A composite electrolyte material, its preparation method and use in solid oxide fuel cells

Abstract

This invention discloses a composite electrolyte material, its preparation method, and its application in solid oxide fuel cells. The composite electrolyte material comprises Pr6O... 11 and CeO2; the Pr6O 11 The mass ratio of praseodymium oxide to CeO2 is 2:3 to 3:2. This invention combines praseodymium oxide with cerium oxide to construct Pr6O. 11 A CeO2 composite electrolyte system was developed, in which two electrolytes were combined in different mass ratios using a solid-state mixing method, and a symmetrical battery with a "NCAL electrode / composite electrolyte layer / NCAL electrode" sandwich structure was prepared using a dry pressing method. This composite electrolyte material exhibits synergistic effects in fuel cells and is suitable for medium-low temperature solid oxide fuel cells operating at 470℃~550℃, contributing to the development and application of low-cost, high-power fuel cells.

Description

Technical Field

[0001] This invention relates to the field of solid oxide fuel cell technology, and in particular to a composite electrolyte material, its preparation method, and its application in solid oxide fuel cells. Background Technology

[0002] Solid oxide fuel cells (SOFCs) are highly efficient electrochemical devices that directly convert chemical energy into electrical energy, offering advantages such as high energy conversion efficiency, rapid start-up, and zero pollution. Unlike traditional combustion technologies, fuel cells do not involve combustion during operation; their main byproducts are water and heat, thus they are considered a clean and sustainable energy conversion technology. However, traditional SOFCs typically require operation at high temperatures (800–1000°C), which leads to problems such as high material costs, sealing difficulties, slow start-up, and poor thermal cycling stability, limiting their large-scale commercial application.

[0003] To reduce operating temperatures to the medium-low temperature range (400~600℃), researchers are dedicated to developing novel high-performance electrolyte materials. Summary of the Invention

[0004] Based on the above, the present invention provides a composite electrolyte material, its preparation method, and its application in solid oxide fuel cells.

[0005] To achieve the above objectives, the present invention provides the following solution: One of the technical solutions of this invention is a composite electrolyte material comprising Pr6O 11 and CeO2; the Pr6O 11 The mass ratio of CeO2 to CeO2 is 2:3 to 3:2.

[0006] The composite electrolyte material of the present invention is an ion conductor-ion conductor composite material.

[0007] In a preferred embodiment of the present invention, the Pr6O 11 The mass ratio of CeO2 to CeO2 is 1:1.

[0008] The second technical solution of the present invention is a method for preparing the above-mentioned composite electrolyte material, comprising the following steps: Pr6O 11 The powder and CeO2 powder are ground and mixed to obtain the composite electrolyte material.

[0009] The third technical solution of the present invention is the application of the above-mentioned composite electrolyte material in solid oxide fuel cells.

[0010] The fourth technical solution of the present invention is a solid oxide fuel cell, comprising a composite electrolyte layer, wherein the composite electrolyte layer comprises the aforementioned composite electrolyte material.

[0011] In a preferred embodiment of the present invention, the battery has a sandwich structure of “NCAL electrode / composite electrolyte layer / NCAL electrode”.

[0012] In a preferred embodiment of the invention, the NCAL electrode is made of nickel foam coated with a mixture of NCAL powder and turpentine slurry.

[0013] NCAL is a nickel cobalt aluminum lithium oxide. The mass ratio of NCAL powder to turpentine in the NCAL powder and turpentine slurry mixture is 3:1. After the coating is completed, the process also includes a step of drying at 120°C for 5 minutes.

[0014] The fifth technical solution of the present invention is a method for preparing the above-mentioned solid oxide fuel cell, wherein a composite electrolyte layer and an NCAL electrode are sequentially laid on the surface of an NCAL electrode and pressed to obtain the solid oxide fuel cell.

[0015] In a preferred embodiment of the present invention, the pressing pressure is 7~10MPa and the pressing time is 3~4min.

