CN102569630A - Laminated inorganic compound/organic matter intercalation compound thermoelectric material and preparation method thereof - Google Patents
Laminated inorganic compound/organic matter intercalation compound thermoelectric material and preparation method thereof Download PDFInfo
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- CN102569630A CN102569630A CN2012100558184A CN201210055818A CN102569630A CN 102569630 A CN102569630 A CN 102569630A CN 2012100558184 A CN2012100558184 A CN 2012100558184A CN 201210055818 A CN201210055818 A CN 201210055818A CN 102569630 A CN102569630 A CN 102569630A
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- fatty amine
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- 238000009830 intercalation Methods 0.000 title claims abstract description 126
- 230000002687 intercalation Effects 0.000 title claims abstract description 126
- 239000000463 material Substances 0.000 title claims abstract description 112
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 47
- 150000002484 inorganic compounds Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title abstract description 27
- 239000005416 organic matter Substances 0.000 title abstract 3
- 150000001412 amines Chemical class 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 21
- 238000011065 in-situ storage Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 239000011147 inorganic material Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 238000010669 acid-base reaction Methods 0.000 claims description 5
- 150000004770 chalcogenides Chemical class 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 29
- 239000000843 powder Substances 0.000 description 29
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 20
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 10
- 239000003708 ampul Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 6
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000002052 molecular layer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
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- 239000002356 single layer Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- MQANMCFSNPBYCQ-UHFFFAOYSA-N decan-2-amine Chemical compound CCCCCCCCC(C)N MQANMCFSNPBYCQ-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
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Abstract
The invention provides a laminated inorganic compound/organic matter intercalation compound thermoelectric material, wherein an organic matter intercalation is a fatty amine intercalation. The invention further provides a preparation method thereof. According to the invention, the intercalation compound thermoelectric material with a complete laminated structure and controllable intercalation degrees as well as the preparation method thereof are obtained.
Description
Technical field
The present invention relates to a kind of composite thermoelectric material and preparation method thereof, relate to a kind of layered inorganic compound/organic substance intercalation composite thermoelectric material and preparation method thereof particularly.
Background technology
Thermoelectric generation technology is to utilize the Sai Beike of semi-conducting material (Seebeck) effect and Pa Er card (Peltier) effect to carry out the directly technology of conversion of energy, and conversion efficiency depends primarily on the dimensionless performance index of material, i.e. ZT value (Z=α
2σ/κ, wherein α is the Seebeck coefficient; σ is a conductivity; κ is a thermal conductivity).Influencing the maximum restraining factors that thermo-electric converting material uses is that its conversion efficiency of thermoelectric is low, but along with modern age technical applications constantly widen the raising with level, the advantage of all kinds of thermoelectric devices that reach its maturity has received extensive concern.
In today that environmental protection comes into one's own day by day; Thermoelectric device further comes into one's own because of the potentiality of its used heat free from environmental pollution, capable of using and regenerative resource again, is used widely at numerous areas such as petrochemical industry, detecting instrument, environmental protection, Aero-Space, health care, household electrical appliance.As all solid state generating and refrigerator, thermoelectric device has incomparable advantage, and characteristics such as having movement-less part, noiseless, easy miniaturization, be easy to control, reliability is high, the life-span is long are used but its lower thermoelectric figure of merit has restricted it widely.
Present research focus is to prepare the multilayer hetero-structure thermoelectric material through intercalation technique to be the exploitation high performance thermoelectric material.
We know; Intercalation Subjective and Objective composite material is meant stratiform or the layer column chemical substance that is made up of lamellar compound and the heterogeneous material (atom, molecule or ion) that inserts its interlayer; Wherein, the atom on the laminate interacts with strong covalent bond, and interlayer interacts with molecular separating force.For some layered inorganic thermoelectric compound; Since the interlayer intermolecular force a little less than; Under certain condition, some organic polar molecules can get into the interlayer of lamellar compound and not destroy its layer structure through power between absorption, insertion, suspension, mode saboteur such as pillared.
