CN100546063C - A kind of preparation method of core-shell structure nano pyroelectric material - Google Patents
A kind of preparation method of core-shell structure nano pyroelectric material Download PDFInfo
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- CN100546063C CN100546063C CNB2008100598819A CN200810059881A CN100546063C CN 100546063 C CN100546063 C CN 100546063C CN B2008100598819 A CNB2008100598819 A CN B2008100598819A CN 200810059881 A CN200810059881 A CN 200810059881A CN 100546063 C CN100546063 C CN 100546063C
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Abstract
The present invention relates to a kind of preparation method of nano pyroelectric material.The nuclear of the core-shell structure nano pyroelectric material of method preparation at present and shell are in conjunction with bad.Method of the present invention is: raw material is added in the reaction vessel, add distilled water, potassium borohydride, NaOH and polyethylene glycol, make spherical nano inner core; With spherical nano inner core washing, drying, be dispersed in the solvent, carry out surface treatment; Spherical nano inner core is added in the autoclave, add raw material, potassium borohydride and NaOH again, add distilled water, core-shell structure nano pyroelectric material.Raw material of the present invention is two or more in soluble-salt, tellurium powder and the selenium powder of Bi, Sb, Zn, Pb, Co, Fe, Sn.Among the present invention, the end group of surface treatment auxiliary agent can carry out complexing with elements such as the spherical nano inner core of thermoelectric material and the bismuth in the shell, antimony, zinc, lead, cobalt, iron, tin, thereby realize that spherical nano inner core and the tight of shell are connected.
Description
Technical field
The invention belongs to the semi-conductor thermoelectric material technical field, relate to thermoelectric material, that concrete is a kind of preparation method of core-shell structure nano pyroelectric material.
Background technology
Thermoelectric material is that a kind of solid interior carrier moving that utilizes is realized the functional material that heat energy and electric energy are directly changed mutually, promptly utilize the Seebeck effect to realize that heat energy is directly changed into electric energy, utilize the Peltier effect to make the transfer of heat from the low-temperature end to the temperature end realize refrigeration on the contrary.Nos drive disk assembly, no dry sound move, excellent properties such as pollution-free, accurate reliable owing to have, the thermoelectric conversion device that is made up by thermoelectric material is desirable power supply and refrigerator, is widely used in many fields such as people's stone petrochemical industry, detecting instrument, Aero-Space, household electrical appliance.
Compare with traditional refrigerator or generator, the conversion efficiency of thermoelectric of thermoelectric material is on the low side (less than 10%), and this also is the maximum bottleneck of thermoelectric material development.The conversion efficiency of thermoelectric of thermoelectric material depends on nondimensional thermoelectric figure of merit ZT:ZT=S
2σ T/K, S are the Seebeck coefficient, and T is an absolute temperature, and σ is a conductivity, and K is a thermal conductivity.The thermoelectric figure of merit ZT of traditional hot electric material is all less than 1.All the time, scientists is attempted the thermoelectric figure of merit that various new approach improves thermoelectric material, solves low this long-term puzzled problem of conversion efficiency of thermoelectric.T.F.Zeng (J.Appl.Phys.2003,93,4163) and R.Prasher (Appl.Phys.Lett.2006,89,063121) study core-shell structure nano pyroelectric material, show that it has high thermoelectric figure of merit.But the preparation of core-shell structure nano pyroelectric material exists nuclear and shell in conjunction with bad difficulty always.
Summary of the invention
Purpose of the present invention is exactly at the deficiencies in the prior art, and a kind of preparation method of core-shell structure nano pyroelectric material is provided, this method can solve well nuclear and shell in conjunction with bad difficulty.
Core-shell structure nano pyroelectric material of the present invention comprises spherical nano inner core and is coated on the outer shell of spherical nano inner core that spherical nano inner core and shell concentric closely cooperate, spherical nano inner core and the different thermoelectric material of shell employing.