[0016] The solid oxide fuel cell of the present invention is a medium-low temperature solid oxide fuel cell, suitable for operating temperatures of 470°C to 550°C.

[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention combines praseodymium oxide and cerium oxide to construct Pr6O 11 -CeO2 composite electrolyte system, using solid-state mixing method to integrate Pr6O 11 Composite with CeO2 at different mass ratios (pure Pr6O) 11 4∶6, 5∶5, 6∶4, pure CeO2), and prepared NCAL / xPr6O by dry pressing. 11 A symmetric cell of yCeO2 / NCAL was constructed. This composite electrolyte material works synergistically in the fuel cell, providing theoretical basis and experimental support for developing low-cost, high-power electrolytes for medium- and low-temperature solid oxide fuel cells. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of the classic sandwich structure of the fuel cell of the present invention.

[0020] Figure 2 This is an X-ray derived image of the composite pre-electrolyte material of the present invention.

[0021] Figure 3 This is an X-ray derived image of the electrolyte material after composite formation according to the present invention.

[0022] Figure 4 This is a scanning electron microscope image of the composite pre-electrolyte material of the present invention.

[0023] Figure 5 This is a scanning electron microscope image of the electrolyte material after composite composition according to the present invention.

[0024] Figure 6 This is a schematic diagram of the battery structure before testing according to the present invention, and a diagram of the composite electrolyte in the electrolyte layer of the battery before testing.

[0025] Figure 7 This is a schematic diagram of the battery structure after testing according to the present invention, and a diagram of the composite electrolyte in the electrolyte layer of the battery after testing.

[0026] Figure 8 The graph shows the IVP test results of fuel cells at the same temperature (550℃) with different scales.

[0027] Figure 9 EIS diagrams for fuel cells with different IVP ratios at the same temperature (550℃).

[0028] Figure 10 For the battery to be in the same ratio (1Pr6O) 11 :1CeO2), IVP test graphs of fuel cells at different temperatures.

[0029] Figure 11 For the battery to be in the same ratio (1Pr6O) 11 EIS diagrams corresponding to IVPs of fuel cells at different temperatures (e.g., 1CeO2).

[0030] Figure 12 Pr6O 11 The it curves of the light film at 550℃ in argon, air, and hydrogen.

[0031] Figure 13 The it curves of a CeO2 optical sheet at 550℃ in argon, air, and hydrogen.

[0032] Figure 14 1Pr6O 11 :1CeO2 optical sheet at 550℃, in argon, air and hydrogen atmospheres, it curves.

[0033] Figure 15 1Pr6O 11:1. It curves of a fuel cell with CeO2 as electrolyte at 550℃ in argon, air, and hydrogen. Detailed Implementation

[0034] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0035] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0036] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0037] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0038] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0039] This invention provides a solid oxide fuel cell, comprising the following steps: (1) Based on Pr6O 11 Preparation and performance of CeO2 composite materials and fuel cells: (i) Preparation of raw materials and composite powders: a:Pr6O 11 Powder synthesis: Take a certain amount of Pr(NO3)3 After grinding, the 6H2O crystals were sintered in a muffle furnace at 525℃ for 4 hours. After cooling, they were ground finely and then sintered again in a muffle furnace at 525℃ for 8 hours. After cooling, they were ground finely again to obtain Pr6O. 11 Powder. Pr6O 11 The XRD pattern was compared with its standard card, and the characteristic peak positions were found to be highly consistent, indicating that the material (such as...) was successfully prepared. Figure 2 (As shown). Pr6O 11 Actual image of the powder Figure 4 As shown in (a).

