CN109852146A - A kind of core-shell structure Ag@Cu nanoparticle conductive ink and its preparation method and application - Google Patents
A kind of core-shell structure Ag@Cu nanoparticle conductive ink and its preparation method and application Download PDFInfo
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- CN109852146A CN109852146A CN201910015697.2A CN201910015697A CN109852146A CN 109852146 A CN109852146 A CN 109852146A CN 201910015697 A CN201910015697 A CN 201910015697A CN 109852146 A CN109852146 A CN 109852146A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/02—Layer formed of wires, e.g. mesh
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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Abstract
The invention discloses a kind of core-shell structure Ag@Cu nanoparticle conductive inks and its preparation method and application, the ink is scattered in liquid by spherical nanoparticles to be formed, the spherical nanoparticles are the Ag@Cu nano particle of silver-colored shell coated copper core, and the liquid is the mixed liquor of deionized water, ethylene glycol and glycerine；The solid content of the spherical nanoparticles is 10~30wt%.Spherical nanoparticles in the present invention are not only conducive to the promotion of copper oxidation stability, can also improve its electromigration resisting property due to having the characteristics that silver-colored shell coated copper core.Therefore the conductive ink of nano particle preparation has preferable stability, and the conductive pattern being printed in the flexible substrates such as polyethylene terephthalate (PET) or photo paper shows good electric conductivity and adhesion.Conductive film based on ink printed of the invention has the characteristics that flexible bendable, and in bending, electric conductivity is good.
Description
Technical field
The invention belongs to metallic conduction field of nanoparticles, in particular to it is a kind of for inkjet printing on a flexible substrate
Core-shell structure Ag@Cu nanoparticle conductive ink and preparation method thereof.
Background technique
Conductive material applied to printing ink is evolving always, is obtained extensive exploitation because of its huge potentiality and is answered
For various electronic equipments, such as radio frequency identification (RFID), photovoltaic cell, conducting channel, sensor, display.Carbon nanotube,
The materials such as conducting polymer and graphene have been used for electroconductive printing ink, but these ink often have lower electric conductivity and
Poor chemical property, and it is poor in the adhesion of these ink on a flexible substrate, and the effect of inkjet printing is also not very
Finely, and metal nanoparticle be applied to printing ink in will efficiently solve the above problem.
Silver nano-grain is widely used in electrically conductive ink, with high conductivity and preferable oxidation stability.However, silver-colored
The high price of nano particle and its serious electromigration, i.e., migrate metal ion under electric field action, when device works
When, there is a constant current to pass through in metal interconnecting wires, metal ion can be generated along conductor and be transported, and result can make certain portions of conductor
Position generates cavity or whisker hinders its application in printing ink.
Since copper is compared with noble metal (gold, silver), with excellent equivalent electric conductivity (only than silver-colored low 6%) and lower valence
Lattice, therefore copper nano particles are considered as the substitute for printing the silver nano-grain of ink, however, copper nano particles are in sky
Easy to oxidize under the conditions of compression ring border, oxide will generate conductivity and seriously affect.
As prioritization scheme, Ag Cu core shell nanoparticles are highly suitable as the substitute of printing ink.The application of copper is not
A possibility that reduced by only cost, and reducing electromigration, meanwhile, external silver shell can be passivated internal copper core to avoid its hair
Raw oxidation.At the same time, according to different solid again preferable more attached to be realized on PET to debug ink than the ratio with solvent
?.The method for preparing Ag Cu core shell nanoparticles at present, which mainly has, utilizes magnetic field the preparation method, high temperature hot extrusion method, the de- conjunction of chemistry
Jin Fa, galvanoplastic etc., but equipment needed for utilizing the methods of magnetic field the preparation method and high temperature extrusion method is expensive, the de- alloyage of chemistry,
The methods of galvanoplastic experiment condition is more harsh.
