CN106159076B - A kind of Cu2-xThe preparation method of Se/ graphene composite materials - Google Patents
A kind of Cu2-xThe preparation method of Se/ graphene composite materials Download PDFInfo
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Abstract
The invention discloses a kind of Cu2‑xThe preparation method of Se/ graphene composite materials prepares Cu using two step of Low Temperature Wet chemical method2‑ xThe composite material of Se/ graphenes, the Cu2‑xIn Se/ graphene composite materials, x is selected from 0~0.1；The material is by Cu2‑xSe particles and graphene are combined, Cu2‑xSe distribution of particles is wrapped up wherein on the surface of graphene or by graphene half.Preparation process of the present invention is simple, low energy consumption, cost is small, short preparation period, is suitable for industrial mass production；Cu obtained2‑xSe/ graphene composite materials have higher conductivity, with important application prospects in thermoelectric material field.
Description
Technical field
The present invention relates to thermoelectric material preparation fields, and in particular to a kind of Cu2-xThe preparation side of Se/ graphene composite materials
Method.
Background technology
Thermoelectric generation technology is a kind of Sai Beike (Seebeck) effect and Peltier using semi-conducting material
(Peltier) effect realizes that the technology directly converted between thermal energy and electric energy, application include mainly thermoelectric power generation and thermoelectricity
Two kinds of refrigeration.The working media of thermoelectric generation technology is mobile carrier has structure letter for traditional heat engine
It is single, without transmission parts, reliability is high, manufacturing process is simple, pollution-free and noiseless the features such as, as particular power source and precision temperature
Control device has been obtained for applying in the high-technology fields such as aerospace technology and military equipment.At civilian aspect, by
This technology is limited by pyroelectric material performance extensive use is not carried out in terms of thermoelectric power generation in the efficiency of thermoelectric power generation,
Application the most main is thermoelectric cooling, the bismuth telluride based alloys (Bi such as synthesized with zone-melting process2Te3) it is the portable of core component
Formula thermoelectric refrigerator etc..Therefore as a kind of novel, environmental harmony type clean energy resource switch technology, thermo-electric device is expected extensive use
In a large amount of and the existing low density heat energy of dispersion thermoelectric power generations, one is provided with problem of environmental pollution is solved for alleviating energy crisis
Important channel.
It is commercialized thermoelectric material Bi2Te3With the thermoelectric figure of merit ZT of PbTe 1 or so, due to these materials ZT values less
Height contains 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
Cut with it is important.Cu2-xSe thermoelectric materials are higher without rare elements, the abundance such as Te, lower cost for material and environmentally safe,
And Cu2-xOn the one hand Se compounds have complicated crystal structure, at high temperature due to Cu+Fluid-like state behavior caused by cross
Wave damping effect, therefore it with lower thermal conductivity, on the other hand, material shows higher Seebeck coefficients so that
Cu2-xSe compounds are likely to become ideal thermoelectric material.This research is quasi- to carry out compound raising material using with graphene
Conductivity optimizes thermoelectricity capability.
Cu is prepared at present2-xThe method of Se thermoelectric materials is mainly high-temperature melting method or solid reaction process, manufacturing cycle
It is long, and need to react under the high temperature conditions, energy consumption is high；Required raw material is high-purity powder, and the cost is relatively high；In addition, physics
Method synthetic composite material is usually used that multistep machinery is compound to be realized, has process complicated, disperses between two-phase uneven etc.
Problem.
Invention content
The object of the present invention is to provide a kind of Cu2-xThe preparation method of the composite material of Se/ graphenes, this method prepare work
Skill is simple, at low cost, low energy consumption, is applicable to mass produce.
