CN116120081A - High-entropy ceramic aerogel material and preparation method and application thereof - Google Patents

High-entropy ceramic aerogel material and preparation method and application thereof Download PDF

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CN116120081A
CN116120081A CN202310039767.4A CN202310039767A CN116120081A CN 116120081 A CN116120081 A CN 116120081A CN 202310039767 A CN202310039767 A CN 202310039767A CN 116120081 A CN116120081 A CN 116120081A
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entropy ceramic
rare earth
based high
dispersion
aerogel
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吴静欣
杨帆
薛丽燕
赵志钢
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Ganjiang Innovation Academy of CAS
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Abstract

The invention provides a high-entropy ceramic aerogel material, a preparation method and application thereof, wherein the high-entropy ceramic aerogel material comprises a rare earth-based high-entropy ceramic material and a YSZ fiber matrix material; compared with the traditional aerogel material, the high-entropy ceramic aerogel material has lower heat conductivity, higher thermal expansion coefficient and good high-temperature stability, the normal-temperature heat conductivity is lower than 0.030W/(m.K), and the heat conductivity is lower than 0.050W/(m.K) at 600 ℃.

Description

High-entropy ceramic aerogel material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of rare earth high-entropy ceramics, and relates to a high-entropy ceramic aerogel material, a preparation method and application thereof.
Background
The high-performance heat-preservation and heat-insulation material is a key component for heat protection in the fields of aerospace, industrial storage tanks, pipelines, military industry and the like, and is also a key material for building energy conservation and environmental protection. Aerogel materials are porous dielectric materials with three-dimensional grid space structures at the nanometer level, and are solid materials with the minimum density in the world at present. The unique nanoscale pore structure of the aerogel material can effectively perform solid and gaseous heat conduction, and meanwhile, the aerogel material has the advantages of low density, high specific surface area, heat stability and the like, so that the aerogel material becomes a heat preservation and heat insulation material with excellent performance. Currently, the existing aerogels mainly include inorganic aerogels including, for example, siO, organic aerogels, and carbon aerogels 2 Aerogels, clay aerogels, metal aerogels, and the like, organic aerogels include, for example, phenolic aerogels, polyimide aerogels, and the like, and carbon aerogels include, for example, activated carbon, graphene, carbon Nanotubes (CNT), and the like.
However, the three-dimensional nano-pore microstructure of the conventional aerogel collapses at high temperature and cannot meet the increasing heat insulation requirement of a high temperature region, so that development of a novel aerogel heat insulation material with good high temperature stability is very necessary. A is that 2 B 2 O 7 Compounds have received considerable attention from researchers over the years. A is that 2 B 2 O 7 The compound is considered to have wide application prospects in the heat insulation field due to excellent heat stability and low heat conductivity. In recent years, entropy-stable oxide materials are increasingly rising, and high-entropy ceramic powders generally refer to solid solutions composed of five or more ceramic powder components, wherein the content of metal elements is equal or nearly equal. The design concept enables the high-entropy ceramic powder to have four major core effects, namely a high-entropy effect, a lattice distortion effect, a delayed diffusion effect and a cocktail effect, and compared with the traditional ceramic powder material, the high-entropy ceramic powder has excellent high-temperature stability and good environmental corrosion resistance, can be applied to various extreme service environments, particularly high-temperature performance temperatures, but the research on the high-entropy ceramic powder aerogel material cannot be practically applied at present, and the performance of the obtained aerogel is to be improved.
Based on the above research, it is necessary to provide a high-entropy ceramic aerogel material, which can exist stably at room temperature and high temperature, has low room temperature thermal conductivity and high temperature thermal conductivity, and can be practically applied to the field of heat preservation and heat insulation.
Disclosure of Invention
The invention aims to provide a high-entropy ceramic aerogel material, a preparation method and application thereof, wherein the high-entropy ceramic aerogel material exists in a stable fluorite structure at room temperature, and various rare earth elements are uniformly distributed.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a high entropy ceramic aerogel material comprising a rare earth-based high entropy ceramic material and a YSZ fiber matrix material.
The high-entropy ceramic aerogel material is a composite material of a rare earth-based high-entropy ceramic material and a YSZ (Yttria-stabilized zirconia, yttrium stabilized zirconia) fiber matrix material, and has a lower heat conductivity coefficient by utilizing the high temperature resistance of the fluorite type high-entropy ceramic material and the coupling of the network structure of the fiber material, and compared with the traditional aerogel material, the high-entropy ceramic aerogel material has a lower heat conductivity, a higher heat expansion coefficient and good high temperature stability, overcomes the defect that the traditional aerogel material is not high-temperature resistant, and has a normal-temperature heat conductivity lower than 0.030W/(m.K) and a heat conductivity coefficient lower than 0.050W/(m.K) at 600 ℃.
