CN107732000A - Pressue device, thermoelectricity thick film and flexible thermo-electric device applied to thick film hot pressed sintering - Google Patents
Pressue device, thermoelectricity thick film and flexible thermo-electric device applied to thick film hot pressed sintering Download PDFInfo
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- CN107732000A CN107732000A CN201710992058.2A CN201710992058A CN107732000A CN 107732000 A CN107732000 A CN 107732000A CN 201710992058 A CN201710992058 A CN 201710992058A CN 107732000 A CN107732000 A CN 107732000A
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- 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
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- 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 pressue device, thermoelectricity thick film and flexible thermo-electric device applied to thick film hot pressed sintering.The pressue device includes multiple compression spring assemblies, the first pressing plate, the second pressing plate, top plate and bottom plate；Bottom plate is used to place thick film, first pressing plate is placed in above thick film and is in contact with thick film, the size of first pressing plate and thick film substrate matches, second pressing plate is placed in the top of the first pressing plate, top plate is placed in the top of second pressing plate, each one end of compression spring assembly is fixedly connected with one end of bottom plate, the other end of each compression spring assembly wears one end of the second pressing plate and top plate respectively, each compression spring assembly includes a compression spring, and the both ends of compression spring abut against with the upper surface of the second pressing plate and the lower surface of top plate respectively.The manufacture method of the flexible thermo-electric device of the present invention has that technique is simple, prepares that controllability is strong, production cost is low, and the thermo-electric device internal resistance prepared is smaller, has the advantage of uniqueness in electronic component heat management application field.
Description
Technical field
The present invention relates to technical field prepared by thermoelectric material and device, more particularly to adding applied to thick film hot pressed sintering
Pressure device, thermoelectricity thick film and flexible thermo-electric device.
Background technology
Thermoelectric material is a kind of functional material that can be directly realized by heat energy and electric energy and mutually change, because its small volume,
Quieter operation and any dusty gas is not produced, the potential application in thermoelectric power generation and refrigeration direction causes researcher's
Extensive concern.Excessive turned into of high-performance electronic element heating amount restricts its key issue further developed, thermoelectricity system at present
It is cold that extensive attention is received due to the unique advantage in electronic component heat management application aspect, it is expected to turn into high hot-fluid of future generation
The mainstream solution of density of electronic element radiating.The miniaturization of electronic component there is an urgent need to thermoelectric cooling device to miniaturization and
Flexibility direction is developed.Compared to block and thin film thermoelectric materials, flexible thick film thermoelectric material has that production cost is low, the cycle
Short, controllability is strong, the advantages that having a wide range of application.
The thermoelectricity slurry prepared is mainly printed onto on substrate by Conventional thermoelectric thick film preparation method using typography, directly
Connect and be thermally treated resulting in thermoelectricity thick film by follow-up.But thermoelectricity thick film is in heat treatment process, due to organic matter decomposition and
Volatilization, the defects of leaving hole and crackle inside the thick film after heat treatment.These holes and crackle can increase the internal resistance of thick film, lead
Send a telegraph and transport hydraulic performance decline.
The thermoelectricity thick film of excellent performance requires higher Seebeck coefficients and relatively low resistivity, higher
Seebeck coefficients ensure there is preferable thermoelectric conversion effect during device work, and relatively low resistivity ensures to produce during device work
Raw less Joule heat.Internal the problem of leaving hole and crackle after being heat-treated for thick film, correlative study person will be heat-treated
Thick film afterwards carries out isostatic cool pressing processing, to improve its electrical conductivity.But the thick film overall structure after heat treatment has been molded,
And mechanical strength is relatively low, cold pressing treatment can cause thick-film material to ftracture and crush.In the packaging technology of thick devices, often at present
Electrode interconnection technique is to be connected using wire by soldering or conductive silver glue, but soldering or elargol connection have contact electricity
The shortcomings of resistance is big, wire is easy to fall off.Therefore, a kind of method and stably that simple efficient hot pressed sintering prepares thermoelectricity thick film is invented
Efficient method of connecting electrodes, to improving thick film thermo-electric device electronic transport performance and realizing that device Integrated manufacture is most important
's.
