CN102603195A - Lead-free glass powder for solar electrode sizing agent and preparation method thereof - Google Patents
Lead-free glass powder for solar electrode sizing agent and preparation method thereof Download PDFInfo
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- CN102603195A CN102603195A CN2012100302727A CN201210030272A CN102603195A CN 102603195 A CN102603195 A CN 102603195A CN 2012100302727 A CN2012100302727 A CN 2012100302727A CN 201210030272 A CN201210030272 A CN 201210030272A CN 102603195 A CN102603195 A CN 102603195A
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- free glass
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Abstract
The invention discloses lead-free glass powder for solar electrode sizing agent and a preparation method of the lead-free glass powder. The components of the lead-free glass powder are as follows in parts by weight: 50-80 of Bi2O3, 1-20 of SiO2, 5-30 of ZnO, 1-5 of Al2O3, 0.1-10 of CaO, 0.1-5 of MgO and 0.1-5 of Sb2O3. The raw materials are dosed, mixed, melted, quenched, ball-milled, dried and screened to be prepared into the lead-free glass powder for the solar electrode sizing agent. The glass powder has suitable expansion coefficient, good chemical stability, appropriate softening temperature and excellent wetting ability, is easy to realize industrial production, and is suitable for the fields of solar electrode sintering sizing agent and sizing agents for sealing glass with metal and ceramics, and the operation process is simple.
Description
Technical field
The present invention relates to technical field of electronic materials, be specifically related to a kind of sun power electrode slurry with lead-free glass powder and preparation method thereof.
Background technology
The silver slurry that silicon solar cell is used, silver-colored aluminium paste and aluminium paste are the key foundation materials of producing the silicon solar photovoltaic cell.Above-mentioned slurry mainly is made up of raw materials such as silver powder aluminium powder, palladium powder, organic carrier and properties-correcting agent according to a certain percentage.The weight percent of palladium powder in slurry is generally less than 10%, but played important effect.Add after the palladium powder, can obviously reduce the sintering peak temperature, make metallic aluminium powder behind peak temperature, form the aluminium film, and the aluminium film surface that forms smooth, do not play ash, film and silicon chip have stronger sticking power simultaneously.In addition, glass powder has fundamental influence to the bending of silicon chip.
Modal glass frit composition has PbO-ZnO-B
2O
3System, PbO-B
2O
3-SiO
2System, PbO-Bi
2O
3-B
2O
3System, PbO-B
2O
3System etc.The benefit that in the glass ingredient of front electrode silver slurry, backplate silver slurry and backplate aluminium paste that crystal silicon solar energy battery is used, contains PbO is effectively to reduce the sintering temperature of glass melting temperature, softening temperature and electrode; And when high temperature once burns fast altogether; Help the interaction with the crystalline silicon matrix, form low resistance contact with crystalline silicon.Yet; Continuous foundation and reinforcement along with global energy-conserving and environment-protective laws and regulations; States such as European Union, the U.S., Japan have put into effect dependent instruction and rules, and China Ministry of Information Industry has also formulated " electronics and information industry portion pollute protection management method " and limited comprehensively or forbid using in the electronic product poisonous and harmful elements such as lead, mercury, cadmium.Therefore in photovoltaic industry, be necessary to seek plumbous surrogate, to meet the ROHS of European Union, the REACH of European Union to the requirement of crystal silicon solar energy battery with silver-colored aluminium paste.
Along with deepening continuously of the unleaded research of glass powder, be used for substituting other glass systems that the material of flint glass powder mainly concentrates on phosphate glass system, vanadate glass system, borate glass system and derived from by above-mentioned system.CN200910102946.8 discloses a kind of B
2O
3-ZnO-CaO-Al
2O
3-BaO-Fe
2O
3-SrO glass powder system, this system has the lower coefficient of expansion, and chemicalstability is good; CN200910102944.9 also discloses the lower SiO of a kind of coefficient of expansion
2-B
2O
3-Al
2O
3-ZnO-MgO-CaO-Li
2O glass powder system.The glass transition point and the softening temperature of above-mentioned glass powder system are higher, are necessary crown glass powder component of the prior art is done further research.
