CN110061123A - A kind of lower thermal conductivity thermo-electric device and preparation method thereof - Google Patents
A kind of lower thermal conductivity thermo-electric device and preparation method thereof Download PDFInfo
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- CN110061123A CN110061123A CN201910438663.4A CN201910438663A CN110061123A CN 110061123 A CN110061123 A CN 110061123A CN 201910438663 A CN201910438663 A CN 201910438663A CN 110061123 A CN110061123 A CN 110061123A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910002012 Aerosil® Inorganic materials 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 239000002356 single layer Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- 239000004065 semiconductor Substances 0.000 claims abstract description 13
- 238000006073 displacement reaction Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 230000005619 thermoelectricity Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000499 gel Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000000352 supercritical drying Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002789 length control Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000003079 width control Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- 230000005680 Thomson effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
Abstract
The present invention relates to a kind of lower thermal conductivity thermo-electric devices and preparation method thereof.The preparation method is that: (1) multipair thermoelectric arm on single-layer ceramic substrate is welded, thermo-electric device is obtained；The thermoelectric arm is made of N-P semiconductor material, and the length of the thermoelectric arm is 1~2mm, and width is 1~2mm, and height is 1~7mm；(2) thermo-electric device for obtaining step (1) and aerosil precursor solution carry out In-situ reaction, and then in turn through collosol and gel, solvent displacement and dry step, lower thermal conductivity thermo-electric device is made；The lower thermal conductivity thermo-electric device includes the thermo-electric device and is compounded in per the aerosil in the gap formed between two pairs of adjacent thermoelectric arms.Lower thermal conductivity thermo-electric device energy conversion efficiency made from the method for the present invention is high, and compared to unmodified preceding thermo-electric device, transfer efficiency can be improved 5% or more.
Description
Technical field
The invention belongs to thermo-electric device technical fields more particularly to a kind of lower thermal conductivity thermo-electric device and preparation method thereof.
Background technique
Thermoelectric material is a kind of functional material that can mutually convert electric energy and thermal energy, have Seebeck effect,
Peltier effect and Thomson effect, performance are evaluated by dimensionless thermoelectric figure of merit ZT, improve the conversion of thermo-electric device
Efficiency main path is to improve the thermoelectric figure of merit of thermoelectric material.The application of thermoelectric material will be realized by thermo-electric device, from function
It can go up to divide, thermo-electric device mainly includes thermoelectric generator and thermoelectric cooling device two major classes.Thermo-electric device biggest advantage is
Environmental-friendly, high stability, easily miniaturization, have broad application prospects.
Thermo-electric device electricity generating principle is usually to combine conductivity higher metal with N-type semiconductor, P-type semiconductor,
And closed circuit is accessed in outer end.There is a large amount of electronics, the carrier original of semiconductor is more much lower than metal, works as phase in metal
Mutually when contact, carrier density gradient will form, electrons spread movement occurs；Simultaneously as material internal is entered by thermal excitation
The carrier quantity of conduction band or valence band increases, and generates electron-hole pair, spreads so as to cause internal carrier, Xiang Leng
End motion.Since directed movement occurs for carrier, inside aggregation forms a built-in field, prevents charge movement, be finally reached
It balances, the both ends of conductor generate electromotive force after balance.
Currently, the energy conversion efficiency of thermo-electric device is all universal relatively low, the transformation efficiency of general thermo-electric device only has 5%-
10%, it can't be widely applied.Restricting the factor that thermo-electric device energy conversion efficiency improves mainly has following two:
(1) from the point of view of thermoelectric material, the thermoelectric figure of merit ZT of thermoelectric material is smaller.
(2) consider from device architecture, device architecture is related to many problems.For example, the contour structures of device, PN material
Diffusion problem, multiple PN profile material connectivity problems, electrode and material contact problems, PN junction length issue, contact resistance, connect
The problems such as touching thermal resistance, these factors will affect the energy conversion efficiency of device.
