CN112531098B - Flexible thermoelectric material and preparation method thereof - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 16
- 239000011669 selenium Substances 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
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- 230000001105 regulatory effect Effects 0.000 claims description 2
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- 239000012265 solid product Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
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- 238000003917 TEM image Methods 0.000 description 5
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- 230000009286 beneficial effect Effects 0.000 description 3
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- 239000002064 nanoplatelet Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 230000005678 Seebeck effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000003477 cochlea Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a flexible thermoelectric material and a preparation method thereof. The flexible thermoelectric material uniformly and effectively combines copper selenide with a carbon material, and has excellent thermoelectric performance and flexibility. According to the preparation method of the flexible thermoelectric material, the copper selenide-graphene composite flexible thermoelectric material can be prepared by a wet chemical method through simple equipment and convenient operation, the flexible thermoelectric material is fused with the high conductivity and the high Seebeck coefficient of copper selenide and the high conductivity and the good flexibility of the graphene material, and meanwhile, the heterojunction interface between the copper selenide and the graphene material improves the phonon scattering capability, so that the material has certain disorder, the heat conductivity is reduced, and the thermoelectric performance is improved.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a flexible thermoelectric material and a preparation method thereof.
Background
The field of thermoelectric materials has entered the practical device stage since the fifty years of the last century, and has been mainly applied to the field of high-end front-end technology, such as the electric power driving device of space satellites, for many years. For more than twenty years, the thermoelectric device gradually enters the field of application of actual life of the masses in society, especially along with miniaturization and micromation of the thermoelectric device and the appearance and development of wearable devices, the thermoelectric device starts to play various purposes on a human body, including cardiac pacemakers, artificial cochlea, body temperature power generation and the like, and life and production modes of people are enriched. In this development trend, the flexible thermoelectric device has many incomparable advantages to the traditional rigid device, including light weight, thin thickness, strong plasticity, high adaptability to human body, strong practicability and the like. The development of the flexible wearable device is an important direction of the subjects in the thermoelectric field in the aspect of practicality, the life and the production modes of people can be greatly enriched by the application and the maturation of the industrial development, and the wearable thermoelectric device industry in China is also in the starting stage, so that the flexible wearable device has great development potential and research value.
Materials used in flexible thermoelectric device research can be largely divided into three categories: conductive organic polymers, inorganic semiconductor materials, and organic-inorganic composite materials. Among them, inorganic bulk thermoelectric materials have higher conductivity and Seebeck coefficient, but have poor flexibility characteristics. The inorganic semiconductor material is nanocrystallized, so that the flexibility of the inorganic semiconductor material can be effectively improved, and the inorganic semiconductor material can be dispersed in a solvent by using a surfactant, so that the flexible thermoelectric film can be prepared by using the inorganic semiconductor material. However, surfactants tend to reduce the conductivity of inorganic semiconductors to some extent, and thus there are limitations to this approach. In order to solve the problems, the main means for preparing the flexible thermoelectric material at present is to regulate and control the thermoelectric performance of the material by combining with organic materials through chemical synthesis and molecular design strategies, morphology control and doping.
In recent years, copper selenide is an inorganic semiconductor material which is focused in the thermoelectric field because of relatively abundant, nontoxic and harmless reserves of constituent elements, and the 'electron crystal-phonon glass' characteristic of high-temperature beta crystalline phase and critical scattering property of phonons during low-temperature alpha-high-temperature beta phase transition. Meanwhile, carbon materials such as graphene and the like have a plurality of unique thermal and mechanical properties, are cheap and environmentally friendly due to high electrical conductivity, and are gradually becoming new pets for thermoelectric research. At present, the thermoelectric figure of merit (thermoelectric figure of merit, abbreviated as ZT) of the two materials in the flexible thermoelectric research is also lower than 1, one of the main reasons is limited by the use temperature of the flexible thermoelectric device itself, and the other is that the intrinsic internal crystal structure of the materials also limits the improvement of thermoelectric performance.
