CN113957566B - Solid oxide battery composite nanofiber and preparation method thereof - Google Patents

Solid oxide battery composite nanofiber and preparation method thereof Download PDF

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CN113957566B
CN113957566B CN202111381223.3A CN202111381223A CN113957566B CN 113957566 B CN113957566 B CN 113957566B CN 202111381223 A CN202111381223 A CN 202111381223A CN 113957566 B CN113957566 B CN 113957566B
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nitrate
composite nanofiber
solid oxide
bglc
gdc
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CN113957566A (en
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陈孔发
孙鼎
陈志逸
乐忠威
艾娜
邵艳群
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Fuzhou University
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Fuzhou University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a solid oxide battery composite nanofiber and a preparation method thereof, according to BaGd 0.8 La 0.2 Co 2 O 5 (BGLC) and Gd 0.1 Ce 0.9 O 1.95 Dissolving barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate in DMF solvent according to the element proportion of (GDC), adding PVP as an organic binder, uniformly stirring to prepare precursor solution, and carrying out electrostatic spinning to obtain a BGLC/GDC composite nanofiber precursor; and calcining the precursor fiber to obtain the BGLC/GDC composite nanofiber. The preparation method has the characteristics of low cost, short flow, simple process, safety, controllability and the like. The diameter of the prepared composite nanofiber is only about 100-200nm, and the fiber length reaches tens of micrometers. According to the different proportions of BGLC and GDC, the composite nano fiber with different morphologies can be obtained. Has great significance for realizing the development and application of the solid oxide cell cathode nanofiber material and has wide application prospect in the field of fuel cell electrode preparation.

Description

Solid oxide battery composite nanofiber and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of solid oxide battery electrode materials, and particularly relates to a solid oxide battery composite nanofiber and a preparation method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is an all-solid chemical power generation device that converts chemical energy stored in fuels and oxidants directly into electrical energy with high efficiency and environmental friendliness. The SOFC has higher energy conversion efficiency and wider fuel adaptability, can directly use hydrogen, methane and the like as fuel, has safer all-solid structure and is more environment-friendly. The reaction kinetics of SOFCs all require high temperatures to perform well, and at high temperatures, a sufficiently high conductivity is obtained. But the high temperature can cause instability of thermal cycle, which leads to agglomeration of cathode materials and reduces the service life of the battery. For lifting at medium and low temperaturesCell performance using Materials (MIEC) with greater mixed ionic electron conductivity and catalysis at medium and low temperatures to reduce activation barriers, e.g. BaGd 0.8 La 0.2 Co 2 O 5 (BGLC) with the incorporation of the electrolyte material Gd in the cathode 0.1 Ce 0.9 O 1.95 (GDC) increases the three-phase reaction interface, and further has better electrochemical performance. The microstructure of the battery cathode can be modified, a one-dimensional nanofiber structure is introduced into the cathode, the one-dimensional nanofiber can form a continuous transmission path, and the nanofiber has small fiber diameter, large specific surface area and large porosity, so that the fiber material has more reaction sites, and the reactivity of the cathode is improved.
However, for the preparation of the composite cathode material, many experiments require the preparation of powder separately and mechanical mixing, or the introduction of a second phase by impregnation, which results in a complex preparation process and a long time.
Disclosure of Invention
The invention aims to provide a solid oxide cell composite nanofiber and a preparation method thereof, wherein an SOFC cathode composite material is prepared by using an electrostatic spinning method in one step, and a BGLC/GDC composite nanofiber is obtained. The preparation method has the advantages of short preparation flow, simple process, safety and controllability, and the prepared fiber material has larger specific surface area and higher catalytic activity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a chemical composition of a composite nanofiber of a solid oxide battery is BaGd 0.8 La 0.2 Co 2 O 5 /Gd 0.1 Ce 0.9 O 1.95 。
The preparation method comprises the following steps:
(1) Dissolving barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate in N, N-Dimethylformamide (DMF), and stirring to completely dissolve nitrate to obtain nitrate-DMF solution;
(2) Adding polyvinylpyrrolidone (PVP) into a nitrate-DMF solution, and stirring until the polyvinylpyrrolidone is completely dissolved to obtain a spinning precursor solution;
(3) Carrying out ultrasonic oscillation on the spinning precursor solution, standing until bubbles are completely removed, and carrying out electrostatic spinning to obtain a composite nanofiber precursor;
(4) Calcining the composite nanofiber precursor in a heat-preserving way to obtain the composite nanofiber BaGd 0.8 La 0.2 Co 2 O 5 /Gd 0.1 Ce 0.9 O 1.95 。
In the step (1), the total mass of barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate in the mixed solution is 10% -15% of the mass of the DMF solvent.
