CN105097071B - Positive conductive silver paste of silicon solar cell and preparation method of positive conductive silver paste - Google Patents
Positive conductive silver paste of silicon solar cell and preparation method of positive conductive silver paste Download PDFInfo
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Abstract
The invention is applicable for the field of a silicon solar cell, and provides a positive conductive silver paste of a silicon solar cell and a preparation method of the positive conductive silver paste. The positive conductive silver paste of the silicon solar cell comprises silver powder, a glass filler and an organic carrier and also comprises rod-like nanometer silver threads and inorganic salt compound crystals, wherein the glass filler is a modified TeO2-Bi2O3-PbO glass filler, the silver powder is micro/submicro silver powder, and based on 100% of total weight of the positive conductive silver paste of the silicon solar cell, the constituents in percent by weight are as follows: 60-90% of micro/submicro silver powder, 0.1-10% of rod-like nanometer silver threads, 0.1-10% of modified TeO2-Bi2O3-PbO glass filler, 0.1-10% of inorganic salt compound crystals and 5-20% of organic carrier. By the positive conductive silver paste of the silicon solar cell, the contact resistance of the silver paste and a cell piece is reduced, and meanwhile, the photoelectric conversion efficiency and the peel strength of the silicon solar cell piece are effectively improved.
Description
Technical field
The invention belongs to silicon solar cell field, more particularly, to silicon solar cell front side conductive silver paste and its preparation side
Method.
Background technology
Solaode is a kind of semiconductor device converting solar energy into electric energy, and its operation principle is quasiconductor pn
The photovoltaic effect of knot, that is, under conditions of extraneous illumination, solar battery sheet produces volta effect, by battery surface
Conductive materials and external connecting leads, form electric current in the case of connecting, and are used with electricity supply and use equipment or are set by electric charge storage
Standby storage.In solaode, photovoltaic effect in cell piece to be produced with electronics and be used it is necessary to using electrode by electricity
Son is derived.
At present, the most ripe solaode on market is silicon solar cell.The electrode of silicon solar energy battery surface
Mainly there are back side silver electrode and front silver electrode, these electrodes are generally printed on silicon by conductive silver paste by the way of silk screen printing
Piece surface is formed.It can be said that conductive silver paste is the electrode material that current silicon solar cell mainly uses.
Silicon solar cell front side conductive silver paste is mainly made up of argentum powder, frit, organic carrier, and the performance of each component is good
The bad overall performance determining described silicon solar cell front side conductive silver paste, and then affect the globality of silicon solar cell
Can, the such as important indicator such as short circuit current, series resistance, photoelectric transformation efficiency, weld strength.Wherein, to silicon solar cell
The maximum group timesharing composition front of overall performance, the such as impact such as short circuit current, series resistance, photoelectric transformation efficiency, weld strength
The frit of conductive silver paste.Use glass-frit containing tellurium more at present, use frit yet with frit containing tellurium and tradition
There is very big difference, compare traditional glass material, frit containing tellurium exists poor with silicon chip affinity and forms network knot after glass
The relatively simple problem of structure, the front side conductive silver paste therefore making of frit containing tellurium easily occurs peeling off with silicon chip and pulling force is attached
Put forth effort the problem of difference.After adding substantial amounts of parent's silicon composition and glass network enhancing thing, electrical property occur again drastically decline etc. asking
Topic.The problems referred to above that frit containing tellurium exists, seriously constrain the silicon solar cell containing tellurium frit in front side conductive silver paste
Performance.
Content of the invention
It is an object of the invention to provide the silicon solar cell front that a kind of photoelectric transformation efficiency is high, welding pulling force is big is led
On the premise of electric silver paste is it is intended to ensure silicon solar cell front side conductive silver paste electrical property, solves frit containing tellurium, particularly contain
teo2-bi2o3The silicon solar cell front side conductive silver paste frit adhesive force of-pbo frit is low, the problem of close silicon difference, from
And improve and contain teo2-bi2o3The short circuit current of silicon solar cell front side conductive silver paste of-pbo frit, open-circuit voltage, conversion
Efficiency, reduces the string resistance of silicon solar cell front side conductive silver paste.
Another object of the present invention is to providing a kind of preparation method of silicon solar cell front side conductive silver paste.
The present invention is achieved in that a kind of silicon solar cell front side conductive silver paste, including argentum powder, frit and organic
Carrier, also includes rod-like nano silver wire, inorganic salt compound crystal, and wherein, described frit is modified teo2-bi2o3- pbo glass
Glass material, described argentum powder is micron/submicron argentum powder, with the gross weight of described silicon solar cell front side conductive silver paste for 100%
Meter, each component weight percentage is as described below:
And, a kind of preparation method of silicon solar cell front side conductive silver paste, comprise the steps:
Prepare inorganic salt compound crystal: take two or more inorganic oxide or described inorganic oxygen can be resolved into
The inorganic salt of compound, carry out successively mixing, heat treatment, pulverize, process of sieving, obtain inorganic salt compound crystal；
The modified teo of preparation2-bi2o3- pbo frit: frit oxide and property-modifying additive are carried out successively mixing, melt
Melt, cold quenching, pulverize, process of sieving, make modified teo2-bi2o3- pbo frit；
Prepare organic carrier: by organic solvent, thickening agent, plasticizer, auxiliary agent through mixed processing, prepare organic carrier；
Prepare silicon solar cell front side conductive silver paste: weigh institute by the formula of above-mentioned solar battery front side conductive silver paste
State micron/submicron level argentum powder, rod-like nano silver wire, modified teo2-bi2o3- pbo frit, inorganic salt compound crystal and
Organic carrier, each component is carried out mixed processing, obtains silicon solar cell front side conductive silver paste.
