CN112201385B - Double-phase potassium lanthanum cerium oxide proton conductor and preparation method thereof - Google Patents

Double-phase potassium lanthanum cerium oxide proton conductor and preparation method thereof Download PDF

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CN112201385B
CN112201385B CN202011109386.1A CN202011109386A CN112201385B CN 112201385 B CN112201385 B CN 112201385B CN 202011109386 A CN202011109386 A CN 202011109386A CN 112201385 B CN112201385 B CN 112201385B
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黄文龙
厉英
倪培远
丁玉石
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Northeastern University China
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Abstract

Double-phase potassium lanthanum cerium oxide proton conductor and its preparing methodPreparation method, molecular formula of proton conductor is K0.5+xLa0.5‑xCeO3‑δ(ii) a The preparation method comprises the following steps: (1) mixing potassium carbonate powder, cerium oxide powder and lanthanum oxide powder according to a molar ratio of K: La: Ce ═ 0.5+ x: 0.5-x: 1; (2) ball milling the mixed powder to a particle size below 400 meshes, and drying; (3) calcining for 1-10 h at 1000-1400 ℃ after compression molding, and cooling along with a furnace; (4) grinding the calcined material to the granularity of below 200 meshes, performing secondary compression molding, sintering at 1450-1650 ℃ for 2-10 h, and cooling along with the furnace. K of the invention0.5+xLa0.5‑xCeO3‑δWith a BaCeO3High conductivity similar to CaZrO3The similar high proton transference number provides a new system and material for proton conductor materials needed in the fields of fuel cells, water electrolysis, ammonia synthesis and the like.

Description

Double-phase potassium lanthanum cerium oxide proton conductor and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a double-phase potassium lanthanum cerium oxide proton conductor and a preparation method thereof.
Technical Field
Proton conductors are functional materials capable of conducting protons, and are classified in many ways, such as organic conductors and inorganic proton conductors, medium-low temperature proton conductors and high-temperature proton conductors, homogeneous proton conductors and heterogeneous proton conductors; the proton conductor with the perovskite structure is used for manufacturing oxygen vacancies by doping or adjusting the stoichiometric ratio of each valence element and conducting protons through the oxygen vacancies, can be used for medium-high temperature experiments at 100-1300 ℃, and is widely used in the fields of gas and aluminum liquid hydrogen measurement sensors, humidity sensors, hydrocarbon sensors, fuel cells, electrolytic water, aluminum liquid and organic matter dehydrogenation, electrochemical ammonia synthesis and the like.
At present, perovskite type proton conductors can be classified as AB1-xMxO3-δAnd A3(B′B″2)O9-δTwo structures are provided. At AB1-xMxO3-δIn the structure, M is doped into ABO3The 3-valent ion In the crystal lattice, usually In3+、Sc3+、Y3+、Yb3+Etc.; ABO3The matrix is typically BaCeO3、BaZrO3、SrCeO3And CaZrO3。A3(B′B″2)O9-δB 'is a 1, 2 or 3 valent ion, B' is a 5 or 6 valent ion, oxygen vacancies are created by adjusting the stoichiometric ratio of B 'to B', a common material is Sr2Ga1.1Ta0.9O5.9、Ba2Ga1.1Nb0.9O5.9、Ba2NaWO5.5、Sr2SrNbO5.5、Ba3Ca1.18Nb1.82O8.73And the like.
ABO3In the perovskite type, the lower the electronegativity of each element in the perovskite, the higher the total alkalinity of the material, the stronger the ability of absorbing protons, and the conductivity of the material can be improved; currently doped with BaCeO3Has the highest conductivity, and the conductivity can reach 1.2 multiplied by 10 at 700 DEG C-2S·cm-1However, the proton migration number is low, and is only 0.6 at 700 ℃, so that the application of the proton migration number in the direction of a high-temperature sensor is limited; ABO3In the perovskite type, the smaller the tolerance factor t, the BO in the perovskite6The larger the distortion of the octahedron is, the more the distortion of the octahedron can inhibit the oxygen ion conductivity of the material, so that the proton transference number of the material is improved; currently doped CaZrO3Has the highest proton transference number of 0.95 at 700 deg.c, but has relatively low conductivity of only 8.0X 10 at 700 deg.c-4S·cm-1And the application of the method in the direction of energy sources is limited.
