CN114665109B - Electrode material of solid oxide fuel cell or electrolytic cell, and preparation method and application thereof - Google Patents

Electrode material of solid oxide fuel cell or electrolytic cell, and preparation method and application thereof Download PDF

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CN114665109B
CN114665109B CN202210268554.4A CN202210268554A CN114665109B CN 114665109 B CN114665109 B CN 114665109B CN 202210268554 A CN202210268554 A CN 202210268554A CN 114665109 B CN114665109 B CN 114665109B
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hydrate
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gas
hydrates
electrode material
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CN114665109A (en
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王福欢
王贺武
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • 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
    • H01M4/9008—Organic or organo-metallic compounds
    • 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
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • 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 relates to a solid oxide fuel cell or electrolytic cell electrode material, a preparation method and application thereof. The preparation method comprises the following steps: providing a first solution comprising a first doped metal source, a base metal source, and a first solvent, and a second solution comprising an organic ligand and a second solvent; mixing the first solution and the second solution to carry out self-assembly reaction to obtain a first solid precursor; mixing the first solid precursor with a second doped metal source to obtain a second solid precursor; and heat treating the second solid precursor. The first solid precursor is obtained by mutual matching and self-assembly of the first doped metal source, the base metal source and the organic ligand, then the first solid precursor is matched with the second doped metal source, and finally the electrode material with high catalytic activity is obtained by heat treatment.

Description

Electrode material of solid oxide fuel cell or electrolytic cell, and preparation method and application thereof
Technical Field
The invention relates to the technical field of solid oxide cells, in particular to an electrode material of a solid oxide fuel cell or an electrolytic cell, and a preparation method and application thereof.
Background
With the progress of technology, solid Oxide Fuel Cells (SOFC) and Solid Oxide Electrolytic Cells (SOEC) are widely used as high-efficiency utilization and conversion technologies of clean energy, have the advantages of good fuel flexibility, high energy conversion efficiency and the like, and become an important technical means for effectively solving the problems of energy crisis and environmental pollution.
As electrode materials in SOFCs and SOECs, the performance of doped materials such as doped ceria, doped zirconia, etc. have a significant impact on the performance of SOFCs and SOECs. In the preparation process of the doped electrode material, the traditional preparation methods mainly include a sol-gel method, a solid phase method, a combustion method and the like, and although the methods can prepare the corresponding doped electrode material, the activity of the doped electrode material still needs to be improved.
Disclosure of Invention
Based on the above, there is a need for a preparation method of an electrode material for a solid oxide fuel cell or an electrolytic cell, and an electrolytic material and an application thereof, wherein the electrode material prepared by the preparation method has higher catalytic activity.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of an electrode material comprises the following steps:
providing a first solution comprising a first doping metal source, a base metal source and a first solvent, and a second solution comprising an organic ligand and a second solvent;
mixing the first solution and the second solution to carry out self-assembly reaction to obtain a first solid precursor;
mixing the first solid precursor with a second doped metal source to obtain a second solid precursor; and
heat treating the second solid precursor;
wherein the first doped metal source and the second doped metal source are respectively and independently selected from at least one of gadolinium source, samarium source, lanthanum source, yttrium source, scandium source, manganese source, iron source, cobalt source, nickel source, copper source, zinc source and tin source;
the base metal source comprises at least one of a cerium source and a zirconium source;
the organic ligand comprises at least one of trimesic acid, terephthalic acid, 4' -biphenyl dicarboxylic acid and [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid.
In one embodiment, the first doped metal source is at least one selected from gadolinium source, samarium source, lanthanum source, yttrium source, and scandium source, and the second doped metal source is at least one selected from iron source, cobalt source, nickel source, and copper source.
In one embodiment, the molar ratio of the first dopant metal source to the base metal source is x (1-x), where 0 < x ≦ 0.5; and/or the presence of a gas in the gas,
the ratio of the total molar amount of the first doping metal source and the base metal source to the molar amount of the organic ligand is 1.1 to 1; and/or
The mass ratio of the second doping metal source to the first solid precursor is 5.
In one embodiment, the reaction temperature of the self-assembly reaction is 60-180 ℃; and/or the presence of a gas in the atmosphere,
the reaction time of the self-assembly reaction is 0.5-48 h; and/or the presence of a gas in the gas,
the temperature of the heat treatment is 400-700 ℃; and/or the presence of a gas in the gas,
the time of the heat treatment is 0.5 to 24 hours.