Preferably, the rare earth-based high-entropy ceramic material is present in an amount of 40-50wt%, such as 40wt%, 42wt%, 44wt%, 46wt%, 48wt%, or 50wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the diameter of the YSZ fiber matrix material is 200-500nm, for example, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the rare earth-based high entropy ceramic material has a chemical formula (RE) x1 La x2 Er x3 Tm x4 Yb x5 ) 2 M 2 O 7 Wherein x is 1 +x 2 +x 3 +x 4 +x 5 ＝1，0.1≤x 1 0.3 or less, for example, 0.1, 0.2 or 0.3,0.1 or less x or less 2 0.3 or less, for example, 0.1, 0.2 or 0.3,0.1 or less x or less 3 0.3 or less, for example, 0.1, 0.2 or 0.3,0.1 or less x or less 4 0.3 or less, for example, 0.1, 0.2 or 0.3,0.1 or less x or less 5 Less than or equal to 0.3, which may be, for example, 0.1, 0.2 or 0.3, RE including Gd and/or Eu, M including Ce and/or Zr preferably being (RE) 0.2 La 0.2 Er 0.2 Tm 0.2 Yb 0.2 ) 2 Ce 2 O 7 。
In a second aspect, the present invention provides a method for preparing the high-entropy ceramic aerogel material according to the first aspect, the method comprising the steps of:
(1) Mixing a rare earth-based high-entropy ceramic material, a YSZ fiber matrix material, a dispersion aid agent and a binder to obtain a mixed dispersion;
(2) Carrying out vacuum degassing and drying on the mixed dispersion in the step (1) to obtain an aerogel precursor;
(3) Calcining the aerogel precursor in the step (2) to obtain the high-entropy ceramic aerogel material.
According to the high-entropy ceramic aerogel material, the skeleton structure of the aerogel material is constructed by the rare earth-based high-entropy ceramic material, the YSZ fiber matrix material and the binder, the mixed dispersion is obtained by dispersion and compounding of the rare earth-based high-entropy ceramic material, and then the porous aerogel material with the three-dimensional grid space structure can be constructed by performing subsequent steps such as vacuum degassing, so that the porous aerogel material can be used as a heat-insulating material.
Preferably, the rare earth-based high-entropy ceramic material in the step (1) is prepared by a sol-gel self-ignition method.
Compared with the conventional sol-gel method, the sol-gel self-combustion method has the advantages that the synthesis temperature is low, partial self-reaction heat can be utilized, the synthesis process is quick and simple, and the product purity is high.
Preferably, the rare earth-based high-entropy ceramic material in the step (1) is prepared by the following method:
(i) Mixing solvent, chelating agent, M salt and at least five rare earth metal salts, regulating pH of the obtained mixed solution, and stirring to obtain sol;
(ii) Drying the sol in the step (i) to obtain xerogel, heating the xerogel to self-propagating combustion, and finally sintering to obtain the rare earth-based high-entropy ceramic material.
Preferably, the mixed solvent, the chelating agent, the M salt and the at least five rare earth metal salts comprise firstly mixing the M salt and the at least five rare earth metal salts with the solvent according to the formula amount to prepare a salt solution, and then adding the chelating agent.
Preferably, the solvent comprises water.
Preferably, the molar ratio of the chelating agent to the total metal ions in the mixed liquor in step (i) is (1.2-1.5): 1, for example, 1.2:1, 1.3:1, 1.4:1 or 1.5:1, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the pH adjustment in step (i) is carried out to a value of 5 to 7, for example, but not limited to 5, 5.5, 6, 6.5 or 7, and other non-enumerated values within the numerical range are equally applicable.
Preferably, ammonia is used to adjust the pH of step (i).
Preferably, the temperature of the stirring in step (i) is 80-90 ℃, for example 80 ℃, 85 ℃ or 90 ℃, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the stirring in step (i) is performed by water bath stirring.
Preferably, the chelating agent comprises citric acid.
Preferably, the M salt comprises a nitrate of M comprising Ce and/or Zr.
Preferably, the at least five rare earth metal salts include La (NO 3 ) 3 ·6H 2 O、Er(NO 3 ) 3 ·6H 2 O、Tm(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·6H 2 O and RE (NO) 3 ) 3 ·6H 2 O, the RE comprises Gd and/or Eu.
