A thermoelectric composite antimonene material doped with graphene, its preparation method and application

Abstract

A doped graphene-based thermoelectric composite antimonene material, its preparation method and application belong to the technical field of thermoelectric nanomaterials. The doped graphene-based thermoelectric composite antimonene material comprises graphene and antimonene. By mass ratio, graphene:antimonene = 1:(268 - 295); for the doped graphene-based thermoelectric composite antimonene material, its conductivity is 1944 - 2160 S / cm, the Seebeck coefficient is 27.10 - 27.50 μV / k, and the power factor is 145 - 160 μW / mK<supgt;2< / supgt;. The doped graphene-based thermoelectric composite antimonene material has high conductivity, Seebeck coefficient, excellent power factor, and greatly improves the thermoelectric performance of thermoelectric materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermoelectric nanomaterials, and particularly relates to a thermoelectric composite antimonene material doped with graphene, its preparation method and application. Background Art

[0002] Thermoelectric materials are a special type of functional materials with the ability to convert electrical and thermal effects into each other. Briefly speaking, thermoelectric materials can achieve the direct conversion between thermal energy and electrical energy. The basic principle of thermoelectric materials is based on the thermoelectric effect, which mainly includes the Seebeck effect, the Peltier effect, and the Thomson effect. The Seebeck effect refers to the phenomenon that when there is a temperature difference between two different conductors or semiconductors, an electromotive force will be generated at their contact point, enabling thermoelectric materials to convert thermal energy into electrical energy. Thermoelectric materials are mainly divided into two types: thermoelectric conversion materials and thermocouple materials. Thermoelectric conversion materials can directly convert thermal energy into electrical energy, while thermocouple materials are sensors for measuring temperature. These materials can work at room temperature and high temperature, and have a long service life.

[0003] The applications of thermoelectric materials in aircraft mainly include: (1) Waste heat recovery system: During flight, an aircraft generates a large amount of waste heat. If the waste heat can be effectively treated, it can not only reduce energy waste but also have a positive impact on environmental protection. Thermoelectric materials can effectively convert waste heat into electrical energy, providing additional energy for the aircraft, thereby achieving the effects of reducing energy consumption and environmental pollution. (2) Micro power supply and temperature control system: Some electronic devices on the aircraft, such as sensors and communication devices, require a stable power supply and temperature environment. Thermoelectric materials can be fabricated into micro power supply and temperature control systems to provide the required power and temperature environment for these devices, thereby improving the overall performance and reliability of the aircraft. From the above applications of thermoelectric materials in aircraft, it can be seen that in terms of environmental pollution and high-end equipment applications, the research on thermoelectric materials has strong practical significance. Currently, the components of thermoelectric materials are relatively single, such as graphene, black phosphorus, silicene, germanene, etc. Such materials often have deficiencies in certain aspects of performance, and thus cannot obtain ideal thermoelectric performance. Summary of the Invention

[0004] In order to solve the above problems, the present invention provides a thermoelectric composite antimonene material doped with graphene, its preparation method and application, so as to solve the problems of insufficient performance in a certain aspect and easy corrosion of existing single thermoelectric materials. The thermoelectric composite antimonene material doped with graphene provided by the present invention has high electrical conductivity, Seebeck coefficient, excellent power factor, and greatly improves the thermoelectric performance of thermoelectric materials.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] The present invention provides a doped graphene thermoelectric composite antimonene material, comprising graphene and antimonene; by mass ratio, graphene:antimonene = 1:(268 - 295).

[0007] The thickness of the graphene is 1.30 - 1.50 nm.

[0008] The unit cell structure of the antimonene is: honeycomb hexagonal lattice.

[0009] For the doped graphene thermoelectric composite antimonene material of the present invention, its conductivity is 1944 - 2160 S / cm, the Seebeck coefficient is 27.10 - 27.50 μV / k, and the power factor is 145 - 160 μW / mK 2 .

[0010] The application of the doped graphene thermoelectric composite antimonene material of the present invention is used as a waste heat power generation recovery device, a thermal management device for microelectronic devices, and a device in a portable electronic device power supply, and is more preferably one of a thermal imaging device, a sensor, a nanogenerator or an energy harvester.