In one embodiment, the first solvent comprises at least one of N, N-dimethylformamide, methanol, ethanol, and water; and/or the presence of a gas in the atmosphere,
the second solvent comprises at least one of N, N-dimethylformamide, methanol and ethanol; and/or the presence of a gas in the atmosphere,
the gadolinium source comprises at least one of gadolinium nitrate and a hydrate thereof, gadolinium chloride and a hydrate thereof, gadolinium sulfate and a hydrate thereof, gadolinium acetate and a hydrate thereof, gadolinium oxalate and a hydrate thereof, gadolinium octoate and a hydrate thereof, gadolinium isopropoxide and a hydrate thereof, gadolinium acetylacetonate and a hydrate thereof, and gadopentetate dimeglumine and a hydrate thereof; and/or the presence of a gas in the atmosphere,
the samarium source comprises at least one of samarium nitrate and hydrate thereof, samarium chloride and hydrate thereof, samarium sulfate and hydrate thereof, samarium acetate and hydrate thereof, samarium oxalate and hydrate thereof, samarium isopropoxide and hydrate thereof, and samarium acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the lanthanum source comprises at least one of lanthanum nitrate and hydrate thereof, lanthanum chloride and hydrate thereof, lanthanum sulfate and hydrate thereof, lanthanum acetate and hydrate thereof, lanthanum oxalate and hydrate thereof, lanthanum isopropoxide and hydrate thereof, and lanthanum acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the yttrium source comprises at least one of yttrium nitrate and hydrates thereof, yttrium chloride and hydrates thereof, yttrium sulfate and hydrates thereof, yttrium acetate and hydrates thereof, yttrium oxalate and hydrates thereof, yttrium isopropoxide and hydrates thereof, and yttrium acetylacetonate and hydrates thereof; and/or the presence of a gas in the gas,
the scandium source comprises at least one of scandium nitrate and a hydrate thereof, scandium chloride and a hydrate thereof, scandium sulfate and a hydrate thereof, scandium acetate and a hydrate thereof, scandium oxalate and a hydrate thereof, and scandium acetylacetonate and a hydrate thereof; and/or the presence of a gas in the gas,
the manganese source comprises at least one of manganese nitrate and a hydrate thereof, manganese sulfate and a hydrate thereof, manganese chloride and a hydrate thereof, manganese acetate and a hydrate thereof, manganese oxalate and a hydrate thereof, and manganese acetylacetonate and a hydrate thereof; and/or the presence of a gas in the gas,
the iron source comprises at least one of ferric nitrate and hydrate thereof, ferric sulfate and hydrate thereof, ferric chloride and hydrate thereof, ferric oxalate and hydrate thereof, ferric acetylacetonate and hydrate thereof, ferrous sulfate and hydrate thereof, ferrous chloride and hydrate thereof, ferrous acetate and hydrate thereof, and ferrous oxalate and hydrate thereof; and/or the presence of a gas in the atmosphere,
the cobalt source comprises at least one of cobalt nitrate and hydrate thereof, cobalt sulfate and hydrate thereof, cobalt chloride and hydrate thereof, cobalt acetate and hydrate thereof, cobalt oxalate and hydrate thereof, cobalt acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the nickel source comprises at least one of nickel nitrate and hydrate thereof, nickel sulfate and hydrate thereof, nickel chloride and hydrate thereof, nickel acetate and hydrate thereof, nickel formate and hydrate thereof, nickel oxalate and hydrate thereof, and nickel acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the copper source comprises at least one of copper nitrate and hydrate thereof, copper sulfate and hydrate thereof, copper chloride and hydrate thereof, copper acetate and hydrate thereof, copper formate and hydrate thereof, copper oxalate and hydrate thereof, and copper acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the zinc source comprises at least one of zinc nitrate and hydrate thereof, zinc sulfate and hydrate thereof, zinc chloride and hydrate thereof, zinc acetate and hydrate thereof, zinc formate and hydrate thereof, zinc oxalate and hydrate thereof, and zinc acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the tin source comprises at least one of tin nitrate and hydrate thereof, tin sulfate and hydrate thereof, tin chloride and hydrate thereof, tin acetate and hydrate thereof, tin formate and hydrate thereof, tin oxalate and hydrate thereof, and tin acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the cerium source comprises at least one of cerium nitrate and hydrate thereof, cerium chloride and hydrate thereof, cerium sulfate and hydrate thereof, cerium acetate and hydrate thereof, cerium oxalate and hydrate thereof, cerium octoate and hydrate thereof, cerium ammonium nitrate and hydrate thereof, cerium ammonium sulfate and hydrate thereof, cerium isopropoxide and hydrate thereof, cerium acetylacetonate and hydrate thereof, and cerium 2-ethylhexanoate and hydrate thereof; and/or the presence of a gas in the gas,
the zirconium source comprises at least one of zirconium chloride and hydrates thereof, zirconyl nitrate and hydrates thereof, zirconium acetate and hydrates thereof, zirconium sulfate and hydrates thereof, zirconium acetylacetonate and hydrates thereof, zirconyl hydroxide and hydrates thereof, and zirconyl chloride and hydrates thereof.
In one embodiment, a conditioning agent comprising at least one of formic acid, acetic acid, benzoic acid, and ammonia is added before the first solution and the second solution are mixed for self-assembly reaction.
In one embodiment, the molar amount of the modifier is within 100 times the total molar amount of the dopant metal source and the base metal source.
An electrode material prepared by the preparation method described in any one of the above embodiments.
An electrode material of a solid oxide fuel cell comprises the electrode material obtained by the preparation method in any one of the above embodiments.
An electrode material for a solid oxide electrolytic cell comprising the electrode material obtained by the method of any one of the preceding examples.
The preparation method of the electrode material utilizes the organic ligand, the first doping metal source and the base metal source to assemble to form the first solid precursor, the organic ligand, the first doping metal element and the base metal element in the first solid precursor are combined through chemical bonds and then physically mixed with the second doping metal element in the second doping metal source to obtain the second solid precursor, and finally the second solid precursor is subjected to heat treatment, so that the organic ligand component is pyrolyzed in a proper crystal phase structure, and the electrode material with high porosity and high specific surface area is formed and has higher catalytic activity. Through the intensive research on organic ligands and raw materials of electrode materials of solid oxide fuel cells or electrolytic cells, the inventor selects proper organic ligands and materials of a first doped metal source, a base metal source and a second doped metal source to be matched with each other, and provides a simple and easy method suitable for popularization for the preparation of high-activity electrode materials of solid oxide fuel cells or electrolytic cells.
