CN104318978B - Electro-conductive paste with core shell conductive particles and preparation method thereof - Google Patents
Electro-conductive paste with core shell conductive particles and preparation method thereof Download PDFInfo
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- CN104318978B CN104318978B CN201410579462.3A CN201410579462A CN104318978B CN 104318978 B CN104318978 B CN 104318978B CN 201410579462 A CN201410579462 A CN 201410579462A CN 104318978 B CN104318978 B CN 104318978B
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Abstract
The invention relates to electro-conductive paste with core shell conductive particles and a preparation method thereof and belongs to the technical field of electro-conductive paste for solar cells. The electro-conductive paste comprises core shell conductive particles, glass frit, an organic vehicle and an additive. The core shell conductive particles are of a core shell structure, cores of the core shell conductive particles are macromolecule spheres, and shells of the core shell conductive particles are coated type conductive layers. The electro-conductive paste, based on the total amount of the electro-conductive paste as a reference, comprises 33-99wt% of the core shell conductive particles, 0.1-20wt% of glass frit, 0.1-25wt% of the organic vehicle and 0.1-25wt% of the additive. The preparation method includes the steps of preparing macromolecule microspheres, combining the prepared macromolecule microspheres with conductive components to form core shell conductive particles with macromolecule cores and conductive shells, and producing the electro-conductive paste with the prepared core shell conductive particles and other auxiliary components. The electro-conductive paste with core shell conductive particles and the preparation method thereof has the advantages that the electro-conductive paste is applicable to the circuit construction of solar cells and electronic products, the cost of the electro-conductive paste composition can be reduced by 20% -40%, the conductivity is good and the size of the particles is controllable.
Description
Technical field
It is more particularly to a kind of comprising nuclear shell conductive granule the invention belongs to conductive paste for solar cell technical field
Electrocondution slurry, further relates to its preparation method.
Background technology
Solar energy is more next so that its is inexhaustible, pollution-free, the advantages of do not limited by resource advantage as a kind of green energy resource
More it is subject to people's attention.The back side of existing solaode is in the n-type region that silicon chip back side is formed n-type silicon to be made anti-
Type is p-type silicon, typically by the back up electrocondution slurry in solaode, forms an aluminium foil for reflecting photon and one
Collect the back of the body electric field of cell back surface current.Afterwards in back of the body electric field and the front of solaode conductive silver slurry shape is printed respectively again
Into electrode coral line, after dry, sintering electrode of solar battery is prepared.
Electrocondution slurry is typically made up of conductive metal powder, glass dust and organic carrier, and prior art is promising to above-mentioned performance
It is modified, the excellent electrocondution slurry of processability, and adds the function such as Ga, In, Ta or tungsten, molybdenum, bronze gold in glass dust
Category powder, metal powder is mixed with metal glass mixed powder and inorganic binder is used as in electrocondution slurry with glass dust mechanical ball milling,
Change the linear expansion coefficient of glass dust, improve the flexibility of solar battery sheet, improve the photoelectric transformation efficiency of cell piece.
Electrocondution slurry generally includes slurry matrix and the silver powder particles being dispersed in slurry matrix by made by resin material.
But traditional electrocondution slurry has the high resistivity between about 20 to 40 μ Ω/cm, while its conductivity is not high.
Electrocondution slurry is aided with other adding ingredients and makes using metal particle mostly, although electric conductivity is superior, but cost
It is higher, particularly noble silver, gold etc..In addition metal particle is more little more is conducive to electric conductivity, but the metal particle of smaller particle
Prepare difficult.
The content of the invention
In order to solve the problems referred to above of prior art presence, the invention provides a kind of conduction comprising nuclear shell conductive granule
Slurry, additionally relates to its preparation method.
The technical scheme that adopted for achieving the above object of the present invention is：A kind of conductive paste comprising nuclear shell conductive granule
Material, it is characterised in that：The electrocondution slurry includes nuclear shell conductive granule, glass dust, organic carrier and auxiliary agent, the nuclear shell conductive
Grain is nucleocapsid structure, and its core is macromolecule spheroid, and its shell is clad type conductive layer.
The electrocondution slurry also includes ultraviolet initiator or ultraviolet initiator and photosensitizer.