[0040] b: Synthesis of CeO2 powder: Weigh out 10g of Ce(NO3)3 Dissolve 6H₂O in 20 ml of deionized water. Then weigh a certain amount of NaOH and dissolve it in deionized water to obtain a 1 mol / L NaOH solution. Add Ce(NO₃)₃... 6H2O solution was added dropwise to NaOH solution until the pH value reached 12, with continuous stirring for 30 minutes. The mixture was then removed and placed in a reaction vessel, where it was subjected to hydrothermal reaction at room temperature for 24 hours. Finally, the reaction product was washed with deionized water until the pH value of the supernatant was 7, and then dried and ground at 60°C to obtain cerium dioxide powder. Figure 2 The image shows the X-ray diffraction pattern. Comparison of the XRD pattern of CeO2 with its standard card revealed a high degree of agreement between the characteristic peak positions, indicating successful material preparation (e.g., Figure 2 (As shown). Actual product image as follows. Figure 4 As shown in (b).

[0041] c:Pr6O 11 Synthesis of composite CeO2 powder: Pr6O was prepared using a solid-state mixing method. 11 Composites with CeO2 at different mass ratios (pure Pr6O) 11 Pr6O was weighed at different mass ratios: 10:0, 4:6, 5:5, 6:4, and pure CeO2 (0:10). 11 The desired powder was obtained by grinding CeO2 in a mortar for 30 minutes. Figure 3 This is an X-ray diffraction pattern. Pr6O 11 Comparison with XRD patterns of CeO2 revealed a high degree of agreement between the characteristic peak positions, indicating successful material preparation. A sample image is shown below. Figure 5 As shown.

[0042] The present invention does not impose any special limitations on the grinding operation; adjustments can be made according to actual needs.

[0043] The present invention does not have a special limitation on the grinding time; the two can be fully combined.

[0044] (ii) Fabrication of fuel cells: In an area of ​​0.64 cm 2 In a circular mold, an NCAL electrode (prepared by coating a circular nickel foam with a slurry mixture of NCAL powder and turpentine in a 3:1 mass ratio, then drying in a drying oven at 120°C for 5 minutes) is first placed as a substrate. Then, 0.3 g of Pr6O is accurately weighed. 11 The CeO2 composite powder was uniformly spread on the NCAL electrode, and then another layer of the same NCAL electrode was added. The mixture was then pressed at 10 MPa for 3 minutes to form the desired shape. Figure 6 In (a) "NCAL / xPr6O" 11 The three-layer structure of "-yCeO2 / NCAL" (where x and y represent Pr6O) 11 Compared to the mass ratio of CeO2, Figure 6 Pr6O 11 (The mass ratio of CeO2 to CeO2 is 1:1), observe Figure 6 The electrolyte layer in (b) clearly shows the electrolyte after the two are combined, which is the fuel cell required by the present invention.

[0045] This invention does not impose any particular restrictions on the porosity, conductivity, areal density, or thickness of the nickel foam used. It employs nickel foam commonly used by those skilled in the art. This invention also does not impose any particular restrictions on the source of the nickel foam, which can be obtained through commercial channels.

[0046] In this invention, there are no special limitations on the drying time of the NCAL electrode; the drying time should be such that it does not shed powder or become wet.

[0047] In this invention, the amount of composite electrolyte in the electrolyte layer is preferably 0.3g, and a certain thickness is required.

[0048] In this step of the invention, a tablet press at 10 MPa is preferably used, but 7-10 MPa can be used for pressing. There is no special limitation on the pressing time.

[0049] The present invention does not impose any special limitations on the battery pressing method; adjustments can be made according to actual needs.

[0050] (iii) Battery assembly and electrochemical testing: Pr6O prepared in (ii) 11Fuel cells with different CeO2 mass ratios were placed in the test system. Hydrogen was introduced at a rate of 150 mL / min at the anode, and air at a rate of 150 mL / min at the cathode. The preferred hydrogen rate in this step was 150 mL / min. The air flow rate should not be too high or too low; too high a flow rate would lower the temperature inside the muffle furnace, while too low a flow rate would affect battery performance. The cells were preheated by increasing the temperature to 550°C at a rate of 10°C / min and holding for 30 minutes. After preheating, the cells were discharged and subjected to IVP testing. Following the IVP test, the same cells were subjected to EIS testing. The IVP test results are as follows: Figure 8 As shown, the EIS test results are as follows: Figure 9 As shown, the data analysis and processing of EIS yields the data in Table 1 (Table 1 is...). Figure 9 (Corresponding conductivity).