Thermo-electric device (Chinese patent application CN201810355482.0) is mainly by improving thermoelectric material at this stage
N, P semiconductor and underlying structure (Chinese patent application CN201810034869.6) are come in chemical structure and change thermo-electric device
Improve the thermoelectricity capability of thermo-electric device.
Summary of the invention
The purpose of the invention is to provide a kind of lower thermal conductivity thermo-electric device that novel energy conversion efficiency is high and its
Preparation method, to solve the problems, such as that thermoelectricity capability existing for existing thermo-electric device is poor, energy conversion efficiency is low.
To achieve the goals above, the present invention provides a kind of preparation side of lower thermal conductivity thermo-electric device in first aspect
Method, described method includes following steps:
(1) multipair thermoelectric arm is welded in single layer substrates, obtains thermo-electric device；The thermoelectric arm is by N-P semiconductor material
It is made, the length of the thermoelectric arm is 1~2mm, and width is 1~2mm, and height is 1~7mm；With
(2) thermo-electric device for obtaining step (1) and aerosil precursor solution carry out In-situ reaction, then
Successively by collosol and gel, solvent displacement and dry step, the lower thermal conductivity thermo-electric device is made；The lower thermal conductivity heat
Electrical part includes the thermo-electric device and is compounded in per the titanium dioxide in the gap formed between two pairs of adjacent thermoelectric arms
Silica aerogel.
Preferably, 64~128 pairs of thermoelectric arms are welded in single layer substrates.
Preferably, the single layer substrates are single-layer ceramic substrate；And/or the length of the single layer substrates is 40mm, width
For 40mm.
Preferably, the energy conversion efficiency at the lower thermal conductivity thermo-electric device is 200 DEG C in the temperature difference is 10%~20%.
Preferably, the concentration of the aerosil precursor solution is 5~25wt%.
It preferably, include nitric acid and/or ammonia-catalyzed agent in the aerosil precursor solution.
Preferably, the solvent for including in the aerosil precursor solution is methanol, ethyl alcohol, acetone and acetonitrile
One of or it is a variety of.
Preferably, the aerosil presoma for including in the aerosil precursor solution is positive silicon
One of sour methyl esters, ethyl orthosilicate, multi-polysiloxane, waterglass and silica solution are a variety of.
Preferably, the N-P semiconductor material is one in bismuth telluride, telluride bismuth alloy, lead telluride and telluride metal
Kind is a variety of.
The present invention provides lower thermal conductivity made from the preparation method as the present invention described in first aspect in second aspect
Thermo-electric device.
The present invention at least have compared with prior art it is following the utility model has the advantages that
(1) thermo-electric device with single layer substrates is carried out In-situ reaction with aerogel precursor liquid solution by the method for the present invention,
Aerosil In-situ reaction shape between every two pairs of adjacent thermoelectric arms that the thermo-electric device includes is obtained
At gap in the lower thermal conductivity thermo-electric device；The method of the present invention preparation process is simple, and preparation cost is low, the method for the present invention
The lower thermal conductivity thermo-electric device thermal conductivity obtained is low, high conversion efficiency, is found by the testing experiment of output power, identical
Under the conditions of, the output power of lower thermal conductivity thermo-electric device of the present invention is compared without aerosil precursor solution
The thermo-electric device transfer efficiency (transformation efficiency) of processing improves 5% or more.
(2) the method for the present invention has carried out stringent control to the size of thermoelectric arm, the inventors discovered that by the thermoelectric arm
Length and width control as 1-2mm, the height control of thermoelectric arm is 1-7mm, can effectively guarantee that transfer efficiency is made
The high lower thermal conductivity thermo-electric device, so that the transfer efficiency at the lower thermal conductivity thermo-electric device is 200 DEG C in the temperature difference reaches
To 10%~20%.
