CN114524440B - High-entropy rare earth co-doped nano low-heat-transfer powder material and preparation method thereof - Google Patents

High-entropy rare earth co-doped nano low-heat-transfer powder material and preparation method thereof Download PDF

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CN114524440B
CN114524440B CN202210436300.9A CN202210436300A CN114524440B CN 114524440 B CN114524440 B CN 114524440B CN 202210436300 A CN202210436300 A CN 202210436300A CN 114524440 B CN114524440 B CN 114524440B
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邓冠南
刘金龙
尹健
秦晓婷
彭维
李璐
张光睿
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Tianjin Baogang Rare Earth Research Institute Co Ltd
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Abstract

The invention provides a high-entropy rare earth co-doped nano low-heat-transfer powder material and a preparation method thereof, and the preparation method comprises the following steps: (1) putting a rare earth source, a boron source and an intermediate into a high-pressure reaction kettle, filling hydrogen, heating to 320-340 ℃, fully stirring for activation, extracting and layering the obtained product, carrying out suction filtration, washing and drying on the precipitate, then carrying out wet grinding, carrying out spray granulation on the obtained slurry, and carrying out dry grinding on the obtained spherical powder to obtain a precursor; (2) loading the precursor into a rotary furnace for calcination, introducing a hydrogen-nitrogen mixed gas into the rotary furnace, heating to 900-; (3) and removing impurities from the primary product to obtain the high-entropy rare earth co-doped nano low-heat-transfer powder material. The high-entropy rare earth co-doped nano low-heat-transfer powder material has the advantages of small powder evacuation fluffy particle size, lower required temperature and low energy consumption.

Description

High-entropy rare earth co-doped nano low-heat-transfer powder material and preparation method thereof
Technical Field
The invention belongs to the field of heat-insulating powder materials, and particularly relates to a high-entropy rare earth co-doped nano low-heat-transfer powder material and a preparation method thereof.
Background
103663482A discloses a method for synthesizing LaB6 powder by a full wet process and a closed cycle. The LaB6 bulk material obtained by the method needs mechanical crushing, is subjected to hydrometallurgy, and is subjected to acid leaching by using sulfuric acid to obtain LaB6 powder. The method has low yield and large pollution, and is not suitable for industrial production.
101372340A discloses a multi-element rare earth boride (LaxRe1-x) B6 cathode material and a preparation method thereof. The method adopts SPS sintering densification to obtain a polycrystalline block. The preparation process is complex in process, high in technical difficulty, expensive in equipment, high in energy consumption, high in cost and low in yield, and the raw materials need high-purity elemental rare earth metal, so that the preparation method is not suitable for industrial production.
104894641A discloses a high-density (LaxCa1-x) B6 polycrystalline cathode material and a preparation method thereof. The method takes two kinds of metal hexaboride as raw materials, the maximum sintering temperature is 1700-1900 ℃, the requirement on a sintering furnace is higher, the energy consumption is high, and the industrial production is difficult.
102515769A discloses a high-purity high-density (CexPr1-x) B6 multi-element rare earth boride cathode material and a preparation method thereof. The invention has strict requirements on raw materials, expensive equipment and difficult industrial production.
Disclosure of Invention
In view of the above, the invention provides a high-entropy rare earth co-doped nano low-heat-transfer powder material and a preparation method thereof, which solve the problem of the existing LaB6The short and narrow near infrared absorption wave of the powder material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material comprises the following steps:
step 1, putting a rare earth source I, a rare earth source II, a rare earth source III, a rare earth source IV, a rare earth source V, a boron source and an intermediate into a high-pressure reaction kettle, flushing hydrogen, heating to 320-plus-340 ℃, fully stirring for activation, extracting and layering the obtained product, performing suction filtration, water washing and drying on the precipitate, performing wet grinding to obtain slurry, performing spray granulation on the slurry to obtain spherical powder, and performing dry grinding on the spherical powder to obtain a precursor;
step 2, loading the precursor into a rotary furnace for calcination, introducing a hydrogen-nitrogen mixed gas into the rotary furnace, heating to 900-1200 ℃, preserving heat for 30-450min, and cooling to obtain a primary product;
and 3, removing impurities from the primary product to obtain the high-entropy rare earth co-doped nano low-heat-transfer powder material.
Further, the flush amount of the hydrogen in the step 1 is 12-15 mol; the stirring step in the step 1 lasts for 2-4 hours; the times of the suction filtration and water washing steps in the step 1 are 3-5 times; the temperature of the drying step in the step 1 is 80-110 ℃, and the time is 3-5 hours; the solvent in the extraction step in the step 1 is water.
Further, the particle size of the slurry in the step 1 is less than or equal to 600 nanometers; the granularity of the spherical powder in the step 1 is less than or equal to 800 nanometers; the granularity of the precursor in the step 1 is less than or equal to 300 nanometers.