In the step (1), the mass ratio of the substances of barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate is 2.36-3.03: 2.19-2.52: 0.47 to 0.61:4.72 to 6.06:0.9 to 2.7.
In the step (1), the heating temperature is 50 ℃.
In the step (2), PVP has a molecular weight of 1.3X10 6 The concentration of PVP in the spinning precursor solution is 0.1-0.15 g/mL.
In the step (2), the heating temperature is 80 ℃.
In the step (3), the working temperature of electrostatic spinning is controlled at 20-30 ℃, the working humidity is controlled at 40-50% RH, the voltage of electrostatic spinning is 17-25kV, the vertical distance between a spinning needle and a rotary drum is 12-18 cm, the injection speed of needle solution is 0.3-0.5 ml/h, and the collection speed of the rotary drum is 100-300 r/min.
In the step (4), the composite nanofiber precursor is insulated for 2-3 hours at 70-80 ℃, heated to 400-500 ℃ at the speed of 2-5 ℃/min, insulated for 2-3 hours at 400-500 ℃, heated to 950 ℃ at the speed of 2-5 ℃/min, and insulated for 2-3 hours at 950 ℃ to obtain the BaGd 0.8 La 0.2 Co 2 O 5 /Gd 0.1 Ce 0.9 O 1.95 Composite nanofibers.
The invention has the beneficial effects that:
(1) The invention utilizes an electrostatic spinning instrument to prepare the BGLC/GDC composite nanofiber by a one-step method, and is used for preparing the cathode material of the solid oxide battery. In the preparation stage of the precursor solution, the elements can be uniformly mixed in a microscopic scale, and the element content is easy to regulate and control. Meanwhile, the GDC particles in the composite nanofiber can inhibit the growth of BGLC particles, so that the fiber diameter is smaller, and the fiber diameter is only about 100-200nm, and the length reaches tens of micrometers. The prepared BGLC/GDC composite nanofiber has a high specific surface area, can provide more reaction sites for a cathode, and enables the battery to have good electrochemical performance.
(2) The method has the advantages of easy obtainment of equipment and chemical reagents, simple and convenient process operation, simple process conditions, strong applicability, simple and effective preparation method, high industrial application value, easy popularization and application, and wide application prospect in the field of preparation of fuel cell cathode materials.
Drawings
FIG. 1 is an X-ray diffraction pattern of the BGLC/GDC composite nanofiber prepared in examples 1-3;
FIG. 2 is a scanning electron microscope image of BGLC/GDC composite nanofibers prepared in examples 1-3;
fig. 3 is an electrochemical performance diagram of the BGLC/GDC composite nanofiber prepared in example 1 in SOFC mode after being prepared into a cathode.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1: preparation of fibers
(1) 10ml of DMF solvent was weighed out according to BaGd 0.8 La 0.2 Co 2 O 5 ：Gd 0.1 Ce 0.9 O 1.95 =3.03: 1, adding barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate, magnetically stirring for 2 hours at 50 ℃ until the metal nitrate is completely dissolved in DMF solvent, and obtaining a precursor solution which is uniformly mixed.
(2) 1g PVP powder is slowly added into the evenly mixed precursor solution, and the mixture is magnetically stirred for 12 hours at 80 ℃ in a room, so that the clear and even precursor solution with certain viscosity is obtained.
(3) Ultrasonically vibrating the precursor solution for 5 minutes, standing for 10 minutes to remove bubbles, sucking 10ml of BGLC precursor solution from a beaker by using a needle tube, and fixing the needle tube on an injection pump of an electrostatic spinning instrument; adjusting the voltage parameter of the electrostatic spinning instrument to 20kV; the drum collection speed was 200 revolutions per minute; the vertical distance between the needle and the rotary drum is set to be 15 cm; the needle injection speed was set at 0.4 ml/hr; and carrying out electrostatic spinning after the parameters are set.
