CN102856486B - Preparation method for nano composite thermoelectric material - Google Patents
Preparation method for nano composite thermoelectric material Download PDFInfo
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- CN102856486B CN102856486B CN201110177355.4A CN201110177355A CN102856486B CN 102856486 B CN102856486 B CN 102856486B CN 201110177355 A CN201110177355 A CN 201110177355A CN 102856486 B CN102856486 B CN 102856486B
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Abstract
The invention discloses a preparation method for a nano composite thermoelectric material. The preparation method comprises the following steps of mixing sodium hydroxide and sodium borohydride in solvent to obtain reducing solution; mixing an antimony source compound, a cobalt source compound, a complexing agent and mesoporous carbon in volatile and polar organic solvent and drying to obtain a first mixture; mixing the reducing solution with the first mixture, and reacting and drying to obtain a second mixture; and placing the second mixture in nitrogen and hydrogen mixing atmosphere at the temperature of 380-550 DEG C to be subjected to heat treatment, and enabling the second mixture to react so as to obtain the nano composite thermoelectric material. Compared with the prior art, the preparation method has the advantage that prepared nano-level cobalt antimonide is filled in ducts of the mesoporous carbon, so that agglomeration and growth of the nano-level cobalt antimonide in a heat treatment process is avoided by a limiting effect of the ducts of the mesoporous carbon. Experiment results show that monodispersity of nano-particles of the cobalt antimonide in the prepared cobalt antinonide nano composite thermoelectric material is good.
Description
Technical field
The present invention relates to field of thermoelectric material technique, more particularly, relate to a kind of preparation method of nano composite thermoelectric materials.
Background technology
In today that the energy and environmental problem become increasingly conspicuous, thermoelectric material, as a kind of material that can realize heat energy and electric energy and directly change, as the alternative energy source of the traditional energies such as oil together with solar energy materials, becomes various countries and to try to be the first the focus of research.Thermoelectric conversion efficiency is the key parameter weighing pyroelectric material performance, and it depends primarily on the thermoelectric figure of merit ZT of thermoelectric material, ZT=S
2σ T/ κ, wherein, S is Seebeck coefficient, and σ is conductivity, and κ is thermal conductivity, and T is absolute temperature.In order to make thermoelectric material have higher thermoelectricity capability, need to make thermoelectric material have high Seebeck coefficient, high conductivity and low thermal conductivity simultaneously.Due to Seebeck coefficient, be mutually related between conductivity and thermal conductivity, therefore, how realize the coordinated regulation of three parameters to obtain the key that best ZT value becomes research thermoelectric material.
Nano composite thermoelectric materials is a class new function material, from theory, it utilizes quantum confined effect to increase conductivity (σ), reduce thermal conductivity (κ) by interfacial effect, thus improves thermoelectric figure of merit, and then improves focus conversion efficiency.Specifically, in thermoelectric material, conductivity affects by electron mean free path; Meanwhile, because thermal conductivity is by phonon conduction, thus thermal conductivity is by the impact of mean free path of phonons, therefore reduces the main path of thermal conductivity for carry out scattering to phonon.Because mean free path of phonons is in nanometer scale, electronics (hole) mean free path is then much bigger than mean free path of phonons, and therefore nano particle can effective scattering phonon do not have an impact on electron transfer processes or affect less.Correlative study shows, the preparation method of desirable thermoelectric material is: nano particle is evenly dispersed in a micron thermoelectricity intercrystalline.In above-mentioned thermoelectric material, on the one hand micron grain can effective conduction electron, and another aspect nano particle can play good scattering process to phonon, thus makes thermoelectric material realize high conductance, the object of low thermal conductance.
Nanometer antimony cobalt thermoelectric material is a kind of one of material near middle temperature with best thermoelectricity conversion usefulness.The preparation method of nanometer antimony cobalt material has more bibliographical information, is wherein mainly mechanical force alloyage, but the antimony cobalt nano-particle activity itself that the method prepares is high, easily reunites, difficult dispersion.Because antimony cobalt nano-particle exists agglomeration, therefore, this antimony cobalt nano-particle and micron particles compound is utilized to obtain in antimony cobalt nano composite thermoelectric materials process, this nano particle is all inevitably grown up, meet or exceed micro-meter scale, make the scattering that antimony cobalt nano-particle cannot realize phonon, and then affect the conversion efficiency of thermoelectric of antimony cobalt nano composite thermoelectric materials.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is the preparation method providing a kind of antimony cobalt nano composite thermoelectric materials, and in the antimony cobalt nano composite thermoelectric materials that the method prepares, antimony cobalt nano-particle monodispersity is good.