From the above, the proton transfer number of the existing high conductivity material is low, the conductivity of the high proton transfer number material is low, and it is of great significance to develop a proton conductor material which can simultaneously take the conductivity and the proton transfer number into consideration.
Disclosure of Invention
The invention aims to provide a biphase potassium lanthanum cerium oxide proton conductor and a preparation method thereof, based on A'0.5A″0.5BO3The structure adopts K ions and La ions as elements A 'and A' to adjust the electronegativity of A site and BO6The distortion degree of the octahedron, thereby achieving the effect of simultaneous existence of high proton transference number and high conductivity of the proton conductor.
The molecular formula of the biphase potassium lanthanum cerium oxide proton conductor is K0.5+xLa0.5-xCeO3-δ(ii) a Wherein x is 0-0.2, and the value of delta is dependent on K0.5+xLa0.5-xCeO3-δThe total valence of (1) is balanced.
The preparation method of the biphase potassium lanthanum cerium oxide proton conductor comprises the following steps:
1. preparing potassium carbonate powder, cerium oxide powder and lanthanum oxide powder as raw materials; mixing the raw materials according to the molar ratio of K to La to Ce (0.5+ x) to (0.5-x) to 1 to prepare mixed powder;
2. ball-milling the mixed powder to a granularity of below 400 meshes by using water or absolute ethyl alcohol as a ball-milling medium, and then drying to remove the ball-milling medium to obtain ball-milled powder;
3. pressing and molding the ball-milled powder, calcining for 1-10 h at 1000-1400 ℃, and cooling to normal temperature along with a furnace to obtain a calcined material;
4. grinding the calcined material to the granularity of below 200 meshes, performing secondary compression molding, heating to 1450-1650 ℃, sintering for 2-10 h, and cooling to normal temperature along with the furnace to obtain the biphase potassium lanthanum cerium oxide proton conductor.
In the step 1, the potassium carbonate powder, the cerium oxide powder and the lanthanum oxide powder are respectively subjected to drying pretreatment before mixing, wherein the temperature of the drying pretreatment is 100-900 ℃, and the time is 1-8 h.
In the step 3, the ball-milling powder is placed in a die and is pressed and molded by a sample press under the pressure of 10-50 MPa.
In the step 4, the secondary compression molding is to place the ground calcined material into a mold, compress the calcined material into tablets under the pressure of 10-50 MPa by using a sample press, and then compress and mold the calcined material into tablets under the pressure of 200 +/-10 MPa for at least 10min by using a cold isostatic pressing device under constant pressure.
In the step 4, after the secondary compression molding, the molded material is placed on a zirconia plate and is buckled by a zirconia crucible to prevent volatilization; then placing the mixture into a sintering furnace for sintering.
The invention adjusts A by changing the proportion of K and La ions of A siteElectronegativity of bits and BO6The degree of distortion of the octahedron; k0.5+xLa0.5-xCeO3-δMiddle K0.5+xLa0.5-xHas an electronegativity of 0.82 to 1.1 and BaCeO3The electronegativity of medium Ba is 0.89, so that K0.5+xLa0.5-xCeO3-δWith a BaCeO3A similar high conductivity; k0.5+xLa0.5-xCeO3-δHas an allowable factor t of 0.81 to 0.89, and CaZrO3Is 0.91, so that K0.5+xLa0.5-xCeO3-δHaving a structure of with CaZrO3Similar high proton transport number. The proton conductor of the invention provides a new system and material for proton conductor materials needed in the fields of fuel cells, water electrolysis, ammonia synthesis and the like.
