CN101420010A - Liquid phase electric deposit N type or P type thin-film thermoelectric material and production method thereof - Google Patents
Liquid phase electric deposit N type or P type thin-film thermoelectric material and production method thereof Download PDFInfo
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- CN101420010A CN101420010A CNA200810153635XA CN200810153635A CN101420010A CN 101420010 A CN101420010 A CN 101420010A CN A200810153635X A CNA200810153635X A CN A200810153635XA CN 200810153635 A CN200810153635 A CN 200810153635A CN 101420010 A CN101420010 A CN 101420010A
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000010409 thin film Substances 0.000 title claims abstract description 38
- 239000007791 liquid phase Substances 0.000 title abstract 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000004070 electrodeposition Methods 0.000 claims abstract description 43
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910002665 PbTe Inorganic materials 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 6
- 229910018989 CoSb Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229930002839 ionone Natural products 0.000 claims description 4
- 150000002499 ionone derivatives Chemical class 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910019001 CoSi Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910005329 FeSi 2 Inorganic materials 0.000 claims description 3
- 229910005866 GeSe Inorganic materials 0.000 claims description 3
- 229910017028 MnSi Inorganic materials 0.000 claims description 3
- 229910018321 SbTe Inorganic materials 0.000 claims description 3
- 229910007657 ZnSb Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- UEVAMYPIMMOEFW-UHFFFAOYSA-N trolamine salicylate Chemical compound OCCN(CCO)CCO.OC(=O)C1=CC=CC=C1O UEVAMYPIMMOEFW-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 229910018985 CoSb3 Inorganic materials 0.000 description 1
- 229910004262 HgTe Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical class [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-N tellurous acid Chemical compound O[Te](O)=O SITVSCPRJNYAGV-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
The invention relates to a liquid-phase electro-deposition N-typed and P-typed thin-film thermoelectric material and a preparation method. The prepared liquid-phase electro-deposition N-typed and P-typed thin-film thermoelectric material comprises various thermoelectric materials used in low-temperature areas, medium-temperature areas and high-temperature areas. The electro-deposition method is adopted to choose appropriate thin-film thermoelectric material element ions, conductive ions which can increase the electrical conductivity of a solution and additives; a controlled-current mode or a voltage-controlled mode is adopted to output electrical energy; and the current or the voltage output by the power supply is one or the superposition of two or more of the following waveforms: the DC waveform, the AC waveform, the pulse waveform, the sawtooth waveform, the triangular waveform, the trapezoidal waveform or the rectangular waveform. The thin-film thermoelectric material and the preparation method are suitable for preparation of micro thermoelectric cells, micro thermoelectric refrigerators or heaters, and thermoelectric detectors.
Description
Technical field
The invention belongs to the thermoelectric material field, particularly a kind of liquid electrodeposition N type and P type thin-film thermoelectric material and preparation method.
Background technology
Thermoelectric material is having a wide range of applications aspect thermoelectric generator, thermoelectric cooling (heating) device and the thermoelectric transducer.The kind of thermoelectric material is a lot, comprises the Bi that low-temperature space uses
2Te
3, Sb
2Te
3, HgTe, Bi
2Se
3, Sb
2Se
3With ZnSb etc., PbTe, SbTe, Bi (SiSb that middle warm area uses
2) and Bi
2(GeSe)
3Deng, the GrSi that use the high-temperature region
2, MnSi
1.7, FeSi
2, CoSi and Ge
0.3Si
0.7Deng.These thermoelectric materials adopt melting or pressing methods preparation more.
Constantly to today of miniaturization and microminiaturized development, the application of miniature thermoelectric cell, miniature thermoelectric cooling (heating) device, thermoelectric transducer constantly enlarges in various high, precision and frontier technology.Miniature thermoelectric cell, miniature thermoelectric cooling (heating) device, thermoelectric transducer preparation need adopt thin-film thermoelectric material.
