CN110364615A - A kind of graphene oxide/molybdenum disulfide composite thermoelectric material and preparation method thereof - Google Patents
A kind of graphene oxide/molybdenum disulfide composite thermoelectric material and preparation method thereof Download PDFInfo
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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Abstract
The present invention provides a kind of graphene oxide/molybdenum disulfide composite thermoelectric material preparation methods, comprising: S1) graphene oxide, molybdenum disulfide nano sheet are mixed in water, ultrasound obtains mixed system；S2) mixed system is coated on substrate, low temperature drying obtains graphene oxide/molybdenum disulfide composite thermoelectric material；Or filter the mixed system, obtain graphene oxide/molybdenum disulfide composite thermoelectric material.Compared with prior art, the present invention is added in stannic oxide/graphene nano lamella by that will vulcanize rice nanoscale twins, energy filtering effect in the composite thermoelectric material that can be improved, the conductivity of composite material can constantly be maintained and reduce thermal conductivity, and the Seebeck coefficient of composite thermoelectric material is improved, and then increase considerably the ZT value of composite thermoelectric material；And the graphene oxide that the present invention obtains/molybdenum disulfide composite thermoelectric material has adjustable P-N type pyroelecthc properties.
Description
Technical field
The invention belongs to thermoelectric material and device arts more particularly to a kind of graphene oxide/molybdenum disulfide are compound
Thermoelectric material and preparation method thereof.
Background technique
Thermoelectric material is that by the material that thermal energy and electric energy are directly mutually converted, the thermo-electric generation based on thermoelectric material
Device and refrigeration device have the characteristics that noiseless, pollution-free, recoverable discards the energy when compact device structure, operation,
Wide application prospect is suffered from fields such as military affairs, medicine, space flight, microelectronics or even household electrical appliance.Wherein, flexible thermoelectricity material
Material compares commercialized block thermoelectric material, has that flexible, preparation cost is low, simple process, applied widely etc. unique excellent
Gesture has attracted scientific research circle and business circles more and more to pay close attention in recent years.
There is many hydrophilic radicals can be dispersed in water on stannic oxide/graphene nano lamellar structure surface, simultaneously because
In its lamellar structure with a large amount of vacancy position can high degree improve phonon defective bit scattering, to effectively reduce
Its thermal conductivity.Possess higher carrier concentration and carrier mobility by the graphene oxide suitably restored, is suitable for making
Standby flexibility thermoelectric material.But since the electronics of reduced graphene and the mobility in hole are almost the same, lead to its Seebeck coefficient
It is very low.
For the Seebeck coefficient for improving reduced graphene, it can be carried out with conducting polymer or inorganic semiconductor material
It is compound.But so far, the composite thermoelectric material based on reduced graphene is by conducting polymer or inorganic semiconductor and to go back
The block materials of former graphene simple composite composition still remain Sai Beike system there is no being effectively matched for compounding ingredients is realized
The disadvantages of number is lower, and Applicable temperature range is relatively narrow, no flexibility.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of graphene oxide/molybdenum disulfide compound thermal
Electric material and preparation method thereof, this method preparation graphene oxide/molybdenum disulfide have superelevation Seebeck coefficient and
Excellent conductivity and lower thermal coefficient.
The present invention provides a kind of graphene oxide/molybdenum disulfide composite thermoelectric material preparation methods, which is characterized in that
Include:
S1) by graphene oxide, molybdenum disulfide nano sheet, aqueous solution is mixed in water, and ultrasound obtains mixed system；
S2) mixed system is coated on substrate, low temperature drying obtains graphene oxide/molybdenum disulfide compound thermal
Electric material film；
Or filter the mixed system, obtain graphene oxide/molybdenum disulfide composite thermoelectric material.
Preferably, the step S1) specifically:
Graphene oxide water solution is mixed with molybdenum disulfide nano sheet aqueous solution, ultrasound obtains mixed system；
The solid content of the graphene oxide water solution is 5~20mg/ml；
The solid content of the molybdenum disulfide nano sheet aqueous solution is 5~20mg/ml.
Preferably, the graphene oxide water solution is the graphene oxide water solution obtained using modified Hummers method；
The molybdenum disulfide nano sheet aqueous solution is water-soluble to remove the molybdenum disulfide nano sheet that molybdenum disulfide particles obtain using butyl lithium
Liquid.