101088670 A of Chinese patent CN discloses a kind of preparation method of Cu-Ag nucleocapsid composite metal powder, uses
Direct plating method carries out preplating to copper particle and then carries out the one layer of silver layer of cladding of glucose bath twice, but required reagent is not environmentally,
Step is complicated and the particle of preparation is micron level.102950282 A of Chinese patent CN discloses a kind of system of silver-bearing copper coated composite powder
Preparation Method, using the method for ultrasonic agitation reduction, but reaction is related to the solvent of strong such as nitric acid, sulfuric acid, and powder shape obtained
It is inhomogenous, it is spherical to be existed simultaneously with sheet.
Summary of the invention
The purpose of the present invention is above-mentioned core-shell structure Ag Cu nanoparticle conductive ink there are aiming at the problem that, provide one
Kind core-shell structure Ag Cu nanoparticle conductive ink and its preparation method and application, preparation method is simple, easily operated.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of core-shell structure Ag@Cu nanoparticle conductive ink, is scattered in liquid by spherical nanoparticles and is formed, institute
The Ag@Cu nano particle that spherical nanoparticles are silver-colored shell coated copper core is stated, the liquid is deionized water, ethylene glycol and glycerine
Mixed liquor；The solid content of the spherical nanoparticles is 10~30wt%.
A kind of preparation method of core-shell structure Ag@Cu nanoparticle conductive ink, comprising the following steps:
(1) it prepares copper source precursor liquid: taking copper sulphate (CuSO4) be placed in reaction vessel, it is added ethylene glycol (EG), magnetic force stirs
It mixes and is uniformly configured to copper source precursor solution；
(2) reducing agent and dispersing agent is added: being added in the copper source precursor solution obtained in step (1) and is used as reducing agent
One hydration sodium hypophosphite (NaH2PO2·H2O) and as dispersing agent polyvinylpyrrolidone (PVP-K30)；
(3) oil bath is handled: the anti-of copper source precursor solution, reducing agent and dispersant solution being housed by what step (2) obtained
It answers container to be transferred to oil bath pan, stirs oil bath, reacted；
(4) centrifuge washing: step (3) are reacted after resulting product carries out centrifuge washing and are dried in vacuo；
(5) it prepares silver-colored source predecessor: taking silver nitrate (AgNO3) be placed in reaction vessel, ethylene glycol is added, magnetic agitation is equal
It is even to be configured to silver-colored source precursor solution；
(6) oil bath is handled: the product of step (4) after dry being placed in reaction vessel, ethylene glycol is added, stirs, then
The silver-colored source precursor solution that a dropping step (5) obtains, is reacted under oil bath；
(7) centrifugal drying: step (6) are reacted after resulting product carries out centrifuge washing and are dried in vacuo, powder is obtained；
(8) it prepares ink: powder obtained in step (7) is dissolved in the mixed liquor of deionized water, ethylene glycol and glycerine
In, ultrasonic disperse obtains the core-shell structure Ag@Cu nanoparticle conductive ink.
In the step (1), the concentration of copper source precursor solution is 0.01M~0.05M；In the step (2), reducing agent
It is 1:1.6 with the mass ratio of copper sulphate, the mass ratio of dispersing agent and copper sulphate is 2:1.6.
In the step (3) and (6), oil bath temperature is 60~80 DEG C, and the reaction time is 10~30min.
In the step (5), the concentration of silver-colored source precursor solution is 0.01~0.05M.
In the step (8), by changing deionized water, the ratio of ethylene glycol and glycerine, so that the ink of preparation
Viscosity is 8~12cps.
Core-shell structure Ag@Cu nanoparticle conductive ink of the invention can be applied in flexible printing, method particularly includes:
Step a handles substrate: carrying out plasma treatment to flexible substrates；
Step b, printing ink: by the core-shell structure Ag@Cu nanoparticle conductive ink inkjet printing at through step a
In flexible substrates after reason, the flexible substrates of attachment conductive pattern are obtained；
Sintering processes: step c the flexible substrates for the attachment conductive pattern that step b is obtained is put into vacuum drying oven and are carried out
Sintering.
In the step a, flexible substrates are PET or photo paper, and the time of plasma treatment is 1~20min；The step
In c, the temperature of sintering is 100~200 DEG C.
The core-shell structure Ag@Cu nanoparticle conductive ink and the contact angle of flexible substrates are 48~100 °.
