CN110098309A - A kind of connection method of N-type bismuth telluride based on nano mattisolda and nickel coating and Cu electrode - Google Patents
A kind of connection method of N-type bismuth telluride based on nano mattisolda and nickel coating and Cu electrode Download PDFInfo
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- CN110098309A CN110098309A CN201910353466.2A CN201910353466A CN110098309A CN 110098309 A CN110098309 A CN 110098309A CN 201910353466 A CN201910353466 A CN 201910353466A CN 110098309 A CN110098309 A CN 110098309A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title claims abstract description 44
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 229910052797 bismuth Inorganic materials 0.000 title description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title description 3
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title description 3
- 229910002899 Bi2Te3 Inorganic materials 0.000 claims abstract description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005476 soldering Methods 0.000 claims abstract description 16
- 230000004888 barrier function Effects 0.000 claims abstract description 12
- 238000009792 diffusion process Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 30
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000003466 welding Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 235000013339 cereals Nutrition 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000006197 hydroboration reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000010008 shearing Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 230000005619 thermoelectricity Effects 0.000 description 4
- 238000007747 plating Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910005642 SnTe Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- -1 metals Compound Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- PDYNJNLVKADULO-UHFFFAOYSA-N tellanylidenebismuth Chemical compound [Bi]=[Te] PDYNJNLVKADULO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 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
- H10N10/80—Constructional details
- H10N10/82—Connection of interconnections
-
- 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
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
Abstract
A kind of N-type Bi based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode, it is related to a kind of Bi2Te3With the connection method of Cu electrode.Purpose is the N-type Bi solved using the connection of Sn base solder2Te3The problem of thermoelectric device is unable to satisfy the poor reliability of temperature requirement and soldered fitting that thermoelectric device is on active service is connected and composed with Cu electrode.Method: first in N-type Bi2Te3Surface to be welded prepares nickel coating as diffusion barrier, then using nano mattisolda to N-type Bi2Te3Surface to be welded and Cu electrode carry out soldering connection.Effective combination between nickel barrier layer and nano silver and between nano silver and Cu ensure that the reliability of connector.Attenuation of shear resistance is small during military service, has good middle low temperature service performance.The present invention is suitable for N-type Bi2Te3With the connection of Cu electrode.
Description
Technical field
The present invention relates to a kind of Bi2Te3With the connection method of Cu electrode.
Background technique
As the mankind are to the continuous growth of energy demand, the increasingly scarcity of traditional non-renewable energy resources inventory, develop novel
Sustainable development source becomes the important topic of current scientific and technological circle.Thermoelectric material is as a kind of defeated using material internal carrier
The functional material that fortune phenomenon mutually converts thermal energy and electric energy, has obtained the great attention of every country and has researched and developed energetically.Heat
Industrial waste heat can be directly changed into electric energy, i.e. thermo-electric generation by electric material, before thermo-electric generation has wide application
Scape.Bismuth telluride (Bi2Te3) it is the thermoelectric material that performance is best at room temperature, a large amount of exploitation has been obtained in terms of thermoelectric cooling,
Realize that it is of great significance with being reliably connected for electrode.Thermoelectric material fusing point is lower, traditional melting welding, laser welding, electronics
The methods of beam welding is easy to that thermoelectric material is made to melt and lose its intrinsic thermoelectricity capability, at present the company of thermoelectric material and electrode
Connecing universal common method is mainly soldering connection.Compared to other such as mechanical connection, the connections of ultrasonic wave auxiliary, it is glued and instantaneous
The connection methods such as liquid phase connection, soldering connection can guarantee that thermoelectric material and Cu electrode are maximum under the premise of realizing effectively combination
Guarantee to degree thermoelectricity capability and conversion efficiency of thermoelectric.