(3) certain preferred embodiments of the invention have carried out stringent control, the present inventor to the size of thermo-electric device
It was found that the length when the single layer substrates is 40mm, width 40mm, 64~128 pairs of thermoelectricity are welded in single layer substrates
Arm, and the concentration of the aerosil precursor solution be 5-25wt% when, be more advantageous to guarantee be made thermal conductivity
The lower thermal conductivity thermo-electric device of low, high conversion efficiency (10%~20%).
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described, it is clear that and described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of lower thermal conductivity thermo-electric device in first aspect, and the method includes as follows
Step:
(1) multipair thermoelectric arm is welded in single layer substrates, obtains thermo-electric device；The thermoelectric arm is by N-P semiconductor material
Be made, the length of the thermoelectric arm is 1~2mm (such as 1,1.2,1.5,1.8 or 2mm), width be 1~2mm (such as 1,1.2,
1.5,1.8 or 2mm), and height is 1~7mm (such as 1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5 or 7mm)；
In the present invention, it is connected between the multipair thermoelectric arm using concatenated mode.
(2) thermo-electric device for obtaining step (1) and aerosil precursor solution carry out In-situ reaction, then
Successively by collosol and gel, solvent displacement and drying (such as supercritical drying) the step of, the lower thermal conductivity thermoelectricity device is made
Part (aeroge In-situ reaction thermo-electric device)；The lower thermal conductivity thermo-electric device includes the thermo-electric device and compound (in situ multiple
Close) the silica airsetting that (is compounded between thermoelectric arm) in the gap that is formed between every two pairs of adjacent thermoelectric arms
Glue；In the present invention, the collosol and gel, solvent displacement and dry step use existing aerosil preparation system
The process conditions of use.
The method of the present invention carries out the thermo-electric device with single layer substrates using pure silicon dioxide aerogel precursor liquid solution
In-situ reaction, the inventors discovered that using pure aerosil precursor solution and thermo-electric device composite effect most
It is good, and the multipair thermoelectric arm is only welded in single layer substrates by the present invention, so that combined efficiency of the present invention is high, compound behaviour
Make simply to have obtained every two pairs of adjacent thermoelectric arms that aerosil In-situ reaction includes in the thermo-electric device
Between the lower thermal conductivity thermo-electric device in the gap that is formed, reduce thermo-electric device thermal conductivity, improve thermo-electric device
Thermoelectricity capability；It is well known that the transformation efficiency of general thermo-electric device only has 5%~10%, on the basis of general thermo-electric device
It is difficult to realize to be converted 5% or more efficiency raising, and the lower thermal conductivity thermo-electric device thermal conductivity made from the method for the present invention
Low, high conversion efficiency is found by the testing experiment of output power, under the same terms, lower thermal conductivity thermoelectricity of the present invention
Device compares the thermo-electric device energy conversion efficiency handled without aerosil precursor solution and improves 5% or more；This
Inventor's discovery needs the size to thermoelectric arm while having the thermo-electric device of single layer substrates by aeroge In-situ reaction
Stringent control is carried out, the inventors discovered that being 1-2mm, the height of thermoelectric arm by the length and width control of the thermoelectric arm
Control is 1-7mm, can effectively guarantee the lower thermal conductivity thermo-electric device that high conversion efficiency is made, so that the low-heat is led
Transfer efficiency at rate thermo-electric device is 200 DEG C in the temperature difference is 10%~20%；And work as the length and width control of the thermoelectric arm
System will lead to the lower thermal conductivity not within the scope of 1-2mm and/or when the height of the thermoelectric arm is not within the scope of 1-7mm
The energy conversion efficiency of thermo-electric device reduces.
According to some preferred embodiments, 64~128 pairs of thermoelectric arms are welded in single layer substrates；I.e. in this hair
In bright, the logarithm of the preferably described thermoelectric arm (N-P semiconductor) should be between 64~128 pairs.
According to some preferred embodiments, the single layer substrates are single-layer ceramic substrate (ceramic bases of single side), i.e.,
In the present invention, it is preferred to for N-P semiconductor material according to certain quantity and arrangement mode, is welded in the ceramic bases of single side
On；And/or the length of the single layer substrates is 40mm, width 40mm.
