CN103387340A - Lead-free glass powder used for solar cell aluminum paste and preparation method thereof - Google Patents
Lead-free glass powder used for solar cell aluminum paste and preparation method thereof Download PDFInfo
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- CN103387340A CN103387340A CN2013103162465A CN201310316246A CN103387340A CN 103387340 A CN103387340 A CN 103387340A CN 2013103162465 A CN2013103162465 A CN 2013103162465A CN 201310316246 A CN201310316246 A CN 201310316246A CN 103387340 A CN103387340 A CN 103387340A
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- glass powder
- lead
- solar cell
- free glass
- aluminium paste
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Abstract
The invention discloses a lead-free glass powder used for solar cell aluminum paste. The lead-free glass powder is characterized by mainly comprising the following components by weight percent: 8-20% of SiO2, 2-8% of Al2O3, 10-15% of B2O3, 0-2% of P2O5 or V2O5 0.1-1.5% of BaCO3, and 60-70% of a zinc compound and a bismuth compound. The glass powder disclosed by the invention can facilitate the sintering of electric conduction aluminite powder, is beneficial to the formation of a BSF (Back Surface Field), reduces the ohmic contact and increases open-circuit voltage.
Description
Technical field
The invention belongs to sun power electrocondution slurry technical field, relate to lead-free glass powder for the solar cell aluminium paste and preparation method thereof.
Background technology
Solar energy power generating has become renewable energy source domain relaying wind-power electricity generation fast, the most maximum industry of industrialized development afterwards.At present, the solar cell in photovoltaic generation remains take crystal-silicon solar cell as main, and the market share reaches more than 95%, and laboratory single crystal silicon solar cell efficiency can reach more than 24%, and on market, the batch commercialization is produced and also can be reached 19%.Aluminium paste is as the back of the body electric field of battery, and open circuit voltage, increase short-circuit current to improving battery, have very important effect thereby improve the cell photoelectric efficiency of conversion.Aluminium paste, by the method for silk screen printing, covers on the silicon substrate back side,, by tunnel sintering oven sintering, forms the 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 that the warpage of cell piece is low simultaneously, also is 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, in order to pursue low softening temperature, contain environmentally harmful Pb element usually, and this element is unfavorable to environment,, if the 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, a kind of both had suitable thermal expansivity and softening temperature are provided, again the lead-free glass powder that is used for the 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 the solar cell aluminium paste, this glass powder are mainly by 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, described lead-free glass powder for the solar cell aluminium paste, this glass powder are mainly by 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, described lead-free glass powder for the solar cell aluminium paste, this glass powder are mainly by 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 in order to reduce the coefficient of expansion of glass powder, can additionally add the zirconium white less than 0.5%.
Zn cpds of the present invention comprises oxide compound, the zinc salt of zinc, the halogenide of 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 oxide compound, the bismuthate of bismuth, the halogenide of 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 respectively each component, each component is fully mixed post-drying, then melting, hardening quenching, finally with glass powder ball milling, dry, break up, sieving obtains lead-free glass powder, concrete preparation process comprises:
(1) taking each component glass powder raw material according to formula rate respectively mixes in mortar, the raw material that mixes is put into mould be pressed into little right cylinder, with the block right cylinder raw material that presses put into can circulating ventilation loft drier, bake out temperature is controlled at 200-350 ℃, and the time is 20-30 minute;
(2) pre-burned frit is put into crucible, carry out melting in elevator furnace, being heated to the elevator furnace temperature is 900 ℃-1400 ℃, and smelting time is 1-2 hour, makes melts become uniform liquid fully;
(3) after melting is completed, crucible is taken out while hot, the frit liquid in crucible is carried out quench treatment, be specially frit liquid is poured in deionized water, the deionized water of every 50 liters adds the frit liquid of 0.5～1.5kg, and the deionized water temperature is that room temperature gets final product;
(4) frit after quenching is pulled drainage out, in following weight ratio: zirconia ball: frit: water=10:1:1 ratio adds in the zirconium white crucible,, with the crucible cover tightening seal, carries out ball milling, time is 4～8 hours, and the rotating speed of ball mill is 300～350 rev/mins;
(5) glass powder that ball milling is good takes out, with 50 purpose screen clothes with zirconia ball and residue filter out, then with the glass powder natural subsidence of having filtered ten minutes, topple over the upper strata deionized water, can dry in the loft drier of circulating ventilation, bake out temperature is 120-180 ℃, time 4-6 hour;
(6) after the glass powder oven dry, with the aluminum oxide mortar, grind evenly, then carry out airflow milling and break up, air pressure is controlled between 2000-7000Pa, and flow is 2-5kg/h; The glass powder of breaing up is crossed vibratory screening apparatus, and the sieve number of sieving is the 300-500 order, obtains the finished glass powder, and particle diameter is at the 1-5 micron.