Existing N-type Bi2Te3The thermoelectric device constituted with Cu electrode mostly uses Sn base solder to be attached；There are the problem of
It is: Bi2Te3Biggish contact resistance is often generated with the soldered fitting of Cu electrode, and with the increase of active time, pricker
Plumb joint can deteriorate, and further decrease Bi2Te3The thermoelectric conversion efficiency of the thermoelectric device of composition, causes thermoelectricity capability to become
Difference.Bi2Te3The Service Environment for connecting and composing thermoelectric device with Cu electrode is up to 250 DEG C, and Sn base solder causes it since fusing point is low
It is lower than 200 DEG C using temperature, therefore is unable to satisfy the temperature requirement of thermoelectric device military service, and then lead to the thermoelectric device of preparation
Joint Reliability is poor；And Sn easily generates excessive SnTe, Cu with Te, Cu etc. in Sn base solder6Sn5、Cu3Sn4Between equal metals
Compound also will affect being reliably connected for connector, and connector strength retrogression during long service is serious, existing to use Sn base
The N-type Bi of solder connection2Te3The structure of the thermoelectric device constituted with Cu electrode is 10MPa or so at room temperature, and in temperature of being on active service
It is only 2MPa or so that degree is lower, and strength retrogression is even more serious during long service, easily generation brittle failure, soldered fitting
Poor reliability.
Summary of the invention
The invention solves the N-type Bi using the connection of Sn base solder2Te3Connecting and composing thermoelectric device with Cu electrode can not expire
The problem of poor reliability for the temperature requirement and soldered fitting that sufficient thermoelectric device is on active service, proposes a kind of based on nano mattisolda and nickel
The connection method of the N-type bismuth telluride and Cu electrode of coating.
The present invention is based on nano mattisolda and the N-type Bi of nickel coating2Te3Connection method with Cu electrode is according to the following steps
It carries out: first in N-type Bi2Te3Surface to be welded prepares nickel coating as diffusion barrier, then using nano mattisolda to N-type Bi2Te3
Surface to be welded and Cu electrode carry out soldering connection, that is, complete.
Further, the nickel coating thickness is 3~10 μm.
Further, described in N-type Bi2Te3Surface to be welded prepares nickel coating using galvanoplastic, prepares nickel plating using galvanoplastic
Contain nickel sulfate, nickel chloride, boric acid and lauryl sodium sulfate in electroplate liquid used in layer process.
Further, the concentration of nickel sulfate is 250~350g/L in the electroplate liquid, and the concentration of nickel chloride is 30~60g/
L, the concentration of boric acid are 30~40g/L, and the concentration of lauryl sodium sulfate is 0.05~0.10g/L.
Further, the purity of the nickel sulfate, nickel chloride, boric acid and lauryl sodium sulfate is 99%~99.99%.
Further, it is described use galvanoplastic to prepare nickel coating during current density for 1~2.5A/dm2, when plating
Between be 5~20min.
Further, it is described use galvanoplastic to prepare nickel coating during the electroplate liquid used PH for 3~5.
Further, described to utilize nano mattisolda to N-type Bi2Te3Surface to be welded and Cu electrode carry out the specific of soldering connection
Method follows the steps below:
One, nano mattisolda is coated in Cu electrode welding surface, by N-type Bi2Te3It covers on nano mattisolda, N-type
Bi2Te3Middle nickel coating constitutes assembly parts towards nano mattisolda, and the pressure for applying 5~15MPa to assembly parts upper and lower surface carries out
It is fixed；
Two, the assembly parts after fixation that step 1 obtains are put into vacuum furnace, adjustment vacuum degree be (1~3) ×
10-3When Pa, then start to be heated to 230~250 DEG C with the speed of 5~10 DEG C/min, then heat with the speed of 3~5 DEG C/min
To 260~350 DEG C and 1~60min is kept the temperature, room temperature is then cooled to the furnace, that is, completes.
It further, further include removal Cu before nano mattisolda being coated in Cu electrode welding surface described in step 1
The greasy dirt process and oxide process of electrode welding surface, and after the greasy dirt and oxide of removal Cu electrode welding surface
Cu electrode is put into 10~30min of ultrasonic cleaning in acetone, finally takes out Cu electrode and natural air drying.
Further, the nano mattisolda is mixed by nano-Ag particles and solvent.