The content of the invention
The problem of existing for prior art, present invention offer is a kind of simply, is efficiently applied to thick film hot pressed sintering
Pressue device, thermoelectricity thick film and flexible thermo-electric device.It is that having invented one kind can apply to thermoelectricity in place of the characteristic of the present invention
The pressue device of thick film hot pressed sintering, solve the problems, such as the crackle and hole of generally existing in the heat treatment of thermoelectricity thick film, significantly
Thermoelectricity thick devices internal resistance is reduced, solves the bottleneck problem that Joule heat is excessive in the thermoelectricity thick devices course of work, is improved
The conversion efficiency of thermoelectric of device.This high performance thermoelectricity thick devices are expected to realize in electronic component heat management is applied and dashed forward
It is broken.
To achieve these goals, technical scheme provided by the invention is：
Applied to the pressue device of thick film hot pressed sintering, the pressue device includes multiple compression spring assemblies, the first pressure
Plate, the second pressing plate, top plate and bottom plate；The bottom plate is used to place thick film, and first pressing plate is placed in above thick film and and thick film
It is in contact, the size of first pressing plate and thick film substrate matches, and second pressing plate is placed in the top of first pressing plate,
The top plate is placed in the top of second pressing plate, and company is fixed in one end of each compression spring assembly and one end of the bottom plate
Connect, the other end of each compression spring assembly wears one end of second pressing plate and top plate, each compression spring assembly respectively
Including a compression spring, the both ends of the compression spring respectively with the upper surface of second pressing plate and the lower surface phase of top plate
Abut.
In such scheme, each compression spring assembly also includes screw rod, nut and pad, and the compression spring is set in spiral shell
On bar, the nut and septum screw are connected on the screw rod, and the nut and pad are arranged at the upper surface of the top plate
On.
A kind of thermoelectricity thick film, the thermoelectricity thick film are prepared by the following method：
1) slurry of flexible base board and thermoelectricity thick film is provided, the slurry of the thermoelectricity thick film is by thermoelectric material powder and epoxy
Resin system forms；
2) slurry of thermoelectricity thick film is printed onto on flexible base board, thick film is placed in adding described in claim 1 or 2 after drying
In pressure device；
3) pressure put on thick-film material is adjusted by adjusting the decrement of compression spring, then fills pressurization
It is placed in atmosphere sintering furnace and is heat-treated, obtains the thermoelectricity thick film.
In such scheme, described thermoelectric material powder is Bi0.5Sb1.5Te3、Bi2Te2.7Se0.3、Sb2Te3Or Bi2Te3Heat
Electric material abrasive flour.
In such scheme, the viscosity of the slurry is 5000cP~10000cP.
In such scheme, the epoxy-resin systems include epoxy resin, curing agent, catalyst and diluent, the ring
The percentage that the quality of epoxy resin system accounts for stock quality is 15%-25%.
In such scheme, the epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin or bisphenol S type epoxy
Resin；The curing agent is methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride；The catalyst is 2-ethyl-4-methylimidazole or 1-
Cyanoethyl -2-ethyl-4-methylimidazole；The diluent be acetone, toluene or butyl glycidyl ether in any one or
Two or more mixing.
In such scheme, described substrate is polyimide substrate, PET substrate or poly- naphthalene two
Formic acid glycol ester substrate.
In such scheme, described printing process is brushing method, silk screen print method, dispensing impact system or ink-jet printing process.
Flexible thermo-electric device, the flexible thermo-electric device are true including passing through to the thermoelectricity thick film that described preparation method obtains
Empty electrode evaporation connects adjacent thermoelectricity leg and assembled.
In such scheme, the material of described vacuum electrode evaporation is Cu, Al, Ni and its alloy material.
In the present invention, the material of compression spring is GH4169 high temperature alloys, spring former long 30mm, stiffness factor K=
43.44N/mm.Pressing plate and top plate base plate size can obtain according to thick film substrate size through linear cutter.First pressing plate size 80
×30mm2, the size of the second pressing plate, top plate and bottom plate is 95 × 45mm2.It is thin that first pressing plate with thick film contact surface sticks high temperature resistant
Film or carbon paper, prevent that thick film is be bonded with the generation of the first pressing plate in heat treatment process.
Compared with prior art, beneficial effects of the present invention are：
1) hot pressed sintering device of the invention has simple in construction, can be placed in atmosphere sintering furnace and realize to thermoelectricity thick film
Hot pressed sintering；Manufacturing cost is low, and existing large-scale hot-press equipment ratio, reduces the production cost of thermoelectricity thick devices；Processing
Controllability is strong, and hot-press arrangement is cut by stainless-steel sheet and formed, thus can by change cutting processing dimension process with
The parameter such as the hot-press arrangement that thick-film material shape and size match, line footpath and the number of turns by changing compression spring can obtain
The device of the different pressures limit.