[0051] Table 1

[0052] observe Figure 7 The structure of the battery in (a) has not changed. Figure 7 In the electrolyte layer of the battery (b), the electrolyte is very dense, which can isolate the reaction gases of the anode and cathode and prevent gas cross-permeation during battery operation.

[0053] Pr6O prepared in (ii) 11 A 1:1 CeO2 composite fuel cell was placed in the test system. Hydrogen was introduced at a rate of 150 mL / min at the anode, and air at a rate of 150 mL / min at the cathode. The preferred hydrogen rate in this step was 150 mL / min, and the air flow rate should not be too high. Too high a flow rate would lower the temperature inside the muffle furnace, while too low a flow rate would affect battery performance. The battery was preheated by increasing the temperature to 550°C at a rate of 10°C / min and holding for 30 minutes. After preheating, it was discharged and subjected to an IVP test. Following the IVP test, the same battery was subjected to an EIS test. Then, the same battery was preheated by decreasing the temperature to 530°C at a rate of 10°C / min and holding for 30 minutes. After preheating, it was discharged and subjected to an IVP test. Following the IVP test, the same battery was subjected to an EIS test. (The same procedure applies to 510°C, 490°C, and 470°C.) The IVP test results are as follows. Figure 10 As shown, the EIS test results are as follows: Figure 11 As shown, the data in Table 2 can be obtained from the data analysis and processing of EIS (Table 2 is...). Figure 11 (Corresponding conductivity).

[0054] Table 2

[0055] This invention does not impose any special restrictions on the heating rate; the temperature can be raised to the desired level.

[0056] The present invention does not have any special restrictions on the 20°C temperature step in this step; it is sufficient to achieve a step comparison effect.

[0057] In this invention, IVP testing is performed using an IT8511 electronic load, and EIS testing is performed using an electrochemical workstation ConrrtestSC210M.

[0058] Analysis of the experimental data of this invention leads to the conclusion that at 550℃, Pr6O 11 The maximum output power is 1100mW / cm² when the CeO₂ mass ratio is 1:1. -2 It also has a minimum ohmic resistance of 0.1281 ohms / cm. 2 .

[0059] Pr6O 11 Battery, 1Pr6O 11 IT testing of 1CeO2 batteries: (2) Based on Pr6O 11 CeO2, 1Pr6O 11 :1. Fabrication of CeO2 material and Pr6O 11 CeO2, 1Pr6O 11 IT testing of 1CeO2 material optical sheets: (i)Pr6O 11 Light film production and Pr6O 11 IT testing: a:Pr6O 11 Production of light sheets: In an area of ​​0.64cm 2 Take 0.6g of Pr6O into the round mold. 11 The powder was evenly spread in a circular mold and pressed at 10 MPa for 4 minutes to become Pr6O. 11 Light film.

[0060] The present invention does not impose any special limitations on the amount of material used, the method of pressing the film, or the time; adjustments can be made according to actual needs.

[0061] b:Pr6O 11 IT testing: The temperature is increased to 550°C in a muffle furnace at a rate of 10°C / min. Platinum paste is evenly applied to the upper and lower surfaces of the wafer to prepare the current collector layer. The wafer is then placed in a battery fixture and placed in the muffle furnace.

[0062] Argon gas at a flow rate of 150 mL / min was simultaneously introduced into both the anode and cathode sides. After 30 minutes of gas introduction, the remaining gas was exhausted. Then, a 1V DC bias voltage was applied to the wafer using a Keithley 2460 digital source meter for IT testing.