Drawings
FIG. 1 is an SEM photograph of an electrode material obtained in example 1 of the present invention;
FIG. 2 is an XRD pattern of an electrode material obtained in example 1 of the present invention and commercially available GDC;
fig. 3 is a graph of voltage-current and power density-current for a solid oxide fuel cell A1;
fig. 4 is a graph of voltage-current and power density-current for the solid oxide fuel cell A2.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, as those skilled in the art will recognize without departing from the spirit and scope of the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An embodiment of the invention provides a preparation method of an electrode material. The preparation method comprises the following steps:
s01: providing a first solution comprising a first doping metal source, a base metal source, and a first solvent; wherein the first doped metal source comprises at least one of a gadolinium source, a samarium source, a lanthanum source, an yttrium source, a scandium source, a manganese source, an iron source, a cobalt source, a nickel source, a copper source, a zinc source and a tin source; the base metal source includes at least one of a cerium source and a zirconium source. The first solvent is any common solvent that can dissolve the first dopant metal source and the base metal source.
S02: providing a second solution comprising an organic ligand and a second solvent; wherein the organic ligand comprises at least one of trimesic acid, terephthalic acid, 4' -biphenyldicarboxylic acid and [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid. The second solvent is any common solvent that can dissolve the organic ligand.
S03: and mixing the first solution and the second solution to carry out self-assembly reaction to obtain a first solid precursor.
S04: mixing the first solid precursor with a second doped metal source to obtain a second solid precursor; the second doped metal source comprises at least one of a gadolinium source, a samarium source, a lanthanum source, an yttrium source, a scandium source, a manganese source, an iron source, a cobalt source, a nickel source, a copper source, a zinc source and a tin source.
S05: the second solid precursor is subjected to a thermal treatment.
In the preparation method of the embodiment, a first solid precursor is obtained mainly by selecting an organic ligand, a first doping metal source and a base metal source to perform a self-assembly reaction; by selecting the second doping metal source to physically combine with the first solid precursor and then thermally treating the combined second solid precursor, the organic ligand component is pyrolyzed in a suitable crystalline phase structure to form an electrode material with high porosity and high specific surface area. The electrode material prepared by the preparation method has higher catalytic activity, so that the performance of a solid oxide fuel cell or an electrolytic cell is improved, and the electrode material can be popularized and applied as an ideal electrode material of SOFC or SOEC.
It will be appreciated that solution formulation of the first solution or the second solution may be carried out according to methods conventional in the art. Specifically, when preparing an electrode material, dissolving a first doped metal source and a base metal source in a first solvent to obtain a first solution; dissolving the organic ligand in a second solvent to obtain a second solution. It is understood that these two steps can be performed separately, sequentially, or simultaneously. That is, S01 and S02 may be performed separately and sequentially, or may be performed simultaneously. For example, in the preparation method, S01 may be performed before S02, S01 may be performed after S02, and S01 and S02 may be performed simultaneously.
In yet another embodiment of the present invention, a method for preparing an electrode material is provided. The preparation method comprises the following steps: dissolving a first doped metal source and a base metal source in a first solvent to obtain a first solution; wherein the first doped metal source comprises at least one of gadolinium source, samarium source, lanthanum source, yttrium source, scandium source, manganese source, iron source, cobalt source, nickel source, copper source, zinc source and tin source; the base metal source includes at least one of a cerium source and a zirconium source. Dissolving an organic ligand in a second solvent to obtain a second solution; wherein the organic ligand comprises at least one of trimesic acid, terephthalic acid, 4' -biphenyldicarboxylic acid and [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid. And mixing the first solution and the second solution to carry out self-assembly reaction to obtain the solid precursor. Mixing the first solid precursor with a second doped metal source to obtain a second solid precursor; the second doped metal source comprises at least one of a gadolinium source, a samarium source, a lanthanum source, an yttrium source, a scandium source, a manganese source, an iron source, a cobalt source, a nickel source, a copper source, a zinc source and a tin source. The solid precursor is heat treated.
It is understood that the first and second doped metal sources may be the same or different. The first doped metal source and the second doped metal source can be respectively and independently selected from at least one of gadolinium source, samarium source, lanthanum source, yttrium source, scandium source, manganese source, iron source, cobalt source, nickel source, copper source, zinc source and tin source. Preferably, the second
In some embodiments, the first source of doping metal is selected from at least one of a source of gadolinium, a source of samarium, a source of lanthanum, a source of yttrium, and a source of scandium, and the second source of doping metal is selected from at least one of a source of manganese, a source of iron, a source of cobalt, a source of nickel, a source of copper, a source of zinc, and a source of tin.
In some preferred embodiments, the first source of dopant metal is selected from at least one of a source of gadolinium, a source of samarium, and a source of lanthanum, the second source of dopant metal is selected from at least one of a source of nickel, a source of cobalt, a source of copper, and a source of iron, and the base metal source is selected from a source of cerium.
In further preferred embodiments, the first doping metal source is selected from at least one of a yttrium source and a scandium source, the second doping metal source is selected from at least one of a nickel source, a cobalt source, a copper source and an iron source, and the base metal source is selected from a zirconium source.
The first doped metal source is used for improving the ionic conductivity of the material, and the second doped metal source is used for improving the electronic conduction and the catalytic activity of the material. Through the selection of the first doped metal source and the second doped metal source, the prepared electrode material is more beneficial to improving the performance of the solid oxide fuel cell or the electrolytic cell.