2) thermoelectricity thick film preparation is simple.Pressurize and be heat-treated after only the thick-film material that printed need to be dried, Ran Houzheng
Plated electrode, you can realize that device is integrated and assembles, the manufacturing cycle of thermo-electric device is greatly shortened, is advantageous to large-scale production.
3) thick film thermo-electric device stability is good.Hot pressed sintering thick-film material contacts with substrates into intimate, and thick film is difficult for drop-off, group
Filling the device formed has certain mechanical strength, substantially increases the performance of device.
Brief description of the drawings
Fig. 1 is pressue device schematic diagram provided by the invention, wherein：Fig. 1 a are device before pressurization, and Fig. 1 b are modulated seamless
The pressure apparatus of power.
Fig. 2 is the brushing method preparation process schematic diagram of thick film thermo-electric device.Wherein：Fig. 2 a are that template coordinates signal with substrate
Figure, template and substrate are 150 μm of Kapton, and template size is 30mm × 70mm, the size of 8 through holes in template
For 4mm × 20mm, substrate size is 30mm × 80mm；Fig. 2 b are that hairbrush dips the thick film after slurry is brushed successively, and surface protrudes
Part is brushing additional size；Fig. 2 c are the thick film after scraper shaping, and scraper is scraped off such as the additional size in Fig. 2 b, make brushing thick
Film surfacing；Fig. 2 d are vacuum drying, the thick film for removing template；Fig. 2 e are that dried thick film is placed in pressue device signal
Figure, pressure process is as described in figure 1 above；Fig. 2 f are the pressue device of modulated seamless power；Fig. 2 g are the thick film after hot pressing；Fig. 2 h are true
Single leg thermoelectricity thick devices schematic diagram after empty electrode evaporation；Fig. 2 i are that the π type thermoelectricity thick devices after vacuum electrode evaporation show
It is intended to.
Fig. 3 is the section SEM image of non-hot pressing thick film and hot pressing thick film.Wherein Fig. 3 a are the section SEM image of non-hot pressing,
It is hole in circle in figure, arrow meaning is crackle；Fig. 3 b and Fig. 3 c represent the section SEM that pressure is 2MPa and 4MPa respectively
Image.
Relation between the thermoelectricity capability and temperature of the thermoelectricity thick film that Fig. 4 is non-hot pressing and hot pressing pressure is 2MPa and 4MPa
Curve.Wherein relation curves of Fig. 4 a between electrical conductivity and temperature；Relations of Fig. 4 b between Seebeck coefficients and temperature is bent
Line；Relation curves of Fig. 4 c between power factor and temperature.
Fig. 5 is composite thick film list leg thermo-electric device pictorial diagram.
Fig. 6 is composite thick film π type thermo-electric device pictorial diagrams.
Fig. 7 be in embodiment 2 composite thick film list leg thermo-electric device under different test electric currents cold end and the temperature in hot junction with
Time Relationship curve.
In figure：1- bottom plates；The dried thick-film materials of 2- and substrate；The pressing plates of 3- first；The pressing plates of 4- second；5- high temperature resistant pressures
Contracting spring；6- top plates；7- nuts and pad；8- screw rods.
Embodiment
For a better understanding of the present invention, present disclosure is expanded on further with reference to embodiment.
Embodiment 1
As shown in figure 1, it provides a kind of pressue device applied to thick film hot pressed sintering, pressue device bag for the present embodiment
Include multiple compression spring assemblies, the first pressing plate 3, the second pressing plate 4, top plate 6 and bottom plate 1.Bottom plate 1 is used to place thick film, the first pressure
Plate 3 is placed in above thick film and is in contact with thick film, and the first pressing plate 3 and the size of thick film substrate match, and the second pressing plate 4 is placed in the
The top of one pressing plate 3, top plate 6 are placed in the top of the second pressing plate 4, and one end and one end of bottom plate 1 of each compression spring assembly are consolidated
Fixed connection, the other end of each compression spring assembly wear one end of the second pressing plate 4 and top plate 6, each compression spring set respectively
Part includes a compression spring 5, the both ends of the compression spring 5 respectively with the upper surface of the second pressing plate 4 and the lower surface of top plate 6
Abut against.