To achieve the above object, the technical solution adopted by the present invention is：A kind of Cu2-xThe preparation of Se/ graphene composite materials
Method includes the following steps：
1) by graphene oxide ultrasonic disperse in water, graphene oxide solution is obtained；
2) sources Cu are added in complex after stirring evenly, obtain mixed liquor I；The sources Se are added in alkaline conditioner and are stirred
It is even, obtain mixed liquor I I；Mixed liquor I and II are mixed, then heat to 90~110 DEG C, is added dropwise hydrazine hydrate, reaction 4~
10h, cooling are simultaneously centrifuged, dry, and obtain Cu2-xSe powder；
3) Cu for obtaining step 2)2-xSe powder is placed in polyelectrolyte, after 20~60min of ultrasonic disperse, is taken out
Filter, obtains Cu2-xSe charged powders；
4) by Cu obtained by step 3)2-xSe charged powders are added graphene oxide water solution and carry out ultrasonic disperse, are warming up to 20
~60 DEG C, hydrazine hydrate is added dropwise, after keeping the temperature 20~60min, cooling is simultaneously centrifuged, dries, and obtains the Cu2-xSe/ stones
Black alkene composite material.
According to said program, a concentration of 0.2~0.5g/L of the graphene oxide solution.
According to said program, Cu sources described in step 2) is elemental copper, or containing bivalent cupric ion or monovalence cuprous ion
Nitrate, sulfate or chloride, the mass ratio of Cu elements and graphene oxide is (6~62) in the sources Cu:1.
According to said program, the complex described in step 2) is ammonium hydroxide, the volume of complex and graphene oxide solution
Than for (0.4~0.6):1.
According to said program, sources Se described in step 2) are elemental selenium, selenium dioxide, selenous acid or sodium thiosulfate,
The molar ratio of Se elements and Cu elements in the sources Cu is 1 in the sources Se:2.
According to said program, alkaline conditioner described in step 2) is sodium hydroxide solution or potassium hydroxide solution, or
The two is mixed by arbitrary proportioning, OH in alkaline conditioner-A concentration of 0.4~0.6mol/L, alkaline conditioner and graphite oxide
The volume ratio of alkene solution is (0.8~1):1.
According to said program, the cationic polyelectrolyte be polydimethyl diallyl ammonium chloride, polyelectrolyte with
The volume ratio of graphene oxide solution is (0.8~1.2):1.
According to said program, the solid-to-liquid ratio of the hydrazine hydrate and Cu elements in the sources Cu is (0.07~0.32):1g/ml；Step
It is rapid 4) in the solid-to-liquid ratio of hydrazine hydrate and graphene oxide be 1:(15~20) g/ml.
According to said program, the graphene oxide is by NaNO3, potassium permanganate and high purity graphite powder be with (0.3~0.7):
(3~4):1 mass ratio is prepared using modified Hummers methods, specifically includes following steps：
1) the low-temp reaction stage weighs NaNO respectively according to the ratio3, potassium permanganate and graphite powder, in dry reaction vessel
It is middle to be added in the concentrated sulfuric acid of 98wt%, it is then cooled to 0~2 DEG C, graphite powder and NaNO are added under agitation3, graphite powder
Solid-to-liquid ratio with the concentrated sulfuric acid of 98wt% is 1:(22~24) g/ml after stirring evenly, is slowly added to potassium permanganate, and control is anti-
It is 0~5 DEG C to answer temperature, stirs 1.5~2h；
2) solution that step 1) obtains is placed in 32~40 DEG C of water bath with thermostatic control by the medium temperature stage of reaction, and stirring 30~
40min；
3) the pyroreaction stage is slowly added to 50~60 DEG C of warm water into the solution for obtaining step 2) and mass concentration is
30% hydrogen peroxide, the wherein solid-to-liquid ratio of graphite powder and 50~60 DEG C of warm water are 1:(40~50) g/ml, graphite powder and hydrogen peroxide
Solid-to-liquid ratio be 1:Reaction was completed after (4~6) g/ml, 15~30min of stirring.Products therefrom is washed with dilute hydrochloric acid and deionized water
To through BaCl2Solution is detected without SO4 2-, it is freeze-dried, obtains the graphene oxide.
According to said program, Cu obtained2-xSe/ graphene composite materials are by Cu2-xSe particles and graphene are combined,
Cu2-xSe distribution of particles is wrapped up wherein on the surface of graphene or by graphene half；The Cu2-xIn Se particles, x be selected from 0~
0.1。
Compared with prior art, beneficial effects of the present invention are：
1) this method prepares Cu using two step of Low Temperature Wet chemical method2-xSe/ graphene composite materials, be related to it is simple for process,
Consuming energy, low, cost is small, short preparation period, is suitable for industrial mass production.