Inorganic/organic composite thermoelectric material normally was studied with the form of simple composite thing in the past; And relevant inorganic/the organic intercalation composite thermoelectric material, research work at present both at home and abroad is all less, and intercalation technology is loaded down with trivial details; Usually the stripping process that needs material of main part causes number of drawbacks easily.The people such as Z.J.Huang of National Taiwan University department of physics once attempted studying superconductor Bi
2Sr
2Superconductor critical transition temperature in Can-1CunOy [Bi-22 (n-1) n] system behind organic molecule Phthalocyanine Zinc (ZnPc) intercalation suppresses the variation of phenomenon, carrier concentration, and the differentiation of Seebeck coefficient.Because Bi
2Sr
2Be weak Van der Waals (Van der Waals) power between two BiO layers among the Can-1CunOy, for the object intercalation provides possibility.Behind the intercalation, the expansion of BiO layer can increase adjacent superconduction framework (CuO
2) spacing distance of n, change the coupling between them; In addition, charge carrier is at intercalation object and superconduction framework (CuO
2) migration between the n can change (CuO
2) carrier density of n framework.In the experiment, they prepare the ZnPc single crystal samples earlier, make Bi-2223 bead and monocrystalline ZnPc that diffusion reaction takes place in the vacuum heat resistant furnace then and prepare the intercalation oxide.Their prepared polycrystalline sample comprises a plurality of sub-districts of random distribution, and each sub-district is made up of the lamellar single crystal particle of 30-100 micron, and its lamellar single crystal is perpendicular to the C axle of unit cell.Their experiment confirm above prediction; (ZnPc) the xBi-2212 oxide and (ZnPc) the Seebeck coefficient of xBi-2223 oxide have significantly been changed behind the organic molecule Phthalocyanine Zinc intercalation; The Seebeck coefficient of two individual system has all taken place to increase substantially; And along with the raising of intercalation degree, the Seebeck coefficient of system progressively rises.
In addition; The researcher of mechanisms such as Regius professor has reported the nanometer sheet preparation method that a kind of UltraDialUp is used nearest in February, 2011 on " Science " magazine; The material that is about to have layer structure places some solvent; Utilize supersonic oscillations then, just can make these material breakdown become to have only the nanometer sheet of one deck atom thick.In the experiment, they utilize the method with WS
2The stripping layer with Graphene and single armed CNT (SWNT) mixed and dispersed, utilizes vacuum filtration or spray technique to be prepared into film then subsequently.They discover, the WS that utilizes the method to prepare
2/ SWNT mixed film shows the conductivity and the thermoelectric (al) power factor of remarkable enhancing.If will there be some problems in inorganic/organic lamination compound but adopt this method to prepare; Because there is high activity in the monolayer nano material that the stripping layer forms; Be easy to take place the oxidation reaction of lamellar compound; And form numerous blemish, thereby destroy the carrier transport of composite thermoelectric material.
In sum, the intercalated compound of inorganic laminated thermoelectric material of the structure of this area and organic material still is in theory and exploratory stage, does not obtain the preparation method of the intercalation composite thermoelectric material that layer structure is complete, the intercalation degree is controlled at present.
Therefore, this area presses for exploitation and obtains intercalation composite thermoelectric material that layer structure is complete, the intercalation degree is controlled and preparation method thereof.
Summary of the invention
First purpose of the present invention is a kind of intercalation composite thermoelectric material that layer structure is complete, the intercalation degree is controlled that obtains.
Second purpose of the present invention is a kind of preparation method who obtains the intercalation composite thermoelectric material that layer structure is complete, the intercalation degree is controlled.
The 3rd purpose of the present invention is a kind of preparation method who obtains the intercalation composite thermoelectric material that layer structure is complete, the intercalation degree is controlled.
In first aspect of the present invention, a kind of layered inorganic compound/organic substance intercalation composite thermoelectric material is provided, said organic substance intercalation is the fatty amine intercalation.