In the present embodiment, each compression spring assembly also includes screw rod 8, nut and pad 7, and compression spring 5 is set in
On screw rod 8, nut and pad 7 are threadedly connected on screw rod 8, and nut and pad 7 are arranged on the upper surface of top plate 6.Pass through tune
The position of section nut and pad 7 can adjust the spring amount of compression spring 5, so as to adjust the pressure for putting on thick film surface.
The present invention also provides a kind of preparation method of thermoelectricity thick film, and it comprises the following steps：
1) preparation of thermoelectricity slurry
(1) p-type Bi is weighed0.5Sb1.5Te3Alloy powder 20g is added in high-energy ball milling tank, ratio of grinding media to material 13:1, add
50ml absolute ethyl alcohols are passed through Ar atmosphere protections as ball-milling medium after vacuumizing.It is placed in planetary ball mill and uses 200r/min
Condition ball milling 2h, the stand-by powder that particle diameter is 1~30 μm is dried to obtain after centrifugation.
(2) Bisphenol F diglycidyl ether epoxy resin 1.25g, methyl hexahydrophthalic anhydride 1.0625g, 2- ethyl -4- first are weighed
P-type Bi after base imidazoles 0.15g and ball milling0.5Sb1.5Te3Alloy powder 16.0063g is mixed in beaker, adds 2.6604g fourths
Mechanical agitation 1-2h after base glycidol ether, ultrasonic disperse 15min, obtain uniform, stable p-type Bi0.5Sb1.5Te3- asphalt mixtures modified by epoxy resin
Fat composite mortar.
2) shaping and hot-pressing processing are brushed (referring to Fig. 2)
The template of brushing method and substrate are coordinated, the size of template makes according to the shape and size of thick film.Hairbrush dips
Slurry is brushed successively, and scraper shaping makes brushing thick film surface smooth.100 DEG C of vacuum drying 30min of thick film after brushing, remove mould
Plate, is dried and uncured thick-film material.Dried thick film is placed on pressue device bottom plate 1, screw rod 8 and bottom plate 1
Coordinate, the contact surface of the first pressing plate 3 and thick film sticks high-temperature resistant membrane, prevents that thick film is Nian Jie with the first pressing plate, causes the demoulding tired
It is difficult.First pressing plate is placed in above thick film, assembles the second pressing plate 4, compression spring 5, top plate 6, pad and nut 7, regulation pressure successively
Contracting amount of spring compression, it is 2MPa thick film is born pressure.Device after pressurization is placed in pipe type sintering furnace, vacuumizes ventilation,
Device is heat-treated 10h for 350 DEG C in an ar atmosphere, unclamps nut after heat treatment, obtains the thick-film material of densification.
3) thick-film material microstructure and thermoelectric property characterization
By the thick-film material after hot pressing take section carry out microstructure characterizations (referring to Fig. 3 b) and thermoelectricity capability test (referring to
Fig. 4), find out from section SEM image, compared with non-hot pressing thick film sample, when hot pressing pressure is 2MPa, film thickness reduces
15 μm, hole and crackle inside thick film are reduced, the consistency increase of thick film.Compared with non-hot pressing thick film sample, hot pressing pressure
For 2MPa when, thick film electrical conductivity is by 6.38 × 103S·m-1Increase to 8.87 × 103S·m-1, electrical conductivity improves 39%.
4) device assembles
Copper electrode is deposited by mask vacuum in thick film after hot pressing, and thick-film material is joined end to end, is assembled into p-type
Bi0.5Sb1.5Te3- epoxy resin composite thick film list leg thermo-electric device (referring to Fig. 5).
5) sign of device refrigeration performance
The thermoelectricity thick devices assembled are tested into refrigeration performance at room temperature, different size of electric current is passed through to device,
The temperature at thick devices both ends is tested simultaneously using patch-type thermocouple, and temperature change is recorded by data acquisition module.With
The increase of test electric current, the temperature difference at device both ends gradually increases.In the range of safety test, as I=0.18A, maximum temperature
Difference reaches 12.6K.
