CN115180946A - Multifunctional ceramic material capable of resisting ultra-fast temperature rise and drop and preparation method and application thereof - Google Patents
Multifunctional ceramic material capable of resisting ultra-fast temperature rise and drop and preparation method and application thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
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- 239000003054 catalyst Substances 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 6
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- 238000000502 dialysis Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000007863 gel particle Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 4
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- 229960001484 edetic acid Drugs 0.000 description 10
- 230000035939 shock Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
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- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 239000006257 cathode slurry Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
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- 230000007547 defect Effects 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 229910002607 Gd0.1Ce0.9O1.95 Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
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- 229910002453 Co-O-Co Inorganic materials 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 230000009881 electrostatic interaction Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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Abstract
The invention provides a multifunctional ceramic material capable of resisting ultra-fast temperature rise and drop, a preparation method and application thereof, wherein the chemical general formula of the multifunctional ceramic material is Ln 0.5 M 0.5 Co 1‑x Bi x O 3‑δ Wherein Ln is the combination of one or more elements of Y, la, ce, pr, nd, sm and Gd, M is the combination of one or more elements of Ba, sr, ca and Mg, and x is more than or equal to 0 and less than or equal to 0.5; delta is the oxygen vacancy content, and delta is more than or equal to 0 and less than or equal to 1. The preparation method comprises the following steps: dissolving a complexing agent in water to obtain a solution I; (2) Adding soluble salts of Ln, M, co and Bi into the solution I; adjusting the pH value of the alkaline solution to obtain a solution II; (3) heating and stirring the solution II at constant temperature to form sol; (4) preparing dry gel particles; (5) pre-sintering; (6) pressing; and (7) high-temperature sintering. The multifunctional ceramic material can resist rapid temperature rise and drop, and has high electronic conductivity, high oxygen catalytic activity and oxygen ion conductivityThe characteristics of (1).
Description
Technical Field
The invention belongs to the technical field of functional ceramics, and particularly relates to a multifunctional ceramic material, and a preparation method and application thereof.
Background
The functional ceramic has wide application in the fields of communication, medical treatment, new energy and the like due to unique mechanical, electrical, optical, thermodynamic and catalytic properties. Particularly in the fields of high-temperature electrocatalysis and ion and electron conduction of new energy, the metal oxide ceramic material can replace the traditional noble metal material, greatly reduce the production and manufacturing cost of new energy devices, and promote the practicability of new energy technology.
However, ceramic materials generally suffer from poor thermal shock resistance. When the temperature rise and fall rate reaches 20 ℃/min, most of the ceramics can be cracked, and the actual service life of the high-temperature electrochemical device is seriously influenced. For example, in the field of solid oxide fuel cells and solid oxide electrolyzers, the oxygen electrode La is commercialized 0.2 Sr 0.8 Co 0.2 Fe 0.8 O 3-δ When the temperature rising and falling rate of the (LSCF) is more than 15 ℃/min, the (LSCF) can generate cracking and falling problems. In response to this problem, attempts have been made to improve the thermal shock resistance of electrodes by preparing composite materials by adding electrolyte materials having a lower coefficient of thermal expansion, such as yttria-stabilized zirconia (YSZ) and gadolinium oxide-doped ceria (GDC), to LSCF electrodes. However, YSZ and GDC particles also burst at ramping rates greater than 20 deg.C/min. For high-temperature electrochemical devices, the temperature rise and fall rate of 20 ℃ per minute is very common under actual working conditions, so that a multifunctional ceramic material capable of resisting rapid temperature rise and fall needs to be developed.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and provides a multifunctional ceramic material which can resist ultra-fast temperature rise and drop, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a multifunctional ceramic material resistant to ultra-fast temperature rise and drop, said materialThe chemical general formula of the multifunctional ceramic material is Ln 0.5 M 0.5 Co 1-x Bi x O 3-δ Wherein Ln is the combination of one or more elements of Y, la, ce, pr, nd, sm and Gd, M is the combination of one or more elements of Ba, sr, ca and Mg, and x is more than or equal to 0 and less than or equal to 0.5; the delta is the content of oxygen vacancy, specifically the content of oxygen vacancy in a single unit cell in the material, and delta is more than or equal to 0 and less than or equal to 1.