The described cylinder height of step (1) is 2-4cm, and weight is 30-60g.
The described ball milling of step (4) is for to be fixed in crucible in omnidirectional planetary ball mill and to carry out ball milling.
In preparation method's step of the present invention (2),, in order to reduce next pollution to crucible, adopt the platinum alloy crucible in this technology of preparing.
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 in the process of sintering, plays good Link role, makes aluminium paste form very strong sticking power at battery surface, causes that the angularity of cell piece is low during the cooling contraction of cell piece, also is not easy shedding during poach; It is large that glass powder right cylinder after pressing mold has loose density, and the advantage that the glass powder treatment capacity is many, improved production efficiency; And deposit raw material with glass powder small cylinder form, be difficult for absorbing moisture; Also can carry out easily the low temperature presintering knot even have part moisture, 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 not only is confined to following examples:
Embodiment
The present invention's glass powder raw material used accounts for the weight percent of total glass composition and lists 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 taking each component frit according to the requirement of filling a prescription respectively mixes in mortar, the raw material that mixes is put into mould to be pressed into little cylindric, every cylinder height 2-4cm, weight 30-60g, with the block raw material that presses put into can circulating ventilation loft drier, bake out temperature is controlled at 200-350 ℃, time is 30 minutes, and this process is equivalent to the frit pre-burning, also portion of water is evaporated simultaneously.
Preparation method of the present invention, in order to reduce next pollution to crucible, adopt the platinum alloy crucible in this technology of preparing, pre-burned frit is put into crucible, carry out melting in elevator furnace, being heated to peak temperature is 900 ℃-1400 ℃, and smelting time is 1-2 hour, makes melts become uniform liquid fully.
After melting is completed, crucible is taken out while hot, frit is carried out quench treatment, at first contain into deionized water in large stainless steel cask, the water yield is generally calculated with the melt liquid that quenches, and the frit of general 1kg needs the deionized water of 50 liters, and the deionized water temperature is that room temperature gets final product.
The glass particle that has quenched needs ball-milling processing, pull the frit that has quenched out drainage, by weight zirconia ball: glass particle: water=10:1:1 ratio adds in the zirconium white crucible,, with the crucible cover tightening seal, is fixed in omnidirectional planetary ball mill and carries out, Ball-milling Time is 4-8 hour, rotating speed is 300～350 rev/mins, sheds owing to having heat in mechanical milling process, therefore, need discontinuous to suspend during ball milling, ball grinder is lowered the temperature naturally.
Glass powder that ball milling is good takes out, with 50 purpose screen clothes with zirconium pearl and residue filter out, and then with the volume glass powder natural subsidence of having filtered ten minutes, topple over the upper strata deionized water, can dry in the loft drier of circulating ventilation, bake out temperature is 120-180 ℃, time 4-6 hour.
After the glass powder oven dry, tentatively grind with the aluminum oxide mortar, then carry out airflow milling and break up, air pressure is controlled between 2000Pa-7000Pa, and flow is 2-5kg/h.The glass powder of breaing up is crossed vibratory screening apparatus, and the sieve number of sieving is the 300-500 order, obtains the finished glass powder, and particle diameter is at the 1-5 micron.
In another embodiment, can carry out the gas phase classification to the finished glass powder, glass powder is divided into particle diameter 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 ℃, and this softening temperature is by differential thermal analyzer, and namely DTA tests, the softening temperature (Ts) take second transformation peaks as glass powder.And thermal expansivity is 45-90 * 10
-7/ ℃, employing be thermal dilatometer test (the described thermal expansivity of this specification sheets is linear expansivity α), use silica glass as standard test specimen, probe temperature rises to 300 ℃ by room temperature.
The glass powder characteristic test:
According to the glass powder formula of table 1, adopt DTA and thermal dilatometer softening temperature (Ts) and the thermal expansivity (α) of tested glass powder respectively, Ts and the α of every kind of glass powder are shown in Table 2.
The slurry preparation
Glass powder, organic carrier and aluminium powder that weighing is suitable.The glass powder of this paper is added in organic carrier and to stir 15 minutes, then adding aluminium powder to stir, the amount that adds counts by weight percentage as glass powder 2.8%, aluminium powder 75%, and organic carrier 21.2%, other additives are 1%.The slurry that mixes is put into three-roll grinder roll evenly, reach below 15um to mesh-of-grind.
Sintering and performance test
To roll on the plated film polysilicon chip that the slurry of having starched is printed in 156mm*156mm sintering in continuous tunnel furnace.Cell piece is carried out electrical property and quantitative measurement.