Summary of the invention
The present invention proposes a kind of method of liquid electrodeposition that adopts and prepare N type and P type thin-film thermoelectric material and preparation method.The method of liquid electrodeposition prepares the N type and P type thin-film thermoelectric material has low cost of manufacture, is easy to the advantage of large-scale production.
The liquid electrodeposition N type and the P type thin-film thermoelectric material of the present invention's preparation comprise: 1) Bi2Te3 of low-temperature space use and doping thermoelectric material, ZnSb and doping thermoelectric material thereof, Sb
4Te
5And doping thermoelectric material; 2) Pb that warm area uses in
1-XSn
XTe and doping thermoelectric material thereof, PbTe and doping thermoelectric material thereof, SbTe and doping thermoelectric material thereof, Bi (SiSb
2) and doping thermoelectric material, Bi
2(GeSe)
3And doping thermoelectric material, CoAs
3And doping thermoelectric material, CoSb
3And doping thermoelectric material, Sr
8Ga
16Ge
30And doping thermoelectric material, Ba
8Ga
xGe
46-xAnd doping thermoelectric material, ZrNiSn and doping thermoelectric material thereof, MNiSn and doping thermoelectric material thereof, CoSb and doping thermoelectric material thereof, CsBi
4Te
6And doping thermoelectric material; .3) MnSi of high-temperature region use
1.7And doping thermoelectric material, FeSi
2And doping thermoelectric material, CoSi and doping thermoelectric material and Ge
1-XSi
XAnd doping thermoelectric material.
The preparation method of liquid electrodeposition N type of the present invention and P type thin-film thermoelectric material is connected in the electro-deposition system that lead, anode, negative electrode, electro-deposition container, electric depositing solution, agitating device constitute by power supply, power supply and to carry out; Two poles of power supply connect lead by two power supplys and are connected respectively to anode and the negative electrode that is arranged in electric depositing solution, and electric depositing solution places in the electro-deposition container, is arranged in the anode of electric depositing solution and the both sides that negative electrode lays respectively at the electro-deposition container; The energized switch starts the solution agitating device electric depositing solution is stirred, and by regulating the size of output current or voltage, the ion in the control electric depositing solution is prepared thin-film thermoelectric material in the deposition rate of negative electrode at cathode surface.
Increase inert gas installation in the electro-deposition system of the present invention, in electric depositing solution, feed inert gas to remove the dissolved oxygen in the electric depositing solution.
The preparation method of a kind of liquid electrodeposition N type of the present invention and P type thin-film thermoelectric material, described electric depositing solution comprises the ion of thin-film thermoelectric material element, the conductive ion and the additive of increase electrical conductivity of solution; The ion of thin-film thermoelectric material element is Bi
3+, GeO
3 2-, Fe
2+, Fe
3+, Co
2+, Mn
2+, HTeO
3 -, SeO
3 2-, Sb
3+, Sn
2+, SiO
3 -2, pb
2+Middle Ni
2+, Sn
2+, Co
3+, Zr
4+, SiO
3 2-, As
5+, Ga
3+, MnO
4 1-, Cs
1+, Zr
4+Or Zn
2+In the ion one or more, the conductive ion in the electric depositing solution is SO
4 2-, NO
3 -, ClO
4 -, F
-, Cl
-, Br
-, I
-, Na
+Or K
+In the ion one or more; These ions are that the form with simple ion exists or exists with the form of complex ion in electric depositing solution; Additive in the electric depositing solution is the electric depositing solution stabilizer, and perhaps electro-deposition is with the stabilizer of pole plate, perhaps complexing agent, or the PH buffer.
Described additive is one or more in formaldehyde, ammoniacal liquor, citric acid, oxalic acid, glycerine, ammonium chloride, Cymag, acetate, tartaric acid, potassium pyrophosphate, ethylenediamine, thiocarbamide, gluconic acid, EDTA, lactic acid or the triethanolamine salicylic acid.
