CN111028977A - Double-layer composite proton conductor material and preparation method thereof - Google Patents

Double-layer composite proton conductor material and preparation method thereof Download PDF

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CN111028977A
CN111028977A CN201911345372.7A CN201911345372A CN111028977A CN 111028977 A CN111028977 A CN 111028977A CN 201911345372 A CN201911345372 A CN 201911345372A CN 111028977 A CN111028977 A CN 111028977A
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CN111028977B (en
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厉英
丁玉石
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Northeastern University China
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Abstract

A double-layer composite proton conductor material is composed of a substrate and a coating, the substrate is composed of a double-layer structureFormula A1‑yA′yB1‑zB′zO3‑αCoating part formula A3(B′1+xB″2‑x)O9‑γ(ii) a The preparation method comprises the following steps: (1) preparing a first raw material A, a first raw material B 'and a raw material B', and mixing and ball-milling to obtain mixed powder I; (2) pressing the mixed powder I into blocks, and calcining to prepare a calcined material I; (3) preparing a second raw material A, a second raw material B, a raw material A 'and a second raw material B', and mixing and ball-milling to obtain mixed powder II; (4) pressing the mixed powder II into blocks, and calcining to prepare a calcined material II; (5) pressing the calcined material II to prepare a matrix blank; covering the calcined material I on a substrate blank by adopting a co-pressing, tape casting, spin coating, magnetron sputtering or laser deposition method to form a coating; (6) and sintering the double-layer blank. The product of the invention ensures that the material has higher proton conductivity, and greatly limits the electronic conduction in the material.

Description

Double-layer composite proton conductor material and preparation method thereof
Technical Field
The invention relates to the technical field of solid electrolyte proton conductors, in particular to a double-layer composite proton conductor material and a preparation method thereof.
Background
The high-temperature oxide proton conductor is a solid electrolyte material capable of transferring protons at high temperature, and has good application prospect in the fields of hydrogen sensors, fuel cells, normal-pressure ammonia synthesis, electrochemical hydrogenation dehydrogenation and the like; simple perovskite ABO doped in high temperature proton conductors3Type material and double perovskite A3(B′1+xB″2-x)O9The material has good proton conductivity.
Simple perovskite structure ABO3Is cubic, tetragonal or orthorhombic, wherein the A site is usually +2 valent cations (such as Ba, Ca, Sr, etc.) and the B site is +4 valent cations (such as Zr, Ce, etc.), and the tetravalent B site element is usually doped with trivalent rare earth elements, so that the raw material generates oxygen vacancy. Water vapor or hydrogen in the oxygen vacancy trapping atmosphere can be introduced into protons to generate proton conduction; however, at higher atmospheric oxygen partial pressures, oxygen vacancies in the material trap oxygen in the atmosphere, creating electron holes; under low oxygen, oxygen ions in the material enter a gas phase to generate oxygen vacancies and free electrons, so that the electrons are generated to conduct electricity, and the application of the material is limited.
Double perovskite A3(B′1+xB″2-x)O9The A site in the material is usually +2 valent cations (such as Ba, Sr, etc.) with larger ionic radius, the B 'site is usually +2 valent cations (such as Sr, Ca, etc.) with smaller ionic radius than the A site ions, and the B' site is usually +5 valent cations (such as Nb, Ta, V, etc.). Oxygen vacancies are generated by adjusting the ion ratio of B 'and B' positions, protons are introduced, and proton conduction is generated; different from ABO3Simple perovskite material, double perovskite A3(B′1+xB″2-x)O9Materials can hinder electron and electron hole conduction; however, at 600 ℃ or higher, the double perovskite A3(B′1+xB″2-x)O9The proton concentration in the material decreases dramatically, resulting in a material with lower proton conductivity at high temperatures.
As can be seen from the above, the conventional simple perovskite ABO3The material is easy to generate electrons and conduct electron holes, and the double perovskite A3(B′1+xB″2-x)O9The proton conductivity of the material is low at high temperature, which limits the application of the material.