[0011] The present invention provides a preparation method of a doped graphene thermoelectric composite antimonene material, comprising the following steps:

[0012] S1: Add graphene into organic alcohol and ultrasonicate to obtain a graphene suspension;

[0013] S2: Add the antimonene material into the graphene suspension and ultrasonicate to obtain a mixed suspension;

[0014] S3: Perform solid-liquid separation on the mixed suspension and dry it to obtain the doped graphene thermoelectric composite antimonene material.

[0015] The above steps are only descriptions of the operation process and do not constitute a limitation on the operation sequence. The operation steps can be adjusted without affecting the final effect.

[0016] In the step S1, by mass ratio, graphene:organic alcohol is 0.01:(100 - 300); preferably methanol and / or ethanol.

[0017] In the step S1, the ultrasonication condition is an ice-water bath, and the ultrasonication time is preferably 1 - 3 h.

[0018] In the step S2, by mass ratio, antimonene:graphene suspension is 1:(10 - 200).

[0019] In the step S2, the ultrasonication condition is an ice-water bath, and the ultrasonication time is preferably 1 - 3 h.

[0020] In the step S3, the drying temperature for drying is 70 - 90 °C, and the drying time is 1 - 3 h.

[0021] Compared with the prior art, a doped graphene thermoelectric composite antimonene material and its preparation method and application of the present invention have the following beneficial effects:

[0022] (1) In the doped graphene thermoelectric composite antimonene material provided by the present invention, antimonene forms a conductive structure, and graphene is doped in the conductive structure. By optimizing the electron and phonon transmission paths, and combining the high electrical conductivity of graphene with the low thermal conductivity of the conductive structure, the thermoelectric figure of merit (ZT value) of the material is significantly improved, realizing more efficient thermoelectric energy conversion; the unique phonon scattering mechanism of antimonene is combined with the interface scattering effect of graphene, greatly reducing the thermal conductivity of the material, thereby improving the thermoelectric conversion efficiency.

[0023] (2) In addition, the high strength, flexibility and stability of graphene enable the doped graphene thermoelectric composite antimonene material to exhibit excellent mechanical properties when subjected to mechanical stress, ensuring the stability and durability of the material in various application environments; the composite structure of graphene and antimonene improves the overall stability of the material. By utilizing the synergistic effect of the two materials, the thermoelectric performance of the material can be significantly improved, avoiding the decomposition or degradation problems that may occur in single materials. Therefore, the present invention provides a novel thermoelectric material with great potential, which not only has efficient thermoelectric conversion performance, but also has excellent mechanical and chemical stability.

[0024] (3) The high electron mobility of graphene improves the electrical conductivity of the doped graphene thermoelectric composite antimonene material, making the transmission of electrons inside the material more efficient, which is beneficial to the improvement of thermoelectric performance; the adjustable bandgap characteristic of antimonene enables the doped graphene thermoelectric composite antimonene material to maintain good thermoelectric performance at different temperatures, with a wider adaptability.

[0025] (4) The results of the examples show that the doped graphene thermoelectric composite antimonene material can be used for industrial waste heat recovery, improving energy utilization efficiency and reducing energy waste; in microelectronic devices, the doped graphene thermoelectric composite antimonene material can be used as an efficient thermal management material to improve the performance and lifespan of the devices; for the power supply of portable electronic devices, it can provide stable and efficient electrical energy output, meeting the high requirements of modern electronic devices for power supplies.

[0026] (5) The present invention provides a doped graphene thermoelectric composite antimonene material and its preparation method. The preparation method provided by the present invention is simple, has excellent operability, can be widely applied, and is further conducive to continuous manufacturing and industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic flow chart of the preparation method of the doped graphene thermoelectric composite antimonene material;

[0028] Figure 2Conductivity graph of the doped graphene-based thermoelectric composite antimonene material prepared in Example 1, Example 2, Example 3, and Example 4 of the present invention;

[0029] Figure 3 Seebeck coefficient graph of the doped graphene-based thermoelectric composite antimonene material prepared in Example 1, Example 2, Example 3, and Example 4 of the present invention;

[0030] Figure 4 Power factor graph of the doped graphene-based thermoelectric composite antimonene material prepared in Example 1, Example 2, Example 3, and Example 4 of the present invention. Detailed implementation mode

[0031] The present invention will be further described in detail below in conjunction with the embodiments.