In order to increase the ZT value of a material, it is necessary to modify the crystal structure of the material to have both high-speed electron transport and good phonon scattering properties, thereby achieving higher electrical conductivity and relatively low thermal conductivity. High-speed electron transmission requires a highly ordered lattice structure network in the crystal to facilitate the diffusion and transmission of carriers and promote conductivity; in contrast, good phonon scattering requires a certain disorder inside the crystal, and defects present in the crystal can reduce the mean free path of phonons, thereby reducing lattice thermal conductivity. The order and disorder of the internal structure of the crystal are a pair of contradictions, and in order to optimize the thermoelectric performance of the material, various adjustments and improvements are needed to be made on the structure of the material to reach the optimal balance point.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides the flexible thermoelectric material which comprises the copper selenide nano-particles and the graphene nano-sheets coated around the copper selenide nano-particles, can uniformly and effectively compound the copper selenide with the carbon material, and has excellent thermoelectric performance and flexibility. In the flexible thermoelectric material, the carbon material is mainly introduced to manufacture a crystalline phase interface in a copper selenide crystal, so that phonon scattering is improved; meanwhile, the carbon material has high conductivity, does not significantly weaken electron transmission, and reduces the heat conductivity while maintaining high conductivity.
The invention also provides a preparation method of the flexible thermoelectric material.
The first aspect of the invention provides a flexible thermoelectric material, which comprises copper selenide nano-particles and graphene nano-sheets coated around the copper selenide nano-particles, wherein the chemical formula of the copper selenide nano-particles is Cu 2- x Se, wherein x is less than or equal to 0.25.
According to some embodiments of the invention, when x=0, cu 2 The phase transition temperature of Se is 340-400K, and the thermoelectric figure of merit ZT is 0.05-0.3.
According to some embodiments of the invention, the particle size of the copper selenide nanoparticle is 1 to 50nm and the particle size of the graphene is 5 to 100nm in the flexible thermoelectric material.
The second aspect of the present invention provides a method for preparing the above flexible thermoelectric material, comprising the steps of:
s1: dissolving copper salt and selenium source in water to obtain a first solution;
s2: heating and melting the organic oxygen acid until the organic oxygen acid is decomposed, and adjusting the pH value to obtain a second solution;
s3: and uniformly mixing the first solution and the second solution, adding an initiator, standing after the reaction, and carrying out solid-liquid separation to obtain a solid product, namely the flexible thermoelectric material.
According to some embodiments of the invention, in step S1, the copper salt comprises copper sulfate pentahydrate, copper chloride, and copper nitrate.
According to some embodiments of the invention, in step S1, the copper salt is copper sulfate pentahydrate.
According to some embodiments of the invention, in step S1, the selenium source comprises selenium dioxide and elemental selenium.
According to some embodiments of the invention, in step S2, the organic oxy acid is citric acid.
According to some embodiments of the invention, in step S2, the heating is performed at a temperature of 150 to 300 ℃.
According to some embodiments of the invention, in step S2, the heating is performed at a temperature of 200 to 300 ℃.
According to some embodiments of the invention, in step S2, the heating is at a temperature of 200 ℃.
According to some embodiments of the invention, in step S3, the initiator comprises sodium ascorbate, sodium sulfite, and sodium borohydride.
According to some embodiments of the invention, in step S3, the reaction time is 1 to 5 hours.
According to some embodiments of the invention, in step S3, the time of standing is 4 to 24 hours.
According to some embodiments of the invention, in step S3, the time of standing is 4 to 16 hours.
According to some embodiments of the invention, in step S3, the time of rest is 8-16 h.
The flexible thermoelectric material has at least the following beneficial effects:
the flexible thermoelectric material of the invention uniformly and effectively combines the copper selenide with the carbon material, and has excellent thermoelectric performance and flexibility.
The flexible thermoelectric material is mainly characterized in that a crystalline phase interface is manufactured in a copper selenide crystal, so that certain disorder is displayed in the crystal, and phonon scattering is improved; meanwhile, the carbon material has high conductivity, maintains certain 'order', does not obviously weaken electron transmission, reduces heat conductivity while maintaining high conductivity, and is beneficial to improving thermoelectric performance.
