CN103559938B - A kind of doping type solar cell positive silver paste - Google Patents
A kind of doping type solar cell positive silver paste Download PDFInfo
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- CN103559938B CN103559938B CN201310429619.XA CN201310429619A CN103559938B CN 103559938 B CN103559938 B CN 103559938B CN 201310429619 A CN201310429619 A CN 201310429619A CN 103559938 B CN103559938 B CN 103559938B
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Abstract
The present invention relates to a kind of doping type solar cell positive silver paste, the composition of this slurry and percetage by weight thereof are: silver powder 75 ~ 90%, glass dust 1 ~ 8%, organic binder bond 1.5 ~ 4%, the compound 0.1 ~ 10% containing indium and zinc, dispersant 0 ~ 1%, and surplus is solvent; Wherein, described glass dust is lanthanum, boron, zinc glass system, and the compound containing indium and zinc is A (Zn (CH
3(CH
2)
16cOO)
2), wherein A is containing element indium In.Because the present invention adopts lanthanum, boron, zinc glass system glass dust, add the compound containing indium and zinc simultaneously, enhance the adhesion strength between electrode and silicon substrate, reduce series resistance and sheet resistor; Meanwhile, containing in the compound of indium and zinc, zinc component is zinc stearate, can reduce this containing indium and the compound of zinc and the capillary effect at organic binder bond and solvent contacts interface, make the electrical property of electrode more even.
Description
Technical field
The present invention relates to a kind of silver slurry, be specifically related to a kind of doping type solar cell positive silver paste.
Background technology
The electrode material silver slurry of solar cell is the very crucial technical essential of in manufacture of solar cells one.Silver slurry mainly relies on silk screen printing, low temperature drying, high temperature sintering three operations to make electrode.
The front electrode of solar battery positive silver paste of currently available technology forms primarily of organic carrier, silver powder, glass dust and additive.As: application number is that the silver slurry of the Chinese patent of 20111016989.3 comprises 63 ~ 80% silver powder, 4 ~ 9% glass dust, 12 ~ 28% organic carriers, 1 ~ 2% additive and 1 ~ 2% dispersant, wherein, additive is lanthanum oxide powder, particle is less than 5 μm, dispersant is bismuth stearate, and glass dust is boron-bismuth-silicon-aluminium-Xi-niobium-titan silicate system.This patent with the addition of the lanthana with high catalysis characteristics owing to adopting, add the lytic activity of silver powder in glassy phase, and make the silver micro-crystallite in glassy phase produce one " pinning " effect at silicon face, make the Adhesion enhancement between the electronic silver paste conductor grid line fired and silicon substrate, improve the stripping machine intensity of electrode, increase the fill factor, curve factor FF of battery simultaneously.But this kind adds as additives such as lanthanas outside glass dust system, additive fusing point is many up to more than 2000 DEG C, what it disperseed near glass dust evenly directly affect silver powder soften glass mutually in dissolubility; If lanthana local occurs reunite, then cause the uneven of electrode adhesion intensity the most at last.
For this reason, application number be 201110184050.6 Chinese patent disclose a kind of glass dust of boron-bismuth-silicon-aluminium-Xi-niobium-titan silicate system, and other silver slurry components such as this glass dust and silver powder etc. are mixed and made into silver slurry used for solar batteries, this glass dust is owing to evenly containing lanthana component, therefore be conducive to silver powder soften glass mutually in uniform dissolution, make secure bond between electrode and silicon substrate, and series resistance is low.But further reduction is still treated in the resistance of the sheet of this silver-colored slurry technology, the permeability of its silk screen printing simultaneously and depth-width ratio need to improve.
In addition, application number be 201110450403.2 Chinese patent disclose and a kind ofly in conventional conductive silver paste, add zinc oxide and containing the technical scheme of indium compound, utilize the physical and chemical performance of zinc oxide and indium compound, to improve the selective collection rate to charge carrier, reduce complex centre to be formed, effectively reduce sheet resistor.Wherein containing indium compound is G
3b (Al (C
2h
5o
7)
3), allocate acquisition by the following method, get the raw material Homogeneous phase mixing containing element boron B, gallium Ga, indium In and thallium Tl, obtain product with compound G
3b represents, by the raw material of aluminiferous metals particulate and absolute ethyl alcohol Homogeneous phase mixing, obtains product with compd A l (C
2h
5o
7)
3represent, by compound G
3b adds compd A l (C
2h
5o
7)
3in, staticly settle after mixing, 300 ~ 600 DEG C of heating, make containing indium compound G
3b (Al (C
2h
5o
7)
3).The shortcoming of this silver-colored slurry technology is: firm not with the bonding of silicon substrate.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of doping type solar cell positive silver paste, and this positive silver paste can improve the bonding fastness of electrode and silicon substrate, lower series and parallel connections resistance simultaneously.