The silicon solar cell front side conductive silver paste that the present invention provides, first, specifically with the addition of described nano bar-shape
Silver wire, due to elongated described rod-like nano silver wire fusion temperature compared with spheroidal particle micron/submicron level argentum powder fusing temperature
Degree is low, and therefore, in sintering process, described rod-like nano silver wire can form molten state with the frit effect of fusing quickly
Complex, the described rod-like nano silver wire in described molten state complex bends deformation, and be attached to spheroidal particle micron/
Submicron order Argent grain surface, improves the contact effect between described micron/submicron level argentum powder.Further, due to described
Nano bar-shape silver wire length is larger, and it not only can increase the contact point of the spherical silver powder closing on, and can also connect and mutually not close on
Spherical silver powder particles, thus significantly increasing the contact area between argentum powder, improve the contact effect between silver powder particles.With this
Meanwhile, nano bar-shape silver wire bends deformation in sintering process, has filled up the space between spherical silver powder particles, increased electricity
Pond piece silver grating line compaction rate, reduces contact resistance, improves the output of cell piece.
Secondly, in silicon solar cell front side conductive silver paste of the present invention, with the addition of specific inorganic salt compound crystal.By
In silicon solar cell front side conductive silver paste of the present invention, described frit amorphous material, there is not fixing fusing point；And no
Machine salt composite crystal is crystalline solid, has crystal structure, there is fixing fusing point.Therefore, heat tracing process progressively melts
Change, when the frit Hybrid Heating of dystectic inorganic salt compound crystal and low Tg, the glass of non crystalline structure
Material first starts to melt, and gradually coats described inorganic salt compound crystal particle surface.The liquid phase ring providing in melten glass material
In border, inorganic salt composite, is reacted with inorganic salt compound crystal or ion exchange is so that the structure of frit tends to multiple
Hydridization.Meanwhile, when melten glass material promotes the fusing of inorganic salt compound crystal, inorganic salt compound crystal needs constantly
From surrounding heat absorption, the temperature of fusing glass so can be controlled well drastically to raise.Therefore, the present invention passes through in silicon too
Sun can add specific inorganic salt compound crystal in battery front side conductive silver paste, so that silicon solar cell front is led
There is above-mentioned interaction between frit and described inorganic salt compound crystal in electric silver paste in sintering process, to change glass
Mobility after material fusing and the complexity of network structure, change viscosity and the thermal coefficient of expansion of melten glass, improve glass
Glass material and the affinity of silicon chip, to improve the adhesive strength in silicon chip surface for the silver paste with this.On the other hand, small described inorganic
The addition of salt composite crystal, non-crystal frit melted during the effect of continuous and described inorganic salt compound crystal,
Can be very good to suppress frit melted after silicon chip p-n saved damage, improve open-circuit voltage, the short circuit current of silicon solar cell
And transformation efficiency, finally increase its output.
The silicon solar cell front side conductive silver paste that the present invention provides, successfully improves teo2-bi2o3- pbo frit
Strength of glass and adhesive force, ensure electrical property on the premise of it is achieved that high efficiency, low resistance, high-tensile strength, low-leakage current silicon
Solar battery front side conductive silver paste.
A kind of preparation method of silicon solar cell front side conductive silver paste that the present invention provides, preparation method is simple, operation
Controlled, it is easy to accomplish industrialization.
Specific embodiment
In order that the technical problem to be solved in the present invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only in order to explain
The present invention, is not intended to limit the present invention.
Embodiments provide a kind of silicon solar cell front side conductive silver paste, including argentum powder, frit and organic
Carrier, also includes rod-like nano silver wire, inorganic salt compound crystal, and wherein, described frit is modified teo2-bi2o3- pbo glass
Glass material, described argentum powder is micron/submicron argentum powder, with the gross weight of described silicon solar cell front side conductive silver paste for 100%
Meter, each component weight percentage is as described below:
Described silicon solar cell front side silver paste, described frit is important function ingredients.In the embodiment of the present invention, with
teo2-bi2o3- pbo, as the main body system of frit, adds property-modifying additive, on this basis thus obtaining modified teo2-
bi2o3- pbo frit.In the embodiment of the present invention, described modification teo2-bi2o3The weight percentage of-pbo frit is
0.1%-10%, as specific embodiment, described modification teo2-bi2o3The weight percentage of-pbo frit can for 0.1%,
0.5%th, the concrete number such as 1.0%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
Specifically, described modification teo2-bi2o3- pbo frit is included as teo2、bi2o3, pbo and property-modifying additive, with
Described modification teo2-bi2o3The gross weight of-pbo frit is 100% meter, and the weight percentage of each component is preferably as follows institute
State:
Further, as the presently preferred embodiments, described modification teo2-bi2o3The particle diameter of-pbo frit is 1-20 μm, in
Position footpath d50 is 1-10 μm；As further preferred embodiments, described modification teo2-bi2o3The particle diameter of-pbo frit is 1-10 μ
M, meso-position radius d50 are 1-5 μm.As specific embodiment, described property-modifying additive is preferably al2o3、zno、ruo2、cao、mgo、
wo3、zro2、tio2、sio2、b2o3、p2o5、nb2o5、v2o5、moo2、sno2、la2o3、sm2o3、eu2o3、er2o3、pr2o3、nd2o3、
tm2o3、ho2o3、ceo2、tb2o3、y2o3、gy2o3In at least one.
