CN112852111A - Preparation method of nano silver wire and epoxy resin type conductive paste - Google Patents
Preparation method of nano silver wire and epoxy resin type conductive paste Download PDFInfo
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- CN112852111A CN112852111A CN202110229407.1A CN202110229407A CN112852111A CN 112852111 A CN112852111 A CN 112852111A CN 202110229407 A CN202110229407 A CN 202110229407A CN 112852111 A CN112852111 A CN 112852111A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 72
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 72
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 117
- 239000000243 solution Substances 0.000 claims description 42
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002042 Silver nanowire Substances 0.000 claims description 14
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical group C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011231 conductive filler Substances 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The application belongs to the technical field of functional nano materials. The application provides a preparation method of a nano silver wire and an epoxy resin type conductive paste. The epoxy resin type conductive paste of the present application includes a nano silver wire, an epoxy resin, a metal powder, a curing agent, and a diluent. The epoxy resin type conductive paste does not drip at high temperature and is not brittle at low temperature; the acting force on metal is strong, and modification or additional addition of a dispersing agent on the conductive filler is not needed; the use temperature range is wide, the surface of the connector can be effectively protected from electrochemical corrosion, the connection resistance is reduced, and the application value in the power transmission and transformation connector is high. The nano silver wire with high length-diameter ratio is prepared by an alcohol reduction method, and is applied to epoxy resin type conductive paste, so that a good metal substrate protection effect is obtained, and the connection resistance is also remarkably reduced.
Description
Technical Field
The application belongs to the technical field of functional nano materials, and particularly relates to a preparation method of a nano silver wire and an epoxy resin type conductive paste.
Background
In the electric energy transmission process, the cable junction often takes place overheated phenomenon, and this not only accelerates the connector ageing, and electric connection is overheated to lead to the contact resistance of junction too big, seriously influences the ability of connecting transmission electric energy and signal in excessive region, can lead to disasters such as fire even, causes the heavy loss of property. With the increase of electric energy demand, power transmission and transformationThe voltage level and the current of the line are gradually increased, and the weak position of the electric connection part is more highlighted. The electrical connection is generally surface-to-surface contact, and for a smooth surface, no matter what processing method is adopted, the surface has many protrusions and depressions, so that many gaps exist at the electrical connection position, the contact resistance is too large, and the gaps are easy to enter corrosive or other harmful substances to influence the electrical connection quality. Moreover, the electric connection surface has an oxide film with poor conductivity, and the resistivity of the oxide film can reach 1 multiplied by 107～1×1010Omega cm, and is difficult to remove, greatly affecting the contact resistance of the contact area.
In order to effectively solve the problems of oxidation and long-time electrification and heating of the connection part, some conductive pastes which take lubricating grease or synthetic ether as a matrix and add lithium salt or metal powder as a conductive filler are widely applied. However, grease or synthetic ethers tend to drip at high temperatures and reduce connector friction, which can cause the connector to become disconnected from the cable. In addition, the metal powder and lithium salt in the insulating matrix require a large amount of addition to form a conductive network, which increases the raw material cost, and the mechanical properties of the composite are affected by too high an amount of addition.
Disclosure of Invention
In view of this, the present application provides a method for preparing a silver nanowire and an epoxy resin type conductive paste, which effectively solve the problem of high temperature matrix loss, and have a small amount of conductive filler, good mechanical properties and good electrochemical corrosion resistance.
The specific technical scheme of the application is as follows:
the application provides an epoxy resin type conductive paste, which comprises the following components:
the nano silver wire comprises nano silver wires, epoxy resin, metal powder, a curing agent and a diluent.
In the application, the nano silver wires are used as the conductive filler, and can be uniformly distributed and mutually overlapped in the epoxy resin composite material to form a layer of conductive network, so that the volume resistivity and the percolation threshold of the epoxy resin type conductive paste can be effectively reduced; the epoxy resin composite material has good low-temperature welding characteristics, and the conductivity of the epoxy resin composite material is further improved. The nano silver wire is less in addition amount as the conductive filler, not only can the mechanical property of the epoxy resin composite material be maintained, but also the thermosetting property of the epoxy resin can be fully exerted, after the epoxy resin and the curing agent are heated by the cable connector or cured at normal temperature, the epoxy resin and the curing agent are in a cross-linking state, even if the temperature of the connector is increased, the resin can not drip, and the raw material cost is greatly reduced. The addition of the metal powder is beneficial to destroying the surface oxide layer of the nano silver wire, reduces the connection resistance and assists in reducing the volume resistivity. The epoxy resin type conductive paste does not drip at high temperature and is not brittle at low temperature; the acting force on metal is strong, and modification or additional addition of a dispersing agent on the conductive filler is not needed; the use temperature range is wide, the surface of the connector can be effectively protected from electrochemical corrosion, the connection resistance is reduced, and the application value in the power transmission and transformation connector is high.
