CN112408481B - Preparation method of high-conductivity layered structure multi-element composite rare earth oxide - Google Patents
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- CN112408481B CN112408481B CN202011098698.7A CN202011098698A CN112408481B CN 112408481 B CN112408481 B CN 112408481B CN 202011098698 A CN202011098698 A CN 202011098698A CN 112408481 B CN112408481 B CN 112408481B
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Abstract
The invention relates to a conductive multi-element composite oxide, and aims to provide a preparation method of a high-conductivity multi-element composite rare earth oxide with a layered structure. The method comprises the following steps: preparing a precursor solution A by using citric acid and a structure inducer X as solutes and using a gel promoter and deionized water as solvents; preparing a precursor solution B by using lanthanum nitrate and stannic chloride pentahydrate as solutes and deionized water as a solvent; dropwise adding the precursor solution A into the precursor solution B to form a uniform transparent solution, and continuously reacting under stirring to obtain uniform sol; after aging treatment to form wet gel, vacuum freeze drying treatment is carried out to prepare a multi-element composite oxide block; grinding, sieving and calcining to obtain the high-conductivity layered structure multi-element composite rare earth oxide. The product obtained by the invention has a multi-microchannel laminated structure, and can increase the concentration of electron-hole pairs in a multi-element composite oxide phase and improve the electric and heat conduction performance of the multi-element composite oxide phase. Simple reaction synthesis conditions, low cost and contribution to large-scale production.
Description
Technical Field
The invention relates to a conductive multi-element composite oxide, in particular to a preparation method of a high-conductive layered multi-element composite rare earth oxide applied to the fields of silver-based conductive alloy and electrocatalysis.
Background
The multicomponent rare earth metal composite oxide has a large amount of oxygen vacancies due to the distortion of the crystal structure, so that the multicomponent rare earth metal composite oxide has good electric transport performance (the resistivity can be as low as 10) in a wide temperature range3Mu omega cm) and high catalytic performance, and has wide application in the fields of electrode materials, fixed resistors, chemically sensitive materials, high-temperature heating materials, redox catalysts and the like. However, the reported applications of the multi-element rare earth metal oxide to the conductive alloy are less related to research at home and abroad. LaFe with perovskite structure is prepared by Liriopsis chinensis task group of Shandong university1-xNixO3-δThe equal-conductive multi-element oxide reinforced silver-based electric contact material has lower resistivity (Ag/LaFe)1-xNixO3-δ(12 wt%) about 2.25 μ Ω · cm) and good processability. Ag/La was prepared by guanweiming et al, university of Zhongnan2NiO4Material with low resistivity (Ag/La)2NiO4(10 wt%) about 2.02. mu. omega. cm) and low and stable contact resistance. The inventor group prepared Ag/La1-xSrxCoO3-δMaterial with low resistivity (Ag/La)1-xSrxCoO3-δ(12 wt%) about 2.03 [ mu ] omega-cm), high hardness, low material transfer loss after electrical life testing, and the likeExcellent performance. The research shows that the multielement rare earth oxide applied to the silver-based electric contact material can effectively reduce the silver content and the resistivity, simultaneously improve the processing performance of the composite material, and is expected to solve the problems of high resistivity, large contact resistance, high temperature rise and poor processing performance of the existing silver-based electric contact material with low silver content.
However, the problems of high resistivity, complex preparation method, difficulty in large-scale preparation and application and the like of the obtained rare earth oxide generally exist in the prior art.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a high-conductivity layered structure multi-element composite rare earth oxide.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the high-conductivity layered structure multi-element composite rare earth oxide is provided, and comprises the following steps:
(1) preparation of precursor solution A
Citric acid and a structure inducer X in a molar ratio of 1.5 to (1.5-0.2) are taken as solutes, and a mixed solution of a gel promoter and deionized water is taken as a solvent; adding a certain amount of solute into a solvent, wherein the molar ratio of a gel accelerator to citric acid is (0.5-2.5) to 1; stirring by magnetic force until the solution is completely dissolved, transferring the solution into a volumetric flask for constant volume, and preparing a colorless transparent solution with the concentration of 0.03mol/L, and marking as a precursor solution A;
(2) preparation of precursor solution B
Lanthanum nitrate and stannic chloride pentahydrate in a molar ratio of 1: 1 are taken as solutes, and deionized water is taken as a solvent; adding the solute into deionized water, and stirring by magnetic force until the solute is completely dissolved; then, the solution is transferred to a volumetric flask for constant volume, and a colorless transparent solution with the concentration of 1.5mol/L is prepared and marked as a precursor solution B;
(3) preparation of layered structure multi-element composite rare earth oxide
Dropwise adding the precursor solution A into the precursor solution B according to the volume ratio of (0.1-0.25) to 1 to form a uniform transparent solution, and continuously reacting under stirring to obtain a uniform sol; after aging treatment to form wet gel, vacuum freeze drying treatment is carried out to prepare a multi-element composite oxide block;
and grinding and sieving the multi-element composite oxide block, and calcining for 2-6 hours at 500-800 ℃ to finally obtain the multi-element composite rare earth oxide (La-Sn-X-O) nano powder with the multi-microchannel laminated structure.
