TWO-DIMENSIONAL HIGH-ENTROPY METAL OXIDE ASSEMBLY WITH HIGH THERMAL CONDUCTIVITY AND PREPARATION METHOD THEREOF

Abstract

The present disclosure relates to the field of new materials, and aims at providing a two-dimensional high-entropy metal oxide assembly with high thermal conductivity and a preparation method thereof. The two-dimensional high-entropy metal oxide assembly with the high thermal conductivity has a molecular formula of (Co.sub.0.3La.sub.0.6Er.sub.0.6Y.sub.0.7Mn.sub.0.4Ga.sub.0.4)O.sub.4. The two-dimensional high-entropy metal oxide assembly with the high thermal conductivity is in a short fiber shape with a length-diameter ratio of the short fiber of 5 to 7 and has a cross section of a regular triangle with the side length of the regular triangle of 100 to 300 nm. The present disclosure achieves one-dimensional high thermal conductivity of metal oxide assembly by means of orderly assembling of high-entropy oxide in the direction perpendicular to nanosheets. Meanwhile, the assembly enables uniform distribution of heterogeneous elements in the two-dimensional plane during the preparation process.

Claims

1. A two-dimensional high-entropy metal oxide assembly with high thermal conductivity, wherein the metal oxide assembly has a molecular formula of (Co.sub.0.3La.sub.0.6Er.sub.0.6Y.sub.0.7Mn.sub.0.4Ga.sub.0.4)O.sub.4; and is in a short fiber shape with a length-diameter ratio of the short fiber of 5 to 7, and has a cross section of a regular triangle with a side length of the regular triangle of 100 to 300 nm.

2. A preparation method of the two-dimensional high-entropy metal oxide assembly with the high thermal conductivity according to claim 1, comprising the following steps: (1) taking Co(NO.sub.3).sub.2, La(NO.sub.3).sub.3, Er(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, MnCl.sub.2 and GaCl.sub.3 as solutes at a molar ratio of 0.3:0.6:0.6:0.7:0.4:0.4, taking methanol, anhydrous ethanol, isopropanol and n-butanol at a molar ratio of 0.3:3:0.5:0.1 to uniformly mix them into a solvent, adding the solutes to the solvent with a ratio of a total mass of the solutes to a mass of the solvent being 17.6%, and stirring the mixture for 20 to 40 min to obtain a first mixed liquid for standby application; (2) taking p-phenol, 1,3-cyclohexanedione, furoin and inositol as solutes at a molar ratio of 0.1 to 0.3:0.7 to 0.9:2.5 to 3.5:0.012 to 0.014 and adding them to n-propanol with a ratio of a total mass of the solutes to a mass of the n-propanol being 6.5%, and stirring the mixture for 3 to 5 h to obtain a second mixed liquid for standby application; (3) taking the first mixed liquid and the second mixed liquid at a molar ratio of 3 to 5:11 to 13, cooling them to 0° C., mixing them in an environment where ultraviolet light is completely shielded, continuously stirring the mixture for 5 to 15 min, and keeping the mixture still standing at 0° C. for 10 to 12 h in an environment where ultraviolet light is completely shielded to obtain a third mixed liquid; (4) pouring the third mixed liquid into a culture dish until a height of a liquid level is 10 mm, heating the third mixed liquid to 20° C., and irradiating the third mixed liquid with the ultraviolet light having a wavelength of 100 nm to 300 nm for 3 to 5 h to obtain a fourth mixed liquid; (5) placing the fourth mixed liquid into a sealed container, performing alternating pulse on the solution with a magnetic force and microwaves to obtain a fifth mixed liquid; and (6) freezing and drying the fifth mixed liquid, washing the frozen and dried fifth mixed liquid with deionized water and acetone 7 times separately, and drying the fifth mixed liquid to obtain the two-dimensional high-entropy metal oxide assembly with the high thermal conductivity.

3. The method according to claim 2, wherein in the step (4), a wavelength of the ultraviolet light is 100 nm to 300 nm.

4. The method according to claim 2, wherein in the step (5), a time interval of magnetic pulse and microwave pulse is 1 min, the magnetic field pulse lasts for 2 to 4 s, and the microwave pulse lasts for 7 to 9 s; and the magnetic pulse is performed 5 times in total, the microwave pulse is performed 5 times in total, magnetic field intensity is 0.75 to 0.85 Tesla (T), and a microwave power is 700 W to 900 W.