Preferably, the length-diameter ratio of the nano silver wire is 100-800.
In this application, adopt high draw ratio's silver nanowire to be applied to epoxy type conductive paste as electrically conductive filler, can reach the filtration threshold value when the addition is only 5%, greatly reduced conductive filler's addition for epoxy conductive paste furthest remains toughness, stable chemical properties and the adhesive force to the substrate of resin, not only obtains better metal substrate protection effect, still is showing and reduces connecting resistance.
Preferably, the coating comprises the following components in parts by mass:
0.1-1.0 part of nano silver wire, 1-5 parts of epoxy resin, 0.5-5 parts of metal powder, 1-5 parts of curing agent and 1-2 parts of diluent.
Preferably, the epoxy resin is selected from epoxy resin E44 or epoxy resin E51;
the metal is selected from Cu or Al;
the curing agent is selected from methyl tetrahydrophthalic anhydride or polyamide;
the diluent is selected from one or more of ethylene glycol, n-butanol, cyclohexanol, n-octanol and glycerol.
The polyamide used in the present application is a low-molecular polyamide.
The application also provides a preparation method of the nano silver wire, which comprises the following steps:
s1: deoxidizing the preheated glycol, adding CuCl2Keeping the temperature of the ethylene glycol solution, and adding AgNO3Keeping the temperature of the ethylene glycol solution to obtain a mixed solution;
s2: and dropwise adding ethylene glycol solution of PVP into the mixed solution, preserving heat, and cooling to obtain the nano silver wire.
In the application, ethylene glycol is preheated to generate a certain amount of aldehyde groups (-CHO) which can be used as a reducing agent for subsequent reaction. Under the action of aldehyde group, firstly adding copper chloride to make Cu2+Reaction to form Cu+While being Cu+To oxygen (O) in solution2) And reducing to reduce the content of dissolved oxygen in the solution, wherein the removal of the dissolved oxygen is beneficial to reducing the etching of the cross section of the silver crystal along the length direction, is beneficial to the growth of the silver wire along the length direction and improves the length-diameter ratio of the silver wire. Due to the presence of a reducing agent, Cu2+Continuously reacts with aldehyde group and is changed back to Cu+Until the dissolved oxygen is dissolved.
And then adding silver nitrate and preserving heat for a period of time to ensure that silver ions are fully diffused in the solution, thereby effectively avoiding the problems of silver line agglomeration and uneven length and thickness of the silver lines caused by the instant generation of the silver lines and the over-fast reaction rate.
And finally, in the process of slowly dripping the PVP, the PVP guides the silver wire to be generated, the lower initial concentration of the PVP is beneficial to reducing the growth speed of the silver wire and the number of the silver wire, and finally the effects of improving the length of the silver wire and promoting the uniform growth of the silver wire are achieved. Along with the continuous supplement of PVP, the growth surface of the silver wire can be covered, and the silver wire is prevented from becoming thick.
Preferably, the CuCl2In glycol solution of (2) CuCl2Has a concentration of 2X 10-3～2×10-2mol/L of said AgNO3In glycol solution of AgNO3The concentration of the PVP is 0.1-2 mol/L, and the concentration of the PVP in the ethylene glycol solution of the PVP is 0.2-4 mol/L.
Preferably, the preheated glycol and the CuCl2B ofGlycol solution, the AgNO3The ratio of the amount of the ethylene glycol solution of PVP to the amount of the ethylene glycol solution of PVP is (25-100) mL: (50-600) μ L: (15-30) mL: (15-30) mL.
Preferably, CuCl is added into S12The temperature of the ethylene glycol solution is kept for 0-60min, and AgNO is added into S13The time for keeping the temperature of the ethylene glycol solution is 10-90 min.