[0063] After the above test, air was simultaneously introduced into the anode and cathode sides at a flow rate of 150 mL / min for 30 minutes to purge the remaining gas. Then, a 1V DC bias voltage was applied to the disc using a Keithley 2460 digital source meter for IT testing.

[0064] The back sheet used in the above test was simultaneously purged with hydrogen gas at a flow rate of 150 mL / min to both the anode and cathode sides. After purging for 30 minutes to purge the remaining gas, a 1V DC bias voltage was applied to the disc using a Keithley 2460 digital source meter for IT testing.

[0065] The results are as follows Figure 12 As shown in the figure. The conductivity data in Table 3 can be obtained by analyzing and processing the it data and using σ=(L / S)×(I / V).

[0066] The present invention does not have a special limitation on the heating rate of the muffle furnace in this step, as long as the desired temperature is reached.

[0067] The gas flow rate is not explicitly limited in this invention, but it is preferably 150 mL / min. Too high a flow rate will cause the temperature inside the muffle furnace to drop, while too low a flow rate will not meet the testing requirements.

[0068] (ii) CeO2 film fabrication and CeO2 IT testing: a: Fabrication of CeO2 film: In an area of ​​0.64cm 2 In a circular mold, 0.6g of CeO2 powder is evenly spread in the mold and pressed at 10MPa pressure for 4min to form a CeO2 sheet.

[0069] The present invention does not impose any special limitations on the amount of material used, the method of pressing the film, or the time; adjustments can be made according to actual needs.

[0070] b: CeO2 IT test: The muffle furnace is heated to 550℃ at a rate of 10℃ / min. A current collector layer is prepared by uniformly coating the upper and lower surfaces of the wafer with platinum paste, and then the wafer is placed in a battery fixture and placed in the muffle furnace.

[0071] Argon gas at a flow rate of 150 mL / min was simultaneously introduced into both the anode and cathode sides. After 30 minutes of gas introduction, the remaining gas was exhausted. Then, a 1V DC bias voltage was applied to the wafer using a Keithley 2460 digital source meter for IT testing.

[0072] After the above test, air was simultaneously introduced into the anode and cathode sides at a flow rate of 150 mL / min for 30 minutes to purge the remaining gas. Then, a 1V DC bias voltage was applied to the disc using a Keithley 2460 digital source meter for IT testing.

[0073] After the above test, hydrogen gas was simultaneously introduced into the anode and cathode sides at a flow rate of 150 mL / min. After 30 minutes of gas introduction, the remaining gas was exhausted. Then, a 1V DC bias voltage was applied to the wafer using a Keithley 2460 digital source meter for IT testing.

[0074] The results are as follows Figure 13 As shown in the figure. The conductivity data in Table 3 can be obtained by analyzing and processing the it data and using σ=(L / S)×(I / V).

[0075] The present invention does not have a special limitation on the heating rate of the muffle furnace in this step, as long as the desired temperature is reached.

[0076] The gas flow rate is not explicitly limited in this invention, but the optimal flow rate is 150 mL / min. If the flow rate is too high, the temperature inside the muffle furnace will decrease, and if the flow rate is too low, the test requirements will not be met.

[0077] (iii) 1Pr6O 11 :1CeO2 film fabrication and 1Pr6O 11 IT test of 1CeO2: a:1Pr6O 11 Fabrication of 1CeO2 film: In an area of ​​0.64cm 2 Take 0.6g of 1Pr6O into the round mold. 11 :1CeO2(Pr6O) 11 Powder (at a mass ratio of 1:1 to CeO2) was evenly spread in a circular mold and pressed at 10 MPa for 4 minutes to form 1Pr6O. 11 ∶1CeO2 light film.

[0078] The present invention does not impose any special limitations on the amount of material used, the method of pressing the film, or the time; adjustments can be made according to actual needs.

