coefficient and electrochemical performance of the perovskite material are better.
本发明提供的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料，Bi 3+和Fe 3+分别同时取代了PrBaCo 2O 5+δ的A位和B位，将BiFeO 3引入到PrBaCo 2O 5+δ钙钛矿中，形成了两种钙钛矿相复合的结构；Bi 3+能够降低A位上原有Ba 2+离子的碱度，且Bi 3+具有高极化性和多种氧化配位化学特性，较低的Bi-O键强度可使钙钛矿氧化物具有较高的氧迁移率；Fe离子可以掺杂到PrBaCo 2O 5+δ的B位，Fe 3+的离子半径比Co 3+大，掺杂可以使PBCO的容差因子接近1，即减少了晶格畸变，改善了晶体结构的对称性。 The BiFeO3 -doped PrBaCo2O5 +δ- based perovskite material provided by the present invention comprises Bi3+ and Fe3 + which replace the A position and B position of PrBaCo2O5 +δ respectively, and BiFeO3 is introduced into the PrBaCo2O5 +δ perovskite to form a composite structure of two perovskite phases; Bi3 + can reduce the basicity of the original Ba2 + ions at the A position, and Bi3 + has high polarizability and multiple oxidation coordination chemical properties, and the lower Bi-O bond strength can make the perovskite oxide have a higher oxygen mobility; Fe ions can be doped into the B position of PrBaCo2O5 +δ , and the ionic radius of Fe3 + is larger than that of Co3 + , and doping can make the tolerance factor of PBCO close to 1, that is, the lattice distortion is reduced and the symmetry of the crystal structure is improved.
BiFeO 3的加入降低了PrBaCo 2O 5+δ钙钛矿中Co元素的浓度，降低了其热膨胀系数，同时也增加了PrBaCo 2O 5+δ钙钛矿中的氧空位浓度，改善了在电池运行温度下材料的氧传输性能。 The addition of BiFeO 3 reduces the concentration of Co element in PrBaCo 2 O 5+δ perovskite and reduces its thermal expansion coefficient. It also increases the oxygen vacancy concentration in PrBaCo 2 O 5+δ perovskite and improves the oxygen transport performance of the material at the battery operating temperature.
本发明还提供了所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料的制备方法，包括以下步骤： The present invention also provides a method for preparing the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material, comprising the following steps:
(1)按照通式PrBaCo 2O 5+δ-xBiFeO 3，称取化学计量比的镨源、钡源、钴源、铁源和铋源充分混合，高温煅烧后得到前驱体粉末； (1) According to the general formula PrBaCo 2 O 5+δ -xBiFeO 3 , weigh praseodymium source, barium source, cobalt source, iron source and bismuth source in a stoichiometric ratio, mix them thoroughly, and calcine them at a high temperature to obtain a precursor powder;
(2)将前驱体粉末球磨、干燥后压片并进一步烧结，制备得到所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料。 (2) The precursor powder is ball-milled, dried, pressed into tablets, and further sintered to prepare the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material.
优选的，所述的镨源为Pr 6O 11，所述的钡源为BaCO 3，所述的钴源为Co 3O 4，所述的铁源为Fe 2O 3，所述的铋源为Bi 2O 3。 Preferably, the praseodymium source is Pr 6 O 11 , the barium source is BaCO 3 , the cobalt source is Co 3 O 4 , the iron source is Fe 2 O 3 , and the bismuth source is Bi 2 O 3 .
优选的，步骤(1)中，将镨源、钡源、钴源、铁源和铋源球磨混合后干燥以充分混匀，球磨时间为10-14h。Preferably, in step (1), the praseodymium source, barium source, cobalt source, iron source and bismuth source are ball-milled and mixed and then dried to be fully mixed, and the ball-milling time is 10-14 hours.
优选的，步骤(1)中，高温煅烧的参数为：空气气氛，800-1000℃，10-14h。Preferably, in step (1), the parameters of high temperature calcination are: air atmosphere, 800-1000° C., 10-14 h.