The technical issues that need to address of the present invention are achieved through the following technical solutions:
A kind of doping type solar cell positive silver paste, it is characterized in that: the composition of this slurry and percetage by weight thereof are: silver powder 75 ~ 90%, glass dust 1 ~ 8%, organic binder bond 1.5 ~ 4%, the compound 0.1 ~ 10% containing indium and zinc, dispersant 0 ~ 1%, surplus is solvent; Wherein, described glass dust is lanthanum, boron, zinc glass system.
Preferably, the described compound containing indium and zinc is A (Zn (CH
3(CH
2)
16cOO)
2), wherein A is containing element indium In; Compd A (Zn (CH
3(CH
2)
16cOO)
2) obtain by the following method, get zinc stearate Zn (CH
3(CH
2)
16cOO)
2raw material dissolve in a solvent, the raw material A added containing element indium In is dispersed, 300 ~ 600 DEG C of heating, makes the compd A (Zn (CH containing indium and zinc
3(CH
2)
16cOO)
2).
Preferably, described dispersant is divalence or trivalent stearate.
Preferably, described divalence stearate is zinc stearate Zn (CH
3(CH
2)
16cOO)
2and/or calcium stearate Ca (CH
3(CH
2)
16cOO)
2.
Preferably, the composition of described glass dust and percetage by weight thereof are: La
2o
30.5 ~ 1%, B
2o
370 ~ 85%, Al
2o
32 ~ 5%, ZnO2 ~ 5%, Na
2o1 ~ 5%, LiO
22 ~ 5%, V
2o
53 ~ 8% and P
2o
50.5 ~ 1%.
Preferably, the average grain diameter of described glass dust is 1 ~ 3 μm.
Preferably, the tap density of described silver powder is 4.5-5.5g/cm
3, average grain diameter is 1 ~ 3 μm.
Compared with prior art, advantage of the present invention and beneficial effect are:
1, positive silver paste of the present invention adopts lanthanum, boron, zinc glass system glass dust, adds the compound containing indium and zinc in formula simultaneously; On the one hand, in glass dust, equally distributed lanthana component can increase the lytic activity of silver powder in glassy phase equably, and the adhesion strength between intensifier electrode and silicon substrate, reduces series resistance, on the other hand, the compound added containing indium and zinc significantly reduces sheet resistor.
2, contain in positive silver paste of the present invention in the compound of indium and zinc, zinc component is zinc stearate, it can reduce this containing indium and the compound of zinc and the surface tension at organic binder bond and solvent contacts interface, makes this compound containing indium and zinc dispersed in solvent and organic binder bond; Meanwhile, this zinc component also can play the effect of silver slurry dispersant, makes silver powder dispersed in solvent and organic carrier; Thus make the electrical property of the adhesive property of electrode and silicon substrate and electrode more even.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described further.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
Embodiment 1 ~ 5
The present invention is a kind of doping type solar cell positive silver paste, and in embodiment 1 ~ 5, the component of slurry and percetage by weight thereof are in table 1.
Table 1:
In embodiment 1 ~ 5, the tap density of silver powder is 4.5-5.5g/cm
3, average grain diameter is 1 ~ 3 μm.Glass dust is lanthanum, boron, zinc glass system, and average grain diameter is 1 ~ 3 μm.Sintering aids is the compd A (Zn (CH containing indium and zinc
3(CH
2)
16cOO)
2), wherein A is containing element indium In.
In embodiment 1, the composition of glass dust and percetage by weight thereof are: La
2o
30.5%, B
2o
385%, Al
2o
32%, ZnO2%, Na
2o1%, LiO
23%, V
2o
56% and P
2o
50.5%.Containing the compd A (Zn (CH of indium and zinc
3(CH
2)
16cOO)
2) in, A is simple substance indium In, this compd A (Zn (CH
3(CH
2)
16cOO)
2) obtain by the following method: get zinc stearate Zn (CH
3(CH
2)
16cOO)
2raw material dissolve in a solvent, it is dispersed to add raw material A, 300 ~ 600 DEG C of heating, makes the compd A (Zn (CH containing indium and zinc
3(CH
2)
16cOO)
2).Wherein, containing the Compound I n (Zn (CH of indium and zinc
3(CH
2)
16cOO)
2) in the percetage by weight of A be 25%, Zn (CH
3(CH
2)
16cOO)
2percetage by weight be 75%.Described dispersant is zinc stearate Zn (CH
3(CH
2)
16cOO)
2.Organic binder bond is ethyl cellulose.Solvent is turpentine oil.