Preferably, the dropping speed in S2 is 10-200mL/h, and the rotating speed is 1500-;
and (3) dripping ethylene glycol solution of PVP into the S2, and keeping the temperature for 30-60 min.
Preferably, the preheating temperature in S1 is 100-180 ℃, and the time is 10-90 min;
the oxygen removal in S1 is specifically as follows: nitrogen was slowly bubbled into the ethylene glycol for 10 min.
Preferably, the cooling in S2 is further followed by:
diluting the solution with anhydrous ethanol or acetone with twice volume, performing ultrasonic homogenization, centrifuging at the rotating speed of 4000r/min for 5-10 min, removing supernatant, washing with ethanol, and repeating for 2-4 times.
Preferably, the method for preparing the epoxy resin type conductive paste includes:
and mixing the nano silver wire with a diluent, adding epoxy resin, a curing agent and metal powder, and uniformly mixing to obtain the nano silver wire.
In summary, the present application provides a method for preparing a silver nanowire and an epoxy resin type conductive paste. The epoxy resin type conductive paste of the present application includes a nano silver wire, an epoxy resin, a metal powder, a curing agent, and a diluent. The epoxy resin type conductive paste does not drip at high temperature and is not brittle at low temperature; the acting force on metal is strong, and modification or additional addition of a dispersing agent on the conductive filler is not needed; the use temperature range is wide, the surface of the connector can be effectively protected from electrochemical corrosion, the connection resistance is reduced, and the application value in the power transmission and transformation connector is high. The nano silver wire with high length-diameter ratio is prepared by an alcohol reduction method, and is applied to epoxy resin type conductive paste, so that a good metal substrate protection effect is obtained, and the connection resistance is also remarkably reduced.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is an SEM image of a silver nanowire manufactured in example 1 of the present application;
FIG. 2 is a graph showing the results of corrosion resistance tests of the epoxy resin type conductive paste of example 2 (a, control group; b, test group);
FIG. 3 is a schematic diagram of a resistance test in example 4 of the present application;
FIG. 4 is a graph showing the change in volume resistivity of the epoxy resin type conductive paste of example 4 of the present application;
FIG. 5 is a thermogravimetric analysis result of the epoxy resin conductive paste of example 5 of the present application (a, control group; b, experimental group).
Detailed Description
In order to make the objects, features and advantages of the present application more obvious and understandable, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the embodiments described below are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
The embodiment of the application relates to preparation of a nano silver wire, and the specific preparation method comprises the following steps:
(1) measuring 100mL of Ethylene Glycol (EG) in a three-neck flask, inserting a nitrogen pipe below the liquid level, slowly adding nitrogen, heating to 160 ℃ by using an oil bath pot, and keeping the temperature for 1 hour;
(2) setting four groups of experiments (a), (b), (c) and (d), respectively adding 0. mu.L, 250. mu.L and 500. mu.L toAnd 1000. mu.L of CuCl2(8×10-3mol/L) EG solution, preserving the temperature for 10min, then adding 30mLAgNO3(0.2mol/L) EG solution, and keeping the temperature for 1 min;
(3) adding 30ml of VP (0.6mol/L) EG solution into the flask by using a constant pressure funnel, dropwise adding for 30min, and preserving heat for 30min after dropwise adding;
(4) and naturally cooling after the reaction is finished, cooling the solution to room temperature, diluting the solution by using 2 times of volume of absolute ethyl alcohol, transferring the solution into a centrifugal tube, shaking for 1min, centrifuging the solution at the rotating speed of 4000r/min for 3min, removing supernatant, washing the solution by using ethanol, and repeating the washing for 3 times to obtain the nano-silver wire.
The prepared silver nanowires were diluted 100 times with the solution and characterized using SEM. The SEM image of the silver nanowires obtained in example 1 of the present application is shown in fig. 1, and it can be seen that the silver nanowires obtained in group (c) have a high aspect ratio of 300, in which the length is 45 μm and the diameter is 0.150 μm. Without addition of CuCl2The group (a) at this time produced almost no silver wire, and as shown in FIG. 1(a), the reaction produced only silver particles having a diameter of about 0.150. mu.m. CuCl2The silver lines produced by the 250. mu.L and 1000. mu.L dosages varied in length, as shown in FIGS. 1(b) and (d), the silver lines had more particles and varied in length.
Example 2
The embodiment of the application tests the protective performance of the epoxy resin conductive paste on the metal substrate.