Disclosure of Invention
The invention aims to provide a double-layer composite proton conductor material and a preparation method thereof, which adopts simple perovskite ABO3The material is a substrate, and a layer of double perovskite A is covered on the surface of the substrate3(B′1+xB″2-x)O9The material layer can block the electronic conduction of the material and improve the proton conductivity of the material.
The double-layer composite proton conductor material of the invention has a double-layer structure consisting of a substrate part and a coating part, wherein the substrate part is a perovskite material and has a molecular formula A1-yA′yB1-zB′zO3-αThe coating part is a double perovskite material with a molecular formula A3(B′1+xB″2-x)O9-γ(ii) a A is described1-yA′yB1-zB′zO3-αWherein, the element A is Ca, Sr and/or Ba, the element A 'is K, Na and/or Li, the element B is Sn, Zr, Hf, Pr, Ce, Th and/or Ti, the element B' is Nd, Sm, Eu, Gd, Tb, Ho, Y, Dy, Er, Tm, Yb, Lu, In, Sc, Ga and/or Al, Y is 0-0.3, z is 0-0.3, Y + z is more than or equal to 0.05, the value of 3- α is taken along with A1-yA′yB1-zB′zO3-αBalancing the total valence of (1); a is described3(B′1+xB″2-x)O9-γIs Ba3(Ca1+xNb2-x)O9-γ、Ba3(Sr1+xNb2-x)O9-γ、Ba3(Sr1+xTa2-x)O9-γ、Sr3(Ca1+xNb2-x)O9-γOr Sr3(Ca1+xTa2-x)O9-γWherein x is more than or equal to 0 and less than or equal to 0.5, and the value of 9-gamma follows A3(B′1+xB″2-x)O9-γThe total valence of (1) is balanced.
In the double-layer composite proton conductor material, the thickness ratio of the coating part to the substrate part is 0.01-0.1.
The preparation method of the double-layer composite proton conductor material comprises the following steps:
1. preparing an oxide, a carbonate or a nitrate of Ba or Sr element as a first A raw material, an oxide, a carbonate or a nitrate of Ca or Sr element as a first B 'raw material, and an oxide, a carbonate or a nitrate of Nb or Ta element as a B' raw material; mixing the first raw material A, the first raw material B 'and the raw material B' and performing ball milling, and grinding until the average particle size is less than or equal to 5 mu m to obtain mixed powder I;
2. pressing the mixed powder I into blocks, calcining for 5-20 hours at 1000-1400 ℃, and cooling to normal temperature along with a furnace to prepare a calcined material I; the molecular formula of the calcined material I is Ba3(Ca1+xNb2-x)O9-γ、Ba3(Sr1+xNb2-x)O9-γ、Ba3(Sr1+ xTa2-x)O9-γ、Sr3(Ca1+xNb2-x)O9-γOr Sr3(Ca1+xTa2-x)O9-γ；
3. Preparing an oxide, a carbonate or a nitrate of the element A as a second raw material A, an oxide, a carbonate or a nitrate of the element B as a raw material B, an oxide, a carbonate or a nitrate of the element A 'as an A' raw material, and an oxide, a carbonate or a nitrate of the element B 'as a second raw material B'; mixing the second raw material A, the raw material A ', the raw material B and the second raw material B', performing ball milling, and grinding until the average particle size is less than or equal to 5 mu m to obtain mixed powder II;
4. pressing the mixed powder II into blocks, calcining for 5-20 hours at 800-1400 ℃, and cooling to normal temperature along with the furnace to prepare a calcined material II; the molecular formula of the calcined material II is A1-yA′yB1-zB′zO3-α；
5. Pressing and forming the calcined material II to prepare a matrix blank; then covering the calcined material I on a substrate blank by adopting a co-pressing, tape casting, magnetron sputtering or laser deposition method to form a coating to obtain a double-layer blank;
6. sintering the double-layer blank at 1300-1700 ℃ for 5-20 hours, and cooling to normal temperature along with the furnace to prepare the double-layer composite proton conductor material.
In the step 1, when the first a raw material contains Sr element, the first B' raw material is oxide, carbonate or nitrate of Ca element; when the first B' raw material contains Sr element, the first a raw material is an oxide, carbonate or nitrate of Ba element.