La (NO) 3 ) 3 ·6H 2 O、Er(NO 3 ) 3 ·6H 2 O、Tm(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·6H 2 O and RE (NO) 3 ) 3 ·6H 2 The purity of O was 99.99%.
Preferably, the heating temperature in step (ii) is 200-300 ℃, for example 200 ℃, 250 ℃, or 300 ℃, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the self-propagating combustion in step (ii) takes place for a period of time ranging from 1 to 2 hours, for example 1 hour, 1.5 hours or 2 hours, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the sintering in step (ii) comprises a primary sintering and a secondary sintering performed sequentially, wherein the primary sintering is performed at a temperature of 200-400 ℃, such as 200 ℃, 250 ℃, 300 ℃, 350 ℃ or 400 ℃ for a period of 4-6 hours, such as 4 hours, 5 hours or 6 hours, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the temperature of the secondary sintering is 1000-1200 ℃, such as 1000 ℃, 1100 ℃ or 1200 ℃, and the time is 4-6 hours, such as 4 hours, 5 hours or 6 hours, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the sintering in step (ii) is completed and further comprises an annealing step, wherein the annealing time is 8-10h, for example, 8h, 9h or 10h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the mixing of the rare earth-based high entropy ceramic material, the YSZ fiber matrix material, the dispersion aid agent and the binder of step (1) comprises: dissolving a rare earth-based high-entropy ceramic material and a YSZ fiber matrix material in ultrapure water, adding a dispersion aid agent for dispersion to obtain a dispersion liquid, and mixing the dispersion liquid with a binder to obtain the mixed dispersion.
When the step (1) is carried out, the binder is added after the rare earth-based high-entropy ceramic material and the YSZ fiber matrix material are uniformly dispersed, so that the stability of the three-dimensional network structure of the aerogel material and the uniformity of pore distribution can be improved, and if the binder is added at the dispersing stage of the rare earth-based high-entropy ceramic material and the YSZ fiber matrix material, the dispersing effect can be influenced, and the stability and the heat conducting property of the aerogel material are reduced.
Preferably, the dispersion is performed using a homogenizer, and the dispersion is mixed with a binder.
Preferably, the dispersing speed is 10000-13000rpm, such as 10000rpm, 11000rpm, 12000rpm or 13000rpm, and the time is 20-30min, such as 20min, 25min or 30min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the stirring rate of mixing the dispersion with the binder is 10000-12000rpm, for example 10000rpm, 11000rpm or 12000rpm, and the stirring time is 5-10min, for example 5min, 8min or 10min, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mass ratio of the YSZ fiber matrix material and the rare earth-based high-entropy ceramic material in the step (1) is (1-1.2): 1, for example, but not limited to, the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mass ratio of the YSZ fiber matrix material, the dispersion aid agent and the binder in the step (1) is 1 (0.02-0.03): (0.8-1.2), and may be, for example, 1:0.02:0.8, 1:0.03:1 or 1:0.03:1.2, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the binder of step (1) comprises an AlSiB sol.
Preferably, the AlSiB sol is prepared by the following method: the AlSiB sol is obtained by mixing tetraethyl orthosilicate, aluminum chloride and boric acid in ultrapure water and stirring for 4-6 hours by using a magnetic stirrer, wherein the stirring time can be 4 hours, 5 hours or 6 hours, for example, but the stirring time is not limited to the listed values, and other non-listed values in the numerical range are applicable.
Preferably, the dispersion aid agent of step (1) comprises any one or a combination of at least two of hexametaphosphate, polyacrylamide or alginic acid, typically but not limited to a combination comprising hexametaphosphate and polyacrylamide, preferably polyacrylamide.
Preferably, the vacuum degassing in step (2) is performed for a period of time ranging from 5 to 10 minutes, for example, 5 minutes, 8 minutes or 10 minutes, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the drying in step (2) comprises sequentially freeze-drying and CO 2 And (5) supercritical drying. The invention carries out CO after freeze drying 2 Supercritical drying, carbon dioxide supercritical drying avoids capillary action, and can obtain aerogel with relatively large mass and good product (less deformation).
