CN105097071A - 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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- CN105097071A CN105097071A CN201510434451.0A CN201510434451A CN105097071A CN 105097071 A CN105097071 A CN 105097071A CN 201510434451 A CN201510434451 A CN 201510434451A CN 105097071 A CN105097071 A CN 105097071A
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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, particularly relate to silicon solar cell front side conductive silver slurry and preparation method thereof.
Background technology
Solar cell is a kind of semiconductor device solar energy being changed into electric energy, its operation principle is the photovoltaic effect of semiconductor PN, namely under the condition of extraneous illumination, solar battery sheet produces volta effect, by conductive materials and the external connecting leads of battery surface, forming electric current when connecting, using with electricity supply and use equipment or being stored by charge storage device.In solar cell, electronics to be produced to photovoltaic effect in cell piece and be used, electrode must be used to be derived by electronics.
At present, the most ripe on market solar cell is silicon solar cell.The electrode of silicon solar energy battery surface mainly contains back silver electrode and front silver electrode, and these electrodes usually adopt the mode of silk screen printing to be printed on silicon chip surface by conductive silver paste and formed.Can say, conductive silver paste is the electrode material that current silicon solar cell mainly uses.
Silicon solar cell front side conductive silver slurry is primarily of silver powder, frit, organic carrier composition, the performance quality of each component determines the overall performance of described silicon solar cell front side conductive silver slurry, and then affect the overall performance of silicon solar cell, as important indicators such as short circuit current, series resistance, photoelectric conversion efficiency, weld strengths.Wherein, to the overall performance of silicon solar cell, the frit of composition front side conductive silver slurry during the component had the greatest impact as short circuit current, series resistance, photoelectric conversion efficiency, weld strength etc.Use contains tellurium glass-frit more at present, but owing to using frit to there is very large difference containing tellurium frit and tradition, compare traditional glass material, there is and forms glass after network configuration comparatively simple question poor with silicon chip compatibility containing tellurium frit, therefore easily occur peeling off with silicon chip and the problem of pulling force poor adhesive force with silver-colored slurry of the front side conductive made containing tellurium frit.After adding a large amount of close silicon compositions and glass network reinforce, occur that again electrical property sharply descends degradation problem.Containing the problems referred to above that tellurium frit exists, seriously constrain the performance containing the silicon solar cell of tellurium frit in front side conductive silver slurry.
Summary of the invention
The object of the present invention is to provide the silicon solar cell front side conductive silver slurry that a kind of photoelectric conversion efficiency is high, welding pulling force is large, under being intended to the prerequisite of guarantee silicon solar cell front side conductive silver slurry electrical property, solving containing tellurium frit, particularly contain TeO
2-Bi
2o
3the problem of low, the close silicon difference of silicon solar cell front side conductive silver slurry frit adhesive force of-PbO frit, thus improve containing TeO
2-Bi
2o
3short circuit current, open circuit voltage, the conversion efficiency of the silicon solar cell front side conductive silver slurry of-PbO frit, the string resistance that reduction silicon solar cell front side conductive silver is starched.
Another object of the present invention is to the preparation method that a kind of silicon solar cell front side conductive silver slurry is provided.
The present invention is achieved in that a kind of silicon solar cell front side conductive silver slurry, comprises silver powder, frit and organic carrier, and also comprise rod-like nano silver line, inorganic salts compound crystal, wherein, described frit is modification TeO
2-Bi
2o
3-PbO frit, described silver powder is micron/submicron silver powder, and in the total weight of described silicon solar cell front side conductive silver slurry for 100%, each composition weight percentage composition is as described below:
And a kind of preparation method of silicon solar cell front side conductive silver slurry, comprises the steps:
Prepare inorganic salts compound crystal: the inorganic oxide getting two or more maybe can resolve into the inorganic salts of described inorganic oxide, carry out successively mixing, heat treatment, pulverize, process of sieving, obtain inorganic salts compound crystal;
Preparation modification TeO
2-Bi
2o
3-PbO frit: frit oxide and property-modifying additive are carried out successively mix, melting, cold quenching, pulverize, process of sieving, make modification TeO
2-Bi
2o
3-PbO frit;
Prepare organic carrier: by organic solvent, thickener, plasticizer, auxiliary agent through mixed processing, prepare organic carrier;
Prepare silicon solar cell front side conductive silver slurry: take described micron/submicron level silver powder, rod-like nano silver line, modification TeO by the formula of above-mentioned solar battery front side conductive silver paste
2-Bi
2o
3-PbO frit, inorganic salts compound crystal and organic carrier, carry out mixed processing by each component, obtains silicon solar cell front side conductive silver slurry.