Preferably, the mass ratio of the graphene oxide and molybdenum disulfide nano sheet is (2~9): (8~1).
Preferably, when the mass ratio of the graphene oxide and molybdenum disulfide nano sheet is less than and is equal to 1, obtained oxidation
Graphene/molybdenum disulfide composite thermoelectric material is p-type thermoelectric material.
Preferably, the crystal phase transition temperature of the p-type thermoelectric material is 323K~343K；In crystal transition point
Seebeck coefficient is 50000~80000 μ V/K.
Preferably, when the mass ratio of the graphene oxide and molybdenum disulfide nano sheet is greater than 1, obtained graphite oxide
Alkene/molybdenum disulfide composite thermoelectric material is N-type thermoelectric material.
Preferably, the crystal phase transition temperature of the N-type thermoelectric material is 323K~343K；In crystal transition point
Seebeck coefficient is -25000~-35000 μ V/K.
Preferably, the time of the ultrasound is 10~30min；Described matrix is flexible substrate.
The present invention also provides a kind of graphene oxide/molybdenum disulfide composite thermoelectric material, by graphene oxide layer with
Molybdenum disulfide nano sheet layer is compound to be obtained.
The present invention provides a kind of graphene oxide/molybdenum disulfide composite thermoelectric material preparation methods, comprising: S1) it will
Graphene oxide, molybdenum disulfide nano sheet mix in water, and ultrasound obtains mixed system；S2) mixed system is coated on
On substrate, low temperature drying obtains graphene oxide/molybdenum disulfide composite thermoelectric material；Or filter the mixed system, it obtains
Graphene oxide/molybdenum disulfide composite thermoelectric material.Compared with prior art, the present invention will be by that will vulcanize the addition of rice nanoscale twins
In stannic oxide/graphene nano lamella, the energy filtering effect in composite thermoelectric material that can be improved, and composite wood can be maintained
The conductivity and reduction thermal conductivity of material, to improve the Seebeck coefficient of composite thermoelectric material, and then make composite thermoelectric material
ZT value increase considerably；And the graphene oxide that the present invention obtains/molybdenum disulfide composite thermoelectric material has adjustable P-N
Type pyroelecthc properties simultaneously should by adjusting content, that is, adjustable composite material P-N characteristic of graphene oxide in composite material
Composite thermoelectric material has good intensity, flexibility and electric conductivity, and thickness is controllable, and shape can be cut out, and preparation method is simple, easily grasps
Make, preparation cost is low, is suitable for thermo-electric generation, solar battery, energy storage, sensing and conducing composite material field.
Experiments have shown that the present invention, which prepares graphene oxide/molybdenum disulfide composite thermoelectric material, is operable with relatively low temperature
Under the conditions of degree (243K~373K).When obtained graphene oxide/molybdenum disulfide composite thermoelectric material be in N-type characteristic when,
Its Seebeck coefficient reachable -30000 μ V/K of peak in the section that temperature is 243K~373K；Seebeck under room temperature
Coefficient is -3000~-9000 μ V/K；Conductivity at room temperature rate is 100~1000S/m；Thermal conductivity is 0.96~1.27W/mK；When made
For standby graphene oxide/molybdenum disulfide composite thermoelectric material when being in p-type characteristic, Seebeck coefficient is 243K in temperature
Peak is up to 72000 μ V/K in the section of~373K；Seebeck coefficient is 1000~5000 μ V/K under room temperature；Room temperature
Conductivity is 1000~3000S/m.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of composite material thermal electric film obtained in the embodiment of the present invention 3；
Fig. 2 is the transmission electron microscope photo of composite material thermal electric film obtained in the embodiment of the present invention 3；
Fig. 3 is the plane thermal conductivity of composite material thermal electric film obtained in the embodiment of the present invention 3 and the relationship song of temperature
Line chart.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of graphene oxide/molybdenum disulfide composite thermoelectric materials, by graphene oxide layer and two
Molybdenum sulfide nanoscale twins are compound to be obtained.
Composite thermoelectric material can be improved by the way that sulfide nanoscale twins are added in stannic oxide/graphene nano lamella in the present invention
In energy filtering effect, and the conductivity of composite material can be maintained and be reduced to thermal conductivity, to improve compound thermoelectricity material
The Seebeck coefficient of material, and then increase considerably the ZT value of composite thermoelectric material.