Preferably, the temperature of the supercritical CO2 drying is 40-70 ℃, for example, 40 ℃, 50 ℃,60 ℃ or 70 ℃, and the time is 5-10 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the CO 2 Supercritical drying of CO 2 The rate is 0.4 to 0.9L/h, for example, 0.4L/h, 0.5L/h, 0.6L/h, 0.7L/h, 0.8L/h or 0.9L/h, and the pressure is 7 to 10MPa, for example, 7MPa, 8MPa, 9MPa or 10MPa, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature of the calcination in the step (3) is 800-900 ℃, for example, 800 ℃, 850 ℃ or 900 ℃, and the time is 30-60min, for example, 30min, 40min, 50min or 60min, and the atmosphere is air.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) Dissolving a rare earth-based high-entropy ceramic material and a YSZ fiber matrix material in ultrapure water, adding a dispersion aid agent, dispersing for 20-30min at a speed of 10000-13000rpm in a homogenizer to obtain a dispersion liquid, and stirring the dispersion liquid and a binder in the homogenizer for 5-10min at a stirring speed of 10000-12000rpm to obtain a mixed dispersion;
the mass ratio of the YSZ fiber matrix material to the rare earth-based high-entropy ceramic material is (1-1.2) 1, and the mass ratio of the YSZ fiber matrix material to the auxiliary dispersing agent to the binder is (0.02-0.03) 1 (0.8-1.2);
(2) Vacuum degassing the mixed dispersion obtained in step (1) for 5-10min, freeze drying, and CO 2 Supercritical drying to obtain aerogel precursor;
the CO 2 The supercritical drying temperature is 40-70deg.C, the time is 5-10h, and CO is used 2 The speed is 0.4-0.9L/h, and the pressure is 7-10Mpa;
(3) Calcining the aerogel precursor in the step (2) in air atmosphere at 800-900 ℃ for 30-60min to obtain the high-entropy ceramic aerogel material;
the rare earth-based high-entropy ceramic material is prepared by the following method:
(i) Mixing solvent, chelating agent, M salt and at least five rare earth metal salts, regulating pH of the obtained mixed solution, and stirring at 80-90 ℃ to obtain sol;
the mol ratio of the chelating agent to the total metal ions in the mixed solution is (1.2-1.5): 1;
(ii) Drying the sol in the step (i) to obtain xerogel, heating the xerogel to self-propagating combustion, sintering for 4-6 hours at 200-400 ℃ for the second time at 1000-1200 ℃ and finally annealing for 8-10 hours to obtain the rare earth-based high-entropy ceramic material.
In a third aspect, the present invention provides a use of the high entropy ceramic aerogel material of the first aspect, comprising a thermal insulation material.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the high-entropy ceramic aerogel material, the rare earth-based high-entropy ceramic material is introduced into the YSZ nanofiber matrix, and the fluorite structure of the rare earth-based high-entropy ceramic material is utilized, so that the high temperature resistance of the aerogel material is improved, and the high-entropy ceramic aerogel material is coupled with the YSZ nanofiber matrix network structure, so that the heat conductivity of the aerogel material is further reduced, the normal-temperature heat conductivity of the aerogel material is lower than 0.030W/(m.K), and the heat conductivity of the aerogel material is lower than 0.050W/(m.K) at 600 ℃, and compared with the traditional aerogel material, the high-entropy ceramic aerogel material has lower heat conductivity, higher heat expansion coefficient and good high-temperature stability;
(2) The preparation method of the high-entropy ceramic aerogel material is simple and easy to realize, and is assisted by CO through sol-gel self-combustion 2 The high-entropy ceramic aerogel material is prepared by a supercritical drying method and then by high-temperature heat treatment, the obtained aerogel material exists in a stable fluorite structure at room temperature, and five rare earth elements are uniformly distributed.
