CN104176939A - Superfine lead-free glass powder for electrode slurry of solar battery, and preparation method thereof - Google Patents

Superfine lead-free glass powder for electrode slurry of solar battery, and preparation method thereof Download PDF

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Publication number
CN104176939A
CN104176939A CN201310200627.7A CN201310200627A CN104176939A CN 104176939 A CN104176939 A CN 104176939A CN 201310200627 A CN201310200627 A CN 201310200627A CN 104176939 A CN104176939 A CN 104176939A
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glass powder
lead
ball
free
free glass
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CN201310200627.7A
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Chinese (zh)
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赵军
陈义祥
琚伟
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New Material Institute of Shandong Academy of Sciences
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New Material Institute of Shandong Academy of Sciences
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Abstract

The invention discloses superfine lead-free glass powder for the electrode slurry of a solar battery and a preparation method thereof. Lead-free glass comprises 20% to 30% of SiO2, 40% to 70% of Bi2O3, 2% to 15% of B2O3, 1% to 10% of Sb2O3, 1 to 3% of ZnO and 1 to 3% of ZrO2. The preparation method comprises the following steps: (1) weighing of a mixture according to the above-mentioned proportion and addition of a pore forming agent (C and PVA); (2) melting of the mixture; (3) water quenching; and (4) planetary ball milling (sieving). The superfine glass powder is prepared through ball milling of environment-friendly lead-free porous glass powder by using this method; and compared with conventional products, the prepared lead-free superfine glass powder has the advantages of short ball milling time, low energy consumption, a small particle size and high activity. A high photoelectric conversion rate is obtained when the lead-free superfine glass powder is used for photovoltaic positive electrode slurry; after electrode silver slurry is sintered, low volume resistance is obtained, bonding strength between an electrode silver layer and Si is improved, and sintering temperature of silver slurry is reduced.