Silicon solar cell front side conductive silver slurry provided by the invention, first, with the addition of described nano bar-shape silver line specifically, because the fusion temperature of elongated described rod-like nano silver line is low compared with the fusion temperature of spheric granules micron/submicron level silver powder, therefore, in sintering process, described rod-like nano silver line can form molten state compound with the frit effect of fusing quickly, described rod-like nano silver line in described molten state compound bends deformation, and be attached to spheric granules micron/submicron level Argent grain surface, improve the contact effect between described micron/submicron level silver powder.Further, because described nano bar-shape silver line length is comparatively large, it not only can increase the contact point of the spherical silver powder closed on, and can also connect the spherical silver powder particles do not closed on mutually, thus the contact area significantly increased between silver powder, improve the contact effect between silver powder particles.Meanwhile, nano bar-shape silver line bends deformation in sintering process, has filled up the space between spherical silver powder particles, has added cell piece silver grating line compaction rate, reduce contact resistance, improve the power output of cell piece.
Secondly, in silicon solar cell front side conductive silver slurry of the present invention, with the addition of specific inorganic salts compound crystal.Due in silicon solar cell front side conductive silver slurry of the present invention, there is not fixing fusing point in described frit amorphous material; And inorganic salts compound crystal is crystalline solid, there is crystal structure, there is fixing fusing point.Therefore, heat tracing process progressively melts, and when the frit Hybrid Heating of dystectic inorganic salts compound crystal and low Tg, the frit of non crystalline structure first starts fusing, and coated described inorganic salts compound crystal particle surface gradually.In the liquid phase environment that melten glass material provides, inorganic salts compound, reacts or ion-exchange with inorganic salts compound crystal, makes the structure of frit tend to complicated.Meanwhile, when melten glass material impels inorganic salts compound crystal to melt, inorganic salts compound crystal needs constantly from surrounding environment heat absorption, can the temperature of controlled melting glass well sharply raise like this.Therefore, the present invention by adding specific inorganic salts compound crystal in silicon solar cell front side conductive silver slurry, silicon solar cell front side conductive silver slurry is made between frit and described inorganic salts compound crystal, above-mentioned interaction to occur on the one hand in sintering process, change frit melted after mobility and the complexity of network configuration, change viscosity and the thermal coefficient of expansion of melten glass, improve the compatibility of frit and silicon chip, improve the adhesive strength of silver slurry at silicon chip surface with this.On the other hand, adding of small described inorganic salts compound crystal, continuous and described inorganic salts compound crystal effect in non-crystal frit melted process, frit melted rear saving silicon chip P-N can well be suppressed to damage, improve the open circuit voltage of silicon solar cell, short circuit current and transformation efficiency, final its power output of increase.
Silicon solar cell front side conductive silver slurry provided by the invention, successfully improves TeO
2-Bi
2o
3the strength of glass of-PbO frit and adhesive force, under the prerequisite ensureing electrical property, achieve the silicon solar cell front side conductive silver slurry of high efficiency, low resistance, high-tensile strength, low-leakage current.
