CN106159076A - A kind of Cu2-Xthe preparation method of Se/ graphene composite material - Google Patents
A kind of Cu2-Xthe preparation method of Se/ graphene composite material Download PDFInfo
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Abstract
The invention discloses a kind of Cu2-xThe preparation method of Se/ graphene composite material, uses Low Temperature Wet chemical method two step to prepare Cu2-xThe composite of Se/ Graphene, described Cu2-xIn Se/ graphene composite material, x is selected from 0～0.1；This material is by Cu2-xSe granule and Graphene are composited, Cu2-xSe distribution of particles is partly wrapped in wherein at graphenic surface or by Graphene.The preparation technology that the present invention relates to is simple, energy consumption is low, cost is little, manufacturing cycle is short, be applicable to industrial mass production；The Cu prepared2-xSe/ graphene composite material has higher electrical conductivity, has important application prospect in thermoelectric material field.
Description
Technical field
The present invention relates to thermoelectric material preparation field, be specifically related to a kind of Cu2-xThe preparation method of Se/ graphene composite material.
Background technology
Thermoelectric generation technology is a kind of Sai Beike (Seebeck) effect utilizing semi-conducting material and Peltier (Peltier) effect
Realizing the technology directly changed between heat energy and electric energy, its application mainly includes thermoelectric power generation and thermoelectric cooling two kinds.Thermoelectricity turns
The working media changing technology is the carrier of movement, for traditional heat engine, have simple in construction, without drive disk assembly,
Reliability is high, manufacturing process is simple, pollution-free and the feature such as noiselessness, navigates in aviation as particular power source and precision temperature controlling device
It high-technology field such as space technology and military equipment has been obtained for application.At civilian aspect, due to the efficiency of thermoelectric power generation
Being limited this technology by pyroelectric material performance to be not carried out extensively applying in terms of thermoelectric power generation, main application is heat
Electroluminescent cold, such as the bismuth telluride based alloys (Bi synthesized with zone-melting process2Te3) it is the Portable thermal electric refrigerator etc. of core component.Therefore make
For a kind of novel, environmental harmony type clean energy resource switch technology, thermo-electric device is expected to be widely used in a large amount of and disperse the low of existence
The thermoelectric power generation of density heat energy, provides an important channel for alleviating energy crisis with solving problem of environmental pollution.
Commercialization thermoelectric material Bi2Te3With the thermoelectric figure of merit ZT of PbTe about 1, owing to the ZT value of these materials is the highest,
Contain a large amount of rare element Te simultaneously, therefore the few Te of research and development or the high performance thermoelectric material without Te seem particularly urgent and
Important.Cu2-xSe thermoelectric material is higher without the rare elements such as Te, abundance, lower cost for material and environmentally safe, and
Cu2-xOn the one hand Se compound has the crystal structure of complexity, at high temperature due to Cu+Fluid-like state behavior cause shear wave resistance
Buddhist nun's effect, therefore it has relatively low thermal conductivity, and on the other hand, material list reveals higher Seebeck coefficient so that Cu2-xSe
Compound is likely to become preferable thermoelectric material.This research is intended employing and is carried out the compound electrical conductivity improving material with Graphene, excellent
Heat-transformation electrical property.
Prepare Cu at present2-xThe method of Se thermoelectric material is mainly high-temperature melting method or solid reaction process, and manufacturing cycle is long, and
Need to react under the high temperature conditions, power consumption height；Needed raw material is high-purity powder, and cost is of a relatively high；Additionally, Physical synthesis
Composite is usually and uses multistep machinery to be combined and realize, and has process complicated, biphase between disperse the problems such as uneven.
Summary of the invention
It is an object of the invention to provide a kind of Cu2-xThe preparation method of the composite of Se/ Graphene, the method preparation technology is simple,
Low cost, energy consumption are low, be applicable to large-scale production.