Further, the structural formula of the high-entropy rare earth co-doped nano low-heat-transfer powder material in the step 3 is R1xR2yR3zR4wR5nB6Wherein, R1, R2, R3, R4 and R5 are all rare earth elements, and R1 ≠ R2 ≠ R3 ≠ R4 ≠ R5, and x + y + z + w + n = 1;
the intermediate in the step 1 is Na and SiO2；
The rare earth element in the rare earth source I is R1, the rare earth element in the rare earth source II is R2, the rare earth element in the rare earth source III is R3, the rare earth element in the rare earth source IV is R4, the rare earth element in the rare earth source V is R5, R1, R2, R3, R4, R5, Na, SiO2The molar ratio of the boron source to boron element in the boron source is 0.01-0.99: 0.01-0.99: 0-0.99: 0-0.99: 0-0.99: 24: 12: 6.
further, R1 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, or scandium;
r2 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r3 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r4 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r5 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
the boron source in the step 1 is one or more of boron trioxide, metaboric acid or boric acid.
Further, the temperature raising step in the step 2 specifically includes: a first temperature rise stage: the temperature is between room temperature and 270 ℃, the heating rate is 3-6 ℃/min, the temperature is kept for 31-45min after the heating is finished, the aeration rate is 2-5mL/min, the inclination angle of the rotary furnace is 5-14 degrees, and the rotation speed is 11-15 rpm; a second temperature rising stage: heating to 471-; a third temperature rise stage: the temperature is increased to 900 ℃ and 1200 ℃, the temperature rising rate is 8-12 ℃/min, the temperature is kept for 30-450min after the temperature rising is finished, the aeration rate is 11-30mL/min, the inclination angle of the rotary furnace is 6-10 ℃, and the rotation speed is 5-14 rpm.
Further, the cooling step in the step 2 specifically comprises: a first cooling stage: cooling from 900-; and a second cooling stage: cooling from 471-550 ℃ to room temperature, the aeration rate is 5-10mL/min, the inclination angle of the rotary furnace is 0-3 ℃, and the rotation speed is 16-25 rpm.
Further, the charging height of the rotary furnace in the step 2 is less than or equal to 9 cm; the volume content of hydrogen in the hydrogen-nitrogen mixed gas in the step 2 is 8-20%.
Further, the impurity removing step in the step 3 specifically comprises the following steps: washing the primary product with 5mol/L hydrochloric acid solution, then washing with deionized water until AgNO is dripped into the washing liquid3The high-entropy rare earth co-doped nano low-heat-transfer powder material is obtained without precipitation of the solution.
The high-entropy rare earth co-doped nano low-heat-transfer powder material prepared by the preparation methodThe structural formula of the high-entropy rare earth co-doped nano low-heat-transfer powder material is R1xR2yR3zR4wR5nB6Wherein, R1, R2, R3, R4 and R5 are all rare earth elements, and R1 ≠ R2 ≠ R3 ≠ R4 ≠ R5, and x + y + z + w + n = 1;
the molar ratio of R1, R2, R3, R4, R5 to B is 0.01-0.99: 0.01-0.99: 0-0.99: 0-0.99: 0-0.99: 6;
r1 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r2 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r3 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r4 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r5 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
and B is one or more of boron trioxide, metaboric acid or boric acid.
Compared with the prior art, the invention has the following advantages:
the high-entropy rare earth co-doped nano low-heat-transfer powder material has an infrared absorption waveband which is higher than that of LaB6The infrared absorption capacity is improved by about 75 percent at the maximum in the wave band of 1000nm to 2500 nm.
The high-entropy rare earth co-doped nano low-heat-transfer powder material is a nano-scale powder material, has single phase, uniform grain distribution, particle size of between 300 and 800 nanometers, controllable particle size, and is influenced by heat treatment temperature and heat preservation time.
The preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material has the advantages of simple process flow, long preparation time, high product added value and the like, and can be used for reducing the content of the rare earth co-doped nano low-heat-transfer powder materialLow R1xR2yR3zR4wR5nB6The production cost of the powder material and the efficient value-added utilization of various types of light rare earth have very important significance.
In the preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material, the particle size of the precursor is finely controlled in a nanocrystallization manner, the surface activity of the high-material and the relatively sufficient ionic thermal motion of the rotary powder material in the reducing atmosphere are the technical key points of reducing energy consumption and cost.
In the preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material, the precursor rare earth source and the boron source are activated, the reaction is extracted, separated and dried to generate the boron hydrogenation rare earth, and the R1 is reducedxR2yR3zR4wR5nB6The synthesis temperature and the reduction of the ionic thermal motion synthesis path are the technical keys for reducing energy consumption and cost.
The preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material disclosed by the invention has the advantages that the raw materials are mixed for four times and are subjected to spherical granulation for two times, and the fully mixed raw materials and the nano spherical powder with excellent fluidity enable the R1 prepared by synthesis to be synthesizedxR2yR3zR4wR5nB6The powder material has the characteristics of single phase, uniform grain distribution and fine final powder grain size.
Drawings
FIG. 1 shows Y in examples 1 to 3 of the present invention0.1La0.6Eu0.1Ce0.1Sm0.1B6、Ce0.1La0.6Eu0.1Nd0.1Sm0.1B6With Eu0.1La0.6Sm0.1Gd0.1Ce0.1B6X-ray diffraction pattern of the powdered material;
FIG. 2 shows Y in comparative examples 1 to 4 of the present invention0.1La0.6Eu0.1Ce0.1Sm0.1B6An X-ray diffraction pattern of the powder material;
FIG. 3 is a schematic view of a rotary kiln.
Description of reference numerals:
1. a furnace body; 2. a base; 3. a material turning plate; 4. a support bar; 5. an electric motor.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The rotary furnace used in the embodiment of the invention comprises a furnace body, wherein the furnace body is positioned on a base, and a support rod is arranged between the furnace body and the base; the material turning plate is arranged in the furnace body and is of a spiral structure, the spiral angle of the material turning plate is 70-89 degrees, and the inner diameter of the rotary furnace is 5-10 times of the width of the material turning plate.
The bracing piece be current structure, adjust the inclination of furnace body through control bracing piece. After the bracing piece will heat the furnace body lifting certain inclination, turn over flitch cooperation inclination, slew rate and carry out the spiral and carry out the formula stirring one by one right side top, one for preventing that the material from bonding on the furnace body, two for turning furnace body bottom material be the abundant contact reducing atmosphere of top layer material, three for the material of gyration in-process mixes once more, promote abundant reaction, four for the material is whole to be heated evenly, the particle diameter uniformity is higher.
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material comprises the following steps:
(1) will Y2（CO3）3 358g、La2（CO3）3 1373g、EuCl3 258g、Ce2(CO3）3460g、Sm2(CO3)3487g、B2O32089g, Na 552g and SiO2 720g（Y：La：Eu：Ce：Sm：B：Na：SiO2The molar ratio was 0.1:0.6:0.1:0.1:0.1:6:24: 12) into a high-pressure reaction kettle, charging 15 moles of hydrogen, heating to 320 ℃, fully stirring for 2 hours, extracting and layering the obtained product, carrying out suction filtration and washing on the precipitate for 5 times, drying at 110 ℃ for 5 hours, then charging the precipitate and 6kg of deionized water into a sand mill for grinding for 12 hours to obtain 506-nanometer slurry, carrying out spray granulation on the slurry to obtain 754-nanometer spherical powder, carrying out fine grinding granulation on the spherical powder by using a high-energy jet mill to obtain 246-nanometer R1xR2yR3zR4wR5nB6Loading the precursor into a rotary furnace, wherein the filling height of the precursor is 3 cm;
(2) after 8% hydrogen-nitrogen mixed gas is introduced into the rotary furnace after the charging and sealing, the speed is 100mL/min for 1min, the temperature is raised, and in the first temperature raising stage: the temperature is increased to 270 ℃ at the rate of 5 ℃/min, the temperature is kept for 35min after the temperature is increased, the aeration rate is 2mL/min, the inclination angle of the rotary furnace is 10 degrees, and the rotation speed is 11 rpm; a second temperature rising stage: the temperature is increased at the rate of 5 ℃/min from 270 ℃ to 490 ℃, the temperature is kept for 35min after the temperature is increased, the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 9 ℃, and the rotation speed is 16 rpm; a third temperature rise stage: heating from 490 ℃ to 1050 ℃, wherein the heating rate is 10 ℃/min, keeping the temperature for 150min after heating, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 6 degrees, and the rotation speed is 14 rpm;
cooling process, first cooling stage: cooling from 1050 ℃ to 490 ℃, wherein the cooling rate is 20 ℃/min, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 6 degrees, and the rotation rate is 14 rpm; and a second cooling stage: cooling from 490 ℃ to room temperature, wherein the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 0 DEG, the rotation speed is 16rpm, and the initial product can be obtained after cooling to room temperature;
(3) washing the initial product with 5mol/L hydrochloric acid and deionized water until the washing solution is dripped with AgNO3No precipitation of the solution occurs to obtain a black reduction product Y0.1La0.6Eu0.1Ce0.1Sm0.1B6. Product 1331g, yield 96.4%. Y is0.1La0.6Eu0.1Ce0.1Sm0.1B6Material is compared with LaB6Infrared energy absorption at 1000nm to 2500nmThe yield increase was about 75%.