[0032] The present invention provides a doped graphene-based thermoelectric composite antimonene material, and the doped graphene-based thermoelectric composite antimonene material includes graphene and antimonene.

[0033] The present invention provides the above-mentioned doped graphene-based thermoelectric composite antimonene material. The doped graphene-based thermoelectric composite antimonene material provided by the present invention has a high conductivity, Seebeck coefficient, excellent power factor, and excellent corrosion resistance, greatly improving the thermoelectric performance and corrosion resistance of the thermoelectric material.

[0034] The present invention provides a preparation method for the doped graphene-based thermoelectric composite antimonene material described in the above solution, including the following steps:

[0035] (1) Ultrasonic graphene in methanol or ethanol to obtain a graphene suspension;

[0036] (2) Add antimonene to the graphene suspension and ultrasonicate to obtain a mixed suspension;

[0037] (3) Filter the mixed suspension by suction and dry it to obtain a doped graphene-based thermoelectric composite antimonene material;

[0038] The present invention ultrasonically treats graphene in methanol or ethanol to obtain a graphene suspension. In the present invention, the mass ratio of graphene to organic alcohol (methanol or ethanol) is preferably 0.01:(100 - 300), more preferably 0.01:(150 - 200). The ultrasonic time is preferably 1 - 3 h, more preferably 1.5 - 2 h. During ultrasonic treatment, ensure that the solution temperature is maintained at 0 °C. The present invention has no special requirements for the source of the graphene, and the corresponding commercially available products in the art can be used. The present invention has no special requirements for the source of the methanol or ethanol, and the corresponding commercially available products in the art can be used.

[0039] In the present invention, antimonene is ultrasonically treated in a graphene suspension to obtain a mixed suspension. The mass ratio of antimonene to the graphene suspension is preferably 1:(10 - 200), more preferably 1:(60 - 80). The ultrasonic treatment time is preferably 1 - 3 h, more preferably 1.5 - 2 h. During ultrasonic treatment, the solution temperature is maintained at 0 °C.

[0040] In the present invention, the mixed suspension is filtered by suction and dried to obtain a thermoelectric composite antimonene material doped with graphene. In the present invention, the drying temperature is preferably 70 - 90 °C, more preferably 75 - 85 °C; the drying time is preferably 1 - 3 h, more preferably 1 - 1.5 h.

[0041] The present invention provides a preparation method of the above-mentioned thermoelectric composite antimonene material doped with graphene. The preparation method provided by the present invention is simple, has relatively loose condition requirements, has excellent operability, can further realize continuous preparation, and is conducive to industrial production.

[0042] The following examples are used to illustrate in detail the thermoelectric composite antimonene material doped with graphene and its preparation method provided by the present invention, but they should not be construed as limiting the protection scope of the present invention.

[0043] Example 1

[0044] A preparation method of a thermoelectric composite antimonene material doped with graphene, the schematic diagram of the preparation process is shown in Figure 1 , and includes the following steps:

[0045] (1) Weigh 0.01 g of graphene and add it to 250 ml of absolute ethanol, and ultrasonically treat it for 2 h under an ice-water bath condition to obtain a graphene suspension.

[0046] (2) Weigh 2.95 g of antimonene and add it to the graphene suspension obtained in step (1), and ultrasonically treat it for 2 h under an ice-water bath condition to obtain a mixed suspension.

[0047] (3) Filter the mixed suspension obtained in step (2) by suction and dry it at 80 °C for 1 h to obtain a thermoelectric composite antimonene material doped with graphene.

[0048] After testing, the conductivity of the thermoelectric composite antimonene material doped with graphene prepared in this example is 2158.22 S / cm, the Seebeck coefficient is 27.17 μV / k, and the power factor is 159.34 μW / mK 2 .

