CN102701595B - Lead-free glass powder and preparation method thereof - Google Patents
Lead-free glass powder and preparation method thereof Download PDFInfo
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- CN102701595B CN102701595B CN201210222693.XA CN201210222693A CN102701595B CN 102701595 B CN102701595 B CN 102701595B CN 201210222693 A CN201210222693 A CN 201210222693A CN 102701595 B CN102701595 B CN 102701595B
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- glass powder
- lead
- free glass
- glass
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Abstract
The invention provides lead-free glass powder and a preparation method thereof, and belongs to the fields of glass powder and solar cell. The lead-free glass powder comprises the following constituents by mass percent: 30-50% of Bi2O3 (bismuth oxide), 10-40% of B2O3, 1-10% of SiO2 (silica), 3-10% of Al2O3 (aluminum oxide), 5-8% of ZnO (zinc oxide), 2-5% of TiO2 (titanium dioxide), 1-5% of MgO (magnesium oxide), 1-3% of NaF (sodium fluoride), 1-3% of MnO2 (manganese dioxide), 1-4% of SnO2 (stannic oxide) and 0-2% of SrCl2 (strontium chloride). Mixture of ingredients of the lead-free glass powder is heated, preserved, fused and quenched by water, and then ball-milled to prepare the lead-free glass powder finally. The lead-free glass powder with low softening temperature, stable chemical property, proper expansion coefficient and wide sintering temperature range is finally prepared by the method disclosed by the invention.
Description
Technical field
The present invention relates to a kind of lead-free glass powder and preparation method thereof, especially for solar battery front side electric slurry, belong to glass powder and area of solar cell.
Background technology
Along with developing rapidly of global economy, energy consumption increases with surprising rapidity, and the world's explored essential mineral fuel storing storage and produced quantity allow of no optimist, and therefore the exploitation of new forms of energy have been become to the extremely urgent most important thing.This provides a very wide market, the main share that solar cell industry is just being captured market with its powerful advantage and prospect also just to the development and utilization of new forms of energy.Solar cell market is mainly taking silicon solar cell as main at present.
In the preparation process of silicon solar cell, conductive silver slurry is printed on the silicon substrate that scribbles antireflective film, form grid, be used for forming the lead-in wire motor of series-parallel connection between cell piece and improve the turnover ratio of battery.
Silver slurry is mainly made up of silver powder, glass powder, organic solvent and some additives thereof.The important role of glass powder, glass powder melts in the time of thermal treatment, and silicon face sunlight antireflection layer is melted, and the silver in slurry can be contacted with silicon face, and metal-powder is attached to silicon chip surface by glass binder simultaneously, forms fine and close conducting film uniformly.
Sun power silver slurry is in the market mainly leaded silver slurry, because the fusing point of lead-free glass powder is high, but the sintering curre cycle of silicon solar cell is short, and general lead-free glass powder can not melting within the extremely short time.Leaded slurry also causes a large amount of pollutions to environment simultaneously, does not meet environmental protection concept of today.So it is extremely urgent to develop solar energy electronic slurry lead-free glass powder.
Existing lead-free glass powder on market, as Na-Ca system and vanadium glass etc.Compare, Bi-B-Si system lead-free glass powder of the present invention has lower softening temperature; After sintering, can obtain the sticking power of more increasing, and ensure that silver electrode has good contacting with silicon substrate.
Summary of the invention
The invention provides a kind of lead-free glass powder, the softening temperature that solves lead-free glass powder in prior art is high, the problems such as temperature of fusion height.The softening temperature of this glass powder is low, and the coefficient of expansion is suitable, and after the silver slurry of system, sintering can obtain good sticking power on silicon substrate, and makes silver electrode and silicon substrate have good contacting.