Description

A kind of ultra-fine lead-free glass powder and preparation method thereof for solar battery electrode slurry
Technical field
The present invention relates to the preparing technical field of lead-free glass powder, particularly the preparation method of ultra-fine lead-free glass powder for front electrode of solar battery conductive silver paste.
Background technology
Sun power is a kind of green, pollution-free, the inexhaustible energy, because these advantages are subject to people's attention.Crystal silicon solar energy battery is a kind of semiconducter device that solar energy converting can be become to electric energy, under the condition of illumination, converts solar energy into electrical energy, and electric current is collected and transferred out by grid line and electrode.Crystal silicon solar batteries surface electrode and grid line are that the technique such as the silk screen printing by high-speed, high precision, oven drying at low temperature, high temperature sintering is made by conductive silver paste.This conductive silver paste is prepared from by silver powder, glass powder and organic carrier conventionally.Secondly wherein glass powder liquefies in the time of Fast Sintering, first plays the effect of etching antireflective coating, plays cohesive action between silver powder and silicon substrate, makes to form between silver powder and silicon substrate good ohmic contact.Simultaneously, glassy phase is propagated intermediary as one and is existed, make silver-colored crystal be able to recrystallization growth on silicon substrate, particularly on the silicon substrate of [111] orientation, this can ensure during lower than the eutectic point of silver-silicon, to obtain the contact of good silver-silicon in processing temperature, makes to realize between silver powder and substrate good adhering to, and make the continuity of sintering rete, consistence better, effectively improve the photoelectric transformation efficiency of solar cell.The composition of glass powder, particle diameter, content, melt temperature all can affect the adhering to of electrode silver line, contact resistance and photoelectric transformation efficiency.
Glass powder in the domestic and international electrode silver plasm material using is at present mostly leaded, because plumbous oxide has reduction melt temperature, improves silica-based soaking, and making has good sticking power after slurry sintering.But lead has wherein caused very large harm to environment, human health.The laws and regulations requirement that China, European Union, Japan, the U.S. etc. have issued and implemented must not contain the elements such as lead, mercury, cadmium, sexavalent chrome in electronic product from 1 day July in 2006.The inexorable trend of electronic industry development so develop applicable lead-free glass powder.
Crown glass in China Patent Publication No. CN 102126829 A application documents, can slightly reduce the melt temperature of glass, but due to the larger 0.5～5um of its particle diameter, its surfactivity is low, can not reach silver slurry sintering time and the effect of the fine combination of silicon layer.
Summary of the invention
Technical problem solved by the invention is that, glass powder particle diameter high for glass ingredient softening temperature in current silica-based photovoltaic electrode slurry is large, large problem consumes energy in preparation process, the present invention has prepared the ultra-fine lead-free glass powder of photovoltaic slurry by ball milling porous glass powder, this lead-free glass powder melt temperature is low, particle diameter is little, production method is simple, less energy-consumption, the photovoltaic electrode adhesion of slurry of preparing with inferior glass powder is good, and optoelectronic transformation efficiency is high.So just, make electrode paste of silicon solar cell low-melting point lead-less glasses powder of the present invention, this glass powder is not containing objectionable impuritiess such as Pb, Cd, Hg, Cr (VI), and glass powder is the palladium powder of submicron, has good activity.
The pattern of glass powder and particle diameter factor also have material impact to its performance.At present, the preparation of glass powder adopts melting-shrend-ball milled conventionally, and pattern and the granularity of ball-milling technology to glass powder has great effect, and suitable ball-milling technology is the important guarantee of preparation high quality glass powder.In general, thick granule materials is milled to 10 μ m ratios to be easier to, required time is also longer, but the particle of 10 μ m is milled to several microns of even ultra-fine level ultrafine powder, Ball-milling Time will extend several times or longer, but along with the prolongation of Ball-milling Time, the corresponding increases of cost such as ball consumption, energy consumption, grinding efficiency declines.
Solving the technical problem the solution of the present invention existing is: the ultra-fine lead-free glass powder of a kind of crystal silicon solar energy battery, its composition comprises SiO 2, Bi 2o 3, B 2o 3, Sb 2o 3, ZnO, ZrO 2, the weight percent of each component is SiO 210%～40%, Bi 2o 330%～70%, B 2o 32%～25%, Sb 2o 31%～20%, ZnO 1～20%, ZrO 20～9%.。
The described ultra-fine lead-free glass powder of a kind of crystal silicon solar energy battery, its feature composition comprises: SiO 2, Bi 2o 3, B 2o 3, Sb 2o 3, the mass percent of each component is: SiO 220%～30%, Bi 2o 340%～70%, B 2o 32%～15%, Sb 2o 31%～10%, ZnO 1～3%, ZrO 21～3%.
A preparation method for ultra-fine lead-free glass powder for electrode of solar battery silver slurry, is characterized in that, the method comprises the following steps:
1 according to the ultra-fine lead-free glass powder proportioning composition raw materials weighing described in step, and its feature adds C, PVA pore-forming material to account for 30～50% of total mass, prepares sintered glass;
2 according to the ultra-fine lead-free glass powder described in step 1, it is characterized in that 1100～1350 DEG C of the lead-free glass powder melt temperatures of compound, and insulation 8～30min melting forms;
3 by unleaded the step 2 melten glass porous that quenching is 1～2cm in deionized water little glass block;
4 4～15mm ball wet methods that step 3 raw glass piece is selected are carried out planetary ball mill to porous crown glass, select dehydrated alcohol, water to do ball-milling medium.Ball-milling medium is water, ethanol, Ball-milling Time 1～10h, rotating speed 80～150r/min;