[0049] Example 2

[0050] A preparation method of a thermoelectric composite antimonene material doped with graphene, including the following steps:

[0051] (1) Weigh 0.01 g of graphene and add it to 250 ml of absolute ethanol. Ultrasonicate for 2 h under an ice-water bath condition to obtain a graphene suspension.

[0052] (2) Weigh 2.89 g of antimonene and add it to the graphene suspension obtained in step (1). Ultrasonicate for 2 h under an ice-water bath condition to obtain a mixed suspension.

[0053] (3) Filter the mixed suspension obtained in step (2) by suction filtration and dry it at 80 °C for 1 h to obtain a thermoelectric composite antimonene material doped with graphene.

[0054] Perform performance tests on the thermoelectric composite two-dimensional nanosheets doped with graphene prepared in this example. The results are shown in Table 1.

[0055] Example 3

[0056] A preparation method of a thermoelectric composite antimonene material doped with graphene, comprising the following steps:

[0057] (1) Weigh 0.01 g of graphene and add it to 250 ml of absolute ethanol. Ultrasonicate for 2 h under an ice-water bath condition to obtain a graphene suspension.

[0058] (2) Weigh 2.83 g of antimonene and add it to the graphene suspension obtained in step (1). Ultrasonicate for 2 h under an ice-water bath condition to obtain a mixed suspension.

[0059] (3) Filter the mixed suspension obtained in step (2) by suction filtration and dry it at 80 °C for 1 h to obtain a thermoelectric composite antimonene material doped with graphene.

[0060] Perform performance tests on the thermoelectric composite antimonene material doped with graphene prepared in this example. The results are shown in Table 1.

[0061] Example 4

[0062] A preparation method of a thermoelectric composite antimonene material doped with graphene, comprising the following steps:

[0063] (1) Weigh 0.01 g of graphene and add it to 250 ml of absolute ethanol. Ultrasonicate for 2 h under an ice-water bath condition to obtain a graphene suspension.

[0064] (2) Weigh 2.68 g of antimonene and add it to the graphene suspension obtained in step (1). Ultrasonicate for 2 h under an ice-water bath condition to obtain a mixed suspension.

[0065] (3) Filter the mixed suspension obtained in step (2) by suction filtration and dry it at 80 °C for 1 h to obtain a thermoelectric composite antimonene material doped with graphene.

[0066] The performance of the doped graphene-based thermoelectric composite antimonene material prepared in this example was tested, and the results are shown in Table 1.

[0067] The products obtained in each example and comparative example were subjected to performance tests. The conductivity diagrams corresponding to the examples are shown in Figure 2 , the Seebeck coefficient diagrams Figure 3 , and the power factor diagrams are shown in Figure 4 . The specific results are shown in Table 1:

[0068] Table 1 Performance test results of the products obtained in each example and comparative example

[0069] Conductivity (S / cm) Seebeck coefficient (µV / k) <![CDATA[Power factor (µW / mK 2) > Example 1 2158.22 27.17 159.34 Example 2 1984.46 27.11 145.88 Example 3 1944.98 27.41 146.17 Example 4 1946.92 27.46 146.85 Comparative Example 1 (Carbon nanotubes) 560.36 9.24 4.78 Comparative Example 2 (Bismuthene) 957.25 10.15 9.86 Comparative Example 3 (Black phosphorene) 1.20 342.91 14.11 Comparative Example 4 (Rectangular unit cell antimonene) 1800.10 25.70 118.90 Comparative Example 5 1860.22 26.10 126.72

[0070] Comparative Example 1

[0071] The preparation of the doped carbon nanomaterial-based thermoelectric composite two-dimensional nanosheets was the same as that in Example 1, except that carbon nanotubes were used for the preparation. The power factor increased but was lower than that of the doped graphene. The reason is that the conductivity of carbon nanotubes themselves is not as high as that of graphene, and the effect on the power factor is not as good as that of graphene.

[0072] Comparative Example 2

[0073] The preparation of the doped graphene-based thermoelectric composite bismuthene material was the same as that in Example 1, except that bismuthene was used instead of antimonene for the preparation. The power factor decreased. The reason is that bismuthene is an n-type material and the carbon nanomaterial is a p-type material. Adding a p-type material will affect the performance of bismuthene, resulting in a decrease in thermoelectric performance, especially the decrease in the power factor.