Drawings
FIG. 1 is a flow chart of the preparation method of example 1 of the present invention;
FIG. 2 is a morphology diagram of a high entropy ceramic aerogel material according to example 1 of the present invention;
FIG. 3 is an XRD pattern of a rare earth-based high entropy ceramic material according to example 1 of the present invention;
FIG. 4 is a graph showing the EDS element distribution of Ce, gd, er, la, yb and Tm in the rare earth-based high-entropy ceramic material according to example 1 of the present invention;
FIG. 5 is a graph showing the EDS element distribution of Ce, eu, er, la, yb and Tm in the rare earth-based high-entropy ceramic material according to example 2 of the present invention;
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a high-entropy ceramic aerogel material, which comprises a rare earth-based high-entropy ceramic material and a YSZ fiber matrix material, wherein the content of the rare earth-based high-entropy ceramic material is 50wt%, and the chemical formula is (La 0.2 Gd 0.2 Er 0.2 Tm 0.2 Yb 0.2 ) 2 Ce 2 O 7 The diameter of the YSZ fiber matrix material is 350nm;
the flow chart of the preparation method of the high-entropy ceramic aerogel material is shown in fig. 1, and the preparation method comprises the following steps:
(1) Firstly, dissolving 1.2g of rare earth-based high-entropy ceramic material and 1.2g of YSZ fiber matrix material in 100mL of ultrapure water, adding 0.03g of dispersing aid agent, dispersing for 20min at 13000rpm in a homogenizer to obtain a dispersion liquid, and stirring the dispersion liquid and a binder in the homogenizer (IKA T21) at a stirring rate of 10000rpm for 10min to obtain a mixed dispersion;
the rare earth-based high-entropy ceramic material is (La) 0.2 Gd 0.2 Er 0.2 Tm 0.2 Yb 0.2 ) 2 Ce 2 O 7 The dispersing aid agent is polyacrylamide, the binder is AlSiB sol, and the AlSiB sol is prepared by the following method: 1.52g of tetraethyl orthosilicate, 0.39g of aluminum chloride and 0.09g of boric acid are mixed in 20ml of water and stirred for 6 hours to prepare AlSiB sol with the molar ratio of Al/Si/B of 2:5:1;
the mass ratio of the YSZ fiber matrix material to the rare earth-based high-entropy ceramic material is 1:1, and the mass ratio of the YSZ fiber matrix material to the auxiliary dispersing agent to the binder is 1:0.025:1.2;
(2) Vacuum degassing the mixed dispersion obtained in the step (1) for 10min, freeze-drying in a liquid nitrogen bath to obtain three-dimensional reticular wet gel, and performing CO (carbon monoxide) 2 Supercritical drying to obtain aerogel precursor;
the CO 2 The supercritical drying temperature is 40 ℃, the time is 5h, and CO 2 Rate of speed0.9L/h and a pressure of 10MPa;
(3) Calcining the aerogel precursor in the step (2) in air atmosphere at 900 ℃ for 30min to obtain the high-entropy ceramic aerogel material;
the rare earth-based high-entropy ceramic material is prepared by the following method:
(i) La (NO) is added according to the formula amount 3 ) 3 ·6H 2 O、Er(NO 3 ) 3 ·6H 2 O、Tm(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 Dissolving O in pure water to prepare a salt solution, adding a chelating agent, regulating the pH of the obtained mixed solution to 5 by adopting ammonia water, and stirring in a water bath at 90 ℃ to obtain sol;
the chelating agent is citric acid, and the molar ratio of the chelating agent to the total metal ions in the mixed solution is 1.2:1;
(ii) Drying the sol in the step (i) to obtain xerogel, heating the xerogel to self-propagating combustion, sintering at 200 ℃ for 6 hours, sintering at 1000 ℃ for 6 hours, and finally annealing for 8 hours to obtain the rare earth-based high-entropy ceramic material;
the morphology diagram of the high-entropy ceramic aerogel material is shown in fig. 2, the XRD diagram of the rare earth-based high-entropy ceramic material is shown in fig. 3, and the EDS element distribution diagrams of Ce, gd, er, la, yb and Tm in the rare earth-based high-entropy ceramic material are shown in fig. 4.
Example 2
The embodiment provides a high-entropy ceramic aerogel material, which comprises a rare earth-based high-entropy ceramic material and a YSZ fiber matrix material, wherein the content of the rare earth-based high-entropy ceramic material is 40wt%, and the chemical formula is (La 0.2 Eu 0.2 Er 0.2 Tm 0.2 Yb 0.2 ) 2 Ce 2 O 7 The diameter of the YSZ fiber matrix material is 500nm;
the preparation method of the high-entropy ceramic aerogel material comprises the following steps:
(1) Firstly, dissolving 1.2g of rare earth-based high-entropy ceramic material and 1.4g of YSZ fiber matrix material in 100mL of ultrapure water, adding 0.03g of dispersing aid agent, dispersing for 20min at a speed of 10000rpm in a homogenizer to obtain a dispersion liquid, and stirring the dispersion liquid and a binder in the homogenizer (IKA T21) for 5min at a stirring speed of 12000rpm to obtain the mixed dispersion;
the rare earth-based high-entropy ceramic material is (La) 0.2 Eu 0.2 Er 0.2 Tm 0.2 Yb 0.2 ) 2 Ce 2 O 7 The dispersing aid agent is polyacrylamide, the binder is AlSiB sol, and the AlSiB sol is prepared by the following method: 1.52g of tetraethyl orthosilicate, 0.39g of aluminum chloride and 0.09g of boric acid are mixed in 20ml of water and stirred for 4 hours to prepare AlSiB sol with the molar ratio of Al/Si/B of 2:5:1;