The invention provides a kind of preparation method of nano composite thermoelectric materials, comprise the following steps:
NaOH, sodium borohydride are mixed in a solvent, obtains reducing solution;
Antimony source compound, cobalt source compound, complexing agent and mesoporous carbon are mixed in volatile polar organic solvent, after drying, obtains the first mixture;
Described reducing solution is mixed with described first mixture, reacts, after drying, obtains the second mixture;
Heat treatment at described second mixture being placed in 380 ~ 550 DEG C under nitrogen and hydrogen mixture atmosphere, obtains nano composite thermoelectric materials after reaction.
Preferably, the mass ratio of described NaOH and sodium borohydride is 1: (0.5 ~ 5).
Preferably, described solvent is the mixed solvent of absolute ethyl alcohol and deionized water.
Preferably, the mol ratio of described sodium borohydride and described antimony source compound is (0.8 ~ 2): 1.
Preferably, described antimony source compound is antimony chloride, and described cobalt source compound is cobalt chloride hexahydrate, and described complexing agent is citric acid or oxalic acid.
Preferably, the mol ratio of described antimony source compound and cobalt source compound is (3 ~ 7): 1.
Preferably, the mol ratio of described complexing agent and described cobalt source compound is (3 ~ 5): 1.
Preferably, the mass ratio of described mesoporous carbon and described cobalt source compound is (3 ~ 12): 1.
Preferably, described heat treatment time is 20 ~ 80 minutes.
The present invention also provides a kind of preparation method of nano composite thermoelectric materials, comprises the following steps:
Hydrazine hydrate is mixed in the first polar organic solvent, obtains reducing solution;
Antimony source compound, cobalt source compound, complexing agent and mesoporous carbon are mixed in polarity second polar organic solvent, after drying, obtains the first mixture;
Described reducing solution is mixed with described first mixture, after drying, obtains the second mixture;
Heat treatment at described second mixture being placed in 380 ~ 550 DEG C under nitrogen and hydrogen mixture atmosphere, obtains nano composite thermoelectric materials after reaction.
The invention provides a kind of preparation method of nano composite thermoelectric materials, comprise the following steps: NaOH, sodium borohydride are mixed in a solvent, obtains reducing solution; Antimony source compound, cobalt source compound, complexing agent and mesoporous carbon are mixed in volatile polar organic solvent, after drying, obtains the first mixture; Described reducing solution is mixed with described first mixture, reacts, after drying, obtains the second mixture; Heat treatment at described second mixture being placed in 380 ~ 550 DEG C under nitrogen and hydrogen mixture atmosphere, obtains nano composite thermoelectric materials after reaction.Compared with prior art, the antimony cobalt of the nanometer scale of preparation is filled in the duct of mesoporous carbon by the present invention, utilizes the duct restriction of mesoporous carbon, avoids the reunion of the antimony cobalt of nanometer scale in heat treatment process and grows up.Experimental result shows, in antimony cobalt nano composite thermoelectric materials prepared by the present invention, antimony cobalt nano-particle monodispersity is good.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the low-angle XRD collection of illustrative plates of antimony cobalt nano composite thermoelectric materials prepared by the embodiment of the present invention 1;
Fig. 2 is the wide-angle XRD collection of illustrative plates of antimony cobalt nano composite thermoelectric materials prepared by the embodiment of the present invention 1;
Fig. 3 is the transmission electron microscope picture of antimony cobalt nano composite thermoelectric materials prepared by the embodiment of the present invention 1;
Fig. 4 is the low-angle XRD collection of illustrative plates of antimony cobalt nano composite thermoelectric materials prepared by the embodiment of the present invention 2;
Fig. 5 is the wide-angle XRD collection of illustrative plates of antimony cobalt nano composite thermoelectric materials prepared by the embodiment of the present invention 2;
Fig. 6 is the transmission electron microscope picture of antimony cobalt nano composite thermoelectric materials prepared by the embodiment of the present invention 2.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention discloses a kind of preparation method of nano composite thermoelectric materials, comprise the following steps:
NaOH, sodium borohydride are mixed in a solvent, obtains reducing solution;
Antimony source compound, cobalt source compound, complexing agent and mesoporous carbon are mixed in volatile polar organic solvent, after drying, obtains the first mixture;
Described reducing solution is mixed with described first mixture, reacts, after drying, obtains the second mixture;
Heat treatment at described second mixture being placed in 380 ~ 550 DEG C under nitrogen and hydrogen mixture atmosphere, obtains nano composite thermoelectric materials after reaction.