Embodiment 2
The present invention also provides a kind of preparation method of thermoelectricity thick film, and it comprises the following steps：
1) preparation of thermoelectricity slurry
(1) p-type Bi is weighed0.5Sb1.5Te3Alloy powder 20g, add in high-energy ball milling tank, ratio of grinding media to material 13:1, add
50ml absolute ethyl alcohols are passed through Ar atmosphere protections as ball-milling medium after vacuumizing.It is placed in planetary ball mill and uses 200r/min
Condition ball milling 2h, the stand-by powder that particle diameter is 1~30 μm is dried to obtain after centrifugation.
(2) Bisphenol F diglycidyl ether epoxy resin 1.25g, methyl hexahydrophthalic anhydride 1.0625g, 2- ethyl -4- first are weighed
P-type Bi after base imidazoles 0.15g and ball milling0.5Sb1.5Te3Alloy powder 16.0063g is mixed in beaker, adds 2.6604g fourths
Mechanical agitation 1-2h after base glycidol ether, ultrasonic disperse 15min, obtain uniform, stable p-type Bi0.5Sb1.5Te3- asphalt mixtures modified by epoxy resin
Fat composite mortar.
2) shaping and hot-pressing processing are brushed (referring to Fig. 2)
The template of brushing method and substrate are coordinated, the size of template makes according to the shape and size of thick film.Hairbrush dips
Slurry is brushed successively, and scraper shaping makes brushing thick film surface smooth.100 DEG C of vacuum drying 30min of thick film after brushing, remove mould
Plate, is dried and uncured thick-film material.Dried thick film is placed on pressue device bottom plate 1, screw rod 8 and bottom plate 1
Coordinate, the contact surface of the first pressing plate 3 and thick film sticks high-temperature resistant membrane, prevents that thick film is be bonded with the first pressing plate 3, causes the demoulding tired
It is difficult.First pressing plate 3 is placed in above thick film, assembles the second pressing plate 4, compression spring 5, top plate 6, pad and nut 7, regulation pressure successively
Contracting amount of spring compression, it is 4MPa thick film is born pressure.Device after pressurization is placed in pipe type sintering furnace, vacuumizes ventilation,
Device is heat-treated 10h for 350 DEG C in an ar atmosphere, unclamps nut after heat treatment.Obtain the thick-film material of densification.
3) thick-film material microstructure and thermoelectric property characterization
By the thick-film material after hot pressing take section carry out microstructure characterizations (referring to Fig. 3 c) and thermoelectricity capability test (referring to
Fig. 4), find out from section SEM image, compared with non-hot pressing thick film sample, during hot pressing pressure 4MPa, film thickness reduces 30
μm, hole and crackle inside thick film disappear, the increase of thick film consistency.Compared with non-hot pressing thick film sample, hot pressing pressure 4MPa
When, thick film electrical conductivity is by 6.38 × 103S·m-1Increase to 11.49 × 103S·m-1, electrical conductivity improves 80%.
4) device assembles
Copper electrode is deposited by mask vacuum in thick film after hot pressing, and thick-film material is joined end to end, is assembled into p-type
Bi0.5Sb1.5Te3- epoxy resin composite thick film list leg thermo-electric device (referring to Fig. 5).
5) sign of device refrigeration performance
The thermoelectricity thick devices assembled are tested into refrigeration performance at room temperature, different size of electric current is passed through to device,
The temperature at thick devices both ends is tested simultaneously using patch-type thermocouple, and temperature change is recorded by data acquisition module.
Relation curve relation is as shown in Figure 7 between cold end and the temperature and time in hot junction under difference test electric current.With test electric current
Increase, the temperature difference at device both ends gradually increase.In the range of safety test, as I=0.18A, maximum temperature difference reaches 17.9K.
Embodiment 3
The present invention also provides a kind of preparation method of thermoelectricity thick film, and it comprises the following steps：
1) preparation of thermoelectricity slurry
(1) n-type Bi is weighed2Te2.7Se0.3Alloy powder 20g, add in high-energy ball milling tank, ratio of grinding media to material 13:1, add
50ml absolute ethyl alcohols are passed through Ar atmosphere protections as ball-milling medium after vacuumizing.It is placed in planetary ball mill and uses 200r/min
Condition ball milling 2h, the stand-by powder that particle diameter is 1~30 μm is dried to obtain after centrifugation.