5 by the planetary ball mill parameter of the ultra-fine lead-free glass powder described in step 4 are: spherolite footpath 3～5mm, Ball-milling Time 10～20h, rotating speed 100～170r/min;
Step 5 is crossed 7000 mesh sieves by 6 removes larger particles, and the ultra-fine lead-free glass powder of palladium powder electrode paste of silicon solar cell, is characterized in that palladium powder is that class is spherical, its particle size range 0.2～0.8um and following palladium powder;
7 according to the ultra-fine lead-free glass powder described in step 6, and the softening temperature that it is characterized in that described glass powder is 450～550 DEG C, and the coefficient of expansion is 60～90 × 10 -7/ DEG C.
SiO in the present invention 2as glass-former, reduce the crystallization of glass; Bi 2o 3can significantly reduce the melt temperature of glass; B 2o 3as glass intermediate, regulate heat, the chemical stability of glass; ZnO is to regulating the chemical stability of glass and reducing linear expansivity; Sb 2o 3mainly to reducing glass softening point, melt temperature.
Embodiment
By specific embodiment, the present invention is specifically described in detail below
1 weighs compound according to mass percent:
SiO 2 10%～40%
Bi 2O 3 30%～70%
B 2O 3 2%～25%
Sb 2O 3 1%～20%
ZnO 1～20%
ZrO 2 0～9%
Add up to 100%
2 according to the ultra-fine lead-free glass powder described in step 1, and it is total amount 30-50% that its feature adds C, PVA pore-forming material, prepares sintered glass.
3 according to the ultra-fine lead-free glass powder described in step 2, it is characterized in that 1100～1350 DEG C of the lead-free glass powder melt temperatures of compound, and insulation 8～30min melting forms.
4 according to the unleaded little glass block of the step 3 melten glass porous that quenching is 1～2cm in deionized water
5 4～15mm ball wet methods of raw glass piece being selected according to step 4 are carried out planetary ball mill to porous crown glass, select dehydrated alcohol, water to do ball-milling medium, Ball-milling Time 3～10h, and rotating speed 80～150r/min, ball-milling medium is water, ethanol.
6 according to the planetary ball mill parameter of the ultra-fine lead-free glass powder described in step 5 are: spherolite footpath 3～5mm, Ball-milling Time 10～20h, rotating speed 100～170r/min.
7 cross 7000 mesh sieves according to step 6 removes larger particles, and the described ultra-fine lead-free glass powder of a kind of crystal silicon solar energy battery, is characterized in that palladium powder is that class is spherical, its particle size range 0.2～0.8um and following palladium powder.
Particle size range 0.2～the 0.8um of its lead-free glass powder of preferentially selecting and following palladium powder, the glass powder that particle diameter is less, specific surface area is larger, and activity is higher, is beneficial to and reduces softening temperature improvement and silica-based soaking and adhere to.
The melt temperature of preferred lead-free glass powder is 450～500 DEG C, and the coefficient of expansion is 50～90 × 10 ～7/ DEG C.
4 specific exampless of the present invention are as following table:
Component Example 1 Example 2 Example 3 Example 4
SiO 2 10 12 16 20
Bi 2O 3 47 52 58 63
B 2O 3 15 14 9 8
ZnO 16 14 9 4
Sb 2O 3 10 7 8 2
ZrO 2 2 1 0 3
Add up to 100 100 100 100
Pore-forming material/(pore-forming material+frit) 45 50 30 35
Heating temperature (DEG C) 1200 1150 1200 1300
Soaking time (min) 15 20 18 10
The radius (mm) of ball 5 6.2 7 9
Ball-milling Time (h) 4 6 3 10
The radius (mm) of ball 1.6 2 3 4.7
Ball-milling Time (h) 25 16 23 30
D50(μm) 0.3 0.8 1.2 2
Rotating speed (r/min) 170 150 130 100
Softening temperature 480 420 500 530
The coefficient of expansion (10 -7/℃） 57 63 51 90
Example 5
A preparation method for low lead crystal glass powder for electrode of solar battery silver slurry, comprises the following steps:
(1) a kind of crystalline silicon solar battery electrode silver slurry is as follows by the raw material composition mass percent of low lead crystal glass powder:
SiO 2 10%%、Bi 2O 3 55%、B 2O 3 15%、ZnO 15%、Sb 2O 32%、ZrO 2 3%
(2) in the selected crown glass compound of step (2), add C pore-forming material mass percent 43%.
(3) the crown glass compound of step (2) is used to crucible melting in retort furnace, temperature is 1100 DEG C, and soaking time is 20min.
(4) by the little glass block of step (3) the melten glass porous that quenching is 1～2cm in deionized water.
(5) the sintered glass piece of step (4) is carried out to Wet planet ball milling with 4～15mm ball to porous crown glass, select dehydrated alcohol, water to do ball-milling medium, Ball-milling Time 10h, rotating speed 80 r/min.
(6) select 1.6～5mm secondary wet process ball milling according to step (5), select dehydrated alcohol, water to do ball-milling medium, Ball-milling Time 20h, rotating speed 100r/min.
(7) cross 7000 mesh sieves and remove larger particles, get the particle size range 0.2～0.8um of its lead-free glass powder and following palladium powder.
Example 6
A preparation method for low lead crystal glass powder for electrode of solar battery silver slurry, comprises the following steps:
(1) a kind of crystalline silicon solar battery electrode silver slurry is as follows by the raw material composition mass percent of low lead crystal glass powder:
SiO 2 20%%、Bi 2O 3 65%、B 2O 3 5%、ZnO 7%、Sb 2O 3 2%、ZrO 2 1%
(2) in the selected crown glass compound of step (1), add polystyrene pore-forming material massfraction 45%.
(3) the crown glass compound of step (2) is used to crucible melting in retort furnace, temperature is 1300 DEG C, and soaking time is 10min.
(4) by the little glass block of step (3) the melten glass porous that quenching is 1～2cm in deionized water.
(5) the sintered glass piece of step (4) is carried out to Wet planet ball milling with 4～15mm ball to porous crown glass, select dehydrated alcohol, water to do ball-milling medium, Ball-milling Time 3h, rotating speed 150 r/min.
(6) select 1.6～5mm secondary wet process ball milling according to step (5), select dehydrated alcohol, water to do ball-milling medium, Ball-milling Time 10h, rotating speed 170r/min.
(7) cross 7000 mesh sieves and remove larger particles, get the particle size range 0.2～0.8um of its lead-free glass powder and following palladium powder.