Test battery efficiency of conversion and open circuit voltage on cell piece efficiency sorter, utilize the angularity of the plug pin test battery sheet that vernier callipers or industry use, cell piece being put into the water-bath of boiling boiled 10 minutes, whether the test battery sheet has the 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 all be shown in Table 2.
Claims (9)
1. lead-free glass powder that is used for the solar cell aluminium paste is characterized in that: this glass powder is mainly by 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%.
2. the lead-free glass powder for the solar cell aluminium paste according to claim 1 is characterized in that: this glass powder is mainly by 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%.
3. the lead-free glass powder for the solar cell aluminium paste according to claim 1 is characterized in that: this glass powder is mainly by 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%.
4. according to claim 1 and 2 or 3 described lead-free glass powders for the solar cell aluminium paste, it is characterized in that: this glass powder also comprises the zirconium white less than 0.5%.
5. the lead-free glass powder for the solar cell aluminium paste according to claim 4, it is characterized in that: described zn cpds is ZnO, ZnF
2, ZnCl
2, ZnS or Zn
3(PO
4)
2
6. the lead-free glass powder for the solar cell aluminium paste according to claim 4, it is characterized in that: described bismuth compound is Bi
2O
3, BiOF, BiOCl, bismuth titanates or pucherite.
7. lead-free glass powder for the solar cell aluminium paste claimed in claim 4, it is characterized in that: preparation process comprises:
(1) taking each component glass powder raw material according to formula rate respectively mixes in mortar, the raw material that mixes is put into mould be pressed into little right cylinder, with the block right cylinder raw material that presses put into can circulating ventilation loft drier, bake out temperature is controlled at 200-350 ℃, and the time is 20-30 minute;
(2) pre-burned frit is put into crucible, carry out melting in elevator furnace, being heated to the elevator furnace temperature is 900 ℃-1400 ℃, and smelting time is 1-2 hour, makes melts become uniform liquid fully;
(3) after melting is completed, crucible is taken out while hot, the frit liquid in crucible is carried out quench treatment, be specially frit liquid is poured in deionized water, the deionized water of every 50 liters adds the frit liquid of 0.5～1.5kg, and the deionized water temperature is that room temperature gets final product;
(4) frit after quenching is pulled drainage out, in following weight ratio: zirconia ball: frit: water=10:1:1 ratio adds in the zirconium white crucible,, with the crucible cover tightening seal, carries out ball milling, time is 4～8 hours, and the rotating speed of ball mill is 300～350 rev/mins;
(5) glass powder that ball milling is good takes out, with 50 purpose screen clothes with zirconia ball and residue filter out, then with the glass powder natural subsidence of having filtered ten minutes, topple over the upper strata deionized water, can dry in the loft drier of circulating ventilation, bake out temperature is 120-180 ℃, time 4-6 hour;
(6) after the glass powder oven dry, with the aluminum oxide mortar, grind evenly, then carry out airflow milling and break up, air pressure is controlled between 2000-7000Pa, and flow is 2-5kg/h; The glass powder of breaing up is crossed vibratory screening apparatus, and the sieve number of sieving is the 300-500 order, obtains the finished glass powder, and particle diameter is at the 1-5 micron.
8. the lead-free glass powder for the solar cell aluminium paste according to claim 7, it is characterized in that: the described cylinder height of step (1) is 2-4cm, and weight is 30-60g.
9. the lead-free glass powder for the solar cell aluminium paste according to claim 7, it is characterized in that: the described ball milling of step (4) is for to be fixed in crucible in omnidirectional planetary ball mill and to carry out ball milling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 CN103387340B (en) | 2016-02-10 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109166646A (en) * | 2018-08-14 | 2019-01-08 | 华中科技大学 | It is a kind of for carry on the back passivation silicon solar cell environment-friendly type aluminum electrode slurry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003095697A (en) * | 2001-09-18 | 2003-04-03 | Nihon Yamamura Glass Co Ltd | Sealing composition |
| JP2010076993A (en) * | 2008-09-29 | 2010-04-08 | Nihon Yamamura Glass Co Ltd | Lead-free and bismuth-free glass composition |
| 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 |
-
2013
- 2013-07-24 CN CN201310316246.5A patent/CN103387340B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003095697A (en) * | 2001-09-18 | 2003-04-03 | Nihon Yamamura Glass Co Ltd | Sealing composition |
| JP2010076993A (en) * | 2008-09-29 | 2010-04-08 | Nihon Yamamura Glass Co Ltd | Lead-free and bismuth-free glass composition |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109166646A (en) * | 2018-08-14 | 2019-01-08 | 华中科技大学 | It is a kind of for carry on the back passivation silicon solar cell environment-friendly type aluminum electrode slurry |
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| Publication number | Publication date |
|---|---|
| CN103387340B (en) | 2016-02-10 |
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