(2) Bisphenol F diglycidyl ether epoxy resin 1.25g, methyl hexahydrophthalic anhydride 1.0625g, 2- ethyl -4- first are weighed
N-type Bi after base imidazoles 0.15g and ball milling2Te2.7Se0.3Alloy powder 16.0063g is mixed in beaker, adds 2.6604g fourths
Mechanical agitation 1-2h after base glycidol ether, ultrasonic disperse 15min, obtain uniform, stable n-type Bi2Te2.7Se0.3- asphalt mixtures modified by epoxy resin
Fat composite mortar.
2) shaping and hot-pressing processing are brushed (referring to Fig. 2)
Brushing method template and substrate are coordinated, the size of template makes according to the shape and size of thick film.Hairbrush dips slurry
Material is brushed successively, and scraper makes surfacing.100 DEG C of vacuum drying 30min of thick film after brushing, remove template, obtain uncured
Thick-film material.Dried thick film is placed on pressue device bottom plate 1, screw rod 8 coordinates with bottom plate 1, the first pressing plate 3 and thick film
Contact surface stick high-temperature resistant membrane, prevent that thick film is be bonded with the first pressing plate 3, cause the demoulding difficult.First pressing plate 3 is placed in thick film
Top, the second pressing plate 4, compression spring 5, top plate 6, pad and nut 7 are assembled successively, adjust compression spring decrement, make thick film
It is 2MPa to bear pressure.Device after pressurization is placed in pipe type sintering furnace, vacuumizes ventilation, 350 DEG C in an ar atmosphere of device
10h is heat-treated, unclamps nut.Obtain the thick-film material of densification.
3) thick-film material thermoelectric property characterization
Electric performance test is carried out to the thick film after hot pressing, test result shows：Compared with non-hot pressing thick film sample, hot pressing pressure
When being by force 2MPa, thick film electrical conductivity is by 2.32 × 103S·m-1Increase to 14.32 × 103S·m-1, electrical conductivity improves 6.17
Times.
4) device assembles
Copper electrode is deposited by mask vacuum in thick film after hot pressing, and thick-film material is sequentially connected, is assembled into n-type
Bi2Te2.7Se0.3- epoxy resin composite thick film list leg thermo-electric device (referring to Fig. 5).
5) sign of device refrigeration performance
The thermoelectricity thick devices assembled are tested into refrigeration performance at room temperature, different size of electric current is passed through to device,
The temperature at thick devices both ends is tested simultaneously using patch-type thermocouple, and temperature change is recorded by data acquisition module.With
The increase of test electric current, the temperature difference at device both ends gradually increases.In the range of safety test, as I=0.18A, maximum temperature
Difference reaches 14K.
Embodiment 4
The present invention also provides a kind of preparation method of thermoelectricity thick film, and it comprises the following steps：
1) preparation of thermoelectricity slurry
(1) n-type Bi is weighed2Te2.7Se0.3Alloy powder 20g, add in high-energy ball milling tank, ratio of grinding media to material 13:1, add
50ml absolute ethyl alcohols are passed through Ar atmosphere protections as ball-milling medium after vacuumizing.It is placed in planetary ball mill and uses 200r/min
Condition ball milling 2h, the stand-by powder that particle diameter is 1~30 μm is dried to obtain after centrifugation.
(2) Bisphenol F diglycidyl ether epoxy resin 1.25g, methyl hexahydrophthalic anhydride 1.0625g, 2- ethyl -4- first are weighed
N-type Bi after base imidazoles 0.15g and ball milling2Te2.7Se0.3Alloy powder 16.0063g is mixed in beaker, adds 2.6604g fourths
Mechanical agitation 1-2h after base glycidol ether, ultrasonic disperse 15min, obtain uniform, stable n-type Bi2Te2.7Se0.3- asphalt mixtures modified by epoxy resin
Fat composite mortar.
2) shaping and hot-pressing processing are brushed (referring to Fig. 2)
Brushing method template and substrate are coordinated, the size of template makes according to the shape and size of thick film.Hairbrush dips in successively
P-type and n-type composite mortar is taken alternately to brush, scraper makes surfacing.100 DEG C of vacuum drying 30min of thick film after brushing, are removed
Template, obtain uncured thick-film material.Dried thick film is placed on pressue device bottom plate 1, screw rod 8 coordinates with bottom plate 1,
The contact surface of first pressing plate 3 and thick film sticks high-temperature resistant membrane, prevents that thick film is be bonded with the first pressing plate 3, causes the demoulding difficult.The
One pressing plate 3 is placed in above thick film, assembles pressing plate 4, compression spring 5, top plate 6, pad and nut 7 successively, adjusts compression spring pressure
Contracting amount, it is 4MPa thick film is born pressure.Device after pressurization is placed in pipe type sintering furnace, vacuumizes ventilation, device is in Ar