The preparation method of a kind of silicon solar cell front side conductive silver slurry provided by the invention, preparation method is simple, operates controlled, is easy to realize industrialization.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiments provide a kind of silicon solar cell front side conductive silver slurry, comprise silver powder, frit and organic carrier, also comprise rod-like nano silver line, inorganic salts compound crystal, wherein, described frit is modification TeO
2-Bi
2o
3-PbO frit, described silver powder is micron/submicron silver powder, and in the total weight of described silicon solar cell front side conductive silver slurry for 100%, each composition weight percentage composition 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 TeO
2-Bi
2o
3-PbO, as the main body system of frit, adds property-modifying additive on this basis, thus obtains modification TeO
2-Bi
2o
3-PbO frit.In the embodiment of the present invention, described modification TeO
2-Bi
2o
3the weight percentage of-PbO frit is 0.1%-10%, as specific embodiment, and described modification TeO
2-Bi
2o
3the weight percentage of-PbO frit can be the concrete number such as 0.1%, 0.5%, 1.0%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
Concrete, described modification TeO
2-Bi
2o
3-PbO frit is included as TeO
2, Bi
2o
3, PbO and property-modifying additive, with described modification TeO
2-Bi
2o
3the total weight of-PbO frit is 100%, described in the weight percentage of each component is preferably as follows:
Further, as preferred embodiment, described modification TeO
2-Bi
2o
3the particle diameter of-PbO frit is 1-20 μm, and meso-position radius D50 is 1-10 μm; As further preferred embodiment, described modification TeO
2-Bi
2o
3the particle diameter of-PbO frit is 1-10 μm, and meso-position radius D50 is 1-5 μm.As specific embodiment, described property-modifying additive is preferably Al
2o
3, ZnO, RuO
2, CaO, MgO, WO
3, ZrO
2, TiO
2, SiO
2, B
2o
3, P
2o
5, Nb
2o
5, V
2o
5, MoO
2, SnO
2, La
2o
3, Sm
2o
3, Eu
2o
3, Er
2o
3, Pr
2o
3, Nd
2o
3, Tm
2o
3, Ho
2o
3, CeO
2, Tb
2o
3, Y
2o
3, Gy
2o
3in at least one.
Described silver powder is as the key component of silicon solar cell front side conductive silver slurry, and the critical substances in conductive silver paste, its content, particle size distribution and the performance of pattern feature to conductive silver paste have a significant impact.Concrete, described in silicon solar cell front side conductive silver slurry, its particle of size distribution requirements of silver powder is unsuitable excessive, and particle size distribution range is unsuitable narrow, the excessive easy network blocking when printing of particle; Particle is too small, in preparation process, easily causes contraction excessive, thus affect the performance of silicon solar cell after sintering processes.In view of this, the embodiment of the present invention selects micron/submicron silver powder as the silver powder material of silicon solar cell front side conductive silver slurry.As preferred embodiment, the diameter of described micron/submicron level silver powder is 0.8-8.0 μm, and the meso-position radius D50 of described micron/submicron level silver powder is 1.5-5 μm; As further preferred embodiment, the diameter of described micron/submicron level silver powder is 0.8-5.0 μm, and the meso-position radius D50 of described micron/submicron level silver powder is 1.5-3 μm.Further, described micron/submicron level silver powder is preferably ball shape silver powder.In the embodiment of the present invention, the weight percentage of described micron/submicron level silver powder is 60%-90%, as specific embodiment, the weight percentage of described micron/submicron level silver powder can be the concrete number such as 60%, 65%, 70%, 75%, 80%, 85%, 90%.
In order to improve the compactness after sintering, effectively improving pulling force simultaneously, reduce string resistance and improve photoelectric conversion efficiency, in the embodiment of the present invention, with the addition of rod-like nano silver line and inorganic salts crystal complex specifically.
In the embodiment of the present invention, due to described TeO
2-Bi
2o
3low, the close silicon of the adhesive force of-PbO frit is poor, after adding close silicon composition and glass network reinforce, occurs again the problem that electrical property sharply declines, and with the addition of described nano bar-shape silver line in described silicon solar cell front side conductive silver slurry.As preferred embodiment, the length of described rod-like nano silver line is 0.8-10.0 μm, and diameter of section is 5-100nm.The silicon solar cell front side conductive silver slurry that the embodiment of the present invention provides, by adding described nano bar-shape silver line specifically, particularly length is 0.8-10.0 μm, diameter of section is at the described nano bar-shape silver line of 5-100nm, the fusion temperature of elongated described rod-like nano silver line is low compared with the fusion temperature of spheric granules micron/submicron level silver powder, therefore, in sintering process, described rod-like nano silver line can form molten state compound with the frit effect of fusing quickly, described rod-like nano silver line in described molten state compound bends deformation, and be attached to spheric granules micron/submicron level Argent grain surface, improve the contact effect between described micron/submicron level silver powder.Further, because described nano bar-shape silver line length is comparatively large, it not only can increase the contact point of the spherical silver powder closed on, and can also connect the spherical silver powder particles do not closed on mutually, thus the contact area significantly increased between silver powder, improve the contact effect between silver powder particles.Meanwhile, described nano bar-shape silver line bends deformation in sintering process, has filled up the space between spherical silver powder particles, has added cell piece silver grating line compaction rate, reduce contact resistance, improve the power output of cell piece.