Further, the nano-Ag particles and solvent mixing before to nano-Ag particles dry, drying temperature be 40~
80 DEG C, the time is 1~3h.
Further, the volume ratio of the nano-Ag particles and solvent is 1:(1~4).
Further, the solvent is ethylene glycol.
Further, the nano-Ag particles are prepared using solution reduction；It is described to be received using solution reduction preparation
The method of rice Argent grain specifically follows the steps below:
One, configure oxidation solution: it is molten to be poured into silver nitrate by configuration silver nitrate solution and sodium citrate solution for sodium citrate solution
In liquid, stirs to solution clear, obtain oxidation solution；
Two, configure reducing solution: the reducing solution is sodium borohydride solution, and when configuration, sodium borohydride was added into deionized water
Powder, magnetic agitation to solution it is colorless and transparent after obtain sodium borohydride solution；
Three, reduced nano Argent grain: oxidation solution is placed on magnetic stirring apparatus, is stirred with the speed of 200~500rpm
To oxidation solution clear, reducing solution is instilled in oxidation solution with the speed of 5~20ml/min, obtains mixed liquor；By mixed liquor
It is placed on blender and continues 5~30min of stirring, obtain nano silver colloidal sol；
Four, the separation and washing of nano-Ag particles: nano silver colloidal sol adding into acetone to nano-Ag particles is precipitated completely,
Then it is ultrasonically treated, obtains suspension, by isolated precipitating after 5~20min of suspension centrifugal treating and wash, obtain
To nano-Ag particles.
Further, the volume ratio of silver nitrate solution described in step 1 and sodium citrate solution is (1~3): 1.
Further, the concentration of silver nitrate solution described in step 1 is 0.5~2mol/L, the concentration of sodium citrate solution
For 0.05~0.10mol/L.
Further, the concentration of sodium borohydride solution described in step 2 is 0.01~0.10mol/L.
Further, the volume ratio of oxidation solution described in step 3 and reducing solution is (1~5): 1.
It the principle of the invention and has the beneficial effect that
1, the present invention is to N-type Bi2Te3During surface to be welded and Cu electrode carry out soldering connection, in N-type Bi2Te3Surface to be welded
Nickel coating is prepared as diffusion barrier, nickel barrier layer can reduce N-type Bi2Te3Ag, Bi, Te, Se occur between nano silver
It is metallurgical bonding Deng the element diffusion of member, and between nickel barrier layer and nano silver, does not generate any intermetallic compound；Nanometer
Silver has excellent conduction and heating conduction, and mechanical behavior under high temperature is good, and nano silver can form Ag-Cu eutectic with Cu, belongs to
Diffusion connection；Effective between above-mentioned nickel barrier layer and nano silver and between nano silver and Cu combine ensure that connector can
By property.The soldering N-type Bi of the method for the present invention preparation2Te3It is 6-8MPa with the shearing strength of Cu acrylonitrile connector at room temperature；And
And attenuation of shear resistance is small during prolonged be on active service, soldered fitting is able to maintain prolonged stabilization；It is on active service at 250 DEG C
After 150h, it is 5-7MPa that soldered fitting, which obtains shearing strength, and strength retrogression is only 10% or so.
2, using connection method of the invention to N-type Bi2Te3It is brazed with Cu electrode, the thickness of obtained connector conversion zone
Degree is not influenced substantially by brazing temperature, and the contact resistance at soldered fitting is smaller, and the continuous zero defect of joint interface conversion zone avoids
As the increase connector of active time deteriorates, prepared electrothermal module has good in 200~250 DEG C of temperature ranges
Thermoelectricity capability.When the use of temperature being 200~250 DEG C, the conversion efficiency of thermoelectric of thermoelectric device can be stablized in 360h
10%, it ensure that the conversion efficiency of thermoelectric of thermoelectric device, there is good middle low temperature service performance.
3, the method for the present invention is based on nano mattisolda, expands since nano silver is just able to carry out soldering and is formed at 300 DEG C or so
Connection is dissipated, and silver point is up to 961 DEG C, therefore the method for the present invention is the preparation for the refrigeration device for being suitble to room temperature to use, and is also fitted
Close the temperature requirement of the military service of the higher SiGe thermoelectric device for the use of temperature being 300~400 DEG C.