The utility model has the advantages that core-shell structure Ag@Cu nanoparticle conductive ink of the invention is scattered in liquid by spherical nanoparticles
It is formed in body, which is not only conducive to the promotion of copper oxidation stability, may be used also due to having the characteristics that silver-colored shell coated copper core
To improve its electromigration resisting property.Therefore the conductive ink of nano particle preparation has preferable stability, and is printed on flexibility
Conductive pattern in substrate shows good electric conductivity and adhesion.Conductive film based on ink printed of the invention has soft
The bent feature of property, in bending, electric conductivity is good.Conductive ink of the invention is suitable for inkjet printing, with flexible base
Bottom is compound securely, and Thin film conductive is good.
The method that preparation method of the invention uses liquid phase alcohothermal, using PVP-K30 as dispersing agent, NaH2PO2·H2O
For reducing agent, reaction temperature is 60~80 DEG C, and 10~30min of reaction prepares copper nano particles.Followed by EG as reducing agent,
By on the copper particle of silver cladding after washing, 10~30min is reacted at 60~80 DEG C.Cu nanometers of the core-shell structure Ag@prepared
Particle is the spheric granules that partial size is about 50nm, be added after the solvent of corresponding ratio be configured to conductive ink can be applied to it is soft
Property printing in.This method is simple, and reaction raw materials are easy to get, and reaction condition is mildly easily operated, is suitble to large-scale industrial production.
Detailed description of the invention
Fig. 1 is core-shell structure Ag@Cu nano particle scanning electron microscope (SEM) figure prepared by embodiment 1；
Fig. 2 is core-shell structure Ag@Cu nano particle power spectrum (EDS) figure prepared by embodiment 1；
Fig. 3 is core-shell structure Ag@Cu nano particle X-ray diffraction (XRD) map prepared by embodiment 1；
Fig. 4 is that core-shell structure Ag@Cu nano particle scanning electron microscope element prepared by embodiment 1 maps (Mapping) figure；
Fig. 5 is contact angle signal of the core-shell structure Ag@Cu nanoparticle conductive ink prepared by embodiment 2 on PET
Figure；
Fig. 6 is that core-shell structure Ag@Cu nanoparticle conductive ink prepared by embodiment 2 is printed upon rear buckling point on PET
Bright small bulbs pictorial diagram.
Specific embodiment
A kind of core-shell structure Ag@Cu nanoparticle conductive ink of the invention, is scattered in liquid by spherical nanoparticles
Middle formation；Wherein:
Spherical nanoparticles are the Ag@Cu nano particle of silver-colored shell coated copper core, and partial size is about 50nm, the nano particle by
In with core-shell structure, a possibility that it is anti-oxidation to the protection of copper core to be not only conducive to silver-colored shell, and reduces electromigration, therefore should
The ink that nano particle is configured to has preferable stability and electric conductivity；
Liquid is the mixed liquor of deionized water, ethylene glycol and glycerine；
In core-shell structure Ag@Cu nanoparticle conductive ink, the solid content of spherical nanoparticles is 10~30wt%.
