CN103387340B - For the lead-free glass powder and preparation method thereof of solar cell aluminium paste - Google Patents
For the lead-free glass powder and preparation method thereof of solar cell aluminium paste Download PDFInfo
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- CN103387340B CN103387340B CN201310316246.5A CN201310316246A CN103387340B CN 103387340 B CN103387340 B CN 103387340B CN 201310316246 A CN201310316246 A CN 201310316246A CN 103387340 B CN103387340 B CN 103387340B
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- glass powder
- solar cell
- lead
- aluminium paste
- crucible
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Abstract
The present invention discloses a kind of lead-free glass powder for solar cell aluminium paste, it is characterized in that: this glass powder is primarily of each component of following weight percent: SiO
28 ~ 20%, Al
2o
32 ~ 8%, B
2o
310 ~ 15%, P
2o
5or V
2o
50 ~ 2%, BaCO
30.1 ~ 1.5%, zn cpds and bismuth compound 60 ~ 70%.Glass powder of the present invention can promote the sintering of conduction aluminium powder, is conducive to the formation of back surface field BSF layer, reduces ohmic contact, improves open circuit voltage.
Description
Technical field
The invention belongs to sun power electrocondution slurry technical field, relate to the lead-free glass powder and preparation method thereof for solar cell aluminium paste.
Background technology
Solar energy power generating become field of renewable energy relaying wind-power electricity generation after fast, the most maximum industry of industrialized development.At present, the solar cell in photovoltaic generation remains based on crystal-silicon solar cell, and the market share reaches more than 95%, and laboratory single crystal silicon solar cell efficiency can reach more than 24%, and on market, batch merchandized handling also can reach 19%.Aluminium paste is as the back of the body electric field of battery, and to the open circuit voltage, the increase short-circuit current that improve battery, thus raising cell photoelectric efficiency of conversion has very important effect.Aluminium paste, by the method for silk screen printing, is covered on the silicon substrate back side, is sintered by tunnel sintering oven, forms BSF layer.Wherein, in the process of sintering, glass powder plays vital Link role, and good glass powder can form strong adhesive force, low ohm contact resistance at battery surface, and process of cooling causes the warpage of cell piece low simultaneously, is also not easy shedding during poach.
Modal glass frit composition has PbO-ZnO-B on the market
2o
3system, PbO-B
2o
3-SiO
2system, PbO-Bi
2o
3-B
2o
3system, PbO-B
2o
3system etc.These P series glass powder are in order to pursue low softening temperature, and usually containing environmentally harmful Pb element, this element is unfavorable to environment, if people sucks a certain amount of Pb accidentally, can cause great injury to health.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, provide a kind of and both there is suitable thermal expansivity and softening temperature, again the lead-free glass powder for solar cell aluminium paste of not leaded, health environment-friendly.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of lead-free glass powder for solar cell aluminium paste, and this glass powder is primarily of each component of following weight percent: SiO
28 ~ 20%, Al
2o
32 ~ 8%, B
2o
310 ~ 15%, P
2o
5or V
2o
50 ~ 2%, BaCO
30.1 ~ 1.5%, zn cpds and bismuth compound 60 ~ 70%.
As preferably, the described lead-free glass powder for solar cell aluminium paste, this glass powder is primarily of each component of following weight percent: SiO
28 ~ 20%, Al
2o
32 ~ 8%, B
2o
310 ~ 15%, P
2o
50.1 ~ 2%, BaCO
30.1 ~ 1.5%, zn cpds and bismuth compound 60 ~ 70%.
As preferably, the described lead-free glass powder for solar cell aluminium paste, this glass powder is primarily of each component of following weight percent: SiO
28 ~ 20%, Al
2o
32 ~ 8%, B
2o
310 ~ 15%, V
2o
50.1 ~ 2%, BaCO
30.1 ~ 1.5%, zn cpds and bismuth compound 60 ~ 70%.
Glass frit composition of the present invention (comprising in table 1 cited) is not restrictive, and expection those skilled in the relevant art can carry out slight change to composition, and substantially can not change the characteristic of glass powder.As the coefficient of expansion in order to reduce glass powder, can additionally add the zirconium white being less than 0.5%.
Zn cpds of the present invention comprises the halogenide of the oxide compound of zinc, zinc salt, zinc, and this compounds comprises ZnO, ZnF
2, ZnCl
2, ZnS, Zn
3(PO
4)
2, preferentially select in ZnO, Zn
3(PO
4)
2.
Bismuth compound of the present invention comprises the halogenide of the oxide compound of bismuth, bismuthate, bismuth, and this compounds is contained in Bi
2o
3, BiOF, BiOCl, bismuth titanates, pucherite, the present invention preferentially selects in Bi
2o
3.