Description

DETAILED DESCRIPTION

[0020] The present invention is described below in details in conjunction with the particular embodiments. The following embodiments facilitate those skilled in the art further understanding the present disclosure, but do not limit the present disclosure in any way. It should be noted that, for those skilled in the art, several alterations and modifications can be made without departing from the concept of the present invention, which fall within the protection scope of the present invention.

Example 1

[0021] The preparation method of a two-dimensional high-entropy metal oxide assembly (Co.sub.0.3La.sub.0.6Er.sub.0.6Y.sub.0.7Mn.sub.0.4Ga.sub.0.4)O.sub.4 with high thermal conductivity includes the following steps.

[0022] (1) Co(NO.sub.3).sub.2, La(NO.sub.3).sub.3, Er(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, MnCl.sub.2 and GaCl.sub.3 were taken at a molar ratio of 0.3:0.6:0.6:0.7:0.4:0.4 and added to a mixed solution of methanol/anhydrous ethanol/isopropanol/n-butanol with a mass ratio of 0.3:3:0.5:0.1, and the mixture was stirred for 20 min, to obtain a first mixed liquid. A ratio of a total mass of Co(NO.sub.3).sub.2, La(NO.sub.3).sub.3, Er(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, MnCl.sub.2 and GaCl.sub.3 to a mass of the mixed solution of methanol/anhydrous ethanol/isopropanol/n-butanol with the mas ratio of 0.3:3:0.5:0.1 was 17.6%.

[0023] (2) P-phenol, 1,3-cyclohexanedione, furoin and inositol were taken at a molar ratio of 0.1:0.7:2.5:0.012 and added to n-propanol, and the mixture was stirred for 3 h, to obtain a second mixed liquid. A ratio of a total mass of p-phenol, 1,3-cyclohexanedione, furoin and inositol to a mass of n-propanol was 6.5%.

[0024] (3) The first mixed liquid obtained in step (1) and the second mixed liquid obtained in step (2) were simultaneously cooled to 0° C., and mixed and stirred for 5 min in an environment where ultraviolet light was completely shielded. The mixture was subjected to still standing for 10 h in an environment where ultraviolet light is completely shielded at 0° C. to obtain a third mixed liquid. A mass ratio of the first mixed liquid to the second mixed liquid was 3:11.

[0025] (4) The third mixed liquid obtained in step (3) was poured into a culture dish until a height of a liquid level was 10 mm, and heated to 20° C., and the third mixed liquid was irradiated with the ultraviolet light having a wavelength of 100 nm for 3 h to obtain a fourth mixed liquid.

[0026] (5) The fourth mixed liquid obtained in step (4) was placed into a sealed container, and subjected to alternating pulse with a magnetic force and microwaves to obtain a fifth mixed liquid. The magnetic field pulse lasted for 2 s, and the microwave pulse lasted for 7 s, a time interval of magnetic pulse and microwave pulse was 1 min. The magnetic pulse was performed 5 times in total, and the microwave pulse was performed 5 times in total, magnetic field intensity was 0.75 Tesla (T), and a microwave power was 700 W.

[0027] (6) The fifth mixed liquid obtained in step (5) was frozen and dried, and the frozen and dried fifth mixed liquid was washed with deionized water and acetone 7 times separately and dried, to obtain the two-dimensional high-entropy metal oxide assembly (Co.sub.0.3La.sub.0.6Er.sub.0.6Y.sub.0.7Mn.sub.0.4Ga.sub.0.4)O.sub.4 with the high thermal conductivity.

[0028] The obtained assembly was in a short fiber shape, had a length-diameter ratio of 5 and a cross section of a regular triangle with a side length of the regular triangle of 100 nm.

[0029] The obtained product was mixed with epoxy resin at a volume ratio of 1:5 and cured, and cut into sheet-like samples having diameters of 12.8 mm and thickness of 1 mm. The thermal conductivity of the product was measured using a laser thermal conductivity tester at a temperature of 100° C.

[0030] As tested, the thermal conductivity of the product was 1890 W/m*K. The thermal conductivity of the epoxy resin was 1 W/m*K. The application of the product of the Example to the epoxy resin by mixing enables an increase by 1200 times in the thermal conductivity of the epoxy resin.