A kind of preparation method of core-shell structure Ag@Cu nanoparticle conductive ink, comprising the following steps:
(1) it prepares copper source precursor liquid: taking copper sulphate (CuSO4) be placed in reaction vessel, it is added ethylene glycol (EG), magnetic force stirs
It mixes and is uniformly configured to copper source precursor solution；Wherein, the concentration of copper source precursor solution is 0.01M~0.05M；
(2) reducing agent and dispersing agent is added: being added in the copper source precursor solution obtained in step (1) and is used as reducing agent
One hydration sodium hypophosphite (NaH2PO2·H2O) and as dispersing agent polyvinylpyrrolidone (PVP-K30)；Wherein, it restores
The mass ratio of agent and copper sulphate is 1:1.6, and the mass ratio of dispersing agent and copper sulphate is 2:1.6；
(3) oil bath is handled: the anti-of copper source precursor solution, reducing agent and dispersant solution being housed by what step (2) obtained
It answers container to be transferred to oil bath pan, stirs oil bath, reacted；Wherein, oil bath temperature be 60~80 DEG C, the reaction time be 10~
30min；
(4) centrifuge washing: step (3) are reacted after resulting product carries out centrifuge washing and are dried in vacuo；Wherein, centrifugation is washed
The solvent washed is deionized water and dehydrated alcohol；
(5) it prepares silver-colored source predecessor: taking silver nitrate (AgNO3) be placed in reaction vessel, ethylene glycol is added, magnetic agitation is equal
It is even to be configured to silver-colored source precursor solution；Wherein, the concentration of silver-colored source precursor solution is 0.01~0.05M；
(6) oil bath is handled: the product of step (4) after dry being placed in reaction vessel, ethylene glycol is added, stirs, then
The silver-colored source precursor solution that a dropping step (5) obtains, is reacted under oil bath；Wherein, oil bath temperature is 60~80 DEG C, reaction
Time is 10~30min；
(7) centrifugal drying: step (6) are reacted after resulting product carries out centrifuge washing and are dried in vacuo, powder is obtained；Its
In, the solvent of centrifuge washing is deionized water and dehydrated alcohol；
(8) it prepares ink: powder obtained in step (7) is dissolved in the mixed liquor of deionized water, ethylene glycol and glycerine
In, ultrasonic disperse obtains the core-shell structure Ag@Cu nanoparticle conductive ink；Wherein, by changing deionized water, second two
The ratio of alcohol and glycerine, so that the viscosity of the ink of preparation is 8~12cps.
Core-shell structure Ag@Cu nanoparticle conductive ink of the invention can be applied in flexible printing, method particularly includes:
Step a handles substrate: carrying out plasma treatment to flexible substrates；Wherein, flexible substrates PET, plasma treatment
Time be 1~20min；
Step b, printing ink: by the core-shell structure Ag@Cu nanoparticle conductive ink inkjet printing at through step a
In flexible substrates after reason, the flexible substrates of attachment conductive pattern are obtained；
Sintering processes: step c the flexible substrates for the attachment conductive pattern that step b is obtained is put into vacuum drying oven and are carried out
Sintering；Wherein, the temperature of sintering is 100~200 DEG C.
Core-shell structure Ag@Cu nanoparticle conductive ink and the contact angle of flexible substrates are 48~100 °.
By the conductive pattern in flexible substrates obtained by the above method after thermal sintering in bending still keep
Good electric conductivity, resistivity is in 18~27 μ Ω cm.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
The present embodiment is implemented premised on technical solution of the present invention, gives detailed embodiment and specific behaviour
Make process, but protection scope of the present invention is not limited to following embodiments, and only protection is specifically addressed.
Embodiment 1
It is a kind of core-shell structure Ag@Cu nano particle in the present embodiment, preparation method includes the following steps:
Step 1, it prepares copper source precursor liquid: weighing 1.6g copper sulphate (CuSO4) set in a round bottom flask, 100mL second is added
Glycol (EG), magnetic agitation are uniformly configured to copper source precursor solution；；
Step 2, reducing agent and dispersing agent is added: the reduction of 1g being added in the copper source precursor solution obtained in step 1
Agent one is hydrated sodium hypophosphite (NaH2PO2·H2) and the polyethylene of dispersing agent pyrrolidones (PVP-K30) of 2g O；
Step 3, oil bath is handled: the circle equipped with copper source precursor solution, reducing agent and dispersant solution that step 2 is obtained
Bottom flask is transferred to oil bath pan, stirs oil bath 15min at 70 DEG C；
Step 4, it centrifuge washing: step 3 is reacted into resulting product is first washed with deionized water and washed again with dehydrated alcohol three times
Three times, it is dry to be subsequently placed into vacuum drying oven by centrifuge speed 6000rpm, centrifugation time 6min；
Step 5, it prepares silver-colored source predecessor: weighing 0.85g silver nitrate (AgNO3) be placed in a beaker, 50mL ethylene glycol is added,
Magnetic agitation uniformly to clear solution, is configured to silver-colored source precursor solution；
Step 6, oil bath is handled: the product that step 4 is obtained is set in a round bottom flask, addition 50mL ethylene glycol, at 70 DEG C
Strong stirring, then the silver-colored source precursor solution in 5min in a dropping step 5, carries out reaction 15min under 70 DEG C of oil baths；
Step 7, centrifugal drying: product obtained in step 6 is first washed with deionized water and washes three with dehydrated alcohol again three times
Secondary, centrifuge speed 6000rpm, centrifugation time 6min are subsequently placed into vacuum drying oven drying, obtain Cu nanometers of core-shell structure Ag@
Particle.