In the steps 2 and 4, the pressing pressure of the pressed blocks is 5-10 MPa.
In the step 5, the pressing pressure of the pressing forming is 50-300 MPa.
In the double-layer blank, the thickness of the substrate blank is 0.5-2 mm, and the thickness of the coating is 0.01-0.1 time of that of the substrate blank.
The principle of the invention is as follows: simple perovskite ABO3The material has high conductivity and high proton concentration at high temperature, ensures that the material has enough proton carriers, improves the proton conductivity of the material, and is double perovskite A3(B′1+xB″2-x)O9The material can prevent electron and electron hole in the material from conducting; thus, the present invention proposes to use simple perovskite ABO3The material is covered with a layer of double perovskite A3(B′1+xB″2-x)O9The material greatly limits the electronic conduction in the material while ensuring the material to have higher proton conductivity, and has good application prospect; the finished material can also improve corrosion resistance.
Drawings
Fig. 1 is a graph showing the conductivity and the proton transference number of the two-layer composite proton conductor material in example 1 of the present invention.
Detailed Description
In the embodiment of the invention, a 1260A impedance phase analyzer with strong power output and a Jishili 2450 multifunctional electric meter are adopted to test the conductivity and the proton transference number of the double-layer solid electrolyte proton conductor.
The raw materials adopted in the embodiment of the invention are commercially available analytical pure reagents.
The grinding tank adopted in the embodiment of the invention is made of agate materials.
The mixed solid electrolyte proton conductor material in the embodiment of the invention has the conductivity less than or equal to 1.2 multiplied by 10 at the temperature of 500-900 DEG C-2S/cm。
The proton migration number of the mixed solid electrolyte proton conductor material in the embodiment of the invention is more than 0.92 at 500-800 ℃.
In the embodiment of the invention, isostatic pressing equipment is adopted for pressing when the step 5 is carried out.
Preparation A in the examples of the invention3(B′1+xB″2-x)O9-γThe raw material of (A) is carbonate, oxide or nitrate of the elements A, B 'and B'.
Preparation A in the examples of the invention1-yA′yB1-zB′zO3-α-is a carbonate, oxide or nitrate of elements A, A ', B and B'.
In the double-layer solid electrolyte proton conductor material in the embodiment of the invention, the coating part and the matrix part are combined through intermolecular force, and the porosity of the material is less than or equal to 10 percent.
The co-pressing method in the examples of the present invention is a method described in "research on Ni/YSZ Cermet Anodes Prepared by calcination Synthesis and Electrochemical behavior" (Ringuede, A.; Bronin, D.I.; Frade, J.R Electrochemical Behaviouur of Ni/YSZ Cermet Anodes Prepared by Combustion Synthesis, Fuel cell. 2001, 1(3-4): 238-242).
The casting method in the embodiment of the invention is a method recorded in the research on the preparation of the PSLZT multilayer composite NZFO material and Ferroelectric and piezoelectric properties by the casting co-firing method (Ferroelectric and piezoelectric properties of PSLZT multilayer layers/NZFO co-sintered magnetic composites by tape casting, the journal of the European society for ceramics, 2019, 39(16): 5267-5276).
The magnetron sputtering method in the embodiment of the invention is a method recorded in the research on the preparation of Mg, Al and Ga co-doped ZnO conductive glass and the performance by the magnetron sputtering method (Liu, Y; Zhu, SM.preparation and characterization of Mg, Al and Gaco-doped ZnO transfer conductive films by magnetic sputtering, physical conclusion, 2019,14: 102514).
The laser deposition method in the embodiment of the invention is a method recorded in the journal of physical application of pulsed laser deposition method for preparing Al-doped Zn1-xMgxO band gap modified conductive glass (K.Matsubara, H.Tampo, H.Shibata, A.Yamada, P.Fons, K.Iwata, et.band-gap modified Al-processed Zn1-xMgxO transferred modulated filtered by pulsed laser deposition, 2004, 85: 1374-.
The thickness variation caused by sintering in the embodiment of the invention is ignored.
