CN105944635A - Preparation method for carbon nanotube-coated thermoelectric nanometer capsule - Google Patents

Preparation method for carbon nanotube-coated thermoelectric nanometer capsule Download PDF

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CN105944635A
CN105944635A CN201610255544.1A CN201610255544A CN105944635A CN 105944635 A CN105944635 A CN 105944635A CN 201610255544 A CN201610255544 A CN 201610255544A CN 105944635 A CN105944635 A CN 105944635A
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solvent
cnt
functionalization
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preparation
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周丽娜
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Shanghai Dianji University
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Shanghai Dianji University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/043—Drying and spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • Engineering & Computer Science (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a preparation method for a carbon nanotube-coated thermoelectric nanometer capsule. The preparation method comprises the following steps: 1) dispersing functionalized multi-walled carbon nanotubes in a solvent and adjusting a pH value to 10 to 14; 2) dissolving a compound containing elemental Sb or Bi in a solvent; 3) dissolving a compound containing elemental Se or Te or elemental Se or Te in a solvent; 4) uniformly mixing a mixed solution obtained in the step 2) with a mixed solution obtained in the step 3) according to a stoichiometric ratio; and 5) adding a mixed solution obtained in the step 4) into a solution obtained in the step 1) step by step according to a mass ratio of the functionalized multi-walled carbon nanotubes to the product in the step 4) of 0.3: 1 to 3: 1, carrying out a reaction at 185 DEG C for 0.5 to 2 h, and then carrying out treatment so as to obtain the carbon nanotube-coated thermoelectric nanometer capsule. The preparation method is simple in process flow and rapid in synthesis; and the prepared carbon nanotube-coated thermoelectric nanometer capsule is extensively applicable to development of micro-nano devices and nano-materials and research in subject areas like mechanics, electromagnetism, catalysis and heat transport.