The core-shell structure Ag@Cu nano particle pattern prepared to embodiment 1 is analyzed, scanning electron microscope
(SEM) figure is as shown in Figure 1, it can be seen that the nano particle journey is spherical, and partial size is about 50nm.Nucleocapsid knot prepared by embodiment 1
Structure Ag@Cu nano particle carries out energy spectrum analysis, such as Fig. 2 this it appears that only existing silver element and copper in nano particle
Peak illustrates the nano particle prepared other than silver-bearing copper almost without remaining impurity element.Core-shell structure prepared by embodiment 1
Ag@Cu nano particle carries out X-ray diffraction analysis, and as shown in Figure 3, prepared nano particle is strictly yellow gold.To reality
The core-shell structure Ag Cu nano particle for applying the preparation of example 2 is scanned Electronic Speculum element mapping characterization, as shown in Figure 4, prepared core
Shell structure Ag@Cu nano particle is strictly a kind of nano particle of silver-colored shell coated copper core, this is to the oxidation-stabilized of the nano particle
Property and electric conductivity have preferable promotion.
Embodiment 2
It is application of the core-shell structure Ag@Cu nanoparticle conductive ink in flexible printing in the present embodiment, including following
Step:
Step 1, substrate is cleaned: using PET as flexible substrates, and being distinguished successively in acetone, dehydrated alcohol, deionized water
It is cleaned by ultrasonic 30min, removes the impurity on surface, naturally dry after cleaning is stand-by after plasma treatment 15min and 2min；
Step 2, ink is prepared: by the resulting core-shell structure Ag@Cu nano particle of embodiment 1 and deionized water, ethylene glycol
It is mixed with glycerine, mass ratio 2:8:1:1, ultrasonic 20min；
Step 3, printing ink: the ink jet prepared in step 2 is printed upon in flexible substrates handled by step 1,
Obtain the flexible substrates of attachment conductive pattern；
Step 10, sintering processes: the flexible substrates for adhering to conductive pattern being put into vacuum drying oven and carry out thermal sintering, and heat is burnt
Junction temperature is 150 DEG C, sintering time 60min.
Contact angle test is carried out to embodiment 2, as shown in figure 5, after corona treatment 15min, ink and substrate
Contact angle is 48 °, and after corona treatment 2min, the contact angle of ink and substrate is 100 °, illustrates ink and base
Infiltration degree, this has certain influence to the circuit fine degree after follow-up sintering.Crooked test, table are carried out to embodiment 2
Bright conductive pattern will not fall off in that case of ben has preferable adhesiveness with substrate, as shown in Figure 6.And in that case of ben according to
Small bulbs can be so lighted, as shown in fig. 6, presenting preferable electric conductivity and application value.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of core-shell structure Ag@Cu nanoparticle conductive ink, it is characterised in that: it is scattered in liquid by spherical nanoparticles
Middle formation, the spherical nanoparticles are the Ag@Cu nano particle of silver-colored shell coated copper core, and the liquid is deionized water, second two
The mixed liquor of pure and mild glycerine；The solid content of the spherical nanoparticles is 10~30wt%.