Wherein, the mass ratio of the graphene oxide layer and molybdenum disulfide nano sheet layer is preferably (2~9): (8~1),
More preferably (1~4): (4~1)；When the mass ratio of graphene oxide and molybdenum disulfide is greater than 1, graphene oxide/bis-
Molybdenum sulfide composite thermoelectric material is N-type thermoelectric material；The crystal phase transition temperature of the N-type thermoelectric material be preferably 323K~
343K；In crystal transition point, highest Seebeck coefficient is preferably -25000~-35000 μ V/K, more preferably -30000 μ V/
K；Room temperature Seebeck coefficient is preferably -3000~-9000 μ V/K；Conductivity at room temperature rate is preferably 100~1000S/m.When oxidation stone
When the mass ratio of black alkene lamella and molybdenum disulfide nano sheet layer is less than and is equal to 1, the graphene oxide/molybdenum disulfide compound thermal
Electric material is p-type thermoelectric material；The crystal phase transition temperature section of the p-type thermoelectric material is preferably 323K~343K；In crystal phase
Highest Seebeck coefficient is preferably 50000~80000 μ V/K when transition point, more preferably 60000~80000 μ V/K, further preferably
For 72 000 μ V/K；Room temperature Seebeck coefficient is preferably 1000~5000 μ V/K；Conductivity at room temperature rate preferably 1000~3000S/m；
Graphene oxide is added in the present invention in composite thermoelectric material, can reduce the thermal conductivity of composite thermoelectric material, relatively
It is thermally conductive in graphene oxide/molybdenum disulfide composite thermoelectric material face for the thermal conductivity (30~40W/mK) of molybdenum disulfide
Rate is only 0.96~1.27W/mK, and lower thermal conductivity can significantly improve the ZT value of composite thermoelectric material, and improves energy and turn
Change efficiency；In addition the effect of the interface of graphene oxide and molybdenum disulfide can be imported by introducing graphene oxide, to change compound thermal
The distribution of forbidden bandwidth (the band gap), interlamellar spacing and internal electron cloud of electric material, to obtain the heat of high Seebeck coefficient
Electric material.
The present invention also provides a kind of preparation methods of above-mentioned graphene oxide/molybdenum disulfide composite thermoelectric material, comprising:
S1) graphene oxide, molybdenum disulfide nano sheet are mixed in water, ultrasound obtains mixed system；S2) by the mixed system
Coated on substrate, obtaining graphene oxide/molybdenum disulfide composite thermoelectric material film；Or filter the mixed system, it obtains
To graphene oxide/molybdenum disulfide composite thermoelectric material.
The present invention is not particularly limited the source of all raw materials, for commercially available or self-control.
Preferably graphene oxide water solution is mixed with molybdenum disulfide nano sheet aqueous solution in the present invention.
The solid content of the graphene oxide water solution is preferably 10~20mg/ml；The graphene oxide water solution is excellent
It is selected as the graphene oxide water solution obtained using modified Hummers method；It is more preferably prepared according to the following steps: in condition of ice bath
Under, graphite, the concentrated sulfuric acid are mixed with sodium nitrate, are then slowly added into KMnO4Reaction, then heats to 30 DEG C~35 DEG C reactions；
It is slowly added deionized water again and reacts and is warming up to 90 DEG C~98 DEG C and is reacted；The deionization that addition temperature is 100 DEG C again
30%H is added after being stirred to react in water2O2Stirring is reacted, and is cooled to room temperature and is centrifuged, and obtaining pH value is 5~7
Graphene oxide water solution.
The solid content of the molybdenum disulfide nano sheet aqueous solution is preferably 10~20mg/ml；The molybdenum disulfide nano sheet
Aqueous solution is preferably to use the obtained molybdenum disulfide nano sheet aqueous solution of butyl lithium removing molybdenum disulfide particles, more preferably according to
Lower step preparation: in nitrogen protection atmosphere, molybdenum disulfide being mixed in n-hexane with butyl lithium, after reaction is stirred at room temperature,
Ultrasound is carried out under condition of ice bath, and deionized water is then added, is centrifuged at a high speed, then reaction product is carried out with deionized water
Dialysis, obtains molybdenum disulfide nano sheet aqueous solution；The partial size of the molybdenum disulfide is preferably 200~500 mesh.