In some specific examples, the molar ratio of the first dopant metal source to the base metal source is x (1-x), where 0 < x ≦ 0.5. When preparing the electrode material, the first doping metal source and the base metal source can be selected in corresponding molar ratios according to the required doping amount. For example, the molar ratio of the first doping metal source to the base metal source may be, but is not limited to, 0.01. Further, the molar ratio of the first dopant metal source to the base metal source may be selected from (0. About.0.5) to (0.5. About.1).
In still other specific examples, the ratio of the total molar amount of the first dopant metal source and the base metal source to the molar amount of the organic ligand is 1. In the method of preparing the electrode material, the molar amount of the organic ligand is selected based on the total molar amount of the first dopant metal source and the base metal source. Alternatively, the ratio of the total molar amount of the first doping metal source and the base metal source to the molar amount of the organic ligand may be 1.
In some specific examples, the mass ratio of the second doping metal source to the first solid precursor is 5. For example, the mass ratio of the second doping metal source and the first solid precursor may be a ratio of 5.
As some examples of the first solvent selection, the first solvent includes at least one of N, N-dimethylformamide, methanol, ethanol, and water. Further, at least one of N, N-dimethylformamide, methanol, ethanol, and water may be selected as the first solvent.
As some examples of the second solvent selection, the second solvent includes at least one of N, N-dimethylformamide, methanol, and ethanol. Further, at least one selected from N, N-dimethylformamide, methanol and ethanol may be used as the second solvent.
As an alternative example of the gadolinium source, the gadolinium source includes at least one of gadolinium nitrate and a hydrate thereof, gadolinium chloride and a hydrate thereof, gadolinium sulfate and a hydrate thereof, gadolinium acetate and a hydrate thereof, gadolinium oxalate and a hydrate thereof, gadolinium octoate and a hydrate thereof, gadolinium isopropoxide and a hydrate thereof, gadolinium acetylacetonate and a hydrate thereof, and gadopentetate dimeglumine and a hydrate thereof.
As an alternative example of the samarium source, the samarium source includes at least one of samarium nitrate and hydrate thereof, samarium chloride and hydrate thereof, samarium sulfate and hydrate thereof, samarium acetate and hydrate thereof, samarium oxalate and hydrate thereof, samarium isopropoxide and hydrate thereof, and samarium acetylacetonate and hydrate thereof.
As alternative examples of the lanthanum source, the lanthanum source includes at least one of lanthanum nitrate and hydrate thereof, lanthanum chloride and hydrate thereof, lanthanum sulfate and hydrate thereof, lanthanum acetate and hydrate thereof, lanthanum oxalate and hydrate thereof, lanthanum isopropoxide and hydrate thereof, and lanthanum acetylacetonate and hydrate thereof.
As an alternative example of the yttrium source, the yttrium source includes at least one of yttrium nitrate and hydrate thereof, yttrium chloride and hydrate thereof, yttrium sulfate and hydrate thereof, yttrium acetate and hydrate thereof, yttrium oxalate and hydrate thereof, yttrium isopropoxide and hydrate thereof, yttrium acetylacetonate and hydrate thereof.
As an alternative example of the scandium source, the scandium source includes at least one of scandium nitrate and a hydrate thereof, scandium chloride and a hydrate thereof, scandium sulfate and a hydrate thereof, scandium acetate and a hydrate thereof, scandium oxalate and a hydrate thereof, and scandium acetylacetonate and a hydrate thereof.
As alternative examples of the manganese source, the manganese source includes at least one of manganese nitrate and a hydrate thereof, manganese sulfate and a hydrate thereof, manganese chloride and a hydrate thereof, manganese acetate and a hydrate thereof, manganese oxalate and a hydrate thereof, and manganese acetylacetonate and a hydrate thereof.
As an alternative example of the iron source, the iron source includes at least one of iron nitrate and its hydrate, iron sulfate and its hydrate, iron chloride and its hydrate, iron oxalate and its hydrate, iron acetylacetonate and its hydrate, ferrous sulfate and its hydrate, ferrous chloride and its hydrate, ferrous acetate and its hydrate, and ferrous oxalate and its hydrate.
As an alternative example of the cobalt source, the cobalt source includes at least one of cobalt nitrate and a hydrate thereof, cobalt sulfate and a hydrate thereof, cobalt chloride and a hydrate thereof, cobalt acetate and a hydrate thereof, cobalt oxalate and a hydrate thereof, and cobalt acetylacetonate and a hydrate thereof.
As alternative examples of the nickel source, the nickel source includes at least one of nickel nitrate and hydrates thereof, nickel sulfate and hydrates thereof, nickel chloride and hydrates thereof, nickel acetate and hydrates thereof, nickel formate and hydrates thereof, nickel oxalate and hydrates thereof, and nickel acetylacetonate and hydrates thereof.
As alternative examples of the copper source, the copper source includes at least one of copper nitrate and hydrate thereof, copper sulfate and hydrate thereof, copper chloride and hydrate thereof, copper acetate and hydrate thereof, copper formate and hydrate thereof, copper oxalate and hydrate thereof, and copper acetylacetonate and hydrate thereof.
As alternative examples of the zinc source, the zinc source includes at least one of zinc nitrate and hydrates thereof, zinc sulfate and hydrates thereof, zinc chloride and hydrates thereof, zinc acetate and hydrates thereof, zinc formate and hydrates thereof, zinc oxalate and hydrates thereof, and zinc acetylacetonate and hydrates thereof.
As alternative examples of the tin source, the tin source includes at least one of tin nitrate and hydrate thereof, tin sulfate and hydrate thereof, tin chloride and hydrate thereof, tin acetate and hydrate thereof, tin formate and hydrate thereof, tin oxalate and hydrate thereof, and tin acetylacetonate and hydrate thereof.