In above-mentioned preparation process, the mass ratio of NaOH and sodium borohydride is preferably 1: (0.5 ~ 5), is more preferably 1: (1 ~ 5), most preferably is 1: (2 ~ 4); Wherein, sodium borohydride uses as reducing agent, and NaOH adds the effect mainly played and suppress sodium borohydride hydrolysis, avoid sodium borohydride to lose efficacy.In the step preparing reducing solution, preferably adopt the mixed solvent of polar organic solvent and water, be more preferably the mixed solvent of absolute ethyl alcohol and deionized water.Because absolute ethyl alcohol has high boiling characteristics, can at room temperature volatilize, therefore, in the step obtaining the second mixture, without the need to adopting the method for heating to realize drying, thus the phenomenon avoiding the second mixture appearance volatilization or reunite.Meanwhile, because the solubility of sodium borohydride in absolute ethyl alcohol is less, therefore, the mixed solvent of preferred employing absolute ethyl alcohol and deionized water, the volume ratio of described absolute ethyl alcohol and deionized water is preferably 0.5 ~ 4: 1, is more preferably 1 ~ 4: 1, most preferably is 2 ~ 3: 1.In described reducing solution, the substance withdrawl syndrome of described NaOH is preferably 1.5 ~ 3mol/L, is preferably 2 ~ 3mol/L, is preferably 2.2 ~ 2.8mol/L.
Meanwhile, in the step obtaining the first mixture, antimony source compound, cobalt source compound, complexing agent are incorporated in the duct of mesoporous carbon, thus are that follow-up reduction reaction and alloying reaction create nanometer reaction compartment.Described antimony source compound is preferably soluble antimony source compound, is more preferably antimony chloride; Described cobalt source compound is preferably solubility cobalt source compound, is more preferably cobalt chloride hexahydrate; Described complexing agent is preferably citric acid or oxalic acid.Because described complexing agent is easy to form complex compound with metal ion, thus avoid the phenomenons such as the too fast volatilization occurring metal ion in heat treatment process, avoid the generation of side reaction.
Because the individual particle of mesoporous carbon is in micron dimension, there is a large amount of open bore in granule interior, and aperture is between 2nm to 50nm, therefore, the present invention take mesoporous material as carrier, take full advantage of the specific area of the orderly pore passage structure of the particle of its micro-meter scale, internal rule and super large, be specially: 1, utilize the space, duct of the specific area Sum fanction of the super large of mesoporous carbon as nanometer reative cell; 2, utilize the restriction in the duct of mesoporous carbon, to effectively prevent in heat treatment process the nanophase easily occurred and reunite and the generation of the phenomenon such as to grow up; 3, due to the pattern of the micro-meter scale of mesoporous carbon itself easily meet shaping on requirement, thus provide necessary condition for obtaining high-density bulk material.
The volatile polar organic solvent of above-mentioned employing is preferably ethanol, acetone or methyl alcohol etc.For ethanol, its Main Function be make antimony source compound, cobalt source compound effectively enters in the duct of mesoporous carbon; In addition, because ethanol has high boiling characteristics, at room temperature can volatilize very easily, thus in the step obtaining the first mixture, can drying be realized without the need to adopting the method for heating.
The mol ratio of sodium borohydride of the present invention and described antimony source compound is preferably (0.8 ~ 2): 1, is preferably (1 ~ 2): 1, is preferably (1.2 ~ 1.8): 1; The mol ratio of described antimony source compound and cobalt source compound is preferably (3 ~ 7): 1, is preferably (4 ~ 6): 1, is preferably (4 ~ 5): 1; The mol ratio of described complexing agent and described cobalt source compound is preferably (3 ~ 5): 1, is preferably (3.5 ~ 4.5): 1, is preferably (4 ~ 4.5): 1; The mass ratio of described mesoporous carbon and described cobalt source compound is preferably (3 ~ 12): 1, is preferably (4 ~ 10): 1, is preferably (5 ~ 8): 1.
Above-mentioned antimony source compound, cobalt source compound, complexing agent and mesoporous carbon to be mixed in volatile polar organic solvent, the step obtaining the first mixture after drying is specially: antimony source compound, cobalt source compound and complexing agent are mixed in volatile polar organic solvent, obtain reaction solution; In described reaction solution, add mesoporous carbon, stir, after drying, obtain the first mixture.Wherein, in described reaction solution, the concentration of the amount of substance of cobalt source compound is preferably 0.08 ~ 2mol/L, is preferably 0.5 ~ 2mol/L, is preferably 1 ~ 1.5mol/L.
