CN102432184A - Low melting point phosphate glass powder for silver paste of solar battery and preparation method thereof - Google Patents

Low melting point phosphate glass powder for silver paste of solar battery and preparation method thereof Download PDF

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Publication number
CN102432184A
CN102432184A CN2011102849584A CN201110284958A CN102432184A CN 102432184 A CN102432184 A CN 102432184A CN 2011102849584 A CN2011102849584 A CN 2011102849584A CN 201110284958 A CN201110284958 A CN 201110284958A CN 102432184 A CN102432184 A CN 102432184A
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Prior art keywords
glass powder
silver paste
melting point
solar cells
lower melting
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CN2011102849584A
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胡晓斌
王鑫
赵斌元
侯小宝
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NINGBO JINGXIN ELECTRONIC MATERIAL CO Ltd
Shanghai Jiaotong University
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NINGBO JINGXIN ELECTRONIC MATERIAL CO Ltd
Shanghai Jiaotong University
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Abstract

The invention relates to low melting point phosphate glass powder for silver paste of a solar battery and a preparation method thereof. The glass powder consists of the components by weight percentage as follows: 0.1-30% of P2O5, 10-40% of Bi2O3, 0-9% of B2O3, 0-20% of Al2O3, 8-25% of SiO2, 0-5% of CuO, 0-9% of LiO2 and 0-7% of ZrO2. Not all the weight percentages of the components are 0 at the same time. The components are heated to form a uniform and clarified glass liquid which is dried, ball-milled and sieved to obtain the low melting point phosphate glass powder for the silver paste of the solar battery. Compared with prior art, the invention has the advantages that the lead free glass powder for the anode silver paste of the solar battery is lead free, meets the requirements of environmental protection and is harmless to human at the same time; the sintered electron slurry prepared by the glass powder provided by the invention is matched with the expansion coefficient of a silicon wafer, and has small contractibility rate, and warping degree of solar battery and high battery flakiness; and the sintered electron slurry prepared by the glass powder provided by the invention has high conversion efficiency.