Example 1
The double-layer composite proton conductor material has a double-layer structure composed of a substrate part and a coating part, wherein the molecular formula of the substrate part is A1-yA′yB1-zB′zO3-αFormula A of the coating part3(B′1+xB″2-x)O9-γ；
A1-yA′yB1-zB′zO3-αThe element A is Ba, the element B is Ce, the element B 'is Y, Y is 0 (without the element A'), z is 0.1, and the values of 3- α are taken along with AB1-zB′zO3-αBalancing the total valence of (1);
A3(B′1+xB″2-x)O9-γis Ba3(Ca1+xNb2-x)O9-γX is 0.18; the value of 9-gamma follows A3(B′1+xB″2-x)O9-γBalancing the total valence of (1);
the thickness ratio of the coating portion to the base portion was 0.1;
the preparation method comprises the following steps:
preparation of BaCO3As the first raw material A, CaCO was prepared3Nb is prepared as the first B' raw material2O5As a raw material of B'; a first AMixing and ball-milling the raw material, the first B 'raw material and the B' raw material until the average particle size is less than or equal to 5 mu m to obtain mixed powder I; the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.18 to 1.82;
pressing the mixed powder I into blocks with the pressing pressure of 5MPa, calcining at 1300 ℃ for 10 hours, cooling to normal temperature along with the furnace to prepare a calcined material I with the molecular formula of A3(B′1+xB″2-x)O9-γ(Ba3(Ca1.18Nb1.82)O9-γ)；
Preparation of BaCO3As a second A raw material, CeO was prepared2As the raw material B, Y was prepared2O3A second B' feedstock; mixing the second raw material A, the raw material A ', the raw material B and the second raw material B', performing ball milling, and grinding until the average particle size is less than or equal to 5 mu m to obtain mixed powder II; the molar ratio of A to B' in the mixed powder II is 1:0.9: 0.1;
pressing the mixed powder II into blocks with the pressing pressure of 5MPa, calcining at 1200 ℃ for 10 hours, cooling to normal temperature along with the furnace to prepare a calcined material II with the molecular formula of AB1-zB′zO3-α(BaCe0.9Y0.1O3-α)；
Pressing and forming the calcined material II, wherein the pressing pressure is 50MPa, and preparing a matrix blank; then covering the calcined material I on the substrate blank by adopting a co-pressing method to form a coating to obtain a double-layer blank; in the double-layer blank, the thickness of the substrate blank is 1mm, and the thickness of the coating is 0.1 time of the thickness of the substrate blank;
sintering the double-layer blank at 1600 ℃ for 10 hours, cooling the double-layer blank to normal temperature along with the furnace to prepare the double-layer composite proton conductor material, wherein the curves of the electric conductivity and the proton migration number are shown in figure 1.
Example 2
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ca, the element A 'is K, the element B is Sn, the element B' is Nd, y is 0.2, and z is 0.3;
A3(B′1+xB″2-x)O9-γis Ba3(Sr1+xNb2-x)O9-γ，x＝0.22；
The thickness ratio of the coating portion to the base portion was 0.01;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 20 hours at the temperature of 1000 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.22 to 1.78;
(3) the mixed powder II is calcined for 20 hours at 800 ℃ under the pressing pressure of 10 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.8 to 0.2 to 0.7 to 0.3;
(5) pressing the calcined material II under the pressure of 300 MPa; covering the calcined material I on a substrate blank by adopting a laser deposition method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 2mm, and the thickness of the coating is 0.01 time of the thickness of the substrate blank;
(6) the two-layer blank was sintered at 1300 ℃ for 20 hours.
Example 3
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Sr, the element A 'is Na, the element B is Hf, the element B' is Sm, y is 0.3, and z is 0.2;
A3(B′1+xB″2-x)O9-γis Ba3(Sr1+xTa2-x)O9-γ，x＝0.31；
The thickness ratio of the coating portion to the base portion was 0.02;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 6MPa and calcined for 19 hours at the temperature of 1000 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B': B ″ -3: 1.31: 1.69;
(3) the mixed powder II is calcined for 19 hours at 900 ℃ under the pressing pressure of 6 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.7 to 0.3 to 0.8 to 0.2;
(5) the pressing pressure of the calcined material II is 80 MPa; covering the calcined material I on a substrate blank by adopting a magnetron sputtering method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 2mm, and the thickness of the coating is 0.02 times of the thickness of the substrate blank;
(6) the two-layer blank was sintered at 1350 c for 19 hours.