the mass ratio of the YSZ fiber matrix material to the rare earth-based high-entropy ceramic material is 1.17:1, and the mass ratio of the YSZ fiber matrix material to the auxiliary dispersing agent to the binder is 1:0.021:0.8;
(2) Vacuum degassing the mixed dispersion obtained in step (1) for 5min, freeze drying in liquid nitrogen bath, and CO 2 Supercritical drying to obtain aerogel precursor;
the CO 2 The supercritical drying temperature is 70 ℃, the time is 10h, and CO 2 The rate is 0.4L/h and the pressure is 7Mpa;
(3) Calcining the aerogel precursor in the step (2) in air atmosphere at 800 ℃ for 60min to obtain the high-entropy ceramic aerogel material;
the rare earth-based high-entropy ceramic material is prepared by the following method:
(i) La (NO) is added according to the formula amount 3 ) 3 ·6H 2 O、Er(NO 3 ) 3 ·6H 2 O、Tm(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·6H 2 O、Eu(NO 3 ) 3 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 Dissolving O in pure water to obtain salt solution, and adding chelateRegulating the pH value of the obtained mixed solution to 7 by adopting ammonia water, and then stirring in a water bath at 80 ℃ to obtain sol;
the chelating agent is citric acid, and the molar ratio of the chelating agent to the total metal ions in the mixed solution is 1.5:1;
(ii) Drying the sol in the step (i) to obtain xerogel, heating the xerogel to self-propagating combustion, sintering at 400 ℃ for 4 hours, sintering at 1200 ℃ for 4 hours, and finally annealing for 10 hours to obtain the rare earth-based high-entropy ceramic material;
the EDS element distribution diagrams of Ce, eu, er, la, yb and Tm in the rare earth-based high-entropy ceramic material are shown in FIG. 5.
Example 3
The present example provides a high-entropy ceramic aerogel material, which is the same as example 1 except that the content of the rare earth-based high-entropy ceramic material is 30 wt%;
the preparation method of the high-entropy ceramic aerogel material is correspondingly changed, so that the content of the rare earth-based high-entropy ceramic material is 30wt% except for the content, and the rest is the same as in the embodiment 1.
Example 4
The present example provides a high-entropy ceramic aerogel material, which is the same as example 1 except that the content of the rare earth-based high-entropy ceramic material is 60 wt%;
the preparation method of the high-entropy ceramic aerogel material is correspondingly changed, so that the content of the rare earth-based high-entropy ceramic material is 60wt% except that the rest is the same as in the embodiment 1.
Example 5
The present embodiment provides a high-entropy ceramic aerogel material, which is the same as that of embodiment 1 except that in the preparation method, in step (1), the rare earth-based high-entropy ceramic material, YSZ fiber matrix material, dispersion aid agent and binder are stirred together in a homogenizer (IKA T21) at a stirring rate of 10000rpm for 10min to obtain the mixed dispersion, so that the obtained high-entropy ceramic aerogel material is changed correspondingly.
Example 6
The present embodiment provides a high-entropy ceramic aerogel material, which is the same as that of embodiment 1 except that in the preparation method, the vacuum degassing is not performed in step (2), so that the obtained high-entropy ceramic aerogel material is changed correspondingly.
Example 7
The present embodiment provides a high-entropy ceramic aerogel material, except for the preparation method, in which step (2) is not performed with CO 2 The procedure of example 1 was followed except that the resulting high entropy ceramic aerogel material was subjected to supercritical drying.
Example 8
The present example provides a high-entropy ceramic aerogel material, which is the same as example 1 except that in the preparation method, the xerogel in step (ii) is not heated to self-propagating combustion, but is directly sintered, so that the obtained high-entropy ceramic aerogel material is changed correspondingly.
Example 9
The present embodiment provides a high-entropy ceramic aerogel material prepared by, except for the preparation method, subjecting the Ce (NO 3 ) 3 ·6H 2 The procedure of example 1 was followed except that the equimolar substitution of O with zirconium nitrate pentahydrate was performed to provide a corresponding change in the resulting high entropy ceramic aerogel material.
Comparative example 1
The present comparative example provides a high entropy ceramic that is (La 0.2 Gd 0.2 Er 0.2 Tm 0.2 Yb 0.2 ) 2 Ce 2 O 7 The preparation method of the high-entropy ceramic is the same as that of example 1.
The high-entropy ceramic aerogel material and the comparative high-entropy ceramic described in the above examples were tested for room temperature thermal conductivity (GB/T10294-2008 national standard test), thermal conductivity at 600 ℃ (GB/T10295-2008 national standard test), and thermal expansion coefficient, respectively.