In the present invention, in the step (1), the structure-inducing agent X is Na2MoO4、Y(NO3)3·6H2O or Na2WO4·2H2O, and the gel accelerator is propylene oxide.
In the invention, in the step (3), the reaction conditions of the precursor solution a and the precursor solution B are as follows: the reaction temperature is 25-60 ℃, the stirring speed is 150-500 rmp, and the reaction time is 5-20 min.
In the invention, in the step (3), the aging treatment time is 24 hours; the conditions of vacuum freeze-drying are as follows: the temperature is minus 20 ℃ to minus 60 ℃, the vacuum degree is 5Pa, and the drying time is 24 hours; after grinding, the mixture is sieved by a 200-mesh sieve.
And finally, performing performance characterization such as current carrier characteristics, thermal conductivity characteristics and the like on the prepared multi-micro-channel multi-element composite rare earth oxide (La-Sn-X-O) nano powder with the layered structure.
Description of the inventive principles:
the invention utilizes the respective technical advantages of a sol-gel method and a freeze drying process, provides a method for preparing the high-conductivity layered-structure multi-element composite rare earth oxide (La-Sn-X-O, structure inducer X ═ Mo, Y and W) by adopting the sol-gel method along with a phase separation self-assembly technology and combining with the freeze drying technology, increases the concentration of electron-hole pairs in the multi-element composite rare earth oxide, constructs a multi-microchannel layered structure, improves the physical and chemical properties of carrier mobility, thermal conductivity and the like of the multi-microchannel layered structure, and lays a foundation for further exerting the high-conductivity and high-thermal conductivity in the field of silver-based conductive alloys.
The sol-gel method can prepare the nano sol with fine size, uniform granularity and uniform dispersion at normal temperature or lower temperature, and the freeze-drying method can furthest maintain the microscopic or macroscopic structure of the material. The invention combines the two methods, and can obtain the nano powder with the uniform laminated structure on the basis of the sol-gel method accompanied with the phase separation self-assembly technology. After grinding, sieving and calcining, the inside of the multi-element composite oxide powder is subjected to chemical reaction, so that the X element enters the crystal lattice of the rare earth oxide.
Compared with the prior art, the invention has the beneficial effects that:
1. the multi-component composite rare earth oxide nano powder has a multi-micro-channel layered structure, and can increase the concentration of electron-hole pairs in a multi-component composite oxide phase and improve the electric and heat conduction performance of the multi-component composite oxide phase.
2. The invention has simple reaction synthesis condition and low cost, and is beneficial to large-scale production.
Drawings
FIG. 1 is SEM photograph (magnification 20000) of multi-micro-channel multi-component composite rare earth oxide with a layered structure in example 3;
FIG. 2 is an SEM photograph (40000 times) of an enlarged multi-rare earth oxide having a multi-microchannel layered structure in example 3.
Detailed Description
The following describes an implementation of the present invention by way of specific embodiments.
Example 1:
(1) preparation of precursor solution A
The solute is citric acid and Na as structure inducer with the mol ratio of 1.5:1.52MoO4Adding a certain amount of solute into the solvent, stirring by magnetic force until the solute is completely dissolved, then transferring liquid to a volumetric flask by a glass rod to a constant volume, and preparing a colorless transparent solution with the concentration of 0.03mol/L, which is marked as a precursor solution A.
(2) Preparation of precursor solution B
The solutes are lanthanum nitrate and stannic chloride pentahydrate in a molar ratio of 1: 1, and the solvent is deionized water; and (3) introducing the solute into deionized water, stirring by magnetic force until the solute is completely dissolved, then transferring liquid to a volumetric flask by using a glass rod for constant volume, and preparing a colorless transparent solution with the concentration of 1.5mol/L, and marking as a precursor solution B.