Compared with the bulk material, the flexible thermoelectric material is favorable for further improving the overall flexibility of the material by preparing the nano material, and has higher application potential in the field of flexible thermoelectric materials.
According to the preparation method of the flexible thermoelectric material, the flexible thermoelectric material compounded by the copper selenide and the graphene can be prepared by a wet chemical method through simple equipment and convenient operation, the flexible thermoelectric material is fused with the high conductivity and the high Seebeck coefficient (Seebeck coefficient can be used for representing the size of the Seebeck effect) of the copper selenide, the expression of the flexible thermoelectric material is S=dV/dT., dT is the temperature difference between two points on the thermoelectric material, dV is the thermoelectric force between the two corresponding points, in the thermoelectric material, when electrons are multiple, the cold end is negative, S is negative, when holes are multiple, the hot end is negative, S is positive), and the graphene material has high conductivity and good flexibility, and meanwhile, the heterojunction interface between the two materials improves the phonon scattering capability, so that the material has certain disorder, reduces the heat conductivity, and is beneficial to improving the thermoelectric performance.
A third aspect of the present invention provides the use of the flexible thermoelectric material described above in a thermoelectric device.
Drawings
Fig. 1 is an XRD pattern of the flexible thermoelectric material prepared in example 1.
Fig. 2 is a TEM image of the flexible thermoelectric material prepared in example 1.
Fig. 3 is an HRTEM image of the flexible thermoelectric material prepared in example 1.
FIG. 4 is a V-T curve of the flexible thermoelectric material prepared in example 1 at different temperature differences.
Fig. 5 is a conductivity curve of the flexible thermoelectric material prepared in example 1 at room temperature to 150 ℃.
Fig. 6 is an XRD pattern of the flexible thermoelectric material prepared in example 2.
Fig. 7 is a TEM image of the flexible thermoelectric material prepared in example 3.
Fig. 8 is a TEM image of the flexible thermoelectric material prepared in example 4.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
Example 1
The flexible thermoelectric material is prepared by the embodiment, and specifically comprises the following components:
s1: dissolving 0.3g of selenium dioxide and 1.5g of copper sulfate pentahydrate in 75mL of deionized water, and stirring until the selenium dioxide and the copper sulfate pentahydrate are completely dissolved to obtain a first solution;
s2: heating 2.0g of citric acid to 200 ℃ in a silicone oil bath, then keeping for 3 hours to obtain a brown-black oily liquid, naturally cooling the liquid to room temperature, stirring the liquid with 10mg/mL of NaOH solution, and adjusting the pH value to 7.0 to obtain a second solution;
s3: 25mL of the second solution was added to the first solution, and after stirring well, 2g of sodium ascorbate was added as an initiator, and the reaction was continued at room temperature with stirring for 2 hours. And after the stirring is finished, standing the reactant overnight, filtering, washing with deionized water for 3 times, and drying at 60 ℃ to obtain a solid, namely the target product flexible thermoelectric material.
In the step S2, alkali is added after the citric acid is pyrolyzed, so that the aqueous solution of graphene nano sheets or graphene quantum dots can be obtained.
The XRD pattern of the flexible thermoelectric material is shown in figure 1, and it can be seen from figure 1 that the obtained product is mainly Cu 2-x Se. Line 1 in FIG. 1 is Cu 2-x Standard diffraction peak of Se (JCPDS 06-0680).
The TEM (Transmission Electron Microscope, transmission electron microscope, abbreviated as TEM) and HRTEM (High Resolution Transmission Electron Microscope, high resolution transmission electron microscope, abbreviated as HRTEM) images of the flexible thermoelectric material are shown in fig. 2 and 3, respectively.
It is clear from fig. 2 that the copper selenide nanoparticle is uniformly coated with a plurality of graphene nanoplatelets around the same.
From fig. 3, it can be seen that the outer coating structure has a interplanar spacing of 0.20nm, which belongs to the interplanar spacing of graphene, indicating that the coating outside the copper selenide is indeed graphene.