For the multifunctional ceramic material of the present invention, if x is greater than 0.5, the material will be too soft and will be difficult to phase.
Preferably, the tolerance of ultra-fast temperature rise and drop refers to the tolerance of temperature rise or temperature drop at a speed of more than 100 ℃/s. The multifunctional ceramic material is heated or cooled at a speed of more than 100 ℃/s, and the multifunctional ceramic material does not crack.
Further preferably, the tolerance of ultra-fast temperature rise and drop refers to tolerance of temperature rise or temperature drop at a rate of more than 500 ℃/s.
Preferably, the multifunctional ceramic material has an electrical conductivity of more than 200S/cm at a temperature of 25-800 ℃. The material of the present invention has this feature because there is a large amount of variable valence Co element in the material and holes as electron conduction carriers can diffuse in the Co-O-Co bonds.
Preferably, the multifunctional ceramic material has a chemical formula of Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ 、La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ Or Pr 0.5 Sr 0.5 Co 0.65 Bi 0.35 O 3-δ 。
Preferably, the multifunctional ceramic material is of a perovskite structure and has a molecular general formula of ABO 3-δ Wherein A is Ln 0.5 M 0.5 B is Co 1-x Bi x The multifunctional ceramic material with the perovskite structure is a cubic phase, a tetragonal phase or an orthogonal phase. The crystal structure of the multifunctional ceramic material can be schematically shown in fig. 11.
As a general inventive concept, the present invention provides a method for preparing a multifunctional ceramic material that is resistant to ultra-fast temperature rise and drop, the method for preparing is a sol-gel method, comprising the steps of:
(1) Dissolving a complexing agent in purified water to obtain a solution I;
(2) Adding soluble salts of Ln, M, co and Bi into the solution I according to the mixture ratio of the molecular formula; adjusting the pH value of the obtained solution to be nearly neutral by using alkali liquor to obtain a solution II;
(3) Placing the solution II in a closed container, heating and stirring at constant temperature to form sol;
(4) Preparing the sol into xerogel particles by using a spray drying method;
(5) Pre-sintering the xerogel particles to obtain pre-sintered powder;
(6) Pressing the pre-sintered powder into a sintered green body;
(7) And sintering the sintered green body at high temperature to obtain the multifunctional ceramic material.
Preferably, in the step (1), the complexing agent comprises citric acid and ethylenediamine tetraacetic acid with a molar ratio of 1; in the invention, citric acid and ethylenediamine tetraacetic acid are used as complexing agents, so that a multifunctional ceramic material with more uniform components can be obtained;
in the step (2), the molar ratio of the total metal cations of the added soluble salt to the sum of the molar amounts of all complexing agent components in the solution I is (1-1); the soluble salts of Ln, M, co and Bi are nitrate of Ln, nitrate of M, nitrate of Co and nitrate of Bi; and the pH value of the obtained solution is adjusted to be close to neutral by using alkali liquor, specifically, the pH value of the obtained solution is adjusted to be 6-7 by using ammonia water.
Preferably, in the step (3), the constant-temperature heating and stirring temperature is 60-95 ℃ and the time is 5-50h;
in the step (4), the temperature of a spray nozzle is 100-200 ℃ during spray drying;
in the step (5), the pre-sintering temperature is 300-700 ℃, and the pre-sintering time is 2-10h;
in the step (6), the pressing pressure is 100-200MPa;
in the step (7), the high-temperature sintering temperature is 1000-1200 ℃, and the high-temperature sintering time is 4-10h.