Above-mentioned mixing time is preferably 1.5 ~ 3 hours, is more preferably 2 ~ 3 hours.In addition, the present invention also preferably includes the preliminary treatment to described mesoporous carbon, is specially: mesoporous carbon is at room temperature vacuumized 10 ~ 20 hours, is more preferably 12 hours.
In the step preparing the first mixture, described drying is preferably adopted with the following method: mixture antimony source compound, cobalt source compound, complexing agent and mesoporous carbon are mixed to get in volatile polar organic solvent, by described mixture 20 ~ 40 DEG C, relative humidity be the environment of 15 ~ 50% under leave standstill within more than 24 hours, all volatilize to volatile polar organic solvent.After the volatilization of volatile polar organic solvent, antimony source compound, cobalt source compound, complexing agent are effectively incorporated in the middle of mesopore orbit, antimony source compound, cobalt source compound and complexing agent is loaded with in the duct of mesoporous carbon, for antimony source compound be antimony chloride, cobalt source compound is cobalt chloride hexahydrate, complexing agent for citric acid, this step defines CoCl
2-SbCl
3-C
6h
8o
7the composite granule of@mesoporous carbon.
After obtaining reducing solution and the first mixture respectively, described reducing solution is mixed with described first mixture, reacts, after drying, obtains the second mixture.Wherein, the mode that reducing solution mixes with described first mixture is preferably: dropped in described first mixture by described reducing solution, constantly stir in dropping process.
In the step obtaining the second mixture, for antimony source compound be antimony chloride, cobalt source compound for cobalt chloride hexahydrate, this step is that reducing agent there occurs following reaction with sodium borohydride:
CoCl
2+2NaBH
4＝Co+2BH
3+2NaCI+H
2
2SbCl
3+6NaBH
4＝2Sb+6BH
3+6NaCI+3H
2
As can be seen from above-mentioned reaction, antimony source compound and cobalt source compound are reduced to metal simple-substance respectively.
In the step obtaining nano composite thermoelectric materials, Co and the Sb in the second mixture there occurs solid phase reaction, and detailed process is: Co+3Sb=CoSb
3
Because the duct of the mesoporous carbon of the present invention's employing has restriction, on the one hand the volatilization of antimony in the second mixture is effectively limited, high temperature solid state reaction is made to be able to carry out smoothly in mesopore orbit on the other hand, thus utilize the iris action of the wall of mesoporous carbon that the nanometer antimony cobalt particle of generation is effectively disperseed, avoid the reunion of antimony cobalt and grow up.
In heat treatment process, complexing agent can be analyzed to CO, CO
2with water etc., thus end product is made only to contain antimony cobalt and mesoporous carbon.In addition, because antimony is easy and oxygen reaction generates Sb
2o
3, this oxide has high boiling characteristics, makes solid phase reaction Co+3Sb=CoSb
3the loss of middle Sb source, thus cause easily following side reaction: Co+2Sb=CoSb occurring
2or Co+2Sb=CoSb, produce accessory substance.Therefore, described heat treatment process is carried out under nitrogen and hydrogen mixture atmosphere, under the existence of hydrogen can ensure that whole reaction is still in certain reducing atmosphere, thus the effective oxidation suppressing antimony.The nitrogen of described nitrogen and hydrogen mixture atmosphere and the volume ratio of hydrogen are preferably (90 ~ 99): (1 ~ 10); Be more preferably (93 ~ 97): (3 ~ 7); Most preferably be (94 ~ 96): (4 ~ 6).
Obtain in the step of reducing solution above-mentioned, hydrazine hydrate can also be adopted to be reducing agent, and therefore, the present invention also provides a kind of preparation method of nano composite thermoelectric materials, comprises the following steps:
Hydrazine hydrate is mixed in the first polar organic solvent, obtains reducing solution;
Antimony source compound, cobalt source compound, complexing agent and mesoporous carbon are mixed in polarity second polar organic solvent, after drying, obtains the first mixture;
Described reducing solution is mixed with described first mixture, after drying, obtains the second mixture;
Heat treatment at described second mixture being placed in 380 ~ 550 DEG C under nitrogen and hydrogen mixture atmosphere, obtains nano composite thermoelectric materials after reaction.