Fig. 4 is a V-T curve of a flexible thermoelectric material at different temperature differentials, with the cold end of the material held at room temperature and the hot end raised by 10 ℃ every 5min from room temperature. The material has excellent thermoelectric response value, the open-circuit voltage of the material output to the outside is about 0.24mV at the temperature difference of 10 ℃, and the open-circuit voltage is steadily and gradually increased along with the increase of the temperature difference.
Fig. 5 is a graph of the electrical conductivity of the flexible thermoelectric material at room temperature to 150 c, from which it can be seen that the flexible thermoelectric material has a higher electrical conductivity in the range of room temperature to 150 c.
Example 2
This example produced a flexible thermoelectric material, as compared to example 1, except that powdered selenium was used as the selenium source, copper chloride as the copper source, and sodium sulfite as the initiator. The method comprises the following steps:
s1: uniformly mixing 0.2g of selenium simple substance powder and 1g of sodium sulfite, adding 70mL of water, then condensing and refluxing in a water bath at 70 ℃ for 2h, filtering out insoluble substances after the solution is cooled to room temperature, and then adding 1g of copper chloride, and uniformly stirring to obtain a first solution;
s2: heating 2.0g of citric acid to 200 ℃ in a silicone oil bath, then keeping for 3 hours to obtain a brown-black oily liquid, naturally cooling the liquid to room temperature, stirring the liquid with 10mg/mL of NaOH solution, and adjusting the pH value to 7.0 to obtain a second solution;
s3: 30mL of the second solution was added to the first solution, and after stirring well, 1.5g of sodium sulfite was added as an initiator, and the reaction was continued at room temperature with stirring for 3 hours. And after the stirring is finished, standing the reactant overnight, filtering, washing with deionized water for 3 times, and drying at 60 ℃ to obtain a solid, namely the target product flexible thermoelectric material.
The flexible thermoelectric materialThe XRD patterns of the materials are shown in FIG. 6, and it can be seen from FIG. 6 that the obtained product is mainly Cu 2-x Se. Line 1 in FIG. 6 is Cu 2-x Standard diffraction peak of Se (JCPDS 06-0680).
Example 3
This example produced a flexible thermoelectric material, which was different from example 1 in that the pyrolysis time of the organic oxy acid as a carbon source was short and sodium borohydride was used as an initiator. The method comprises the following steps:
s1: dissolving 0.3g of selenium dioxide and 1.5g of copper sulfate pentahydrate in 75mL of deionized water, and stirring until the selenium dioxide and the copper sulfate pentahydrate are completely dissolved to obtain a first solution;
s2: heating 2.0g of citric acid to 200 ℃ in a silicone oil bath, then keeping for 0.5h to obtain orange-red oily liquid, naturally cooling to room temperature, stirring with 10mg/mL NaOH solution, and adjusting the pH value to 7.0 to obtain a second solution;
s3: 25mL of the second solution was added to the first solution, and after stirring well, 1.2g of NaBH4 was added as an initiator, and the reaction was continued at room temperature with stirring for 1.5h. And after the stirring is finished, standing the reactant overnight, filtering, washing with deionized water for 3 times, and drying at 60 ℃ to obtain a solid, namely the target product flexible thermoelectric material.
A TEM image of the flexible thermoelectric material is shown in fig. 7, and it can be seen from fig. 7 that many graphene nanoplatelets are uniformly coated around the copper selenide nanoparticles.
Example 4
This example produced a flexible thermoelectric material, as compared to example 1, except that copper nitrate was used as the copper source, hydrazine hydrate as the initiator, and EDTA as the carbon source. The method comprises the following steps:
s1: dissolving 0.4g of selenium dioxide and 1.8g of cupric nitrate hexahydrate in 75mL of deionized water, and stirring until the selenium dioxide and the cupric nitrate hexahydrate are completely dissolved to obtain a first solution;
s2: heating 2.5g of EDTA to 270 ℃ in a muffle furnace and keeping for 5 hours, stirring with 10mg/mL NaOH solution after naturally cooling to room temperature, and regulating the pH value to 7.0 to obtain a second solution;
s3: 25mL of the second solution is added into the first solution, and after being uniformly stirred, 10mL of hydrazine hydrate aqueous solution is added as an initiator, and the stirring reaction is kept at room temperature for 1h. And after the stirring is finished, standing the reactant overnight, filtering, washing with deionized water for 3 times, and drying at 60 ℃ to obtain a solid, namely the target product flexible thermoelectric material.