Drawings
FIG. 1 shows K in example 4 of the present invention0.65La0.35CeO2.85XRD pattern of proton conductor;
FIG. 2 shows K in example 4 of the present invention0.65La0.35CeO2.85Electron micrograph of proton conductor;
FIG. 3 is a graph of Arrhenius electrical conductivity of a two-phase potassium lanthanum cerium oxide proton conductor at 300-800 deg.C, 3% oxygen volume concentration, 4.7% water vapor volume concentration, and the balance argon atmosphere in accordance with an embodiment of the present invention; in the figure, ■ is embodiment 1, good is embodiment 2, a-solidup is embodiment 3,
Figure BDA0002728084240000021
example 4, example 5;
FIG. 4 shows K in an embodiment of the present invention0.5+xLa0.5-xCeO3-δThe variation curve of electromotive force of the proton conductor in the oxygen concentration cell along with temperature; in the figure, ■ is embodiment 1, good is embodiment 2, a-solidup is embodiment 3,
Figure BDA0002728084240000031
for example 4,. diamond-o is the theoretical electromotive force of example 5; the volume concentration of water vapor on both sides of the electrolyte was 4.7%, and the oxygen on both sides of the electrolyte wasThe volume concentration of the argon gas is respectively 4 percent and 2 percent, and the rest is argon atmosphere;
FIG. 5 shows K in an embodiment of the present invention0.5+xLa0.5-xCeO3-δThe variation curve of electromotive force of the proton conductor in the water concentration cell along with temperature; in the figure, ■ is embodiment 1, good is embodiment 2, a-solidup is embodiment 3,
Figure BDA0002728084240000032
for example 4,. diamond-o is the theoretical electromotive force of example 5; the volume concentration of oxygen on two sides of the electrolyte is 3%, the volume concentration of water vapor on two sides of the electrolyte is 2.3% and 7.3% respectively, and the rest is argon atmosphere;
FIG. 6 shows K in an embodiment of the present invention0.5+xLa0.5-xCeO3-δA proton conductor is characterized by comprising a proton conductor transfer number, an oxygen ion transfer number and an electron transfer number curve chart under the condition of 300-800 ℃, 3% of oxygen volume concentration, 4.7% of water vapor volume concentration and the balance of argon atmosphere; in the figure, ■ represents the proton transport number in example 1, □ represents the oxygen ion transport number in example 1,
Figure BDA0002728084240000033
for the electron transfer number in example 1, ● is the proton transfer number in example 2, O is the oxygen ion transfer number in example 2,
Figure BDA0002728084240000034
for the electron transference number in example 2, a is the proton transference number in example 3, Δ is the oxygen ion transference number in example 3,
Figure BDA0002728084240000035
for the electron transport number in example 3,
Figure BDA0002728084240000036
for the proton transference number in example 4,
Figure BDA0002728084240000037
is oxygen in example 4The transport number of the ions is the same as the ion transport number,
Figure BDA0002728084240000038
for the electron transport number in example 4,. diamond-solid is the proton transport number in example 5,. diamond-solid is the oxygen ion transport number in example 5,
Figure BDA0002728084240000039
the electron transport number in example 5.
Detailed Description
The use temperature of the biphase potassium lanthanum cerium oxide proton conductor is 100-1300 ℃.
The potassium carbonate powder, the cerium oxide powder and the lanthanum oxide powder in the embodiment of the invention are commercially available analytical pure reagents, and the particle size is 50 μm.
The water in the embodiment of the invention is deionized water.
The absolute ethyl alcohol in the embodiment of the invention is a commercially available analytical pure reagent.
In step 3 of the invention, a cylinder is formed after compression molding, and the size of the cylinder is the same as that of the cylinder
Figure BDA00027280842400000310
In step 4 of the invention, the tablets are formed after compression to the dimensions of the tablets
Figure BDA00027280842400000311
In the embodiment of the invention, when ball milling is carried out, a zirconia ball milling tank is adopted for placing materials, the grinding balls are zirconia grinding balls, and the ball milling rotating speed is 300-500 rpm; after ball milling for 10h, sieving with a 200-mesh sieve, and feeding the sieved materials into the next step.
In the embodiment of the invention, an agate mortar is adopted for grinding, the ground material is sieved by a 200-mesh sieve, and the sieved material enters the next step.
In the embodiment of the invention, the molybdenum disilicide sintering furnace is adopted for calcination and sintering.
In the embodiment of the invention, the potassium carbonate powder, the cerium oxide powder and the lanthanum oxide powder are respectively subjected to drying pretreatment before mixing, wherein the drying pretreatment temperature is 100-900 ℃, and the drying pretreatment time is 1-8 h
In the embodiment of the invention, delta is 0-0.2.
The biphase potassium lanthanum cerium oxide proton conductor in the embodiment of the invention has the conductivity of 1.1 multiplied by 10 under the conditions of the temperature of 300-800 ℃, the volume concentration of oxygen of 3 percent, the volume concentration of water vapor of 4.7 percent and the balance of argon atmosphere-6～3.4×10-2S·cm-1The proton transference number is 0.31 to 0.99; wherein the conductivity at 700 deg.C is 7.5 × 10-3～1.8×10-2S·cm-1The proton transference number is 0.47 to 0.91. .