(4) Calcining the spun BGLC/GDC nanofiber precursor at a high temperature, preserving heat at 80 ℃ for 2 hours, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat at 500 ℃ for 2 hours, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat at 950 ℃ for 3 hours, cooling to 500 ℃ at a heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain the BGLC/GDC composite nanofiber.
Example 2: preparation of fibers
(1) 10ml of DMF solvent was weighed out according to BaGd 0.8 La 0.2 Co 2 O 5 ：Gd 0.1 Ce 0.9 O 1.95 =2.7: 2, adding barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate, magnetically stirring for 2 hours at 50 ℃ until the metal nitrate is completely dissolved in DMF solvent, and obtaining a precursor solution which is uniformly mixed.
(2) 1g PVP powder is slowly added into the evenly mixed precursor solution, and the mixture is magnetically stirred for 12 hours at 80 ℃ in a room to obtain the clear and even precursor solution with certain viscosity.
(3) Ultrasonically vibrating the precursor solution for 5 minutes, standing for 10 minutes to remove bubbles, sucking 10ml of BGLC precursor solution from a beaker by using a needle tube, and fixing the needle tube on an injection pump of an electrostatic spinning instrument; adjusting the voltage parameter of the electrostatic spinning instrument to 20kV; the drum collection speed was 200 revolutions per minute; the vertical distance between the needle and the rotary drum is set to be 15 cm; the needle injection speed was set at 0.4 ml/hr; and carrying out electrostatic spinning after the parameters are set.
(4) Calcining the spun BGLC/GDC nanofiber precursor at a high temperature, preserving heat at 80 ℃ for 2 hours, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat at 500 ℃ for 2 hours, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat at 950 ℃ for 3 hours, cooling to 500 ℃ at a heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain the BGLC/GDC composite nanofiber.
Example 3: preparation of fibers
(1) 10ml of DMF solvent was weighed out according to BaGd 0.8 La 0.2 Co 2 O 5 ：Gd 0.1 Ce 0.9 O 1.95 =2.36: 3, adding barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate, magnetically stirring for 2 hours at 50 ℃ until the metal nitrate is completely dissolved in DMF solvent, and obtaining a precursor solution which is uniformly mixed.
(2) 1g PVP powder is slowly added into the evenly mixed precursor solution, and the mixture is magnetically stirred for 12 hours at 80 ℃ in a room to obtain the clear and even precursor solution with certain viscosity.
(3) Ultrasonically vibrating the precursor solution for 5 minutes, standing for 10 minutes to remove bubbles, sucking 10ml of BGLC precursor solution from a beaker by using a needle tube, and fixing the needle tube on an injection pump of an electrostatic spinning instrument; adjusting the voltage parameter of the electrostatic spinning instrument to 20kV; the drum collection speed was 200 revolutions per minute; the vertical distance between the needle and the rotary drum is set to be 15 cm; the needle injection speed was set at 0.4 ml/hr; and carrying out electrostatic spinning after the parameters are set.
(4) Calcining the spun BGLC/GDC nanofiber precursor at a high temperature, preserving heat at 80 ℃ for 2 hours, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat at 500 ℃ for 2 hours, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat at 950 ℃ for 3 hours, cooling to 500 ℃ at a heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain the BGLC/GDC composite nanofiber.
Characterization of the properties:
FIG. 1 shows XRD diffraction patterns of BGLC/GDC composite nanofibers with different GDC contents prepared in examples 1-3. At the calcining temperature of 950 ℃, sharp diffraction peaks of BGLC and GDC can be observed, and other impurity crystal phases are not seen, which indicates that the crystallinity of BGLC and GDC in the BGLC/GDC composite nano fiber is good, and no impurity phase is generated. And with the increase of the GDC content, the peak intensity of the GDC diffraction peak gradually increases, which indicates that the GDC content is controllable when preparing the BGLC/GDC composite nano fiber.