According to some preferred embodiments, the concentration of the aerosil precursor solution is 5~25wt%
(such as 5wt%, 10wt%, 15wt%, 20wt% or 25wt%) (mass percent).The present invention is preferably to thermo-electric device
Size carries out stringent control, the inventors discovered that the length when the single layer substrates is 40mm, width 40mm, in single layer base
It is welded with 64~128 pairs of thermoelectric arms on bottom, and is 5- by the concentration of the aerosil precursor solution
When 25wt%, it is more advantageous to guarantee and is made that thermal conductivity is low, the lower thermal conductivity thermoelectricity device of high conversion efficiency (10%~20%)
Part.
According to some preferred embodiments, the energy at the lower thermal conductivity thermo-electric device is 200 DEG C in the temperature difference is converted
Efficiency be 10%~20% (such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or
20%).
It include nitric acid and/or ammonia in the aerosil precursor solution according to some preferred embodiments
Water catalyst.
According to some preferred embodiments, the solvent for including in the aerosil precursor solution is first
One of alcohol, ethyl alcohol, acetone and acetonitrile are a variety of (two kinds and two or more)；Preferably, the aerosil
The solvent for including in precursor solution is ethyl alcohol.
According to some preferred embodiments, the silica gas that includes in the aerosil precursor solution
Gel Precursor (silica precursor) is in methyl orthosilicate, ethyl orthosilicate, multi-polysiloxane, waterglass and silica solution
One or more (two kinds and two or more).
According to some preferred embodiments, the N-P semiconductor material be bismuth telluride, telluride bismuth alloy, lead telluride and
One of telluride metal is a variety of (two kinds and two or more).
The present invention provides lower thermal conductivity made from the preparation method as the present invention described in first aspect in second aspect
Thermo-electric device.
Hereafter the present invention will be further detailed by way of example, but protection scope of the present invention is unlimited
In these embodiments.
Embodiment 1
1. the bismuth telluride thermoelectric arm of 64 pairs, long 1mm* wide 1mm* high 3mm to be welded in the ceramic bases of 40*40mm single side
On, obtain thermo-electric device.
2. the thermo-electric device 1. obtained and aerosil precursor solution are carried out In-situ reaction, silica gas
Gel precursor solution is using ethyl orthosilicate as presoma, and using ethyl alcohol as solvent, it is molten to configure the ethyl alcohol that its concentration is 10wt%
Liquid prepares silica hydrogel under catalyst nitric acid and ammonium hydroxide effect, then passes through alcohol solvent displacement, supercritical drying mistake
Journey obtains the modified thermo-electric device (lower thermal conductivity thermo-electric device) of aerosil；The lower thermal conductivity thermo-electric device includes
The thermo-electric device and the aerosil being compounded in the gap formed between per two pairs of adjacent thermoelectric arms.
The present embodiment carries out output work in the environment of 200 DEG C of the temperature difference as the lower thermal conductivity thermo-electric device to made from
The testing experiment of rate, measuring its energy conversion efficiency is 10%.
Embodiment 2
1. the bismuth telluride thermoelectric arm of 128 pairs, long 1mm* wide 1mm* high 5mm to be welded in the ceramic bases of 40*40mm single side
On, obtain thermo-electric device.
2. the thermo-electric device 1. obtained and aerosil precursor solution are carried out In-situ reaction, silica gas
Gel precursor solution is using ethyl orthosilicate as presoma, and using ethyl alcohol as solvent, it is molten to configure the ethyl alcohol that its concentration is 15wt%
Liquid prepares silica hydrogel under catalyst nitric acid and ammonium hydroxide effect, then passes through alcohol solvent displacement, supercritical drying mistake
Journey obtains the modified thermo-electric device (lower thermal conductivity thermo-electric device) of aerosil；The lower thermal conductivity thermo-electric device includes
The thermo-electric device and the aerosil being compounded in the gap formed between per two pairs of adjacent thermoelectric arms.