Described argentum powder is as the key component of silicon solar cell front side conductive silver paste, the key thing in conductive silver paste
Matter, its content, particle size distribution and pattern feature have a significant impact to the performance of conductive silver paste.Specifically, silicon solar cell
Its granule of the size distribution requirements of argentum powder described in front side conductive silver paste are unsuitable excessive, unsuitable narrow, the granule of particle size distribution range
The excessive easy network blocking in printing；Granule is too small, in preparation process, easily causes contraction excessive, thus shadow after sintering processes
Ring the performance of silicon solar cell.In view of this, the embodiment of the present invention selects micron/submicron argentum powder as silicon solar electricity
The argentum powder material of pond front side conductive silver paste.As the presently preferred embodiments, a diameter of 0.8-8.0 μ of described micron/submicron level argentum powder
M, the meso-position radius d50 of described micron/submicron level argentum powder is 1.5-5 μm；As further preferred embodiments, described micron/Asia
A diameter of 0.8-5.0 μm of micron order argentum powder, the meso-position radius d50 of described micron/submicron level argentum powder is 1.5-3 μm.Further
, the preferably spherical argentum powder of described micron/submicron level argentum powder.In the embodiment of the present invention, described micron/submicron level argentum powder
Weight percentage is 60%-90%, and as specific embodiment, the weight percentage of described micron/submicron level argentum powder can
For the concrete number such as 60%, 65%, 70%, 75%, 80%, 85%, 90%.
In order to improve the compactness after sintering, effectively improve pulling force simultaneously, reduce string resistance and improve photoelectric transformation efficiency, this
Rod-like nano silver wire and inorganic salt crystal complex is specifically with the addition of in inventive embodiments.
In the embodiment of the present invention, due to described teo2-bi2o3The adhesive force of-pbo frit is low, close silicon is poor, adds parent
After silicon composition and glass network enhancing thing, the problem that electrical property drastically declines occurs again, described silicon solar cell front is led
Described nano bar-shape silver wire is with the addition of in electric silver paste.As the presently preferred embodiments, the length of described rod-like nano silver wire is 0.8-
10.0 μm, diameter of section is 5-100nm.Silicon solar cell front side conductive silver paste provided in an embodiment of the present invention, by special
Property ground add described nano bar-shape silver wire, particularly length be 0.8-10.0 μm, diameter of section is in the described nanometer rods of 5-100nm
Shape silver wire, the fusion temperature of elongated described rod-like nano silver wire is compared with the fusion temperature of spheroidal particle micron/submicron level argentum powder
Low, therefore, in sintering process, it is multiple that described rod-like nano silver wire can form molten state with the frit effect of fusing quickly
Compound, the described rod-like nano silver wire in described molten state complex bends deformation, and is attached to spheroidal particle micron/Asia
Micro nanometer silver particle surface, improves the contact effect between described micron/submicron level argentum powder.Further, received due to described
The bar-shaped silver wire length of rice is larger, it not only can increase the contact point of the spherical silver powder closing on, and can also connect and mutually not close on
Spherical silver powder particles, thus significantly increasing the contact area between argentum powder, improve the contact effect between silver powder particles.Same with this
When, described nano bar-shape silver wire bends deformation in sintering process, has filled up the space between spherical silver powder particles, increased
Cell piece silver grating line compaction rate, reduces contact resistance, improves the output of cell piece.
In the embodiment of the present invention, the weight percentage of described nano bar-shape silver wire is 0.1%-10%, as concrete reality
Apply example, the weight percentage of described nano bar-shape silver wire powder can for 0.1%, 0.5%, 1.0%, 2%, 3%, 4%, 5%,
6%th, the concrete number such as 7%, 8%, 9%, 10%.
In silicon solar cell front side silver paste of the present invention, described inorganic salt compound crystal is as indispensable work(
Can component, play and improve that adhesive force is low, the effect of close silicon.Described inorganic salt compound crystal be containing two kinds or two kinds with
On inorganic oxide or can be decomposed into inorganic oxide inorganic salt formation compound crystal, be different from non crystalline structure
Described frit oxide, described inorganic salt compound crystal be crystal structure.