After mixing, ultrasonic disperse obtains mixed system；The power of the ultrasound is preferably 100~300W, more preferably
100~200W；The time of the ultrasound is preferably 10~30min；The ultrasound preferably carries out at room temperature.
The mixed system is coated on substrate；The substrate is preferably flexible parent metal, more preferably plastic film, knit
Object or paper；Then the substrate is coated with mixed system preferably after surface hydrophilic is handled.
After on substrate, after preferably volatilization removes moisture naturally at room temperature, graphene oxide/curing is obtained
Molybdenum composite thermoelectric material film；After also preferably volatilization removes moisture naturally at room temperature, it is freeze-dried, thoroughly to move
Moisture removal obtains graphene oxide/molybdenum disulfide composite thermoelectric material film；The graphene oxide/molybdenum disulfide compound thermal
The thickness of electric material film is preferably 1~10 micron, and more preferably 1~6 micron, be further preferably 1~4 micron, most preferably 1~
2 microns；The temperature of the freeze-drying is preferably -30 DEG C~-40 DEG C；The time of the freeze-drying is preferably 36~72 small
When.
In the present invention, also directly the mixed system can be filtered, obtains the compound thermoelectricity of graphene oxide/molybdenum disulfide
Material；The method of the filtering is preferably filtered by vacuum.Also preferably after filtering, it is freeze-dried, thoroughly to remove moisture,
Obtain graphene oxide/molybdenum disulfide composite thermoelectric material；It is freeze-dried, is aoxidized again after also preferable directly freezed
Graphene/molybdenum disulfide composite thermoelectric material, the composite material obtained at this time have porous structure, can carry out compressing tablet process；Pressure
The thickness of the material obtained after piece processing is preferably 0.1~10mm, and more preferably 0.5~5mm is further preferably 1~2mm；It is described
The temperature of freeze-drying is preferably -30 DEG C~-40 DEG C；The time of the freeze-drying is preferably 36~72 hours.
The present invention is added in stannic oxide/graphene nano lamella by that will vulcanize rice nanoscale twins, the compound thermal that can be improved
Energy filtering effect in electric material can constantly maintain the conductivity of composite material and reduce thermal conductivity, and improve compound
The Seebeck coefficient of thermoelectric material, and then increase considerably the ZT value of composite thermoelectric material；And the oxidation that the present invention obtains
Graphene/molybdenum disulfide composite thermoelectric material has adjustable P-N type pyroelecthc properties, by adjusting graphite oxide in composite material
Content, that is, adjustable composite material P-N characteristic of alkene, while the composite thermoelectric material has good intensity, flexibility and conduction
Property, thickness is controllable, and shape can be cut out, and preparation method is simple, and easy to operate, preparation cost is low, is suitable for thermo-electric generation, solar-electricity
Pond, energy storage, sensing and conducing composite material field.
In order to further illustrate the present invention, with reference to embodiments to a kind of graphene oxide/bis- sulphur provided by the invention
Change molybdenum composite thermoelectric material and preparation method thereof to be described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
The preparation of graphene oxide: under ice bath, 5g is added to 130mL concentration having a size of the graphite powder of 300 mesh and is greater than
It is stirred evenly in 98% concentrated sulfuric acid, to be added after 2.5g sodium nitrate, is then slowly added to potassium permanganate under mechanical stirring
15g is warming up to 30 DEG C after continuing mixing time 2 hours, continues stirring 0.5 hour.Then it is slowly added dropwise into 230ml deionization
Water stirs 0.5 hour.95 DEG C are warming up to, the deionized water that 350ml temperature is 100 DEG C is added, is stirred 10 minutes.Dropwise addition 5~
The H of 2mL concentration 30%2O2, stir 20 minutes.It is cooled to room temperature to temperature and resulting brown solution is subjected to high speed centrifugation point
From to remove the impurity such as remaining metal salt, to obtain the yellowish-brown graphene oxide that pH value is 5-7 after being repeatedly centrifugated
Dispersion liquid, wherein the solid content of graphene oxide is 5~20%.