2) present invention after polyelectrolyte ionization using positive charge is generated, with Cu2-xSe particles combine, and make its surface with just
Electricity, and graphene oxide ionize in water after carry negative electricity, the two by electrostatic interaction in conjunction with the Cu2-xSe/ graphenes are multiple
Condensation material.
3) due to the peptizaiton of graphene, Cu in obtained composite material2-xSe particles dispersion on the surface of graphene or by
Graphene half wraps up wherein, and composite material exhibits is made to go out higher conductivity.For the material of different Cu contents, graphene is equal
Its conductivity can be reduced.The composite material has important application foreground in thermoelectric material field.
Description of the drawings
The invention will be further described below in conjunction with the accompanying drawings, in attached drawing：
Fig. 1 is Cu made from embodiment 12-xThe X ray diffracting spectrum of Se/ graphene composite materials.
Fig. 2 is Cu made from embodiment 12-xThe field emission scanning electron microscope picture of Se/ graphene composite materials.
Fig. 3 is Cu made from embodiment 22-xThe X ray diffracting spectrum of Se/ graphene composite materials.
Fig. 4 is Cu made from embodiment 22-xThe field emission scanning electron microscope picture of Se/ graphene composite materials.
Fig. 5 is Cu made from embodiment 32-xThe X ray diffracting spectrum of Se/ graphene composite materials.
Fig. 6 is Cu made from embodiment 32-xThe field emission scanning electron microscope picture of Se/ graphene composite materials.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
In following embodiment, unless specific instructions, the reagent of use is commercially available chemical reagent.
Embodiment 1
A kind of Cu2-xThe preparation method of Se/ graphene composite materials, graphene oxide and Cu in preparation process2-xThe matter of Se
Amount is than about 1%：1, include the following steps：
1) graphene oxide (GO) is prepared using modified Hummers methods, by NaNO3, potassium permanganate and graphite powder be 0.3：
3：1 mass ratio weighs each raw material, is added in the concentrated sulfuric acid of 98wt% in dry reaction vessel, is then cooled to 0~2
DEG C, graphite powder and NaNO are added under agitation3, the solid-to-liquid ratio of the concentrated sulfuric acid of graphite powder and 98wt% is 1:22g/ml is stirred
After mixing uniformly, it is slowly added to potassium permanganate, controlling reaction temperature is 0~5 DEG C, stirs 1.5h；Obtained solution is placed in 35 DEG C
Water bath with thermostatic control in, stir 30min；It is slowly added to 50 DEG C of warm water and mass concentration into solution as 30% hydrogen peroxide, stirs
15min, the wherein solid-to-liquid ratio of graphite powder and 50~60 DEG C of warm water are 1:The solid-to-liquid ratio of 40g/ml, graphite powder and hydrogen peroxide is 1:
4g/ml.After reaction, products therefrom dilute hydrochloric acid and deionized water are washed to through BaCl2Solution is detected without SO4 2-, freeze dry
It is dry, obtain the graphene oxide (GO).
2) by the graphene oxide ultrasonic disperse after drying in water, the GO aqueous solutions of a concentration of 0.5g/L are configured to.
3) 20ml ammonium hydroxide, 2.4022g CuCl are weighed, mixed solution is stirred evenly to obtain.
4) 0.8g NaOH are weighed, is placed in 50ml deionized waters and stirs to obtain NaOH solution, 0.9580g Se powder is added
It in NaOH solution, is mixed with mixed solution obtained by step 3) after stirring evenly, then sealing is placed in oil bath pan, heat temperature raising
To 90 DEG C, be added dropwise 10ml reducing agent hydrazine hydrates, keep the temperature 4h, cooled to room temperature, washed repeatedly with deionized water centrifugation,
Freeze-drying, obtains the Cu2-xSe powder.