A TEM image of the flexible thermoelectric material is shown in fig. 8, and it can be seen from fig. 8 that many graphene nanoplatelets are uniformly coated around the copper selenide nanoparticles.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. A preparation method of a flexible thermoelectric material is characterized in that the flexible thermoelectric material comprises copper selenide nano-particles and graphene nano-sheets coated around the copper selenide nano-particles, and the chemical formula of the copper selenide nano-particles is Cu 2-x Se, wherein x is less than or equal to 0.25;
the preparation method of the flexible thermoelectric material comprises the following steps:
s1: dissolving copper salt and selenium source in water to obtain a first solution;
s2: heating and melting the organic oxygen acid until the organic oxygen acid is decomposed, and regulating the pH value to obtain a second solution;
s3: uniformly mixing the first solution and the second solution, adding an initiator, standing after reaction, and carrying out solid-liquid separation to obtain a solid product, namely the flexible thermoelectric material;
in step S3, the initiator includes sodium ascorbate, sodium sulfite or sodium borohydride.
2. The method according to claim 1, wherein in the chemical formula, cu when x=0 2 The phase transition temperature of Se is 340-400K, and the thermoelectric figure of merit ZT is 0.05-0.3.
3. The method according to claim 1, wherein in step S1, the copper salt comprises copper sulfate pentahydrate, copper chloride or copper nitrate.
4. The method of claim 1, wherein in step S1, the selenium source comprises selenium dioxide or elemental selenium.
5. The method according to claim 1, wherein in step S2, the organic oxy acid is citric acid.
6. The method according to claim 1, wherein in step S2, the heating is performed at a temperature of 150 to 300 ℃.
7. The method according to claim 1, wherein the reaction time in step S3 is 1 to 5 hours.
8. Use of a flexible thermoelectric material prepared according to the preparation method of any one of claims 1 to 7 in a thermoelectric device.
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| CN202011554063.3A CN112531098B (en) | 2020-12-24 | 2020-12-24 | Flexible thermoelectric material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106159076A (en) * | 2015-04-10 | 2016-11-23 | 武汉理工大学 | A kind of preparation method of Cu2-XSe/graphene composite material |
| CN107658469A (en) * | 2017-10-23 | 2018-02-02 | 南昌航空大学 | A kind of quick method for preparing the graphene-based positive electrode of fast charging type |
| CN109329306A (en) * | 2018-11-19 | 2019-02-15 | 江苏科技大学 | A kind of CuO/GQDs composite antibacterial material and its preparation method and application |
| CN110155958A (en) * | 2019-05-13 | 2019-08-23 | 东华大学 | A hydrangea-like Cu2-xSe nanomaterial and its preparation and application |
Family Cites Families (1)
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159076A (en) * | 2015-04-10 | 2016-11-23 | 武汉理工大学 | A kind of preparation method of Cu2-XSe/graphene composite material |
| CN107658469A (en) * | 2017-10-23 | 2018-02-02 | 南昌航空大学 | A kind of quick method for preparing the graphene-based positive electrode of fast charging type |
| CN109329306A (en) * | 2018-11-19 | 2019-02-15 | 江苏科技大学 | A kind of CuO/GQDs composite antibacterial material and its preparation method and application |
| CN110155958A (en) * | 2019-05-13 | 2019-08-23 | 东华大学 | A hydrangea-like Cu2-xSe nanomaterial and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| 陈立飞 等.石墨烯负载金属纳米粒子新功能材料的制.《上海第二工业大学学报》.2015,第32卷(第3期),第185-189页. * |
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