As a general inventive concept, the present invention provides an application of the above multifunctional ceramic material or the multifunctional ceramic material prepared by the above preparation method, wherein the multifunctional ceramic material is used as a membrane material of a high temperature oxygen dialysis membrane, a cathode catalyst of a solid oxide fuel cell, an anode catalyst of a solid oxide electrolysis cell or a catalyst of a high temperature oxygen sensor; when the multifunctional ceramic material is applied in the fields, the multifunctional ceramic material has the characteristics of high catalytic activity and good thermal shock resistance;
or the multifunctional ceramic material is applied to preparing an oxygen electrode of a metal-air battery, wherein the metal-air battery is a magnesium-air battery, a zinc-air battery, an aluminum-air battery or a lithium-air battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the multifunctional ceramic material can resist extremely rapid temperature rise and drop, and has the following innovation compared with the traditional material: (1) Due to the difference of the radius of the metal element ions in the unit cell, the metal element is often subjected to tensile or compressive stress and deviates from the original lattice point position, and the release of the strain can cause the cracking of the material in the process of rapid temperature rise and drop, while the electrostatic interaction among the chemical defects, among the chemical defects and the metal cations and among the metal cations in the multifunctional ceramic material can counteract the stress applied to the metal element to a certain extent, so that the metal element returns to the original lattice point position, and the perovskite lattice strain of the material is very small. (2) In the multifunctional ceramic material, ln, M, co and/or Bi elements are uniformly distributed in perovskite lattices, the vibration is mainly elastic simple harmonic vibration, and the phase change cannot occur in the temperature rise and fall process. (3) The multifunctional ceramic material has very high heat conductivity, can quickly conduct heat, and avoids internal thermal stress concentration.
2. The multifunctional ceramic material has a certain amount of oxygen vacancies in a free state besides high electronic conductivity, the oxidation or reduction of oxygen is very easy to realize under the combined action of the oxygen vacancies on the surface of the material and electrons, and the oxygen vacancies in the free state in the bulk phase of the material are carriers for oxygen ion conduction, so that the material can be ensured to have high oxygen ion conductivity.
3. The multifunctional ceramic material has potential application in the fields of high-temperature oxygen dialysis membranes, solid oxide fuel cells, solid oxide electrolytic cells, high-temperature oxygen sensors, metal air batteries and the like; the adaptability to actual working conditions is strong, the production and operation costs are greatly reduced, the preparation method is simple, the success rate of preparation is high, and the method is suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ Ceramic material is processed by>A real object graph after annealing at 500 ℃/s;
FIG. 2 shows Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ Ceramic material is processed by>A real object graph after heating at 500 ℃/s;
FIG. 3 shows Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ A graph of the electrical conductivity of a ceramic material in air as a function of temperature;
FIG. 4 shows a view of a lens having Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ Electrochemical impedance spectrum of symmetric cell with cathode coating;
FIG. 5 shows a view of a lens having Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ Voltage-current and output power density-current curves for cathode coated cells;
FIG. 6 is La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ Passing a ceramic material through>Scanning electron microscope image after annealing at 500 ℃/s;
FIG. 7 is La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ A graph of the electrical conductivity of a ceramic material in air as a function of temperature;
FIG. 8 shows a cross-sectional view of a film having La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ Electrochemical impedance spectrum of symmetric cell with cathode coating;
FIG. 9 shows Pr 0.5 Sr 0.5 Co 0.65 Bi 0.35 O 3-δ Passing a ceramic material through>Scanning electron microscope image after 500 ℃/s annealing;
FIG. 10 is La 0.2 Sr 0.8 Co 0.2 Fe 0.8 O 3-δ Passing a ceramic material through<1 ℃/s annealed material object diagram;
FIG. 11 is a schematic diagram of the crystal structure of the multifunctional ceramic material of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings, and the scope of the invention is not limited to the following specific embodiments.
Unless otherwise defined, 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 herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a multifunctional ceramic material with high resistance to ultra-fast heating and cooling has a chemical formula of Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ (delta is more than or equal to 0 and less than or equal to 1), wherein delta is the content of oxygen vacancy, and the material has a perovskite structure of an orthorhombic phase.