Another technical problem that the present invention will solve is to provide a kind of preparation method of above-mentioned lead-free glass powder: take each component respectively, each component is fully mixed post-drying, then melting, hardening quenching, finally by glass powder ball milling, dry, break up, sieving obtains lead-free glass powder, concrete preparation process comprises:
(1) take each component glass powder raw material according to formula rate respectively to mix in mortar, the raw material mixed is put into mould and is pressed into little right cylinder, being put into by the massive cylinder raw material pressed can the loft drier of circulating ventilation, bake out temperature controls at 200-350 DEG C, and the time is 20-30 minute;
(2) frit burned is in advance put into crucible, in elevator furnace, carry out melting, being heated to elevator furnace temperature is 900 DEG C-1400 DEG C, and smelting time is 1-2 hour, makes melts become uniform liquid completely;
(3) after melting completes, crucible is taken out while hot, quench treatment is carried out to the frit liquid in crucible, be specially and frit liquid is poured in deionized water, the deionized water of every 50 liters adds the frit liquid of 0.5 ~ 1.5kg, and deionized water temperature is room temperature;
(4) frit after quenching is pulled out drainage, in following weight ratio: zirconia ball: frit: water=10:1:1 ratio adds in zirconium white crucible, by crucible cover tightening seal, carry out ball milling, time is 4 ~ 8 hours, and the rotating speed of ball mill is 300 ~ 350 revs/min;
(5) glass powder good for ball milling is taken out, with 50 object screen clothes by zirconia ball and residue filter out, then by the glass powder natural subsidence of having filtered ten minutes, topple over upper strata deionized water, can dry in the loft drier of circulating ventilation, bake out temperature is 120-180 DEG C, time 4-6 hour;
(6) after glass powder is dried, even with aluminum oxide mortar grinder, then carry out airflow milling and break up, air pressure controls between 2000-7000Pa, and flow is 2-5kg/h; The glass powder broken up is crossed vibratory screening apparatus, and sieve number of sieving is 300-500 order, obtains finished glass powder, and particle diameter is at 1-5 micron.
Cylinder height described in step (1) is 2-4cm, and weight is 30-60g.
Ball milling described in step (4) carries out ball milling for being fixed in omnidirectional planetary ball mill by crucible.
In preparation method's step (2) of the present invention, in order to reduce the pollution come to crucible, in this technology of preparing, adopt platinum alloy crucibles.
Advantage of the present invention and beneficial effect:
1. glass powder of the present invention can promote the sintering of conduction aluminium powder, is conducive to the formation of back surface field BSF layer, reduces ohmic contact, improves open circuit voltage.
2. glass powder of the present invention is in the process of sintering, plays good Link role, makes aluminium paste form very strong sticking power at battery surface, causes the angularity of cell piece low, be also not easy shedding during poach during cell piece cooling meat; It is large that glass powder right cylinder after pressing mold has loose density, and the advantage that glass powder treatment capacity is many, improves production efficiency; And deposit raw material with glass powder small cylinder form, not easily absorb moisture; Even if having portion of water also can carry out low temperature presintering knot easily, remove moisture, realize solid state reaction, after being conducive to, a step liquid phase reaction is more complete.
Embodiment
Below by embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples:
Embodiment
The weight percent that the present invention's glass powder raw material used accounts for total glass composition is listed in table one, and wherein zn cpds and bismuth compound are also listed in table.
Table 1
Glass powder technology of preparing scheme of the present invention, accurately take each component frit according to the requirement of formula respectively to mix in mortar, the raw material mixed being put into mould is pressed into little cylindric, every block cylinder height 2-4cm, weight 30-60g, being put into by the block stock pressed can the loft drier of circulating ventilation, bake out temperature controls at 200-350 DEG C, time is 30 minutes, and this process is equivalent to frit pre-burning, also portion of water is evaporated simultaneously.
Preparation method of the present invention, in order to reduce the pollution come to crucible, platinum alloy crucibles is adopted in this technology of preparing, frit burned is in advance put into crucible, melting is carried out in elevator furnace, being heated to peak temperature is 900 DEG C-1400 DEG C, and smelting time is 1-2 hour, makes melts become uniform liquid completely.
After melting completes, crucible is taken out while hot, quench treatment is carried out to frit, first contain into deionized water in large stainless steel cask, the water yield generally calculates with the melt liquid of quenching, and the frit of general 1kg needs the deionized water of 50 liters, and deionized water temperature is room temperature.
