Graphene-doped thermoelectric composite antimonene material and preparation method and application thereof

Abstract

The invention discloses a graphene-doped thermoelectric composite antimonene material and a preparation method and application thereof, and belongs to the technical field of thermoelectric nano materials. The thermoelectric composite antimonene material doped with the graphene comprises graphene and antimonene, and the mass ratio of the graphene to the antimonene is 1: (268-295); the conductivity of the thermoelectric composite antimonene material doped with the graphene ranges from 1944 S / cm to 2160 S / cm, the Seebeck coefficient ranges from 27.10 V / k to 27.50 V / k, and the power factor ranges from 145 W / mK < 2 > to 160 W / mK < 2 >. The graphene-doped thermoelectric composite antimonene material has relatively high conductivity, Seebeck coefficient and excellent power factor, and the thermoelectric performance of the thermoelectric material is greatly improved.

Description

Technical Field

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

[0002] Thermoelectric materials are a special type of functional material that has the ability to convert electrical effects into thermal effects. In simple terms, thermoelectric materials can realize 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, which can enable thermoelectric materials to convert thermal energy into electrical energy. There are two main types of thermoelectric materials: thermoelectric conversion materials and thermocouple materials. Thermoelectric conversion materials can directly convert thermal energy into electrical energy, while thermocouple materials are a sensor for measuring temperature. These materials can work at both room temperature and high temperature, and have a long service life.

[0003] The application of thermoelectric materials in aircraft is mainly in: (1) Waste heat recovery system: Aircraft will generate a lot of waste heat during flight. If the waste heat can be effectively treated, it can not only reduce energy waste, but also have a good impact on environmental protection. Thermoelectric materials can effectively convert waste heat into electrical energy, thereby providing additional energy for the aircraft, achieving the effect of reducing energy consumption and reducing environmental pollution. (2) Micro power supply and temperature control system: Some electronic equipment on the aircraft, such as sensors and communication equipment, require a stable power supply and temperature environment. Thermoelectric materials can be prepared into micro power supply and temperature control systems to provide these devices with the required power and temperature environment, thereby improving the overall performance and reliability of the aircraft. From the above applications of thermoelectric materials on aircraft, it can be seen that the research on thermoelectric materials has a strong practical significance in environmental pollution and high-end equipment applications. At present, the composition of thermoelectric materials is relatively simple, such as graphene, black phosphorus, silicene, germanene, etc. Such materials often have insufficient performance in one aspect, so they cannot obtain ideal thermoelectric performance. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a graphene-doped thermoelectric composite antimonene material and its preparation method and application, so as to solve the problem that the existing single thermoelectric material has a certain performance deficiency and is easy to corrode. The graphene-doped thermoelectric composite antimonene material provided by the present invention has high electrical conductivity, Seebeck coefficient, and excellent power factor, which greatly improves the thermoelectric performance of the thermoelectric material.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: The invention provides a graphene-doped thermoelectric composite antimonene material, comprising graphene and antimonene; in terms of mass ratio, graphene:antimonene=1:(268-295).

[0006] The thickness of the graphene is 1.30-1.50 nm.

[0007] The unit cell structure of antimonene is a honeycomb hexagonal lattice.

[0008] 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 / mK. 2 .

[0009] The application of the graphene-doped thermoelectric composite antimonene material of the present invention is used as a waste heat power generation recovery device, a microelectronic device thermal management device, a portable electronic device power supply device, and more preferably as a thermal imager, a sensor, a nanogenerator or an energy harvester.

[0010] The present invention provides a method for preparing a graphene-doped thermoelectric composite antimonene material, comprising the following steps: 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.

[0011] The above steps are merely 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.

[0012] In the step S1, the mass ratio of graphene to organic alcohol is 0.01:(100-300); preferably methanol and / or ethanol.

[0013] In step S1, the ultrasonic condition is an ice water bath, and the ultrasonic time is preferably 1 to 3 hours.