[0079] b: 1Pr6O 11 IT test of 1CeO2: The muffle furnace is heated to 550℃ at a rate of 10℃ / min. A current collector layer is prepared by uniformly coating the upper and lower surfaces of the wafer with platinum paste, and then the wafer is placed in a battery fixture and placed in the muffle furnace.

[0080] Argon gas at a flow rate of 150 mL / min was simultaneously introduced into both the anode and cathode sides. After 30 minutes of gas introduction, the remaining gas was exhausted. Then, a 1V DC bias voltage was applied to the wafer using a Keithley 2460 digital source meter for IT testing.

[0081] After the above test, air was simultaneously introduced into the anode and cathode sides at a flow rate of 150 mL / min for 30 minutes to purge the remaining gas. Then, a 1V DC bias voltage was applied to the wafer using a Keithley 2460 digital source meter for IT testing.

[0082] After the above test, hydrogen gas at a flow rate of 150 mL / min was simultaneously introduced into the anode and cathode sides of the wafer. After 30 minutes of gas introduction, the remaining gas was exhausted. Then, a 1V DC bias voltage was applied to the wafer using a Keithley 2460 digital source meter for IT testing.

[0083] The results are as follows Figure 14 As shown. After analyzing and processing the I / V data, the conductivity data in Table 3 can be obtained according to σ=(L / S)×(I / V). (Table 3 is...) Figure 12 , Figure 13 , Figure 14 (Corresponding conductivity).

[0084] Table 3

[0085] The present invention does not have a special limitation on the heating rate of the muffle furnace in this step, as long as the desired temperature is reached.

[0086] The gas flow rate is not explicitly limited in this invention, but it is preferably 150 mL / min. Too high a flow rate will cause the temperature inside the muffle furnace to drop, while too low a flow rate will not meet the testing requirements.

[0087] Analysis and processing of the experimental data of this invention lead to the conclusion that Pr6O 11 The conductivity is enhanced after recombination with CeO2.

[0088] This invention provides a high-performance low-temperature solid oxide fuel cell composite electrolyte material, which is of great significance to the field of fuel cells.

[0089] This invention uses ion conductor-ion conductor composite materials as raw materials. These materials are widely available, yet offer high performance, low cost, and no environmental pollution. Furthermore, this material can boost the economy of the fuel cell industry and drive advancements in sustainable energy technologies.

[0090] Praseodymium undecoxide (Pr6O) 11 Praseodymium ions have high stability and exist in various stable phases, therefore the oxidation state of praseodymium ions (Pr) is...3+ and Pr 4+ Pr6O can change rapidly, which makes it possible for Pr6O to change rapidly. 11 Among lanthanide oxides, it exhibits the highest oxygen ion mobility. Higher oxygen ion mobility can promote the redox reaction of surface fuel gas, thereby further accelerating the reaction rate of intermediates and eliminating carbon deposits. Praseodymium undecyl oxide has higher low-temperature catalytic activity, which is more beneficial for improving the output performance of SOFCs at medium and low temperatures. Cerium ions in cerium dioxide (CeO2) can transform between +3 and +4 valences, exhibiting excellent oxygen storage and release performance, making it an excellent electrolyte and catalyst material. This invention employs a solid-state mixing method, grinding two materials in a mortar at different mass ratios for 30 minutes to obtain the composite electrolyte material used in this invention. Analysis of the experimental data of this invention shows that at 550℃, Pr6O… 11 The maximum power of a CeO2 mass ratio of 1:1 is 1100 mW / cm³. -2 And the ohmic resistance is 0.1281 ohmcm. 2 .

[0091] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used are all purchased from commercial channels or are publicly available unless otherwise specified.