In said method, the reducing solution be mixed to get with hydrazine hydrate and the first polar organic solvent, described first polar organic solvent is preferably absolute ethyl alcohol.
Described antimony source compound is preferably soluble antimony source compound, is more preferably antimony chloride; Described cobalt source compound is preferably solubility cobalt source compound, is more preferably cobalt chloride hexahydrate; Described complexing agent is preferably citric acid or oxalic acid.The mol ratio of described antimony source compound and cobalt source compound is preferably (3 ~ 7): 1, is preferably (4 ~ 6): 1, is preferably (4 ~ 5): 1; The mol ratio of described complexing agent and described cobalt source compound is preferably (3 ~ 5): 1, is preferably (3.5 ~ 4.5): 1, is preferably (4 ~ 4.5): 1; The mass ratio of described mesoporous carbon and described cobalt source compound is preferably (3 ~ 12): 1, is preferably (4 ~ 10): 1, is preferably (5 ~ 8): 1.
Compared with prior art, the antimony cobalt of the nanometer scale of preparation is filled in the duct of the mesoporous carbon of micron dimension by the present invention, utilizes the duct restriction of mesoporous carbon, avoids the reunion of the antimony cobalt of nanometer scale in heat treatment process and grows up
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
Embodiment 1
1) by mass ratio be 1: 1 NaOH, sodium borohydride join in the mixed solvent by absolute ethyl alcohol and deionized water successively, obtain reducing solution, the volume ratio of described absolute ethyl alcohol and deionized water is 1: 1, and the substance withdrawl syndrome of described NaOH is 2mol/L;
2) by mol ratio be 5: 5: 1 citric acid, antimony chloride and cobalt chloride hexahydrate be dissolved in absolute ethyl alcohol, forming reactions solution, the substance withdrawl syndrome of described cobalt chloride hexahydrate is 1mol/L;
Meso-porous carbon material is at room temperature vacuumized 12 hours, then add in above-mentioned reaction solution, stir while adding, after having added, continue stirring 3 hours, obtain black mixture, then by described black mixture 30 DEG C, relative humidity be 30% environment lower open mouth leave standstill 25 and littlely all to volatilize up to ethanol, obtain the first mixture, wherein, the mass ratio of described mesoporous carbon and described cobalt chloride hexahydrate is 4: 1;
3) dropwise joined in described first mixture by described reducing solution, dropping process constantly stirs, and obtains the second mixture, and the mol ratio of described sodium borohydride and described antimony chloride is 1: 1;
4) preparation of nanometer antimony cobalt@mesoporous carbon
Heat treatment under the nitrogen and hydrogen mixture atmosphere that described second mixture is 5% at hydrogen content, heat treatment temperature is 500 DEG C, and heat treatment time is 45 minutes, obtains nanometer antimony cobalt@mesoporous carbon composite granule, i.e. antimony cobalt nano composite thermoelectric materials.
Fig. 1, Fig. 2 are respectively the XRD collection of illustrative plates of antimony cobalt nano composite thermoelectric materials prepared by the present embodiment.As can be seen from Figure 1, being about 1.0 degree in the angle of diffraction has diffraction maximum, shows that the duct of mesoporous carbon has certain order.The collection of illustrative plates of Fig. 2 meets corresponding peak in PDF standard card (PDF 65-3144), can obtain purer antimony cobalt nano-particle under this embodiment is described.
Fig. 3 is the transmission electron microscope picture of antimony cobalt nano composite thermoelectric materials prepared by the present embodiment, as can be seen from the figure, nanometer antimony cobalt particle size is at about 20nm, this nanometer antimony cobalt particle is under orderly mesopore orbit effect, scatter equably, mesoporous playing nanometer antimony cobalt particle is well adsorbed and peptizaiton, and in antimony cobalt nano composite thermoelectric materials prepared by the present embodiment, antimony cobalt nano-particle monodispersity is good.