The multifunctional ceramic material is prepared by a sol-gel method, and the method comprises the following specific steps:
(1) Dissolving complexing agent citric acid and ethylene diamine tetraacetic acid into purified water according to the molar ratio of 1.
(2) Adding neodymium nitrate, barium nitrate, strontium nitrate, cobalt nitrate and bismuth nitrate into the solution I according to the formula ratio, wherein the molar ratio of the total metal cations of the nitrate to complexing agents (citric acid and ethylene diamine tetraacetic acid) is 1; then, the pH value of the solution is adjusted to 6 by ammonia water to obtain a solution II.
(3) And (3) placing the solution II in a closed container, heating at the constant temperature of 60 ℃ and stirring for 50 hours to form sol.
(4) The sol is formed into xerogel particles by a spray drying method, wherein the temperature of a spray opening is 200 ℃.
(5) And placing the xerogel particles in a box furnace to be presintered for 2 hours at 700 ℃ to obtain presintered powder.
(6) And placing the pre-sintered powder in a circular grinding tool, and pressing under the pressure of 200MPa to prepare a sintered green body.
(7) Sintering the sintered green body at 1000 ℃ for 10h to obtain Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ A ceramic material.
And (4) performance testing:
to verify the thermal shock resistance of the material, nd prepared in example 1 was used 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ The ceramic material wafer was removed from the sintering furnace at 1000 c and dropped into liquid nitrogen within 2 seconds, with the actual cooling rate being greater than 500 c/s. Nd taken out of liquid nitrogen 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ The ceramic wafer is shown in figure 1, and the surface does not crack, which shows that the material has excellent thermal shock resistance.
To further verify Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ The ceramic material wafer is cut into a rectangular strip with the performance of resisting rapid temperature rise. And directly placing the strip into a box-type furnace hearth heated to 1000 ℃, wherein the actual temperature rise rate is more than 500 ℃/s. After 5 minutes, the tube was directly taken out and cooled to room temperature in air. As shown in FIG. 2, the resulting strip was rapidly heated, and no cracking or the like was observed. Description of Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ Ceramic materials are able to withstand rapid temperature rise processes.
To verify the Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ Electron-conductive properties of ceramic materials, nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ The ceramic material wafer is cut into rectangular strip, and the electronic conductivity of the ceramic material wafer in air at 100-850 ℃ is analyzed by a four-electrode method. The test results are shown in FIG. 3, the electronic conductivity of the material is higher than 200S/cm in the test temperature range, and the requirement of the fuel cell on the electronic conductivity of the cathode catalyst is met.
To verify Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ The ceramic material is used as the oxygen catalytic performance of the cathode of the solid oxide fuel cell and Nd is added 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ Ball-milling and crushing ceramic material wafer to prepare cathode slurry, and coating the cathode slurry on Gd 0.1 Ce 0.9 O 1.95 On both sides of the electrolyte sheet, a symmetrical cell is formed. And the oxygen catalytic activity of the corresponding symmetrical cell in the air at 600-800 ℃ is characterized by utilizing an electrochemical impedance spectroscopy technology, and the result is shown in figure 4. It can be seen from the figure that the polarization resistance of the material at 700 deg.C is onlyIs 0.04 omega cm 2 The ceramic material is proved to have excellent oxygen catalytic activity.
Further, by preparing based on Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ The cathode single cell mode characterizes the electrochemical performance of the ceramic material. FIG. 5 is a graph of output power density at 650-800 deg.C for a single cell using pure hydrogen fuel. From FIG. 5, it can be seen that the material has an output power density of up to 1.6W/cm at 800 deg.C 2 The material is proved to have excellent oxygen catalytic activity and oxygen ion conduction performance. Is a potential cathode material of the solid oxide fuel cell.
Example 2:
a multifunctional ceramic material with high resistance to ultra-fast heating and cooling is represented by the chemical formula La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ (delta is more than or equal to 0 and less than or equal to 1), and the material has a cubic phase perovskite structure.