On the basis of the total amount of electrocondution slurry, the electrocondution slurry includes nuclear shell conductive granule, the 0.4- of 55-90wt%
The glass dust of 20wt%, the organic carrier of 0.4-15wt%, the auxiliary agent of 0.3-20wt%, 0.1-10wt% ultraviolet initiators and
0-10wt% photosensitizer.
On the basis of the total amount of electrocondution slurry, the electrocondution slurry includes nuclear shell conductive granule, the 0.4- of 55-95wt%
The auxiliary agent of the glass dust of 20wt%, the organic carrier of 0.5-25wt% and 0.4-10wt%.
The nuclear shell conductive particle diameter is 10 nanometers -800 microns, and the macromolecule spheroid is containing carboxyl polymer shape
Into spheroid, its a diameter of 8 nanometers -700 microns, clad type conduction composition of layer is gold, silver, copper or aluminum.
The glass dust is Pb-B-Si-Zn-Ti-Al-O system glass dust, wherein mass percent difference shared by each composition
For：PbO 50-70%, B2O32-5%, SiO220-30%, ZnO 1-5%, TiO20.1-5%, Al2O32-8%；It is described organic
Carrier is terpineol, pine oil, carbitol, ethyl cellulose, acrylate, NC Nitroncellulose, one kind of stearate or several
Kind；The auxiliary agent is one or more of thixotropic agent, penetrating agent, surfactant, levelling agent, defoamer, coupling agent.
The ultraviolet initiator is benzophenone and/or acetophenones；Photosensitizer be camphorquinone, Benzoin derivative,
One or more of acyl group phosphorous oxide, the luxuriant titanium of fluorination, diaryl group iodized salt, triaryl sulfonium salts, iron arene complexes.
A kind of preparation method of the electrocondution slurry comprising nuclear shell conductive granule, it is characterised in that：Including step in detail below：
(1) macromolecule spheroid is prepared
Macromolecule spheroid by monomer as raw material in the way of radical polymerization preparing, prepare macromolecule by raw material of monomer
Polymer spheres step be followed successively by emulsion polymerization, emulsifier-free emulsion polymerization, dispersin polymerization, precipitation polymerization, suspension polymerisation, microemulsion gather
Close, thin breast is polymerized and forms macromolecule spheroid；
(2) nuclear shell conductive granule is prepared
Using macromolecule spheroid in step (1) as metal source carrier, using soluble metallic salt as source metal, using alcohols
As reducing agent, in the medium of alcohol/water composition, by reduction reaction so that metal ion deposition adsorbs in macromolecule spheroid table
Face, reacts Jing 3000-6000r/min centrifugations after terminating, and removes water-dispersible again, repeated centrifugation, dispersion after supernatant liquid
Three times, obtain stably dispersing with polymer microsphere as core, nuclear shell conductive granule of the conductive compositions as shell；
(3) organic carrier is prepared
Resin and solvent are weighed, in pouring the closed rustless steel container with mechanical agitator into respectively, at 70-90 DEG C,
High-speed stirred dissolves, and sieves, and organic carrier is obtained after inspection；
(4) dispensing batch mixing
Nuclear shell conductive granule obtains primary conductive with other auxiliary elements according to batch mixing after following content dispensing by made by
Slurry：
A) on the basis of the total amount of electrocondution slurry, by weight 55% to 95% nuclear shell conductive granule；
B) on the basis of the total amount of electrocondution slurry, by weight 0.4% to 20% glass dust；
C) on the basis of the total amount of electrocondution slurry, by weight 0.5% to 25% organic carrier；
D) on the basis of the total amount of electrocondution slurry, by weight 0.4% to 10% auxiliary agent；
(5) slurry parameter is adjusted
Through rolling to fineness it is 10-14 μm by primary conductive slurry, then adjusts its viscosity for 100-200CPS, filters
Inspection afterwards obtains electrocondution slurry.
The step (2) is prepared in nuclear shell conductive granule, and in the medium of the alcohol/water composition, alcohol is 1 with the volume ratio of water
: 0～1：0.8；Each reactant ratio is：Macromolecule spheroid concentration be 1.0～100.0g/L, metal salt concentrations be 0.1～
30g/L；The temperature of the reduction reaction is 50 DEG C～100 DEG C, and the response time is 1～8 hour；The macromolecule spherome surface is inhaled
The particle diameter of attached metal is 1～40nm.