In the embodiment of the present invention, the weight percentage of described nano bar-shape silver line is 0.1%-10%, as specific embodiment, the weight percentage of described nano bar-shape silver line powder can be the concrete number such as 0.1%, 0.5%, 1.0%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
In silicon solar cell front side silver paste of the present invention, described inorganic salts compound crystal, as indispensable function ingredients, plays the effect improving adhesive force low, close silicon.Described inorganic salts compound crystal be containing two or more inorganic oxide, maybe can be decomposed into inorganic oxide inorganic salts formed compound crystal, be different from the described frit oxide of non crystalline structure, described inorganic salts compound crystal is crystal structure.
In silicon solar cell front side conductive silver slurry of the present invention, because described frit is amorphous material, there is not fixing fusing point; And inorganic salts compound crystal is crystalline solid, there is crystal structure, there is fixing fusing point.Therefore, heat tracing process progressively melts, and when the frit Hybrid Heating of dystectic inorganic salts compound crystal and low Tg, the frit of non crystalline structure first starts fusing, and coated described inorganic salts compound crystal particle surface gradually.In the liquid phase environment that melten glass material provides, inorganic salts compound, reacts or ion-exchange with inorganic salts compound crystal, makes the structure of frit tend to complicated.Meanwhile, when melten glass material impels inorganic salts compound crystal to melt, inorganic salts compound crystal needs constantly from surrounding environment heat absorption, can the temperature of controlled melting glass well sharply raise like this.Therefore, the present invention by adding specific inorganic salts compound crystal in silicon solar cell front side conductive silver slurry, silicon solar cell front side conductive silver slurry is made between frit and described inorganic salts compound crystal, above-mentioned interaction to occur on the one hand in sintering process, change frit melted after mobility and the complexity of network configuration, change viscosity and the thermal coefficient of expansion of melten glass, improve the compatibility of frit and silicon chip, improve the adhesive strength of silver slurry at silicon chip surface with this.On the other hand, adding of small described inorganic salts compound crystal, continuous and described inorganic salts compound crystal effect in non-crystal frit melted process, frit melted rear saving silicon chip P-N can well be suppressed to damage, improve the open circuit voltage of silicon solar cell, short circuit current and transformation efficiency, final its power output of increase.
As preferred embodiment, the particle diameter of described inorganic salts compound crystal is 0.001-10 μm, and further, the particle diameter of described inorganic salts compound crystal is preferably 0.01-5 μm.
As another preferred embodiment, described inorganic salts compound crystal be Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn oxide and can decompose obtain described Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn oxide inorganic salts at least two kinds formed crystal complexes.In other words, inorganic salts compound crystal described in the embodiment of the present invention is Bi
2o
3, Al
2o
3, ZnO, RuO
2, PbO, CaO, MgO, WO
3, ZrO
2, TiO
2, SiO
2, B
2o
3, P
2o
5, Nb
2o
5, V
2o
5, MoO
2, TeO
2, SnO
2, and Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn other oxides and can decompose obtain the various oxides of described Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn inorganic salts at least two kinds of formation.
Further, described in the embodiment of the present invention, inorganic salts compound crystal is preferably Pb
1/3mg
2/3nbO
3, MgCa (SiO
3)
2, CaMg (RuO
3)
2, PbWO
4, ZnTiO
3, CaSiO
3, (RuO
2) (MoO
2) (CaO)
2, Bi
4te
3o
12in at least one.Wherein, above-mentioned preferred each content of material follows mole metering proportion of the chemical formula forming inorganic salts compound crystal.Of course it is to be understood that above-mentioned cited described inorganic salts compound crystal, being only optimal way, absolutely not for limiting whole execution mode of the present invention.
In the embodiment of the present invention, the weight percentage of described inorganic salts compound crystal is 0.1%-10%, as specific embodiment, the weight percentage of described inorganic salts compound crystal can be the concrete number such as 0.1%, 0.5%, 1.0%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
In the embodiment of the present invention, the effect of described organic carrier mainly regulates the printing of silver slurry.As preferred embodiment, described organic carrier comprises organic solvent, thickener, plasticizer and auxiliary agent, and in the total weight of described organic carrier for 100%, the weight percentage of each component is as described below:
As a concrete preferred embodiment, described organic solvent is at least two kinds in terpinol, carbitol, tributyl citrate, tributyl phosphate, lecithin, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, cyclohexanone, acetone, butyl carbitol, diethylene glycol ether, octanol, butyl carbitol acetate.