优选的，步骤(2)中，为了将高温煅烧后的样品充分混匀且进一步烧结获得成分均匀的陶瓷产物，球磨参数为10-14h。Preferably, in step (2), in order to fully mix the sample after high-temperature calcination and further sinter it to obtain a ceramic product with uniform composition, the ball milling parameter is 10-14h.
进一步优选的，步骤(1)和步骤(2)的球磨过程中，选用异丙醇作为球磨分散剂。Further preferably, during the ball milling process of step (1) and step (2), isopropyl alcohol is selected as the ball milling dispersant.
优选的，步骤(2)中，烧结的参数为：空气气氛，1000-1100℃，10-14h。Preferably, in step (2), the sintering parameters are: air atmosphere, 1000-1100° C., 10-14 h.
本发明方法采用两步烧结，第一步烧结是为了生成预产物，降低第一步烧结所需的化学势能，第二步烧结是为了获得致密的陶瓷材料。The method of the present invention adopts two-step sintering. The first step of sintering is to generate a pre-product and reduce the chemical potential energy required for the first step of sintering. The second step of sintering is to obtain a dense ceramic material.
本发明还提供了所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料在固态氧化物燃料电池中的应用。 The present invention also provides the application of the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material in a solid oxide fuel cell.
具体的，将所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料作为阴极 材料用于制备固态氧化物燃料电池，利用该BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料制得的单电池，600℃非欧姆电阻为0.19Ω·cm 2，最大功率密度为592±64mW·cm -2。 Specifically, the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material is used as a cathode material to prepare a solid oxide fuel cell. The single cell prepared using the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material has a non-ohmic resistance of 0.19Ω·cm 2 at 600°C and a maximum power density of 592±64mW·cm -2 .
与现有技术相比，本发明的有益效果在于：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明提供的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料的制备方法简单、生产成本低、环境友好，适用于大规模制备，较溶胶凝胶法步骤减少1-2步，反应过程中无任何重金属污染的废液产生，且制备得到的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料晶体结构简单，纯度高，反应过程中无杂质或除钙钛矿外其他物相产生。 (1) The preparation method of the BiFeO3- doped PrBaCo2O5 +δ- based perovskite material provided by the present invention is simple, has low production cost, is environmentally friendly, is suitable for large-scale preparation, reduces 1-2 steps compared with the sol-gel method, and no waste liquid contaminated by any heavy metals is generated during the reaction process. The prepared BiFeO3- doped PrBaCo2O5 +δ- based perovskite material has a simple crystal structure and high purity, and no impurities or other phases except perovskite are generated during the reaction process.
(2)BiFeO 3的加入降低了PrBaCo 2O 5+δ钙钛矿中Co元素的浓度，降低了其热膨胀系数，同时也增加了PrBaCo 2O 5+δ钙钛矿中的氧空位浓度，改善了在电池运行温度下材料的氧传输性能。 (2) The addition of BiFeO 3 reduces the concentration of Co element in PrBaCo 2 O 5+δ perovskite and its thermal expansion coefficient. It also increases the oxygen vacancy concentration in PrBaCo 2 O 5+δ perovskite and improves the oxygen transport performance of the material at the battery operating temperature.
(3)本发明提供的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料热膨胀系数适中，为18.04*10 -6k -1，低于未掺杂改性的PrBaCo 2O 5+δ，便于与电解质材料Sm 0.20Ce 0.80O 1.95相配合，组成在固体氧化物燃料电池在运行温度(>500℃)阴极涂料不易脱落，电化学性能优异、极化电阻小、输出功率高。 (3) The BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material provided by the present invention has a moderate thermal expansion coefficient of 18.04*10 -6 k -1 , which is lower than that of undoped modified PrBaCo 2 O 5+δ , and is easy to match with the electrolyte material Sm 0.20 Ce 0.80 O 1.95. The cathode coating of the solid oxide fuel cell is not easy to fall off at the operating temperature (>500°C), and the electrochemical performance is excellent, the polarization resistance is small, and the output power is high.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1中制备的PrBaCo 2O 5+δ-0.05BiFeO 3、实施例2中制备的PrBaCo 2O 5+δ-0.1BiFeO 3和PrBaCo 2O 5+δ的X射线衍射图。 FIG1 is an X-ray diffraction diagram of PrBaCo 2 O 5+δ -0.05BiFeO 3 prepared in Example 1, PrBaCo 2 O 5+δ -0.1BiFeO 3 prepared in Example 2, and PrBaCo 2 O 5+δ .