The multifunctional ceramic material is prepared by a sol-gel method, and the method comprises the following specific steps:
(1) Dissolving complexing agent citric acid and ethylene diamine tetraacetic acid into purified water according to a molar ratio of 2.
(2) Lanthanum nitrate, barium nitrate, calcium nitrate, cobalt nitrate and bismuth nitrate are added into the solution I according to the mixture ratio of the molecular formula, and the molar ratio of the total metal cations of the nitrate to complexing agents (citric acid and ethylene diamine tetraacetic acid) is 1; then, the pH value of the solution is adjusted to 7 by ammonia water to obtain a solution II.
(3) And (3) placing the solution II in a closed container, heating and stirring at the constant temperature of 90 ℃ for 5 hours to form sol.
(4) The sol is formed into xerogel particles by a spray drying method, wherein the temperature of a spray opening is 100 ℃.
(5) And (3) placing the xerogel particles into a box type furnace to be pre-sintered for 10 hours at the temperature of 300 ℃ to obtain pre-sintered powder.
(6) And placing the pre-sintered powder in a circular grinding tool, and pressing into a sintered green body under the pressure of 100 MPa.
(7) Sintering the sintered green body at 1200 ℃ for 4h to obtain La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ A ceramic material.
And (3) performance testing:
to verify the thermal shock resistance of the material, la prepared in example 2 was used 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ The ceramic material wafer was removed from the sintering furnace at 1200 c and thrown into liquid nitrogen within 2 seconds, actually causing the sample to cool at a rate greater than 500 c/s. The appearance of the sample after being cooled at an extremely high speed is observed by using a scanning electron microscope technology. Typical pictures are shown in FIG. 6, no cracks were observed throughout the test area, indicating La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ The ceramic material has excellent thermal shock resistance.
To verify the electronic conductivity properties of the material, la was used 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ The ceramic material wafer is cut into rectangular strips, and the electronic conductivity of the ceramic material wafer in the air at 100-850 ℃ is analyzed by a four-electrode method. The test result is shown in FIG. 7, the electronic conductivity of the material is higher than 200S/cm in the test temperature range, and the requirement of the fuel cell on the electronic conductivity of the cathode catalyst is met.
To verify La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ The ceramic material is used as the oxygen catalytic performance of the cathode of the solid oxide fuel cell, and La is added 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ Ball-milling and crushing ceramic material wafer to prepare cathode slurry, and coating the cathode slurry on Gd 0.1 Ce 0.9 O 1.95 On both sides of the electrolyte sheet, a symmetrical cell is formed. The oxygen catalytic activity of the corresponding symmetrical cell in the air at 600-800 ℃ is characterized by utilizing an electrochemical impedance spectroscopy technology, and the result is shown in figure 8. It can be seen from the figure that the material is at 700 deg.CHas a polarization impedance of only 0.042 omega cm 2 The ceramic material is proved to have excellent oxygen catalytic activity.
Example 3:
a multifunctional ceramic material with resistance to ultrafast temperature rise and drop has a chemical formula of Pr 0.5 Sr 0.5 Co 0.65 Bi 0.35 O 3-δ (delta is more than or equal to 0 and less than or equal to 1), and the material has a tetragonal perovskite structure.
The multifunctional ceramic material is prepared by a sol-gel method, and the method comprises the following specific steps:
(1) Dissolving complexing agent citric acid and ethylene diamine tetraacetic acid into purified water according to the molar ratio of 5.
(2) Adding praseodymium nitrate, strontium nitrate, cobalt nitrate and bismuth nitrate into the solution I according to the mixture ratio of the molecular formula, wherein the molar ratio of the total metal cations of the nitrate to the complexing agent (citric acid and ethylene diamine tetraacetic acid) is 1; then, the pH value of the solution is adjusted to 7 by ammonia water to obtain a solution II.
(3) And (3) placing the solution II in a closed container, heating and stirring at the constant temperature of 80 ℃ for 10 hours to form sol.
(4) The above sol was formed into xerogel particles by a spray drying process in which the spray outlet temperature was 150 ℃.