[0014] In the step S2, the mass ratio of antimonene to graphene suspension is 1:(10-200).

[0015] In step S2, the ultrasonic condition is an ice water bath, and the ultrasonic time is preferably 1 to 3 hours.

[0016] In step S3, the drying temperature is 70-90° C. and the drying time is 1-3 hours.

[0017] Compared with the prior art, the thermoelectric composite antimonene material doped with graphene of the present invention and its preparation method and application have the following beneficial effects: (1) The antimonene in the graphene-doped thermoelectric composite antimonene material provided by the present invention forms a conductive structure, and graphene is doped in the conductive structure. By optimizing the electron and phonon transmission paths and utilizing the high electrical conductivity of graphene and the low thermal conductivity of the conductive structure, the thermoelectric figure of merit (ZT value) of the material is significantly improved, thereby achieving more efficient thermoelectric energy conversion; the unique phonon scattering mechanism of antimonene is combined with the interface scattering effect of graphene, which greatly reduces the thermal conductivity of the material, thereby improving the thermoelectric conversion efficiency.

[0018] (2) In addition, the high strength, flexibility and stability of graphene make the thermoelectric composite antimonene material doped with graphene show 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, and the synergistic effect of the two materials can significantly improve the thermoelectric performance of the material, avoiding the decomposition or degradation problems that may occur in a single material. Therefore, the present invention provides a new thermoelectric material with great potential, which has both efficient thermoelectric conversion performance and excellent mechanical and chemical stability.

[0019] (3) The high electron mobility of graphene improves the electrical conductivity of graphene-doped thermoelectric composite antimonene materials, making the transmission of electrons within the material more efficient, which is beneficial to the improvement of thermoelectric performance; the adjustable band gap characteristics of antimonene enable graphene-doped thermoelectric composite antimonene materials to maintain good thermoelectric performance at different temperatures and have a wider adaptability.

[0020] (4) The results of the embodiment show that the graphene-doped thermoelectric composite antimonene material can be used for industrial waste heat recovery, improving energy utilization and reducing energy waste; in microelectronic devices, the graphene-doped thermoelectric composite antimonene material can be used as an efficient thermal management material to improve the performance and life of the device; it can be used as a power source for portable electronic devices to provide stable and efficient power output, meeting the high requirements of modern electronic devices for power supply.

[0021] (5) The present invention provides a graphene-doped thermoelectric composite antimonene material and a preparation method thereof. The preparation method provided by the present invention is simple, has excellent operability, can be widely used, and further continuous manufacturing is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 A schematic diagram of a method for preparing a thermoelectric composite antimonene material doped with graphene; Figure 2The electrical conductivity diagram of the thermoelectric composite antimonene material doped with graphene prepared in Examples 1, 2, 3 and 4 of the present invention; Figure 3 Seebeck coefficient diagram of the thermoelectric composite antimonene material doped with graphene prepared in Example 1, Example 2, Example 3 and Example 4 of the present invention; Figure 4 This is a power factor diagram of the graphene-doped thermoelectric composite antimonene material prepared in Examples 1, 2, 3 and 4 of the present invention. DETAILED DESCRIPTION

[0023] The present invention is further described in detail below in conjunction with embodiments.

[0024] The invention provides a graphene-doped thermoelectric composite antimonene material. The graphene-doped thermoelectric composite antimonene material comprises graphene and antimonene.

[0025] The present invention provides the above graphene-doped thermoelectric composite antimonene material. The graphene-doped thermoelectric composite antimonene material provided by the present invention has high electrical conductivity, Seebeck coefficient, excellent power factor and excellent corrosion resistance, which greatly improves the thermoelectric performance and corrosion resistance of the thermoelectric material.