图2为实施例2制备的PrBaCo 2O 5+δ-0.1BiFeO 3扫描电子显微镜图。 FIG. 2 is a scanning electron microscope image of PrBaCo 2 O 5+δ -0.1BiFeO 3 prepared in Example 2.
图3为实施例2制备的PrBaCo 2O 5+δ-0.1BiFeO 3进一步制得的氧离子导体高温固态燃料电池电化学性能测试图，其中A为单电池500-650℃欧姆阻抗图，B为单电池500-650℃输出功率曲线。 FIG3 is a graph showing the electrochemical performance of an oxygen ion conductor high temperature solid fuel cell prepared from PrBaCo2O5 +δ - 0.1BiFeO3 prepared in Example 2, wherein A is the ohmic impedance graph of a single cell at 500-650°C, and B is the output power curve of a single cell at 500-650°C.
具体实施方式Detailed ways
下面结合实施例与附图，进一步阐明本发明。应理解，这些实施例仅 用于说明本发明，而不用于限制本发明的范围。The present invention will be further described below in conjunction with the embodiments and accompanying drawings. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.
实施例1-3中，BaCO 3、Pr 6O 11等原料的纯度均在99.9％以上。 In Examples 1-3, the purity of raw materials such as BaCO 3 and Pr 6 O 11 is above 99.9%.
实施例1Example 1
本实施例的PrBaCo 2O 5+δ-0.05BiFeO 3(PBCO-0.05BFO)的制备方法具体包括以下过程： The preparation method of PrBaCo 2 O 5+δ -0.05BiFeO 3 (PBCO-0.05BFO) in this embodiment specifically includes the following steps:
(1)前驱体粉末的合成(1) Synthesis of precursor powder
称取BaCO 3 0.9073g，Pr 6O 11 0.7827g，Fe 2O 3 0.0184g，Co 3O 4 0.7381g，Bi 2O 3 0.0536g和15mL球磨分散剂异丙醇，加入30克氧化锆小球，在球磨机中球磨12小时；将球磨得到的浑浊混合液在100℃烘箱中干燥3小时后，放置在马弗炉中900℃焙烧12小时，焙烧过程中升温和降温速率均为5℃/min，得到前驱体粉末； Weigh 0.9073 g of BaCO 3 , 0.7827 g of Pr 6 O 11 , 0.0184 g of Fe 2 O 3 , 0.7381 g of Co 3 O 4 , 0.0536 g of Bi 2 O 3 and 15 mL of isopropanol as a ball milling dispersant, add 30 g of zirconium oxide balls, and ball mill in a ball mill for 12 hours; dry the turbid mixed solution obtained by ball milling in an oven at 100° C. for 3 hours, place it in a muffle furnace and calcine it at 900° C. for 12 hours, and during the calcination process, the heating and cooling rates are both 5° C./min to obtain a precursor powder;
(2)PrBaCo 2O 5+δ-0.05BiFeO 3的合成 (2) Synthesis of PrBaCo 2 O 5+δ -0.05BiFeO 3
将步骤(1)得到的前驱体粉末与15mL异丙醇、30克氧化锆小球在球磨机中球磨12小时，将球磨得到的浑浊混合液在100℃烘箱中干燥3小时后得到干燥的粉末；然后使用单轴压片机将干燥后的粉末压成直径10毫米，厚度1毫米的圆片，然后在1000℃空气氛中烧结12小时，烧结过程中加热和冷却速度均为5℃/min，得到所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料。 The precursor powder obtained in step (1) is ball-milled with 15 mL of isopropanol and 30 g of zirconium oxide balls in a ball mill for 12 hours, and the turbid mixed solution obtained by ball milling is dried in an oven at 100° C. for 3 hours to obtain a dry powder; the dried powder is then pressed into a disc with a diameter of 10 mm and a thickness of 1 mm using a uniaxial tablet press, and then sintered in an air atmosphere at 1000° C. for 12 hours, with the heating and cooling rates during the sintering process being 5° C./min, to obtain the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material.