(1) 0.2g of the silver nanowire obtained in example 1, 1g of epoxy resin E44, 1g of Low Molecular weight polyamide 650 (PA650), 0.5g of copper powder and 1g of ethylene glycol were mixed uniformly to obtain an epoxy resin type conductive paste. Coating the iron sheet on an iron sheet, putting the iron sheet into an oven with the temperature of 80 ℃ for baking for 2 hours, and taking out the iron sheet;
(2) the edges of the iron sheet were edge sealed using scotch tape to prevent salt water from corroding into the substrate from the edges. Preparing 3 wt% saline, taking the iron sheet coated with the conductive paste as an experimental group and the iron sheet without any coating as a control group, putting the iron sheets into the saline together, standing and observing regularly.
The comparison graph of the corrosion resistance test results of the epoxy resin type conductive paste in example 2 of the present application is shown in fig. 2, which shows that rust appears in the control group iron sheet a for 6 hours in the salt water, but no rust appears in the test group iron sheet b coated with the epoxy resin type conductive paste after being soaked for 72 hours, and the result shows that the epoxy resin type conductive paste of the present application has a good electrochemical corrosion resistance effect.
Comparative example
0.2g of self-made nano silver powder (the diameter is about 200nm), 1g of epoxy resin E44, 1g of low molecular weight polyamide (PA650), 0.5g of copper powder and 1g of ethylene glycol are uniformly mixed to obtain the epoxy resin type conductive paste.
Example 3
The embodiment of the application tests the influence of the epoxy resin conductive paste on the volume resistivity and the connection resistance.
0.2g of the silver nanowire obtained in example 1, 1g of epoxy resin E44, 1g of low molecular weight polyamide (PA650), 0.5g of copper powder, and 1g of ethylene glycol were mixed uniformly to obtain an epoxy resin type conductive paste. The epoxy resin type conductive pastes prepared in the examples and comparative examples were poured into a teflon tank, cured at 80 ℃ for 2 hours, and the resistance was measured using a multimeter and the volume resistivity was calculated.
The results show that when the addition amount of the silver nanowires is 8%, the volume resistivity of the epoxy resin type conductive paste is 20.36 Ω · cm, which is significantly lower than that of the conductive paste on the market which takes grease or synthetic ether as a matrix and lithium salt or metal powder as a conductive filler. The resistance of the conductive paste added with the nano silver powder is infinite, and the conductive paste is an insulator.
The epoxy resin type conductive paste prepared in the embodiment of the application is smeared at two ends of a simple connector, the resistance of the connector is tested, and the conductive paste has the same formula as the conductive paste, and is only different from a comparison group without the nano silver wire.
The results showed that the resistance of the control group without the added nano silver wire was 0.9 Ω, and the resistance of the epoxy type conductive paste prepared in the present application was 0.5 Ω, so that the resistance of the connector was decreased by about 44%.
The above results demonstrate that the epoxy resin type conductive paste of the present application has an effect of significantly reducing connection resistance.
Example 4
The embodiment of the application tests the influence of the content of the nano silver wires on the volume resistivity of the epoxy resin type conductive paste.
0.1g, 0.2g, 0.3g, 0.4g and 0.5g of the nano silver wire prepared in example 1, 1g of epoxy resin E44, 1g of PA650, 0.5g of copper powder and 1g of ethylene glycol were mixed uniformly, poured into a polytetrafluoroethylene cell, cured at 80 ℃ for 2 hours, and the resistance was measured using a multimeter in the connection manner shown in FIG. 3. Using formula in combination
The volume resistivity is calculated.
Fig. 4 shows a graph of the change in volume resistivity of the epoxy resin conductive paste of example 4 of the present application, which shows that the volume resistivity of the epoxy resin conductive paste of the present application abruptly changes between 4% and 6%, and the resistance sharply decreases. The volume resistivity and percolation threshold of the epoxy resin type conductive paste can be effectively reduced under the condition that the addition amount of the nano silver wires is less.
Example 5
The thermo-gravimetric performance of the epoxy resin type conductive paste was tested in the examples of the present application.
0.4g of the silver nanowires prepared in example 1, 1g of epoxy resin E44, 1g of PA650, 0.5g of copper powder and 1g of ethylene glycol were mixed uniformly to obtain an epoxy resin type conductive paste.