[0026] The present invention provides a method for preparing the thermoelectric composite antimonene material doped with graphene described in the above scheme, comprising the following steps: (1) ultrasonically treating graphene in methanol or ethanol to obtain a graphene suspension; (2) adding antimonene to the graphene suspension and ultrasonicating to obtain a mixed suspension; (3) filtering and drying the mixed suspension to obtain a graphene-doped thermoelectric composite antimonene material; 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 1~3h, more preferably 1.5~2h. During the ultrasonic treatment, the solution temperature is maintained at 0°C. The present invention has no special requirements for the source of the graphite, and the corresponding products commercially available in the art can be used. The present invention has no special requirements for the source of the methanol or ethanol, and the corresponding products commercially available in the art can be used.

[0027] In the present invention, antimonene is ultrasonically treated in a graphene suspension to obtain a mixed suspension, and the mass ratio of antimonene to the graphene suspension is preferably 1:(10-200), more preferably 1:(60-80). The ultrasonic time is preferably 1-3 hours, more preferably 1.5-2 hours, and during the ultrasonic treatment, the solution temperature is maintained at 0°C.

[0028] In the present invention, the mixed suspension is filtered and dried to obtain the graphene-doped thermoelectric composite antimonene material. In the present invention, the drying temperature is preferably 70-90° C., more preferably 75-85° C.; the drying time is preferably 1-3 hours, more preferably 1-1.5 hours.

[0029] The present invention provides a method for preparing the above-mentioned graphene-doped thermoelectric composite antimonene material. The preparation method provided by the present invention is simple, has relatively loose conditions, has excellent operability, can further realize continuous preparation, and is conducive to industrial production.

[0030] The graphene-doped thermoelectric composite antimonene material and the preparation method thereof provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0031] Example 1

[0032] A method for preparing a thermoelectric composite antimonene material doped with graphene, the schematic diagram of the preparation process is shown in Figure 1 , including the following steps: (1) Weigh 0.01 g of graphene and add it to 250 ml of anhydrous ethanol. Ultrasonicate for 2 h in an ice-water bath to obtain a graphene suspension.

[0033] (2) Weigh 2.95 g of antimonene and add it to the graphene suspension obtained in step (1), and ultrasonicate it in an ice-water bath for 2 h to obtain a mixed suspension.

[0034] (3) The mixed suspension obtained in step (2) is filtered and dried at 80° C. for 1 h to obtain a graphene-doped thermoelectric composite antimonene material.

[0035] After testing, the conductivity of the graphene-doped thermoelectric composite antimonene material prepared in this embodiment is 2158.22S / cm, the Seebeck coefficient is 27.17µV / k, and the power factor is 159.34µW / mK. 2 .

[0036] Example 2

[0037] A method for preparing a graphene-doped thermoelectric composite antimonene material comprises the following steps: (1) Weigh 0.01 g of graphene and add it to 250 ml of anhydrous ethanol. Ultrasonicate for 2 h in an ice-water bath to obtain a graphene suspension.

[0038] (2) Weigh 2.89 g of antimonene and add it to the graphene suspension obtained in step (1), and ultrasonicate it in an ice-water bath for 2 h to obtain a mixed suspension.

[0039] (3) The mixed suspension obtained in step (2) is filtered and dried at 80° C. for 1 h to obtain a graphene-doped thermoelectric composite antimonene material.

[0040] The performance of the graphene-doped thermoelectric composite two-dimensional nanosheet prepared in this example was tested, and the results are shown in Table 1.

[0041] Example 3

[0042] A method for preparing a graphene-doped thermoelectric composite antimonene material comprises the following steps: (1) Weigh 0.01 g of graphene and add it to 250 ml of anhydrous ethanol. Ultrasonicate for 2 h in an ice-water bath to obtain a graphene suspension.

[0043] (2) Weigh 2.83 g of antimonene and add it to the graphene suspension obtained in step (1), and ultrasonicate it in an ice-water bath for 2 h to obtain a mixed suspension.