For achieving the above object, the technical solution used in the present invention is: a kind of Cu2-xThe preparation method of Se/ graphene composite material,
Comprise the following steps:
1) by graphene oxide ultrasonic disperse in water, graphene oxide solution is obtained；
2), after addition coordination compound in Cu source stirring, mixed liquor I is obtained；Se source is added in alkaline conditioner and stirs,
Obtain mixed liquor I I；Mixed liquor I and II are mixed, then heat to 90～110 DEG C, be added dropwise over hydrazine hydrate, react 4～10h,
Cool down and carry out centrifugation, be dried, obtain Cu2-xSe powder；
3) by step 2) Cu that obtains2-xSe powder is placed in polyelectrolyte, after ultrasonic disperse 20～60min, carries out sucking filtration,
Obtain Cu2-xSe charged powder；
4) by step 3) gained Cu2-xSe charged powder adds graphene oxide water solution and carries out ultrasonic disperse, is warming up to 20～60 DEG C,
It is added dropwise over hydrazine hydrate, after insulation 20～60min, cools down and carry out centrifugation, be dried, obtain described Cu2-xSe/ Graphene is multiple
Condensation material.
According to such scheme, the concentration of described graphene oxide solution is 0.2～0.5g/L.
According to such scheme, step 2) described in Cu source be elemental copper, or containing bivalent cupric ion or the nitric acid of monovalence cuprous ion
Salt, sulfate or chloride, in Cu source, Cu element is (6～62) with the mass ratio of graphene oxide: 1.
According to such scheme, step 2) described in coordination compound be ammonia, coordination compound with the volume ratio of graphene oxide solution is
(0.4～0.6): 1.
According to such scheme, step 2) described in Se source be elemental selenium, selenium dioxide, Monohydrated selenium dioxide or sodium thiosulfate, Se
In source, Se element is 1:2 with the mol ratio of Cu element in Cu source.
According to such scheme, step 2) described in alkaline conditioner be sodium hydroxide solution or potassium hydroxide solution, or both
Mix by any proportioning, OH in alkaline conditioner-Concentration be 0.4～0.6mol/L, alkaline conditioner and graphene oxide solution
Volume ratio is (0.8～1): 1.
According to such scheme, described cationic polyelectrolyte is PDDA, polyelectrolyte and oxidation stone
The volume ratio of ink alkene solution is (0.8～1.2): 1.
According to such scheme, described hydrazine hydrate is (0.07～0.32): 1g/ml with the solid-to-liquid ratio of Cu element in Cu source；Step 4) in
Hydrazine hydrate is 1:(15～20 with the solid-to-liquid ratio of graphene oxide) g/ml.
According to such scheme, described graphene oxide is by NaNO3, potassium permanganate and high purity graphite powder be with (0.3～0.7): (3～4): 1
Mass ratio, uses modified Hummers method to be prepared from, and specifically includes following steps:
1) the low-temp reaction stage, NaNO is weighed respectively by proportioning3, potassium permanganate and graphite powder, in dry reaction vessel
Add in the concentrated sulphuric acid of 98wt%, be then cooled to 0～2 DEG C, add graphite powder and NaNO under agitation3, graphite powder with
The solid-to-liquid ratio of the concentrated sulphuric acid of 98wt% is 1:(22～24) g/ml, after stirring, it is slowly added to potassium permanganate, controls reaction temperature
It is 0～5 DEG C, stirs 1.5～2h；
2) the middle temperature stage of reaction, by step 1) solution that obtains is placed in the water bath with thermostatic control of 32～40 DEG C, stirs 30～40min；
3) the pyroreaction stage, to by step 2) solution that obtains is slowly added to 50～60 DEG C of warm water and mass concentration is 30%
Hydrogen peroxide, wherein the solid-to-liquid ratio of graphite powder and 50～60 DEG C of warm water is 1:(40～50) g/ml, the solid-to-liquid ratio of graphite powder and hydrogen peroxide
For 1:(4～6) g/ml, terminates reaction after stirring 15～30min.Products therefrom dilute hydrochloric acid and deionized water wash are to through BaCl2
Solution detects without SO4 2-, lyophilization, obtain described graphene oxide.
According to such scheme, prepared Cu2-xSe/ graphene composite material is by Cu2-xSe granule and Graphene are composited, Cu2-xSe
Distribution of particles is partly wrapped in wherein at graphenic surface or by Graphene；Described Cu2-xIn Se granule, x is selected from 0～0.1.
Compared with prior art, the invention have the benefit that
1) this method uses Low Temperature Wet chemical method two step to prepare Cu2-xSe/ graphene composite material, the technique related to is simple, power consumption
Low, cost is little, manufacturing cycle is short, be applicable to industrial mass production.
2) present invention produces positive charge, with Cu after using polyelectrolyte ionization2-xSe granule combine so that it is surface with positive electricity,
And graphene oxide ionize in water after with negative electricity, both combine to obtain described Cu by electrostatic interaction2-xSe/ graphene composite material.