[0092] Used in the embodiments of the present invention The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0093] Example 1 IVP and EIS tests of a low-temperature solid oxide fuel cell composite electrolyte with different mass ratios: This low-temperature solid oxide fuel cell has a three-layer structure: "electrode (NCAL) + electrolyte (xPr6O)". 11 The preparation method of "-yCeO2)+ electrode (NCAL)" is as follows: a: Bottom layer: Lay in foamed nickel NCAL electrodes and gently press them flat.

[0094] b: Electrolyte layer: Accurately weigh 0.30 g xPr6O 11 -yCeO2 composite powder, evenly spread (the values ​​of x and y represent Pr6O) 11 (mass ratio to CeO2).

[0095] c: Top layer: Lay in foamed nickel NCAL electrodes and gently press them flat.

[0096] The three-layer fuel cell was placed in a muffle furnace using a battery clamp and preheated to 550°C at a rate of 10°C / min for 30 min. Then, hydrogen gas was introduced at a flow rate of 150 mL / min at the anode and oxygen gas at a flow rate of 150 mL / min at the cathode. The cell performance was tested by discharging it using an IT8511 load. After the test, EIS testing was performed using a Conrrtest SC210M electrochemical workstation. The results are as follows: Figure 8 , Figure 9 As shown in the figure. It can be seen that at 550℃, Pr6O 11 A CeO2 mass ratio of 1:1 yields a maximum output power of 1100 mW / cm². -2 The minimum ohmic resistance is 0.1281 ohm cm. 2 .

[0097] Example 2 IVP and EIS tests of a low-temperature solid oxide fuel cell composite electrolyte at different temperatures: This low-temperature solid oxide fuel cell has a three-layer structure: "electrode (NCAL) + electrolyte (1Pr6O)". 11 -1CeO2) + electrode (NCAL)". The preparation method is as follows: a: Bottom layer: Lay in foamed nickel NCAL electrodes and gently press them flat.

[0098] b: Electrolyte layer: Accurately weigh 0.30 g of 1Pr6O 11 -1CeO2 composite powder, evenly spread.

[0099] c: Top layer: Lay in foamed nickel NCAL electrodes and gently press them flat.

[0100] A three-layer fuel cell was placed in a muffle furnace using a battery clamp and preheated to 550°C at a rate of 10°C / min for 30 min. Then, hydrogen gas was introduced at a flow rate of 150 mL / min at the anode and oxygen gas at a flow rate of 150 mL / min at the cathode. The cell was then connected to an IT8511 load for discharge testing. After the test, an EIS test was performed using a Conrrtest SC210M electrochemical workstation. The cell was then cooled to 525°C at a rate of 10°C / min and preheated for 30 min. Then, hydrogen gas was introduced at a flow rate of 150 mL / min at the anode and oxygen gas at a flow rate of 150 mL / min at the cathode. The cell was then connected to an IT8511 load for discharge testing. After the test, an EIS test was performed using a Conrrtest SC210M electrochemical workstation. Similarly, test at 500℃, 475℃, and 450℃ (i.e., preheat to 500℃ for 30 minutes, preheat to 475℃ for 30 minutes, and preheat to 450℃ for 30 minutes, respectively, at a rate of 10℃ / min).

[0101] The results are as follows Figure 10 , Figure 11 As shown in the figure, the output power decreases as the temperature decreases.

[0102] Example 3 A low-temperature solid oxide fuel cell Pr6O 11 CeO2, 1Pr6O 11 IT testing of 1CeO2 material optical sheets: In an area of ​​0.64 cm 2 Take 0.6g of Pr6O into the round mold. 11 The powder was evenly spread in a circular mold and pressed at 10 MPa for 4 minutes to become Pr6O. 11 A light film was prepared by heating it to 550°C in a muffle furnace at a rate of 10°C / min. Platinum paste was evenly applied to the upper and lower surfaces of the wafer to create a current collector layer. The wafer was then placed in a battery holder within the muffle furnace. Air was simultaneously introduced into both the anode and cathode sides at a flow rate of 150 mL / min for 30 minutes to purge the remaining gas. A 1V DC bias voltage was then applied to the wafer using a Keithley 2460 digital source meter for IT testing. (CeO2, 1Pr6O) 11 The same applies to CeO2 materials, i.e., the preparation method and testing are the same as for Pr6O. 11 The only difference is that Pr6O is used in the light film. 11 The powder was replaced with CeO2 powder or 1Pr6O 11 ∶1CeO2 material powder).