In " layered inorganic compound/organic substance intercalation " of the present invention, "/" be the representative " with " relation.In the layered structure, layered inorganic compound is as material of main part, and organic substance is as the intercalation guest materials.
In an embodiment, layered inorganic compound is meant to have the molecular layer structure of taking as the leading factor with Van der Waals force in the structure cell.
In an embodiment of the present invention, layered inorganic compound/organic substance intercalation composite thermoelectric material has significantly reduced lattice thermal conductivity.Preferred, said lattice thermal conductivity is at 1.2W/m.K～0.1W/m.K.
In an embodiment of the present invention, the intercalation guest materials of said fatty amine intercalation is weakly alkaline fatty amine.
In an embodiment, said " alkalescent " be meant alkalescence at pKb (25 ℃) between 3～5, preferred pKb (25 ℃) is between 3～4.
In an embodiment of the present invention, described intercalation guest materials is the C4～C20 fatty amine of side chain or straight chain.
In a preferred implementation, described intercalation guest materials is butylamine, lauryl amine, hexadecylamine or its combination.
In an embodiment of the present invention, the material of main part of said inorganic compound is oxide and/or the sulfide with layer structure.
In an embodiment of the present invention, the material of main part of said inorganic compound is oxide and/or the sulfide with lamellar single crystal structure.
In an embodiment, the material of main part of the inorganic compound in the invention is to be raw material with high pure metal and nonmetal, semiconductor etc., according to the reactant ratio of setting, the layered inorganic thermoelectric material powder that adopts conventional solid reaction process to prepare.
In an embodiment, the process conditions of said solid reaction process are: with high pure metal Ti powder, sulphur powder is raw material, and by Ti: the S mole is 1: proportioning (2+0.05) is fully mixed both in quartz ampoule.Ampoule is evacuated, and reaction is 90 hours under 600 ℃ of conditions, cooling subsequently, and evaporate remaining sulphur composition, prepare TiS
2Powder; Thereby acquisition mono-crystalline structures.
In an embodiment of the present invention, the material of main part of said inorganic compound is to be selected from Bi
2Sr
2Ca
N-1Cu
nO
y(n=1,2,3,4, y=0,1,2), Nd
2-yCe
yCuO
4Or La
2-ySr
yCuO
4(y=0,1,2), Pb
2Sr
2Y
1-yCa
yCu
3O
8Or HgBa
2Y
1-yCa
yCu
nO
2n+2The layered oxide of (y=0,1),
Perhaps be selected from TiS
2, Bi
2S
3, Bi
2Te
3, Bi
2Se
3The stratiform chalcogenide.
Second aspect of the present invention provides the preparation method of a kind of layered inorganic compound of the present invention/organic substance intercalation composite thermoelectric material, and described intercalation mode is the in-situ chemical reaction that acid-base reaction drives.
In the present invention, said " in-situ chemical reaction " is meant: this intercalation need not earlier stripping layer, the technology of lamination again.Intercalation solution among the present invention itself has alkalescent, through the diffusion and the electron transfer of anion, can bring out that intercalation is spontaneous to carry out.
In an embodiment of the present invention, said preparation method may further comprise the steps:
The material of main part of layered inorganic compound is provided;
Adopt the intercalation guest materials that said material of main part is carried out intercalation, described intercalation mode is the in-situ chemical reaction that acid-base reaction drives, and obtains layered inorganic compound/organic substance intercalation composite thermoelectric material.
In an embodiment of the present invention, the reaction temperature of said in-situ chemical reaction is in room temperature to the 160 ℃ scope.The present invention adopt in room temperature to the 160 ℃ scope than low reaction temperatures, to keep the stable of inorganic material of main part composition and structure.
In an embodiment of the present invention, regulate in the intercalation process interlamellar spacing of inorganic matter material of main part in the in-situ chemical reaction through the length of alkyl chain in the fatty amine of selecting the intercalation guest materials.