For achieving the above object, technical scheme of the present invention is: the composition of lead-free glass powder and mass percent are: Bi
2o
330～50%, B
2o
310～40%, SiO
21～10%, Al
2o
33～10%, ZnO 5～8%, TiO
21～5%, MgO 1～5%, NaF 1～3%, MnO
21～3%, SnO
21～4%, SrCl
20～2%.By shrend after the mixed material heating insulation melting of lead-free glass powder ingredient composition, and then carry out ball milling, finally make lead-free glass powder.Concrete preparation process comprises as follows:
(1) carry out mix by the composition of lead-free glass powder and mass percent, heating and thermal insulation makes compound fully be melt into glass metal;
(2) glass metal is poured into water to shrend, makes its quick cooling formation glass particle;
(3) glass particle ball milling is become to glass powder, obtain solar battery front side barium crown glass powder for electronic slurry.
The batch mixing heating of described step (1) is to heat up from room temperature, and heat-up rate is 5～8 DEG C/min before 800 DEG C, and heat-up rate is 3～5 DEG C/min to 1100 DEG C～1300 DEG C insulation 60～120 minutes after 800 DEG C.
The particle diameter of the glass powder after described glass particle ball milling is 1 μ m～5 μ m.
The Bi that described preparation compound uses
2o
3, B
2o
3, SiO
2, Al
2o
3, ZnO, TiO
2, MgO, NaF, MnO
2, SnO
2and SrCl
2be common commercial powder, purity is more than 99.9wt%.
Principle of the present invention is: B
2o
3be the main glass forming agent in glass, in glass, exist with laminate structure, adding of boron can reduce softening temperature and the coefficient of expansion, makes the stable chemical nature of glass.
Bismuth is in adjacent position with plumbous on the periodic table of elements, and nucleidic mass is close, and atomic radius is more or less the same, and the two electronic level is close, and bismuth and lead all promote glass formation too, so Bi is the best element that replaces Pb in theory.Along with Bi
2o
3the increase of content, [BO
3] triangle body is broken, [BiO
4] tetrahedron result increases.Due to the scission of link effect of added Oxides, make [BO
3] and [BiO
4] be that main glass structure is weakened, the characteristic temperature of glass significantly reduces.
SiO
2and Al
2o
3add the tendency towards devitrification that can reduce glass, improve the chemical stability of glass simultaneously, and can regulate the coefficient of linear expansion of glass.
ZnO adds the chemical stability that can increase glass, reduces the coefficient of expansion of glass simultaneously.
Advantage of the present invention and positively effect:
(1) lead-free glass powder of the present invention and silicon substrate have higher sticking power and suitable coefficient of linear expansion 70 × 10
-7/ DEG C～78 × 10
-7/ DEG C, after ball milling, can obtain palladium powder, there is good wetting property with silver powder, silicon substrate, when slurry sintering, can effectively penetrate sintered membrane and silicon substrate has good ohmic contact, can replace traditional lead-free glass powder, prepare lead free solar electric slurry;
(2) the present invention finally obtains that softening temperature is minimum can be reached for 420 DEG C, and softening temperature, lower than general glass powder, is conducive to glass powder melting in sintering and fully wraps up silver-colored particle, makes the conductive network of silver-colored particle finer and close, and conductivity is better;
(3) the lead-free glass powder stable chemical nature that the present invention obtains, sintering range is wide 500 DEG C～and 900 DEG C, after sintering, be 2.6 N～5.8 N with the sticking power of silicon substrate.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the invention is not restricted to the following stated scope.
Embodiment 1: the concrete composition of lead-free glass powder prepared by the present invention is: Bi
2o
335%, B
2o
330%, SiO
22.5%, Al
2o
310%, ZnO 8%, TiO
22%, MgO 4%, NaF 1%, MnO
23%, SnO
22%, SrCl
21%.
The preparation method of lead-free glass powder of the present invention is as follows:
(1) carry out mix by the composition of above-mentioned lead-free glass powder and mass percent, heating and thermal insulation makes compound fully be melt into glass metal; Heating rate is to heat up from room temperature, and 800 DEG C of former heat-up rates are 5 DEG C/min, and 800 DEG C of later heat-up rates are 3 DEG C/min to 1100 DEG C insulation 120 minutes.
(2) glass metal is poured into shrend in deionized water, made its quick cooling formation glass particle;
(3) glass particle ball milling being become to particle diameter is the glass powder of 1 μ m～2 μ m, obtains solar battery front side barium crown glass powder for electronic slurry.