[0103] The results are as follows Figure 12 , Figure 13 , Figure 14 As shown in the figure, the conductivity increases after the two materials are combined.

[0104] Example 4 A low-temperature solid oxide fuel cell 1Pr6O 11 IT test of 1CeO2: In an area of ​​0.64 cm 2 NCAL electrodes were placed in a circular mold, and 0.6g of 1Pr6O was taken. 11A 1:1 CeO2 powder was evenly spread in a circular mold, and then an NCAL electrode was added. The mixture was pressed at 10 MPa for 3 minutes to form a three-layer fuel cell. The temperature was increased to 550°C in a muffle furnace at a rate of 10°C / min. The battery was placed in a battery holder within the muffle furnace, and air was simultaneously introduced to both the anode and cathode sides at a flow rate of 150 mL / min. After a discharge test, the remaining gas was purged for 30 minutes. Then, a 1V DC bias voltage was applied to the wafer using a Keithley 2460 digital source meter for IT testing.

[0105] The results are as follows Figure 15 As shown, the IT data was analyzed and processed. Based on σ=(L / S)×(I / V), the conductivity data shown in Table 4 can be obtained. (In Table 4, argon atmosphere and hydrogen atmosphere refer to replacing the air in "air flowing simultaneously to the anode and cathode sides at a flow rate of 150 mL / min" with equal flow rates of argon and hydrogen, respectively; Table 4 is...) Figure 15 (Corresponding conductivity).

[0106] It can be seen that the electronic conductivity of the battery prepared by dry pressing with NCAL as electrode is significantly improved after SOFC testing.

[0107] As can be seen from the above embodiments, the steps and preparation method provided by the present invention provide a high-performance composite electrolyte material, which, at 550℃, Pr6O 11 A CeO2 mass ratio of 1:1 yields a maximum output power of 1100 mW / cm². -2 .

[0108] Table 4

[0109] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A composite electrolyte material, characterized in that, Including Pr6O 11 and CeO2; the Pr6O 11 The mass ratio of CeO2 to CeO2 is 2:3 to 3:

2.

2. The composite electrolyte material according to claim 1, characterized in that, The Pr6O 11 The mass ratio of CeO2 to CeO2 is 1:

1.

3. A method for preparing the composite electrolyte material according to claim 1 or 2, characterized in that, Includes the following steps: Pr6O 11 The powder and CeO2 powder are ground and mixed to obtain the composite electrolyte material.

4. The application of the composite electrolyte material as described in claim 1 or 2 in solid oxide fuel cells.

5. A solid oxide fuel cell, characterized in that, It includes a composite electrolyte layer, wherein the composite electrolyte layer comprises the composite electrolyte material as described in claim 1 or 2.

6. The solid oxide fuel cell according to claim 5, characterized in that, The battery has a sandwich structure of "NCAL electrode / composite electrolyte layer / NCAL electrode".

7. The solid oxide fuel cell according to claim 6, characterized in that, The NCAL electrode is made of nickel foam coated with a mixture of NCAL powder and turpentine slurry.

8. A method for preparing a solid oxide fuel cell according to any one of claims 5 to 7, characterized in that, A composite electrolyte layer and an NCAL electrode are sequentially laid on the surface of the NCAL electrode and then pressed to obtain the solid oxide fuel cell.

9. The preparation method according to claim 8, characterized in that, The pressing pressure is 7~10MPa, and the pressing time is 3~4min.

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