Description

A kind of preparation method of the thermoelectricity Nano capsule of CNT cladding
Technical field
The present invention relates to the preparation method of a kind of thermoelectricity Nano capsule, particularly relate to one and prepare CNT bag The method of the thermoelectricity Nano capsule covered.
Background technology
Thermoelectric material (thermoelectric material) is capable of between heat energy and electric energy the most mutually conversion, its device Have that volume is little, noiselessness, pollution-free, movement-less part, the outstanding advantages such as non-maintaining.Development and popularization Freezing by thermoelectric action and thermoelectric generation, for China or even global utilization of energy, economic development and ring Border protection etc. all has important value.With Bi2Te3Compound be the V-VI main group alloy of representative be to study the earliest Thermoelectric material, the room temperature cooling element of current most of commercial all uses this kind of material.
CNT has the microstructure features such as one-dimensional, hollow, nanoscale, has outstanding catalysis, suction The performance such as attached, electricity, mechanics, thermotransport.The composite wood that the nano-particle of CNT cladding assembles Material, is now widely used in the fields such as ultracapacitor, catalysis, chemical sensor, biomedicine.But so far The report in thermoelectric material field it is not used in till the present.
Summary of the invention
The present invention provides a kind of simplicity, the method quickly preparing the thermoelectricity Nano capsule of CNT cladding, With the drawbacks described above overcoming prior art to exist.
The preparation method of the thermoelectricity Nano capsule of CNT of the present invention cladding, uses the synthesis of solvent thermal Technique, comprises the steps:
1) being disperseed in a solvent by the multi-walled carbon nano-tubes after functionalization, pH is at 10-14 in regulation；
2) by the compound dissolution containing Sb or Bi element in solvent；
3) compound containing Se or Te element or Se or Te simple substance are dissolved in solvent；
4) according to Sb2Te3、Sb2Se3、Bi2Te3Or Bi2Se3Bi determined by chemical composition (Sb): Te (Se) For the mol ratio of 2:3, by step 2) mixed liquor and step 3) mixed liquor mix homogeneously；
5) by the multi-walled carbon nano-tubes after described functionalization and Sb2Te3、Sb2Se3、Bi2Te3Or Bi2Se3Matter Amount than be 0.3:1～3:1, by step 4) mixed liquor be progressively added drop-wise to step 1) solution in, in 135-185 DEG C Lower reaction 0.5-2 hour, reaction is collected solid product through post-processing step after terminating, is obtained described carbon after drying The thermoelectricity Nano capsule of nanotube cladding.Described post-processing step includes reactant liquor sample centrifugation, washes Wash away solvent and other by-products.
In the present invention, the described multi-walled carbon nano-tubes after functionalization refers to through oxidizing, purification also After opening its two ends end cap, then the CNT processed through chelating agent functionalization.Processing method can be found in: burnt Will brightness, Zhang Xiaobin, Cheng Jipeng, " preparation of CNT/ZnS composite and performance characterization thereof ", inorganic Material journal, Vol.23, No.3 (2008), the 491-495 page.
The described compound containing Sb or Bi element is the chloride containing Sb or Bi element, sulfate, oxidation Thing, nitrate or carbonate, the preferably chloride containing Sb or Bi element or nitrate.
The described compound containing Se or Te element is the oxide containing Se or Te element, sulfate, chlorination Thing, nitrate, nitrite or carbonate, the preferably oxide containing Se or Te element.
Multi-walled carbon nano-tubes after described functionalization uses ultrasonic mode to disperse in a solvent, and described solvent can To select the Conventional solvents of this area, such as 1,2-PD, 1,3-PD, ethylene glycol, butanediol and sweet Oil etc., preferably ethylene glycol.
The thermoelectricity Nano capsule of the CNT cladding that the inventive method prepares, is that V-VI main group nano-particle enters Enter in the pipe of multi-walled carbon nano-tubes, form this composite of Nano capsule.V-VI main group nano pyroelectric material Be packed in multi-walled carbon nano-tubes the Nano capsule formed, can comprehensively both in microstructure, pattern and heat The advantage of electrical property, becomes the composite thermoelectric material of a kind of excellence.And solvent-thermal process technological process is easy, Reaction is quickly, it is easy to controls, adapts to extensive commercial production.
The thermoelectricity Nano capsule of the CNT cladding of the present invention, synthesis technique is simple, quick, is expected to improve With Bi2Te3For the thermoelectricity capability of V-VI main group thermoelectric material represented, and can be widely applied to energy storage, catalysis, The field such as chemical sensor, biomedicine.
Accompanying drawing explanation
Fig. 1 is the Bi of embodiment 1 CNT cladding2Te3The XRD figure picture of thermoelectricity Nano capsule；
Fig. 2 is the Bi of embodiment 1 CNT cladding2Te3The TEM image of thermoelectricity Nano capsule.
Detailed description of the invention
Provide present pre-ferred embodiments below in conjunction with the accompanying drawings, to describe technical scheme in detail.
Embodiment 1
1) CNT ultrasonic disperse 0.024g functionalization crossed is in ethylene glycol, moves to three necks of 100ml In round-bottomed flask, regulate pH to 12.The functionizing method of CNT is: CNT is placed in dense nitre Acid is heated to 120 DEG C, oxidation, purification, it is washed with deionized to neutrality, goes the removal of impurity, then by carbon Nanotube is ultrasonic disperse 2h in strong aqua ammonia, again washs to neutrality, is placed in the concentrated solution of EDTA super Sound oscillation 2h, completes functionalization and processes.