The glass particle quenched needs ball-milling processing, pull the frit quenched out drainage, by weight zirconia ball: glass particle: water=10:1:1 ratio adds in zirconium white crucible, by crucible cover tightening seal, be fixed in omnidirectional planetary ball mill and carry out, Ball-milling Time is 4-8 hour, rotating speed is 300 ~ 350 revs/min, sheds, therefore owing to having heat in mechanical milling process, need discontinuous to suspend during ball milling, make ball grinder Temperature fall.
Glass powder good for ball milling is taken out, with 50 object screen clothes by zirconium pearl and residue filter out, then by the volume glass powder natural subsidence of having filtered ten minutes, topple over upper strata deionized water, can dry in the loft drier of circulating ventilation, bake out temperature is 120-180 DEG C, time 4-6 hour.
After glass powder is dried, tentatively grind with aluminum oxide mortar, then carry out airflow milling and break up, air pressure controls between 2000Pa-7000Pa, and flow is 2-5kg/h.The glass powder broken up is crossed vibratory screening apparatus, and sieve number of sieving is 300-500 order, obtains finished glass powder, and particle diameter is at 1-5 micron.
In another embodiment, gas phase classification can be carried out to finished glass powder, glass powder is divided into particle diameter and be respectively 1-2um, 2-3um, 3-4um, 4-5um equal-specification.
The softening temperature of glass powder of the present invention is between 300-500 DEG C, and this softening temperature is by differential thermal analyzer, and namely DTA tests, the softening temperature being glass powder with second transformation peaks (Ts).And thermal expansivity is 45-90 × 10
-7/ DEG C, employing be thermal dilatometer test (thermal expansivity described in this specification sheets is linear expansivity α), using silica glass as standard test specimen, probe temperature rises to 300 DEG C by room temperature.
Glass powder characteristic test:
According to the glass powder formula of table 1, adopt softening temperature (Ts) and the thermal expansivity (α) of DTA and thermal dilatometer difference tested glass powder, Ts and α of often kind of glass powder is shown in Table 2.
Prepared by slurry
Weigh suitable glass powder, organic carrier and aluminium powder.Glass powder is herein added in organic carrier and stirs 15 minutes, then stir adding aluminium powder, the amount added count by weight percentage into: glass powder 2.8%, aluminium powder 75%, organic carrier 21.2%, other additives are 1%.The slurry mixed is put into three-roll grinder to be rolled even, reaches below 15um to mesh-of-grind.
Sintering and performance test
Being printed in rolling the slurry starched on the plated film polysilicon chip of 156mm*156mm, sintering in continuous tunnel furnace.Electrical property and quantitative measurement are carried out to cell piece.
Test battery efficiency of conversion and open circuit voltage on cell piece efficiency sorter, utilize the angularity of the plug pin test battery sheet of vernier callipers or industry, the water-bath of cell piece being put into boiling boils 10 minutes, whether test battery sheet has shedding phenomenon, stick EVA film and backboard at cell piece, then carry out lamination, then test the sticking power of aluminium back surface field, test angles is 45 degree, live width 1cm.So test result be all shown in Table 2.
Claims (8)
1. for a lead-free glass powder for solar cell aluminium paste, it is characterized in that: this glass powder is primarily of each component of following weight percent: SiO
28 ~ 20%, Al
2o
32 ~ 8%, B
2o
310 ~ 15%, P
2o
5or V
2o
50 ~ 2%, BaCO
30.1 ~ 1.5%, zn cpds and bismuth compound 60 ~ 70%; Also comprise the zirconium white being more than or equal to 0.15%, being less than 0.5%.
2. the lead-free glass powder for solar cell aluminium paste according to claim 1, is characterized in that: this glass powder is primarily of each component of following weight percent: SiO
28 ~ 20%, Al
2o
32 ~ 8%, B
2o
310 ~ 15%, P
2o
50.1 ~ 2%, BaCO
30.1 ~ 1.5%, zn cpds and bismuth compound 60 ~ 70%; Also comprise the zirconium white being more than or equal to 0.15%, being less than 0.5%.
3. the lead-free glass powder for solar cell aluminium paste according to claim 1, is characterized in that: this glass powder is primarily of each component of following weight percent: SiO
28 ~ 20%, Al
2o
32 ~ 8%, B
2o
310 ~ 15%, V
2o
50.1 ~ 2%, BaCO
30.1 ~ 1.5%, zn cpds and bismuth compound 60 ~ 70%; Also comprise the zirconium white being more than or equal to 0.15%, being less than 0.5%.
4. the lead-free glass powder for solar cell aluminium paste according to the arbitrary claim of claim 1-3, is characterized in that: described zn cpds is ZnO, ZnF
2, ZnCl
2, ZnS or Zn
3(PO
4)
2.