Nucleocapsid conductive particle can be with according to following content dispensing with other auxiliary elements in step (4) the dispensing batch mixing
Afterwards batch mixing obtains primary conductive slurry：
A) on the basis of the total amount of electrocondution slurry, by weight 55% to 90% nuclear shell conductive granule；
B) on the basis of the total amount of electrocondution slurry, by weight 0.4% to 20% glass dust；
C) on the basis of the total amount of electrocondution slurry, by weight 0.4% to 15% organic carrier；
D) on the basis of the total amount of electrocondution slurry, by weight 0.3% to 20% auxiliary agent；
E) on the basis of the total amount of electrocondution slurry, by weight 0.1% to 10% ultraviolet initiator；
F) on the basis of the total amount of electrocondution slurry, by weight 0 to 10% photosensitizer.
The beneficial effect to be brought of electrocondution slurry and preparation method thereof of the present invention is：
(1) this electrocondution slurry can be solidified with employing heating or ultraviolet light irradiation mode；
(2) electrocondution slurry can be used for the structure of solaode and electron product circuit；
(3) conductive particle in the conductive paste composition adopts macromolecule spheroid for core, and metal conducting layer is the knot of shell
Structure, reduces the usage amount of metal, and manufacturing cost can reduce 20%-40%；
(4) electric conductivity of the electrocondution slurry is excellent, and the size of conductive particle therein can be with effective control.
Specific embodiment
The present invention is described in detail with reference to specific embodiment, but the invention is not limited in specific embodiment.
Embodiment 1
A kind of electrocondution slurry comprising nuclear shell conductive granule, on the basis of the total amount of electrocondution slurry, the electrocondution slurry includes
The auxiliary agent of the nuclear shell conductive granule of 55wt%, the glass dust of 20wt%, the organic carrier of 15wt% and 10wt%, nuclear shell conductive
Grain is nucleocapsid structure, and its core is macromolecule spheroid, and its shell is clad type conductive layer.
Nuclear shell conductive particle diameter be 10 nanometers, macromolecule spheroid be containing carboxyl polymer formed spheroid, its diameter
For 8 nanometers, clad type conduction composition of layer is silver.
Glass dust is Pb-B-Si-Zn-Ti-Al-O system glass dust, wherein mass percent shared by each composition is respectively：
PbO 50%, B2O35%th, SiO230%th, ZnO5%, TiO25%th, Al2O35%；Organic carrier is terpineol；Auxiliary agent is penetrating agent
And surfactant.
The preparation method of the electrocondution slurry, it is characterised in that：Including step in detail below：
(1) macromolecule spheroid is prepared
Macromolecule spheroid by monomer as raw material in the way of radical polymerization preparing, prepare macromolecule by raw material of monomer
Polymer spheres step be followed successively by emulsion polymerization, emulsifier-free emulsion polymerization, dispersin polymerization, precipitation polymerization, suspension polymerisation, microemulsion gather
Close, thin breast is polymerized and forms macromolecule spheroid；
(2) nuclear shell conductive granule is prepared
Using macromolecule spheroid in step (1) as metal source carrier, using soluble metallic salt as source metal, using alcohols
As reducing agent, in the medium of alcohol/water composition, by reduction reaction so that metal ion deposition adsorbs in macromolecule spheroid table
Face, reacts Jing 3000r/min centrifugations after terminating, and removes water-dispersible again after supernatant liquid, repeated centrifugation, dispersion three times,
Obtain stably dispersing with polymer microsphere as core, nuclear shell conductive granule of the conductive compositions as shell；
Wherein, in the medium of alcohol/water composition, alcohol is 1: 0 with the volume ratio of water；Each reactant ratio is：Macromolecule spheroid
Concentration is 1.0g/L, and metal salt concentrations are 0.1g/L；The temperature of reduction reaction is 50 DEG C, and the response time is 1 hour；High score bulbec
The particle diameter of body surface face adsorbing metal is 1nm.