Embodiment 2
Nano-lamellar structure MoS2Preparation: take be added MoS of the 1g having a size of 300~500 mesh2It is placed in the glass with rubber plug
In reactor, it is passed through nitrogen in the reactor then to exclude the air in reactor.It keeps delaying in the case that reactor is closed
It is slow that n-BuLi/hexane solution that 10ml molar concentration is 1.6mol/L is added.It is obtained after reaction being stirred at room temperature 2 days
LixMoS2Intermediate；Then reaction system is placed in ultrasound 1 hour in ice bath, is slow added into 20ml deionized water later；It will
Solution after reaction is centrifuged at a high speed, to remove n-hexane and other impurities；Reaction product is finally placed in dialysis
In bag, required molybdenum disulfide nano sheet aqueous solution, MoS in final product were obtained later using deionized water dialysis 2 days2's
Solid content is 5~20%.
Embodiment 3
It pipettes graphene oxide solution obtained in embodiment 1 (preferably solid content is 10mg/ml) 10ml and is placed in 100ml's
In beaker, MoS obtained in embodiment 2 is then added2Solution (solid content 10mg/ml) 2.5ml, wherein graphene oxide and
MoS2Mass ratio be 4:1.Ultrasonic (ultrasonic power 100W) is handled 10 minutes under room temperature, makes graphene oxide and MoS2
Nanoscale twins be uniformly mixed.Then resulting mixed solution is uniformly applied on aramid paper by (setting painting film thickness using film applicator
Degree is 80 microns), vaporing away under room temperature environment can be obtained required composite material thermal electric film after moisture, and film thickness is about
It is 1 micron.Prepared composite material film is placed in the refrigerator that temperature is 4 degrees Celsius and stores.
Composite material thermal electric film obtained in embodiment 3 is tested using four probe method, obtains its conductivity about
For 135S/m.
Using thermoelectricity test equipment (TEP 600, Seepel instrument) to composite material obtained in embodiment 3
Thermal electric film is tested, and obtaining its room temperature Seebeck coefficient is -3410 μ V/K.
Composite material thermal electric film obtained in embodiment 3 is carried out using alternating temperature X diffraction and differential scanning calorimetry
Test (Range of measuring temp is -30 DEG C~100 DEG C), obtains the crystal phase transition temperature section of molybdenum disulfide in composite system
About 323~343K；The Seebeck coefficient of composite material hot spot film is -29000 μ V/K when crystal orientation transition point.
Composite material thermal electric film obtained in embodiment 3 is detected using scanning electron microscope, it is obtained and sweeps
It is as shown in Figure 1 to retouch electromicroscopic photograph.By Fig. 1 it can be seen that graphene oxide and MoS2The configuration of surface of composite material film.
Composite material thermal electric film obtained in embodiment 3 is detected using transmission electron microscope, obtains it thoroughly
Electromicroscopic photograph is penetrated, as shown in Figure 2.By Fig. 2 it can be seen that graphene oxide and MoS2Composite material lamella structure.
Composite material thermal electric film obtained in embodiment 3 is detected using Hot Disk thermal constant analyzer, is obtained
To the relation curve of its plane thermal conductivity and temperature, as shown in Figure 3.By Fig. 3 it can be seen that graphene oxide and MoS2Composite material
Plane thermal conductivity be 0.96~1.27W/mK.
Embodiment 4
It pipettes graphene oxide solution obtained in embodiment 1 (preferably solid content is 10mg/ml) 10ml and is placed in 100ml's
In beaker, MoS obtained in embodiment 2 is then added2Solution (solid content 10mg/ml) 40ml, wherein graphene oxide and
MoS2Mass ratio be 1:4.Ultrasonic (ultrasonic power 100W) is handled 10 minutes under room temperature, makes graphene oxide and MoS2
Nanoscale twins be uniformly mixed.Then use film applicator resulting mixed solution is uniformly applied on aramid paper (coating thickness for
80 microns), vaporing away under room temperature environment can be obtained required composite material thermal electric film after moisture, and film thickness is about 2
Micron.
Composite material thermal electric film obtained in embodiment 4 is tested using four probe method, obtaining its conductivity is
About 1800S/m.
Using thermoelectricity test equipment (TEP.600, Seepel instrument) to composite material obtained in embodiment 4
Thermal electric film is tested, and obtaining its room temperature Seebeck coefficient is 1596 μ V/K.