Example 4
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ba, the element A 'is Li, the element B is Pr, the element B' is Eu, y is 0.1, and z is 0.15;
A3(B′1+xB″2-x)O9-γis Sr3(Ca1+xNb2-x)O9-γ，x＝0.1；
The method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 7MPa and calcined for 15 hours at the temperature of 1100 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B': B ═ 3 to 1.1 to 1.9;
(3) the mixed powder II is calcined for 15 hours at 1000 ℃ under the pressing pressure of 7 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.9 to 0.1 to 0.85 to 0.15;
(5) pressing the calcined material II under the pressure of 100 MPa; covering the calcined material I on a substrate blank by adopting a laser deposition method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 0.5mm, and the thickness of the coating is 0.01 times of that of the substrate blank;
(6) the bi-layer blank was sintered at 1380 ℃ for 18 hours.
Example 5
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ca, the element A 'is Li, the element B is Zr, the element B' is Gd, y is 0.15, and z is 0.25;
A3(B′1+xB″2-x)O9-γis Sr3(Ca1+xTa2-x)O9-γ，x＝0.12；
The thickness ratio of the coating portion to the base portion was 0.02;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 8MPa and calcined for 15 hours at the temperature of 1100 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.12 to 1.88;
(3) calcining the mixed powder II at 1000 ℃ for 15 hours under the pressing pressure of 8 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.85 to 0.15 to 0.75 to 0.25;
(5) the pressing pressure of the calcined material II is 120 MPa; covering the calcined material I on a substrate blank by adopting a laser deposition method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 2mm, and the thickness of the coating is 0.02 times of the thickness of the substrate blank;
(6) the bi-layer blank was sintered at 1400 ℃ for 16 hours.
Example 6
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Sr, the element A 'is Na, the element B is Th, the element B' is Tb, y is 0.25, and z is 0.05;
A3(B′1+xB″2-x)O9-γis Ba3(Ca1+xNb2-x)O9-γ，x＝0.14；
The thickness ratio of the coating portion to the base portion was 0.03;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 9MPa and calcined for 12 hours at the temperature of 1200 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.14 to 1.86;
(3) calcining the mixed powder II at 1100 ℃ for 12 hours under the pressing pressure of 9 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.75 to 0.25 to 0.95 to 0.05;
(5) pressing the calcined material II under the pressure of 180 MPa; covering the calcined material I on the substrate blank by adopting a tape casting method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 2mm, and the thickness of the coating is 0.03 times of the thickness of the substrate blank;
(6) the double layered blank was sintered at 1400 ℃ for 15 hours.
Example 7
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ba, the element A 'is K, the element B is Ti, the element B' is Ho, y is 0.05, and z is 0.13;
A3(B′1+xB″2-x)O9-γis Ba3(Sr1+xNb2-x)O9-γ，x＝0.15；
The thickness ratio of the coating portion to the base portion was 0.04;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 12 hours at the temperature of 1200 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.15 to 1.85;
(3) calcining the mixed powder II at 1100 ℃ for 12 hours under the pressing pressure of 10 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.95 to 0.05 to 0.87 to 0.13;
(5) the pressing pressure of the calcined material II is 200 MPa; covering the calcined material I on the substrate blank by adopting a tape casting method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 1.5mm, and the thickness of the coating is 0.04 times of that of the substrate blank;
(6) the double layer blank was sintered at 1450 ℃ for 12 hours.
Example 8
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ca, the element A 'is K, the element B is Zr, the element B' is Dy, y is 0.02, and z is 0.04;
A3(B′1+xB″2-x)O9-γis Ba3(Sr1+xTa2-x)O9-γ，x＝1.2；
The thickness ratio of the coating portion to the base portion was 0.05;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 8 hours at 1250 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.2 to 1.8;
(3) the mixed powder II is calcined for 8 hours at 1200 ℃ under the pressing pressure of 10 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.98 to 0.02 to 0.96 to 0.04;
(5) the pressing pressure of the calcined material II is 220 MPa; covering the calcined material I on the substrate blank by adopting a tape casting method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 1.5mm, and the thickness of the coating is 0.05 times of the thickness of the substrate blank;
(6) the double layer blank was sintered at 1450 ℃ for 12 hours.