(5) And (3) placing the dry gel particles in a box furnace, and pre-sintering for 8 hours at 600 ℃ to obtain pre-sintered powder.
(6) And placing the pre-sintered powder in a circular grinding tool, and pressing into a sintered green body under the pressure of 150 MPa.
(7) Sintering the sintered green body at 1150 ℃ for 8h to obtain Pr 0.5 Sr 0.5 Co 0.65 Bi 0.35 O 3-δ A ceramic material.
And (3) performance testing:
to verify the thermal shock resistance of the material, pr from example 3 was prepared 0.5 Sr 0.5 Co 0.65 Bi 0.35 O 3-δ The ceramic material wafer was removed from the sintering furnace at 1150 ℃ and thrown into liquid nitrogen within 2 seconds, actually creating a sampleThe cooling rate of the product is more than 500 ℃/min. The appearance of the sample after being cooled at an extremely high speed is observed by using a scanning electron microscope technology. A typical picture is shown in FIG. 9, no cracks were observed throughout the test area, indicating that Pr was observed 0.5 Sr 0.5 Co 0.65 Bi 0.35 O 3-δ The ceramic has excellent thermal shock resistance and has the potential of being used as an oxygen dialysis membrane material. And the above Pr 0.5 Sr 0.5 Co 0.65 Bi 0.35 O 3-δ The ceramic has high oxygen ion conductivity and oxygen catalytic activity, and can be applied to a high-temperature oxygen dialysis membrane.
Comparative example 1:
a ceramic material with chemical formula of La 0.2 Sr 0.8 Co 0.2 Fe 0.8 O 3-δ 。
The ceramic material is prepared by a sol-gel method, and the specific steps are as follows:
(1) Dissolving complexing agent citric acid and ethylene diamine tetraacetic acid into purified water according to the molar ratio of 2.
(2) Lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate are added into the solution I according to the mixture ratio of the molecular formula, and the molar ratio of the total metal cations of the nitrate to complexing agents (citric acid and ethylene diamine tetraacetic acid) is 1; then, the pH value of the solution is adjusted to 7 by ammonia water to obtain a solution II.
(3) And (3) placing the solution II in a closed container, heating and stirring at the constant temperature of 80 ℃ for 10 hours to form sol.
(4) The above sol was formed into xerogel particles by a spray drying process in which the spray outlet temperature was 150 ℃.
(5) And (3) placing the dry gel particles in a box furnace, and pre-sintering for 8 hours at 600 ℃ to obtain pre-sintered powder.
(6) And placing the pre-sintered powder in a circular grinding tool, and pressing under the pressure of 150MPa to prepare a sintered green body.
(7) Sintering the sintered green body at 1150 ℃ for 8h to obtain La 0.2 Sr 0.8 Co 0.2 Fe 0.8 O 3-δ A ceramic material.
And (3) performance testing:
in order to verify the thermal shock resistance of the material, la prepared in comparative example 1 was used 0.2 Sr 0.8 Co 0.2 Fe 0.8 O 3-δ And opening the furnace cavity door of the ceramic material wafer at 1150 ℃, and naturally cooling the ceramic material wafer in the air atmosphere, wherein the actual cooling rate of the sample is less than 1 ℃/s. As shown in fig. 10, la at this time 0.2 Sr 0.8 Co 0.2 Fe 0.8 O 3-δ The rupture of the ceramic material wafer indicates that the ceramic material does not have the performance of resisting the extreme speed temperature rise and fall under the condition of not meeting the molecular formula of the invention.
Claims (10)
1. The multifunctional ceramic material is characterized in that the chemical general formula of the multifunctional ceramic material is Ln 0.5 M 0.5 Co 1-x Bi x O 3-δ Wherein Ln is the combination of one or more elements of Y, la, ce, pr, nd, sm and Gd, M is the combination of one or more elements of Ba, sr, ca and Mg, and x is more than or equal to 0 and less than or equal to 0.5; the delta is the oxygen vacancy content, and is more than or equal to 0 and less than or equal to 1.