Example 2

[0031] A preparation method of a two-dimensional high-entropy metal oxide assembly (Co.sub.0.3La.sub.0.6Er.sub.0.6Y.sub.0.7Mn.sub.0.4Ga.sub.0.4)O.sub.4 with high thermal conductivity includes the following steps.

[0032] (1) Co(NO.sub.3).sub.2, La(NO.sub.3).sub.3, Er(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, MnCl.sub.2 and GaCl.sub.3 were taken at a molar ratio of 0.3:0.6:0.6:0.7:0.4:0.4 and added to a mixed solution of methanol/anhydrous ethanol/isopropanol/n-butanol with a mass ratio of 0.3:3:0.5:0.1, and the mixture was stirred for 40 min, to obtain a first mixed liquid. A ratio of a total mass of Co(NO.sub.3).sub.2, La(NO.sub.3).sub.3, Er(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, MnCl.sub.2 and GaCl.sub.3 to a mass of the mixed solution of methanol/anhydrous ethanol/isopropanol/n-butanol with the mas ratio of 0.3:3:0.5:0.1 was 17.6%.

[0033] (2) P-phenol, 1,3-cyclohexanedione, furoin and inositol were taken at a molar ratio of 0.3:0.9:3.5:0.014 and added to n-propanol, and the mixture was stirred for 5 h, to obtain a second mixed liquid. A ratio of a total mass of p-phenol, 1,3-cyclohexanedione, furoin and inositol to a mass of n-propanol was 6.5%.

[0034] (3) The first mixed liquid obtained in step (1) and the second mixed liquid obtained in step (2) were simultaneously cooled to 0° C. and mixed and stirred for 15 min in an environment where ultraviolet light was completely shielded, the mixture was subjected to still standing for 12 h in an environment where ultraviolet light is completely shielded at 0° C. to obtain a third mixed liquid. A mass ratio of the first mixed liquid to the second mixed liquid was 5:13.

[0035] (4) The third mixed liquid obtained in step (3) was poured into a culture dish until a height of a liquid level was 10 mm, and heated to 20° C., and the third mixed liquid was irradiated with the ultraviolet light having a wavelength of 300 nm for 5 h, to obtain a fourth mixed liquid.

[0036] (5) The fourth mixed liquid obtained in step (4) was placed into a sealed container, and subjected to alternating pulse with a magnetic force and microwaves, to obtain a fifth mixed liquid. The magnetic field pulse lasted for 4 s, and the microwave pulse lasted for 9 s, a time interval of magnetic pulse and microwave pulse was 1 min. The magnetic pulse was performed 5 times in total, the microwave pulse was performed 5 times in total, magnetic field intensity was 0.85 Tesla (T), and a microwave power was 900 W.

[0037] (6) The fifth mixed liquid obtained in step (5) was frozen and dried, and the frozen and dried fifth mixed liquid was washed with deionized water and acetone 7 times separately and dried, to obtain the two-dimensional high-entropy metal oxide assembly (Co.sub.0.3La.sub.0.6Er.sub.0.6Y.sub.0.7Mn.sub.0.4Ga.sub.0.4)O.sub.4 with the high thermal conductivity.

[0038] The obtained assembly was in a short fiber shape, had a length-diameter ratio of 7, and had a cross section of a regular triangle with the side length of the regular triangle of 300 nm.

[0039] The obtained product was mixed with epoxy resin at a volume ratio of 1:5 and cured, and cut into sheet-like samples having diameters of 12.8 mm and thickness of 1 mm. The thermal conductivity of the product was measured using a laser thermal conductivity tester at a temperature of 100° C.

[0040] As tested, the thermal conductivity of the product was 1670 W/m*K. The thermal conductivity of the epoxy resin was 1 W/m*K. The application of the product of the Example to the epoxy resin by mixing enables an increase by 820 times in the thermal conductivity of the epoxy resin.

Example 3

[0041] A preparation method of a two-dimensional high-entropy metal oxide assembly (Co.sub.0.3La.sub.0.6Er.sub.0.6Y.sub.0.7Mn.sub.0.4Ga.sub.0.4)O.sub.4 with high thermal conductivity includes the following steps.