Summary of the invention
The objective of the invention is to overcome the defective that exists in the prior art; Provide a kind of sun power electrode slurry to form with lead-free glass powder, and a kind of preparation method who is applicable to this sun power electrode slurry with lead-free glass powder is provided, this lead-free glass powder has the suitable coefficient of expansion; Chemicalstability is good; Softening temperature is suitable, and has good wetting ability, and the preparation method is simple to operation.
For realizing above-mentioned purpose, technical scheme of the present invention is: the component of lead-free glass powder comprises the Bi of 50～80wt%
2O
3, 1～20wt% SiO
2, the ZnO of 5～30wt%, the Al of 1～5wt%
2O
3, the CaO of 0.1～10wt%, the MgO of 0.1～5wt% and the Sb of 0.1～5wt%
2O
3
Optimized technical scheme is that the component of said lead-free glass powder comprises: the Bi of 65～80wt%
2O
3, 5～20wt% SiO
2, the ZnO of 5～20wt%, the Al of 2～5wt%
2O
3, the CaO of 1～2wt%, the MgO of 0.1～2wt%, the Sb of 0.5～2wt%
2O
3
Optimized technical scheme is that the granularity of said lead-free glass powder is not more than 5 μ m.
Another technical scheme of the present invention is, the preparation method of a kind of sun power electrode slurry with lead-free glass powder is provided, and it is characterized in that said preparation method may further comprise the steps:
The first step: press following proportional arrangement raw material: the Bi of 50～80wt%
2O
3, 1～20wt% SiO
2, the ZnO of 5～30wt%, the Al of 1～5wt%
2O
3, the CaO of 0.1～10wt%, the MgO of 0.1～5wt% and the Sb of 0.1～5wt%
2O
3
Second step: raw material described in the first step is fully mixed;
The 3rd step: the mixture of the second step gained is added in the crucible, crucible is placed High Temperature Furnaces Heating Apparatus, the stage is warming up to 1250～1400 ℃, is incubated 30～60 minutes;
The 4th step: pour the glass metal of the 3rd step gained into the de-ionized quenching-in water;
The 5th step: the frit after will quenching is put into the ball mill ball milling;
The 6th step: the frit behind the ball milling is dry, sieve, promptly obtain lead-free glass powder.
Optimized technical scheme does, the said stage heats up at first being warming up to 300～350 ℃ and be incubated 10～20 minutes, is incubated 30～40 minutes after being heated to 700～800 ℃ then, is heated to 1250～1400 ℃ once more.
Optimized technical scheme is also promising, and the time of said ball milling was at least 12 hours.
Advantage of the present invention and beneficial effect are: this glass powder has the suitable coefficient of expansion; Chemicalstability is good; Softening temperature is suitable, and has good wetting ability, and operating procedure is simple; Be prone to realize suitability for industrialized production, be applicable to fields such as sun power electrode sintering slurry and glass and metal, ceramic seal slurry.(Pb, Cd, Hg, Cr (VI) help the internationalization of homemade solar cell to use lead-free glass powder not contain six materials that the RoHS of European Union instruction forbidden as the slurry of adhesive preparation.
Embodiment
Below in conjunction with embodiment, specific embodiments of the invention further describes.Following examples only are used for technical scheme of the present invention more clearly is described, and can not limit protection scope of the present invention with this.
Embodiment 1
The component of lead-free glass powder comprises the Bi of 50wt%
2O
3, 20wt% SiO
2, the ZnO of 25wt%, the Al of 2wt%
2O
3, the CaO of 1wt%, the MgO of 0.1wt% and the Sb of 1.9wt%
2O
3, the granularity of this lead-free glass powder is 3～5 μ m.