5) 50ml cationic polyelectrolytes are weighed in beaker, the Cu that will be obtained2-xSe powder is placed in polyelectrolyte, is surpassed
It is filtered after sound 30min.
6) powder obtained by step 5) is added to 50ml graphene oxide water solution ultrasounds, is warming up to 20 DEG C, instills 0.5ml
Hydrazine hydrate, after keeping the temperature 60min, cooling is simultaneously centrifuged, dries, and obtains the Cu2-xSe/ graphene composite powders.
The X ray diffracting spectrum and field emission scanning electron microscope picture of products therefrom are respectively Fig. 1 and Fig. 2, can be seen by figure
It is Cu to go out products therefrom2-xSe/ graphene composite materials (x=0.1), Cu2-xSe distribution of particles is on the surface of graphene or by graphite
Alkene half wraps up wherein.Wherein peak all in XRD spectrum corresponds to Cu2-xThe characteristic peak of Se, because of the peak value sheet of pure graphene
Body is very weak, with the good Cu of crystallinity2-xSe comparisons have a long way to go, and the content of graphene is limited, thus can not in XRD
Observe the characteristic peak of graphene.By Cu made from the present embodiment2-xSe/ graphene composite materials carry out conducting performance test,
Room-temperature conductivity is 9 × 104S/m。
Embodiment 2
A kind of Cu2-xThe preparation method of Se/ graphene composite materials, graphene oxide and Cu in preparation process2-xThe matter of Se
Amount is than about 4%：1, include the following steps：
1) graphene oxide (GO) is prepared using modified Hummers methods, by NaNO3, potassium permanganate and graphite powder be 0.5：
3.5：1 mass ratio weighs each raw material, is added in the concentrated sulfuric acid of 98wt% in dry reaction vessel, is then cooled to 0~2
DEG C, graphite powder and NaNO are added under agitation3, the solid-to-liquid ratio of the concentrated sulfuric acid of graphite powder and 98wt% is 1:22g/ml is stirred
After mixing uniformly, it is slowly added to potassium permanganate, controlling reaction temperature is 0~5 DEG C, stirs 1.5h；Obtained solution is placed in 35 DEG C
Water bath with thermostatic control in, stir 30min；It is slowly added to 50 DEG C of warm water and mass concentration into solution as 30% hydrogen peroxide, stirs
15min, the wherein solid-to-liquid ratio of graphite powder and 50~60 DEG C of warm water are 1:The solid-to-liquid ratio of 50g/ml, graphite powder and hydrogen peroxide is 1:
4g/ml.After reaction, products therefrom dilute hydrochloric acid and deionized water are washed to through BaCl2Solution is detected without SO4 2-, freeze dry
It is dry, obtain the graphene oxide (GO).
2) by the graphene oxide ultrasonic disperse after drying in water, compound concentration is the GO aqueous solutions of 0.2g/L.
3) 25ml ammonium hydroxide, 0.6058g CuSO are weighed4·5H2O stirs evenly to obtain mixed solution.
4) 0.96g NaOH are weighed, is placed in 40ml deionized waters and stirs to obtain NaOH solution, by 0.1346g SeO2Powder adds
Enter in NaOH solution, mixed with mixed solution obtained by step 3) after stirring evenly, then sealing is placed in oil bath pan, and heating rises
2ml reducing agent hydrazine hydrates are added dropwise to 100 DEG C in temperature, keep the temperature 4h, cooled to room temperature, washed repeatedly with deionized water from
The heart, freeze-drying obtain the Cu2-xSe。
5) 40ml cationic polyelectrolytes are weighed in beaker, by Cu2-xSe is placed in polyelectrolyte, is taken out after ultrasonic 30min
Filter
6) powder obtained by step 5) is added to 50ml graphene oxide water solution ultrasounds, is warming up to 60 DEG C, instills 0.2ml
Hydrazine hydrate, after keeping the temperature 20min, cooling is simultaneously centrifuged, dries, and obtains the Cu2-xSe/ graphene composite powders.