(3) Preparation of layered structure multi-element composite oxide
And (3) introducing the precursor solution A into the precursor solution B in a dropwise manner by adopting a pear-shaped separating funnel to form a uniform and transparent solution, wherein the volume ratio of the precursor solution A to the precursor solution B is 0.1: 1. Regulating the environmental temperature to 25 ℃, and continuously reacting for 5min at a magnetic stirring speed of 150rmp to form uniform sol. Forming wet gel after 24h aging treatment; and (3) carrying out vacuum freeze drying for 24h by adopting a vacuum freeze dryer under the conditions of the condensation temperature of-20 ℃ and the vacuum degree of 5Pa, and preparing the multi-microchannel multi-element composite oxide block with the laminated structure. And then grinding the multi-element composite oxide block, and sieving the multi-element composite oxide block by a 200-mesh sieve. Calcining the dried powder after grinding and sieving for 2h at the calcining temperature of 500 ℃ to finally obtain the multi-micro-channel multi-element composite rare earth oxide (La-Sn-Mo-O) nano powder with the laminated structure.
Finally, the multi-micro-channel multi-element composite rare earth oxide (La-Sn-Mo-O) with the laminated structure prepared by the process is subjected to performance characterization such as current carrier characteristics, thermal conductivity characteristics and the like (see table 1).
Example 2:
(1) preparation of precursor solution A
Citric acid with solute molar ratio of 1.5:0.2 and structure inducer Y (NO)3)3·6H2And O, adding a certain amount of a propylene oxide gel accelerator (a mixed solution of propylene oxide and citric acid in a molar ratio of 2.5: 1) into a solvent, adding a certain amount of a solute into the solvent, stirring by using a magnetic force until the solute is completely dissolved, then transferring liquid by using a glass rod into a volumetric flask to achieve a constant volume, and preparing a colorless transparent solution with the concentration of 0.03mol/L, wherein the solution is marked as a precursor solution A.
(2) Preparation of precursor solution B
The solutes are lanthanum nitrate and stannic chloride pentahydrate in a molar ratio of 1: 1, and the solvent is deionized water; and (3) introducing the solute into deionized water, stirring by magnetic force until the solute is completely dissolved, then transferring liquid to a volumetric flask by using a glass rod for constant volume, and preparing a colorless transparent solution with the concentration of 1.5mol/L, and marking as a precursor solution B.
(3) Preparation of layered structure multi-element composite oxide
And (3) introducing the precursor solution A into the precursor solution B in a dropwise manner by adopting a pear-shaped separating funnel to form a uniform and transparent solution, wherein the volume ratio of the precursor solution A to the precursor solution B is 0.25: 1. Regulating the environmental temperature to 60 ℃, and continuously reacting for 20min at a magnetic stirring speed of 500rmp to form uniform sol. Forming wet gel after 24h aging treatment; vacuum freeze drying for 24 hr in a vacuum freeze drier at the condensing temperature of-60 deg.c and vacuum degree of 5Pa to prepare the multicomponent composite RE oxide block. And then grinding the multi-element composite oxide block, and sieving the multi-element composite oxide block by a 200-mesh sieve. Calcining the dried powder after grinding and sieving for 6h at the calcining temperature of 800 ℃ to finally obtain the multi-micro-channel multi-element composite rare earth oxide (La-Sn-Y-O) nano powder with the laminated structure.
Finally, the multi-micro-channel multi-element composite rare earth oxide (La-Sn-Y-O) with the laminated structure prepared by the process is subjected to performance characterization such as current carrier characteristics, thermal conductivity characteristics and the like (see table 1).
Example 3:
(1) preparation of precursor solution A
The solute is citric acid and Na as structure inducer with the mol ratio of 1.5:0.82WO4·2H2And O, adding a certain amount of a propylene oxide gel accelerator (a mixed solution of propylene oxide and citric acid in a molar ratio of 1.2: 1) into a solvent, adding a certain amount of a solute into the solvent, stirring by using a magnetic force until the solute is completely dissolved, then transferring liquid into a volumetric flask by using a glass rod to fix the volume, and preparing a colorless transparent solution with the concentration of 0.03mol/L, wherein the solution is marked as a precursor solution A.