In an embodiment of the present invention, the length of alkyl chain is 4 in fatty amine, and the interlamellar spacing of inorganic matter material of main part is controlled in 6.3 dusts that expand; The length of alkyl chain is 12 in fatty amine, and the interlamellar spacing of inorganic matter material of main part is controlled in 17.1 dusts that expand.The length of alkyl chain is 16 in fatty amine, and the interlamellar spacing of inorganic matter material of main part is controlled in 22 dusts that expand.
In an embodiment of the present invention, regulate intercalation quantity and the arrangement mode of organic substance intercalation in layer in the composite thermoelectric material through proportioning, control reaction temperature and the time of selecting object fatty amine and inorganic material of main part.
In an embodiment,
The proportioning of selecting object fatty amine and inorganic material of main part is that mol ratio 1～5, control reaction temperature are room temperature～50 degree, and controlling reaction time is 0.5h～5h, makes that the interior arrangement mode of organic substance intercalation in layer of composite thermoelectric material is the monolayer intercalation;
The proportioning of selecting object fatty amine and inorganic material of main part is that mol ratio 6～20, control reaction temperature are 50～160 degree; Controlling reaction time is 5h～160h, makes that interior intercalation quantity of composite thermoelectric material and the arrangement mode of organic substance intercalation in layer are the bilayer intercalation.
In an embodiment of the present invention,, can be embodied directly in the intercalation in the inorganic host molecule for having weakly alkaline fatty amine molecule.
The third aspect of the invention provides the thermoelectric device that a kind of described layered inorganic compound/organic substance intercalation composite thermoelectric material makes.
Description of drawings
Fig. 1 is layered inorganic compound/fatty amine intercalation composite thermoelectric material schematic arrangement, (a) individual layer alkylamine molecule intercalation, (b) double-deck alkylamine molecule intercalation;
Fig. 2 is TiS
2The TEM figure of/lauryl amine intercalated compound;
The initial TiS of Fig. 3
2Powder, TiS
2/ butylamine intercalated compound, TiS
2The XRD diffracting spectrum of/lauryl amine intercalated compound;
Fig. 4 is TiS
2Briquetting, TiS
2/ butylamine intercalation compound briquetting, TiS
2/ lauryl amine intercalation compound briquetting, TiS
2The thermal conductivity of/hexadecylamine intercalation compound briquetting and the graph of a relation of temperature.
Embodiment
The inventor through improving preparation technology, has obtained intercalation composite thermoelectric material that layer structure is complete, the intercalation degree is controlled and preparation method thereof through extensive and deep research.Accomplished the present invention on this basis.
The preparation method who the objective of the invention is the inorganic matter that layer structure is complete in order to obtain, the intercalation degree is controlled/fatty amine intercalation composite thermoelectric material.
In order to achieve the above object, the present invention adopts following technical conceive:
Some oxide and sulfide stratiform inorganic matter, its carrier transport mainly carry out through jumping between lattice layer or between lattice point.Especially; These stratiform thermoelectric materials are different from the traditional hot electric material; Its electronic structure is relevant with the degree of freedom of electron spin, lattice and track, might realize the independent regulation and control to conductivity and Seebeck coefficient, for the exploitation high performance thermoelectric material provides possibility.
And the intercalated compound that makes up inorganic laminated thermoelectric material and organic material is a very significant exploration.Theoretical prediction shows; If inorganic thermoelectric compound molecular layer by interlayer between the organic substance material; Can cause strong phonon confinement effect, promptly this soft interface can produce the space confinement and change its group velocity phonon, improves the phonon relaxation velocity; Reduce lattice thermal conductivity significantly, thereby improve the thermoelectric figure of merit of material.
Among the present invention, term " contains " or the various compositions of " comprising " expression can be applied in mixture of the present invention or the composition together.Therefore, term " mainly by ... form " be included in " by ... composition " that term " contains " or in " comprising ".