As another concrete preferred embodiment, described thickener is at least one in lanolin, ethyl cellulose, phenolic resins.
As another concrete preferred embodiment, described plasticizer is at least one in dibutyl phthalate, dioctyl phthalate.
As another specific embodiment, described auxiliary agent is at least one in hydrogenation polyethylene glycol, polyglyceryl fatty acid ester, isooctanol.
Of course it is to be understood that above-mentioned specific embodiment can two or more combine, form new embodiment.
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 the concrete number such as 5%, 6%, 8%, 10%, 12%, 15%, 16%, 18%, 20%.
The silicon solar cell front side conductive silver slurry that the embodiment of the present invention provides, successfully improves TeO
2-Bi
2o
3the strength of glass of-PbO frit and adhesive force, under the prerequisite ensureing electrical property, achieve the silicon solar cell front side conductive silver slurry of high efficiency, low resistance, high-tensile strength, low-leakage current, mainly through following 2 realizations:
First, described silicon solar cell front side conductive silver slurry with the addition of described nano bar-shape silver line specifically, and the length of described nano bar-shape silver line is 0.8-10.0 μm, and diameter of section is 5-100nm.Because the fusion temperature of elongated described rod-like nano silver line is low compared with the fusion temperature of spheric granules micron/submicron level silver powder, therefore, in sintering process, described rod-like nano silver line can form molten state compound with the frit effect of fusing quickly, described rod-like nano silver line in described molten state compound bends deformation, and be attached to spheric granules micron/submicron level Argent grain surface, improve the contact effect between described micron/submicron level silver powder.Further, because described nano bar-shape silver line length is comparatively large, it not only can increase the contact point of the spherical silver powder closed on, and can also connect the spherical silver powder particles do not closed on mutually, thus the contact area significantly increased between silver powder, improve the contact effect between silver powder particles.Meanwhile, nano bar-shape silver line bends deformation in sintering process, has filled up the space between spherical silver powder particles, has added cell piece silver grating line compaction rate, reduce contact resistance, improve the power output of cell piece.
Secondly, in silicon solar cell front side conductive silver slurry of the present invention, with the addition of specific inorganic salts compound crystal.Due in silicon solar cell front side conductive silver slurry of the present invention, there is not fixing fusing point in described frit amorphous material; And inorganic salts compound crystal is crystalline solid, there is crystal structure, there is fixing fusing point.Therefore, heat tracing process progressively melts, and when the frit Hybrid Heating of dystectic inorganic salts compound crystal and low Tg, the frit of non crystalline structure first starts fusing, and coated described inorganic salts compound crystal particle surface gradually.In the liquid phase environment that melten glass material provides, inorganic salts compound, reacts or ion-exchange with inorganic salts compound crystal, makes the structure of frit tend to complicated.Meanwhile, when melten glass material impels inorganic salts compound crystal to melt, inorganic salts compound crystal needs constantly from surrounding environment heat absorption, can the temperature of controlled melting glass well sharply raise like this.Therefore, the present invention by adding specific inorganic salts compound crystal in silicon solar cell front side conductive silver slurry, silicon solar cell front side conductive silver slurry is made between frit and described inorganic salts compound crystal, above-mentioned interaction to occur on the one hand in sintering process, change frit melted after mobility and the complexity of network configuration, change viscosity and the thermal coefficient of expansion of melten glass, improve the compatibility of frit and silicon chip, improve the adhesive strength of silver slurry at silicon chip surface with this.On the other hand, adding of small described inorganic salts compound crystal, continuous and described inorganic salts compound crystal effect in non-crystal frit melted process, frit melted rear saving silicon chip P-N can well be suppressed to damage, improve the open circuit voltage of silicon solar cell, short circuit current and transformation efficiency, final its power output of increase.
Described in the embodiment of the present invention, silicon solar cell front side conductive silver slurry can be prepared by following method, certainly, also can be prepared by additive method.