Description

A kind of silver paste of solar cells is with lower melting point phosphate glass powder and preparation method thereof
Technical field
The present invention relates to technical field of electronic materials, especially relate to a kind of silver paste of solar cells with lower melting point phosphate glass powder and preparation method thereof.
Background technology
Receive the shortage and the requirement on environmental protection of international energy; The new forms of energy relevant item is the just speed development to make rapid progress under the support energetically of country, and wherein crystal silicon solar energy battery is especially obvious in the effect of performance aspect the energy-saving and emission-reduction as most important a kind of new forms of energy battery.
In the preparation process of crystalline silicon, by serigraphy the silver slurry is printed on the silicon chip, by sintering, form good silver-colored silicon alloy, play the effect of lead, the electric energy that solar cell is produced converges derivation.
The composition of silver slurry mainly by: silver powder, glass powder, solvent, resin and other additives are formed.Wherein the effect of glass powder is in the process of silver powder and silicon chip formation alloy, to play short molten effect, makes silver and silicon formation good Ohmic contact.
Because solar cell is to adopt to dodge the special process that burns, therefore require used for solar batteries silver slurry to be different from the special sintering curre of other high temperature silver slurries.The preparation of glass powder need be considered the matching with the slurry sintering curre, except in prescription and technologic singularity, also suitable softening temperature, the coefficient of expansion, granularity etc. need be arranged.
There is following weak point in present domestic glass powder existing techniques: behind (1) made electric slurry sintering and the silicon chip coefficient of expansion do not match, shrinking percentage is big, causes that the solar cell angularity is big, causes battery sheet yield rate low.(2) ohmic contact resistance with silicon chip is big behind the made electric slurry sintering, therefore causes the transformation efficiency of solar cell low.
Summary of the invention
The object of the invention is exactly to provide a kind of not leaded, compliance with environmental protection requirements for the defective that overcomes above-mentioned prior art existence.With silicon chip linear expansivity coupling, the silver paste of solar cells of yield rate and transformation efficiency that has improved solar cell is with lower melting point phosphate glass powder and preparation method thereof behind the electric slurry sintering after preparing.
The object of the invention can be realized through following technical scheme:
A kind of silver paste of solar cells comprises following composition and weight percent content with lower melting point phosphate glass powder:
P 2O 50.1 Bi～30%, 2O 310～40%, B 2O 30～9%, Al 2O 30～20%, SiO 28～25%, CuO0～5%, Li 2O 0～9%, ZrO 20～7%, above-mentionedly down be limited to 0 component, its lower limit all is not 0 simultaneously.
Form and weight percent content below described glass powder is preferred:
P 2O 5?10～25％、Bi 2O 3?20～30％、B 2O 3?3～7％、Al 2O 3?8～16％、SiO 2?8～24％、CuO1～4％、Li 2O?2～7％、ZrO 2?5～7％。
Described P 2O 5Weight percent content preferred 17～20%.
Described B 2O 3Weight percent content preferred 3～5%.
Described SiO 2Weight percent content preferred 17～18%.
Described Li 2The weight percent content of O preferred 5～6%.
A kind of silver paste of solar cells may further comprise the steps with the preparation method of lower melting point phosphate glass powder:
(1) get the raw materials ready according to following component and weight percent content:
P 2O 50.1 Bi～30%, 2O 310～40%, B 2O 30～9%, Al 2O 30～20%, SiO 28～25%, CuO0～5%, Li 2O 0～9%, ZrO 20～7%, above-mentionedly down be limited to 0 component, its lower limit all is not 0 simultaneously;
(2) said components is through mix fully; Guarantee homogeneity, the alumina crucible of packing into is with crucible preheating half a hour in 200～300 ℃ retort furnace; Transfer to 1100～1300 ℃ high temperature resistance furnace internal heating 0.5～2 hour then, form even clarifying glass metal;
(3) with founding the glass metal shrend in deionized water that obtains in the step (2), after cooling, with glass 70～110 ℃ of forced air dryings;
(4) step (3) is made the glass obtain with 100～150 rev/mins of the big abrading-balls of φ 20～30mm, dry grinded 0.5～2 hour;
(5) the big abrading-ball in the step (4) is changed into the little abrading-ball of φ 1～6mm, add alcohol, 150～300 rev/mins, ball milling 8～20 hours;
(6) glass powder behind step (5) ball milling is filtered through 200～400 purpose woven wires;
(7) with the glass powder in the step (6) 60～80 ℃ of forced air dryings, promptly obtain silver paste of solar cells with lower melting point phosphate glass powder.
Preferred 250～280 ℃ of the preheating temperature of the retort furnace described in the step (2).
Preferred 1190～1280 ℃ of the temperature of the high temperature resistance furnace described in the step (2).
Compared with prior art, the present invention possesses following three characteristics:
One, the anodal silver slurry of the solar cell of preparation is unleaded with lead-free glass powder, and compliance with environmental protection requirements is simultaneously harmless.
Two, with behind the made electric slurry sintering of glass powder of the present invention and silicon chip coefficient of expansion coupling, shrinking percentage is little, and the solar cell angularity is little, and battery rate in blocks is high.
Three, high with transformation efficiency behind the made electric slurry sintering of glass powder of the present invention.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1～4
(1) the anodal silver slurry of a kind of crystal silicon solar energy battery is used lead-free glass powder, and its composition is as shown in table 1;
(2) with the raw material of narrating in (1) proportionally weighing good after; Through mixing fully; Guarantee homogeneity, the alumina crucible of packing into is with crucible preheating half a hour in 200～300 ℃ retort furnace; Transfer to 1100～1300 ℃ high temperature resistance furnace internal heating 0.5～2 hour then, form even clarifying glass metal.
(3) with founding the glass metal shrend in deionized water that performs in the step (2), after cooling, with glass 70～110 ℃ of forced air dryings.
(4) with the glass of step (3) with 100～150 rev/mins of the big abrading-balls of φ 20～30mm, dry grinded 0.5～2 hour.
(5) the big abrading-ball in the step (4) is changed into the little abrading-ball of φ 1～6mm, add alcohol, 150～300 rev/mins, ball milling 8～20 hours.
(6) the glass powder solution after good with step (5) ball milling filters through 200～400 purpose woven wires.
(7) with the glass powder solution in the step (6) 60～80 ℃ of forced air dryings, just make silver paste of solar cells of the present invention with lower melting point phosphate glass powder, the processing parameter of above-mentioned each step is specifically as shown in table 1.
4 specific exampless of the present invention are as shown in the table:
Table 1
Figure BDA0000093601260000041
Embodiment 5
A kind of silver paste of solar cells is with lower melting point phosphate glass powder, and this glass powder is made up of and content is formed: P following 2O 50.1kg, Bi 2O 340kg, B 2O 36.9kg, Al 2O 315kg, SiO 225kg, Li 2O 6kg, ZrO 27kg, this silver paste of solar cells may further comprise the steps with the preparation method of lower melting point phosphate glass powder:
(1) gets the raw materials ready according to above-mentioned recipe ingredient and content;
(2) said components guarantees homogeneity through mixing fully, and the alumina crucible of packing into crucible preheating half a hour in 200 ℃ retort furnace, is transferred to 1100 ℃ high temperature resistance furnace internal heating 2 hours then, forms even clarifying glass metal;
(3) with founding the glass metal shrend in deionized water that obtains in the step (2), after cooling, with glass 70 ℃ of forced air dryings;
(4) step (3) is made the glass obtain with 100 rev/mins of the big abrading-balls of φ 20mm, dry grinded 2 hours;
(5) the big abrading-ball in the step (4) is changed into the little abrading-ball of φ 1mm, add alcohol, 150 rev/mins, ball milling 20 hours;
(6) glass powder behind step (5) ball milling is filtered through 200 purpose woven wires;
(7) with the glass powder in the step (6) 60 ℃ of forced air dryings, promptly obtain silver paste of solar cells with lower melting point phosphate glass powder.
Embodiment 6
A kind of silver paste of solar cells is with lower melting point phosphate glass powder, and this glass powder is made up of and content is formed: P following 2O 530kg, Bi 2O 335kg, Al 2O 313kg, SiO 28kg, CuO 5kg, Li 2O 9kg, silver paste of solar cells may further comprise the steps with the preparation method of lower melting point phosphate glass powder:
(1) gets the raw materials ready according to above-mentioned recipe ingredient and content;
(2) said components guarantees homogeneity through mixing fully, and the alumina crucible of packing into crucible preheating half a hour in 300 ℃ retort furnace, is transferred to 1200 ℃ high temperature resistance furnace internal heating 1 hour then, forms even clarifying glass metal;
(3) with founding the glass metal shrend in deionized water that obtains in the step (2), after cooling, with glass 100 ℃ of forced air dryings;
(4) step (3) is made the glass obtain with 120 rev/mins of the big abrading-balls of φ 20mm, dry grinded 1 hour;
(5) the big abrading-ball in the step (4) is changed into the little abrading-ball of φ 5mm, add alcohol, 200 rev/mins, ball milling 12 hours;
(6) glass powder behind step (5) ball milling is filtered through 300 purpose woven wires;
(7) with the glass powder in the step (6) 70 ℃ of forced air dryings, promptly obtain silver paste of solar cells with lower melting point phosphate glass powder.
Embodiment 7
A kind of silver paste of solar cells is with lower melting point phosphate glass powder, and this glass powder is made up of and content is formed: P following 2O 528kg, Bi 2O 331kg, B 2O 39kg, SiO 222kg, CuO 4kg, ZrO 26kg, silver paste of solar cells may further comprise the steps with the preparation method of lower melting point phosphate glass powder:
(1) gets the raw materials ready according to above-mentioned recipe ingredient and content;
(2) said components guarantees homogeneity through mixing fully, and the alumina crucible of packing into crucible preheating half a hour in 300 ℃ retort furnace, is transferred to 1300 ℃ high temperature resistance furnace internal heating 0.5 hour then, forms even clarifying glass metal;
(3) with founding the glass metal shrend in deionized water that obtains in the step (2), after cooling, with glass 110 ℃ of forced air dryings;
(4) step (3) is made the glass obtain with 150 rev/mins of the big abrading-balls of φ 30mm, dry grinded 0.5 hour;
(5) the big abrading-ball in the step (4) is changed into the little abrading-ball of φ 1～6mm, add alcohol, 300 rev/mins, ball milling 8 hours;
(6) glass powder behind step (5) ball milling is filtered through 400 purpose woven wires;
(7) with the glass powder in the step (6) 80 ℃ of forced air dryings, promptly obtain silver paste of solar cells with lower melting point phosphate glass powder.