As an alternative example of the cerium source, the cerium source includes at least one of cerium nitrate and a hydrate thereof, cerium chloride and a hydrate thereof, cerium sulfate and a hydrate thereof, cerium carbonate and a hydrate thereof, cerium phosphate and a hydrate thereof, cerium acetate and a hydrate thereof, cerium oxalate and a hydrate thereof, cerium octoate and a hydrate thereof, cerium ammonium nitrate and a hydrate thereof, cerium ammonium sulfate and a hydrate thereof, cerium isopropoxide and a hydrate thereof, cerium acetylacetonate and a hydrate thereof, and cerium 2-ethylhexanoate and a hydrate thereof.
As alternative examples of the zirconium source, the zirconium source includes at least one of zirconium chloride and hydrates thereof, zirconyl nitrate and hydrates thereof, zirconium acetate and hydrates thereof, zirconium sulfate and hydrates thereof, zirconium acetylacetonate and hydrates thereof, zirconyl hydroxide and hydrates thereof, zirconyl chloride and hydrates thereof.
In some specific examples, the reaction temperature of the self-assembly reaction is 60 ℃ to 180 ℃. When the first solution and the second solution are mixed for self-assembly reaction, the reaction temperature of the self-assembly reaction is controlled to be 60-180 ℃, so that the generation of the solid precursor is facilitated. Alternatively, the reaction temperature of the self-assembly reaction is 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃ or the like. It is understood that the reaction temperature of the self-assembly reaction may be selected from the range of 60 ℃ to 180 ℃.
Furthermore, the reaction time of the self-assembly reaction is 0.5 h-48 h. When the first solution and the second solution are mixed for self-assembly reaction, the reaction time of the self-assembly reaction is controlled to be 0.5-48 h, which is beneficial to improving the yield of the electrode material of the solid oxide fuel cell/electrolytic cell produced by the self-assembly reaction. Alternatively, the reaction time of the self-assembly reaction is 0.5h, 1h, 5h, 8h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 48h, or the like. It is understood that the reaction time of the self-assembly reaction can be selected within the range of 0.5h to 48h.
In some specific examples, the stirring speed of the self-assembly reaction is within 1500r/min. After the first solution and the second solution are mixed, the self-assembly reaction is promoted by stirring. Optionally, the stirring speed of the self-assembly reaction is 100r/min, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, 1100r/min, 1200r/min, 1300r/min, 1400r/min or 1500r/min. Preferably, the stirring speed of the self-assembly reaction is within 800r/min. For example, the stirring speed of the self-assembly reaction is 100r/min to 800r/min.
In some specific examples, the temperature of the heat treatment is 400 ℃ to 1200 ℃. When the solid precursor is subjected to heat treatment, a good heat treatment effect can be obtained when the heat treatment temperature is 400-1200 ℃. Compared with the traditional heat treatment, the preparation method effectively reduces the heat treatment temperature, and is beneficial to reducing the energy consumption cost when preparing the electrode material of the solid oxide fuel cell or the electrolytic cell. Optionally, the heat treatment temperature is 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, 1000 deg.C, 1050 deg.C, 1100 deg.C, 1150 deg.C, 1200 deg.C. It is understood that the temperature of the heat treatment may be otherwise selected within the range of 400 c to 1200 c. For example, the heat treatment temperature is 400 ℃ to 800 ℃. Further, the temperature of the heat treatment is 400 ℃ to 600 ℃.
Further, the time of the heat treatment is 0.5 h-12 h. For example, the heat treatment time is 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h. It is understood that the time of the heat treatment can be selected within the range of 0.5h to 12h.
In some specific examples, the particle size of the electrode material obtained after the heat treatment is 10nm to 500nm. The nano-sized electrode material can be obtained after the heat treatment, and the particle size uniformity is excellent. Specifically, the particle size of the solid oxide fuel cell/electrolytic cell electrode material obtained after the heat treatment is 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 150nm, 200nm, 250nm, 300nm, 400nm, 500nm, or the like.
In some specific examples, the specific surface area of the electrode material obtained after the heat treatment is 50m 2 G to 300m 2 (ii) in terms of/g. The electrode material with high specific surface area can be obtained after the heat treatment, so that the catalytic activity of the electrode material is improved, and further, the performance of the solid oxide fuel cell or the electrolytic cell can be improved by applying the electrode material to the solid oxide fuel cell or the electrolytic cell. Specifically, the specific surface area of the electrode material for a solid oxide fuel cell or an electrolytic cell obtained after the heat treatment was 50m 2 /g、60m 2 /g、70m 2 /g、80m 2 /g、90m 2 /g、100m 2 /g、120m 2 /g、140m 2 /g、160m 2 /g、180m 2 /g、200m 2 /g、220m 2 /g、240m 2 /g、260m 2 /g、280m 2 /g、300m 2 /g。
In some specific examples, a conditioning agent comprising at least one of formic acid, acetic acid, benzoic acid, and ammonia is added to the mixture prior to mixing the first solution and the second solution for the self-assembly reaction. Specifically, the molar amount of modifier is within 100 times the total molar amount of the dopant metal source and the base metal source. Further, the molar amount of the modifier is within 90 times the total molar amount of the dopant metal source and the base metal source. Further, the molar amount of the modifier is within 80 times the total molar amount of the dopant metal source and the base metal source. Further, the molar amount of the modifier is within 50 times the total molar amount of the dopant metal source and the base metal source. Further, the molar amount of the modifier is within 10 times the total molar amount of the dopant metal source and the base metal source. Further, the molar amount of the modifier is within 5 times the total molar amount of the dopant metal source and the base metal source.