The present embodiment carries out output work in the environment of 200 DEG C of the temperature difference as the lower thermal conductivity thermo-electric device to made from
The testing experiment of rate, measuring its energy conversion efficiency is 15%.
Embodiment 3
1. the bismuth telluride thermoelectric arm of 64 pairs, long 1mm* wide 1mm* high 5mm to be welded in the ceramic bases of 40*40mm single side
On, obtain thermo-electric device.
2. the thermo-electric device 1. obtained and aerosil precursor solution are carried out In-situ reaction, silica gas
Gel precursor solution is using ethyl orthosilicate as presoma, and using ethyl alcohol as solvent, it is molten to configure the ethyl alcohol that its concentration is 20wt%
Liquid prepares silica hydrogel under catalyst nitric acid and ammonium hydroxide effect, then passes through alcohol solvent displacement, supercritical drying mistake
Journey obtains the modified thermo-electric device (lower thermal conductivity thermo-electric device) of aerosil；The lower thermal conductivity thermo-electric device includes
The thermo-electric device and the aerosil being compounded in the gap formed between per two pairs of adjacent thermoelectric arms.
The present embodiment carries out output work in the environment of 200 DEG C of the temperature difference as the lower thermal conductivity thermo-electric device to made from
The testing experiment of rate, measuring its energy conversion efficiency is 13%.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that:
Step 1. in, the bismuth telluride thermoelectric arm of 64 pairs, long 2mm* wide 2mm* high 7mm is welded in 40*40mm single side
In ceramic bases, thermo-electric device is obtained.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 2, the difference is that:
Step 1. in, the bismuth telluride thermoelectric arm of 196 pairs, long 1mm* wide 1mm* high 5mm is welded in 40*40mm single side
In ceramic bases, thermo-electric device is obtained.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, the difference is that: do not include step 2..
Comparative example 2
Comparative example 2 is substantially the same manner as Example 2, the difference is that: do not include step 2..
Comparative example 3
Comparative example 3 is substantially the same manner as Example 3, the difference is that: do not include step 2..
Comparative example 4
1. the bismuth telluride thermoelectric arm of 64 pairs, long 1mm* wide 1mm* high 3mm to be welded in the ceramic bases of 40*40mm single side
On, obtain thermo-electric device.
2. the thermo-electric device 1. obtained and the aerosil precursor solution comprising glass fibre are carried out original position
Compound, the aerosil precursor solution comprising glass fibre is using ethyl orthosilicate as presoma, with glass fibre
For reinforced phase, using ethyl alcohol as solvent, the concentration of aerosil presoma of the configuration comprising glass fibre is 10wt%'s
Ethanol solution prepares glass fiber reinforcement silica hydrogel under catalyst nitric acid and ammonium hydroxide effect, then molten by ethyl alcohol
Agent displacement, supercritical drying process obtain thermo-electric device (the modified thermoelectricity that the aerosil of glass fiber reinforcement is modified
Device)；The modified thermo-electric device includes that the thermo-electric device and being compounded in is formed per between two pairs of adjacent thermoelectric arms
Gap in glass fiber reinforcement aerosil.
This comparative example carries out output power as the modified thermo-electric device to made from the environment of 200 DEG C of the temperature difference
Testing experiment, measuring its energy conversion efficiency is 7.5%.
Comparative example 5
1. the bismuth telluride thermoelectric arm of 64 pairs, long 2.5mm* wide 2.5mm* high 8mm to be welded in the ceramic base of 40*40mm single side
On bottom, thermo-electric device is obtained.