Example 2
A preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material comprises the following steps:
(1) adding Ce (NO)3)3 326g、La2（CO3）3 1373g、EuCl3 258g、NdCl3 256g、Sm2(CO3)3 487g、B2O3 2089g、Na 552g、SiO2 720g（Ce：La：Eu：Nd：Sm:B：Na：SiO2The molar ratio is 0.1:0.6:0.1:0.1:0.1:6:24: 12), charging into a high-pressure reaction kettle, charging hydrogen gas 15 mol, heating to 320 ℃, fully stirring for 2 hours, extracting and layering the obtained product, carrying out suction filtration and washing for 5 times, drying for 5 hours at 110 ℃, then charging into a sand mill together with 6kg deionized water for grinding for 12 hours, carrying out spray granulation on the obtained 508 nano slurry, carrying out secondary grinding on the obtained 781 nano spherical powder by using a high-energy jet mill, and obtaining 152 nano R1xR2yR3zR4wR5nB6Loading the precursor into a rotary furnace, wherein the filling height of the precursor is 3 cm;
(2) after the rotary furnace after the material charging and sealing is filled with 10% hydrogen-nitrogen mixed gas at the speed of 100mL/min for 1min, starting temperature rising, wherein in the first temperature rising stage: the temperature is increased to 270 ℃ at the rate of 5 ℃/min, the temperature is kept for 45min after the temperature is increased, the aeration rate is 2mL/min, the inclination angle of the rotary furnace is 14 degrees, and the rotation speed is 11 rpm; a second temperature rising stage: from 270 ℃ to 500 ℃, the heating rate is 5 ℃/min, the temperature is kept for 45min after the heating is finished, the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 9 degrees, and the rotation speed is 16 rpm; a third temperature rise stage: heating from 500 ℃ to 1050 ℃, wherein the heating rate is 8 ℃/min, keeping the temperature for 250min after the heating is finished, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 6 degrees, and the rotation speed is 14 rpm;
cooling process, first cooling stage: cooling from 1050 ℃ to 500 ℃, wherein the cooling rate is 20 ℃/min, the aeration rate is 30mL/min, the rotation rate is 14rpm, and the inclination angle of the rotary furnace is 6 degrees; and a second cooling stage: cooling from 500 ℃ to room temperature, wherein the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 0 ℃, and the rotation speed is 16 rpm;
(3) washing the initial product with 5mol/L hydrochloric acid and deionized water until the washing solution is dripped with AgNO3No precipitation of the solution is generated to obtain a black reduction product Ce0.1La0.6Eu0.1Nd0.1Sm0.1B6. 1341g of product, yield 97.1%. Ce0.1La0.6Eu0.1Nd0.1Sm0.1B6Material is compared with LaB6The infrared absorption capacity of the material is improved by about 75 percent when the material is used for the infrared absorption of 1000nm to 2500 nm.
Example 3
A preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material comprises the following steps:
(1) mixing EuCl3 258g、La2（CO3）3 1373g、Sm2(CO3)3 487g、GdCl3 264g、Ce(NO3)3 326g、B2O3 2089g、Na 552g、SiO2 720g（Eu：La：Sm：Gd：Ce：B：Na：SiO2The molar ratio is 0.1:0.6:0.1:0.1:0.1:6:24: 12), charging into a high-pressure reaction kettle, charging hydrogen gas 15 mol, heating to 320 ℃, fully stirring for 2 hours, extracting and layering the obtained product, carrying out suction filtration and washing for 5 times, drying for 5 hours at 110 ℃, then charging into a sand mill together with 6kg deionized water for grinding for 12 hours, carrying out spray granulation on the obtained 594 nm slurry, grinding the obtained 782 nm spherical powder by using an air mill, and obtaining 166 nm R1xR2yR3zR4wR5nB6Loading the precursor into a rotary furnace, wherein the filling height of the precursor is 3 cm;
(2) after the speed of introducing 12% hydrogen-nitrogen mixed gas into the rotary furnace after the charging and sealing is 100mL/min for 1min, starting temperature rising, wherein in the first temperature rising stage: the temperature is increased to 270 ℃ at the rate of 5 ℃/min, the temperature is kept for 40min after the temperature is increased, the aeration rate is 2mL/min, the inclination angle of the rotary furnace is 14 degrees, and the rotation speed is 11 rpm; a second temperature rising stage: from 270 ℃ to 500 ℃, the heating rate is 5 ℃/min, the temperature is kept for 40min after the heating is finished, the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 9 degrees, and the rotation speed is 16 rpm; a third temperature rise stage: heating from 500 ℃ to 1200 ℃, wherein the heating rate is 12 ℃/min, keeping the temperature for 250min after the heating is finished, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 7 ℃, and the rotation rate is 10 rpm;
cooling process, first cooling stage: cooling from 1200 ℃ to 500 ℃, wherein the cooling rate is 20 ℃/min, the aeration rate is 30mL/min, the rotation rate is 10rpm, and the inclination angle of the rotary furnace is 6 degrees; and a second cooling stage: cooling from 500 ℃ to room temperature, wherein the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 0 degree, the rotation rate is 16rpm, and the initial product can be obtained after cooling to room temperature;
(3) washing the initial product with 5mol/L hydrochloric acid and deionized water until the washing solution is dripped with AgNO3No precipitation of the solution is generated to obtain a black reduction product Eu0.1La0.6Sm0.1Gd0.1Ce0.1B6. Product 1355g, yield 98.2%. Eu (Eu)0.1La0.6Sm0.1Gd0.1Ce0.1B6Material is compared with LaB6The infrared absorption capacity of the material is improved by about 75 percent when the material is used for the infrared absorption of 1000nm to 2500 nm.