2. a kind of preparation method of core-shell structure Ag@Cu nanoparticle conductive ink, it is characterised in that: the following steps are included:
(1) it prepares copper source precursor liquid: copper sulphate being taken to be placed in reaction vessel, ethylene glycol is added, magnetic agitation is uniformly configured to copper
Source precursor solution；
(2) reducing agent and dispersing agent is added: one as reducing agent being added in the copper source precursor solution obtained in step (1)
It is hydrated sodium hypophosphite and the polyvinylpyrrolidone as dispersing agent；
(3) oil bath is handled: the reaction equipped with copper source precursor solution, reducing agent and dispersant solution that step (2) is obtained is held
Device is transferred to oil bath pan, stirs oil bath, is reacted；
(4) centrifuge washing: step (3) are reacted after resulting product carries out centrifuge washing and are dried in vacuo；
(5) it prepares silver-colored source predecessor: silver nitrate being taken to be placed in reaction vessel, ethylene glycol is added, magnetic agitation is uniformly configured to silver
Source precursor solution；
(6) oil bath is handled: the product of step (4) after dry being placed in reaction vessel, ethylene glycol is added, stirring is then added dropwise
The silver-colored source precursor solution that step (5) obtains, is reacted under oil bath；
(7) centrifugal drying: step (6) are reacted after resulting product carries out centrifuge washing and are dried in vacuo, powder is obtained；
(8) it prepares ink: powder obtained in step (7) is dissolved in the mixed liquor of deionized water, ethylene glycol and glycerine, surpass
Sound dispersion, obtains the core-shell structure Ag@Cu nanoparticle conductive ink.
3. the preparation method of core-shell structure Ag@Cu nanoparticle conductive ink according to claim 2, it is characterised in that:
In the step (1), the concentration of copper source precursor solution is 0.01M~0.05M；In the step (2), reducing agent and copper sulphate
Mass ratio be 1:1.6, the mass ratio of dispersing agent and copper sulphate is 2:1.6.
4. the preparation method of core-shell structure Ag@Cu nanoparticle conductive ink according to claim 2, it is characterised in that:
In the step (3) and (6), oil bath temperature is 60~80 DEG C, and the reaction time is 10~30min.
5. the preparation method of core-shell structure Ag@Cu nanoparticle conductive ink according to claim 2, it is characterised in that:
In the step (5), the concentration of silver-colored source precursor solution is 0.01~0.05M.
6. the preparation method of core-shell structure Ag@Cu nanoparticle conductive ink according to claim 2, it is characterised in that:
In the step (8), by change deionized water, the ratio of ethylene glycol and glycerine so that preparation ink viscosity be 8~
12cps。
7. core-shell structure Ag@Cu nanoparticle conductive ink described in claim 1 is applied to the purposes in flexible electronic printing.
8. purposes according to claim 7, it is characterised in that: specific steps are as follows:
Step a handles substrate: carrying out plasma treatment to flexible substrates；
Step b, printing ink: by the core-shell structure Ag@Cu nanoparticle conductive ink inkjet printing after step a processing
Flexible substrates on, obtain attachment conductive pattern flexible substrates；
Sintering processes: step c the flexible substrates for the attachment conductive pattern that step b is obtained is put into vacuum drying oven and are sintered.
9. purposes according to claim 8, it is characterised in that: in the step a, flexible substrates PET, plasma treatment
Time be 1~20min；In the step c, the temperature of sintering is 100~200 DEG C.
10. purposes according to claim 8, it is characterised in that: the core-shell structure Ag@Cu nanoparticle conductive ink with
The contact angle of flexible substrates is 48~100 °.