2) a certain amount of Bi (NO is weighed3)3·5H2O, is dissolved in ethylene glycol, and heats, and makes 10mmol/l Solution.
3) a certain amount of Na is weighed2TeO3, it is dissolved in ethylene glycol, and heats, make the solution of 20mmol/l.
4) according to Bi2Te3The mol ratio of Bi:Te determined by chemical composition is 2:3, by 20.0ml's Bi(NO3)3·5H2The ethylene glycol solution of O and the Na of 15.0ml2TeO3Ethylene glycol solution and mixing, machinery Stir.
5) CNT and Bi are pressed2Te3Mass ratio is 0.3:1, by step 4) mixed liquor progressively be added drop-wise to step Rapid 1) in solution, reaction temperature is 165 DEG C, and the response time is 30min, reaction terminate rear centrifugation, With deionized water, absolute ethanol washing, collection solid product, dry, obtain the Bi of CNT cladding2Te3 Thermoelectricity Nano capsule.
Using the thing phase of X-ray polycrystalline diffractometer assay products, result contains Bi2Te3And CNT (see Fig. 1). Using transmission electron microscopy product morphology, result is to have Bi inside CNT2Te3Nano-particle Enter, form the Bi of CNT cladding2Te3Thermoelectricity Nano capsule (see Fig. 2).
Embodiment 2
1) CNT ultrasonic disperse 0.063g functionalization crossed is in ethylene glycol, moves to three necks of 100ml In round-bottomed flask, regulate pH to 13.The functionizing method of CNT is: CNT is placed in dense nitre Acid is heated to 120 DEG C, oxidation, purification, it is washed with deionized to neutrality, goes the removal of impurity, then by carbon Nanotube is ultrasonic disperse 2h in strong aqua ammonia, again washs to neutrality, is placed in the concentrated solution of EDTA super Sound oscillation 2h, completes functionalization and processes.
2) a certain amount of SbCl is weighed3, it is dissolved in ethylene glycol, and heats, make the solution of 10mmol/l.
3) a certain amount of Na is weighed2TeO3, it is dissolved in ethylene glycol, and heats, make the solution of 20mmol/l.
4) according to Sb2Te3The mol ratio of Sb:Te determined by chemical composition is 2:3, by the SbCl of 20.0ml3 Ethylene glycol solution and the Na of 15.0ml2TeO3Ethylene glycol solution and mixing, mechanical agitation is uniform.
5) CNT and Sb are pressed2Te3Mass ratio is 1:1, by step 4) mixed liquor be progressively added drop-wise to step 1) in solution, reaction temperature is 175 DEG C, and the response time is 1h, and reaction terminates rear centrifugation, spends Ionized water, absolute ethanol washing, collection solid product, dry, and obtains the Sb of CNT cladding2Te3Thermoelectricity Nano capsule.
Using the thing phase of X-ray polycrystalline diffractometer assay products, result contains Sb2Te3And CNT.
Embodiment 3
1) CNT ultrasonic disperse 0.144g functionalization crossed is in ethylene glycol, moves to three necks of 100ml In round-bottomed flask, regulate pH to 14.The functionizing method of CNT is: CNT is placed in dense nitre Acid is heated to 120 DEG C, oxidation, purification, it is washed with deionized to neutrality, goes the removal of impurity, then by carbon Nanotube is ultrasonic disperse 2h in strong aqua ammonia, again washs to neutrality, is placed in the concentrated solution of EDTA super Sound oscillation 2h, completes functionalization and processes.
2) a certain amount of SbCl is weighed3, it is dissolved in ethylene glycol, and heats, make the solution of 10mmol/l.
3) weigh a certain amount of Se powder, be dissolved in ethylene glycol, and heat, make the solution of 20mmol/l.
4) according to Sb2Se3The mol ratio of Sb:Se determined by chemical composition is 2:3, by the SbCl of 20.0ml3 Ethylene glycol solution and the ethylene glycol solution of Se of 15.0ml and mixing, mechanical agitation is uniform.
5) CNT and Sb are pressed2Se3Mass ratio is 3:1, by step 4) mixed liquor be progressively added drop-wise to step 1) in solution, reaction temperature is 185 DEG C, and the response time is 1.5h, and reaction terminates rear centrifugation, use Deionized water, absolute ethanol washing, collection solid product, dry, and obtains the Sb of CNT cladding2Se3Heat Electricity Nano capsule.
Using the thing phase of X-ray polycrystalline diffractometer assay products, result contains Sb2Se3And CNT.
Embodiment 4
1) CNT ultrasonic disperse 0.131g functionalization crossed is in ethylene glycol, moves to three necks of 100ml In round-bottomed flask, regulate pH to 14.The functionizing method of CNT is: CNT is placed in dense nitre Acid is heated to 120 DEG C, oxidation, purification, it is washed with deionized to neutrality, goes the removal of impurity, then by carbon Nanotube is ultrasonic disperse 2h in strong aqua ammonia, again washs to neutrality, is placed in the concentrated solution of EDTA super Sound oscillation 2h, completes functionalization and processes.
2) a certain amount of Bi (NO is weighed3)3·5H2O, is dissolved in ethylene glycol, and heats, and makes 10mmol/l Solution.
3) weigh a certain amount of Se powder, be dissolved in ethylene glycol, and heat, make the solution of 20mmol/l.
4) according to Bi2Se3The mol ratio of Bi:Se determined by chemical composition is 2:3, by 20.0ml's Bi(NO3)3·5H2The ethylene glycol solution of O and the ethylene glycol solution of the Se of 15.0ml and mixing, mechanical agitation is equal Even.
5) CNT and Bi are pressed2Se3Mass ratio is 2:1, by step 4) mixed liquor be progressively added drop-wise to step 1) in solution, reaction temperature is 185 DEG C, and the response time is 2h, and reaction terminates rear centrifugation, spends Ionized water, absolute ethanol washing, collection solid product, dry, and obtains the Sb of CNT cladding2Se3Thermoelectricity Nano capsule.
Using the thing phase of X-ray polycrystalline diffractometer assay products, result contains Bi2Se3And CNT.