Detailed description of the invention
Fig. 1 is the TEM shape appearance figure of nano-Ag particles in embodiment 1；
Fig. 2 is single nano-Ag particles TEM shape appearance figure in embodiment 1；
Fig. 3 is that nano mattisolda connects Bi in embodiment 12Te2.7Se0.3/ Ni and Cu typical interface figure.
Specific embodiment
In order to keep the objectives, technical solutions, and advantages of the present invention more clear, with reference to the accompanying drawings and embodiments,
This hair is further described.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and unlimited
The fixed present invention.
Embodiment 1: N-type Bi of the present embodiment based on nano mattisolda and nickel coating2Te3Connection method with Cu electrode is pressed
It is carried out according to following steps: first using galvanoplastic in N-type Bi2Te3It is 3 μm of nickel coatings as diffusion barrier that surface to be welded, which prepares thickness, so
Afterwards using nano mattisolda to N-type Bi2Te3Surface to be welded and Cu electrode carry out soldering connection, that is, complete.The present embodiment is in N-type
Bi2Te3Surface to be welded prepares nickel coating as diffusion barrier, and nickel barrier layer can reduce N-type Bi2Te3Occur between nano silver
The element diffusion of the member such as Ag, Bi, Te, Se, and be metallurgical bonding between nickel barrier layer and nano silver, it does not generate between any metal
Compound；Nano silver has excellent conduction and heating conduction, and mechanical behavior under high temperature is good, and nano silver can form Ag- with Cu
Cu eutectic belongs to diffusion connection；
It is described to utilize nano mattisolda to N-type Bi2Te3Surface to be welded and Cu electrode carry out the specific method of soldering connection according to
Following steps carry out:
One, the greasy dirt process and oxide of Cu electrode welding surface are removed, it is clear that Cu electrode is then put into ultrasound in acetone
20min is washed, Cu electrode and natural air drying are finally taken out；Nano mattisolda is coated in Cu electrode welding surface, by N-type Bi2Te3
It covers on nano mattisolda, N-type Bi2Te3Middle nickel coating constitutes assembly parts, applies to assembly parts upper and lower surface towards nano mattisolda
The pressure of 10MPa is added to be fixed；
Two, the assembly parts after fixation that step 1 obtains are put into vacuum furnace, adjustment vacuum degree is 1 × 10-3Pa
When, then start to be heated to 250 DEG C with the speed of 10 DEG C/min, then be heated to 320 DEG C with the speed of 5 DEG C/min and keep the temperature
Then 30min cools to room temperature with the furnace, that is, completes.
The concentration of the nickel sulfate contained in the electroplate liquid used in the nickel coating preparation process for 300g/L, nickel chloride
Concentration is 40g/L, and the concentration of boric acid is 40g/L, and the concentration of lauryl sodium sulfate is 0.1g/L, and the PH of electroplate liquid is 3.8, electricity
Current density during plating is 2A/dm2, electroplating time 5min；
The preparation process of the nano mattisolda are as follows: nano-Ag particles to be dried, drying temperature is 50 DEG C, time 3h,
Then nano-Ag particles and ethylene glycol are mixed for 1:3 by volume, obtains nano mattisolda.The wherein preparation of nano-Ag particles
Method follows the steps below:
One, configure oxidation solution: configuration concentration be 1mol/L silver nitrate solution and 0.06mol/L sodium citrate solution,
Sodium citrate solution is poured into silver nitrate solution, stirs to solution clear, obtains oxidation solution；Silver nitrate solution and lemon
The volume ratio of acid sodium solution is 3:2；
Two, configure reducing solution: it is 0.03mol/L sodium borohydride solution that the reducing solution, which is concentration, and when configuration goes to 80mL
Be added 0.1g sodium borohydride powder in ionized water, magnetic agitation to solution it is colorless and transparent after to obtain 0.03mol/L sodium borohydride molten