Composite material thermal electric film obtained in embodiment 3 is carried out using alternating temperature X diffraction and differential scanning calorimetry
Test, the crystal phase transition temperature section for obtaining molybdenum disulfide in composite system is about 323~343K；It is answered when crystal orientation transition point
The Seebeck coefficient of condensation material hot spot film is 71957 μ V/K.
Embodiment 5
It pipettes graphene oxide solution obtained in embodiment 1 (preferably solid content is 10mg/ml) 10ml and is placed in 100ml's
In beaker, MoS obtained in embodiment 2 is then added2Solution (solid content 10mg/ml) 10ml, wherein graphene oxide and
MoS2Mass ratio be 1:1.Ultrasonic (ultrasonic power 100W) is handled 10 minutes under room temperature, makes graphene oxide and MoS2
Nanoscale twins be uniformly mixed.Then use film applicator resulting mixed solution is uniformly applied on aramid paper (coating thickness for
80 microns), vaporing away under room temperature environment can be obtained required composite material thermal electric film after moisture, and film thickness is about 1
Micron.
Composite material thermal electric film obtained in embodiment 5 is tested using four probe method, obtains its conductivity about
For 1620S/m.
Using thermoelectricity test equipment (TEP.600, Seepel instrument) to composite material obtained in embodiment 5
Thermal electric film is tested, and obtaining its room temperature Seebeck coefficient is 2384 μ V/K.
Composite material thermal electric film obtained in embodiment 5 is carried out using alternating temperature X diffraction and differential scanning calorimetry
Test, the crystal phase transition temperature section for obtaining molybdenum disulfide in composite system is about 323~343K；It is answered when crystal orientation transition point
The Seebeck coefficient of condensation material thermal electric film is about 55442 μ V/K.
Embodiment 6
It pipettes graphene oxide solution obtained in embodiment 1 (preferably solid content is 10mg/ml) 10ml and is placed in 100ml's
In beaker, MoS obtained in embodiment 2 is then added2Solution (solid content 10mg/ml) 10ml, wherein graphene oxide and
MoS2Mass ratio be 1:1.Ultrasonic (ultrasonic power 100W) is handled 10 minutes under room temperature, makes graphene oxide and MoS2
Nanoscale twins be uniformly mixed.Then it is freezed 12 hours in the refrigerator for being -10 degrees Celsius as temperature by above-mentioned mixed solution, it
Graphene oxide/molybdenum disulfide/water compound system for having freezed will be changed afterwards as carrying out vacuum refrigeration in freeze drier
Dry, freeze-drying temperature is -30 DEG C, and drying time is 48 hours.Obtain p-type graphene oxide/bis- with porous structure
Molybdenum sulfide composite thermoelectric material.
By p-type graphene oxide/molybdenum disulfide composite thermoelectric material 100mg with porous structure in embodiment 6 into
Row Mechanical pressing (preferably pressure is 10 tons), obtains the composite sheet that thickness is about 1mm.
Composite material thermal electric film obtained in embodiment 6 is tested using four probe method, obtains its conductivity about
For 1780S/m.
Using thermoelectricity test equipment (TEP.600, Seepel instrument) to composite material obtained in embodiment 6
It is tested, obtaining its room temperature Seebeck coefficient is 2384 μ V/K.
Claims (10)
1. a kind of graphene oxide/molybdenum disulfide composite thermoelectric material preparation method characterized by comprising
S1) by graphene oxide, molybdenum disulfide nano sheet, aqueous solution is mixed in water, and ultrasound obtains mixed system；
S2) mixed system is coated on substrate, low temperature drying obtains the compound thermoelectricity material of graphene oxide/molybdenum disulfide
Expect film；
Or filter the mixed system, obtain graphene oxide/molybdenum disulfide composite thermoelectric material.
2. preparation method according to claim 1, which is characterized in that the step S1) specifically:
Graphene oxide water solution is mixed with molybdenum disulfide nano sheet aqueous solution, ultrasound obtains mixed system；
The solid content of the graphene oxide water solution is 5~20mg/ml；
The solid content of the molybdenum disulfide nano sheet aqueous solution is 5~20mg/ml.
3. preparation method according to claim 2, which is characterized in that the graphene oxide water solution is using modification
The graphene oxide water solution that Hummers method obtains；The molybdenum disulfide nano sheet aqueous solution is to remove two sulphur using butyl lithium
Change the molybdenum disulfide nano sheet aqueous solution that molybdenum particle obtains.