Fig. 2 is a scanning electron microscope image of BGLC/GDC composite nanofibers with different GDC contents prepared in examples 1-3, where the molar ratio of BGLC to GDC in the image (a) is 3.03:1, the average diameter of the fiber is about 210nm, and the specific surface area of the fiber is 7.07 and 7.07 m 2 ·g -1 Fig. (d) is a partial enlarged view of fig. (a); the molar ratio of BGLC to GDC in fig. (b) is 2.7:2, the average diameter of the fiber is about 180nm, and the specific surface area of the fiber is 7.14 and 7.14 m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of BGLC to GDC in fig. (c) is 2.36:3, the average diameter of the fiber is about 110nm, and the specific surface area of the fiber is 8.62. 8.62 m 2 ·g -1 . From the figure, the BGLC/GDC composite nanofiber structure with good morphology can be formed by different GDC contents, the fibers are mutually overlapped to form a three-dimensional net structure, and the fibers have larger porosity and larger specific surface area. And the average diameter of the BGLC/GDC composite nano fiber is obviously reduced along with the increase of the GDC content, and the specific surface area is gradually increased.
Fig. 3 is an electrochemical performance diagram of the BGLC/GDC composite nanofiber prepared in example 1 in SOFC mode after being prepared into a cathode. Its maximum power density at 800 deg.C is 0.86W cm -2 . The figure shows that the BGLC/GDC composite nanofiber cathode has better electrochemical performance at medium and high temperatures.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (8)

1. A solid oxide cell composite nanofiber, characterized by: chemical composition of BaGd 0.8 La 0.2 Co 2 O 5 /Gd 0.1 Ce 0.9 O 1.95 ；
The preparation method comprises the following steps:
(1) Dissolving barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate in DMF, stirring to completely dissolve nitrate, and obtaining nitrate-DMF solution;
(2) PVP is added into the nitrate-DMF solution, and stirring is carried out until the PVP is completely dissolved, so as to obtain spinning precursor solution;
(3) Carrying out ultrasonic oscillation on the spinning precursor solution, standing until bubbles are completely removed, and carrying out electrostatic spinning to obtain a composite nanofiber precursor;
(4) Calcining the composite nanofiber precursor in a heat-preserving way to obtain the composite nanofiber BaGd 0.8 La 0.2 Co 2 O 5 /Gd 0.1 Ce 0.9 O 1.95 ；
In the step (1), the molar ratio of barium nitrate, gadolinium nitrate, lanthanum nitrate, cobalt nitrate and cerium nitrate is 2.36-3.03: 2.19-2.52: 0.47 to 0.61:4.72 to 6.06:0.9 to 2.7.
2. The solid oxide cell composite nanofiber according to claim 1, wherein: in the step (1), the total mass of the barium nitrate, the gadolinium nitrate, the lanthanum nitrate, the cobalt nitrate and the cerium nitrate is 10% -15% of the mass of the DMF solvent.
3. The solid oxide cell composite nanofiber according to claim 1, wherein: the heating temperature in the step (1) is 50 ℃.
4. The solid oxide cell composite nanofiber according to claim 1, wherein: PVP in step (2) has a molecular weight of 1.3X10 6 The concentration of PVP in the spinning precursor solution is 0.1-0.15 g/mL.
5. The solid oxide cell composite nanofiber according to claim 1, wherein: the heating temperature in the step (2) is 80 ℃.
6. The solid oxide cell composite nanofiber according to claim 1, wherein: in the step (3), the working temperature of electrostatic spinning is 20-30 ℃, the working humidity is 40-50% RH, the working voltage is 17-25kV, the vertical distance between a spinning needle and a rotary drum is 12-18 cm, the injection speed of a needle solution is 0.3-0.5 ml/h, and the collection speed of the rotary drum is 100-300 r/min.
7. The solid oxide cell composite nanofiber according to claim 1, wherein: the specific process of heat preservation and calcination in the step (4) comprises the following steps: and (3) preserving heat for 2-3 hours at 70-80 ℃, heating to 400-500 ℃ at the speed of 2-5 ℃/min, preserving heat for 2-3 hours, heating to 950 ℃ at the speed of 2-5 ℃/min, and preserving heat for 2-3 hours.
8. Use of the composite nanofiber according to claim 1 in a solid oxide cell cathode material.
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WO2004013882A2 (en) * 2001-06-29 2004-02-12 Nextech Materials, Ltd. Nano-composite electrodes and method of making the same
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