In embodiment 2, the composition of glass dust and percetage by weight thereof are: La
2o
31%, B
2o
370%, Al
2o
35%, ZnO5%, Na
2o5%, LiO
25%, V
2o
58% and P
2o
51%.Containing the compd A (Zn (CH of indium and zinc
3(CH
2)
16cOO)
2) in, A is simple substance indium In, this compd A (Zn (CH
3(CH
2)
16cOO)
2) preparation method with embodiment 1; In this compound, containing the Compound I n (Zn (CH of indium and zinc
3(CH
2)
16cOO)
2) in the percetage by weight of A be 2%, Zn (CH
3(CH
2)
16cOO)
2percetage by weight be 98%.Described dispersant is calcium stearate Ca (CH
3(CH
2)
16cOO)
2.Organic binder bond is CMC.Solvent is terpinol.
In embodiment 3, the composition of glass dust and percetage by weight thereof are: La
2o
30.8%, B
2o
383%, Al
2o
34%, ZnO4%, Na
2o2.4%, LiO
22%, V
2o
53% and P
2o
50.8%.Containing the compd A (Zn (CH of indium and zinc
3(CH
2)
16cOO)
2) in, A is simple substance indium In, this compd A (Zn (CH
3(CH
2)
16cOO)
2) preparation method with embodiment 1; In this compound, containing the Compound I n (Zn (CH of indium and zinc
3(CH
2)
16cOO)
2) in the percetage by weight of A be 20%, Zn (CH
3(CH
2)
16cOO)
2percetage by weight be 80%.Described dispersant is zinc stearate Zn (CH
3(CH
2)
16cOO)
2with calcium stearate Ca (CH
3(CH
2)
16cOO)
2the mixture of 50:50 by weight.Organic binder bond is butyl cellulose.Solvent is octanol.
In embodiment 4, the composition of glass dust and percetage by weight thereof are: La
2o
30.8%, B
2o
379%, Al
2o
33%, ZnO3.4%, Na
2o4%, LiO
24%, V
2o
55% and P
2o
50.8%.Containing the compd A (Zn (CH of indium and zinc
3(CH
2)
16cOO)
2) in, A is indium oxide, and the method described in the preparation method of this compound and embodiment 1 is similar, is indium oxide unlike raw material A; In this compound, the percetage by weight of A is 15%, Zn (CH
3(CH
2)
16cOO)
2percetage by weight be 85%.Described dispersant is aluminum stearate Al (CH
3(CH
2)
16cOO)
3.Organic binder bond is NC Nitroncellulose.Solvent is terpinol and the turpentine oil mixed liquor by weight 50:50.
In embodiment 5, the composition of glass dust and percetage by weight thereof are: La
2o
30.8%, B
2o
379%, Al
2o
33%, ZnO3.4%, Na
2o4%, LiO
24%, V
2o
55% and P
2o
50.8%.Containing the compd A (Zn (CH of indium and zinc
3(CH
2)
16cOO)
2) in, A is inidum chloride, and the method that the preparation method of this compound is corresponding with embodiment 1 is similar, is inidum chloride unlike raw material A; In this compound, the percetage by weight of A is 20%, Zn (CH
3(CH
2)
16cOO)
2percetage by weight be 80%.Described dispersant is zinc stearate Zn (CH
3(CH
2)
16cOO)
2.Organic binder bond is ethyl cellulose.Solvent is terpinol.
Be printed on the monocrystalline silicon piece of 125 × 125 with above-mentioned positive silver paste, prepare solar cell, test series resistance, parallel resistance and adhesive force etc.Test data is in table 1.From table 1, adhesive force
fall reach more than 3.5N, series resistance
r s1.5 ~ 1.7m Ω can be low to moderate, sheet resistor
r sh30m Ω/below sq can be low to moderate.