Specify like nothing, various raw materials of the present invention all can obtain through commercially available; Or prepare according to the conventional method of this area.Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
The term of this area can be referring to following content:
(1) Alexander Balandin and Kang L.Wang; " Effect of phonon confinement on the thermoelectric figure of merit of quantum wells "; Applied chemistry magazine (Journal of Applied Physics); 84,6149 (1998).
(2) Z.J.Huang, J.G.Lin, J.J.Lin; C.Y.Huang, L.Grigoryan, and K.Yakushi; " Thermoelectric power study on high-Tc Bi-2212 and-2223 oxides Iintercalated with organic molecules zincphthalocyanine "; Physics C part (Physica C), 244,305 (1995).
(3) Jonathan N.Coleman, Mustafa Lotya, Arlene O ' Neill, Shane D.Bergin; Paul J.King, Umar Khan, Karen Young, Alexandre Gaucher; Sukanta De, Ronan J.Smith, Igor V.Shvets, et al; " Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials ", science (Science), 331,568 (2011).
Below detail to various aspects of the present invention:
Thermoelectric material
A kind of layered inorganic compound of the present invention/organic substance intercalation composite thermoelectric material, said organic substance intercalation is the fatty amine intercalation.
In " layered inorganic compound/organic substance intercalation " of the present invention, "/" be the representative " with " relation.In the layered structure, layered inorganic compound is as material of main part, and organic substance is as the intercalation guest materials.
The intercalation guest materials
Intercalation guest materials among the present invention is preferably multiple fatty amine molecules such as butylamine, lauryl amine, hexadecylamine.
In an embodiment of the present invention, layered inorganic compound/organic substance intercalation composite thermoelectric material has significantly reduced lattice thermal conductivity.Preferred, said lattice thermal conductivity is at 1.2W/m.K～0.1W/m.K.
In an embodiment of the present invention, the intercalation guest materials of said fatty amine intercalation is weakly alkaline fatty amine.
In an embodiment, said " alkalescent " is meant alkaline pKb (25 ℃) between between 3～5, and preferred pKb (25 ℃) is between 3～4.
In an embodiment of the present invention, described intercalation guest materials is butylamine, lauryl amine, hexadecylamine or its combination.
The material of main part of inorganic compound
Having the molecular layer structure of taking as the leading factor with Van der Waals force in the inorganic compound employing structure cell of the present invention gets final product.
In an embodiment of the present invention, the material of main part of said inorganic compound is oxide and/or the sulfide with layer structure.
In an embodiment of the present invention, the material of main part of said inorganic compound is oxide and/or the sulfide with lamellar single crystal structure.
In an embodiment, the material of main part of the inorganic compound in the invention is to be raw material with high pure metal and nonmetal, semiconductor etc., according to the reactant ratio of setting, the layered inorganic thermoelectric material powder that adopts conventional solid reaction process to prepare.
In an embodiment, the process conditions of said solid reaction process are: with high pure metal Ti powder, sulphur powder is raw material, and by Ti: the S mole is 1: proportioning (2+0.05) is fully mixed both in quartz ampoule.Ampoule is evacuated, and reaction is 90 hours under 600 ℃ of conditions, cooling subsequently, and evaporate remaining sulphur composition, prepare TiS
2Powder; Thereby acquisition mono-crystalline structures.
In an embodiment of the present invention, the material of main part of said inorganic compound is to be selected from Bi
2Sr
2Ca
N-1Cu
nO
y(n=1,2,3,4, y=0,1,2), Nd
2-yCe
yCuO
4Or La
2-ySr
yCuO
4(y=0,1,2), Pb
2Sr
2Y
1-yCa
yCu
3O
8Or HgBa
2Y
1-yCa
yCu
nO
2n+2The layered oxide of (y=0,1).
Perhaps the material of main part of said inorganic compound is selected from TiS
2, Bi
2S
3, Bi
2Te
3, Bi
2Se
3The stratiform chalcogenide.
The preparation method
The present invention also provides the preparation method of layered inorganic compound of the present invention/organic substance intercalation composite thermoelectric material, and described intercalation mode is the in-situ chemical reaction that acid-base reaction drives.