Embodiment 2
1) by mass ratio be 1: 3 NaOH, sodium borohydride join in the mixed solvent by absolute ethyl alcohol and deionized water successively, obtain reducing solution, the volume ratio of described absolute ethyl alcohol and deionized water is 1: 1, and the substance withdrawl syndrome of described NaOH is 2mol/L;
2) by mol ratio be 5: 7: 1 citric acid, antimony chloride and cobalt chloride hexahydrate be dissolved in absolute ethyl alcohol, forming reactions solution, the substance withdrawl syndrome of described cobalt chloride hexahydrate is 1mol/L;
Meso-porous carbon material is at room temperature vacuumized 12 hours, then add in above-mentioned reaction solution, stir while adding, after having added, continue stirring 3 hours, obtain black mixture, then by described black mixture 30 DEG C, relative humidity be 30% environment lower open mouth leave standstill 25 and littlely all to volatilize up to ethanol, obtain the first mixture, wherein, the mass ratio of described mesoporous carbon and described cobalt chloride hexahydrate is 4: 1;
3) dropwise joined in described first mixture by described reducing solution, dropping process constantly stirs, and obtains the second mixture, and the mol ratio of described sodium borohydride and described antimony chloride is 1: 1;
4) preparation of nanometer antimony cobalt@mesoporous carbon
Heat treatment under the nitrogen and hydrogen mixture atmosphere that described second mixture is 5% at hydrogen content, heat treatment temperature is 430 DEG C, and heat treatment time is 60 minutes, obtains nanometer antimony cobalt@mesoporous carbon composite granule, i.e. antimony cobalt nano composite thermoelectric materials.
Fig. 4, Fig. 5 are respectively the XRD collection of illustrative plates of antimony cobalt nano composite thermoelectric materials prepared by the present embodiment.As can be seen from Figure 4, being about 1.0 degree in the angle of diffraction has diffraction maximum, shows that the duct of mesoporous carbon has certain order.The collection of illustrative plates of Fig. 5 meets corresponding peak in PDF standard card (PDF 65-3144), can obtain purer antimony cobalt nano-particle under these examples of implementation are described.
Fig. 6 is the transmission electron microscope picture of antimony cobalt nano composite thermoelectric materials prepared by the present embodiment, as can be seen from the figure, nanometer antimony cobalt particle size is at about 40nm, this nanometer antimony cobalt particle is under orderly mesopore orbit effect, scatter equably, mesoporous playing nanometer antimony cobalt particle is well adsorbed and peptizaiton, and in antimony cobalt nano composite thermoelectric materials prepared by the present embodiment, antimony cobalt nano-particle monodispersity is good.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for nano composite thermoelectric materials, comprises the following steps:
NaOH, sodium borohydride are mixed in a solvent, obtains reducing solution;
Antimony source compound, cobalt source compound, complexing agent and mesoporous carbon are mixed in volatile polar organic solvent, after drying, obtains the first mixture;
The aperture of described mesoporous carbon is between 2nm to 50nm;
Described reducing solution is mixed with described first mixture, reacts, after drying, obtains the second mixture;
Heat treatment at described second mixture being placed in 380 ~ 550 DEG C under nitrogen and hydrogen mixture atmosphere, obtains nano composite thermoelectric materials after reaction.
2. preparation method according to claim 1, it is characterized in that, the mass ratio of described NaOH and sodium borohydride is 1:(0.5 ~ 5).
3. preparation method according to claim 1, it is characterized in that, described solvent is the mixed solvent of absolute ethyl alcohol and deionized water.
4. preparation method according to claim 1, it is characterized in that, the mol ratio of described sodium borohydride and described antimony source compound is (0.8 ~ 2): 1.
5. preparation method according to claim 1, it is characterized in that, described antimony source compound is antimony chloride, and described cobalt source compound is cobalt chloride hexahydrate, and described complexing agent is citric acid or oxalic acid.
6. preparation method according to claim 1, it is characterized in that, the mol ratio of described antimony source compound and cobalt source compound is (3 ~ 7): 1.
7. preparation method according to claim 1, it is characterized in that, the mol ratio of described complexing agent and described cobalt source compound is (3 ~ 5): 1.
8. preparation method according to claim 1, it is characterized in that, the mass ratio of described mesoporous carbon and described cobalt source compound is (3 ~ 12): 1.
9. preparation method according to claim 1, it is characterized in that, described heat treatment time is 20 ~ 80 minutes.
10. a preparation method for nano composite thermoelectric materials, comprises the following steps:
Hydrazine hydrate is mixed in the first polar organic solvent, obtains reducing solution;
Antimony source compound, cobalt source compound, complexing agent and mesoporous carbon are mixed in polarity second polar organic solvent, after drying, obtains the first mixture;
The aperture of described mesoporous carbon is between 2nm to 50nm;
Described reducing solution is mixed with described first mixture, after drying, obtains the second mixture;
Heat treatment at described second mixture being placed in 380 ~ 550 DEG C under nitrogen and hydrogen mixture atmosphere, obtains nano composite thermoelectric materials after reaction.
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