(2) Preparation of precursor solution B
The solutes are lanthanum nitrate and stannic chloride pentahydrate in a molar ratio of 1: 1, and the solvent is deionized water; and (3) introducing the solute into deionized water, stirring by magnetic force until the solute is completely dissolved, then transferring liquid to a volumetric flask by using a glass rod for constant volume, and preparing a colorless transparent solution with the concentration of 1.5mol/L, and marking as a precursor solution B.
(3) Preparation of layered structure multi-element composite oxide
And (3) introducing the precursor solution A into the precursor solution B in a dropwise manner by adopting a pear-shaped separating funnel to form a uniform and transparent solution, wherein the volume ratio of the precursor solution A to the precursor solution B is 0.2: 1. Regulating the environmental temperature to 45 ℃, and continuously reacting for 12min at a magnetic stirring speed of 350rmp to form uniform sol. Forming wet gel after 24h aging treatment; vacuum freeze drying is carried out for 24h by adopting a vacuum freeze dryer under the conditions of the condensation temperature of minus 40 ℃ and the vacuum degree of 5Pa, and the multi-micro-channel multi-element composite rare earth oxide block with the laminated structure is prepared. And then grinding the multi-element composite oxide block, and sieving the multi-element composite oxide block by a 200-mesh sieve. Calcining the powder after grinding and sieving for 4.5h at the calcining temperature of 580 ℃ to finally obtain the multi-micro-channel multi-element composite rare earth oxide (La-Sn-W-O) nano powder with the laminated structure.
Finally, the multi-micro-channel multi-element composite rare earth oxide (La-Sn-W-O) with the laminated structure prepared by the process is subjected to performance characterization such as current carrier characteristics, thermal conductivity characteristics and the like (see table 1).
TABLE 1 Electrical and thermal characterization of the layered multicomponent composite rare earth oxides
Through detection, the carrier mobility of the layered structure multi-element composite oxide obtained in the examples 1-3 is obviously higher than that of a pure La-Sn-O composite oxide without a structure inducer, and a foundation is laid for the application of the layered structure multi-element composite oxide in the field of silver-based conductive alloys to play high electric conductivity and high heat conductivity.
Claims (3)
1. A preparation method of a high-conductivity layered structure multi-element composite rare earth oxide is characterized by comprising the following steps:
(1) preparation of precursor solution A
Citric acid and a structure inducer in a molar ratio of 1.5 to (1.5-0.2)XAs a solute, a mixed solution of a gel accelerator and deionized water is used as a solvent; adding a solute to the solvent in an amount sufficient to promote the gelation of the gel promoter relative to the citric acidThe molar ratio is = (0.5-2.5): 1; stirring by magnetic force until the solution is completely dissolved, transferring the solution into a volumetric flask for constant volume, and preparing a colorless transparent solution with the concentration of 0.03mol/L, and marking as a precursor solution A;
the structure-inducing agentXIs Na2MoO4、Y(NO3)3·6H2O or Na2WO4·2H2O, the gel accelerator is propylene oxide;
(2) preparation of precursor solution B
Lanthanum nitrate and stannic chloride pentahydrate in a molar ratio of 1: 1 are taken as solutes, and deionized water is taken as a solvent; adding the solute into deionized water, and stirring by magnetic force until the solute is completely dissolved; then, the solution is transferred to a volumetric flask for constant volume, and a colorless transparent solution with the concentration of 1.5mol/L is prepared and marked as a precursor solution B;
(3) preparation of layered structure multi-element composite rare earth oxide
Dropwise adding the precursor solution A into the precursor solution B according to the volume ratio of (0.1-0.25) to 1 to form a uniform transparent solution, and continuously reacting under stirring to obtain a uniform sol; after aging treatment to form wet gel, vacuum freeze drying treatment is carried out to prepare a multi-element composite oxide block;
and grinding and sieving the multi-element composite oxide block, and calcining for 2-6 hours at 500-800 ℃ to finally obtain the multi-element composite rare earth oxide (La-Sn-X-O) nano powder with the multi-microchannel laminated structure.
2. The method according to claim 1, wherein in the step (3), the reaction conditions of the precursor solution A and the precursor solution B are as follows: the reaction temperature is 25-60 ℃, the stirring speed is 150-500 rmp, and the reaction time is 5-20 min.
3. The method according to claim 1, wherein in the step (3), the aging treatment time is 24 h; the conditions of vacuum freeze-drying are as follows: the temperature is minus 20 ℃ to minus 60 ℃, the vacuum degree is 5Pa, and the drying time is 24 hours; after grinding, the mixture is sieved by a 200-mesh sieve.
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