Power supply in the described electro-deposition system adopts control current system output electric energy, or adopts control voltage system output electric energy; The electric current or the voltage waveform of power supply output are the stacks of a kind of or two or more waveforms in dc waveform, AC wave shape, impulse waveform, sawtooth waveform, triangular waveform, trapezoidal waveform or the square waveform.
Described material as negative electrode and anode need have excellent conducting performance, can be stainless steel, copper, gold, platinum, nickel, tungsten, silver, zinc, silicon chip, material with carbon element or conducting polymer composite.
The present invention has introduced a kind of employing liquid electrodeposition technology and has prepared N type and P type thin-film thermoelectric material and method.This thickness is highly suitable for preparing miniature thermoelectric cell, miniature thermoelectric cooling or heater and thermoelectric detector at the thin-film thermoelectric material of micro-meter scale.
Description of drawings
The surface topography of Fig. 1 deposit N type Bi-Te-Se thin-film thermoelectric material;
The surface topography of Fig. 2 electro-deposition PbTe thin-film thermoelectric material.
Embodiment
Embodiment 1: adopt control voltage to exchange the electric energy way of output deposit N type Bi-Te-Se thin-film thermoelectric material of stack direct current
Get the 10ml analytical pure sulfuric acid, 50ml distilled water is made into sulfuric acid solution.Take by weighing 10 gram bismuth sulfates then, slowly adding institute joins in the sulfuric acid solution, and constantly stirring makes it dissolving, adds 4 gram selenous acid stirrings again and makes it dissolving.Get the 10ml analytical pure sulfuric acid more in addition, 50ml distilled water is made into sulfuric acid solution.Take by weighing 8 gram tellurous acid then, slowly add institute and join in the sulfuric acid solution, and constantly stirring makes it dissolving.Get 100ml distilled water again, add 30g gram citric acid, stir and make it dissolving.Afterwards above-mentioned solution is slowly poured in the 1000ml volumetric flask.Slowly add distilled water to the 1L scale, make electric depositing solution.The electric depositing solution that makes is poured in the electro-deposition container.
Power supply adopts the constant voltage electric energy way of output that exchanges the stack direct current, and the direct voltage of output is 0.6V, and the amplitude of alternating voltage is 0.3V, frequency 50Hz.Adopt magnetic stirring apparatus that electric depositing solution is stirred, electrodeposition process feeds nitrogen in electric depositing solution.Electro-deposition 1 hour, the surface topography of the thin-film thermoelectric material that makes as shown in Figure 1.Embodiment 2: adopt the electro-deposition mode liquid electrodeposition of constant current unidirectional pulse to prepare the PbTe thin-film thermoelectric material
Electric depositing solution is formed: Cl
-Concentration 1.3M, pb
4+Concentration 0.02M, HTeO
3 -Concentration 0.01M, thiocarbamide 1M, K
+0.5M..With the copper sheet is negative electrode, and the titanium net is an anode, adopts the mode of electromagnetic agitation to stir electric depositing solution.Power supply adopts the way of output of constant current unidirectional pulse, pulse current density 5mA/cm
2, the current lead-through time is 10ms, electric current opening time is 0.5ms.The PbTe thin-film thermoelectric material was prepared in electro-deposition in 1.5 hours.The surface topography of the thin-film thermoelectric material that makes as shown in Figure 2.
Embodiment 3: the dc electrodeposition mode liquid electrodeposition CoSb3 thin-film thermoelectric material that adopts constant current
Electric depositing solution is formed: the nitric acid of thiocarbamide+1M of sodium nitrate+0.5M of selenous acid+1M of cobalt nitrate+0.1M of 0.2M..Be negative electrode and anode with the platinized platinum respectively, adopt churned mechanically mode to stir electric depositing solution.Power supply adopts the direct current way of output of constant current, current density 4mA/cm
2, CoSb was prepared in electro-deposition in 2 hours
3Thin-film thermoelectric material.