In the present invention, said " in-situ chemical reaction " is meant: this intercalation need not earlier stripping layer, the technology of lamination again.Intercalation solution among the present invention itself has alkalescent, through the diffusion and the electron transfer of anion, can bring out that intercalation is spontaneous to carry out.
In order not destroy the lamellar single crystal structure of inorganic main body inorganic layered compounds, the present invention mainly adopts micromolecule original position insertion to implement the intercalation of organic molecule.
Intercalation process among the present invention is reacted based on lewis base, in the inorganic layered compounds molecule, can directly insert alkalescent organic molecules such as fatty amine.Organic molecule is dissolved in the solution such as ethanol and makes intercalation solution, prepared layered inorganic thermoelectric material powder is joined in the intercalation solution, under the magnetic agitation condition of uniform temperature, react.Adopt centrifugation to extract intercalated compound then, obtain powder body material after the vacuumize.
In an embodiment of the present invention, said preparation method may further comprise the steps:
The material of main part of layered inorganic compound is provided;
Adopt the intercalation guest materials that said material of main part is carried out intercalation, described intercalation mode is the in-situ chemical reaction that acid-base reaction drives, and obtains layered inorganic compound/organic substance intercalation composite thermoelectric material.
In an embodiment of the present invention, the reaction temperature of said in-situ chemical reaction is in room temperature to the 160 ℃ scope.The present invention adopt in room temperature to the 160 ℃ scope than low reaction temperatures, to keep the stable of inorganic material of main part composition and structure.
In an embodiment of the present invention, regulate in the intercalation process interlamellar spacing of inorganic matter material of main part in the in-situ chemical reaction through the length of alkyl chain in the fatty amine of selecting the intercalation guest materials.
When the length of alkyl chain in the fatty amine was 4～16, the interlamellar spacing of inorganic matter material of main part was controlled in 6.3 dusts～22 dusts.Said interlamellar spacing increases and increases gradually along with length.
In an embodiment of the present invention, the length of alkyl chain is 4 in fatty amine, and the interlamellar spacing of inorganic matter material of main part is controlled in 6.3 ± 0.1 dusts; The length of alkyl chain is 12 in fatty amine, and the interlamellar spacing of inorganic matter material of main part is controlled in 17.1 ± 0.1 dusts.The length of alkyl chain is 16 in fatty amine, and the interlamellar spacing of inorganic matter material of main part is controlled in 22 ± 0.1 dusts that expand.
Also be that the present invention has realized regulating in the intercalation process interlamellar spacing of inorganic matter material of main part in the in-situ chemical reaction through alkyl chain length in the fatty amine.
In an embodiment of the present invention, regulate intercalation quantity and the arrangement mode of organic substance intercalation in layer in the composite thermoelectric material through proportioning, control reaction temperature and the time of selecting object fatty amine and inorganic material of main part.
In an embodiment,
The proportioning of selecting object fatty amine and inorganic material of main part is that mol ratio 1～5, control reaction temperature are room temperature～50 degree, and controlling reaction time is 0.5h～5h, makes that the interior arrangement mode of organic substance intercalation in layer of composite thermoelectric material is the monolayer intercalation;
The proportioning of selecting object fatty amine and inorganic material of main part is that mol ratio 6～20, control reaction temperature are 50～160 degree; Controlling reaction time is 5h～160h, makes that interior intercalation quantity of composite thermoelectric material and the arrangement mode of organic substance intercalation in layer are the bilayer intercalation.
In an embodiment of the present invention,, can be embodied directly in the intercalation in the inorganic host molecule for having weakly alkaline fatty amine molecule.
Advantage
Process conditions of the present invention are simple, and cost is low, reaction temperature is low, controllability is high, are suitable for the preparation of multiple laminated inorganic matter/fatty amine intercalation composite thermoelectric material.
Other aspects of the present invention are because the disclosure of this paper is conspicuous to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example is measured according to national standard usually.If there is not a corresponding national standards, then carry out according to general international standard, normal condition or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight portion, and all percentages are weight percentage, and described polymer molecular weight is a number-average molecular weight.
Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
Example 1: the preparation of titanium disulfide/butylamine intercalation composite thermoelectric material
With high pure metal Ti powder, sulphur powder is raw material, and by Ti: the S mole is 1: the proportioning of 2+0.05 is fully mixed both in quartz ampoule, and ampoule is evacuated; Reaction is 90 hours under 600 ℃ of conditions; Cooling subsequently, and evaporate remaining sulphur composition, prepare TiS
2Powder.
The 1g butylamine is dissolved in the 20mL absolute ethyl alcohol, adds prepared TiS
2Powder 1g after ultrasonic dispersion forms uniform suspension, puts into 90 ℃ of water-baths and reacts 48h, and deposition becomes pitchy by celadon.Product repeatedly washs the back centrifugation with hot absolute ethyl alcohol, subsequently extract is put into vacuum drying chamber, in 60 ℃ of oven dry 24h.XRD analysis confirms that its thing is TiS mutually
2/ butylamine intercalation compound (Fig. 3), TiS in the intercalation compound
2Interlamellar spacing expands, and the expansion yardstick is suitable with the butylamine molecular size.The transmissioning electric mirror test analysis shows simultaneously, being kept perfectly property of titanium disulfide crystal layer structure.Test obtains its thermal conductivity and compares initial TiS behind the powder briquetting
2Remarkable reduction (Fig. 4) has taken place in the powder briquetting.
Example 2: the preparation of titanium disulfide/lauryl amine intercalation composite thermoelectric material
With high pure metal Ti powder, sulphur powder is raw material, and by Ti: the S mole is 1: the proportioning of 2+0.05 is fully mixed both in quartz ampoule, and ampoule is evacuated; Reaction is 90 hours under 600 ℃ of conditions; Cooling subsequently, and evaporate remaining sulphur composition, prepare TiS
2Powder.
The 1g lauryl amine is dissolved in the 20mL absolute ethyl alcohol, adds prepared TiS
2Powder 1g after ultrasonic dispersion forms uniform suspension, puts into 70 ℃ of water-baths and reacts 12h, and deposition becomes pitchy by celadon.Product repeatedly washs the back centrifugation with hot absolute ethyl alcohol, subsequently extract is put into vacuum drying chamber, in 60 ℃ of oven dry 24h.XRD analysis confirms that its thing is TiS mutually
2/ lauryl amine intercalation compound (Fig. 3), TEM analysis is confirmed TiS in the intercalation compound
2Interlamellar spacing expands, and expansion yardstick and lauryl amine molecular size be (Fig. 2) quite.The transmissioning electric mirror test analysis shows simultaneously, being kept perfectly property of titanium disulfide crystal layer structure.Test obtains its thermal conductivity and compares initial TiS behind the powder briquetting
2Remarkable reduction has taken place in the powder briquetting, and is lower than the thermal conductivity (Fig. 4) of butylamine intercalated compound.
Example 3: the preparation of titanium disulfide/hexadecylamine intercalation composite thermoelectric material
With high pure metal Ti powder, sulphur powder is raw material, and by Ti: the S mole is 1: the proportioning of 2+0.05 is fully mixed both in quartz ampoule, and ampoule is evacuated; Reaction is 90 hours under 600 ℃ of conditions; Cooling subsequently, and evaporate remaining sulphur composition, prepare TiS
2Powder.
The 1g hexadecylamine is dissolved in the 20mL absolute ethyl alcohol, adds prepared TiS
2Powder 1g after ultrasonic dispersion forms uniform suspension, puts into 50 ℃ of water-baths and reacts 10h, and deposition becomes pitchy by celadon.Product repeatedly washs the back centrifugation with hot absolute ethyl alcohol, subsequently extract is put into vacuum drying chamber, in 60 ℃ of oven dry 24h.XRD analysis confirms that its thing is TiS mutually
2/ hexadecylamine intercalation compound.The transmissioning electric mirror test analysis shows simultaneously, being kept perfectly property of titanium disulfide crystal layer structure.Test obtains its thermal conductivity and compares initial TiS behind the powder briquetting
2Remarkable reduction has taken place in the powder briquetting, and is lower than the thermal conductivity (Fig. 4) of lauryl amine intercalated compound.