In some specific examples, the self-assembly of the first solid precursor further comprises the following steps: the first solid precursor is subjected to a drying process. Specifically, the temperature of the drying treatment is-50 ℃ to 300 ℃; and/or the drying time is 0.5-48 h. For example, the drying temperature may be-50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃, 0 ℃, 10 ℃, 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃. It is understood that the temperature of the drying process may be otherwise selected within the range of-50 deg.C to 300 deg.C. Alternatively, the drying treatment time is 0.5h, 1h, 5h, 8h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 48h, or the like. It is understood that the time of the drying treatment can be selected from the range of 0.5h to 48h.
Further, the method comprises the following steps after the first solid precursor is obtained and before the first solid precursor is dried: the first solid precursor is subjected to a washing treatment.
It is understood that the first solid precursor and the mixed solution may be separated by a filtering process.
In some specific examples, the method of mixing the first solid precursor with the second doping metal source may be solid-solid mixing, solid-liquid mixing, or liquid-liquid mixing. It is to be understood that the first solid precursor may be a solid, or the first solid precursor may be dispersed in a third solvent, and the second dopant metal source may be a solid, or the second dopant metal source may be dispersed in a third solvent. For example, the first solid precursor and the second doping metal source are both solids, and the first solid precursor and the second doping metal source are mixed in a solid-solid mixing manner. For another example, the first solid precursor is a solid, the second doping metal source is dispersed in the third solvent, and the first solid precursor and the second doping metal source are mixed in a solid-liquid mixing manner. Alternatively, the second doping metal source is a solid, the first solid precursor is dispersed in the third solvent, and the first solid precursor and the second doping metal source are mixed in a solid-liquid mixing manner. For another example, the first solid precursor is dispersed in the third solvent, and the second doping metal source is also dispersed in the third solvent, and the first solid precursor and the second doping metal source are mixed in a liquid-liquid mixing manner. Preferably, the solid-liquid mixing or liquid-liquid mixing is more favorable for improving the uniformity of the mixing of the first solid precursor and the second doping metal source, and compared with the solid-solid mixing, the solid-liquid mixing or liquid-liquid mixing is favorable for promoting the particle size of the solid oxide fuel cell/electrolytic cell electrode material to form a nanometer-scale particle size.
The third solvent may be selected from the same solvents as the first solvent, and is usually low boiling point methanol and ethanol, which are not described herein again.
It is understood that for the embodiment of solid-liquid mixing or liquid-liquid mixing, the step of heating with stirring to evaporate the solvent is further included after the first solid precursor is mixed with the second doping metal source. Further, it is necessary to perform a washing treatment and/or a drying treatment of the solid phase after the solvent evaporation. The specific method of the washing treatment or the drying treatment is the same as that of the washing treatment or the drying treatment of the first solid precursor, and is not described herein again.
Yet another embodiment of the present invention provides an electrode material. The electrode material is prepared by the preparation method. The electrode material has high purity, large specific surface area, uniform particles and adjustable particle size at the nanometer level, is favorable for sintering and forming in the electrode preparation process, and can be popularized and applied as an ideal electrode material of SOFC or SOEC.
The invention also provides an electrode material obtained by the preparation method and/or application of the electrode material in a solid oxide fuel cell or a solid oxide electrolytic cell.
In still another embodiment of the present invention, an electrode material of a solid oxide fuel cell includes the electrode material obtained by the above preparation method and/or the above electrode material.
In a further embodiment of the invention, a solid oxide electrolytic cell is provided, wherein the electrolyte and/or electrode material of the solid oxide electrolytic cell comprises the electrode material obtained by the preparation method and/or the electrode material.
The following are specific examples.
The following english abbreviations have the following meanings:
GOC: gadolinium-doped ceria;
YSZ: yttrium-stabilized zirconia;
LSCF: lanthanum strontium cobalt iron powder;
DMF: n, N-dimethylformamide.
Example 1
In this example, an electrode material was prepared. The preparation method comprises the following steps:
s101: dissolving a gadolinium source and a cerium source in a first solvent to obtain a first solution. Wherein the gadolinium source is gadolinium nitrate hexahydrate, the cerium source is cerium nitrate hexahydrate, and the first solvent is N, N-Dimethylformamide (DMF). The molar ratio of the gadolinium source to the cerium source is 0.1.
S102: dissolving an organic ligand in a second solvent to obtain a second solution; wherein the organic ligand is terephthalic acid, and the second solvent is N, N-Dimethylformamide (DMF). The ratio of the total molar weight of the gadolinium source and the cerium source to the molar weight of the organic ligand is 1.
S103: and mixing the first solution and the second solution, adding a regulator, and carrying out self-assembly reaction to obtain a first solid precursor. Wherein the regulator is acetic acid. The molar amount of the regulator is 0.1 times the total molar amount of the gadolinium source and the cerium source. The reaction temperature of the self-assembly reaction is 120 ℃, and the reaction time of the self-assembly reaction is 24 hours.
And washing and drying the first solid precursor. Wherein the drying temperature is 80 ℃, and the drying time is 12h.
S104: and dispersing the dried first solid precursor into a third solvent, adding a nickel source, stirring and dispersing at 60 ℃ until the solvent is completely evaporated, and drying the solid obtained after evaporation to obtain a second solid precursor. Wherein the third solvent is ethanol, the nickel source is nickel nitrate hexahydrate, and the mass ratio of the first solid precursor to the nickel nitrate is 1; the temperature of the drying treatment is 80 ℃, and the time of the drying treatment is 12h.