Claims (9)

1. a silver paste of solar cells is characterized in that with lower melting point phosphate glass powder this glass powder comprises following composition and weight percent content:
P 2O 50.1 Bi～30%, 2O 310～40%, B 2O 30～9%, Al 2O 30～20%, SiO 28～25%, CuO0～5%, Li 2O 0～9%, ZrO 20～7%, above-mentionedly down be limited to 0 component, its lower limit all is not 0 simultaneously.
2. a kind of silver paste of solar cells according to claim 1 is characterized in that with lower melting point phosphate glass powder, forms and weight percent content below described glass powder is preferred:
P 2O 5?10～25％、Bi 2O 3?20～30％、B 2O 3?3～7％、Al 2O 3?8～16％、SiO 2?8～24％、CuO1～4％、Li 2O?2～7％、ZrO 2?5～7％。
3. a kind of silver paste of solar cells according to claim 1 is characterized in that with lower melting point phosphate glass powder, described P 2O 5Weight percent content preferred 17～20%.
4. a kind of silver paste of solar cells according to claim 1 is characterized in that with lower melting point phosphate glass powder, described B 2O 3Weight percent content preferred 3～5%.
5. a kind of silver paste of solar cells according to claim 1 is characterized in that with lower melting point phosphate glass powder, described SiO 2Weight percent content preferred 17～18%.
6. a kind of silver paste of solar cells according to claim 1 is characterized in that with lower melting point phosphate glass powder, described Li 2The weight percent content of O preferred 5～6%.
7. a silver paste of solar cells as claimed in claim 1 is characterized in that with the preparation method of lower melting point phosphate glass powder this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight percent content:
P 2O 50.1 Bi～30%, 2O 310～40%, B 2O 30～9%, Al 2O 30～20%, SiO 28～25%, CuO0～5%, Li 2O 0～9%, ZrO 20～7%, above-mentionedly down be limited to 0 component, its lower limit all is not 0 simultaneously;
(2) said components is through mix fully; Guarantee homogeneity, the alumina crucible of packing into is with crucible preheating half a hour in 200～300 ℃ retort furnace; Transfer to 1100～1300 ℃ high temperature resistance furnace internal heating 0.5～2 hour then, form even clarifying glass metal;
(3) with founding the glass metal shrend in deionized water that obtains in the step (2), after cooling, with glass 70～110 ℃ of forced air dryings;
(4) step (3) is made the glass obtain with 100～150 rev/mins of the big abrading-balls of φ 20～30mm, dry grinded 0.5～2 hour;
(5) the big abrading-ball in the step (4) is changed into the little abrading-ball of φ 1～6mm, add alcohol, 150～300 rev/mins, ball milling 8～20 hours;
(6) glass powder behind step (5) ball milling is filtered through 200～400 purpose woven wires;
(7) with the glass powder in the step (6) 60～80 ℃ of forced air dryings, promptly obtain silver paste of solar cells with lower melting point phosphate glass powder.
8. a kind of silver paste of solar cells according to claim 7 is characterized in that with the preparation method of lower melting point phosphate glass powder, preferred 250～280 ℃ of the preheating temperature of the retort furnace described in the step (2).
9. a kind of silver paste of solar cells according to claim 7 is characterized in that with the preparation method of lower melting point phosphate glass powder, preferred 1190～1280 ℃ of the temperature of the high temperature resistance furnace described in the step (2).
CN2011102849584A 2011-09-22 2011-09-22 Low melting point phosphate glass powder for silver paste of solar battery and preparation method thereof Pending CN102432184A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875020A (en) * 2012-09-27 2013-01-16 广东风华高新科技股份有限公司 Lead-free glass material and preparation method thereof
CN103553345A (en) * 2013-09-22 2014-02-05 江苏瑞德新能源科技有限公司 Phosphate glass powder for solar cell silver paste
CN104064286A (en) * 2014-07-10 2014-09-24 吴旦英 Preparation method for silver paste used for solar battery
CN104058595A (en) * 2014-07-06 2014-09-24 吴旦英 Lead-free glass powder used for solar battery silver paste
CN110372220A (en) * 2019-08-16 2019-10-25 西北大学 A kind of Bi base lead-free glass powder and its preparation method and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1870180A (en) * 2006-06-28 2006-11-29 华东微电子技术研究所合肥圣达实业公司 Environment pretection leadless surface silver coating for PTC ceramic and its preparation method
CN101271929A (en) * 2008-05-04 2008-09-24 常州亿晶光电科技有限公司 Lead-free solar cell silver paste and preparation method thereof
CN101630695A (en) * 2009-08-05 2010-01-20 贵研铂业股份有限公司 Lead-free cadmium-free electrode slurry for crystalline silicon solar battery and preparation method thereof
CN101984494A (en) * 2010-12-09 2011-03-09 东南大学 Anti-settling photosensitive silver paste and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1870180A (en) * 2006-06-28 2006-11-29 华东微电子技术研究所合肥圣达实业公司 Environment pretection leadless surface silver coating for PTC ceramic and its preparation method
CN101271929A (en) * 2008-05-04 2008-09-24 常州亿晶光电科技有限公司 Lead-free solar cell silver paste and preparation method thereof
CN101630695A (en) * 2009-08-05 2010-01-20 贵研铂业股份有限公司 Lead-free cadmium-free electrode slurry for crystalline silicon solar battery and preparation method thereof
CN101984494A (en) * 2010-12-09 2011-03-09 东南大学 Anti-settling photosensitive silver paste and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875020A (en) * 2012-09-27 2013-01-16 广东风华高新科技股份有限公司 Lead-free glass material and preparation method thereof
CN103553345A (en) * 2013-09-22 2014-02-05 江苏瑞德新能源科技有限公司 Phosphate glass powder for solar cell silver paste
CN104058595A (en) * 2014-07-06 2014-09-24 吴旦英 Lead-free glass powder used for solar battery silver paste
CN104058595B (en) * 2014-07-06 2016-06-22 吴旦英 A kind of lead-free glass powder of silver paste of solar cells
CN104064286A (en) * 2014-07-10 2014-09-24 吴旦英 Preparation method for silver paste used for solar battery
CN104064286B (en) * 2014-07-10 2016-04-20 吴旦英 A kind of preparation method of silver slurry used for solar batteries
CN110372220A (en) * 2019-08-16 2019-10-25 西北大学 A kind of Bi base lead-free glass powder and its preparation method and application

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Inventor after: Hu Xiaobin

Inventor after: Wang Xin

Inventor after: Zhao Binyuan

Inventor after: Hou Xiaobao

Inventor before: Hu Xiaobin

Inventor before: Wang Xin

Inventor before: Zhao Binyuan

Inventor before: Hou Xiaobao

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Application publication date: 20120502