Example 1
The molecular formula of the biphase potassium lanthanum cerium oxide proton conductor is K0.5+xLa0.5-xCeO3-δ(ii) a Wherein x is 0 and δ is 0;
the preparation method comprises the following steps:
preparing potassium carbonate powder, cerium oxide powder and lanthanum oxide powder as raw materials; mixing the raw materials according to the molar ratio of K to La to Ce of 0.5 to 1 to prepare mixed powder;
ball-milling the mixed powder to a particle size of below 400 meshes by using absolute ethyl alcohol as a ball-milling medium, and then drying to remove the ball-milling medium to obtain ball-milled powder;
pressing and molding the ball-milled powder, calcining for 5 hours at 1200 ℃, and cooling to normal temperature along with the furnace to obtain a calcined material; the compression molding is to place the ball-milled powder in a die and adopt a sample press to perform compression molding under the pressure of 30 MPa;
grinding the calcined material to the granularity of below 200 meshes, and then performing secondary compression molding, wherein the secondary compression molding is to place the ground calcined material into a mold, press the calcined material into a tablet by using a sample press under the pressure of 30MPa, and then perform compression molding by using a cold isostatic pressing device under the pressure of 200 +/-10 MPa for 10min at constant pressure;
after the secondary compression molding, placing the molded material on a zirconia plate, and then buckling the molded material by using a zirconia crucible to prevent volatilization; then placing the mixture into a sintering furnace, heating the mixture to 1550 ℃, sintering the mixture for 6 hours, and cooling the mixture to normal temperature along with the furnace to obtain a double-phase potassium lanthanum cerium oxide proton conductor;
biphase potassium lanthanum cerium oxideThe electrical conductivity Arrhenius curve of the sub-conductor under the conditions of the temperature of 300-800 ℃, the oxygen volume concentration of 3 percent, the water vapor volume concentration of 4.7 percent and the balance of argon atmosphere is shown in figure 3 ■, the variation curve of electromotive force in the oxygen concentration cell along with the temperature is shown in figure 4 ■, the variation curve of electromotive force in the water concentration cell along with the temperature is shown in figure 5 ■, the proton transfer number, the oxygen ion transfer number and the electron transfer number curve under the conditions of the temperature of 300-800 ℃, the oxygen volume concentration of 3 percent, the water vapor volume concentration of 4.7 percent and the balance of argon atmosphere are respectively shown in figures 6 ■, □ and figure 6
Figure BDA0002728084240000041
Shown;
the conductivity is 1.1 multiplied by 10 at the temperature of 300-800 DEG C-6～1.8×10-2S·cm-1The proton transference number is 0.74-0.99; wherein the conductivity at 700 deg.C is 7.5 × 10-3S·cm-1The proton transference number was 0.91.
Example 2
The molecular formula of the biphase potassium lanthanum cerium oxide proton conductor is K0.5+xLa0.5-xCeO3-δ(ii) a Wherein x is 0.05 and δ is 0.05;
the preparation method is the same as example 1, and is different from the following steps:
(1) the molar ratio of the mixed powder K to the La to the Ce is 0.55 to 0.45 to 1;
(2) ball milling is carried out by taking water as a ball milling medium;
(3) calcining at 1000 ℃ for 10 h; pressing and forming under the pressure of 50 MPa;
(4) pressing into tablets under 50MPa by using a sample press, and keeping constant pressure for 20min under 200 +/-10 MPa by using a cold isostatic pressing device;
(5) sintering for 10h at 1450 ℃;
the Arrhenius curve of the conductivity of the biphase potassium lanthanum cerium oxide proton conductor under the conditions of 300-800 ℃ of temperature, 3% of oxygen volume concentration, 4.7% of water vapor volume concentration and the balance of argon atmosphere is shown as good in figure 3, the variation curve of electromotive force along with temperature in an oxygen concentration cell is shown as good in figure 4, the variation curve of electromotive force along with temperature in a water concentration cell is shown as good in figure 5, and the variation curve of electromotive force along with temperature in a water concentration cell is shown as good in figure 5 and is shown as good in 300-80 DEG0 ℃, 3 percent of oxygen volume concentration, 4.7 percent of water vapor volume concentration and the balance of proton transfer number, oxygen ion transfer number and electron transfer number curves under the argon atmosphere condition are shown in figure 6 ● for good and good quality
Figure BDA0002728084240000051
Shown;
the conductivity is 2.5 multiplied by 10 at the temperature of 300-800 DEG C-6～2.1×10-2S·cm-1The proton transference number is 0.49-0.99; wherein the conductivity at 700 deg.C is 9.0 × 10-3S·cm-1The proton transference number was 0.69.