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| CN201910015697.2A CN109852146A (en) | 2019-01-08 | 2019-01-08 | A kind of core-shell structure Ag@Cu nanoparticle conductive ink and its preparation method and application |
| PCT/CN2019/112849 WO2020143273A1 (en) | 2019-01-08 | 2019-10-23 | Core-shell structured ag@cu nanoparticle conductive ink, preparation method therefor and use thereof |
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| CN201910015697.2A CN109852146A (en) | 2019-01-08 | 2019-01-08 | A kind of core-shell structure Ag@Cu nanoparticle conductive ink and its preparation method and application |
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| WO2020143273A1 (en) * | 2019-01-08 | 2020-07-16 | 南京邮电大学 | Core-shell structured ag@cu nanoparticle conductive ink, preparation method therefor and use thereof |
| CN111500121A (en) * | 2020-05-09 | 2020-08-07 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Conductive ink for flexible printed electronics and phonochemical synthesis method |
| CN112543686A (en) * | 2019-07-15 | 2021-03-23 | 帕沃派株式会社 | Preparation method of silver-copper mixed powder with core-shell structure by using wet process |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024246A (en) * | 2006-02-24 | 2007-08-29 | 三星电机株式会社 | Core-shell structure metall nanoparticles and its manufacturing method |
| CN103151113A (en) * | 2013-01-31 | 2013-06-12 | 中国科学院化学研究所 | Preparation method of pressure-sensitive conductive membrane |
| CN105855538A (en) * | 2016-04-08 | 2016-08-17 | 广东工业大学 | Nano silver-coated copper powder and preparation method and application thereof |
| CN108084799A (en) * | 2017-11-30 | 2018-05-29 | 哈尔滨工业大学深圳研究生院 | A kind of material for radio frequency discrimination RFID antenna conductive patterns |
| CN108237222A (en) * | 2018-01-05 | 2018-07-03 | 广东工业大学 | A kind of nuclear shell structure nano metal interconnection process |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7625637B2 (en) * | 2006-05-31 | 2009-12-01 | Cabot Corporation | Production of metal nanoparticles from precursors having low reduction potentials |
| CA2665219C (en) * | 2007-08-03 | 2018-07-10 | Fry's Metals, Inc. | Conductive patterns and methods of using them |
| CN102766371A (en) * | 2011-05-04 | 2012-11-07 | 上海鑫力新材料科技有限公司 | Preparation method for nanometer conductive ink |
| CN105598468B (en) * | 2016-03-17 | 2018-05-15 | 中国科学院深圳先进技术研究院 | A kind of preparation method of wicker copper nano particle available for electrically conductive ink |
| CN109852146A (en) * | 2019-01-08 | 2019-06-07 | 南京邮电大学 | A kind of core-shell structure Ag@Cu nanoparticle conductive ink and its preparation method and application |
-
2019
- 2019-01-08 CN CN201910015697.2A patent/CN109852146A/en active Pending
- 2019-10-23 WO PCT/CN2019/112849 patent/WO2020143273A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024246A (en) * | 2006-02-24 | 2007-08-29 | 三星电机株式会社 | Core-shell structure metall nanoparticles and its manufacturing method |
| CN103151113A (en) * | 2013-01-31 | 2013-06-12 | 中国科学院化学研究所 | Preparation method of pressure-sensitive conductive membrane |
| CN105855538A (en) * | 2016-04-08 | 2016-08-17 | 广东工业大学 | Nano silver-coated copper powder and preparation method and application thereof |
| CN108084799A (en) * | 2017-11-30 | 2018-05-29 | 哈尔滨工业大学深圳研究生院 | A kind of material for radio frequency discrimination RFID antenna conductive patterns |
| CN108237222A (en) * | 2018-01-05 | 2018-07-03 | 广东工业大学 | A kind of nuclear shell structure nano metal interconnection process |
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| WO2020143273A1 (en) * | 2019-01-08 | 2020-07-16 | 南京邮电大学 | Core-shell structured ag@cu nanoparticle conductive ink, preparation method therefor and use thereof |
| CN112543686A (en) * | 2019-07-15 | 2021-03-23 | 帕沃派株式会社 | Preparation method of silver-copper mixed powder with core-shell structure by using wet process |
| CN111500121A (en) * | 2020-05-09 | 2020-08-07 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Conductive ink for flexible printed electronics and phonochemical synthesis method |
| CN111500121B (en) * | 2020-05-09 | 2022-07-22 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Conductive ink for flexible printed electronics and sonochemical synthesis method |
| CN114799195A (en) * | 2022-03-10 | 2022-07-29 | 昆明理工大学 | Preparation method of self-assembled micro-nano structure Cu-Ag nano particles |
| CN114603153A (en) * | 2022-03-19 | 2022-06-10 | 昆明理工大学 | Preparation method of bimetallic particles formed by self-assembly of nano copper and silver |
| CN114603153B (en) * | 2022-03-19 | 2024-01-23 | 昆明理工大学 | Preparation method of bimetal particles formed by self-assembly of nano copper and silver |
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