实施例2Example 2
本实施例的PrBaCo 2O 5+δ-0.1BiFeO 3(PBCO-0.1BFO)的制备方法具体包括以下过程： The preparation method of PrBaCo 2 O 5+δ -0.1BiFeO 3 (PBCO-0.1BFO) in this embodiment specifically includes the following steps:
(1)前驱体粉末的合成(1) Synthesis of precursor powder
称取BaCO 3 0.8819g，Pr 6O 11 0.7608g，Fe 2O 3 0.0357g，Co 3O 4 0.7174g，Bi 2O 3 0.1041g和15mL球磨分散剂异丙醇，加入30克氧化锆小球，在球磨机中球磨12小时；将球磨得到的浑浊混合液在100℃烘箱中干燥3小时后，放置在马弗炉中900℃焙烧12小时，焙烧过程中升温和降温速率 均为5℃/min，得到前驱体粉末； Weigh 0.8819 g of BaCO 3 , 0.7608 g of Pr 6 O 11 , 0.0357 g of Fe 2 O 3 , 0.7174 g of Co 3 O 4 , 0.1041 g of Bi 2 O 3 and 15 mL of isopropanol as a ball milling dispersant, add 30 g of zirconium oxide balls, and ball mill in a ball mill for 12 hours; dry the turbid mixed solution obtained by ball milling in an oven at 100° C. for 3 hours, place it in a muffle furnace and calcine it at 900° C. for 12 hours, and during the calcination process, the heating and cooling rates are both 5° C./min to obtain a precursor powder;
(2)PrBaCo 2O 5+δ-0.1BiFeO 3的合成 (2) Synthesis of PrBaCo 2 O 5+δ -0.1BiFeO 3
将步骤(1)得到的前驱体粉末与15mL异丙醇、30克氧化锆小球在球磨机中球磨12小时，将球磨得到的浑浊混合液在100℃烘箱中干燥3小时后得到干燥的粉末；然后使用单轴压片机将干燥后的粉末压成直径10毫米，厚度1毫米的圆片，然后在1100℃空气氛中烧结12小时，烧结过程中加热和冷却速度均为5℃/min，得到所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料。 The precursor powder obtained in step (1) is ball-milled with 15 mL of isopropanol and 30 g of zirconium oxide balls in a ball mill for 12 hours, and the turbid mixed solution obtained by ball milling is dried in an oven at 100° C. for 3 hours to obtain a dry powder; the dried powder is then pressed into a disc with a diameter of 10 mm and a thickness of 1 mm using a uniaxial tablet press, and then sintered in an air atmosphere at 1100° C. for 12 hours, with the heating and cooling rates during the sintering process being 5° C./min, to obtain the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material.