Liquid；
Three, reduced nano Argent grain: oxidation solution is placed on magnetic stirring apparatus, is stirred with the speed of 300rpm to oxidation
Reducing solution is instilled in oxidation solution with the speed of 10ml/min, obtains mixed liquor by liquid clear；Mixed liquor is placed on stirring
Continue to stir 10min on device, obtains nano silver colloidal sol；The volume ratio of the oxidation solution and reducing solution is 5:1；Reducing solution drips
Bi Hou, continuing stirring 10min can react fully；
Four, the separation and washing of nano-Ag particles: nano silver colloidal sol adding into acetone to nano-Ag particles is precipitated completely,
Then it is ultrasonically treated, obtains suspension, by the thick isolated precipitating of suspension centrifugal treating 10min and wash, obtain
Nano-Ag particles.Ultrasonic treatment can be such that nano-Ag particles substantially uniformity is distributed in acetone, be received using solution reduction preparation
During rice silver, silver nitrate is silver-colored source, and sodium borohydride is reducing agent, and sodium citrate is protective agent.Fig. 1 is the present embodiment preparation
Nano-Ag particles TEM shape appearance figure, from FIG. 1, it can be seen that the nano-Ag particles uniform particle sizes prepared, particle diameter are equal
Less than 20nm, Argent grain size is within the scope of nanoscale；Fig. 2 is single nano-Ag particles TEM shape appearance figure, can from Fig. 2
Find out, nano silver grain growth is complete, is mono-crystalline structures；Fig. 3 is that nano mattisolda connects Bi2Te2.7Se0.3/ Ni and Cu is typical
Surface chart, it can be seen that soldered fitting is well combined, flawless, stomata, the generation for the defects of being mingled with.The joint gap of connector
Less than 10 μm, nano silver sintering is good, has good consistency, and Ni coating and Bi2Te2.7Se0.3It is well combined.
The soldered fitting room temperature shearing strength that the present embodiment obtains is 8MPa, and soldered fitting is able to maintain the steady of long period
It is fixed；After 250 DEG C of military service 150h, shearing strength 7MPa, strength of joint variation is small, and only 10% or so, joint interface is fine and close, nothing
Defect.
Embodiment 2: the present embodiment unlike the first embodiment, using nano mattisolda to N-type Bi2Te3Surface to be welded and Cu
Electrode carried out in the step of soldering connection process two, and the assembly parts after fixation that step 1 obtains are put into vacuum furnace,
Adjusting vacuum degree is 1 × 10-3When Pa, then start to be heated to 250 DEG C with the speed of 10 DEG C/min, then with the speed of 5 DEG C/min
It is heated to 260 DEG C and keeps the temperature 30min, then cool to room temperature with the furnace.Other steps and technological parameter are same as Example 1.
The connector room temperature shearing strength that the present embodiment obtains is 6MPa, after 250 DEG C of military service 150h, shearing strength 5MPa,
Strength of joint variation is small, and only 10% or so, soldered fitting interface is fine and close, is well combined.
Embodiment 3: the present embodiment unlike the first embodiment, using nano mattisolda to N-type Bi2Te3Surface to be welded and Cu
Electrode carried out in the step of soldering connection process two, and the assembly parts after fixation that step 1 obtains are put into vacuum furnace,
Adjusting vacuum degree is 1 × 10-3When Pa, then start to be heated to 250 DEG C with the speed of 10 DEG C/min, then with the speed of 5 DEG C/min
It is heated to 290 DEG C and keeps the temperature 30min, then cool to room temperature with the furnace.Other steps and technological parameter are same as Example 1.
The connector room temperature shearing strength that the present embodiment obtains is 7MPa, after 250 DEG C of military service 150h, shearing strength 6MPa,
Strength of joint variation is small, soldered fitting flawless, stomata, the defects of being mingled with.