Claims (7)
1. liquid electrodeposition N type and P type thin-film thermoelectric material is characterized in that the liquid electrodeposition thin-film thermoelectric material comprises: the 1) Bi that uses of low-temperature space
2Te
3And doping thermoelectric material, ZnSb and doping thermoelectric material thereof, Sb
4Te
5And doping thermoelectric material; 2) Pb that warm area uses in
1-XSn
XTe and doping thermoelectric material thereof, PbTe and doping thermoelectric material thereof, SbTe and doping thermoelectric material thereof, Bi (SiSb
2) and doping thermoelectric material, Bi
2(GeSe)
3And doping thermoelectric material, CoAs
3And doping thermoelectric material, CoSb
3And doping thermoelectric material, Sr
8Ga
16Ge
30And doping thermoelectric material, Ba
8Ga
xGe
46-xAnd doping thermoelectric material, ZrNiSn. and doping thermoelectric material thereof, MNiSn and doping thermoelectric material thereof, CoSb and doping thermoelectric material thereof, CsBi
4Te
6And doping thermoelectric material; .3) MnSi of high-temperature region use
1.7And doping thermoelectric material, FeSi
2And doping thermoelectric material, CoSi and doping thermoelectric material and Ge
1-XSi
XAnd doping thermoelectric material.
2. the preparation method of the liquid electrodeposition N type of claim 1 and P type thin-film thermoelectric material is connected in the electro-deposition system that lead, anode, negative electrode, electro-deposition container, electric depositing solution, agitating device constitute by power supply, power supply and to carry out; Two poles that it is characterized in that power supply are connected respectively to anode and the negative electrode that is arranged in electric depositing solution by two power supplys connection leads, electric depositing solution places in the electro-deposition container, is arranged in the anode of electric depositing solution and the both sides that negative electrode lays respectively at the electro-deposition container; The energized switch starts the solution agitating device electric depositing solution is stirred, and by regulating the size of output current or voltage, the ion in the control electric depositing solution is prepared thin-film thermoelectric material in the deposition rate of negative electrode at cathode surface.
3. the preparation method of a kind of liquid electrodeposition N type as claimed in claim 2 and P type thin-film thermoelectric material, it is characterized in that increasing inert gas installation in the described electro-deposition system, in electric depositing solution, feed inert gas to remove the dissolved oxygen in the electric depositing solution.
4. the preparation method of a kind of liquid electrodeposition N type as claimed in claim 2 and P type thin-film thermoelectric material is characterized in that described electric depositing solution comprises the ion of thin-film thermoelectric material element, the conductive ion and the additive of increase electrical conductivity of solution; The ion of thin-film thermoelectric material element is Bi
3+, GeO
3 2-, Fe
2+, Fe
3+, Co
2+, Mn
2+, HTeO
3 -, SeO
3 2-, Sb
3+, Sn
2+, SiO
3 -2, pb
2+Middle Ni
2+, Sn
2+, Co
3+, Zr
4+, SiO
3 2-, As
5+, Ga
3+, MnO
4 1-, Cs
1+, Zr4
+Or Zn
2+In the ion one or more, the conductive ion in the electric depositing solution is SO
4 2-, NO
3 -, ClO
4 -, F
-, Cl
-, Br
-, I
-, Na
+Or K
+In the ion one or more; These ions are that the form with simple ion exists or exists with the form of complex ion in electric depositing solution; Additive in the electric depositing solution is the electric depositing solution stabilizer, and perhaps electro-deposition is with the stabilizer of pole plate, perhaps complexing agent, or the PH buffer.
5. the preparation method of a kind of liquid electrodeposition N type as claimed in claim 4 and P type thin-film thermoelectric material is characterized in that described additive is one or more in formaldehyde, ammoniacal liquor, citric acid, oxalic acid, glycerine, ammonium chloride, Cymag, acetate, tartaric acid, potassium pyrophosphate, ethylenediamine, thiocarbamide, gluconic acid, EDTA, lactic acid or the triethanolamine salicylic acid.