In silicon solar cell front side conductive silver paste of the present invention, because described frit is amorphous material, do not exist solid
Fixed fusing point；And inorganic salt compound crystal is crystalline solid, there is crystal structure, there is fixing fusing point.Therefore, with plus
Thermal process progressively melts, when the frit Hybrid Heating of dystectic inorganic salt compound crystal and low Tg, non-
The frit of crystal structure first starts to melt, and gradually coats described inorganic salt compound crystal particle surface.In melten glass material
In the liquid phase environment providing, inorganic salt composite, is reacted with inorganic salt compound crystal or ion exchange is so that frit
Structure tend to complicate.Meanwhile, when melten glass material promotes the fusing of inorganic salt compound crystal, inorganic salt composite
Crystal needs constantly to absorb heat from surrounding, and the temperature of fusing glass so can be controlled well drastically to raise.Therefore, this
Bright by adding specific inorganic salt compound crystal in silicon solar cell front side conductive silver paste, on the one hand make the silicon sun
Above-mentioned phase interaction in sintering process battery front side conductive silver paste can occur between frit and described inorganic salt compound crystal
With, to change frit melted after mobility and network structure complexity, change melten glass viscosity and heat swollen
Swollen coefficient, improves the affinity of frit and silicon chip, to improve the adhesive strength in silicon chip surface for the silver paste with this.On the other hand,
The addition of small described inorganic salt compound crystal, non-crystal frit melted during continuous and described inorganic salt multiple
Solvate crystal acts on, can be very good to suppress frit melted after silicon chip p-n saved damage, improve the open circuit of silicon solar cell
Voltage, short circuit current and transformation efficiency, finally increase its output.
As the presently preferred embodiments, the particle diameter of described inorganic salt compound crystal is 0.001-10 μm, further, described nothing
The particle diameter of machine salt composite crystal is preferably 0.01-5 μm.
As another preferred embodiment, described inorganic salt compound crystal is bi, al, zn, ru, pb, ca, mg, w, zr,
The oxide of ti, si, b, p, nb, v, mo, te, sn and its can decompose obtain described bi, al, zn, ru, pb, ca, mg, w,
The crystal complex of at least two formation in the inorganic salt of zr, ti, si, b, p, nb, v, mo, te, sn oxide.In other words
Say, inorganic salt compound crystal described in the embodiment of the present invention is bi2o3、al2o3、zno、ruo2、pbo、cao、mgo、wo3、zro2、
tio2、sio2、b2o3、p2o5、nb2o5、v2o5、moo2、teo2、sno2, and bi, al, zn, ru, pb, ca, mg, w, zr, ti,
Other oxides of si, b, p, nb, v, mo, te, sn and its can decompose obtain described bi, al, zn, ru, pb, ca,
At least two formation in the inorganic salt of the various oxides of mg, w, zr, ti, si, b, p, nb, v, mo, te, sn.
Further, described in the embodiment of the present invention, inorganic salt compound crystal is preferably pb1/3mg2/3nbo3、mgca
(sio3)2、camg(ruo3)2、pbwo4、zntio3、casio3、(ruo2)·(moo2)·(cao)2、bi4te3o12In at least one
Kind.Wherein, above-mentioned preferably each content of material follows mole metering proportion of the chemical formula forming inorganic salt compound crystal.When
So it will be appreciated that above-mentioned cited described inorganic salt compound crystal, only optimal way, it is used for absolutely not limiting the present invention
Whole embodiments.
In the embodiment of the present invention, the weight percentage of described inorganic salt compound crystal is 0.1%-10%, as tool
Body embodiment, the weight percentage of described inorganic salt compound crystal can for 0.1%, 0.5%, 1.0%, 2%, 3%, 4%,
5%th, the concrete number such as 6%, 7%, 8%, 9%, 10%.
In the embodiment of the present invention, the effect of described organic carrier is mainly the printing adjusting silver paste.As being preferable to carry out
Example, described organic carrier comprises organic solvent, thickening agent, plasticizer and auxiliary agent, with the gross weight of described organic carrier for 100%
Meter, the weight percentage of each component is as described below:
As a particular preferred embodiment, described organic solvent is terpineol, carbitol, tributyl citrate, phosphoric acid
Tributyl, lecithin, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, Ketohexamethylene, acetone, butyl card must
In alcohol, diethylene glycol ether, capryl alcohol, butyl carbitol acetate at least two.
As another particular preferred embodiment, described thickening agent is lanoline, in ethyl cellulose, phenolic resin extremely
Few one kind.
As another particular preferred embodiment, described plasticizer is dibutyl phthalate, phthalic acid two is pungent
At least one in ester.
As another specific embodiment, described auxiliary agent is hydrogenation Polyethylene Glycol, polyglyceryl fatty acid ester, in isooctanol
At least one.
Of course it is to be understood that above-mentioned specific embodiment can form new embodiment with two or more combinations.
In the embodiment of the present invention, the weight percentage of described organic carrier is 0.1%-10%, as specific embodiment,
The weight percentage of described organic carrier can be concrete for 5%, 6%, 8%, 10%, 12%, 15%, 16%, 18%, 20% etc.