实施例3Example 3
本实施例的PrBaCo 2O 5+δ-0.1BiFeO 3(PBCO-0.1BFO)的制备方法具体包括以下过程： The preparation method of PrBaCo 2 O 5+δ -0.1BiFeO 3 (PBCO-0.1BFO) in this embodiment specifically includes the following steps:
(1)前驱体粉末的合成(1) Synthesis of precursor powder
称取BaCO 3 0.8819g，Pr 6O 11 0.7608g，Fe 2O 3 0.0357g，Co 3O 4 0.7174g，Bi 2O 3 0.1041g和15mL球磨分散剂异丙醇，加入30克氧化锆小球，在球磨机中球磨14小时；将球磨得到的浑浊混合液在100℃烘箱中干燥3小时后，放置在马弗炉中1000℃焙烧10小时，焙烧过程中升温和降温速率均为5℃/min，得到前驱体粉末； Weigh 0.8819 g of BaCO 3 , 0.7608 g of Pr 6 O 11 , 0.0357 g of Fe 2 O 3 , 0.7174 g of Co 3 O 4 , 0.1041 g of Bi 2 O 3 and 15 mL of isopropanol as a ball milling dispersant, add 30 g of zirconium oxide balls, and ball mill in a ball mill for 14 hours; dry the turbid mixed solution obtained by ball milling in an oven at 100° C. for 3 hours, place it in a muffle furnace and calcine it at 1000° C. for 10 hours, and during the calcination process, the heating and cooling rates are both 5° C./min, to obtain a precursor powder;
(2)PrBaCo 2O 5+δ-0.1BiFeO 3的合成 (2) Synthesis of PrBaCo 2 O 5+δ -0.1BiFeO 3
将步骤(1)得到的前驱体粉末与15mL异丙醇、30克氧化锆小球在球磨机中球磨14小时，将球磨得到的浑浊混合液在100℃烘箱中干燥3小时后得到干燥的粉末；然后使用单轴压片机将干燥后的粉末压成直径10毫米，厚度1毫米的圆片，然后在1100℃空气氛中烧结14小时，烧结过程中加热和冷却速度均为5℃/min，得到所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料。 The precursor powder obtained in step (1) is ball-milled with 15 mL of isopropanol and 30 g of zirconium oxide balls in a ball mill for 14 hours, and the turbid mixed solution obtained by ball milling is dried in an oven at 100° C. for 3 hours to obtain a dry powder; the dried powder is then pressed into a disc with a diameter of 10 mm and a thickness of 1 mm using a uniaxial tablet press, and then sintered in an air atmosphere at 1100° C. for 14 hours, with the heating and cooling rates during the sintering process being 5° C./min, to obtain the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material.
样品分析Sample analysis
图1为实施例1中制备的PrBaCo 2O 5+δ-0.05BiFeO 3、实施例2中制备 的PrBaCo 2O 5+δ-0.1BiFeO 3和PrBaCo 2O 5+δ的X射线衍射图，在BiFeO 3掺杂后，晶体结构相比未掺杂PrBaCo 2O 5+δ未发生明显变化，均为正交晶系双钙钛矿结构(空间点群为Pmmm)，通过对XRD结果进行精修，发现晶胞参数发生了变化(见表1)。说明铁酸铋成功掺杂，且其掺杂虽然没有改变晶体的原有对称性结构，但改变了晶胞大小。 Figure 1 is the X-ray diffraction diagram of PrBaCo 2 O 5+δ -0.05BiFeO 3 prepared in Example 1, PrBaCo 2 O 5+δ -0.1BiFeO 3 and PrBaCo 2 O 5+δ prepared in Example 2. After BiFeO 3 doping, the crystal structure does not change significantly compared with undoped PrBaCo 2 O 5+δ , and both are orthorhombic double perovskite structures (space point group is Pmmm). By refining the XRD results, it is found that the unit cell parameters have changed (see Table 1). This shows that bismuth ferrite is successfully doped, and although its doping does not change the original symmetry structure of the crystal, it changes the unit cell size.
表1 PBCO和PBCO-0.1BFO样品的XRD精修结果Table 1 XRD refinement results of PBCO and PBCO-0.1BFO samples
Figure PCTCN2022131879-appb-000001
Figure PCTCN2022131879-appb-000001
图2为实施例2制备的PrBaCo 2O 5+δ-0.1BiFeO 3扫描电子显微镜图，SEM结果显示PrBaCo 2O 5+δ-0.1BiFeO 3样品在第二次烧结后形成了大小均匀的晶粒，晶粒平均尺寸为1μm。 FIG2 is a scanning electron microscope image of PrBaCo 2 O 5+δ -0.1BiFeO 3 prepared in Example 2. The SEM result shows that the PrBaCo 2 O 5+δ -0.1BiFeO 3 sample forms uniform grains after the second sintering, and the average grain size is 1 μm.