Claims (7)

1. the preparation method of the thermoelectricity Nano capsule of a CNT cladding, it is characterised in that include as follows Step:
1) being disperseed in a solvent by the multi-walled carbon nano-tubes after functionalization, pH is at 10-14 in regulation；
2) by the compound dissolution containing Sb or Bi element in solvent；
3) compound containing Se or Te element or Se or Te simple substance are dissolved in solvent；
4) according to Sb2Te3、Sb2Se3、Bi2Te3Or Bi2Se3Bi or Sb:Te determined by chemical composition or Se is the mol ratio of 2:3, by step 2) mixed liquor and step 3) mixed liquor mix homogeneously；
5) by the multi-walled carbon nano-tubes after described functionalization and Sb2Te3、Sb2Se3、Bi2Te3Or Bi2Se3Matter Amount than be 0.3:1～3:1, by step 4) mixed liquor be progressively added drop-wise to step 1) solution in, in 135-185 DEG C Lower reaction 0.5-2 hour, reaction is collected solid product through post-processing step after terminating, is obtained described carbon after drying The thermoelectricity Nano capsule of nanotube cladding.
2. the method for claim 1, it is characterised in that the multi-walled carbon nano-tubes after described functionalization It is through oxidizing, purification and after opening its two ends end cap, then the carbon processed through chelating agent functionalization Nanotube.
3. the method for claim 1, it is characterised in that the described compound containing Sb or Bi element It is the chloride containing Sb or Bi element, sulfate, oxide, nitrate or carbonate.
4. the method for claim 1, it is characterised in that the described compound containing Sb or Bi element It is the chloride containing Sb or Bi element or nitrate.
5. the method for claim 1, it is characterised in that the described compound containing Se or Te element It is the oxide containing Se or Te element, sulfate, chloride, nitrate, nitrite or carbonate.
6. the method for claim 1, it is characterised in that the described compound containing Se or Te element It it is the oxide containing Se or Te element.
7. the method for claim 1, it is characterised in that described solvent is ethylene glycol.
CN201610255544.1A 2016-04-22 2016-04-22 Preparation method for carbon nanotube-coated thermoelectric nanometer capsule Pending CN105944635A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113398904A (en) * 2021-05-06 2021-09-17 桂林电子科技大学 Preparation method and application of catalyst for medium-low temperature photo-thermoelectric synergistic catalytic oxidation of VOCs (volatile organic compounds)
CN114759188A (en) * 2022-06-16 2022-07-15 暨南大学 Potassium ion battery negative electrode material and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113398904A (en) * 2021-05-06 2021-09-17 桂林电子科技大学 Preparation method and application of catalyst for medium-low temperature photo-thermoelectric synergistic catalytic oxidation of VOCs (volatile organic compounds)
CN114759188A (en) * 2022-06-16 2022-07-15 暨南大学 Potassium ion battery negative electrode material and preparation method and application thereof
CN114759188B (en) * 2022-06-16 2022-09-06 暨南大学 Potassium ion battery negative electrode material and preparation method and application thereof

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Application publication date: 20160921