Correspondingly, the embodiment of the present invention is the silver-colored preparation method starched of a kind of silicon solar cell front side conductive also, comprises the steps:
S01. prepare inorganic salts compound crystal: the inorganic oxide getting two or more maybe can resolve into the inorganic salts of described inorganic oxide, carry out successively mixing, heat treatment, pulverize, process of sieving, obtain inorganic salts compound crystal;
S02. modification TeO is prepared
2-Bi
2o
3-PbO frit: frit oxide and property-modifying additive are carried out successively mix, melting, cold quenching, pulverize, process of sieving, make modification TeO
2-Bi
2o
3-PbO frit;
S03. organic carrier is prepared: by organic solvent, thickener, plasticizer, auxiliary agent through mixed processing, prepare organic carrier;
S04. silicon solar cell front side conductive silver slurry is prepared: take described micron/submicron level silver powder, rod-like nano silver line, modification TeO by the formula of above-mentioned solar battery front side conductive silver paste
2-Bi
2o
3-PbO frit, inorganic salts compound crystal and organic carrier, carry out mixed processing by each component, obtains silicon solar cell front side conductive silver slurry.
Concrete, in above-mentioned steps S01, as preferred embodiment, described inorganic oxide is the oxide of Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn, concrete, comprises Bi
2o
3, Al
2o
3, ZnO, RuO
2, PbO, CaO, MgO, WO
3, ZrO
2, TiO
2, SiO
2, B
2o
3, P
2o
5, Nb
2o
5, V
2o
5, MoO2, TeO
2, SnO
2, also comprise the oxide of other valence states of Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn.In the embodiment of the present invention, the inorganic salts of above-mentioned inorganic oxide can be resolved into, after Overheating Treatment, decompose the oxide obtaining Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn.As preferred embodiment, described heat treatment temperature is preferably 500-1800 DEG C, and heat treatment time is preferably 60-600min.As another preferred embodiment, the particle diameter of described inorganic salts compound crystal is 0.001-10 μm, more preferably 0.01-5 μm.
In above-mentioned steps S02, described frit oxide is the described modification TeO of preparation
2-Bi
2o
3the oxide of-PbO frit, comprises TeO
2, Bi
2o
3, PbO and property-modifying additive.In order to obtain physical property and one-tenth is grouped into the good described modification TeO of consistency
2-Bi
2o
3-PbO frit, as preferred embodiment, the temperature of described melt process is 400-1500 DEG C, and temperature retention time is 30-300 minute, specifically can be 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 customary preparation methods of this area organic carrier, as preferred embodiment, the detailed process preparing described organic carrier can be: take organic solvent by recipe ingredient and be placed in glass container, use oil bath at 100 DEG C of heated at constant temperature glass containers, then the thickening plasticizer of the ratio of recipe requirements or plasticizer and thickener, auxiliary agent is added successively, the stirring of homogenizer is used to mix successively, finally add auxiliary agent and eliminate air entrapment, each composition of carrier is mixed and bubble-free.
In above-mentioned steps S04, take described micron/submicron level silver powder, rod-like nano silver line, modification TeO by the formula of solar battery front side conductive silver paste described in above-mentioned any embodiment
2-Bi
2o
3-PbO frit, inorganic salts compound crystal and organic carrier, each component preferred content in the formula of described solar battery front side conductive silver paste and formula and kind as described above, in order to save length, do not repeat them here.
The preparation method of a kind of silicon solar cell front side conductive silver slurry that the embodiment of the present invention provides, preparation method is simple, operates controlled, is easy to realize industrialization.Prepare silicon solar cell front side conductive silver slurry adhesive force and close silicon good, there is the advantage of high efficiency, low resistance, high-tensile strength, low-leakage current simultaneously
Be described below in conjunction with specific embodiment.
Embodiment 1-6
A silicon solar cell front side conductive silver slurry, comprises silver powder, modification TeO
2-Bi
2o
3-PbO frit, inorganic salts compound crystal, multi-solvent organic carrier and rod-like nano silver line, wherein, described silver powder is micron/submicron silver powder, and in the total weight of silicon solar cell front side conductive silver slurry for 100%, each composition weight percentage composition is respectively as described in following table 1 embodiment 1-6.