2. The multifunctional ceramic material of claim 1, wherein said resistance to ultra-fast temperature increase or decrease is resistance to temperature increase or decrease at a rate greater than 100 ℃/s.
3. The multifunctional ceramic material of claim 2, wherein said resistance to ultra-fast temperature increase or decrease is resistance to temperature increase or decrease at a rate greater than 500 ℃/s.
4. The multifunctional ceramic material according to claim 1, wherein the multifunctional ceramic material has an electrical conductivity of more than 200S/cm at a temperature range of 25-800 ℃.
5. The multifunctional ceramic material according to any one of claims 1 to 4, wherein the formula of the multifunctional ceramic material is Nd 0.5 Ba 0.2 Sr 0.3 Co 0.8 Bi 0.2 O 3-δ 、La 0.5 Ba 0.1 Ca 0.4 Co 0.9 Bi 0.1 O 3-δ Or Pr 0.5 Sr 0.5 Co 0.65 Bi 0.35 O 3-δ 。
6. The multifunctional ceramic material according to any of claims 1 to 4, wherein said multifunctional ceramic material has a perovskite structure and a general molecular formula of ABO 3-δ Wherein A is Ln 0.5 M 0.5 B is Co 1-x Bi x The multifunctional ceramic material with the perovskite structure is a cubic phase, a tetragonal phase or an orthogonal phase.
7. A method for preparing the multifunctional ceramic material with resistance to ultrafast temperature rise and drop according to any one of claims 1 to 6, comprising the steps of:
(1) Dissolving a complexing agent in purified water to obtain a solution I;
(2) Adding soluble salts of Ln, M, co and Bi into the solution I according to the formula ratio; adjusting the pH value of the obtained solution to be nearly neutral by using alkali liquor to obtain a solution II;
(3) Placing the solution II in a closed container, heating and stirring at constant temperature to form sol;
(4) Preparing the sol into xerogel particles by using a spray drying method;
(5) Pre-sintering the xerogel particles to obtain pre-sintered powder;
(6) Pressing the pre-sintered powder into a sintered green body;
(7) And sintering the sintered green body at high temperature to obtain the multifunctional ceramic material.
8. The preparation method according to claim 7, wherein in the step (1), the complexing agent comprises citric acid and ethylenediamine tetraacetic acid with a molar ratio of 1;
in the step (2), the molar ratio of the total metal cations of the added soluble salt to the sum of the molar amounts of all complexing agent components in the solution I is (1-1); the soluble salts of Ln, M, co and Bi are nitrate of Ln, nitrate of M, nitrate of Co and nitrate of Bi; and the pH value of the obtained solution is adjusted to be close to neutral by using alkali liquor, specifically, the pH value of the obtained solution is adjusted to be 6-7 by using ammonia water.
9. The preparation method according to claim 7, wherein in the step (3), the constant-temperature heating and stirring temperature is 60-95 ℃ and the time is 5-50h;
in the step (4), the temperature of a spray nozzle is 100-200 ℃ during spray drying;
in the step (5), the pre-sintering temperature is 300-700 ℃, and the pre-sintering time is 2-10h;
in the step (6), the pressing pressure is 100-200MPa;
in the step (7), the high-temperature sintering temperature is 1000-1200 ℃, and the high-temperature sintering time is 4-10h.
10. Use of the multifunctional ceramic material according to any one of claims 1 to 6 or the multifunctional ceramic material prepared by the preparation method according to any one of claims 7 to 9 as a membrane material for a high temperature oxygen dialysis membrane, a cathode catalyst for a solid oxide fuel cell, an anode catalyst for a solid oxide electrolysis cell or a catalyst for a high temperature oxygen sensor;
or the multifunctional ceramic material is applied to preparing an oxygen electrode of a metal-air battery, wherein the metal-air battery is a magnesium-air battery, a zinc-air battery, an aluminum-air battery or a lithium-air battery.
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Application publication date: 20221014 |