(3) organic carrier is prepared
Resin and solvent are weighed, in pouring the closed rustless steel container with mechanical agitator into respectively, at 70 DEG C, at a high speed
Stirring and dissolving, sieves, and organic carrier is obtained after inspection；
(4) dispensing batch mixing
Nuclear shell conductive granule obtains primary conductive with other auxiliary elements according to batch mixing after following content dispensing by made by
Slurry：
On the basis of the total amount of electrocondution slurry, the nuclear shell conductive granule of 55wt%, the glass dust of 20wt%, 15wt% have
The auxiliary agent of airborne body and 10wt%；
(5) slurry parameter is adjusted
Through rolling to fineness it is 10 μm by primary conductive slurry, then adjusts its viscosity for 100CPS, checks after filtration
Obtain electrocondution slurry.
Embodiment 2
A kind of electrocondution slurry comprising nuclear shell conductive granule, on the basis of the total amount of electrocondution slurry, the electrocondution slurry includes
The auxiliary agent of the nuclear shell conductive granule of 95wt%, the glass dust of 0.4wt%, the organic carrier of 0.5wt% and 4.1wt%, nucleocapsid is led
Electric granule is nucleocapsid structure, and its core is macromolecule spheroid, and its shell is clad type conductive layer.
Nuclear shell conductive particle diameter be 800 nanometers, macromolecule spheroid be containing carboxyl polymer formed spheroid, its diameter
For 500 nanometers, clad type conduction composition of layer is copper.
Glass dust is Pb-B-Si-Zn-Ti-Al-O system glass dust, wherein mass percent shared by each composition is respectively：
PbO 70%, B2O32%th, SiO220%th, ZnO1%, TiO22%th, Al2O35%；Organic carrier is pine oil and carbitol；Auxiliary agent
For thixotropic agent and levelling agent.
The preparation method of the electrocondution slurry, it is characterised in that：Including step in detail below：
(1) macromolecule spheroid is prepared
Macromolecule spheroid by monomer as raw material in the way of radical polymerization preparing, prepare macromolecule by raw material of monomer
Polymer spheres step be followed successively by emulsion polymerization, emulsifier-free emulsion polymerization, dispersin polymerization, precipitation polymerization, suspension polymerisation, microemulsion gather
Close, thin breast is polymerized and forms macromolecule spheroid；
(2) nuclear shell conductive granule is prepared
Using macromolecule spheroid in step (1) as metal source carrier, using soluble metallic salt as source metal, using alcohols
As reducing agent, in the medium of alcohol/water composition, by reduction reaction so that metal ion deposition adsorbs in macromolecule spheroid table
Face, reacts Jing 4500r/min centrifugations after terminating, and removes water-dispersible again after supernatant liquid, repeated centrifugation, dispersion three times,
Obtain stably dispersing with polymer microsphere as core, nuclear shell conductive granule of the conductive compositions as shell；
Wherein, in the medium of alcohol/water composition, alcohol is 1: 0.5 with the volume ratio of water；Each reactant ratio is：High score bulbec
Bulk concentration is 25g/L, and metal salt concentrations are 3g/L；The temperature of reduction reaction is 70 DEG C, and the response time is 5 hours；High score bulbec
The particle diameter of body surface face adsorbing metal is 10nm.
(3) organic carrier is prepared
Resin and solvent are weighed, in pouring the closed rustless steel container with mechanical agitator into respectively, at 80 DEG C, at a high speed
Stirring and dissolving, sieves, and organic carrier is obtained after inspection；
(4) dispensing batch mixing
Nuclear shell conductive granule obtains primary conductive with other auxiliary elements according to batch mixing after following content dispensing by made by
Slurry：
On the basis of the total amount of electrocondution slurry, the nuclear shell conductive granule of 95wt%, the glass dust of 0.4wt%, 0.5wt%
The auxiliary agent of organic carrier and 4.1wt%；
(5) slurry parameter is adjusted
Through rolling to fineness it is 12 μm by primary conductive slurry, then adjusts its viscosity for 150CPS, checks after filtration
Obtain electrocondution slurry.
Embodiment 3
A kind of electrocondution slurry comprising nuclear shell conductive granule, on the basis of the total amount of electrocondution slurry, the electrocondution slurry includes
The auxiliary agent of the nuclear shell conductive granule of 70wt%, the glass dust of 4.6wt%, the organic carrier of 25wt% and 0.4wt%, nuclear shell conductive
Granule is nucleocapsid structure, and its core is macromolecule spheroid, and its shell is clad type conductive layer.
Nuclear shell conductive particle diameter be 20 microns, macromolecule spheroid be containing carboxyl polymer formed spheroid, its diameter
For 10 microns, clad type conduction composition of layer is gold.