5. the lead-free glass powder for solar cell aluminium paste according to the arbitrary claim of claim 1-3, is characterized in that: described bismuth compound is Bi
2o
3, BiOF, BiOCl, bismuth titanates or pucherite.
6. a preparation method for the lead-free glass powder for solar cell aluminium paste according to claim 1, is characterized in that: preparation process comprises:
(1) take each component glass powder raw material according to formula rate respectively to mix in mortar, the raw material mixed is put into mould and is pressed into little right cylinder, being put into by the massive cylinder raw material pressed can the loft drier of circulating ventilation, bake out temperature controls at 200-350 DEG C, and the time is 20-30 minute;
(2) frit burned is in advance put into crucible, in elevator furnace, carry out melting, being heated to elevator furnace temperature is 900 DEG C-1400 DEG C, and smelting time is 1-2 hour, makes melts become uniform liquid completely;
(3) after melting completes, crucible is taken out while hot, quench treatment is carried out to the frit liquid in crucible, be specially and frit liquid is poured in deionized water, the deionized water of every 50 liters adds the frit liquid of 0.5 ~ 1.5kg, and deionized water temperature is room temperature;
(4) frit after quenching is pulled out drainage, in following weight ratio: zirconia ball: frit: water=10:1:1 ratio adds in zirconium white crucible, by crucible cover tightening seal, carries out ball milling, and the time is 4 ~ 8 hours, and the rotating speed of ball mill is 300 ~ 350 revs/min;
(5) glass powder good for ball milling is taken out, with 50 object screen clothes by zirconia ball and residue filter out, then by the glass powder natural subsidence of having filtered ten minutes, topple over upper strata deionized water, can dry in the loft drier of circulating ventilation, bake out temperature is 120-180 DEG C, time 4-6 hour;
(6) after glass powder is dried, even with aluminum oxide mortar grinder, then carry out airflow milling and break up, air pressure controls between 2000-7000Pa, and flow is 2-5kg/h; The glass powder broken up is crossed vibratory screening apparatus, and sieve number of sieving is 300-500 order, obtains finished glass powder, and particle diameter is at 1-5 micron.
7. the crown glass powder, preparation method thereof for solar cell aluminium paste according to claim 6, it is characterized in that: the cylinder height described in step (1) is 2-4cm, weight is 30-60g.
8. the preparation method of the lead-free glass powder for solar cell aluminium paste according to claim 6, is characterized in that: the ball milling described in step (4) carries out ball milling for being fixed in omnidirectional planetary ball mill by crucible.
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|---|---|---|---|
| CN201310316246.5A CN103387340B (en) | 2013-07-24 | 2013-07-24 | For the lead-free glass powder and preparation method thereof of solar cell aluminium paste |
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| CN103387340B true CN103387340B (en) | 2016-02-10 |
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| CN104150777A (en) * | 2014-08-07 | 2014-11-19 | 贵阳晶华电子材料有限公司 | Tellurium-containing glass for solar positive electrode silver paste and preparation method of tellurium-containing glass |
| CN106082681A (en) * | 2016-06-06 | 2016-11-09 | 怀远县金浩电子科技有限公司 | A kind of preparation method of gas sensing resistance unleaded environmental protection glass dust |
| CN107117824A (en) * | 2017-05-18 | 2017-09-01 | 江苏东昇光伏科技有限公司 | A kind of lead-free glass powder used for solar batteries and preparation method thereof |
| CN109166646B (en) * | 2018-08-14 | 2020-05-19 | 华中科技大学 | Environment-friendly aluminum electrode paste for back-passivated silicon solar cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097318A (en) * | 2010-09-08 | 2013-05-08 | 株式会社东进世美肯 | Zinc oxide-based glass frit composition and aluminum paste composition for back contact of solar cell using the same |
| CN103204632A (en) * | 2012-01-14 | 2013-07-17 | 比亚迪股份有限公司 | Conductive glass powder and its preparation method, crystalline silicon solar battery aluminum conductive paste and preparation method |
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| JP4136346B2 (en) * | 2001-09-18 | 2008-08-20 | 日本山村硝子株式会社 | Sealing composition |
| JP5683778B2 (en) * | 2008-09-29 | 2015-03-11 | 日本山村硝子株式会社 | Lead free bismuth glass composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097318A (en) * | 2010-09-08 | 2013-05-08 | 株式会社东进世美肯 | Zinc oxide-based glass frit composition and aluminum paste composition for back contact of solar cell using the same |
| CN103204632A (en) * | 2012-01-14 | 2013-07-17 | 比亚迪股份有限公司 | Conductive glass powder and its preparation method, crystalline silicon solar battery aluminum conductive paste and preparation method |
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