The test results are shown in table 1:
TABLE 1
Figure BDA0004050545310000141
Figure BDA0004050545310000151
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From table 1, the following points can be seen:
(1) The high-entropy ceramic aerogel material provided by the invention has lower thermal conductivity, higher thermal expansion coefficient and good high-temperature stability, and can be seen from a physical diagram of fig. 2, the aerogel material is white three-dimensional ultra-light aerogel, as can be seen from fig. 3, the obtained rare earth-based high-entropy ceramic material is a typical fluorite structural material, meanwhile, the characteristic peak has no impurity peak, the crystallinity is better, the product crystal form is complete, and as can be seen from fig. 4 and fig. 5, rare earth ions are uniformly distributed, and uniform doping of rare earth metal is realized; from examples 1 and 3-5, it is known that the content of the high entropy ceramic material and the timing of the addition of the binder can have an effect on the performance of the aerogel material.
(2) As can be seen from examples 1, 6 and 7, the present invention requires vacuum degassing and CO 2 The aerogel material with excellent performance can be obtained by supercritical drying; as can be seen from examples 1 and 8, the sol-gel self-combustion method can further improve the comprehensive performance of the aerogel material; as can be seen from example 1 and comparative example 1, the present invention can couple fluorite structure and network combination by compounding YSZ nanofiber material and rare earth-based high-entropy ceramic material, thereby further reducing the thermal conductivity of aerogel material and improving the thermal expansion coefficient.
In summary, the invention provides a high-entropy ceramic aerogel material, a preparation method and application thereof, wherein the high-entropy ceramic aerogel material exists in a stable fluorite structure at room temperature, and various rare earth elements are uniformly distributed.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.

Claims (10)

1. A high-entropy ceramic aerogel material, characterized in that the high-entropy ceramic aerogel material comprises a rare earth-based high-entropy ceramic material and a YSZ fiber matrix material.
2. The high-entropy ceramic aerogel material according to claim 1, wherein the content of the rare earth-based high-entropy ceramic material is 40-50wt%;
preferably, the diameter of the YSZ fiber matrix material is 200-500nm;
preferably, the rare earth-based high entropy ceramic material has a chemical formula (RE) x1 La x2 Er x3 Tm x4 Yb x5 ) 2 M 2 O 7 Wherein x is 1 +x 2 +x 3 +x 4 +x 5 ＝1，0.1≤x 1 ≤0.3，0.1≤x 2 ≤0.3，0.1≤x 3 ≤0.3，0.1≤x 4 ≤0.3，0.1≤x 5 Less than or equal to 0.3, RE comprises Gd and/or Eu, M comprises Ce and/or Zr, preferably (RE) 0.2 La 0.2 Er 0.2 Tm 0.2 Yb 0.2 ) 2 Ce 2 O 7 。
3. A method of preparing the high entropy ceramic aerogel material of claim 1 or 2, comprising the steps of:
(1) Mixing a rare earth-based high-entropy ceramic material, a YSZ fiber matrix material, a dispersion aid agent and a binder to obtain a mixed dispersion;
(2) Carrying out vacuum degassing and drying on the mixed dispersion in the step (1) to obtain an aerogel precursor;
(3) Calcining the aerogel precursor in the step (2) to obtain the high-entropy ceramic aerogel material.
4. The method according to claim 3, wherein the rare earth-based high-entropy ceramic material of step (1) is prepared by a sol-gel self-combustion method;
preferably, the rare earth-based high-entropy ceramic material in the step (1) is prepared by the following method:
(i) Mixing solvent, chelating agent, M salt and at least five rare earth metal salts, regulating pH of the obtained mixed solution, and stirring to obtain sol;
(ii) Drying the sol in the step (i) to obtain xerogel, heating the xerogel to self-propagating combustion, and finally sintering to obtain the rare earth-based high-entropy ceramic material.
5. The method according to claim 4, wherein the molar ratio of the chelating agent to the total metal ions in the mixed liquor in the step (i) is (1.2-1.5): 1;
preferably, step (i) said adjusting the pH to 5-7;
preferably, the temperature of the stirring in step (i) is 80-90 ℃;
preferably, the chelating agent comprises citric acid;
preferably, the M salt comprises a nitrate of M comprising Ce and/or Zr;
preferably, the at least five rare earth metal salts include La (NO 3 ) 3 ·6H 2 O、Er(NO 3 ) 3 ·6H 2 O、Tm(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·6H 2 O and RE (NO) 3 ) 3 ·6H 2 O, the RE comprises Gd and/or Eu.