Embodiment 4: the present embodiment unlike the first embodiment, using nano mattisolda to N-type Bi2Te3Surface to be welded and Cu
Electrode carried out in the step of soldering connection process two, and the assembly parts after fixation that step 1 obtains are put into vacuum furnace,
Adjusting vacuum degree is 1 × 10-3When Pa, then start to be heated to 250 DEG C with the speed of 10 DEG C/min, then with the speed of 5 DEG C/min
It is heated to 350 DEG C and keeps the temperature 30min, then cool to room temperature with the furnace.Other steps and technological parameter are same as Example 1.
The connector room temperature shearing strength that the present embodiment obtains is 8MPa, after 250 DEG C of military service 150h, shearing strength 6MPa,
Strength of joint variation is smaller, and soldered fitting is well combined, no significant defect.
Claims (18)
1. a kind of N-type Bi based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode, it is characterised in that: the party
Method follows the steps below: first in N-type Bi2Te3Surface to be welded prepares nickel coating as diffusion barrier, then utilizes nano silver
Soldering paste is to N-type Bi2Te3Surface to be welded and Cu electrode carry out soldering connection, that is, complete.
2. the N-type Bi according to claim 1 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by: the nickel coating thickness is 3~10 μm.
3. the N-type Bi according to claim 1 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by: described in N-type Bi2Te3Surface to be welded prepares nickel coating using galvanoplastic, prepares nickel coating process using galvanoplastic
Used in contain nickel sulfate, nickel chloride, boric acid and lauryl sodium sulfate in electroplate liquid.
4. the N-type Bi according to claim 3 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by: the concentration of nickel sulfate is 250~350g/L in the electroplate liquid, the concentration of nickel chloride is 30~60g/L, boric acid
Concentration be 30~40g/L, the concentration of lauryl sodium sulfate is 0.05~0.10g/L.
5. the N-type Bi according to claim 3 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by: the nickel sulfate, nickel chloride, boric acid and lauryl sodium sulfate purity be 99%~99.99%.
6. the N-type Bi according to claim 3 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by: it is described use galvanoplastic to prepare nickel coating during current density for 1~2.5A/dm2, electroplating time 5
~20min.
7. the N-type Bi according to claim 3 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by: it is described use galvanoplastic to prepare nickel coating during the electroplate liquid used PH for 3~5.
8. the N-type Bi according to claim 1 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by:
It is described to utilize nano mattisolda to N-type Bi2Te3Surface to be welded and Cu electrode carry out the specific method of soldering connection according to following
Step carries out:
One, nano mattisolda is coated in Cu electrode welding surface, by N-type Bi2Te3It covers on nano mattisolda, N-type Bi2Te3In
Nickel coating constitutes assembly parts towards nano mattisolda, and the pressure for applying 5~15MPa to assembly parts upper and lower surface is fixed；
Two, the assembly parts after fixation that step 1 obtains are put into vacuum furnace, adjustment vacuum degree is (1~3) × 10-3Pa
When, then start to be heated to 230~250 DEG C with the speed of 5~10 DEG C/min, then be heated to 260 with the speed of 3~5 DEG C/min
It~350 DEG C and 1~60min of heat preservation, then cools to room temperature with the furnace, that is, completes.
9. the N-type Bi according to claim 8 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by: further including removal Cu electrode before nano mattisolda is coated in Cu electrode welding surface described in step 1
The greasy dirt process and oxide process of welding surface, and by Cu after the greasy dirt and oxide of removal Cu electrode welding surface
Electrode is put into 10~30min of ultrasonic cleaning in acetone, finally takes out Cu electrode and natural air drying.
10. the N-type Bi according to claim 1 based on nano mattisolda and nickel coating2Te3With the connection method of Cu electrode,
It is characterized by: the nano mattisolda is mixed by nano-Ag particles and solvent.
11. the N-type Bi according to claim 10 based on nano mattisolda and nickel coating2Te3With the connection side of Cu electrode
Method, it is characterised in that: nano-Ag particles are dried before the nano-Ag particles and solvent mixing, drying temperature is 40~80
DEG C, the time is 1~3h.
12. the N-type Bi according to claim 10 based on nano mattisolda and nickel coating2Te3With the connection side of Cu electrode
Method, it is characterised in that: the volume ratio of the nano-Ag particles and solvent is 1:(1~4).