Number.
Silicon solar cell front side conductive silver paste provided in an embodiment of the present invention, successfully improves teo2-bi2o3- pbo glass
The strength of glass of glass material and adhesive force, it is achieved that high efficiency, low resistance, high-tensile strength, Low dark curient on the premise of ensureing electrical property
The silicon solar cell front side conductive silver paste of stream, mainly passes through at following 2 points and realizes:
First, described silicon solar cell front side conductive silver paste specifically with the addition of described nano bar-shape silver wire, described
The length of nano bar-shape silver wire is 0.8-10.0 μm, and diameter of section is 5-100nm.Due to elongated described rod-like nano silver wire
Fusion temperature is low compared with the fusion temperature of spheroidal particle micron/submicron level argentum powder, therefore, in sintering process, described bar-shaped receives
Rice silver wire can form molten state complex, the described rod in described molten state complex with the frit effect of fusing quickly
Shape nano-silver thread bends deformation, and is attached to spheroidal particle micron/submicron level Argent grain surface, improve described micron/
Contact effect between submicron silver powder.Further, because described nano bar-shape silver wire length is larger, it not only can increase
Plus the contact point of the spherical silver powder closing on, the spherical silver powder particles mutually not closed on can also be connected, thus significantly increasing argentum powder
Between contact area, improve the contact effect between silver powder particles.Meanwhile, nano bar-shape silver wire occurs in sintering process
Bending Deformation, has filled up the space between spherical silver powder particles, increased cell piece silver grating line compaction rate, reduces contact electricity
Resistance, improves the output of cell piece.
Secondly, in silicon solar cell front side conductive silver paste of the present invention, with the addition of specific inorganic salt compound crystal.By
In silicon solar cell front side conductive silver paste of the present invention, described frit amorphous material, there is not fixing fusing point；And no
Machine salt composite crystal is crystalline solid, has crystal structure, there is fixing fusing point.Therefore, heat tracing process progressively melts
Change, when the frit Hybrid Heating of dystectic inorganic salt compound crystal and low Tg, the glass of non crystalline structure
Material first starts to melt, and gradually coats described inorganic salt compound crystal particle surface.The liquid phase ring providing in melten glass material
In border, inorganic salt composite, is reacted with inorganic salt compound crystal or ion exchange is so that the structure of frit tends to multiple
Hydridization.Meanwhile, when melten glass material promotes the fusing of inorganic salt compound crystal, inorganic salt compound crystal needs constantly
From surrounding heat absorption, the temperature of fusing glass so can be controlled well drastically to raise.Therefore, the present invention passes through in silicon too
Sun can add specific inorganic salt compound crystal in battery front side conductive silver paste, so that silicon solar cell front is led
There is above-mentioned interaction between frit and described inorganic salt compound crystal in electric silver paste in sintering process, to change glass
Mobility after material fusing and the complexity of network structure, change viscosity and the thermal coefficient of expansion of melten glass, improve glass
Glass material and the affinity of silicon chip, to improve the adhesive strength in silicon chip surface for the silver paste with this.On the other hand, small described inorganic
The addition of salt composite crystal, non-crystal frit melted during the effect of continuous and described inorganic salt compound crystal,
Can be very good to suppress frit melted after silicon chip p-n saved damage, improve open-circuit voltage, the short circuit current of silicon solar cell
And transformation efficiency, finally increase its output.
Described in the embodiment of the present invention, silicon solar cell front side conductive silver paste can be prepared by following methods, when
So it is also possible to be prepared by additive method.
Correspondingly, also a kind of preparation method of silicon solar cell front side conductive silver paste of the embodiment of the present invention, including following
Step:
S01. prepare inorganic salt compound crystal: take two or more inorganic oxide or described nothing can be resolved into
The inorganic salt of machine oxide, carry out successively mixing, heat treatment, pulverize, process of sieving, obtain inorganic salt compound crystal；
S02. prepare modified teo2-bi2o3- pbo frit: frit oxide and property-modifying additive are mixed successively
Conjunction, melting, cold quenching, pulverize, process of sieving, make modified teo2-bi2o3- pbo frit；
S03. prepare organic carrier: by organic solvent, thickening agent, plasticizer, auxiliary agent through mixed processing, preparation has airborne
Body；
S04. prepare silicon solar cell front side conductive silver paste: claim by the formula of above-mentioned solar battery front side conductive silver paste
Take described micron/submicron level argentum powder, rod-like nano silver wire, modified teo2-bi2o3- pbo frit, inorganic salt compound crystal
And organic carrier, each component is carried out mixed processing, obtains silicon solar cell front side conductive silver paste.