Comparative example 1
A preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material comprises the following steps:
(1) will Y2（CO3）3 358g、La2（CO3）3 1373g、EuCl3 258g、Ce2(CO3）3460g、Sm2(CO3)3487g、B2O32089g, Na 552g and SiO2 720g（Y：La：Eu：Ce：Sm：B：Na：SiO20.1:0.6:0.1:0.1:0.1:6:24: 12) and 6kg of deionized water were put into a sand mill together and ground for 12 hours, the obtained 506 nm slurry was subjected to spray granulation, the obtained 754 nm spherical powder was subjected to jet milling and ground, and the obtained 246 nm R1 was obtainedxR2yR3zR4wR5nB6The precursor is filled into a rotary furnace, and the filling height of the precursor is 3 cmRice;
(2) after 8% hydrogen-nitrogen mixed gas is introduced into the rotary furnace after the charging and sealing, the speed is 100mL/min for 1min, the temperature is raised, and in the first temperature raising stage: the temperature is increased to 270 ℃ at the rate of 5 ℃/min, the temperature is kept for 35min after the temperature is increased, the aeration rate is 2mL/min, the inclination angle of the rotary furnace is 10 degrees, and the rotation speed is 11 rpm; a second temperature rising stage: from 270 ℃ to 490 ℃, the heating rate is 5 ℃/min, the temperature is kept for 35min after the heating is finished, the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 9 degrees, and the rotation speed is 16 rpm; a third temperature rise stage: heating from 490 ℃ to 1050 ℃, wherein the heating rate is 10 ℃/min, keeping the temperature for 150min after heating, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 6 degrees, and the rotation speed is 14 rpm;
cooling process, first cooling stage: cooling from 1050 ℃ to 490 ℃, wherein the cooling rate is 20 ℃/min, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 6 degrees, and the rotation speed is 14 rpm; and a second cooling stage: cooling from 490 ℃ to room temperature, wherein the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 0 DEG, the rotation speed is 16rpm, and the initial product can be obtained after cooling to room temperature;
(3) washing the initial product with 5mol/L hydrochloric acid and deionized water until the washing solution is dripped with AgNO3No precipitation of the solution occurs to obtain a black reduction product Y0.1La0.6Eu0.1Ce0.1Sm0.1B6. 806g of product, yield 58%. The reason for the low yield is that the raw materials without activation treatment have strong chemical stability, are mostly in amorphous six-membered ring structure, the calcination temperature requirement is high, and the current heat treatment temperature cannot be effectively crystallized. After the activation treatment, a boron source which is easy to crystallize is formed, and the heat treatment temperature required in the calcination preparation process is lower.
Comparative example 2
A preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material comprises the following steps:
(1) will Y2（CO3）3 358g、La2（CO3）3 1373g、EuCl3 258g、Ce2(CO3）3460g、Sm2(CO3)3487g、B2O32089g, Na 552g and SiO2 720g（Y：La：Eu：Ce：Sm：B：Na：SiO2The molar ratio is 0.1:0.6:0.1:0.1:0.1:6:24: 12), the mixture is put into a high-pressure reaction kettle, 15 moles of hydrogen are added, the temperature is raised to 320 ℃, the mixture is fully stirred for 2 hours, the obtained product is extracted and layered, the precipitate is filtered, washed by water for 5 times, dried for 5 hours at 110 ℃, the dried product is put into a rotary furnace, and the filling height of the precursor is 3 cm;
(2) after 8% hydrogen-nitrogen mixed gas is introduced into the rotary furnace after the charging and sealing, the speed is 100mL/min for 1min, the temperature is raised, and in the first temperature raising stage: the temperature is increased to 270 ℃ at the rate of 5 ℃/min, the temperature is kept for 35min after the temperature is increased, the aeration rate is 2mL/min, the inclination angle of the rotary furnace is 10 degrees, and the rotation speed is 11 rpm; a second temperature rising stage: from 270 ℃ to 490 ℃, the heating rate is 5 ℃/min, the temperature is kept for 35min after the heating is finished, the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 9 degrees, and the rotation speed is 16 rpm; a third temperature rise stage: heating from 490 ℃ to 1050 ℃, wherein the heating rate is 10 ℃/min, keeping the temperature for 150min after heating, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 6 degrees, and the rotation speed is 14 rpm;
cooling process, first cooling stage: cooling from 1050 ℃ to 490 ℃, wherein the cooling rate is 20 ℃/min, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 6 degrees, and the rotation speed is 14 rpm; and a second cooling stage: cooling from 490 ℃ to room temperature, wherein the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 0 DEG, the rotation speed is 16rpm, and the initial product can be obtained after cooling to room temperature;
(3) washing the initial product with 5mol/L hydrochloric acid and deionized water until the washing solution is dripped with AgNO3No precipitation of the solution occurs to obtain a black reduction product Y0.1La0.6Eu0.1Ce0.1Sm0.1B6. 920g of product, 66.7 percent of yield, and low yield because the powder has large particle size, weak surface activity and poor ionic thermal motion, so that too many impurities are caused, and the yield is reduced.