3) due to the peptizaiton of Graphene, Cu in the composite obtained2-xSe granule is dispersed in graphenic surface or by graphite
Alkene is partly wrapped in wherein, makes composite material exhibits go out higher electrical conductivity.For the material of different Cu content, Graphene
To reduce its electrical conductivity.This composite has important application prospect in thermoelectric material field.
Accompanying drawing explanation
The invention will be further described below in conjunction with the accompanying drawings, in accompanying drawing:
Fig. 1 is the Cu that embodiment 1 prepares2-xThe X ray diffracting spectrum of Se/ graphene composite material.
Fig. 2 is the Cu that embodiment 1 prepares2-xThe field emission scanning electron microscope picture of Se/ graphene composite material.
Fig. 3 is the Cu that embodiment 2 prepares2-xThe X ray diffracting spectrum of Se/ graphene composite material.
Fig. 4 is the Cu that embodiment 2 prepares2-xThe field emission scanning electron microscope picture of Se/ graphene composite material.
Fig. 5 is the Cu that embodiment 3 prepares2-xThe X ray diffracting spectrum of Se/ graphene composite material.
Fig. 6 is the Cu that embodiment 3 prepares2-xThe field emission scanning electron microscope picture of Se/ graphene composite material.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, to this
Bright it is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
In following example, as no specific instructions, the reagent of employing is commercially available chemical reagent.
Embodiment 1
A kind of Cu2-xThe preparation method of Se/ graphene composite material, graphene oxide and Cu in preparation process2-xThe mass ratio of Se is about
For 1%:1, comprise the following steps:
1) modified Hummers method is used to prepare graphene oxide (GO), by NaNO3, potassium permanganate and graphite powder be 0.3:3:
The mass ratio of 1 weighs each raw material, adds in the concentrated sulphuric acid of 98wt%, be then cooled to 0～2 DEG C in dry reaction vessel,
Graphite powder and NaNO is added under stirring condition3, graphite powder is 1:22g/ml with the solid-to-liquid ratio of the concentrated sulphuric acid of 98wt%, stirs
After, it is slowly added to potassium permanganate, controlling reaction temperature is 0～5 DEG C, stirs 1.5h；The solution obtained is placed in the constant temperature of 35 DEG C
In water-bath, stir 30min；In solution, it is slowly added to 50 DEG C of warm water and mass concentration is the hydrogen peroxide of 30%, stir 15min,
Wherein the solid-to-liquid ratio of graphite powder and 50～60 DEG C of warm water is 1:40g/ml, and graphite powder is 1:4g/ml with the solid-to-liquid ratio of hydrogen peroxide.Reaction
After end, products therefrom dilute hydrochloric acid and deionized water wash are to through BaCl2Solution detects without SO4 2-, lyophilization, obtain described
Graphene oxide (GO).
2) by dried graphene oxide ultrasonic disperse in water, it is configured to the GO aqueous solution that concentration is 0.5g/L.
3) weighing 20ml ammonia, 2.4022g CuCl, stir to obtain mixed solution.
4) weigh 0.8g NaOH, be placed in 50ml deionized water and stir to obtain NaOH solution, 0.9580g Se powder is added NaOH
In solution, with step 3 after stirring) gained mixed solution mixes, and then seal and be placed in oil bath pan, be heated to 90 DEG C,
It is added dropwise over 10ml reducing agent hydrazine hydrate, is incubated 4h, naturally cools to room temperature, centrifugal, freezing with deionized water cyclic washing
It is dried, obtains described Cu2-xSe powder.
5) 50ml cationic polyelectrolyte is weighed in beaker, the Cu that will obtain2-xSe powder is placed in polyelectrolyte, ultrasonic
Sucking filtration after 30min.
6) by step 5) to join 50ml graphene oxide water solution ultrasonic for gained powder body, is warming up to 20 DEG C, instills 0.5ml
Hydrazine hydrate, after insulation 60min, cools down and carries out centrifugation, is dried, obtain described Cu2-xSe/ graphene composite powder.