420 DEG C of the softening temperatures of gained solar battery front side electric slurry use glass powder are 3.8N with the sticking power of silicon substrate after sintering.
Embodiment 2: the concrete composition of lead-free glass powder prepared by the present invention is: Bi
2o
350%, B
2o
310%, SiO
210%, Al
2o
38%, ZnO 6%, TiO
21%, MgO 1%, NaF 3%, MnO
22%, SnO
21%.
The preparation method of lead-free glass powder of the present invention is as follows:
(1) carry out mix by the composition of above-mentioned lead-free glass powder and mass percent, heating and thermal insulation makes compound fully be melt into glass metal; Heating rate is to heat up from room temperature, and 800 DEG C of former heat-up rates are 6 DEG C/min, and 800 DEG C of later heat-up rates are 4 DEG C/min to 1200 DEG C insulation 60 minutes.
(2) glass metal is poured into shrend in deionized water, made its quick cooling formation glass particle;
(3) glass particle ball milling being become to particle diameter is the glass powder of 3 μ m～5 μ m, obtains solar battery front side barium crown glass powder for electronic slurry.
483 DEG C of the softening temperatures of gained solar battery front side electric slurry use glass powder are 3.6N with the sticking power of silicon substrate after sintering.
Embodiment 3: the concrete composition of lead-free glass powder prepared by the present invention is: Bi
2o
330%, B
2o
340%, SiO
21%, Al
2o
33%, ZnO 5%, TiO
25%, MgO 5%, NaF 2%, MnO
21%, SnO
24%, SrCl
22%.
The preparation method of lead-free glass powder of the present invention is as follows:
(1) carry out mix by the composition of above-mentioned lead-free glass powder and mass percent, heating and thermal insulation makes compound fully be melt into glass metal; Heating rate is to heat up from room temperature, and 800 DEG C of former heat-up rates are 8 DEG C/min, and 800 DEG C of later heat-up rates are 5 DEG C/min to 1300 DEG C insulation 80 minutes.
(2) glass metal is poured into shrend in deionized water, made its quick cooling formation glass particle;
(3) glass particle ball milling being become to particle diameter is the glass powder of 2 μ m～4 μ m, obtains solar battery front side barium crown glass powder for electronic slurry.
487 DEG C of the softening temperatures of gained solar battery front side electric slurry use glass powder are 3.3N with the sticking power of silicon substrate after sintering.
Embodiment 4: the concrete composition of lead-free glass powder prepared by the present invention is: Bi
2o
340%, B
2o
320%, SiO
210%, Al
2o
33%, ZnO 5%, TiO
23%, MgO 5%, NaF 2%, MnO
21%, SnO
24%, SrCl
22%.
The preparation method of lead-free glass powder of the present invention is as follows:
(1) carry out mix by the composition of above-mentioned lead-free glass powder and mass percent, heating and thermal insulation makes compound fully be melt into glass metal; Heating rate is to heat up from room temperature, and 800 DEG C of former heat-up rates are 7 DEG C/min, and 800 DEG C of later heat-up rates are 4 DEG C/min to 1220 DEG C insulation 90 minutes.
(2) glass metal is poured into shrend in deionized water, made its quick cooling formation glass particle;
(3) glass particle ball milling being become to particle diameter is the glass powder of 1 μ m～4 μ m, obtains solar battery front side barium crown glass powder for electronic slurry.
439 DEG C of the softening temperatures of gained solar battery front side electric slurry use glass powder are 3.3N with the sticking power of silicon substrate after sintering.
Claims (4)
1. a lead-free glass powder, is characterized in that the composition of lead-free glass powder and mass percent are: Bi
2o
330～50%, B
2o
310～40%, SiO
21～10%, Al
2o
33～10%, ZnO 5～8%, TiO
21～5%, MgO 1～5%, NaF 1～3%, MnO
21～3%, SnO
21～4%, SrCl
20～2%.
2. a preparation method for lead-free glass powder as claimed in claim 1, is characterized in that concrete steps comprise as follows:
(1) carry out mix by the composition of lead-free glass powder and mass percent, heating and thermal insulation makes compound be melt into glass metal;
(2) glass metal is poured into water to shrend, makes its cooling formation glass particle;
(3) glass particle ball milling is become to glass powder, obtain lead-free glass powder.