Claims (3)

1. a solar cell anode silver paste low lead crystal glass powder, is characterized in that, the raw material of this low lead crystal glass powder comprises following component and weight percentage: SiO 210%～40%, Bi 2o 330%～70%, B 2o 32%～25%, Sb 2o 31%～20%, ZnO 1～20%, ZrO 20～9%.
2. the ultra-fine lead-free glass powder of a kind of crystal silicon solar energy battery according to claim 1, its feature composition comprises: SiO 2, Bi 2o 3, B 2o 3, Sb 2o 3, the mass percent of each component is: SiO 220%～30%, Bi 2o 340%～70%, B 2o 32%～15%, Sb 2o 31%～10%, ZnO 1～3%, ZrO 21～3%.
3. a preparation method for low lead crystal glass powder for solar cell anode silver paste according to claim 2, is characterized in that, the method comprises the following steps:
(1) weigh compound according to proportioning raw materials.Wherein, the raw material of this low lead crystal glass powder comprises following component and weight percentage: SiO 210%～40%, Bi 2o 330%～70%, B 2o 32%～25%, Sb 2o 31%～20%, ZnO 1～20%, ZrO 20～9%.
(2), according to ultra-fine lead-free glass powder step (1) Suo Shu, its feature adds C, PVA pore-forming material to account for the percentage 30～50% of total mass, prepares sintered glass.
(3) according to ultra-fine lead-free glass powder step (2) Suo Shu, it is characterized in that 1100～1350 DEG C of the lead-free glass powder melt temperatures of compound, insulation 8～30min melting forms.
(4) according to the unleaded little glass block of step (3) the melten glass porous that quenching is 1～2cm in deionized water.
(5) 4～15mm ball wet method of according to step (4), raw glass piece being selected is carried out planetary ball mill to porous crown glass, selects dehydrated alcohol, water to do ball-milling medium, Ball-milling Time 1～10h, and rotating speed 80～150r/min, ball-milling medium is water, ethanol.
(6) according to the planetary ball mill parameter of ultra-fine lead-free glass powder step (5) Suo Shu be: spherolite footpath 3～5mm, Ball-milling Time 10～20h, rotating speed 100～170r/min.
(7), according to the ultra-fine lead-free glass powder of a kind of crystal silicon solar energy battery step (6) Suo Shu, it is characterized in that palladium powder is that class is spherical, its particle size range 0.2～0.8um and following palladium powder.
(8) cross 7000 mesh sieve according to step (7), the ultra-fine lead-free glass powder of described silicon solar cell, the softening temperature that it is characterized in that described glass powder is 450～550 DEG C, the coefficient of expansion is 6～9 × 10 -7/ DEG C.
CN201310200627.7A 2013-05-27 2013-05-27 Superfine lead-free glass powder for electrode slurry of solar battery, and preparation method thereof Pending CN104176939A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105731812A (en) * 2016-01-14 2016-07-06 西安宏星电子浆料科技有限责任公司 Lead-free low-softening point acid-resistant glass powder for chip component paste and preparation method
CN106565101A (en) * 2016-11-08 2017-04-19 中国建筑材料科学研究总院 Vacuum glass supporting material, preparation method and vacuum glass
CN107500549A (en) * 2017-08-14 2017-12-22 广东工业大学 A kind of microcrystalline glass powder, its preparation method and silver paste
CN107892483A (en) * 2017-11-11 2018-04-10 蚌埠承永玻璃制品有限公司 A kind of insulating foam method for glass preparation
CN113149445A (en) * 2021-02-01 2021-07-23 上海大学 Method for uniformly refining low-temperature lead-free glass powder by using ultrahigh-pressure microjet and application thereof
CN113345622A (en) * 2021-06-28 2021-09-03 河源市飞利华电子有限公司 High-temperature sintered silver paste special for ceramic substrate RFID and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105731812A (en) * 2016-01-14 2016-07-06 西安宏星电子浆料科技有限责任公司 Lead-free low-softening point acid-resistant glass powder for chip component paste and preparation method
CN106565101A (en) * 2016-11-08 2017-04-19 中国建筑材料科学研究总院 Vacuum glass supporting material, preparation method and vacuum glass
CN107500549A (en) * 2017-08-14 2017-12-22 广东工业大学 A kind of microcrystalline glass powder, its preparation method and silver paste
CN107892483A (en) * 2017-11-11 2018-04-10 蚌埠承永玻璃制品有限公司 A kind of insulating foam method for glass preparation
CN113149445A (en) * 2021-02-01 2021-07-23 上海大学 Method for uniformly refining low-temperature lead-free glass powder by using ultrahigh-pressure microjet and application thereof
CN113345622A (en) * 2021-06-28 2021-09-03 河源市飞利华电子有限公司 High-temperature sintered silver paste special for ceramic substrate RFID and preparation method thereof
CN113345622B (en) * 2021-06-28 2023-02-28 河源市飞利华电子有限公司 High-temperature sintered silver paste special for ceramic substrate RFID and preparation method thereof

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Application publication date: 20141203