X ray diffracting spectrum and the field emission scanning electron microscope picture of products therefrom are respectively Fig. 1 and Fig. 2, institute as seen from the figure
Obtaining product is Cu2-xSe/ graphene composite material (x=0.1), Cu2-xSe distribution of particles is at graphenic surface or by Graphene half bag
It is rolled in wherein.The wherein all corresponding Cu in all of peak in XRD figure spectrum2-xThe characteristic peak of Se, because the peak value of pure Graphene itself is very
Weak, Cu good with degree of crystallinity2-xSe contrast has a long way to go, and the content of Graphene is limited, thus cannot see in XRD
Measure the characteristic peak of Graphene.The Cu that the present embodiment is prepared2-xSe/ graphene composite material carries out conducting performance test, its room temperature
Electrical conductivity is 9 × 104S/m。
Embodiment 2
A kind of Cu2-xThe preparation method of Se/ graphene composite material, graphene oxide and Cu in preparation process2-xThe mass ratio of Se is about
For 4%:1, comprise the following steps:
1) modified Hummers method is used to prepare graphene oxide (GO), by NaNO3, potassium permanganate and graphite powder be 0.5:
The mass ratio of 3.5:1 weighs each raw material, adds in the concentrated sulphuric acid of 98wt%, be then cooled to 0～2 DEG C in dry reaction vessel,
Add graphite powder and NaNO under agitation3, graphite powder is 1:22g/ml with the solid-to-liquid ratio of the concentrated sulphuric acid of 98wt%, and stirring is all
After even, being slowly added to potassium permanganate, controlling reaction temperature is 0～5 DEG C, stirs 1.5h；The solution obtained is placed in the perseverance of 35 DEG C
In tepidarium, stir 30min；In solution, it is slowly added to 50 DEG C of warm water and mass concentration is the hydrogen peroxide of 30%, stir 15min,
Wherein the solid-to-liquid ratio of graphite powder and 50～60 DEG C of warm water is 1:50g/ml, and graphite powder is 1:4g/ml with the solid-to-liquid ratio of hydrogen peroxide.Reaction
After end, products therefrom dilute hydrochloric acid and deionized water wash are to through BaCl2Solution detects without SO4 2-, lyophilization, obtain described
Graphene oxide (GO).
2) by dried graphene oxide ultrasonic disperse in water, compound concentration is the GO aqueous solution of 0.2g/L.
3) 25ml ammonia, 0.6058g CuSO are weighed4·5H2O, stir to obtain mixed solution.
4) weigh 0.96g NaOH, be placed in 40ml deionized water and stir to obtain NaOH solution, by 0.1346g SeO2Powder adds
In NaOH solution, with step 3 after stirring) gained mixed solution mixes, and then seal and be placed in oil bath pan, heat temperature raising
To 100 DEG C, be added dropwise over 2ml reducing agent hydrazine hydrate, be incubated 4h, naturally cool to room temperature, with deionized water cyclic washing from
The heart, lyophilization, obtain described Cu2-xSe。
5) 40ml cationic polyelectrolyte is weighed in beaker, by Cu2-xSe is placed in polyelectrolyte, takes out after ultrasonic 30min
Filter
6) by step 5) to join 50ml graphene oxide water solution ultrasonic for gained powder body, is warming up to 60 DEG C, instills 0.2ml
Hydrazine hydrate, after insulation 20min, cools down and carries out centrifugation, is dried, obtain described Cu2-xSe/ graphene composite powder.
X ray diffracting spectrum and the field emission scanning electron microscope picture of products therefrom are respectively Fig. 3 and Fig. 4, institute as seen from the figure
Obtaining product is Cu2-xSe/ graphene composite material (x=0.05), wherein Cu2-xSe distribution of particles is at graphenic surface or by Graphene
Partly it is wrapped in wherein.The wherein all corresponding Cu in all of peak in XRD figure spectrum2-xThe characteristic peak of Se, because the peak value of pure Graphene is originally
Body is the most weak, Cu good with degree of crystallinity2-xSe contrast has a long way to go, and the content of Graphene is limited, thus in XRD nothing
Method observes the characteristic peak of Graphene.The Cu that the present embodiment is prepared2-xSe/ graphene composite material carries out conducting performance test, its
Room-temperature conductivity is 7 × 104S/m。
Embodiment 3
A kind of Cu2-xThe preparation method of Se/ graphene composite material, graphene oxide and Cu in preparation process2-xThe mass ratio of Se is about
For 5%:1, comprise the following steps:
1) modified Hummers method is used to prepare graphene oxide (GO), by NaNO3, potassium permanganate and graphite powder be 0.7:4:
The mass ratio of 1 weighs each raw material, adds in the concentrated sulphuric acid of 98wt%, be then cooled to 0～2 DEG C in dry reaction vessel,
Graphite powder and NaNO is added under stirring condition3, graphite powder is 1:24g/ml with the solid-to-liquid ratio of the concentrated sulphuric acid of 98wt%, stirs
After, it is slowly added to potassium permanganate, controlling reaction temperature is 0～5 DEG C, stirs 2h；The solution obtained is placed in the thermostatted water of 40 DEG C
In bath, stir 40min；In solution, it is slowly added to 60 DEG C of warm water and mass concentration is the hydrogen peroxide of 30%, stir 30min,
Wherein the solid-to-liquid ratio of graphite powder and 50～60 DEG C of warm water is 1:40g/ml, and graphite powder is 1:6g/ml with the solid-to-liquid ratio of hydrogen peroxide.Reaction
After end, products therefrom dilute hydrochloric acid and deionized water wash are to through BaCl2Solution detects without SO4 2-, lyophilization, obtain described
Graphene oxide (GO).