The material of described spherical nano inner core is Sb
2Te
3Or Bi
2Te
3, and the thermoelectric material that replaces or partly replace Sb, Bi and Te with Sn, Se, Pb, Zn, Co, Fe.
The material of described shell is Sb
2Te
3Or Bi
2Te
3, and the thermoelectric material that replaces or partly replace Sb, Bi and Te with Sn, Se, Pb, Zn, Co, Fe.
Preparation method's concrete steps of core-shell structure nano pyroelectric material of the present invention are:
A. with in two or more adding reaction vessel in soluble-salt, tellurium powder and the selenium powder raw material of Bi, Sb, Zn, Pb, Co, Fe, Sn, add distilled water, potassium borohydride, NaOH and macromolecular compound polyethylene glycol (molecular weight is 20000) then, under 50 ℃～100 ℃ conditions, reacted 12～48 hours, make the spherical nano inner core of core-shell structure nano pyroelectric material;
B. the spherical nano inner core of gained is successively also dry with ethanol and distilled water washing, dried nanometer inner core is dispersed in the solvent, normal temperature stirs down and carries out surface treatment behind the adding surface treatment auxiliary agent;
C. will add through the spherical nano inner core after the surface treatment in the autoclave, again with in two or more adding reaction vessel in soluble-salt, tellurium powder and the selenium powder raw material of Bi, Sb, Zn, Pb, Co, Fe, Sn, add potassium borohydride and NaOH then, add distilled water to 70%～90% of reactor volume, under 120 ℃～200 ℃ conditions, reacted 12～48 hours, obtain core-shell structure nano pyroelectric material.
Wherein the soluble-salt of the Bi described in step a and the c, Sb, Zn, Pb, Co, Fe, Sn is nitrate, sulfate or chloride.
Wherein the solvent described in the step b is one or more the mixture in water, methyl alcohol, ethanol, acetone, the toluene; Described surface treatment auxiliary agent be an end have-SH group, the other end have-functional compounds of COOH group, the concentration of surface treatment auxiliary agent is 0.1wt%～20wt%.
Among the present invention, the end group of surface treatment auxiliary agent can carry out complexing with elements such as the spherical nano inner core of thermoelectric material and the bismuth in the shell, antimony, zinc, lead, cobalt, iron, tin, thereby realize that spherical nano inner core and the tight of shell are connected.
Description of drawings
Fig. 1 is the structural representation of core-shell structure nano pyroelectric material of the present invention.
Embodiment
As shown in Figure 1, core-shell structure nano pyroelectric material comprises spherical nano inner core 1 and is coated on the outer shell 2 of spherical nano inner core that spherical nano inner core 1 and shell 2 closely cooperate with the garden heart, spherical nano inner core 1 and the different thermoelectric material of shell 2 employings.
The material of spherical nano inner core 1 is Sb
2Te
3Or Bi
2Te
3, and the thermoelectric material that replaces and partly replace Sb, Bi and Te with Sn, Se, Pb, Zn, Co, Fe.
The material of shell 2 is Sb
2Te
3Or Bi
2Te
3, and the thermoelectric material that replaces and partly replace Sb, Bi and Te with Sn, Se, Pb, Zn, Co, Fe.
The preparation method is specially among the present invention:
Embodiment 1:
(1) in reaction vessel, adds 0.1 gram tellurium powder, 0.12 gram bismuth chloride, 200 ml distilled waters, 5 gram polyethylene glycol, 1.5 gram NaOH, 1 gram sodium borohydride successively.Stirring also makes temperature of reaction kettle be controlled at 50 ℃, and insulation 48h obtains Bi
2Te
3Spherical nano inner core.
(2) with Bi
2Te
3Spherical nano inner core powder takes out, and is dry with ethanol and distilled water washing back respectively then.
(3) with the Bi that cleans
2Te
3Spherical nano inner core powder is put into 200 ml beakers, adds 100 ml waters, and uses magnetic agitation.Add 0.1 gram surface treatment reagent then and dredge guanidine-acetic acid, normal temperature stirs 5h down and carries out surface treatment.