S105: the second solid precursor after drying at S104 is subjected to heat treatment. Wherein the heat treatment temperature is 600 ℃, and the heat treatment time is 1h.
Test example
1. Morphology testing and Crystal testing
After the heat treatment, the electrode material in the present example is obtained, and its SEM image is shown in fig. 1, and its XRD pattern is shown in fig. 2. In addition, an XRD (X-ray diffraction) pattern of a commercially available electrode material GDC is provided, and the comparison shows that the crystal form of the electrode material prepared by the method is consistent with that of a conventional GDC electrode material, and the chemical component of the electrode material is NiO-GOC.
2. Specific surface area test
The test method comprises the following steps: measurement of BET specific surface area of electrode Material by static Capacity method
The specific surface area of the electrode material obtained in the embodiment can reach 120m 2 Therefore, the catalyst has higher catalytic activity.
Comparative example 1
Substantially the same as the preparation method of example 1, except that the electrode material was prepared by the coprecipitation method. 0.1M aqueous solutions of cerium nitrate hexahydrate and gadolinium nitrate hexahydrate were prepared, respectively. Adding ammonia water dropwise to the mixture, and continuously stirring while adjusting the pH to complete precipitation; stirring the mixture for 2h and aging for 6h, filtering and washing the obtained solid, washing and drying the obtained solid, dispersing the washed and dried solid in ethanol, adding nickel nitrate hexahydrate, stirring and dispersing the mixture at the temperature of 60 ℃ until the solvent is completely evaporated, and drying the solid obtained after evaporation; and (3) carrying out heat treatment on the dried solid, wherein the heat treatment temperature is 600 ℃, and the heat treatment time is 1h.
Example 2 solid oxide Fuel cell A1
S201, grinding and uniformly mixing the electrode material prepared in the example 1 and the organic binder according to the mass ratio of 6. Wherein the organic binder is terpineol solution containing ethyl cellulose.
And S202, combining the obtained slurry with a YSZ electrolyte sheet by adopting a screen printing method, and sintering for 2 hours at 1300 ℃ in an air atmosphere to obtain the solid oxide fuel cell electrode functional layer half cell. Wherein the electrolyte layer is YSZ.
And S203, screen printing GDC and LSCF/GDC on the other surface of the obtained half cell for two times, sintering and assembling to obtain the button full cell A1.
Example 3 solid oxide Fuel cell A2
Substantially the same preparation method as in example 2 was used except that the electrode material prepared in comparative example 1 was used.
Battery performance testing
The test method comprises the following steps: respectively installing the assembled button full batteries A1 and A2 on a test bench, and leading H into the anode 2 The cathode side was exposed to air and the electrochemical performance was tested by an electrochemical workstation at 850 c operating temperature.
As a result, as shown in FIGS. 3 and 4, the maximum current density of the battery A1 was 589mA cm -2 The power density is 174mW cm -2 (ii) a The maximum current density of the battery A2 was 275mA cm -2 The power density is 83mW cm -2 . Therefore, the electrode material provided by the invention has higher catalytic activity, and can effectively improve the electrochemical performance of the battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims, and the description and the drawings can be used for explaining the contents of the claims.

Claims (10)

1. The preparation method of the electrode material is characterized by comprising the following steps of:
providing a first solution comprising a first doping metal source, a base metal source and a first solvent, and a second solution comprising an organic ligand and a second solvent;
mixing the first solution and the second solution to carry out self-assembly reaction to obtain a first solid precursor;
mixing the first solid precursor with a second doping metal source to obtain a second solid precursor; and
heat treating the second solid precursor;
wherein the first doped metal source and the second doped metal source are respectively and independently selected from at least one of gadolinium source, samarium source, lanthanum source, yttrium source, scandium source, manganese source, iron source, cobalt source, nickel source, copper source, zinc source and tin source;
the base metal source comprises at least one of a cerium source and a zirconium source;
the organic ligand comprises at least one of trimesic acid, terephthalic acid, 4' -biphenyldicarboxylic acid and [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid.
2. The method of claim 1, wherein the first doped metal source is selected from at least one of gadolinium, samarium, lanthanum, yttrium, and scandium, and the second doped metal source is selected from at least one of iron, cobalt, nickel, and copper.
3. The method of claim 1, wherein the molar ratio of the first dopant metal source to the base metal source is x (1-x), wherein 0 < x ≦ 0.5; and/or the presence of a gas in the atmosphere,
the ratio of the total molar amount of the first doping metal source and the base metal source to the molar amount of the organic ligand is 1.1 to 1; and/or
The mass ratio of the second doping metal source to the first solid precursor is 5.
4. The method for preparing an electrode material according to claim 1, wherein the reaction temperature of the self-assembly reaction is 60 ℃ to 180 ℃; and/or the presence of a gas in the gas,
the reaction time of the self-assembly reaction is 0.5-48 h; and/or the presence of a gas in the gas,
the temperature of the heat treatment is 400-1200 ℃; and/or the presence of a gas in the gas,
the time of the heat treatment is 0.5 to 12 hours.