Specifically, in above-mentioned steps s01, as the presently preferred embodiments, described inorganic oxide be bi, al, zn, ru, pb,
The oxide of ca, mg, w, zr, ti, si, b, p, nb, v, mo, te, sn, specifically, including bi2o3、al2o3、zno、ruo2、pbo、
cao、mgo、wo3、zro2、tio2、sio2、b2o3、p2o5、nb2o5、v2o5、moo2、teo2、sno2, also include bi, al, zn, ru,
The oxide of other valence states of pb, ca, mg, w, zr, ti, si, b, p, nb, v, mo, te, sn.In the embodiment of the present invention, can decompose
Become the inorganic salt of above-mentioned inorganic oxide, after Overheating Treatment, decompose obtain bi, al, zn, ru, pb, ca, mg, w, zr, ti,
The oxide of si, b, p, nb, v, mo, te, sn.As the presently preferred embodiments, described heat treatment temperature is preferably 500-1800 DEG C, heat
Process time is preferably 60-600min.As another preferred embodiment, the particle diameter of described inorganic salt compound crystal is
0.001-10 μm, more preferably 0.01-5 μm.
In above-mentioned steps s02, described frit oxide as prepares described modification teo2-bi2o3The oxygen of-pbo frit
Compound, including teo2、bi2o3, pbo and property-modifying additive.In order to obtain physical property and become be grouped into concordance good described in change
Property teo2-bi2o3- pbo frit, as the presently preferred embodiments, the temperature of described melt process is 400-1500 DEG C, temperature retention time
For 30-300 minute, concretely 60 minutes, 120 minutes, 180 minutes, 240 minutes, 300 minutes etc..
In above-mentioned steps s03, the preparation method of described organic carrier can adopt the conventional preparation side of this area organic carrier
Method, as the presently preferred embodiments, the detailed process preparing described organic carrier can be: weigh organic solvent by recipe ingredient and be placed in glass
In glass container, using oil bath in 100 DEG C of heated at constant temperature glass containers, then sequentially add the thickening plasticising of the ratio of recipe requirements
Agent or plasticizer and thickening agent, auxiliary agent, using the stirring mix homogeneously successively of homogenizer, are eventually adding auxiliary agent and eliminate inside
Bubble, makes carrier each composition mix homogeneously and bubble-free.
In above-mentioned steps s04, as described in any of the above-described embodiment, the formula of solar battery front side conductive silver paste weighs institute
State micron/submicron level argentum powder, rod-like nano silver wire, modified teo2-bi2o3- pbo frit, inorganic salt compound crystal and
Organic carrier, each component preferred content in the formula of described solar battery front side conductive silver paste and formula and species are as above
Literary composition is described, in order to save length, will not be described here.
A kind of preparation method of silicon solar cell front side conductive silver paste provided in an embodiment of the present invention, preparation method letter
Single, operation is controlled, it is easy to accomplish industrialization.The silicon solar cell front side conductive silver paste adhesive force preparing and close silicon
Good, there is high efficiency, low resistance, high-tensile strength, low-leakage current simultaneously
Illustrate with reference to specific embodiment.
Embodiment 1-6
A kind of silicon solar cell front side conductive silver paste, including argentum powder, modified teo2-bi2o3- pbo frit, inorganic salt
Compound crystal, multi-solvent organic carrier and rod-like nano silver wire, wherein, described argentum powder is micron/submicron argentum powder, with silicon too
The gross weight of sun energy battery front side conductive silver paste is 100% meter, and each component weight percentage is respectively as table 1 below embodiment 1-6
Described.
A kind of preparation method of silicon solar cell front side conductive silver paste, comprises the steps:
Prepare inorganic salt compound crystal: weigh raw material bi2o393.2g、teo232.3g, is mixed and is uniformly placed in
In Muffle furnace 630 DEG C insulation 2 hours after be cooled to room temperature take out, then pulverize obtain the powder that particle diameter is at 0.01-5 μm, that is,
For bi4te3o12Tiny crystals powder；Weigh raw material zno 40.5g, tio again239.94g, is mixed and is uniformly placed in Muffle furnace
In 1100 DEG C insulation 4 hours after be cooled to room temperature take out, then ball milling obtains the powder that particle diameter is at 0.01-5 μm, as
zntio3Tiny crystals powder；Weigh raw material pbo44.6g, mgo16.0g, nb2o526.6, it is mixed and be uniformly placed in Muffle
In stove 800 DEG C insulation 4 hours after be cooled to room temperature take out, then pulverize obtain the powder that particle diameter is at 0.01-5 μm, as
pb1/3mg2/3nbo3Tiny crystals powder；Equally, prepare mgca (sio3)2、camg(ruo3)2、pbwo4、(zntio3)·
(casio3)、(ruo2)·(moo2)·(nb2o5)2Tiny crystals powder.
The modified teo of preparation2-bi2o3- pbo frit: by rare earth modified lead-less glasses material raw material teo243g、bi2o316g、
Pbo 37g, rare earth oxide cao 0.5g, zro20.5g、la2o32g、sio2Crucible is loaded after 1g, mix homogeneously
In, by crucible as being heated to 400-1500 DEG C in Muffle furnace, temperature retention time is 30-300 minute, particularly, can be heated to
1050 DEG C and be incubated 30 minutes, treat that Muffle furnace runs and stop, taking out high temperature molten glass and carry out cold quenching and obtain thick level frit, will
After thick level frit is pulverized, then sieved with 600 eye mesh screens, obtain required frit.