(4) will be through the Bi after the surface conditioning agent processing
2Te
3Spherical nano inner core powder is used ethanol and distilled water clean dry respectively, adds then in the autoclave, adds 0.1 gram tellurium powder, 0.12 gram antimony chloride, 1.5 gram NaOH, 1 gram sodium borohydride more successively.Add distilled water to 70% of reactor volume, carry out solvent thermal reaction and make temperature of reaction kettle be controlled at 120 ℃, insulation 48h obtains Bi
2Te
3Be kernel, Sb
2Te
3Core-shell structure nano pyroelectric material for shell.
Embodiment 2:
(1) in reaction vessel, adds 0.1 gram tellurium powder, 0.12 gram antimony chloride, 200 ml distilled waters, 5 gram polyethylene glycol, 1.5 gram NaOH, 1 gram sodium borohydride successively.Stirring also makes temperature of reaction kettle be controlled at 100 ℃, and insulation 12h obtains Sb
2Te
3Spherical nano inner core.
(2) with Sb
2Te
3Spherical nano inner core powder takes out, and is dry with ethanol and distilled water washing back respectively then.
(3) with the Sb that cleans
2Te
3Spherical nano inner core powder is put into 200 ml beakers, adds 100 milliliters of ethanol, and uses magnetic agitation.Add 20 gram surface treatment reagent then and dredge basic propionic acid, normal temperature stirs 5h down and carries out surface treatment.
(4) will be through the Sb after the surface conditioning agent processing
2Te
3Nano-powder is used ethanol and distilled water clean dry respectively, adds then in the autoclave, adds 0.1 gram tellurium powder, 0.12 gram bismuth chloride, 1.5 gram NaOH, 1 gram sodium borohydride again.Add distilled water to 90% of reactor volume, carry out solvent thermal reaction and make temperature of reaction kettle be controlled at 200 ℃, insulation 12h obtains Sb
2Te
3Be kernel, Bi
2Te
3Core-shell structure nano pyroelectric material for shell.
Embodiment 3:
(1) in reaction vessel, adds 0.1 gram selenium powder, 0.12 gram nitric acid antimony, 200 ml distilled waters, 5 gram polyethylene glycol, 1.5 gram NaOH, 1 gram sodium borohydride successively.Stirring also makes temperature of reaction kettle be controlled at 80 ℃, and insulation 18h obtains Sb
2Se
3Spherical nano inner core material.
(2) with Sb
2Se
3Spherical nano inner core powder takes out, and is dry with ethanol and distilled water washing back respectively then.
(3) with the Sb that cleans
2Se
3Spherical nano inner core powder is put into 200 ml beakers, adds 100 ml waters, and uses magnetic agitation.Add the two thin basic ethanedioic acids of 10 gram surface treatment reagent then, normal temperature stirs 5h down and carries out surface treatment.
(4) will be through the Sb after the surface conditioning agent processing
2Se
3Spherical nano inner core powder is used ethanol and distilled water clean dry respectively, adds then in the autoclave, adds 0.1 gram tellurium powder, 0.06 gram bismuth chloride, 0.06 gram ferric sulfate, 1.5 gram NaOH, 1 gram sodium borohydride more successively.Add distilled water to 90% of reactor volume, carry out solvent thermal reaction and make temperature of reaction kettle be controlled at 180 ℃, insulation 18h obtains Sb
2Se
3Be kernel, BiFeTe
3Core-shell structure nano pyroelectric material for shell.
Embodiment 4:
(1) in reaction vessel, adds 0.1 gram tellurium powder, 0.12 gram antimony chloride, 200 ml distilled waters, 5 gram polyethylene glycol, 1.5 gram NaOH, 1 gram sodium borohydride successively.Stirring also makes temperature of reaction kettle be controlled at 100 ℃, and insulation 12h obtains Sb
2Te
3Spherical nano inner core material.
(2) with Sb
2Te
3Spherical nano inner core powder takes out, and is dry with ethanol and distilled water washing back respectively then.