6. The method of claim 4 or 5, wherein the heating in step (ii) is at a temperature of 200-300 ℃;
preferably, the self-propagating combustion of step (ii) takes from 1 to 2 hours;
preferably, the sintering in the step (ii) comprises primary sintering and secondary sintering which are sequentially carried out, wherein the temperature of the primary sintering is 200-400 ℃ and the time is 4-6h;
preferably, the temperature of the secondary sintering is 1000-1200 ℃ and the time is 4-6h;
preferably, the sintering in the step (ii) is finished and further comprises an annealing step, wherein the annealing time is 8-10h.
7. The method of any one of claims 3-6, wherein the mixing of the rare earth-based high entropy ceramic material, YSZ fiber matrix material, co-dispersant, and binder of step (1) comprises: dissolving a rare earth-based high-entropy ceramic material and a YSZ fiber matrix material in ultrapure water, adding a dispersion aid agent for dispersion to obtain a dispersion liquid, and mixing the dispersion liquid with a binder to obtain the mixed dispersion;
preferably, the dispersion is performed using a homogenizer, and the dispersion is mixed with a binder;
preferably, the dispersing speed is 10000-13000rpm, and the time is 20-30min;
preferably, the stirring speed of mixing the dispersion liquid and the binder is 10000-12000rpm, and the stirring time is 5-10min;
preferably, the mass ratio of the YSZ fiber matrix material and the rare earth-based high-entropy ceramic material in the step (1) is (1-1.2): 1;
preferably, the mass ratio of the YSZ fiber matrix material, the dispersion aid agent and the binder in the step (1) is 1 (0.02-0.03): 0.8-1.2);
preferably, the binder of step (1) comprises an AlSiB sol;
preferably, the dispersing aid in step (1) comprises any one or a combination of at least two of hexametaphosphate, polyacrylamide or alginic acid, preferably polyacrylamide.
8. The method according to any one of claims 3 to 7, wherein the time for vacuum degassing in step (2) is 5 to 10min;
preferably, the drying in step (2) comprises sequentially freeze-drying and CO 2 Supercritical drying;
preferably, the CO 2 The temperature of supercritical drying is 40-70 ℃ and the time is 5-10h;
preferably, the CO 2 Supercritical drying of CO 2 The speed is 0.4-0.9L/h, and the pressure is 7-10Mpa;
preferably, the temperature of the calcination in the step (3) is 800-900 ℃, the time is 30-60min, and the atmosphere is air.
9. The preparation method according to any one of claims 3 to 8, characterized in that the preparation method comprises the steps of:
(1) Dissolving a rare earth-based high-entropy ceramic material and a YSZ fiber matrix material in ultrapure water, adding a dispersion aid agent, dispersing for 20-30min at a speed of 10000-13000rpm in a homogenizer to obtain a dispersion liquid, and stirring the dispersion liquid and a binder in the homogenizer for 5-10min at a stirring speed of 10000-12000rpm to obtain a mixed dispersion;
the mass ratio of the YSZ fiber matrix material to the rare earth-based high-entropy ceramic material is (1-1.2) 1, and the mass ratio of the YSZ fiber matrix material to the auxiliary dispersing agent to the binder is (0.02-0.03) 1 (0.8-1.2);
(2) Vacuum degassing the mixed dispersion obtained in step (1) for 5-10min, freeze drying, and CO 2 Supercritical drying to obtain aerogel precursor;
the CO 2 The supercritical drying temperature is 40-70deg.C, the time is 5-10h, and CO is used 2 The speed is 0.4-0.9L/h, and the pressure is 7-10Mpa;
(3) Calcining the aerogel precursor in the step (2) in air atmosphere at 800-900 ℃ for 30-60min to obtain the high-entropy ceramic aerogel material;
the rare earth-based high-entropy ceramic material is prepared by the following method:
(i) Mixing solvent, chelating agent, M salt and at least five rare earth metal salts, regulating pH of the obtained mixed solution, and stirring at 80-90 ℃ to obtain sol;
the mol ratio of the chelating agent to the total metal ions in the mixed solution is (1.2-1.5): 1;
(ii) Drying the sol in the step (i) to obtain xerogel, heating the xerogel to self-propagating combustion, sintering for 4-6 hours at 200-400 ℃ for the second time at 1000-1200 ℃ and finally annealing for 8-10 hours to obtain the rare earth-based high-entropy ceramic material.
10. Use of the high entropy ceramic aerogel material according to claim 1 or 2, wherein the use comprises for insulating thermal insulation materials.
CN202310039767.4A 2023-01-12 2023-01-12 High-entropy ceramic aerogel material and preparation method and application thereof Pending CN116120081A (en)

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