Glass dust is Pb-B-Si-Zn-Ti-Al-O system glass dust, wherein mass percent shared by each composition is respectively：
PbO65%, B2O33%th, SiO221%th, ZnO2.9%, TiO20.1%th, Al2O38%；Organic carrier is ethyl cellulose, propylene
Acid esters and stearate；Auxiliary agent is thixotropic agent, penetrating agent, surfactant and levelling agent.
The preparation method of the electrocondution slurry, it is characterised in that：Including step in detail below：
(1) macromolecule spheroid is prepared
Macromolecule spheroid by monomer as raw material in the way of radical polymerization preparing, prepare macromolecule by raw material of monomer
Polymer spheres step be followed successively by emulsion polymerization, emulsifier-free emulsion polymerization, dispersin polymerization, precipitation polymerization, suspension polymerisation, microemulsion gather
Close, thin breast is polymerized and forms macromolecule spheroid；
(2) nuclear shell conductive granule is prepared
Using macromolecule spheroid in step (1) as metal source carrier, using soluble metallic salt as source metal, using alcohols
As reducing agent, in the medium of alcohol/water composition, by reduction reaction so that metal ion deposition adsorbs in macromolecule spheroid table
Face, reacts Jing 6000r/min centrifugations after terminating, and removes water-dispersible again after supernatant liquid, repeated centrifugation, dispersion three times,
Obtain stably dispersing with polymer microsphere as core, nuclear shell conductive granule of the conductive compositions as shell；
Wherein, in the medium of alcohol/water composition, alcohol is 1: 0.8 with the volume ratio of water；Each reactant ratio is：High score bulbec
Bulk concentration is 100g/L, and metal salt concentrations are 30g/L；The temperature of reduction reaction is 100 DEG C, and the response time is 8 hours；Macromolecule
The particle diameter of spherome surface adsorbing metal is 30nm.
(3) organic carrier is prepared
Resin and solvent are weighed, in pouring the closed rustless steel container with mechanical agitator into respectively, at 80 DEG C, at a high speed
Stirring and dissolving, sieves, and organic carrier is obtained after inspection；
(4) dispensing batch mixing
Nuclear shell conductive granule obtains primary conductive with other auxiliary elements according to batch mixing after following content dispensing by made by
Slurry：
On the basis of the total amount of electrocondution slurry, the nuclear shell conductive granule of 70wt%, the glass dust of 4.6wt%, 25wt%
The auxiliary agent of organic carrier and 0.4wt%；
(5) slurry parameter is adjusted
Through rolling to fineness it is 14 μm by primary conductive slurry, then adjusts its viscosity for 200CPS, checks after filtration
Obtain electrocondution slurry.
Embodiment 4
A kind of electrocondution slurry comprising nuclear shell conductive granule, on the basis of the total amount of electrocondution slurry, the electrocondution slurry includes
The auxiliary agent of the nuclear shell conductive granule of 80wt%, the glass dust of 10wt%, the organic carrier of 8wt% and 2wt%, nuclear shell conductive granule
For nucleocapsid structure, its core is macromolecule spheroid, and its shell is clad type conductive layer.
Nuclear shell conductive particle diameter be 800 microns, macromolecule spheroid be containing carboxyl polymer formed spheroid, its diameter
For 700 microns, clad type conduction composition of layer is aluminum.
Glass dust is Pb-B-Si-Zn-Ti-Al-O system glass dust, wherein mass percent shared by each composition is respectively：
PbO60%, B2O35%th, SiO225%th, ZnO4%, TiO23%th, Al2O33%；Organic carrier is terpineol, NC Nitroncellulose, hard
Fat acid salt；The auxiliary agent is surfactant, levelling agent, defoamer and coupling agent.