应用例Application Examples
以Sm 0.20Ce 0.80O 1.95(SDC)、6g NiO粉末和1.5g土豆淀粉等为原料制备阳极前驱体圆片；进一步利用甲基乙基酮、乙醇、三乙醇胺、聚环氧乙烷聚环氧丙烷单丁基醚、邻苯二甲酸甲苯基丁酯和聚乙烯醇缩丁醛酯混合配制得到空白电解质溶液，制备电解质-阳极单电池基底； An anode precursor disc was prepared using Sm 0.20 Ce 0.80 O 1.95 (SDC), 6 g NiO powder and 1.5 g potato starch as raw materials; a blank electrolyte solution was prepared by mixing methyl ethyl ketone, ethanol, triethanolamine, polyethylene oxide polypropylene oxide monobutyl ether, toluyl butyl phthalate and polyvinyl butyral to prepare an electrolyte-anode single cell substrate;
再分别将实施例1和实施例2制得的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料与阴极浆料粘合剂V600充分搅拌混合得到两种阴极浆料，将上述两种阴极浆料分别均匀涂覆在电解质-阳极单电池基底电解质层表面，常温干燥后，置于马弗炉中950℃焙烧1小时，焙烧过程中升温和降温速率分别为1.8℃/min及3℃/min，冷却后分别获得待测试单电池1和待测试单电池2。 The BiFeO3- doped PrBaCo2O5 +δ- based perovskite materials prepared in Example 1 and Example 2 were fully stirred and mixed with the cathode slurry binder V600 to obtain two cathode slurries. The two cathode slurries were uniformly coated on the surface of the electrolyte-anode single cell base electrolyte layer, dried at room temperature, and placed in a muffle furnace for calcination at 950°C for 1 hour. The heating and cooling rates during the calcination process were 1.8°C/min and 3°C/min, respectively. After cooling, the single cell 1 to be tested and the single cell 2 to be tested were obtained, respectively.
将待测试单电池阳极面封装在固态燃料电池测试系统中，升温到500-650℃，阳极处通氢气(流速200mL/min)，阴极处通干燥空气(流速100mL/min)，完成单电池非欧姆电阻及最大输出功率的测试；实施例2 中的PrBaCo 2O 5+δ-0.1BiFeO 3制得的单电池2的测试结果分别如图3中的A和B所示，其在650℃，600℃，550℃，和500℃测得的非欧姆阻抗值分别为0.146Ω·cm 2，0.205Ω·cm 2，0.240Ω·cm 2，0.453Ω·cm 2，测得的峰值输出功率分别为868mW·cm -2，677mW·cm -2，428mW·cm -2，226mW·cm -2，极化电阻小、输出功率高。 The anode surface of the single cell to be tested was encapsulated in a solid fuel cell test system, the temperature was raised to 500-650°C, hydrogen was passed through the anode (flow rate 200mL/min), and dry air was passed through the cathode (flow rate 100mL/min), to complete the test of the non-ohmic resistance and maximum output power of the single cell; the test results of the single cell 2 prepared from PrBaCo2O5 +δ - 0.1BiFeO3 in Example 2 are shown in A and B in Figure 3, respectively, and the non-ohmic impedance values measured at 650°C, 600°C, 550°C, and 500°C are 0.146Ω· cm2 , 0.205Ω· cm2 , 0.240Ω· cm2 , and 0.453Ω·cm2, respectively, and the peak output powers measured are 868mW·cm -2 , 677mW·cm -2 , 428mW·cm- 2 , and 226mW·cm -2 , respectively. , small polarization resistance and high output power.
以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述的仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本发明的保护范围之内。The embodiments described above provide a detailed description of the technical solutions of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements or similar substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims (10)

  1. 一种BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料，其特征在于，化学通式为PrBaCo 2O 5+δ-xBiFeO 3，0＜x≤0.15，δ为氧缺陷数。 A BiFeO 3 doped PrBaCo 2 O 5+δ -based perovskite material, characterized in that the general chemical formula is PrBaCo 2 O 5+δ -xBiFeO 3 , 0＜x≤0.15, δ is the number of oxygen defects.