350 DEG C of heat treatment 10h, unclamp nut in atmosphere.Obtain the thick-film material of densification.
3) thick-film material thermoelectric property characterization
Electric performance test is carried out to the thick film after hot pressing, test result shows：Compared with non-hot pressing thick film sample, hot pressing pressure
When being by force 4MPa, thick film electrical conductivity is by 2.32 × 103S·m-1Increase to 16.2 × 103S·m-1, electrical conductivity improves 7 times.
4) device assembles
Copper electrode is deposited by mask vacuum in thick film after hot pressing, and thick-film material is sequentially connected, is assembled into n-type
Bi2Te2.7Se0.3- epoxy resin composite thick film list leg thermo-electric device (referring to Fig. 5).
5) sign of device refrigeration performance
The thermoelectricity thick devices assembled are tested into refrigeration performance at room temperature, different size of electric current is passed through to device,
The temperature at thick devices both ends is tested simultaneously using patch-type thermocouple, and temperature change is recorded by data acquisition module.With
The increase of test electric current, the temperature difference at device both ends gradually increases.In the range of safety test, as I=0.18A, maximum temperature
Difference reaches 15.9K.
Embodiment 5
The present invention also provides a kind of preparation method of thermoelectricity thick film, and it comprises the following steps：
1) preparation of thermoelectricity slurry
(1) p-type Bi is weighed0.5Sb1.5Te3With n-type Bi2Te2.7Se0.3Each 20g of alloy powder, add in high-energy ball milling tank, ball
Material is than being 13:1,50m absolute ethyl alcohols are added as ball-milling medium, and Ar atmosphere protections are passed through after vacuumizing.It is placed in planetary ball mill
It is middle to use 200r/min condition ball milling 2h, the stand-by powder that particle diameter is 1~30 μm is dried to obtain after centrifugation.
(2) Bisphenol F diglycidyl ether epoxy resin 1.25g, methyl hexahydrophthalic anhydride 1.0625g, 2- ethyl -4- first are weighed
P-type Bi after base imidazoles 0.15g and ball milling0.5Sb1.5Te3Alloy powder 16.0063g is mixed in beaker, adds 2.6604g fourths
Mechanical agitation 1-2h after base glycidol ether, ultrasonic disperse 15min, obtain uniform, stable p-type Bi0.5Sb1.5Te3- asphalt mixtures modified by epoxy resin
Fat composite mortar.
(3) Bisphenol F diglycidyl ether epoxy resin 1.25g, methyl hexahydrophthalic anhydride 1.0625g, 2- ethyl -4- first are weighed
N-type Bi after base imidazoles 0.15g and ball milling2Te2.7Se0.3Alloy powder 16.0063g is mixed in beaker, adds 2.6604g fourths
Mechanical agitation 1-2h after base glycidol ether, ultrasonic disperse 15min, obtain uniform, stable n-type Bi2Te2.7Se0.3- asphalt mixtures modified by epoxy resin
Fat composite mortar.
2) shaping and hot-pressing processing are brushed (referring to Fig. 2)
Brushing method template and substrate are coordinated, the size of template makes according to the shape and size of thick film.Hairbrush dips in successively
P-type and n-type composite mortar is taken alternately to brush, scraper makes surfacing.100 DEG C of vacuum drying 30min of thick film after brushing, are removed
Template, obtain uncured thick-film material.Dried thick film is placed on pressue device bottom plate 1, screw rod 8 coordinates with bottom plate 1,
The contact surface of first pressing plate 3 and thick film sticks high-temperature resistant membrane, prevents that thick film is be bonded with the first pressing plate 3, causes the demoulding difficult.The
One pressing plate 3 is placed in above thick film, assembles pressing plate 4, compression spring 5, top plate 6, pad and nut 7 successively, adjusts compression spring pressure
Contracting amount, it is 4MPa thick film is born pressure.Device after pressurization is placed in pipe type sintering furnace, vacuumizes ventilation, device is in Ar
350 DEG C of heat treatment 10h, unclamp nut in atmosphere.Obtain the thick-film material of densification.
3) device assembles
Copper electrode is deposited by mask vacuum in thick film after hot pressing, and thick-film material is connected, and is assembled into π types composite thick film heat
Electrical part (referring to Fig. 6).