Above-mentioned each embodiment is further illustrating of making foregoing of the present invention, but the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to above-described embodiment.It should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. a doping type solar cell positive silver paste, it is characterized in that: the composition of this slurry and percetage by weight thereof are: silver powder 75 ~ 90%, glass dust 1 ~ 8%, organic binder bond 1.5 ~ 4%, the compound 0.1 ~ 10% containing indium and zinc, dispersant 0 ~ 1%, surplus is solvent; Wherein, described glass dust is lanthanum, boron, zinc glass system; The described compound containing indium and zinc is A (Zn (CH
3(CH
2)
16cOO)
2), wherein A is containing element indium In; Compd A (Zn (CH
3(CH
2)
16cOO)
2) obtain by the following method, get zinc stearate Zn (CH
3(CH
2)
16cOO)
2raw material dissolve in a solvent, the raw material A added containing element indium In is dispersed, 300 ~ 600 DEG C of heating, makes the compd A (Zn (CH containing indium and zinc
3(CH
2)
16cOO)
2), A is simple substance indium, indium oxide or inidum chloride.
2. solar cell positive silver paste according to claim 1, is characterized in that: described dispersant is divalence or trivalent stearate.
3. solar cell positive silver paste according to claim 2, is characterized in that: described divalence stearate is zinc stearate Zn (CH
3(CH
2)
16cOO)
2and/or calcium stearate Ca (CH
3(CH
2)
16cOO)
2.
4. the solar cell positive silver paste according to claims 1 to 3 any one, is characterized in that: the composition of described glass dust and percetage by weight thereof are: La
2o
30.5 ~ 1%, B
2o
370 ~ 85%, Al
2o
32 ~ 5%, ZnO2 ~ 5%, Na
2o1 ~ 5%, LiO
22 ~ 5%, V
2o
53 ~ 8% and P
2o
50.5 ~ 1%.
5. solar cell positive silver paste according to claim 4, is characterized in that: the average grain diameter of described glass dust is 1 ~ 3 μm.
6. solar cell positive silver paste according to claim 4, is characterized in that: the tap density of described silver powder is 4.5-5.5g/cm
3, average grain diameter is 1 ~ 3 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310429619.XA CN103559938B (en) | 2013-09-22 | 2013-09-22 | A kind of doping type solar cell positive silver paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310429619.XA CN103559938B (en) | 2013-09-22 | 2013-09-22 | A kind of doping type solar cell positive silver paste |
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| Publication Number | Publication Date |
|---|---|
| CN103559938A CN103559938A (en) | 2014-02-05 |
| CN103559938B true CN103559938B (en) | 2016-01-20 |
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|---|---|---|---|
| CN201310429619.XA Active CN103559938B (en) | 2013-09-22 | 2013-09-22 | A kind of doping type solar cell positive silver paste |
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| CN112562883B (en) * | 2020-12-01 | 2022-10-28 | 广州市儒兴科技开发有限公司 | Electrode slurry contacted with N-type solar cell p + emitter |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118362A (en) * | 1990-09-24 | 1992-06-02 | Mobil Solar Energy Corporation | Electrical contacts and methods of manufacturing same |
| CN101935876A (en) * | 2010-09-14 | 2011-01-05 | 浙江大学 | In-doped ZnO monodisperse nano granules and synthesizing method thereof |
| CN102324263A (en) * | 2011-07-04 | 2012-01-18 | 江苏瑞德新能源科技有限公司 | Silver paste for solar cells and preparation method thereof |
| CN103081114A (en) * | 2011-05-12 | 2013-05-01 | 横滨橡胶株式会社 | Electroconductive composition for forming solar cell collector electrode, and solar cell |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5144857B2 (en) * | 2010-03-01 | 2013-02-13 | 株式会社ノリタケカンパニーリミテド | Conductive paste composition for solar cell |
-
2013
- 2013-09-22 CN CN201310429619.XA patent/CN103559938B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118362A (en) * | 1990-09-24 | 1992-06-02 | Mobil Solar Energy Corporation | Electrical contacts and methods of manufacturing same |
| CN101935876A (en) * | 2010-09-14 | 2011-01-05 | 浙江大学 | In-doped ZnO monodisperse nano granules and synthesizing method thereof |
| CN103081114A (en) * | 2011-05-12 | 2013-05-01 | 横滨橡胶株式会社 | Electroconductive composition for forming solar cell collector electrode, and solar cell |
| CN102324263A (en) * | 2011-07-04 | 2012-01-18 | 江苏瑞德新能源科技有限公司 | Silver paste for solar cells and preparation method thereof |
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| CN103559938A (en) | 2014-02-05 |
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