[0044] (3) The mixed suspension obtained in step (2) is filtered and dried at 80° C. for 1 h to obtain a graphene-doped thermoelectric composite antimonene material.

[0045] The performance of the graphene-doped thermoelectric composite antimonene material prepared in this example was tested, and the results are shown in Table 1.

[0046] Example 4

[0047] A method for preparing a graphene-doped thermoelectric composite antimonene material comprises the following steps: (1) Weigh 0.01 g of graphene and add it to 250 ml of anhydrous ethanol. Ultrasonicate for 2 h in an ice-water bath to obtain a graphene suspension.

[0048] (2) Weigh 2.68 g of antimonene and add it to the graphene suspension obtained in step (1), and ultrasonicate it in an ice-water bath for 2 h to obtain a mixed suspension.

[0049] (3) The mixed suspension obtained in step (2) is filtered and dried at 80° C. for 1 h to obtain a graphene-doped thermoelectric composite antimonene material.

[0050] The performance of the graphene-doped thermoelectric composite antimonene material prepared in this example was tested, and the results are shown in Table 1.

[0051] The performance tests were carried out on the products obtained from each embodiment and comparative example. The conductivity diagrams corresponding to the embodiments are shown in Figure 2 , Seebeck coefficient diagram Figure 3 , power factor diagram see Figure 4 The specific results are shown in Table 1: Table 1 Performance test results of the products obtained from various embodiments and comparative examples 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 Comparative Example 1 The preparation of thermoelectric composite two-dimensional nanosheets doped with carbon nanomaterials is the same as in Example 1, except that carbon nanotubes are used for preparation, and the power factor increases but is lower than the power factor of doped graphene. The reason is that the electrical conductivity of carbon nanotubes themselves is not as high as that of graphene, and the effect of affecting the power factor is not as good as that of graphene.

[0052] Comparative Example 2 The preparation of the graphene-doped thermoelectric composite bismuthene material is the same as in Example 1, except that bismuthene is used instead of antimonene for preparation, and the power factor decreases. The reason is that bismuthene is an n-type material and the carbon nanomaterial is a p-type material. The addition of p-type material will affect the performance of bismuthene, thereby resulting in a decrease in thermoelectric performance, especially a decrease in the power factor.

[0053] Comparative Example 3 The preparation of graphene-doped thermoelectric composite black phosphorene is the same as in Example 1, except that black phosphorene is used instead of antimonene for preparation, and the power factor decreases. The reason is that the electrical 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 of the application field of thermoelectric materials.

[0054] Comparative Example 4 The preparation of the graphene-doped thermoelectric composite antimonene material is the same as in Example 1, except that the antimonene material is a rectangular structure unit cell. Although the increase in conductivity is consistent, the Seebeck coefficient and power factor are reduced, which cannot meet the performance requirements of thermoelectric materials for environmental pollution and high-end equipment application processes.

[0055] Comparative Example 5 The preparation of the thermoelectric composite antimonene material doped with graphene is the same as in Example 1, except that, by mass ratio, the carbon nanomaterial: the two-dimensional crystal material = 1:200, and the conductivity is improved but not much. The reason is that doping a large amount of carbon nanomaterial will cause agglomeration, affecting the conductivity and failing to meet the performance requirements of the thermoelectric material.

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).

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 unit cell structure of antimonene is a honeycomb hexagonal lattice.

4. 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 / mK. 2 .

5. Application of the graphene-doped thermoelectric composite antimonene material according to any one of claims 1 to 4, 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.

6. The method for preparing the graphene-doped thermoelectric composite antimonene material according to any one of claims 1 to 4, 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.

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

8. The method for preparing the graphene-doped thermoelectric composite antimonene material according to claim 6, characterized in that: The ultrasonic condition is an ice water bath, and the ultrasonic time is 1~3h.

9. The method for preparing the graphene-doped thermoelectric composite antimonene material according to claim 6, 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 6, 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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