2) by dried graphene oxide ultrasonic disperse in water, it is configured to the GO aqueous solution that concentration is 0.5g/L.
3) 0.8273g CuCl is weighed2·2H2O, 30ml ammonia, stir to obtain mixed solution.
4) weigh 0.96g NaOH, be placed in 40ml deionized water stirring and form solution, by 0.3129g H2SeO3It is placed in above-mentioned
In NaOH solution, with step 2 after stirring) gained mixed solution mixes, and then seal and be placed in oil bath pan, heat temperature raising
To 110 DEG C, it is added dropwise over 3ml reducing agent hydrazine hydrate insulation 10h, naturally cools to room temperature, centrifugal with deionized water cyclic washing,
Lyophilization, obtains described Cu2-xSe。
5) 60ml cationic polyelectrolyte is weighed in beaker, by Cu2-xSe is placed in polyelectrolyte, takes out after ultrasonic 30min
Filter.
6) by step 5) to join 50ml graphene oxide water solution ultrasonic for gained powder body, is warming up to 40 DEG C, instills 0.4ml
Hydrazine hydrate, after insulation 60min, cools down and carries out centrifugation, is dried, obtain described Cu2-xSe/ graphene composite powder.
X ray diffracting spectrum and the field emission scanning electron microscope picture of products therefrom are respectively Fig. 5 and Fig. 6, institute as seen from the figure
Obtaining product is Cu2-xSe/ graphene composite material (x=0), wherein Cu2-xSe distribution of particles is at graphenic surface or by Graphene half
It is wrapped in wherein.The wherein all corresponding Cu in all of peak in XRD figure spectrum2-xThe characteristic peak of Se, because the peak value of pure Graphene itself
The most weak, Cu good with degree of crystallinity2-xSe contrast has a long way to go, and the content of Graphene is limited, thus cannot in XRD
Observe the characteristic peak of Graphene.The Cu that the present embodiment is prepared2-xSe/ graphene composite material carries out conducting performance test, its room
Temperature electrical conductivity is 4 × 104S/m。
The above is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art,
On the premise of conceiving without departing from the invention, making some modifications and variations, these broadly fall into protection scope of the present invention.
Claims (10)
1. a Cu2-xThe preparation method of Se/ graphene composite material, it is characterised in that comprise the following steps:
1) by graphene oxide ultrasonic disperse in water, graphene oxide solution is obtained；
2), after addition coordination compound in Cu source stirring, mixed liquor I is obtained；Se source is added in alkaline conditioner and stirs,
Obtain mixed liquor I I；Mixed liquor I and II are mixed, then heat to 90～110 DEG C, be added dropwise over hydrazine hydrate, react 4～10h,
Cool down and carry out centrifugation, be dried, obtain Cu2-xSe powder；
3) by step 2) Cu that obtains2-xSe powder is placed in polyelectrolyte, after ultrasonic disperse 20～60min, carries out sucking filtration,
Obtain Cu2-xSe charged powder；
4) by step 3) gained Cu2-xSe charged powder addition graphene oxide water solution carries out ultrasonic disperse, is warming up to
20～60 DEG C, it is added dropwise over hydrazine hydrate, after insulation 20～60min, cools down and carry out centrifugation, be dried, obtain described Cu2-xSe/
Graphene composite material.
Preparation method the most according to claim 1, it is characterised in that the concentration of described graphene oxide solution is
0.2～0.5g/L.