4. preparation method according to claim 1, which is characterized in that the graphene oxide and molybdenum disulfide nano sheet
Mass ratio is (2~9): (8~1).
5. the preparation method according to claim 4, which is characterized in that the graphene oxide and molybdenum disulfide nano sheet
When mass ratio is less than and is equal to 1, obtained graphene oxide/molybdenum disulfide composite thermoelectric material is p-type thermoelectric material.
6. preparation method according to claim 5, which is characterized in that the crystal phase transition temperature of the p-type thermoelectric material is
The K of 323 K~343；In crystal transition point, Seebeck coefficient is 50000~80000 μ V/K.
7. the preparation method according to claim 4, which is characterized in that the graphene oxide and molybdenum disulfide nano sheet
When mass ratio is greater than 1, obtained graphene oxide/molybdenum disulfide composite thermoelectric material is N-type thermoelectric material.
8. preparation method according to claim 7, which is characterized in that the crystal phase transition temperature of the N-type thermoelectric material is
The K of 323 K~343；In crystal transition point, Seebeck coefficient is -25000~-35000 μ V/K.
9. preparation method according to claim 1, which is characterized in that the time of the ultrasound is 10~30min；The base
Body is flexible substrate.
10. a kind of graphene oxide/molybdenum disulfide composite thermoelectric material, which is characterized in that by graphene oxide layer and two sulphur
Change that molybdenum nanoscale twins are compound obtains.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200533A (en) * | 2021-05-07 | 2021-08-03 | 南开大学 | Preparation method of high-performance graphene/bismuth telluride microwave absorption composite material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142551A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene nano sheet/MoS2 composite nano material and synthesis method thereof |
| CN102796590A (en) * | 2012-08-24 | 2012-11-28 | 江苏大学 | Preparation method for tubular graphene/MoS2 nanocomposite material |
| CN104137282A (en) * | 2011-12-30 | 2014-11-05 | 三星电子株式会社 | Heterogeneous laminate including graphene, and thermoelectric material, thermoelectric module, and thermoelectric apparatus including the heterogeneous laminate |
| US20140373891A1 (en) * | 2013-06-24 | 2014-12-25 | Samsung Electronics Co., Ltd. | Thermoelectric structure, and thermoelectric device and thermoelectric apparatus including the same |
| CN104733604A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院上海硅酸盐研究所 | Composite thermoelectric material and preparing method thereof |
| CN105591088A (en) * | 2016-03-22 | 2016-05-18 | 北京科技大学 | Lithium ion battery cathode material and preparing method thereof |
| US20180323359A1 (en) * | 2015-05-26 | 2018-11-08 | George Mason University | Mechanical and thermal electric generators |
| CN109411592A (en) * | 2016-11-11 | 2019-03-01 | 优材科技有限公司 | Thermoelectric material structure |
-
2019
- 2019-07-18 CN CN201910650272.9A patent/CN110364615B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142551A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene nano sheet/MoS2 composite nano material and synthesis method thereof |
| CN104137282A (en) * | 2011-12-30 | 2014-11-05 | 三星电子株式会社 | Heterogeneous laminate including graphene, and thermoelectric material, thermoelectric module, and thermoelectric apparatus including the heterogeneous laminate |
| CN102796590A (en) * | 2012-08-24 | 2012-11-28 | 江苏大学 | Preparation method for tubular graphene/MoS2 nanocomposite material |
| US20140373891A1 (en) * | 2013-06-24 | 2014-12-25 | Samsung Electronics Co., Ltd. | Thermoelectric structure, and thermoelectric device and thermoelectric apparatus including the same |
| CN104733604A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院上海硅酸盐研究所 | Composite thermoelectric material and preparing method thereof |
| US20180323359A1 (en) * | 2015-05-26 | 2018-11-08 | George Mason University | Mechanical and thermal electric generators |
| CN105591088A (en) * | 2016-03-22 | 2016-05-18 | 北京科技大学 | Lithium ion battery cathode material and preparing method thereof |
| CN109411592A (en) * | 2016-11-11 | 2019-03-01 | 优材科技有限公司 | Thermoelectric material structure |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200533A (en) * | 2021-05-07 | 2021-08-03 | 南开大学 | Preparation method of high-performance graphene/bismuth telluride microwave absorption composite material |
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