5. The method of preparing an electrode material according to claim 1, wherein the first solvent comprises at least one of N, N-dimethylformamide, methanol, ethanol, and water; and/or the presence of a gas in the gas,
the second solvent comprises at least one of N, N-dimethylformamide, methanol and ethanol; and/or the presence of a gas in the atmosphere,
the gadolinium source comprises at least one of gadolinium nitrate and a hydrate thereof, gadolinium chloride and a hydrate thereof, gadolinium sulfate and a hydrate thereof, gadolinium acetate and a hydrate thereof, gadolinium oxalate and a hydrate thereof, gadolinium octoate and a hydrate thereof, gadolinium isopropoxide and a hydrate thereof, gadolinium acetylacetonate and a hydrate thereof, and gadopentetate dimeglumine and a hydrate thereof; and/or the presence of a gas in the gas,
the samarium source comprises at least one of samarium nitrate and hydrate thereof, samarium chloride and hydrate thereof, samarium sulfate and hydrate thereof, samarium acetate and hydrate thereof, samarium oxalate and hydrate thereof, samarium isopropoxide and hydrate thereof, and samarium acetylacetonate and hydrate thereof; and/or the presence of a gas in the atmosphere,
the lanthanum source comprises at least one of lanthanum nitrate and hydrate thereof, lanthanum chloride and hydrate thereof, lanthanum sulfate and hydrate thereof, lanthanum acetate and hydrate thereof, lanthanum oxalate and hydrate thereof, lanthanum isopropoxide and hydrate thereof, and lanthanum acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the yttrium source comprises at least one of yttrium nitrate and hydrates thereof, yttrium chloride and hydrates thereof, yttrium sulfate and hydrates thereof, yttrium acetate and hydrates thereof, yttrium oxalate and hydrates thereof, yttrium isopropoxide and hydrates thereof, and yttrium acetylacetonate and hydrates thereof; and/or the presence of a gas in the gas,
the scandium source comprises at least one of scandium nitrate and hydrate thereof, scandium chloride and hydrate thereof, scandium sulfate and hydrate thereof, scandium acetate and hydrate thereof, scandium oxalate and hydrate thereof, and scandium acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the manganese source comprises at least one of manganese nitrate and hydrate thereof, manganese sulfate and hydrate thereof, manganese chloride and hydrate thereof, manganese acetate and hydrate thereof, manganese oxalate and hydrate thereof, and manganese acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the iron source comprises at least one of ferric nitrate and hydrate thereof, ferric sulfate and hydrate thereof, ferric chloride and hydrate thereof, ferric oxalate and hydrate thereof, ferric acetylacetonate and hydrate thereof, ferrous sulfate and hydrate thereof, ferrous chloride and hydrate thereof, ferrous acetate and hydrate thereof, and ferrous oxalate and hydrate thereof; and/or the presence of a gas in the gas,
the cobalt source comprises at least one of cobalt nitrate and hydrate thereof, cobalt sulfate and hydrate thereof, cobalt chloride and hydrate thereof, cobalt acetate and hydrate thereof, cobalt oxalate and hydrate thereof, cobalt acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the nickel source comprises at least one of nickel nitrate and hydrates thereof, nickel sulfate and hydrates thereof, nickel chloride and hydrates thereof, nickel acetate and hydrates thereof, nickel formate and hydrates thereof, nickel oxalate and hydrates thereof, and nickel acetylacetonate and hydrates thereof; and/or the presence of a gas in the gas,
the copper source comprises at least one of copper nitrate and hydrate thereof, copper sulfate and hydrate thereof, copper chloride and hydrate thereof, copper acetate and hydrate thereof, copper formate and hydrate thereof, copper oxalate and hydrate thereof, and copper acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the zinc source comprises at least one of zinc nitrate and hydrate thereof, zinc sulfate and hydrate thereof, zinc chloride and hydrate thereof, zinc acetate and hydrate thereof, zinc formate and hydrate thereof, zinc oxalate and hydrate thereof, and zinc acetylacetonate and hydrate thereof; and/or the presence of a gas in the gas,
the tin source comprises at least one of tin nitrate and hydrate thereof, tin sulfate and hydrate thereof, tin chloride and hydrate thereof, tin acetate and hydrate thereof, tin formate and hydrate thereof, tin oxalate and hydrate thereof, and tin acetylacetonate and hydrate thereof; and/or the presence of a gas in the atmosphere,
the cerium source comprises at least one of cerium nitrate and hydrate thereof, cerium chloride and hydrate thereof, cerium sulfate and hydrate thereof, cerium acetate and hydrate thereof, cerium oxalate and hydrate thereof, cerium octoate and hydrate thereof, cerium ammonium nitrate and hydrate thereof, cerium ammonium sulfate and hydrate thereof, cerium isopropoxide and hydrate thereof, cerium acetylacetonate and hydrate thereof, and cerium 2-ethylhexanoate and hydrate thereof; and/or the presence of a gas in the gas,
the zirconium source comprises at least one of zirconium chloride and hydrates thereof, zirconyl nitrate and hydrates thereof, zirconium acetate and hydrates thereof, zirconium sulfate and hydrates thereof, zirconium acetylacetonate and hydrates thereof, zirconyl hydroxide and hydrates thereof, and zirconyl chloride and hydrates thereof.
6. The method for producing an electrode material according to any one of claims 1 to 5, wherein a conditioning agent comprising at least one of formic acid, acetic acid, benzoic acid, and ammonia water is added to the mixed solution before the self-assembly reaction by mixing the first solution and the second solution.
7. The method of claim 6, wherein the molar amount of the modifier is within 100 times the total molar amount of the dopant metal source and the base metal source.
8. An electrode material, characterized in that the electrode material is prepared by the preparation method of any one of claims 1 to 7.
9. A solid oxide fuel cell, characterized in that an electrode material thereof comprises an electrode material obtained by the production method according to any one of claims 1 to 7.
10. A solid oxide electrolytic cell characterized in that an electrode material thereof comprises an electrode material obtained by the production method described in any one of claims 1 to 7.
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