The above is merely preferred embodiment of the present invention; Be not in order to limit essence technology contents scope of the present invention; Essence technology contents of the present invention is broadly to be defined in the claim scope of application, and if any technological entity or method that other people accomplish are defined identical with the claim scope of application; Also or a kind of change of equivalence, all will be regarded as and be covered by among this claim scope.
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition that after having read foregoing of the present invention those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. layered inorganic compound/organic substance intercalation composite thermoelectric material is characterized in that said organic substance intercalation is the fatty amine intercalation.
2. thermoelectric material as claimed in claim 1 is characterized in that, the intercalation guest materials of said fatty amine intercalation is weakly alkaline fatty amine.
3. thermoelectric material as claimed in claim 1 is characterized in that, described intercalation guest materials is the C4～C20 fatty amine of side chain or straight chain.
4. thermoelectric material as claimed in claim 1 is characterized in that, the material of main part of said inorganic compound is oxide and/or the sulfide with layer structure.
5. thermoelectric material as claimed in claim 1 is characterized in that, the material of main part of said inorganic compound is oxide and/or the sulfide with lamellar single crystal structure.
6. thermoelectric material as claimed in claim 1 is characterized in that the material of main part of said inorganic compound is to be selected from Bi
2Sr
2Ca
N-1Cu
nO
y(n=1,2,3,4, y=0,1,2), Nd
2-yCe
yCuO
4Or La
2-ySr
yCuO
4(y=0,1,2), Pb
2Sr
2Y
1-yCa
yCu
3O
8Or HgBa
2Y
1-yCa
yCu
nO
2n+2The layered oxide of (y=0,1),
Perhaps be selected from TiS
2, Bi
2S
3, Bi
2Te
3, Bi
2Se
3The stratiform chalcogenide.
7. the preparation method of layered inorganic compound as claimed in claim 1/organic substance intercalation composite thermoelectric material is characterized in that, described intercalation mode is the in-situ chemical reaction that acid-base reaction drives.
8. method as claimed in claim 7 is characterized in that, regulates in the intercalation process interlamellar spacing of inorganic matter material of main part in the in-situ chemical reaction through the length of alkyl chain in the fatty amine of selecting the intercalation guest materials.
9. method as claimed in claim 7 is characterized in that, regulates intercalation quantity and the arrangement mode of organic substance intercalation in layer in the composite thermoelectric material through proportioning, control reaction temperature and the time of selecting object fatty amine and inorganic material of main part.
10. thermoelectric device that layered inorganic compound as claimed in claim 1/organic substance intercalation composite thermoelectric material makes.
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| KR20160059111A (en) * | 2014-11-18 | 2016-05-26 | 연세대학교 산학협력단 | A method of preparing single-layer metal chalcogenide |
| CN106629682A (en) * | 2016-12-27 | 2017-05-10 | 江汉大学 | Method for preparing hollow graphene nanospheres through confined catalysis |
| KR20170088747A (en) * | 2014-12-23 | 2017-08-02 | 유씨엘 비즈니스 피엘씨 | Method for producing dispersions of nanosheets |
| CN110190177A (en) * | 2019-05-14 | 2019-08-30 | 清华大学 | A kind of selenizing bismuthino organic intercalation thermoelectric material and preparation method thereof |
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| CN108878429B (en) * | 2018-06-28 | 2020-06-26 | 上海电力学院 | Two-dimensional material-organic ferroelectric material superlattice memory unit and preparation thereof |
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| KR102394239B1 (en) | 2014-12-23 | 2022-05-04 | 유씨엘 비즈니스 리미티드 | Method for producing dispersions of nanosheets |
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