The X ray diffracting spectrum and field emission scanning electron microscope picture of products therefrom are respectively Fig. 3 and Fig. 4, can be seen by figure
It is Cu to go out products therefrom2-xSe/ graphene composite materials (x=0.05), wherein Cu2-xSe distribution of particles on the surface of graphene or by
Graphene half wraps up wherein.Wherein peak all in XRD spectrum corresponds to Cu2-xThe characteristic peak of Se, because of the peak of pure graphene
Value itself is very weak, with the good Cu of crystallinity2-xSe comparisons have a long way to go, and the content of graphene is limited, thus in XRD
It can not observe the characteristic peak of graphene.By Cu made from the present embodiment2-xSe/ graphene composite materials carry out electric conductivity survey
Examination, room-temperature conductivity are 7 × 104S/m。
Embodiment 3
A kind of Cu2-xThe preparation method of Se/ graphene composite materials, graphene oxide and Cu in preparation process2-xThe matter of Se
Amount is than about 5%：1, include the following steps：
1) graphene oxide (GO) is prepared using modified Hummers methods, by NaNO3, potassium permanganate and graphite powder be 0.7：
4：1 mass ratio weighs each raw material, is added in the concentrated sulfuric acid of 98wt% in dry reaction vessel, is then cooled to 0~2
DEG C, graphite powder and NaNO are added under agitation3, the solid-to-liquid ratio of the concentrated sulfuric acid of graphite powder and 98wt% is 1:24g/ml is stirred
After mixing uniformly, it is slowly added to potassium permanganate, controlling reaction temperature is 0~5 DEG C, stirs 2h；Obtained solution is placed in 40 DEG C
In water bath with thermostatic control, 40min is stirred；It is slowly added to 60 DEG C of warm water and mass concentration into solution as 30% hydrogen peroxide, stirs
30min, the wherein solid-to-liquid ratio of graphite powder and 50~60 DEG C of warm water are 1:The solid-to-liquid ratio of 40g/ml, graphite powder and hydrogen peroxide is 1:
6g/ml.After reaction, products therefrom dilute hydrochloric acid and deionized water are washed to through BaCl2Solution is detected without SO4 2-, freeze dry
It is dry, obtain the graphene oxide (GO).
2) by the graphene oxide ultrasonic disperse after drying in water, the GO aqueous solutions of a concentration of 0.5g/L are configured to.
3) 0.8273g CuCl are weighed2·2H2O, 30ml ammonium hydroxide stirs evenly to obtain mixed solution.
4) 0.96g NaOH are weighed, stirring in 40ml deionized waters is placed in and forms solution, by 0.3129g H2SeO3It is placed in
It states in NaOH solution, is mixed with mixed solution obtained by step 2) after stirring evenly, then sealing is placed in oil bath pan, and heating rises
Temperature to 110 DEG C, be added dropwise 3ml reducing agent hydrazine hydrates heat preservation 10h, cooled to room temperature, washed repeatedly with deionized water from
The heart, freeze-drying obtain the Cu2-xSe。
5) 60ml cationic polyelectrolytes are weighed in beaker, by Cu2-xSe is placed in polyelectrolyte, is taken out after ultrasonic 30min
Filter.
6) powder obtained by step 5) is added to 50ml graphene oxide water solution ultrasounds, is warming up to 40 DEG C, instills 0.4ml
Hydrazine hydrate, after keeping the temperature 60min, cooling is simultaneously centrifuged, dries, and obtains the Cu2-xSe/ graphene composite powders.
The X ray diffracting spectrum and field emission scanning electron microscope picture of products therefrom are respectively Fig. 5 and Fig. 6, can be seen by figure
It is Cu to go out products therefrom2-xSe/ graphene composite materials (x=0), wherein Cu2-xSe distribution of particles is on the surface of graphene or by stone
Black alkene half wraps up wherein.Wherein peak all in XRD spectrum corresponds to Cu2-xThe characteristic peak of Se, because of the peak value of pure graphene
Itself is very weak, with the good Cu of crystallinity2-xSe comparisons have a long way to go, and the content of graphene is limited, thus the nothing in XRD
Method observes the characteristic peak of graphene.By Cu made from the present embodiment2-xSe/ graphene composite materials carry out conducting performance test,
Its room-temperature conductivity is 4 × 104S/m。
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, makes several modifications and variations, these belong to the protection model of the present invention
It encloses.