Prepare organic carrier: take terpineol 100g, carbitol 100g, butyl carbitol acetate 80g to add glass container
In, using water-bath in 80 DEG C of heated at constant temperature glass containers, sequentially add ethyl cellulose 50g, O-phthalic in organic solvent
Dioctyl phthalate 40g, dioctyl phthalate 10g, hydrogenation Polyethylene Glycol 10g, after fatty acid glyceride 5g, using high-speed stirred
Machine stirs respectively, and homogeneous organic carrier 400g is obtained.
Prepare silicon solar cell front side conductive silver paste: by the described organic carrier preparing, argentum powder, frit, crystal
Complex additive, described according to the form below embodiment 1-6, the formula of silicon solar cell front side conductive silver paste weighs simultaneously successively respectively
It is added in suitable container, is stirred using homogenizer afterwards, reuse three-roll mill and mill 30 minutes, obtain thin
Below 15 μm, viscosity uses silk screen printing in the silicon solar cell silver paste of 250-350pa s, the silver paste preparing to degree
Mode is printed on polysilicon or the monocrystalline silicon substrate of 156mm × 156mm, and is sintered into silicon solar cell at 900 DEG C
Piece.
The described silicon solar cell front side conductive silver paste of above-described embodiment 1-6 preparation is carried out open-circuit voltage, short circuit electricity
Stream, conversion efficiency, string resistance size, average tension big Small Indicators performance test, test result see table 2, the survey of its indices
Method for testing is this area conventional method.
Table 1
Table 2
From table 2, silicon solar cell front side conductive silver paste provided in an embodiment of the present invention, improve teo2-bi2o3-
The strength of glass of pbo frit and adhesive force, and then obtained the silicon solar of high efficiency, low resistance, high-tensile strength, low-leakage current
Battery front side conductive silver paste.
In the embodiment of the present invention, especially it is emphasised that it will be appreciated that in described silicon solar cell front side conductive silver paste
Inorganic salt compound crystal, contains the oxygen of bi, al, zn, ru, pb, ca, mg, w, zr, ti, si, b, p, nb, v, mo, te, sn
Compound and its can decompose and obtain described bi, al, zn, ru, pb, ca, mg, w, zr, ti, si, b, p, nb, v, mo, te, sn oxygen
The form of ownership of the crystal complex of at least two formation in the inorganic salt of compound.Due to enumerating impossible limit, the present invention
List several forms, only optimal way in specific embodiment 1-6, be in no way intended to limit whole embodiment party of the present invention
Formula.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of silicon solar cell front side conductive silver paste, including argentum powder, frit and organic carrier it is characterised in that also wrapping
Include rod-like nano silver wire, inorganic salt compound crystal, wherein, described frit is modified teo2-bi2o3- pbo frit, described
Argentum powder is micron/submicron argentum powder, is counted with the gross weight of described silicon solar cell front side conductive silver paste for 100%, each component
Weight percentage is as described below:
Wherein, described modification teo2-bi2o3- pbo frit is by teo2、bi2o3, pbo and property-modifying additive composition, changed with described
Property teo2-bi2o3The gross weight of-pbo frit is 100% meter, and the weight percentage of each component is as described below:
And described property-modifying additive is al2o3、zno、ruo2、cao、mgo、wo3、zro2、tio2、sio2、b2o3、p2o5、nb2o5、
v2o5、moo2、sno2、la2o3、sm2o3、eu2o3、er2o3、pr2o3、nd2o3、tm2o3、ho2o3、ceo2、tb2o3、y2o3、gy2o3In
At least one.
2. silicon solar cell front side conductive silver paste as claimed in claim 1 is it is characterised in that described rod-like nano silver wire
Length is 0.8-10.0 μm, and diameter of section is 5-100nm.
3. silicon solar cell front side conductive silver paste as claimed in claim 1 is it is characterised in that described inorganic salt composite is brilliant
Body is the oxide of bi, al, zn, ru, pb, ca, mg, w, zr, ti, si, b, p, nb, v, mo, te, sn and its can decompose
To in the inorganic salt of described bi, al, zn, ru, pb, ca, mg, w, zr, ti, si, b, p, nb, v, mo, te, sn oxide at least
The crystal complex of two kinds of formation.
4. described silicon solar cell front side conductive silver paste as arbitrary in claim 1-3 is it is characterised in that described inorganic salt is multiple
The particle diameter of solvate crystal is 0.001-10 μm.
5. described silicon solar cell front side conductive silver paste as arbitrary in claim 1-3 it is characterised in that described modification teo2-
bi2o3The particle diameter of-pbo frit is 1-20 μm, and meso-position radius d50 is 1-10.0 μm.
6. described silicon solar cell front side conductive silver paste as arbitrary in claim 1-3 is it is characterised in that described micron/Asia
Micron order argentum powder is spherical argentum powder, a diameter of 0.8-8.0 μm of described micron/submicron level argentum powder, and meso-position radius d50 is 1.5-
5.0μm.