Preparation method the most according to claim 1, it is characterised in that step 2) described in Cu source be elemental copper, or contain
Bivalent cupric ion or the nitrate of monovalence cuprous ion, sulfate or chloride, Cu element and the matter of graphene oxide in Cu source
Amount ratio is (6～62): 1.
Preparation method the most according to claim 1, it is characterised in that step 2) described in coordination compound be ammonia, coordinate
Thing is (0.4～0.6) with the volume ratio of graphene oxide solution: 1.
Preparation method the most according to claim 1, it is characterised in that step 2) described in Se source be elemental selenium, two
Selenium oxide, Monohydrated selenium dioxide or sodium thiosulfate, in Se source, Se element is 1:2 with the mol ratio of Cu element in Cu source.
Preparation method the most according to claim 1, it is characterised in that step 2) described in alkaline conditioner be hydroxide
Sodium solution or potassium hydroxide solution, or both are by the mixing of any proportioning；OH in alkaline conditioner-Concentration be 0.4～0.6mol/L,
Alkaline conditioner is (0.8～1) with the volume ratio of graphene oxide solution: 1.
Preparation method the most according to claim 1, it is characterised in that described step 3) cationic polyelectrolyte is poly-two
Methyl diallyl ammonium chloride, polyelectrolyte is (0.8～1.2) with the volume ratio of graphene oxide solution: 1.
Preparation method the most according to claim 1, it is characterised in that step 2) described in Cu in hydrazine hydrate and Cu source
The solid-to-liquid ratio of element is (0.07～0.32): 1g/ml；Step 4) in the solid-to-liquid ratio of hydrazine hydrate and graphene oxide be 1:(15～20) g/ml.
9. according to the Cu described in any one of claim 2～82-xThe preparation method of Se/ graphene composite material, it is characterised in that institute
State graphene oxide by NaNO3, potassium permanganate and graphite powder be with (0.3～0.7): (3～4): the mass ratio of 1 uses modified Hummers
Method is prepared from.
10. the Cu that preparation method described in claim 1 prepares2-xSe/ graphene composite material, it is characterised in that it is by Cu2-xSe
Granule and Graphene are composited, Cu2-xSe distribution of particles is partly wrapped in wherein at graphenic surface or by Graphene；Described
Cu2-xIn Se granule, x is selected from 0～0.1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242500A (en) * | 2016-12-26 | 2018-07-03 | 中国科学院上海硅酸盐研究所 | A kind of copper seleno nano composite thermoelectric materials and preparation method thereof |
| CN111453732A (en) * | 2020-04-08 | 2020-07-28 | 北京化工大学 | Three-dimensional porous MXene/rGO composite material and preparation method thereof |
| CN112531098A (en) * | 2020-12-24 | 2021-03-19 | 广东省科学院化工研究所 | Flexible thermoelectric material and preparation method thereof |
| CN112582527A (en) * | 2020-12-13 | 2021-03-30 | 安徽大学 | Preparation method of graphite-doped GeS2 thermoelectric material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010124212A2 (en) * | 2009-04-23 | 2010-10-28 | The University Of Chicago | Materials and methods for the preparation of nanocomposites |
| CN103072979B (en) * | 2013-02-04 | 2014-12-10 | 上海交通大学 | Preparation method for reduced-oxidized graphene/cuprous sulfide hybrid structure |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242500A (en) * | 2016-12-26 | 2018-07-03 | 中国科学院上海硅酸盐研究所 | A kind of copper seleno nano composite thermoelectric materials and preparation method thereof |
| CN111453732A (en) * | 2020-04-08 | 2020-07-28 | 北京化工大学 | Three-dimensional porous MXene/rGO composite material and preparation method thereof |
| CN112582527A (en) * | 2020-12-13 | 2021-03-30 | 安徽大学 | Preparation method of graphite-doped GeS2 thermoelectric material |
| CN112582527B (en) * | 2020-12-13 | 2022-12-02 | 安徽大学 | Preparation method of graphite-doped GeS2 thermoelectric material |
| CN112531098A (en) * | 2020-12-24 | 2021-03-19 | 广东省科学院化工研究所 | Flexible thermoelectric material and preparation method thereof |
| CN112531098B (en) * | 2020-12-24 | 2023-08-22 | 广东省科学院化工研究所 | Flexible thermoelectric material and preparation method thereof |
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