Claims (10)
1. a kind of Cu2-xThe preparation method of Se/ graphene composite materials, which is characterized in that include the following steps：
1) by graphene oxide ultrasonic disperse in water, graphene oxide solution is obtained；
2) sources Cu are added in ammonium hydroxide after stirring evenly, obtain mixed liquor I；The sources Se are added in alkaline conditioner and are stirred evenly, are obtained
Mixed liquor I I；Mixed liquor I and II are mixed, then heat to 90~110 DEG C, hydrazine hydrate is added dropwise, reacts 4~10h, it is cooling
And be centrifuged, dry, obtain Cu2-xSe powder；
3) Cu for obtaining step 2)2-xSe powder is placed in polyelectrolyte, after 20~60min of ultrasonic disperse, is filtered, is obtained
Cu2-xSe charged powders；
4) by Cu obtained by step 3)2-xSe charged powders are added in graphene oxide water solution and carry out ultrasonic disperse, it is warming up to 20~
60 DEG C, hydrazine hydrate is added dropwise, after keeping the temperature 20~60min, cooling is simultaneously centrifuged, dries, and obtains the Cu2-xSe/ graphite
Alkene composite material.
2. preparation method according to claim 1, which is characterized in that a concentration of the 0.2 of the graphene oxide solution~
0.5g/L。
3. preparation method according to claim 1, which is characterized in that Cu sources described in step 2) is elemental copper, or contains two
The nitrate of valence copper ion or monovalence cuprous ion, sulfate or chloride, the quality of Cu elements and graphene oxide in the sources Cu
Than for (6~62):1.
4. preparation method according to claim 1, which is characterized in that complex described in step 2) and graphene oxide are molten
The volume ratio of liquid is (0.4~0.6):1.
5. preparation method according to claim 1, which is characterized in that the sources Se described in step 2) are elemental selenium, dioxy
Change selenium, selenous acid or sodium thiosulfate, the molar ratio of Se elements and Cu elements in the sources Cu is 1 in the sources Se:2.
6. preparation method according to claim 1, which is characterized in that the alkaline conditioner described in step 2) is hydroxide
Sodium solution or potassium hydroxide solution, or both by arbitrary proportioning mixing；OH in alkaline conditioner-A concentration of 0.4~0.6mol/
The volume ratio of L, alkaline conditioner and graphene oxide solution is (0.8~1):1.
7. preparation method according to claim 1, which is characterized in that cationic polyelectrolyte is poly- two in the step 3)
The volume ratio of methyl diallyl ammonium chloride, polyelectrolyte and graphene oxide solution is (0.8~1.2):1.
8. preparation method according to claim 1, which is characterized in that hydrazine hydrate described in step 2) and Cu elements in the sources Cu
Solid-to-liquid ratio be (0.07~0.32):1g/ml；The solid-to-liquid ratio of hydrazine hydrate and graphene oxide is 1 in step 4):(15~20) g/
ml。
9. according to claim 2~8 any one of them Cu2-xThe preparation method of Se/ graphene composite materials, which is characterized in that
The graphene oxide is by NaNO3, potassium permanganate and graphite powder be with (0.3~0.7):(3~4):1 mass ratio is using modification
Hummers methods are prepared.
10. Cu made from preparation method described in claim 12-xSe/ graphene composite materials, which is characterized in that it is by Cu2-xSe
Particle and graphene are combined, Cu2-xSe distribution of particles is wrapped up wherein on the surface of graphene or by graphene half；It is described
Cu2-xIn Se particles, x is selected from 0~0.1.
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| CN112582527B (en) * | 2020-12-13 | 2022-12-02 | 安徽大学 | Preparation method of graphite-doped GeS2 thermoelectric material |
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| WO2010124212A3 (en) * | 2009-04-23 | 2011-03-10 | The University Of Chicago | Materials and methods for the preparation of nanocomposites |
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