Example 9
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Sr, the element A 'is Na, the element B is Sn, the element B' is Er, y is 0.08, and z is 0.22;
A3(B′1+xB″2-x)O9-γis Sr3(Ca1+xNb2-x)O9-γ，x＝0.25；
The thickness ratio of the coating portion to the base portion was 0.06;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 8 hours at 1250 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.25 to 1.75;
(3) the mixed powder II is calcined for 8 hours at 1200 ℃ under the pressing pressure of 10 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.92 to 0.08 to 0.78 to 0.22;
(5) the pressing pressure of the calcined material II is 240 MPa; covering the calcined material I on a substrate blank by adopting a co-pressing method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 1.5mm, and the thickness of the coating is 0.06 time of the thickness of the substrate blank;
(6) the double-layer blank was sintered at 1500 ℃ for 8 hours.
Example 10
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ba, the element A 'is Li, the element B is Hf, the element B' is Tm, y is 0.14, and z is 0.16;
A3(B′1+xB″2-x)O9-γis Sr3(Ca1+xTa2-x)O9-γ，x＝0.3；
The thickness ratio of the coating portion to the base portion was 0.06;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 7 hours at 1350 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B': B ″ -3 to 1.3 to 1.7;
(3) calcining the mixed powder II at 1200 ℃ for 7 hours under the pressing pressure of 10 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.86 to 0.14 to 0.84 to 0.16;
(5) the pressing pressure of the calcined material II is 260 MPa; covering the calcined material I on a substrate blank by adopting a magnetron sputtering method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 0.8mm, and the thickness of the coating is 0.06 times of the thickness of the substrate blank;
(6) the double-layer blank was sintered at 1500 ℃ for 8 hours.
Example 11
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ca, the element A 'is K, the element B is Pr, the element B' is Yb, y is 0.23, and z is 0.02;
A3(B′1+xB″2-x)O9-γis Ba3(Ca1+xNb2-x)O9-γ，x＝0.35；
The thickness ratio of the coating portion to the base portion was 0.05;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 7 hours at 1350 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B ': B' to 3 to 1.35 to 1.65;
(3) calcining the mixed powder II at 1300 ℃ for 7 hours under the pressing pressure of 10 MPa;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.77 to 0.23 to 0.98 to 0.02;
(5) the pressing pressure of the calcined material II is 270 MPa; covering the calcined material I on a substrate blank by adopting a co-pressing method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 1.8mm, and the thickness of the coating is 0.05 times of the thickness of the substrate blank;
(6) the bi-layer billet was sintered at 1550 ℃ for 7 hours.
Example 12
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Sr, the element A 'is Na, the element B is Ce, the element B' is Lu, y is 0.19, and z is 0.21;
A3(B′1+xB″2-x)O9-γis Ba3(Sr1+xNb2-x)O9-γ，x＝0.4；
The thickness ratio of the coating portion to the base portion was 0.08;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 5 hours at the temperature of 1400 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B': B ″ -3: 1.4: 1.6;
(3) calcining the mixed powder II at the pressing pressure of 10MPa and the temperature of 1400 ℃ for 5 hours;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.81 to 0.19 to 0.79 to 0.21;
(5) the pressing pressure of the calcined material II is 280 MPa; covering the calcined material I on a substrate blank by adopting a magnetron sputtering method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 0.5mm, and the thickness of the coating is 0.08 times of the thickness of the substrate blank;
(6) the bi-layer billet was sintered at 1550 ℃ for 7 hours.