(3) with the Sb that cleans
2Te
3Spherical nano inner core powder is put into 200 ml beakers, adds 50 milliliters of distillations and 50 milliliters of acetone, and uses magnetic agitation.Add 8 gram surface treatment reagent then and dredge basic propionic acid, normal temperature stirs 5h down and carries out surface treatment.
(4) will be through the Sb after the surface conditioning agent processing
2Te
3Spherical nano inner core powder is used ethanol and distilled water clean dry respectively, adds then in the autoclave, adds 0.1 gram cobalt nitrate, 0.25 gram nitric acid antimony, 1.5 gram NaOH, 2 gram sodium borohydrides more successively.Add distilled water to 80% of reactor volume, carry out solvent thermal reaction and make temperature of reaction kettle be controlled at 200 ℃, insulation 12h obtains Sb
2Te
3Be kernel, CoSb
3Core-shell structure nano pyroelectric material for shell.
Embodiment 5:
(1) in reaction vessel, adds 0.1 gram tellurium powder, 0.15 gram bismuth sulfate, 200 ml distilled waters, 5 gram polyethylene glycol, 1.5 gram NaOH, 1 gram sodium borohydride successively.Stirring also makes temperature of reaction kettle be controlled at 60 ℃, and insulation 40h obtains Bi
2Te
3Spherical nano inner core material.
(2) with Bi
2Te
3Spherical nano inner core powder takes out, and is dry with ethanol and distilled water washing back respectively then.
(3) with the Bi that cleans
2Te
3Spherical nano inner core powder is put into 200 ml beakers, adds 100 milliliters of toluene, and uses magnetic agitation.Add 0.2 gram surface treatment reagent then and dredge guanidine-acetic acid, normal temperature stirs 5h down and carries out surface treatment.
(4) will be through the Bi after the surface conditioning agent processing
2Te
3Spherical nano inner core powder is used ethanol and distilled water clean dry respectively, adds then in the autoclave, adds 0.1 gram cobalt nitrate, 0.25 gram nitric acid antimony, 1.5 gram NaOH, 2 gram sodium borohydrides more successively.Add distilled water to 80% of reactor volume, carry out solvent thermal reaction and make temperature of reaction kettle be controlled at 150 ℃, insulation 20h obtains Bi
2Te
3Be kernel, CoSb
3Core-shell structure nano pyroelectric material for shell.
Claims (1)
1, a kind of preparation method of core-shell structure nano pyroelectric material is characterized in that these preparation method's concrete steps are:
A. with in two or more adding reaction vessel in soluble-salt, tellurium powder and the selenium powder raw material of Bi, Sb, Zn, Pb, Co, Fe, Sn, add distilled water, potassium borohydride, NaOH and polyethylene glycol then, under 50 ℃～100 ℃ conditions, reacted 12～48 hours, make the spherical nano inner core of core-shell structure nano pyroelectric material;
B. the spherical nano inner core of gained is successively also dry with ethanol and distilled water washing, dried spherical nano inner core is dispersed in the solvent, normal temperature stirs down and carries out surface treatment behind the adding surface treatment auxiliary agent;
C. will add through the spherical nano inner core after the surface treatment in the autoclave, again with in two or more adding reaction vessel in soluble-salt, tellurium powder and the selenium powder raw material of Bi, Sb, Zn, Pb, Co, Fe, Sn, add potassium borohydride and NaOH then, add distilled water to 70%～90% of reactor volume, under 120 ℃～200 ℃ conditions, reacted 12～48 hours, obtain core-shell structure nano pyroelectric material;
Wherein the soluble-salt of the Bi described in step a and the c, Sb, Zn, Pb, Co, Fe, Sn is nitrate, sulfate or chloride;
Wherein the solvent described in the step b is one or more the mixture in water, methyl alcohol, ethanol, acetone, the toluene; Described surface treatment auxiliary agent be an end have-SH group, the other end have-functional compounds of COOH group;
The kernel of described core-shell structure nano pyroelectric material adopts different thermoelectric materials with shell.
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