[0042] (1) Co(NO.sub.3).sub.2, La(NO.sub.3).sub.3, Er(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, MnCl.sub.2 and GaCl.sub.3 were taken at a molar ratio of 0.3:0.6:0.6:0.7:0.4:0.4 and added to a mixed solution of methanol/anhydrous ethanol/isopropanol/n-butanol with a mass ratio of 0.3:3:0.5:0.1, and the mixture was stirred for 30 min, to obtain a first mixed liquid. A ratio of a total mass of Co(NO.sub.3).sub.2, La(NO.sub.3).sub.3, Er(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, MnCl.sub.2 and GaCl.sub.3 to a mass of the mixed solution of methanol/anhydrous ethanol/isopropanol/n-butanol with the mas ratio of 0.3:3:0.5:0.1 was 17.6%.

[0043] (2) P-phenol, 1,3-cyclohexanedione, furoin and inositol were taken at a molar ratio of 0.2:0.8:3.0:0.013 and added to n-propanol, and the mixture was stirred for 4 h, to obtain a second mixed liquid. A ratio of a total mass of p-phenol, 1,3-cyclohexanedione, furoin and inositol to a mass of n-propanol was 6.5%.

[0044] (3) The first mixed liquid obtained in step (1) and the second mixed liquid obtained in step (2) were simultaneously cooled to 0° C. and mixed and stirred for 10 min in an environment where ultraviolet light was completely shielded, the mixture was subjected to still standing for 11 h in an environment where ultraviolet light is completely shielded at 0° C., to obtain a third mixed liquid. A mass ratio of the first mixed liquid to the second mixed liquid was 4:12.

[0045] (4) The third mixed liquid obtained in step (3) was poured into a culture dish until a height of a liquid level was 10 mm, and heated to 20° C., and the third mixed liquid was irradiated with the ultraviolet light having a wavelength of 200 nm for 4 h, to obtain a fourth mixed liquid.

[0046] (5) The fourth mixed liquid obtained in step (4) was placed into a sealed container, and subjected to alternating pulse with a magnetic force and microwaves, to obtain a fifth mixed liquid. The magnetic field pulse lasted for 3 s, and the microwave pulse lasted for 8 s, a time interval of magnetic pulse and microwave pulse was 1 min. The magnetic pulse was performed 5 times in total, the microwave pulse was performed 5 times in total, magnetic field intensity was 0.80 Tesla (T), and a microwave power was 800 W.

[0047] (6) The fifth mixed liquid obtained in step (5) was frozen and dried, and the frozen and dried fifth mixed liquid was washed with deionized water and acetone 7 times separately and dried, to obtain the two-dimensional high-entropy metal oxide assembly with the high thermal conductivity (Co.sub.0.3La.sub.0.6Er.sub.0.6Y.sub.0.7Mn.sub.0.4Ga.sub.0.4)O.sub.4.

[0048] The obtained assembly was in a short fiber shape, had a length-diameter ratio of 6, and had a cross section of a regular triangle with the side length of the regular triangle of 200 nm.

[0049] The obtained product was mixed with epoxy resin at a volume ratio of 1:5 and cured, and cut into sheet-like samples having diameters of 12.8 mm and thickness of 1 mm. The thermal conductivity of the product was measured using a laser thermal conductivity tester at a temperature of 100° C.

[0050] As tested, the thermal conductivity of the product was 1710 W/m*K. The thermal conductivity of the epoxy resin was 1 W/m*K. The application of the product of the Example to the epoxy resin by mixing enables an increase by 910 times in the thermal conductivity of the epoxy resin.

Comparative Example 1

[0051] A commercially available high-entropy oxide powder (MnNiFeCrCo).sub.3O.sub.4 was measured for the thermal conductivity according to the method the same as the above.

[0052] As tested the thermal conductivity of the commercially available high-entropy oxide powder (MnNiFeCrCo).sub.3O.sub.4 was 210 W/m*K. The thermal conductivity of the epoxy resin was 1 W/m*K.

[0053] The application of the commercially available high-entropy oxide powder product (MnNiFeCrCo).sub.3O.sub.4 by mixing enable an increase by 12 times in the thermal conductivity of the epoxy resin.

[0054] The particular examples in the present disclosure are described above. It should be understood that the present invention is not limited to specific embodiments described above, and various alterations or modifications may be made by those skilled in the art within the scope of the claims, not affecting essential contents in the present disclosure.