  2. 根据权利要求1所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料，其特征在于，x的取值范围为0.05≤x≤0.1。 The BiFeO3- doped PrBaCo2O5 +δ- based perovskite material according to claim 1 is characterized in that the value range of x is 0.05≤x≤0.1.
  3. 根据权利要求1或2所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料的制备方法，其特征在于，包括以下步骤： The method for preparing the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material according to claim 1 or 2, characterized in that it comprises the following steps:
    (1)按照通式PrBaCo 2O 5+δ-xBiFeO 3，称取化学计量比的镨源、钡源、钴源、铁源和铋源充分混合，高温煅烧后得到前驱体粉末； (1) According to the general formula PrBaCo 2 O 5+δ -xBiFeO 3 , weigh praseodymium source, barium source, cobalt source, iron source and bismuth source in a stoichiometric ratio, mix them thoroughly, and calcine them at a high temperature to obtain a precursor powder;
    (2)将前驱体粉末球磨、干燥后压片并进一步烧结，制备得到所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料。 (2) The precursor powder is ball-milled, dried, pressed into tablets, and further sintered to prepare the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material.
  4. 根据权利要求3所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料的制备方法，其特征在于，所述的镨源为Pr 6O 11，所述的钡源为BaCO 3，所述的钴源为Co 3O 4，所述的铁源为Fe 2O 3，所述的铋源为Bi 2O 3。 The method for preparing the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material according to claim 3 is characterized in that the praseodymium source is Pr 6 O 11 , the barium source is BaCO 3 , the cobalt source is Co 3 O 4 , the iron source is Fe 2 O 3 , and the bismuth source is Bi 2 O 3 .
  5. 根据权利要求3所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料的制备方法，其特征在于，步骤(1)中，将镨源、钡源、钴源、铁源和铋源球磨混合后干燥以充分混匀，球磨时间为10-14h。 The method for preparing a BiFeO3 -doped PrBaCo2O5 +δ -based perovskite material according to claim 3 is characterized in that, in step (1), the praseodymium source, barium source, cobalt source, iron source and bismuth source are ball-milled and mixed and then dried to be fully mixed, and the ball milling time is 10-14 hours.
  6. 根据权利要求3所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料的制备方法，其特征在于，步骤(1)中，高温煅烧的参数为：空气气氛，800-1000℃，10-14h。 The method for preparing the BiFeO3- doped PrBaCo2O5 +δ -based perovskite material according to claim 3 is characterized in that in step (1), the parameters of high-temperature calcination are: air atmosphere, 800-1000°C, 10-14h.
  7. 根据权利要求3所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料的制备方法，其特征在于，步骤(2)中，球磨参数为10-14h。 The method for preparing the BiFeO 3 -doped PrBaCo 2 O 5+δ- based perovskite material according to claim 3, characterized in that in step (2), the ball milling parameter is 10-14h.
  8. 根据权利要求3所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料的制备方法，其特征在于，步骤(2)中，烧结的参数为：空气气氛，1000-1100℃，10-14h。 The method for preparing the BiFeO 3 -doped PrBaCo 2 O 5+δ -based perovskite material according to claim 3 is characterized in that in step (2), the sintering parameters are: air atmosphere, 1000-1100° C., 10-14 h.
  9. 根据权利要求1或2所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料在固态氧化物燃料电池中的应用。 Use of the BiFeO3 - doped PrBaCo2O5 +δ- based perovskite material according to claim 1 or 2 in a solid oxide fuel cell.
  10. 根据权利要求9所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料在固态氧化物燃料电池中的应用，其特征在于，将所述的BiFeO 3掺杂的PrBaCo 2O 5+δ基钙钛矿材料作为阴极材料用于制备固态氧化物燃料电池。 The use of the BiFeO3- doped PrBaCo2O5 +δ -based perovskite material in a solid oxide fuel cell according to claim 9 is characterized in that the BiFeO3- doped PrBaCo2O5 +δ- based perovskite material is used as a cathode material for preparing a solid oxide fuel cell.
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