Example 13
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ba, the element A 'is Li, the element B is Th, the element B' is In, y is 0.15, and z is 0.05;
A3(B′1+xB″2-x)O9-γis Ba3(Sr1+xTa2-x)O9-γ，x＝0.45；
The thickness ratio of the coating portion to the base portion was 0.08;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 5 hours at the temperature of 1400 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.45 to 1.55;
(3) calcining the mixed powder II at the pressing pressure of 10MPa and the temperature of 1400 ℃ for 5 hours;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.85 to 0.15 to 0.95 to 0.05;
(5) pressing the calcined material II under the pressure of 300 MPa; covering the calcined material I on a substrate blank by adopting a co-pressing method to form a coating to obtain a double-layer blank; the thickness of the coating is 0.08 times of the thickness of the base blank;
(6) the double layered blank was sintered at 1600 ℃ for 6 hours.
Example 14
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ca, the element A 'is K, the element B is Ti, the element B' is Sc, y is 0.2, and z is 0.05;
A3(B′1+xB″2-x)O9-γis Sr3(Ca1+xNb2-x)O9-γ，x＝0.5；
The thickness ratio of the coating portion to the base portion was 0.01;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 11 hours at the temperature of 1200 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.5;
(3) calcining the mixed powder II at the pressing pressure of 10MPa and the temperature of 1000 ℃ for 11 hours;
(4) the mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.8 to 0.2 to 0.95 to 0.05;
(5) pressing the calcined material II under the pressure of 300 MPa; covering the calcined material I on a substrate blank by adopting a laser deposition method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 2mm, and the thickness of the coating is 0.01 time of the thickness of the substrate blank;
(6) the double layered blank was sintered at 1600 ℃ for 6 hours.
Example 15
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Sr, the element A 'is Na, the element B is Ce, the element B' is Ga, y is 0.25, and z is 0.25;
A3(B′1+xB″2-x)O9-γis Sr3(Ca1+xTa2-x)O9-γ，x＝0.15；
The thickness ratio of the coating portion to the base portion was 0.02;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 13 hours at the temperature of 1150 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B' of 3 to 1.15 to 1.85;
(3) calcining the mixed powder II at 950 ℃ for 13 hours under the pressing pressure of 10 MPa; (ii) a
(4) The mixed powder II comprises the following components in a molar ratio of A to A 'to B' of 0.75 to 0.25 to 0.75 to 0.25;
(5) the pressing pressure of the calcined material II is 200 MPa; covering the calcined material I on a substrate blank by adopting a magnetron sputtering method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 2mm, and the thickness of the coating is 0.02 times of the thickness of the substrate blank;
(6) the double-layered blank was sintered at 1700 ℃ for 5 hours.
Example 16
In the double-layer composite proton conductor material, A1-yA′yB1-zB′zO3-αThe element A is Ba, the element A 'is Li, the element B is Ce, the element B' is Al, y is 0.19, and z is 0.21;
A3(B′1+xB″2-x)O9-γis Ba3(CaNb)O9，x＝0；
The thickness ratio of the coating portion to the base portion was 0.05;
the method is the same as example 1, except that:
(1) the mixed powder I is pressed under the pressure of 10MPa and calcined for 5 hours at the temperature of 1400 ℃;
(2) the mixed powder I comprises the following components in a molar ratio of A to B': B ″ -3 to 1 to 2;
(3) calcining the mixed powder II at the pressing pressure of 10MPa and the temperature of 1400 ℃ for 5 hours;
(4) the molar ratio of A to A 'to B' is 0.81 to 0.19 to 0.79 to 0.21 in the mixed powder II;
(5) the pressing pressure of the calcined material II is 150 MPa; covering the calcined material I on the substrate blank by adopting a tape casting method to form a coating to obtain a double-layer blank; the thickness of the substrate blank is 1.5mm, and the thickness of the coating is 0.05 times of the thickness of the substrate blank;
(6) the double-layered blank was sintered at 1700 ℃ for 5 hours.