[0074] Comparative Example 3

[0075] The preparation of the doped graphene-based thermoelectric composite black phosphorene was the same as that in Example 1, except that black phosphorene was used instead of antimonene for the preparation. The power factor decreased. The reason is that the conductivity of black phosphorene itself is very low and the power factor is also very low. Even by adding graphene, it is difficult to meet the performance requirements in the application field of thermoelectric materials.

[0076] Comparative Example 4

[0077] The preparation of the doped graphene-based thermoelectric composite antimonene material was the same as that in Example 1, except that the antimonene material had a rectangular structure primitive cell. Although the increase in conductivity was the same, the Seebeck coefficient and power factor decreased, and it could not meet the performance requirements of thermoelectric materials in the process of environmental pollution and high-end equipment applications.

[0078] Comparative Example 5

[0079] Preparation of a thermoelectric composite antimonene material doped with graphene, which is the same as in Example 1, except that, by mass ratio, carbon nanomaterials: two-dimensional crystal materials = 1:200. The conductivity is improved but not much. The reason is that doping a large amount of carbon nanomaterials will cause agglomeration, which affects the conductivity and cannot meet the performance requirements of thermoelectric materials.

Claims

1. A thermoelectric composite antimonene material doped with graphene, characterized in that: The graphene-doped thermoelectric composite antimonene material comprises graphene and antimonene; in terms of mass ratio, graphene: antimonene=1:(268-295); the unit cell structure of the antimonene is a honeycomb hexagonal lattice; The graphene-doped thermoelectric composite antimonene material is prepared by the following preparation method: S1: adding graphene to organic alcohol and ultrasonically obtaining a graphene suspension; S2: adding the antimonene material to the graphene suspension and ultrasonicating to obtain a mixed suspension; S3: performing solid-liquid separation on the mixed suspension, and drying the mixed suspension to obtain a graphene-doped thermoelectric composite antimonene material.

2. The graphene-doped thermoelectric composite antimonene material according to claim 1, characterized in that: The thickness of the graphene is 1.30-1.50 nm.

3. The graphene-doped thermoelectric composite antimonene material according to claim 1, characterized in that: The graphene-doped thermoelectric composite antimonene material has an electrical conductivity of 1944-2160 S / cm, a Seebeck coefficient of 27.10-27.50 µV / k, and a power factor of 145-160 µW / mK2.

4. The application of the graphene-doped thermoelectric composite antimonene material according to any one of claims 1 to 3, characterized in that: It is used as a waste heat power generation recovery device, a microelectronic device thermal management device or a power source for portable electronic devices.

5. The method for preparing the graphene-doped thermoelectric composite antimonene material according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1: adding graphene to organic alcohol and ultrasonically obtaining a graphene suspension; S2: adding the antimonene material to the graphene suspension and ultrasonicating to obtain a mixed suspension; S3: performing solid-liquid separation on the mixed suspension, and drying the mixed suspension to obtain a graphene-doped thermoelectric composite antimonene material.

6. The method for preparing the graphene-doped thermoelectric composite antimonene material according to claim 5, characterized in that: In the step S1, the mass ratio of graphene to organic alcohol is 0.01:(100-300).

7. The method for preparing the graphene-doped thermoelectric composite antimonene material according to claim 5, characterized in that: In the S1, the ultrasonic condition is an ice water bath, and the ultrasonic time is 1 to 3 hours.

8. The method for preparing the graphene-doped thermoelectric composite antimonene material according to claim 5, characterized in that: In the S2, the ultrasonic condition is an ice water bath, and the ultrasonic time is 1 to 3 hours.

9. The method for preparing the graphene-doped thermoelectric composite antimonene material according to claim 5, characterized in that: In the step S2, the mass ratio of antimonene to graphene suspension is 1:(10-200).

10. The method for preparing the graphene-doped thermoelectric composite antimonene material according to claim 5, characterized in that: In step S3, the drying temperature is 70-90° C. and the drying time is 1-3 hours.

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