The prepared epoxy resin type conductive paste was used as an experimental group for TG test, and the formulation thereof was the same as that of the conductive paste except that a control group to which no silver nanowire was added was compared. Wherein the testing temperature is 40-600 ℃, and the heating rate is 10 ℃/min.
The thermogravimetric analysis result of the epoxy resin type conductive paste of example 5 of the present application is shown in fig. 5. As can be seen from the TG line, the epoxy resin type conductive paste (b) of the present invention starts to evaporate a part of the diluent at 100 ℃ or higher, and can be used normally in practical applications at a temperature higher than the operating environment temperature of 100 ℃ and the temperature of the connector at the time of peak power consumption (70 ℃ to 90 ℃). At about 350 deg.C, the matrix begins to decompose until about 470 deg.C, and the application temperature is from room temperature to 350 deg.C. And the conductive paste (a) without the nano silver wire is decomposed at about 250 ℃ until about 470 ℃ is completely decomposed, and the use temperature is between room temperature and 250 ℃. The epoxy resin type conductive paste of the present application has an advantage of a wide range of use temperature.
From the DSC, the epoxy resin conductive paste (b) of the present application shows two endothermic peaks at 75 ℃ and 150 ℃ as compared with the conductive paste (a) without the nano silver wire, and these two endothermic peaks are endothermic peaks when the silver wire is soldered at low temperature. The epoxy resin type conductive paste has good low-temperature welding characteristics and has high application value in power transmission and transformation connectors.
The above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
Claims (10)
1. An epoxy resin type conductive paste is characterized by comprising the following components:
the nano silver wire comprises nano silver wires, epoxy resin, metal powder, a curing agent and a diluent.
2. The epoxy resin type conductive paste according to claim 1, wherein the aspect ratio of the silver nanowires is 100 to 800.
3. The epoxy resin type conductive paste according to claim 1, comprising the following components in parts by mass:
0.1-1.0 part of nano silver wire, 1-5 parts of epoxy resin, 0.5-5 parts of metal powder, 1-5 parts of curing agent and 1-2 parts of diluent.
4. The epoxy resin type conductive paste according to claim 1, wherein the epoxy resin is selected from epoxy resin E44 or epoxy resin E51;
the metal is selected from Cu or Al;
the curing agent is selected from methyl tetrahydrophthalic anhydride or polyamide;
the diluent is selected from one or more of ethylene glycol, n-butanol, cyclohexanol, n-octanol and glycerol.
5. The method for preparing the silver nanowire of claim 1, comprising the steps of:
s1: deoxidizing the preheated glycol, adding CuCl2Keeping the temperature of the ethylene glycol solution, and adding AgNO3Keeping the temperature of the ethylene glycol solution to obtain a mixed solution;
s2: and dropwise adding ethylene glycol solution of PVP into the mixed solution, preserving heat, and cooling to obtain the nano silver wire.
6. The method of claim 5, wherein the CuCl is present2In glycol solution of (2) CuCl2Has a concentration of 2X 10-3～2×10-2mol/L of said AgNO3In glycol solution of AgNO3The concentration of the PVP is 0.1-2 mol/L, and the concentration of the PVP in the ethylene glycol solution of the PVP is 0.2-4 mol/L.
7. The method of claim 5, wherein the preheated glycol, the CuCl2Ethylene glycol solution of (A), the AgNO3The ratio of the amount of the ethylene glycol solution of PVP to the amount of the ethylene glycol solution of PVP is (25-100) mL: (50-600) μ L: (15-30) mL: (15-30) mL.
8. The method according to claim 5, wherein CuCl is added to S12The temperature of the ethylene glycol solution is kept for 0-60min, and AgNO is added into S13The time for keeping the temperature of the ethylene glycol solution is 10-90 min.
9. The preparation method according to claim 5, wherein the dropping rate in S2 is 10-200mL/h, and the rotation speed is 1500-2000 r/min;
and (3) dripping ethylene glycol solution of PVP into the S2, and keeping the temperature for 30-60 min.
10. The preparation method according to claim 5, wherein the preheating in S1 is performed at 100-180 ℃ for 10-90 min;
the oxygen removal in S1 is specifically as follows: nitrogen was slowly bubbled into the ethylene glycol for 10 min.
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| WO2023083287A1 (en) * | 2021-11-12 | 2023-05-19 | 福建江夏学院 | Low-silver-content high-performance conductive paste and preparation method therefor |
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