The preparation method of the electrocondution slurry, it is characterised in that：Including step in detail below：
(1) macromolecule spheroid is prepared
Macromolecule spheroid by monomer as raw material in the way of radical polymerization preparing, prepare macromolecule by raw material of monomer
Polymer spheres step be followed successively by emulsion polymerization, emulsifier-free emulsion polymerization, dispersin polymerization, precipitation polymerization, suspension polymerisation, microemulsion gather
Close, thin breast is polymerized and forms macromolecule spheroid；
(2) nuclear shell conductive granule is prepared
Using macromolecule spheroid in step (1) as metal source carrier, using soluble metallic salt as source metal, using alcohols
As reducing agent, in the medium of alcohol/water composition, by reduction reaction so that metal ion deposition adsorbs in macromolecule spheroid table
Face, reacts Jing 5000r/min centrifugations after terminating, and removes water-dispersible again after supernatant liquid, repeated centrifugation, dispersion three times,
Obtain stably dispersing with polymer microsphere as core, nuclear shell conductive granule of the conductive compositions as shell；
Wherein, in the medium of alcohol/water composition, alcohol is 1: 0.6 with the volume ratio of water；Each reactant ratio is：High score bulbec
Bulk concentration is 50g/L, and metal salt concentrations are 15g/L；The temperature of reduction reaction is 90 DEG C, and the response time is 6 hours；High score bulbec
The particle diameter of body surface face adsorbing metal is 40nm.
(3) organic carrier is prepared
Resin and solvent are weighed, in pouring the closed rustless steel container with mechanical agitator into respectively, at 85 DEG C, at a high speed
Stirring and dissolving, sieves, and organic carrier is obtained after inspection；
(4) dispensing batch mixing
Nuclear shell conductive granule obtains primary conductive with other auxiliary elements according to batch mixing after following content dispensing by made by
Slurry：
On the basis of the total amount of electrocondution slurry, the nuclear shell conductive granule of 80wt%, the glass dust of 10wt%, 8wt% have
The auxiliary agent of airborne body and 2wt%；
(5) slurry parameter is adjusted
Through rolling to fineness it is 13 μm by primary conductive slurry, then adjusts its viscosity for 180CPS, checks after filtration
Obtain electrocondution slurry.
Embodiment 5
The embodiment from embodiment 1 in addition to following parameter is different, other guide all same：
(1) on the basis of the total amount of electrocondution slurry, the nuclear shell conductive granule of the electrocondution slurry including 55wt%, 20wt%
Glass dust, the organic carrier of 5wt%, the auxiliary agent of 10wt% and 10wt% ultraviolet initiators.
(2) ultraviolet initiator is benzophenone.
Embodiment 6
The embodiment from embodiment 2 in addition to following parameter is different, other guide all same：
(1) on the basis of the total amount of electrocondution slurry, the electrocondution slurry includes nuclear shell conductive granule, the 0.4wt% of 60wt%
Glass dust, the organic carrier of 15wt%, the auxiliary agent of 20wt%, 0.1wt% ultraviolet initiators and 4.5wt% photosensitizer.
(2) ultraviolet initiator is benzophenone；Photosensitizer is camphorquinone.
Embodiment 7
The embodiment from embodiment 3 in addition to following parameter is different, other guide all same：
(1) on the basis of the total amount of electrocondution slurry, the nuclear shell conductive granule of the electrocondution slurry including 80wt%, 2wt%
Glass dust, the organic carrier of 2wt%, the auxiliary agent of 4wt%, 2wt% ultraviolet initiators and 10wt% photosensitizer.
(2) ultraviolet initiator is 1-Phenylethanone.；Photosensitizer is Benzoin derivative and acyl group phosphorous oxide.
Embodiment 8
The embodiment from embodiment 4 in addition to following parameter is different, other guide all same：
(1) on the basis of the total amount of electrocondution slurry, the nuclear shell conductive granule of the electrocondution slurry including 90wt%, 6wt%
Glass dust, the organic carrier of 0.4wt%, the auxiliary agent of 0.3wt%, 3wt% ultraviolet initiators and 0.3wt% photosensitizer.
(2) ultraviolet initiator is benzophenone and 1-Phenylethanone.；Photosensitizer is the luxuriant titanium of fluorination, diaryl group iodized salt, three fragrant
Base sulfosalt and iron arene complexes.
Claims (9)
1. a kind of electrocondution slurry comprising nuclear shell conductive granule, it is characterised in that：The electrocondution slurry includes nuclear shell conductive granule, glass
Glass powder, organic carrier and auxiliary agent, the nuclear shell conductive granule is nucleocapsid structure, and its core is macromolecule spheroid, and its shell is clad type
Conductive layer；
The nuclear shell conductive particle diameter is 10 nanometers -800 microns, and the macromolecule spheroid is to be formed containing carboxyl polymer
Spheroid, its a diameter of 8 nanometers -700 microns, the clad type conduction composition of layer is gold, silver, copper or aluminum.