6. the preparation method of a kind of liquid electrodeposition N type as claimed in claim 2 and P type thin-film thermoelectric material is characterized in that the power supply in the described electro-deposition system adopts control current system output electric energy, or adopts control voltage system output electric energy; The electric current or the voltage waveform of power supply output are the stacks of a kind of or two or more waveforms in dc waveform, AC wave shape, impulse waveform, sawtooth waveform, triangular waveform, trapezoidal waveform or the square waveform.
7. the preparation method of a kind of liquid electrodeposition N type as claimed in claim 2 and P type thin-film thermoelectric material, it is characterized in that described material as negative electrode and anode need have excellent conducting performance, comprises stainless steel, copper, gold, platinum, nickel, tungsten, silver, zinc, silicon chip, material with carbon element or conducting polymer composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810153635XA CN101420010A (en) | 2008-11-28 | 2008-11-28 | Liquid phase electric deposit N type or P type thin-film thermoelectric material and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810153635XA CN101420010A (en) | 2008-11-28 | 2008-11-28 | Liquid phase electric deposit N type or P type thin-film thermoelectric material and production method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101420010A true CN101420010A (en) | 2009-04-29 |
Family
ID=40630706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200810153635XA Pending CN101420010A (en) | 2008-11-28 | 2008-11-28 | Liquid phase electric deposit N type or P type thin-film thermoelectric material and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101420010A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613867B (en) * | 2009-07-25 | 2011-05-11 | 天津大学 | Preparation method of electrodepositing Bi2Te3 mixed with thin-film thermoelectric material |
| CN105439106A (en) * | 2015-12-17 | 2016-03-30 | 山东建筑大学 | Method for preparing bismuth selenide thermoelectric thin film with bismuth sulfate |
| CN105552205A (en) * | 2015-12-17 | 2016-05-04 | 山东建筑大学 | Method for preparing bismuth selenide thermoelectric film from bismuth chloride |
| CN105541121A (en) * | 2015-12-17 | 2016-05-04 | 山东建筑大学 | Method for preparing bismuth selenide thermoelectric thin film from bismuth nitrate |
| CN105932150A (en) * | 2016-05-18 | 2016-09-07 | 深圳大学 | Sb-base flexible film thermoelectric cell and manufacturing method therefor |
| CN109616678A (en) * | 2018-12-03 | 2019-04-12 | 华中科技大学 | A kind of high Seebeck coefficient water system heat chemistry battery and device |
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2008
- 2008-11-28 CN CNA200810153635XA patent/CN101420010A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613867B (en) * | 2009-07-25 | 2011-05-11 | 天津大学 | Preparation method of electrodepositing Bi2Te3 mixed with thin-film thermoelectric material |
| CN105439106A (en) * | 2015-12-17 | 2016-03-30 | 山东建筑大学 | Method for preparing bismuth selenide thermoelectric thin film with bismuth sulfate |
| CN105552205A (en) * | 2015-12-17 | 2016-05-04 | 山东建筑大学 | Method for preparing bismuth selenide thermoelectric film from bismuth chloride |
| CN105541121A (en) * | 2015-12-17 | 2016-05-04 | 山东建筑大学 | Method for preparing bismuth selenide thermoelectric thin film from bismuth nitrate |
| CN105552205B (en) * | 2015-12-17 | 2018-05-11 | 山东建筑大学 | A kind of method that bismuth selenide thermal electric film is prepared with bismuth chloride |
| CN105932150A (en) * | 2016-05-18 | 2016-09-07 | 深圳大学 | Sb-base flexible film thermoelectric cell and manufacturing method therefor |
| CN109616678A (en) * | 2018-12-03 | 2019-04-12 | 华中科技大学 | A kind of high Seebeck coefficient water system heat chemistry battery and device |
| CN109616678B (en) * | 2018-12-03 | 2020-10-02 | 华中科技大学 | high-Seebeck-coefficient water-based thermochemical battery and device |
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