13. the N-type Bi according to claim 10 based on nano mattisolda and nickel coating2Te3With the connection side of Cu electrode
Method, it is characterised in that: the solvent is ethylene glycol.
14. the N-type Bi according to claim 10 based on nano mattisolda and nickel coating2Te3With the connection side of Cu electrode
Method, it is characterised in that:
The nano-Ag particles are prepared using solution reduction；The method that nano-Ag particles are prepared using solution reduction
Specifically follow the steps below:
One, configure oxidation solution: sodium citrate solution is poured into silver nitrate solution by configuration silver nitrate solution and sodium citrate solution
In, it stirs to solution clear, obtains oxidation solution；
Two, configure reducing solution: the reducing solution is sodium borohydride solution, and hydroboration sodium powder is added when configuration into deionized water
End, magnetic agitation to solution it is colorless and transparent after obtain sodium borohydride solution；
Three, reduced nano Argent grain: oxidation solution is placed on magnetic stirring apparatus, is stirred with the speed of 200~500rpm to oxygen
Change liquid clear, reducing solution is instilled in oxidation solution with the speed of 5~20ml/min, obtains mixed liquor；Mixed liquor is placed
Continue 5~30min of stirring on blender, obtains nano silver colloidal sol；
Four, the separation and washing of nano-Ag particles: nano silver colloidal sol adding into acetone to nano-Ag particles is precipitated completely, then
Ultrasonic treatment, obtains suspension, by isolated precipitating after 5~20min of suspension centrifugal treating and washs, received
Rice Argent grain.
15. the N-type Bi according to claim 14 based on nano mattisolda and nickel coating2Te3With the connection side of Cu electrode
Method, it is characterised in that: the volume ratio of silver nitrate solution described in step 1 and sodium citrate solution is (1~3): 1.
16. the N-type Bi according to claim 14 based on nano mattisolda and nickel coating2Te3With the connection side of Cu electrode
Method, it is characterised in that: the concentration of silver nitrate solution described in step 1 is 0.5~2mol/L, and the concentration of sodium citrate solution is
0.05~0.10mol/L.
17. the N-type Bi according to claim 14 based on nano mattisolda and nickel coating2Te3With the connection side of Cu electrode
Method, it is characterised in that: the concentration of sodium borohydride solution described in step 2 is 0.01~0.10mol/L.
18. the N-type Bi according to claim 14 based on nano mattisolda and nickel coating2Te3With the connection side of Cu electrode
Method, it is characterised in that: the volume ratio of oxidation solution described in step 3 and reducing solution is (1~5): 1.
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| CN201910353466.2A CN110098309A (en) | 2019-04-28 | 2019-04-28 | A kind of connection method of N-type bismuth telluride based on nano mattisolda and nickel coating and Cu electrode |
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| CN201910353466.2A CN110098309A (en) | 2019-04-28 | 2019-04-28 | A kind of connection method of N-type bismuth telluride based on nano mattisolda and nickel coating and Cu electrode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112214875A (en) * | 2020-09-11 | 2021-01-12 | 东方电气集团东方汽轮机有限公司 | Method for evaluating real service temperature of workpiece through precipitated particle phase size |
| CN112621116A (en) * | 2020-12-07 | 2021-04-09 | 哈尔滨工业大学 | Low-temperature nano connection method for skutterudite thermoelectric material and Cu-based electrode |
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2019
- 2019-04-28 CN CN201910353466.2A patent/CN110098309A/en active Pending
Non-Patent Citations (1)
| Title |
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| 刘显鹏: ""N型Bi2Te2.7Se0.3热电材料的制备工艺及其Cu连接机制研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112214875A (en) * | 2020-09-11 | 2021-01-12 | 东方电气集团东方汽轮机有限公司 | Method for evaluating real service temperature of workpiece through precipitated particle phase size |
| CN112621116A (en) * | 2020-12-07 | 2021-04-09 | 哈尔滨工业大学 | Low-temperature nano connection method for skutterudite thermoelectric material and Cu-based electrode |
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Application publication date: 20190806 |