2. the thermo-electric device 1. obtained and aerosil precursor solution are carried out In-situ reaction, silica gas
Gel precursor solution is using ethyl orthosilicate as presoma, and using ethyl alcohol as solvent, it is molten to configure the ethyl alcohol that its concentration is 30wt%
Liquid prepares silica hydrogel under catalyst nitric acid and ammonium hydroxide effect, then passes through alcohol solvent displacement, supercritical drying mistake
Journey obtains the modified thermo-electric device of aerosil (modified thermo-electric device)；The modified thermo-electric device includes the thermoelectricity
Device and the aerosil being compounded in the gap formed between per two pairs of adjacent thermoelectric arms.
This comparative example carries out output power as the modified thermo-electric device to made from the environment of 200 DEG C of the temperature difference
Testing experiment, measuring its energy conversion efficiency is 8%.
Table 1: Examples 1 to 5 and comparative example 1~3, the energy conversion efficiency test result of comparative example 5.
From the result of the embodiment of the present invention 1 and comparative example 4 it is found that being compounded in shape between per two pairs of adjacent thermoelectric arms
At gap in pure silicon dioxide aeroge be not any other modification or fibre-reinforced aerosil institute energy
Substitution, the inventors discovered that it is best using the composite effect of pure aerosil precursor solution and thermo-electric device,
The energy conversion efficiency of thermo-electric device is enabled to improve to 10% or more.Lower thermal conductivity heat in the embodiment of the present invention 2
For electrical part compared with unmodified thermo-electric device, energy conversion efficiency improves significant, energy conversion efficiency up to 15%, and compares
Example 4 compares unmodified thermo-electric device with thermo-electric device modified in comparative example 5, and energy conversion efficiency is raising slightly
?.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of lower thermal conductivity thermo-electric device, which is characterized in that described method includes following steps:
(1) multipair thermoelectric arm is welded in single layer substrates, obtains thermo-electric device；The thermoelectric arm is made of N-P semiconductor material,
The length of the thermoelectric arm is 1~2mm, and width is 1~2mm, and height is 1~7mm；With
(2) thermo-electric device for obtaining step (1) and aerosil precursor solution carry out In-situ reaction, then successively
By collosol and gel, solvent displacement and dry step, the lower thermal conductivity thermo-electric device is made；The lower thermal conductivity thermoelectricity device
Part includes the thermo-electric device and is compounded in per the silica gas in the gap formed between two pairs of adjacent thermoelectric arms
Gel.
2. preparation method according to claim 1, it is characterised in that:
64~128 pairs of thermoelectric arms are welded in single layer substrates.
3. preparation method according to claim 2, it is characterised in that:
The single layer substrates are single-layer ceramic substrate；And/or
The length of the single layer substrates is 40mm, width 40mm.
4. preparation method according to claim 1, it is characterised in that:
Energy conversion efficiency at the lower thermal conductivity thermo-electric device is 200 DEG C in the temperature difference is 10%~20%.
5. preparation method according to any one of claims 1 to 4, it is characterised in that:
The concentration of the aerosil precursor solution is 5~25wt%.
6. preparation method according to any one of claims 1 to 4, it is characterised in that:
It include nitric acid and/or ammonia-catalyzed agent in the aerosil precursor solution.
7. preparation method according to any one of claims 1 to 4, it is characterised in that:
The solvent for including in the aerosil precursor solution be one of methanol, ethyl alcohol, acetone and acetonitrile or
It is a variety of.
8. preparation method according to any one of claims 1 to 4, it is characterised in that:
The aerosil presoma for including in the aerosil precursor solution is methyl orthosilicate, positive silicon
One of acetoacetic ester, multi-polysiloxane, waterglass and silica solution are a variety of.
9. preparation method according to any one of claims 1 to 4, it is characterised in that:
The N-P semiconductor material is one of bismuth telluride, telluride bismuth alloy, lead telluride and telluride metal or a variety of.
10. the lower thermal conductivity thermo-electric device as made from claim 1 to 9 described in any item preparation methods.
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| CN201910438663.4A CN110061123A (en) | 2019-05-24 | 2019-05-24 | A kind of lower thermal conductivity thermo-electric device and preparation method thereof |
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Application publication date: 20190726 |