7. described silicon solar cell front side conductive silver paste as arbitrary in claim 1-3 is it is characterised in that described organic carrier
Comprise organic solvent, thickening agent, plasticizer and auxiliary agent, counted for 100% with the gross weight of described organic carrier, the weight of each component
Percentage composition is as described below:
8. silicon solar cell front side conductive silver paste as claimed in claim 7 is it is characterised in that described organic solvent is Oleum Pini
Alcohol, carbitol, tributyl citrate, tributyl phosphate, lecithin, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol list
In butyl ether, Ketohexamethylene, acetone, butyl carbitol, diethylene glycol ether, capryl alcohol, butyl carbitol acetate at least two；
And/or
Described thickening agent is lanoline, ethyl cellulose, at least one in phenolic resin；And/or
Described plasticizer is dibutyl phthalate, at least one in dioctyl phthalate；And/or
Described auxiliary agent is hydrogenation Polyethylene Glycol, polyglyceryl fatty acid ester, at least one in isooctanol.
9. a kind of preparation method of silicon solar cell front side conductive silver paste, comprises the steps:
Prepare inorganic salt compound crystal: take two or more inorganic oxide or described inorganic oxide can be resolved into
Inorganic salt, carry out successively mixing, heat treatment, pulverize, process of sieving, obtain inorganic salt compound crystal；
The modified teo of preparation2-bi2o3- pbo frit: frit oxide and property-modifying additive are carried out successively mixing, melt,
Cold quenching, pulverize, process of sieving, make modified teo2-bi2o3- pbo frit；
Prepare organic carrier: by organic solvent, thickening agent, plasticizer, auxiliary agent through mixed processing, prepare organic carrier；
Prepare silicon solar cell front side conductive silver paste: conductive by the arbitrary described solar battery front side of the claims 1-8
The formula of silver paste weighs described micron/submicron level argentum powder, rod-like nano silver wire, modified teo2-bi2o3- pbo frit, inorganic
Salt composite crystal and organic carrier, each component is carried out mixed processing, obtains silicon solar cell front side conductive silver paste.
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| CN106251929A (en) * | 2016-08-10 | 2016-12-21 | 中国科学院电工研究所 | Copper slurry for crystal silicon solar battery front side conductive layer electrode and preparation method thereof |
| CN108666008A (en) * | 2017-03-27 | 2018-10-16 | 苏州晶银新材料股份有限公司 | Electrocondution slurry for solar cell |
| CN106898412A (en) * | 2017-04-14 | 2017-06-27 | 北京市合众创能光电技术有限公司 | A kind of positive silver paste of crystal silicon solar energy battery containing microcrystalline glass powder |
| CN106935311A (en) * | 2017-04-14 | 2017-07-07 | 北京市合众创能光电技术有限公司 | A kind of photovoltaic conductive ink of sintering temperature and low |
| CN107274963B (en) * | 2017-05-31 | 2019-05-24 | 深圳磐汩新能源有限公司 | Silicon solar cell front side conductive silver paste and preparation method thereof |
| CN108198648A (en) * | 2017-12-27 | 2018-06-22 | 乐凯胶片股份有限公司 | A kind of back of the body passivation rear surface of solar cell silver paste |
| CN109215836B (en) * | 2018-09-30 | 2021-03-16 | 江苏正能电子科技有限公司 | Thermal-aging-resistant back silver paste for crystalline silicon solar cell and preparation method thereof |
| CN110174412B (en) * | 2019-05-21 | 2021-04-27 | 常州聚和新材料股份有限公司 | Method for testing corrosion depth of glass in silver paste on surface of silicon wafer |
| CN112592068B (en) * | 2020-12-15 | 2022-11-15 | 广州市儒兴科技股份有限公司 | Glass powder, preparation method thereof and application of glass powder in TOPCon battery |
| CN113257453A (en) * | 2021-04-15 | 2021-08-13 | 中国科学院山西煤炭化学研究所 | Phosphorus-containing organic carrier PERC solar front silver paste and preparation method thereof |
| CN114012308B (en) * | 2021-11-05 | 2023-04-25 | 南京恩瑞科技有限公司 | Low-temperature lead-free vacuum solder and preparation method thereof |
| CN114702240B (en) * | 2022-04-15 | 2023-12-22 | 北京大学深圳研究生院 | Glass composition and preparation method and application thereof |
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| CN102262914B (en) * | 2010-05-31 | 2014-04-02 | 比亚迪股份有限公司 | Conductive silver paste and preparation method thereof as well as solar cell slice |
| KR101193286B1 (en) * | 2010-09-01 | 2012-10-19 | 삼성전기주식회사 | Electroconductive paste, fabricating method the same and electrode using the same |
| CN102139368B (en) * | 2011-03-18 | 2013-01-02 | 中科院广州化学有限公司 | High-dispersion silver powder and solar battery electrode conductive silver paste |
| CN103545016B (en) * | 2013-10-21 | 2016-06-29 | 深圳市首骋新材料科技有限公司 | Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof |
| CN104157332A (en) * | 2014-08-29 | 2014-11-19 | 天津市职业大学 | Silicon solar cell front face electrode lead-free silver paste and preparing method thereof |
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