2. a kind of electrocondution slurry comprising nuclear shell conductive granule according to claim 1, it is characterised in that：The conductive paste
Material also includes ultraviolet initiator or ultraviolet initiator and photosensitizer.
3. a kind of electrocondution slurry comprising nuclear shell conductive granule according to claim 2, it is characterised in that：With electrocondution slurry
Total amount on the basis of, nuclear shell conductive granule, the glass dust of 0.4-20wt%, the 0.4- of the electrocondution slurry including 55-90wt%
The organic carrier of 15wt%, the auxiliary agent of 0.3-20wt%, 0.1-10wt% ultraviolet initiators and 0-10wt% photosensitizer.
4. a kind of electrocondution slurry comprising nuclear shell conductive granule according to claim 1, it is characterised in that：With electrocondution slurry
Total amount on the basis of, nuclear shell conductive granule, the glass dust of 0.4-20wt%, the 0.5- of the electrocondution slurry including 55-95wt%
The organic carrier of 25wt% and the auxiliary agent of 0.4-10wt%.
5. a kind of electrocondution slurry comprising nuclear shell conductive granule according to claim 1, it is characterised in that：The glass dust
For Pb-B-Si-Zn-Ti-Al-O system glass dust, wherein mass percent shared by each composition is respectively：PbO 50-70%, B2O3
2-5%, SiO220-30%, ZnO 1-5%, TiO20.1-5%, Al2O32-8%；The organic carrier is terpineol, pine
One or more of wood oil, carbitol, ethyl cellulose, acrylate, NC Nitroncellulose, stearate；The auxiliary agent is tactile
One or more of change agent, penetrating agent, surfactant, levelling agent, defoamer, coupling agent.
6. a kind of electrocondution slurry comprising nuclear shell conductive granule according to claim 2, it is characterised in that：The ultraviolet light
Initiator is benzophenone and/or 1-Phenylethanone.；Photosensitizer be camphorquinone, Benzoin derivative, acyl group phosphorous oxide, the luxuriant titanium of fluorination,
One or more of diaryl group iodized salt, triaryl sulfonium salts, iron arene complexes.
7. a kind of preparation method of the electrocondution slurry comprising nuclear shell conductive granule, it is characterised in that：Including step in detail below：
(1) macromolecule spheroid is prepared
Macromolecule spheroid by monomer as raw material in the way of radical polymerization preparing, prepare high molecular polymerization by raw material of monomer
Thing spheroid step is followed successively by emulsion polymerization, emulsifier-free emulsion polymerization, dispersin polymerization, precipitation polymerization, suspension polymerisation, microemulsion, thin
Breast is polymerized and forms macromolecule spheroid；
(2) nuclear shell conductive granule is prepared
Using macromolecule spheroid in step (1) as metal source carrier, using soluble metallic salt as source metal, using alcohols conduct
Reducing agent, in the medium of alcohol/water composition, by reduction reaction so that metal ion deposition adsorbs in macromolecule spherome surface,
Jing 3000-6000r/min centrifugations after terminating are reacted, water-dispersible again after supernatant liquid, repeated centrifugation, dispersion three is removed
It is secondary, obtain stably dispersing with polymer microsphere as core, nuclear shell conductive granule of the conductive compositions as shell；
(3) organic carrier is prepared
Resin and solvent are weighed, in pouring the closed rustless steel container with mechanical agitator into respectively, at 70-90 DEG C, at a high speed
Stirring and dissolving, sieves, and organic carrier is obtained after inspection；
(4) dispensing batch mixing
Nuclear shell conductive granule obtains primary conductive slurry with other auxiliary elements according to batch mixing after following content dispensing by made by：
A) on the basis of the total amount of electrocondution slurry, by weight 55% to 95% nuclear shell conductive granule；
B) on the basis of the total amount of electrocondution slurry, by weight 0.4% to 20% glass dust；
C) on the basis of the total amount of electrocondution slurry, by weight 0.5% to 25% organic carrier；
D) on the basis of the total amount of electrocondution slurry, by weight 0.4% to 10% auxiliary agent；
(5) slurry parameter is adjusted
Through rolling to fineness it is 10-14 μm by primary conductive slurry, then adjusts its viscosity for 100-200CPS, examines after filtration
Test and obtain electrocondution slurry.