Claims (7)

1. A double-layer composite proton conductor material is characterized in that the double-layer composite proton conductor material is of a double-layer structure consisting of a substrate part and a coating part, wherein the substrate part is a perovskite material and has a molecular formula A1-yA′yB1-zB′zO3-αThe coating part is a double perovskite material with a molecular formula A3(B′1+xB″2-x)O9-γ(ii) a A is described1-yA′yB1-zB′zO3-αWherein the element A is Ca, Sr and/or Ba, and the element A' is K, Na andor Li, B is Sn, Zr, Hf, Pr, Ce, Th and/or Ti, B' is Nd, Sm, Eu, Gd, Tb, Ho, Y, Dy, Er, Tm, Yb, Lu, In, Sc, Ga and/or Al, Y is 0-0.3, z is 0-0.3, Y + z is more than or equal to 0.05, and the value of 3- α is selected along with A1-yA′yB1-zB′zO3-αBalancing the total valence of (1); a is described3(B′1+xB″2-x)O9-γIs Ba3(Ca1+xNb2-x)O9-γ、Ba3(Sr1+xNb2-x)O9-γ、Ba3(Sr1+xTa2-x)O9-γ、Sr3(Ca1+xNb2-x)O9-γOr Sr3(Ca1+xTa2-x)O9-γWherein x is more than or equal to 0 and less than or equal to 0.5, and the value of 9-gamma follows A3(B′1+xB″2-x)O9-γThe total valence of (1) is balanced.
2. The double-layer composite proton conductor material as claimed in claim 1, wherein the thickness ratio of the coating portion to the base portion is 0.01 to 0.1.
3. A method for preparing a double-layer composite proton conductor material as claimed in claim 1, which is characterized by comprising the following steps:
(1) preparing an oxide, a carbonate or a nitrate of Ba or Sr element as a first A raw material, an oxide, a carbonate or a nitrate of Ca or Sr element as a first B 'raw material, and an oxide, a carbonate or a nitrate of Nb or Ta element as a B' raw material; mixing the first raw material A, the first raw material B 'and the raw material B' and performing ball milling, and grinding until the average particle size is less than or equal to 5 mu m to obtain mixed powder I;
(2) pressing the mixed powder I into blocks, calcining for 5-20 hours at 1000-1400 ℃, and cooling to normal temperature along with a furnace to prepare a calcined material I; the molecular formula of the calcined material I is Ba3(Ca1+xNb2-x)O9-γ、Ba3(Sr1+xNb2-x)O9-γ、Ba3(Sr1+ xTa2-x)O9-γ、Sr3(Ca1+xNb2-x)O9-γOr Sr3(Ca1+xTa2-x)O9-γ；
(3) Preparing an oxide, a carbonate or a nitrate of the element A as a second raw material A, an oxide, a carbonate or a nitrate of the element B as a raw material B, an oxide, a carbonate or a nitrate of the element A 'as an A' raw material, and an oxide, a carbonate or a nitrate of the element B 'as a second raw material B'; mixing the second raw material A, the raw material A ', the raw material B and the second raw material B', performing ball milling, and grinding until the average particle size is less than or equal to 5 mu m to obtain mixed powder II;
(4) pressing the mixed powder II into blocks, calcining for 5-20 hours at 800-1400 ℃, and cooling to normal temperature along with the furnace to prepare a calcined material II; the molecular formula of the calcined material II is A1-yA′yB1-zB′zO3-α；
(5) Pressing and forming the calcined material II to prepare a matrix blank; then covering the calcined material I on a substrate blank by adopting a co-pressing, tape casting, magnetron sputtering or laser deposition method to form a coating to obtain a double-layer blank;
(6) sintering the double-layer blank at 1300-1700 ℃ for 5-20 hours, and cooling to normal temperature along with the furnace to prepare the double-layer composite proton conductor material.
4. The method for preparing a double-layer composite proton conductor material according to claim 3, wherein in the steps (2) and (4), the pressing pressure for pressing into a block is 5-10 MPa.
5. The method for preparing a double-layer composite proton conductor material according to claim 3, wherein in the step (5), the compression pressure for compression molding is 50-300 MPa.
6. The method for preparing a double-layer composite proton conductor material according to claim 3, wherein the thickness of the substrate blank in the double-layer blank is 0.5-2 mm, and the thickness of the coating is 0.01-0.1 times of the thickness of the substrate blank.
7. The method for producing a two-layer composite proton conductor material according to claim 3, wherein in the step (1), when the first A raw material contains Sr element, the first B' raw material is an oxide, carbonate or nitrate of Ca element; when the first B' raw material contains Sr element, the first a raw material is an oxide, carbonate or nitrate of Ba element.
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