Example 3
The molecular formula of the biphase potassium lanthanum cerium oxide proton conductor is K0.5+xLa0.5-xCeO3-δ(ii) a Wherein x is 0.1 and δ is 0.1;
the preparation method is the same as example 1, and is different from the following steps:
(1) the molar ratio of the mixed powder K to the La to the Ce is 0.6 to 0.4 to 1;
(2) calcining at 1400 ℃ for 1 h; pressing and forming under the pressure of 10 MPa;
(3) pressing into tablets under 10MPa by using a sample press, and keeping constant pressure for 30min under 200 +/-10 MPa by using a cold isostatic pressing device;
(4) postsintering at 1650 ℃ for 2 h;
the temperature of the biphase potassium lanthanum cerium oxide proton conductor is 300-800 ℃, the oxygen volume concentration is 3%, the water vapor volume concentration is 4.7%, the electric conductivity Arrhenius curve under the condition of argon atmosphere for the rest is shown as a curve in figure 3, the electromotive force variation curve along with the temperature in the oxygen concentration difference battery is shown as a curve in figure 4, the electromotive force variation curve along with the temperature in the water concentration difference battery is shown as a curve in figure 5, the proton transference number, the oxygen ion transference number and the electron transference number curve under the condition of argon atmosphere for the rest is shown as a curve in figure 6
Figure BDA0002728084240000052
Shown;
the conductivity is 4.2 multiplied by 10 at the temperature of 300-800 DEG C-6～2.4×10-2S·cm-1The proton transference number is 0.43-0.99; wherein the conductivity at 700 deg.C is 1.3 × 10-2S·cm-1The proton transference number was 0.60.
Example 4
The molecular formula of the biphase potassium lanthanum cerium oxide proton conductor is K0.5+xLa0.5-xCeO3-δ(ii) a Wherein x is 0.15 and δ is 0.15;
the preparation method is the same as example 1, and is different from the following steps:
(1) the molar ratio of the mixed powder K to the La to the Ce is 0.65 to 0.35 to 1;
(2) ball milling is carried out by taking water as a ball milling medium;
(3) calcining at 1300 ℃ for 3 h; pressing and forming under the pressure of 20 MPa;
(4) pressing into tablets under 20MPa by using a sample press, and keeping constant pressure for 15min under 200 +/-10 MPa by using a cold isostatic pressing device;
(5) sintering for 4h at 1600 ℃; the XRD pattern of the biphase potassium lanthanum cerium oxide proton conductor is shown in figure 1, and the electron microscope micrograph is shown in figure 2;
the Arrhenius curve of the conductivity of the biphase potassium lanthanum cerium oxide proton conductor under the conditions of the temperature of 300-800 ℃, the volume concentration of oxygen of 3 percent, the volume concentration of water vapor of 4.7 percent and the balance of argon atmosphere is shown in the figure
Figure BDA0002728084240000061
The variation curve of electromotive force with temperature in the oxygen concentration cell is shown as the figure
Figure BDA0002728084240000062
The variation curve of electromotive force with temperature in the water concentration cell is shown as the figure
Figure BDA0002728084240000063
Shown in the figure, the curves of proton migration number, oxygen ion migration number and electron migration number under the conditions of 300-800 ℃, 3% of oxygen volume concentration, 4.7% of water vapor volume concentration and the balance of argon atmosphere are shown in the figure
Figure BDA0002728084240000064
And
Figure BDA0002728084240000065
shown;
the conductivity is 1.3 multiplied by 10 at the temperature of 300-800 DEG C-5～3.4×10-2S·cm-1The proton transference number is 0.35-0.99; wherein the conductivity at 700 ℃ is 1.8X 10-2S·cm-1The proton transference number was 0.50.