Comparative example 3
A preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material comprises the following steps:
(1) will Y2（CO3）3 358g、La2（CO3）3 1373g、EuCl3 258g、Ce2(CO3）3460g、Sm2(CO3)3487g、B2O32089g, Na 552g and SiO2 720g（Y：La：Eu：Ce：Sm：B：Na：SiO2The molar ratio is 0.1:0.6:0.1:0.1:0.1:6:24: 12), charging into a high-pressure reaction kettle, charging hydrogen gas 15 mol, heating to 320 ℃, fully stirring for 2 hours, extracting and layering the obtained product, carrying out suction filtration and washing for 5 times, drying for 5 hours at 110 ℃, then charging into a sand mill together with 6kg deionized water, grinding for 12 hours to obtain 506 nm slurry, carrying out spray granulation on the slurry to obtain 754 nm spherical powder, carrying out fine grinding granulation on the spherical powder by using a high-energy jet mill to obtain 246 nm R1xR2yR3zR4wR5nB6Loading the precursor into a rotary furnace, wherein the filling height of the precursor is 3 cm;
(2) after 8% hydrogen-nitrogen mixed gas is introduced into the rotary furnace after the charging and sealing, the speed is 100mL/min for 1min, the temperature is raised, and in the first temperature raising stage: the temperature is increased to 270 ℃ at the rate of 5 ℃/min, the temperature is kept for 35min after the temperature is increased, the aeration rate is 2mL/min, and the inclination angle of the rotary furnace is 10 degrees; a second temperature rise stage: the temperature is increased at the rate of 5 ℃/min from 270 ℃ to 490 ℃, the temperature is kept for 35min after the temperature is increased, the ventilation rate is 5mL/min, and the inclination angle of the rotary furnace is 9 degrees; a third temperature rise stage: heating from 490 ℃ to 1050 ℃, wherein the heating rate is 10 ℃/min, keeping the temperature for 150min after the heating is finished, the aeration rate is 30mL/min, and the inclination angle of the rotary furnace is 6 degrees; a cooling process, namely a first cooling stage: cooling from 1050 ℃ to 490 ℃, wherein the cooling rate is 20 ℃/min, the aeration rate is 30mL/min, and the inclination angle of the rotary furnace is 6 degrees; and a second cooling stage: cooling from 490 ℃ to room temperature, wherein the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 0 ℃, and the initial product can be obtained after cooling to room temperature;
(3) washing the initial product with 5mol/L hydrochloric acid and deionized water until the washing solution is dripped with AgNO3No precipitation of the solution occurs to obtain a black reduction product Y0.1La0.6Eu0.1Ce0.1Sm0.1B6. 1041g of product, 75.4% of yield and low yield are caused by that the powder slides integrally on the inner wall of the furnace tube during the synthesis reaction, so that the powder is heated unevenly, the reducing atmosphere is difficult to permeate into the whole furnace tube, and simultaneously the powder is easy to agglomerate, the ionic heat movement is insufficient, and the loose and fluffy powder material cannot be prepared.