4) sign of device refrigeration performance
The thermoelectricity thick devices assembled are tested into refrigeration performance at room temperature, different size of electric current is passed through to device,
The temperature at thick devices both ends is tested simultaneously using patch-type thermocouple, and temperature change is recorded by data acquisition module.With
The increase of test electric current, the temperature difference at device both ends gradually increases.In the range of safety test, as I=0.18A, maximum temperature
Difference reaches 19K.
Embodiments of the invention are described above in conjunction with accompanying drawing, but the invention is not limited in above-mentioned specific
Embodiment, above-mentioned embodiment is only schematical, rather than restricted, one of ordinary skill in the art
Under the enlightenment of the present invention, in the case of present inventive concept and scope of the claimed protection is not departed from, it can also make a lot
Form, these are belonged within the protection of the present invention.
Claims (10)
1. the pressue device applied to thick film hot pressed sintering, it is characterised in that the pressue device includes multiple compression spring sets
Part, the first pressing plate, the second pressing plate, top plate and bottom plate；The bottom plate is used to place thick film, and first pressing plate is placed in above thick film
And be in contact with thick film, the size of first pressing plate and thick film substrate matches, and second pressing plate is placed in first pressure
The top of plate, the top plate are placed in the top of second pressing plate, one end of each compression spring assembly and the one of the bottom plate
End is fixedly connected, and the other end of each compression spring assembly wears one end of second pressing plate and top plate respectively, each compression
Spring assembly includes a compression spring, the both ends of the compression spring respectively with the upper surface of second pressing plate and top plate
Lower surface abuts against.
2. it is applied to the pressue device of thick film hot pressed sintering as claimed in claim 1, it is characterised in that each compression spring set
Part also includes screw rod, nut and pad, and the compression spring is set on screw rod, and the nut and septum screw are connected to described
On screw rod, the nut and pad are arranged at the upper surface of the top plate.
3. a kind of thermoelectricity thick film, it is characterised in that the thermoelectricity thick film is prepared by the following method：
1) slurry of flexible base board and thermoelectricity thick film is provided, the slurry of the thermoelectricity thick film is by thermoelectric material powder and epoxy resin
System forms；
2) slurry of thermoelectricity thick film is printed onto on flexible base board, thick film is placed in the pressurization dress described in claim 1 or 2 after drying
In putting；
3) it is 0-4Mpa so as to adjust the pressure put on thick-film material by adjusting the decrement of compression spring, then will adds
Pressure device is placed in atmosphere sintering furnace and is heat-treated, and obtains the thermoelectricity thick film.
4. preparation method as claimed in claim 3, it is characterised in that described thermoelectric material powder is Bi0.5Sb1.5Te3、
Bi2Te2.7Se0.3、Sb2Te3Or Bi2Te3Thermoelectric material abrasive flour.
5. preparation method as claimed in claim 3, it is characterised in that the viscosity of the slurry is 5000cP~10000cP.
6. preparation method as claimed in claim 3, it is characterised in that the epoxy-resin systems include epoxy resin, solidification
Agent, catalyst and diluent, the percentage that the quality of the epoxy-resin systems accounts for stock quality is 15%-25%.
7. preparation method as claimed in claim 6, it is characterised in that the epoxy resin is bisphenol A type epoxy resin, bis-phenol
F types epoxy resin or bisphenol-s epoxy resin；The curing agent is methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride；The catalysis
Agent is 2-ethyl-4-methylimidazole or 1- cyanoethyls -2-ethyl-4-methylimidazole；The diluent is acetone, toluene or butyl
Any one in glycidol ether or two or more mixing.
8. preparation method as claimed in claim 3, it is characterised in that described substrate is polyimide substrate, gathered to benzene two
Formic acid glycol ester substrate or PEN substrate.
9. preparation method as claimed in claim 3, it is characterised in that described printing process be brushing method, silk screen print method,
Dispensing impact system or ink-jet printing process.
10. flexible thermo-electric device, it is characterised in that the flexible thermo-electric device is included to described in claim any one of 3-9
The thermoelectricity thick film that preparation method obtains connects adjacent thermoelectricity leg by vacuum electrode evaporation and assembled.
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| CN107732000B (en) | 2020-01-31 |
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