Example 5
The molecular formula of the biphase potassium lanthanum cerium oxide proton conductor is K0.5+xLa0.5-xCeO3-δ(ii) a Wherein x is 0.2 and δ is 0.2;
the preparation method is the same as example 1, and is different from the following steps:
(1) the molar ratio of the mixed powder K to the La to the Ce is 0.7 to 0.3 to 1;
(2) calcining at 1100 deg.C for 8 h; pressing and forming under the pressure of 40 MPa;
(3) pressing into tablets under 40MPa by using a sample press, and keeping constant pressure for 25min under 200 +/-10 MPa by using a cold isostatic pressing device;
(4) sintering for 9h at 1500 ℃;
the temperature of the two-phase potassium lanthanum cerium oxide proton conductor is 300-800 ℃, the oxygen volume concentration is 3%, the water vapor volume concentration is 4.7%, the rest is the electric conductivity Arrhenius curve under the argon atmosphere condition is shown in figure 3 diamond-solid, the electromotive force variation curve along with the temperature in the oxygen concentration cell is shown in figure 4 diamond-solid, the electromotive force variation curve along with the temperature in the water concentration cell is shown in figure 5 diamond-solid, the oxygen volume concentration is 3%, the water vapor volume concentration is 4.7% at the temperature of 300-800 ℃, and the rest is the proton migration number, the oxygen ion migration number and the electron migration number curve under the argon atmosphere condition is shown in figure 6 diamond-solid, sum and
Figure BDA0002728084240000066
shown;
the conductivity is 1.6 multiplied by 10 at the temperature of 300-800 DEG C-6～1.9×10-2S·cm-1The proton transference number is 0.31 to 0.99; wherein the conductivity at 700 ℃ is 7.8X 10-3S·cm-1The proton transference number was 0.47.

Claims (3)

1. The preparation method of the biphase potassium lanthanum cerium oxide proton conductor is characterized by comprising the following steps of:
(1) preparing potassium carbonate powder, cerium oxide powder and lanthanum oxide powder as raw materials; mixing the raw materials according to the molar ratio of K to La to Ce = (0.5+ x) to (0.5-x) to 1 to prepare mixed powder; wherein x = 0-0.2;
(2) ball-milling the mixed powder to a granularity of below 400 meshes by using water or absolute ethyl alcohol as a ball-milling medium, and then drying to remove the ball-milling medium to obtain ball-milled powder;
(3) pressing and molding the ball-milled powder, calcining for 1-10 h at 1000-1400 ℃, and cooling to normal temperature along with a furnace to obtain a calcined material; the compression molding is to place the ball-milled powder in a mold and adopt a sample press to perform compression molding under the pressure of 10-50 MPa;
(4) grinding the calcined material to the granularity of below 200 meshes, and then performing secondary compression molding, wherein the secondary compression molding is to place the ground calcined material into a mold, press the calcined material into a tablet by using a sample press under the pressure of 10-50 MPa, and press the tablet by using a cold isostatic pressing device under the pressure of 200 +/-10 MPa for at least 10 min; then heating to 1450-1650 ℃, sintering for 2-10 h, cooling to normal temperature along with the furnace to obtain the biphase potassium lanthanum cerium oxide proton conductor with the molecular formula of K x0.5+La x0.5-CeO δ3-；δIs taken to be K0.5+ x La x0.5-CeO δ3-The total valence of (1) is balanced.
2. The method for preparing a bi-phase potassium lanthanum cerium oxide proton conductor as claimed in claim 1, wherein in the step (1), the potassium carbonate powder, the cerium oxide powder and the lanthanum oxide powder are respectively subjected to drying pretreatment before mixing, wherein the drying pretreatment temperature is 100-900 ℃ and the drying pretreatment time is 1-8 h.
3. The method for preparing a bi-phase potassium lanthanum cerium oxide proton conductor as claimed in claim 1, wherein in the step (4), after the secondary compression molding, the molded material is placed on a zirconia plate and then is covered by a zirconia crucible to prevent volatilization; then placing the mixture into a sintering furnace for sintering.
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CN104078687B (en) * 2013-03-25 2017-03-15 中国科学院物理研究所 Anode material of SOFC containing alkali metal or alkali earth metal and its production and use
CN110970148B (en) * 2019-12-24 2021-03-02 东北大学 Composite oxide proton conductor material and preparation method thereof
CN110937897B (en) * 2019-12-24 2022-02-01 东北大学 Mixed solid electrolyte proton conductor material and preparation method thereof

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