Comparative example 4
A preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material comprises the following steps:
(1) will Y2（CO3）3 358g、La2（CO3）3 1373g、EuCl3 258g、Ce2(CO3）3460g、Sm2(CO3)3487g、B2O32089g, Na 552g and SiO2 720g（Y：La：Eu：Ce：Sm：B：Na：SiO2The molar ratio is 0.1:0.6:0.1:0.1:0.1:6:24: 12), charging into a high-pressure reaction kettle, charging hydrogen gas 15 mol, heating to 320 ℃, fully stirring for 2 hours, extracting and layering the obtained product, carrying out suction filtration and washing for 5 times, drying for 5 hours at 110 ℃, then charging into a sand mill together with 6kg deionized water, grinding for 12 hours to obtain 506 nm slurry, carrying out spray granulation on the slurry to obtain 754 nm spherical powder, carrying out fine grinding granulation on the spherical powder by using a high-energy jet mill to obtain 246 nm R1xR2yR3zR4wR5nB6Loading the precursor into a rotary furnace, wherein the filling height of the precursor is 3 cm;
after 8% hydrogen-nitrogen mixed gas is introduced into the rotary furnace after the charging and sealing, the speed is 100mL/min for 1min, the temperature is raised, and in the first temperature raising stage: the temperature is increased to 270 ℃ at the rate of 5 ℃/min, the temperature is kept for 35min after the temperature is increased, the aeration rate is 2mL/min, the inclination angle of the rotary furnace is 10 degrees, and the rotation speed is 11 rpm; a second temperature rising stage: from 270 ℃ to 490 ℃, the heating rate is 5 ℃/min, the temperature is kept for 35min after the heating is finished, the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 9 degrees, and the rotation speed is 16 rpm; a third temperature rise stage: heating from 490 ℃ to 1050 ℃, wherein the heating rate is 10 ℃/min, keeping the temperature for 150min after heating, the aeration rate is 30mL/min, the inclination angle of the rotary furnace is 6 degrees, and the rotation speed is 14 rpm;
cooling from 1050 ℃ to room temperature along with furnace air cooling, wherein the aeration rate is 5mL/min, the inclination angle of the rotary furnace is 0 DEG, the rotation speed is 16rpm, and the initial product can be obtained after cooling to room temperature;
(3) washing the initial product with 5mol/L hydrochloric acid and deionized water until AgNO is dripped into the washing liquid3No precipitation of the solution occurs to obtain a black reduction product Y0.1La0.6Eu0.1Ce0.1Sm0.1B6. 731g of product, 53% of yield, no temperature control process is used in the temperature reduction process, a large amount of ionic thermal motion still occurs in a high-temperature section, and simultaneously the reducing atmosphere is reduced, so that Y, La, Eu, Ce, Sm and other ions can not stably exist in the octahedral gaps of B and can only stably exist in an oxide form, and therefore the yield is reduced.
(4) In the figure, LaB is used6The characteristic diffraction peak is used as the standard diffraction peak contrast pattern of the high-entropy boride and is compared with the LaB6The diffraction peaks with different characteristic diffraction peaks are impurity diffraction peaks.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A preparation method of a high-entropy rare earth co-doped nano low-heat-transfer powder material is characterized by comprising the following steps: the method comprises the following steps:
step 1, putting a rare earth source I, a rare earth source II, a rare earth source III, a rare earth source IV, a rare earth source V, a boron source and an intermediate into a high-pressure reaction kettle, filling hydrogen, heating to 320-340 ℃, fully stirring for activation, extracting and layering obtained products, carrying out suction filtration, washing and drying on precipitates, then carrying out wet grinding to obtain slurry, carrying out spray granulation on the slurry to obtain spherical powder, and carrying out dry grinding on the spherical powder to obtain a precursor;
step 2, loading the precursor into a rotary furnace for calcination, introducing a hydrogen-nitrogen mixed gas into the rotary furnace, heating to 900-1200 ℃, preserving heat for 30-450min, and cooling to obtain a primary product;
step 3, removing impurities from the primary product to obtain the high-entropy rare earth co-doped nano low-heat-transfer powder material;
the granularity of the slurry in the step 1 is less than or equal to 600 nanometers; the granularity of the spherical powder in the step 1 is less than or equal to 800 nanometers; the granularity of the precursor in the step 1 is less than or equal to 300 nanometers;
the temperature raising step in the step 2 is specifically as follows: a first temperature rise stage: the temperature is between room temperature and 270 ℃, the heating rate is 3-6 ℃/min, the temperature is kept for 31-45min after the heating is finished, the aeration rate is 2-5mL/min, the inclination angle of the rotary furnace is 5-14 degrees, and the rotation speed is 11-15 rpm; a second temperature rising stage: heating to 471-; a third temperature rise stage: heating to 900-1200 ℃, wherein the heating rate is 8-12 ℃/min, keeping the temperature for 30-450min after the heating is finished, the aeration rate is 11-30mL/min, the inclination angle of the rotary furnace is 6-10 ℃, and the rotation speed is 5-14 rpm;
the intermediate in the step 1 is Na and SiO2。
2. The preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material according to claim 1, characterized by comprising the following steps: the filling amount of the hydrogen in the step 1 is 12-15 mol; the stirring step in the step 1 lasts for 2-4 hours; the times of the suction filtration and water washing steps in the step 1 are 3-5 times; the temperature of the drying step in the step 1 is 80-110 ℃, and the time is 3-5 hours; the solvent of the extraction step in the step 1 is water.