A preparation method for silicon solar cell front side conductive silver slurry, comprises the steps:
Prepare inorganic salts compound crystal: raw materials weighing Bi
2o
393.2g, TeO
232.3g, mixed and be placed in Muffle furnace 630 DEG C insulation after 2 hours cool to room temperature take out, then pulverizing and obtaining particle diameter is powder at 0.01-5 μm, is Bi
4te
3o
12tiny crystals powder; Raw materials weighing ZnO40.5g, TiO again
239.94g, mixed and be placed in Muffle furnace 1100 DEG C insulation after 4 hours cool to room temperature take out, then ball milling obtains particle diameter is powder at 0.01-5 μm, is ZnTiO
3tiny crystals powder; Raw materials weighing PbO44.6g, MgO16.0g, Nb
2o
526.6, mixed and be placed in Muffle furnace 800 DEG C insulation after 4 hours cool to room temperature take out, then pulverizing and obtaining particle diameter is powder at 0.01-5 μm, is Pb
1/3mg
2/3nbO
3tiny crystals powder; Equally, MgCa (SiO is prepared
3)
2, CaMg (RuO
3)
2, PbWO
4, (ZnTiO
3) (CaSiO
3), (RuO
2) (MoO
2) (Nb
2o
5)
2tiny crystals powder.
Preparation modification TeO
2-Bi
2o
3-PbO frit: by rare earth modified lead-less glasses material raw material TeO
243g, Bi
2o
316g, PbO37g, rare earth oxide CaO0.5g, ZrO
20.5g, La
2o
32g, SiO
21g, mix in rear loading crucible, crucible is heated to 400-1500 DEG C as in Muffle furnace, temperature retention time is 30-300 minute, especially, 1050 DEG C can be heated to and be incubated 30 minutes, treating that Muffle furnace runs and stop, taking-up high temperature molten glass carries out cold quenching and obtains thick level frit, after thick level frit is pulverized, then sieve with 600 eye mesh screens, obtain required frit.
Prepare organic carrier: get terpinol 100g, carbitol 100g, butyl carbitol acetate 80g adds in glass container, use water-bath at 80 DEG C of heated at constant temperature glass containers, add ethyl cellulose 50g, dioctyl phthalate 40g, dioctyl phthalate 10g, hydrogenation polyethylene glycol 10g, fatty acid glyceride 5g successively in organic solvent after, homogenizer is used to stir respectively, obtained homogeneous organic carrier 400g.
Prepare silicon solar cell front side conductive silver slurry: by the described organic carrier prepared, silver powder, frit, crystal complex additive, described according to the form below embodiment 1-6, the formula of silicon solar cell front side conductive silver slurry takes successively and joins in suitable container respectively, rear use homogenizer stirs, re-use three roller grinding mills to mill 30 minutes, obtain fineness below 15 μm, viscosity is at the silicon solar cell silver slurry of 250-350Pas, on the polysilicon that the silver slurry prepared uses the mode of silk screen printing to be printed on 156mm × 156mm or monocrystalline silicon substrate, and silicon solar cell is sintered at 900 DEG C.
The described silicon solar cell front side conductive silver slurry prepared by above-described embodiment 1-6 carries out open circuit voltage, short circuit current, conversion efficiency, string resistance size, the large Small Indicators performance test of average tension, test result sees the following form 2, and the method for testing of its indices is this area conventional method.
Table 1
Table 2
From table 2, the silicon solar cell front side conductive silver slurry that the embodiment of the present invention provides, improves TeO
2-Bi
2o
3the strength of glass of-PbO frit and adhesive force, and then the silicon solar cell front side conductive silver slurry obtaining high efficiency, low resistance, high-tensile strength, low-leakage current.
In the embodiment of the present invention, benly be, be to be understood that, inorganic salts compound crystal in described silicon solar cell front side conductive silver slurry, contain Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn oxide and can decompose obtain described Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn oxide inorganic salts in the form of ownership of at least two kinds of crystal complexes formed.Owing to enumerating impossible limit, listing several form in specific embodiment of the invention 1-6, be only optimal way, is never for limiting whole execution mode of the present invention.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a silicon solar cell front side conductive silver slurry, comprises silver powder, frit and organic carrier, it is characterized in that, also comprise rod-like nano silver line, inorganic salts compound crystal, wherein, described frit is modification TeO
2-Bi
2o
3-PbO frit, described silver powder is micron/submicron silver powder, and in the total weight of described silicon solar cell front side conductive silver slurry for 100%, each composition weight percentage composition is as described below:
2. silicon solar cell front side conductive silver slurry as claimed in claim 1, is characterized in that, the length of described rod-like nano silver line is 0.8-10.0 μm, and diameter of section is 5-100nm.