8. the preparation method of a kind of electrocondution slurry comprising nuclear shell conductive granule according to claim 7, it is characterised in that：
The step (2) is prepared in nuclear shell conductive granule, and in the medium of the alcohol/water composition, alcohol is 1: 0～1 with the volume ratio of water：
0.8；Macromolecule spheroid concentration is 1.0～100.0g/L, and metal salt concentrations are 0.1～30g/L；The temperature of the reduction reaction is
50 DEG C～100 DEG C, the response time is 1～8 hour；The particle diameter of the macromolecule spherome surface adsorbing metal is 1～40nm.
9. the preparation method of a kind of electrocondution slurry comprising nuclear shell conductive granule according to claim 7, it is characterised in that：
Nucleocapsid conductive particle obtains primary with other auxiliary elements according to batch mixing after following content dispensing in step (4) the dispensing batch mixing
Electrocondution slurry：
A) on the basis of the total amount of electrocondution slurry, by weight 55% to 90% nuclear shell conductive granule；
B) on the basis of the total amount of electrocondution slurry, by weight 0.4% to 20% glass dust；
C) on the basis of the total amount of electrocondution slurry, by weight 0.4% to 15% organic carrier；
D) on the basis of the total amount of electrocondution slurry, by weight 0.3% to 20% auxiliary agent；
E) on the basis of the total amount of electrocondution slurry, by weight 0.1% to 10% ultraviolet initiator；
F) on the basis of the total amount of electrocondution slurry, by weight 0 to 10% photosensitizer.
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| CN108538444B (en) * | 2018-04-16 | 2020-03-10 | 广东工业大学 | Conductive paste for semiconductor packaging and preparation method thereof |
| CN109108278B (en) * | 2018-05-16 | 2021-05-18 | 清远市宝晶新材料有限公司 | Silver-plated plastic microsphere for solar cell conductive circuit and preparation method thereof |
| KR20210011373A (en) * | 2018-05-17 | 2021-02-01 | 니폰 제온 가부시키가이샤 | Slurry for nonaqueous secondary batteries, separator for nonaqueous secondary batteries, electrodes for nonaqueous secondary batteries, laminate for nonaqueous secondary batteries, and nonaqueous secondary batteries |
| CN110586003A (en) * | 2019-07-30 | 2019-12-20 | 上海匡宇科技股份有限公司 | Composite microsphere and preparation method thereof |
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| CN101952904A (en) * | 2008-02-26 | 2011-01-19 | E.I.内穆尔杜邦公司 | Conductive paste and grid electrode for silicon solar cells |
| CN102479568A (en) * | 2010-11-30 | 2012-05-30 | 比亚迪股份有限公司 | Conductive paste for solar cell and preparation method thereof |
| CN103443867A (en) * | 2011-01-18 | 2013-12-11 | 赫劳斯贵金属北美康舍霍肯有限责任公司 | Electroconductive paste compositions and solar cell electrodes and contacts made therefrom |
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| CN101295739B (en) * | 2007-04-26 | 2010-09-29 | 比亚迪股份有限公司 | Conductive slurry for solar battery front side electrode and production method thereof |
| CN102347091B (en) * | 2010-07-26 | 2013-03-27 | 比亚迪股份有限公司 | Composite silver powder, preparation method thereof, and conductive silver slurry containing composite silver powder |
| JP2012182111A (en) * | 2011-02-28 | 2012-09-20 | Samsung Electro-Mechanics Co Ltd | Conductive metal paste composition and manufacturing method thereof |
| CN102990062B (en) * | 2012-12-17 | 2014-07-23 | 苏州纳微科技有限公司 | Method for preparing composite microsphere |
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| CN101952904A (en) * | 2008-02-26 | 2011-01-19 | E.I.内穆尔杜邦公司 | Conductive paste and grid electrode for silicon solar cells |
| CN102479568A (en) * | 2010-11-30 | 2012-05-30 | 比亚迪股份有限公司 | Conductive paste for solar cell and preparation method thereof |
| CN103443867A (en) * | 2011-01-18 | 2013-12-11 | 赫劳斯贵金属北美康舍霍肯有限责任公司 | Electroconductive paste compositions and solar cell electrodes and contacts made therefrom |
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