3. The preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material according to claim 1, characterized by comprising the following steps: the structural formula of the high-entropy rare earth co-doped nano low-heat-transfer powder material in the step 3 is R1xR2yR3zR4wR5nB6Wherein, R1, R2, R3, R4 and R5 are all rare earth elements, and R1 ≠ R2 ≠ R3 ≠ R4 ≠ R5, and x + y + z + w + n = 1;
the rare earth element in the rare earth source I is R1, the rare earth element in the rare earth source II is R2, the rare earth element in the rare earth source III is R3, the rare earth element in the rare earth source IV is R4, the rare earth element in the rare earth source V is R5, R1, R2, R3, R4, R5, Na, SiO2The molar ratio of the boron source to boron element in the boron source is 0.01-0.99: 0.01-0.99: 0-0.99: 0-0.99: 0-0.99: 24: 12: 6.
4. the preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material according to claim 3, characterized by comprising the following steps: r1 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r2 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r3 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r4 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r5 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
the boron source in the step 1 is one or more of boron trioxide, metaboric acid or boric acid.
5. The preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material according to claim 1, characterized by comprising the following steps: the cooling step in the step 2 is specifically as follows: a first cooling stage: cooling from 900-; and a second cooling stage: cooling from 471-.
6. The preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material according to claim 1, characterized by comprising the following steps: the charging height of the rotary furnace in the step 2 is less than or equal to 9 cm; the volume content of hydrogen in the hydrogen-nitrogen mixed gas in the step 2 is 8-20%.
7. The preparation method of the high-entropy rare earth co-doped nano low-heat-transfer powder material according to claim 1, characterized by comprising the following steps: the impurity removing step in the step 3 is specifically as follows: washing the primary product with 5mol/L hydrochloric acid solution, then washing with deionized water until AgNO is dripped into the washing liquid3The high-entropy rare earth co-doped nano low-heat-transfer powder material is obtained without precipitation of the solution.
8. The high-entropy rare earth co-doped nano low-heat-transfer powder material prepared by the preparation method of any one of claims 1 to 7 is characterized in that: the structural formula of the high-entropy rare earth co-doped nano low-heat-transfer powder material is R1xR2yR3zR4wR5nB6Wherein, R1, R2, R3, R4 and R5 are all rare earth elements, and R1 ≠ R2 ≠ R3 ≠ R4 ≠ R5, and x + y + z + w + n = 1;
the molar ratio of R1, R2, R3, R4, R5 to B is 0.01-0.99: 0.01-0.99: 0-0.99: 0-0.99: 0-0.99: 6;
r1 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r2 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r3 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r4 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
r5 is one of lanthanum, cerium, samarium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium;
the boron source is one or more of boron trioxide, metaboric acid or boric acid.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101287680A (en) * 2005-10-13 2008-10-15 罗地亚管理公司 Sub-micron rare earth borate, a method for the production thereof and the use in the form of luminophor
CN101434394A (en) * 2008-12-12 2009-05-20 北京工业大学 Multicomponent rare earth boride (LaxBa1-x)B6 cathode material and preparation thereof
CN106395843A (en) * 2016-09-09 2017-02-15 中国人民解放军国防科学技术大学 Preparation method of lanthanum hexaboride nanometer powder and application of lanthanum hexaboride nanometer powder
CN111285380A (en) * 2020-02-04 2020-06-16 天津包钢稀土研究院有限责任公司 Preparation method and application of multi-rare earth co-doped boride and nano heat insulation powder thereof
CN112028083A (en) * 2020-09-15 2020-12-04 湖南澎越新材料有限公司 Preparation method of rare metal boride
CN113582190A (en) * 2021-08-25 2021-11-02 湖南稀土金属材料研究院有限责任公司 Multi-element rare earth boride nano powder and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5051412B2 (en) * 2005-08-18 2012-10-17 独立行政法人物質・材料研究機構 Rare earth polyboride-based high-temperature acid-resistant n-type thermoelectric material doped with carbon and nitrogen and method for producing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101287680A (en) * 2005-10-13 2008-10-15 罗地亚管理公司 Sub-micron rare earth borate, a method for the production thereof and the use in the form of luminophor
CN101434394A (en) * 2008-12-12 2009-05-20 北京工业大学 Multicomponent rare earth boride (LaxBa1-x)B6 cathode material and preparation thereof
CN106395843A (en) * 2016-09-09 2017-02-15 中国人民解放军国防科学技术大学 Preparation method of lanthanum hexaboride nanometer powder and application of lanthanum hexaboride nanometer powder
CN111285380A (en) * 2020-02-04 2020-06-16 天津包钢稀土研究院有限责任公司 Preparation method and application of multi-rare earth co-doped boride and nano heat insulation powder thereof
CN112028083A (en) * 2020-09-15 2020-12-04 湖南澎越新材料有限公司 Preparation method of rare metal boride
CN113582190A (en) * 2021-08-25 2021-11-02 湖南稀土金属材料研究院有限责任公司 Multi-element rare earth boride nano powder and preparation method thereof

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