3. silicon solar cell front side conductive silver slurry as claimed in claim 1, it is characterized in that, described inorganic salts compound crystal be Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn oxide and can decompose obtain described Bi, Al, Zn, Ru, Pb, Ca, Mg, W, Zr, Ti, Si, B, P, Nb, V, Mo, Te, Sn oxide inorganic salts at least two kinds formed crystal complexes.
4. the silicon solar cell front side conductive silver slurry as described in as arbitrary in claim 1-3, it is characterized in that, the particle diameter of described inorganic salts compound crystal is 0.001-10 μm.
5. the silicon solar cell front side conductive silver slurry as described in as arbitrary in claim 1-3, is characterized in that, described modification TeO
2-Bi
2o
3-PbO frit is included as TeO
2, Bi
2o
3, PbO and property-modifying additive, with described modification TeO
2-Bi
2o
3the total weight of-PbO frit is 100%, and the weight percentage of each component is as described below:
6. the silicon solar cell front side conductive silver slurry as described in as arbitrary in claim 1-3, is characterized in that, described modification TeO
2-Bi
2o
3the particle diameter of-PbO frit is 1-20 μm, and meso-position radius D50 is 1-10.0 μm, and described property-modifying additive is Al
2o
3, ZnO, RuO
2, CaO, MgO, WO
3, ZrO
2, TiO
2, SiO
2, B
2o
3, P
2o
5, Nb
2o
5, V
2o
5, MoO
2, SnO
2, La
2o
3, Sm
2o
3, Eu
2o
3, Er
2o
3, Pr
2o
3, Nd
2o
3, Tm
2o
3, Ho
2o
3, CeO
2, Tb
2o
3, Y
2o
3, Gy
2o
3in at least one.
7. the silicon solar cell front side conductive silver slurry as described in as arbitrary in claim 1-3, it is characterized in that, described micron/submicron level silver powder is spherical silver powder, and the diameter of described micron/submicron level silver powder is 0.8-8.0 μm, and meso-position radius D50 is 1.5-5.0 μm.
8. the silicon solar cell front side conductive silver slurry as described in as arbitrary in claim 1-3, it is characterized in that, described organic carrier comprises organic solvent, thickener, plasticizer and auxiliary agent, and in the total weight of described organic carrier for 100%, the weight percentage of each component is as described below:
9. silicon solar cell front side conductive silver slurry as claimed in claim 7, it is characterized in that, described organic solvent is at least two kinds in terpinol, carbitol, tributyl citrate, tributyl phosphate, lecithin, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, cyclohexanone, acetone, butyl carbitol, diethylene glycol ether, octanol, butyl carbitol acetate; And/or
Described thickener is at least one in lanolin, ethyl cellulose, phenolic resins; And/or
Described plasticizer is at least one in dibutyl phthalate, dioctyl phthalate; And/or
Described auxiliary agent is at least one in hydrogenation polyethylene glycol, polyglyceryl fatty acid ester, isooctanol.
10. a preparation method for silicon solar cell front side conductive silver slurry, comprises the steps:
Prepare inorganic salts compound crystal: the inorganic oxide getting two or more maybe can resolve into the inorganic salts of described inorganic oxide, carry out successively mixing, heat treatment, pulverize, process of sieving, obtain inorganic salts compound crystal;
Preparation modification TeO
2-Bi
2o
3-PbO frit: frit oxide and property-modifying additive are carried out successively mix, melting, cold quenching, pulverize, process of sieving, make modification TeO
2-Bi
2o
3-PbO frit;
Prepare organic carrier: by organic solvent, thickener, plasticizer, auxiliary agent through mixed processing, prepare organic carrier;
Prepare silicon solar cell front side conductive silver slurry: take described micron/submicron level silver powder, rod-like nano silver line, modification TeO by the formula of the arbitrary described solar battery front side conductive silver paste of the claims 1-9
2-Bi
2o
3-PbO frit, inorganic salts compound crystal and organic carrier, carry out mixed processing by each component, obtains silicon solar cell front side conductive silver slurry.
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