3. the preparation method of lead-free glass powder according to claim 2, it is characterized in that: the batch mixing heating of step (1) is to heat up from room temperature, heat-up rates are 5～8 DEG C/min before 800 DEG C, and heat-up rate is 3～5 DEG C/min to 1100 DEG C～1300 DEG C insulation 60～120 minutes after 800 DEG C.
4. the preparation method of lead-free glass powder according to claim 2, is characterized in that: the particle diameter of the glass powder after glass particle ball milling is 1 μ m～5 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210222693.XA CN102701595B (en) | 2012-07-02 | 2012-07-02 | Lead-free glass powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210222693.XA CN102701595B (en) | 2012-07-02 | 2012-07-02 | Lead-free glass powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102701595A CN102701595A (en) | 2012-10-03 |
| CN102701595B true CN102701595B (en) | 2014-10-01 |
Family
ID=46894728
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|---|---|---|---|
| CN201210222693.XA Expired - Fee Related CN102701595B (en) | 2012-07-02 | 2012-07-02 | Lead-free glass powder and preparation method thereof |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347688A (en) * | 2015-12-14 | 2016-02-24 | 周妙思 | Preparation method of glass powder for electronic paste |
| CN105417954A (en) * | 2015-12-14 | 2016-03-23 | 周妙思 | Unleaded glass powder |
| CN105502952A (en) * | 2015-12-14 | 2016-04-20 | 周妙思 | Glass powder |
| CN105679410B (en) * | 2016-04-26 | 2017-02-15 | 江阴市天邦涂料股份有限公司 | High-adhesion-stability silver-aluminum slurry for solar battery |
| CN105810759B (en) * | 2016-04-26 | 2017-07-25 | 江阴市天邦涂料股份有限公司 | A kind of silver-colored aluminum slurry used for solar batteries |
| CN105741907B (en) * | 2016-04-26 | 2017-07-07 | 江阴市天邦涂料股份有限公司 | A kind of unleaded silver paste used for solar batteries |
| CN107151099A (en) * | 2017-06-16 | 2017-09-12 | 北京市合众创能光电技术有限公司 | A kind of preparation method of conductive silver paste lead-free glass powder |
| CN110240414A (en) * | 2019-07-02 | 2019-09-17 | 黄山市晶特美新材料有限公司 | Acidproof environmentally friendly glass powder with low melting point of one kind and preparation method thereof |
| CN112551904A (en) * | 2020-12-18 | 2021-03-26 | 中国振华集团云科电子有限公司 | Acid-resistant glass powder for end coating of silver paste and preparation method thereof |
| CN115215544B (en) * | 2022-07-25 | 2023-07-25 | 昆明理工大学 | Semiconductor laser-induced color-changing lead-free glass and preparation method and application thereof |
| CN116332520A (en) * | 2023-03-27 | 2023-06-27 | 昆明理工大学 | Leadless glass powder and preparation method and application thereof |
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| CN101964219A (en) * | 2010-08-10 | 2011-02-02 | 上海九晶电子材料股份有限公司 | Silver paste for positive of crystalline silicon solar cell and preparation method thereof |
| CN102001833A (en) * | 2010-12-20 | 2011-04-06 | 昆明理工大学 | Unleaded glass powder used for electronic paste and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4839539B2 (en) * | 2001-07-24 | 2011-12-21 | 旭硝子株式会社 | Lead-free glass, glass frit, glass paste, electronic circuit components and electronic circuits |
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2012
- 2012-07-02 CN CN201210222693.XA patent/CN102701595B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101964219A (en) * | 2010-08-10 | 2011-02-02 | 上海九晶电子材料股份有限公司 | Silver paste for positive of crystalline silicon solar cell and preparation method thereof |
| CN102001833A (en) * | 2010-12-20 | 2011-04-06 | 昆明理工大学 | Unleaded glass powder used for electronic paste and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-34550A 2003.02.07 |
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Granted publication date: 20141001 Termination date: 20160702 |