The method for preparing lead-free glass powder may further comprise the steps:
The first step: dispose raw material according to the above ratio;
Second step: raw material described in the first step is fully mixed;
The 3rd step: the mixture of the second step gained is added in the crucible, crucible is placed High Temperature Furnaces Heating Apparatus, the stage is warming up to 1250～1300 ℃, is incubated 30 minutes;
The 4th step: pour the glass metal of the 3rd step gained into the de-ionized quenching-in water;
The 5th step: the frit after will quenching is put into the ball mill ball milling;
The 6th step: the frit behind the ball milling is dry, sieve, promptly obtain lead-free glass powder.
Wherein, the stage heats up at first being warming up to 300～325 ℃ and be incubated 10 minutes, is incubated 40 minutes after being heated to 700～750 ℃ then, is heated to 1250～1300 ℃ once more.
Wherein, the 12 hours time of ball milling.
Embodiment 2
The component of lead-free glass powder comprises the Bi of 60wt%
2O
3, 15wt% SiO
2, the ZnO of 20wt%, the Al of 3wt%
2O
3, the CaO of 1wt%, the MgO of 0.5wt% and the Sb of 0.5wt%
2O
3, the granularity of this lead-free glass powder is 1～3 μ m.
The method for preparing lead-free glass powder may further comprise the steps:
The first step: dispose raw material according to the above ratio;
Second step: raw material described in the first step is fully mixed;
The 3rd step: the mixture of the second step gained is added in the crucible, crucible is placed High Temperature Furnaces Heating Apparatus, the stage is warming up to 1300～1350 ℃, is incubated 40 minutes;
The 4th step: pour the glass metal of the 3rd step gained into the de-ionized quenching-in water;
The 5th step: the frit after will quenching is put into the ball mill ball milling;
The 6th step: the frit behind the ball milling is dry, sieve, promptly obtain lead-free glass powder.
Wherein, the stage heats up at first being warming up to 300～325 ℃ and be incubated 15 minutes, is incubated 35 minutes after being heated to 700～750 ℃ then, is heated to 1300～1350 ℃ once more.
Wherein, the 14 hours time of ball milling.
Embodiment 3
The component of lead-free glass powder comprises the Bi of 70wt%
2O
3, 10wt% SiO
2, the ZnO of 10wt%, the Al of 4wt%
2O
3, the CaO of 2wt%, the MgO of 1wt% and the Sb of 3wt%
2O
3, the granularity of this lead-free glass powder is 1～3 μ m.
The method for preparing lead-free glass powder may further comprise the steps:
The first step: dispose raw material according to the above ratio;
Second step: raw material described in the first step is fully mixed;
The 3rd step: the mixture of the second step gained is added in the crucible, crucible is placed High Temperature Furnaces Heating Apparatus, the stage is warming up to 1350～1400 ℃, is incubated 50 minutes;
The 4th step: pour the glass metal of the 3rd step gained into the de-ionized quenching-in water;
The 5th step: the frit after will quenching is put into the ball mill ball milling;
The 6th step: the frit behind the ball milling is dry, sieve, promptly obtain lead-free glass powder.
Wherein, the stage heats up at first being warming up to 325～350 ℃ and be incubated 20 minutes, is incubated 30 minutes after being heated to 750～800 ℃ then, is heated to 1300～1350 ℃ once more.
Wherein, the 15 hours time of ball milling.
Embodiment 4
The component of lead-free glass powder comprises the Bi of 80wt%
2O
3, 5wt% SiO
2, the ZnO of 5wt%, the Al of 5wt%
2O
3, the CaO of 1.5wt%, the MgO of 2wt% and the Sb of 1.5wt%
2O
3, the granularity of this lead-free glass powder is 3～5 μ m.
The method for preparing lead-free glass powder may further comprise the steps:
The first step: dispose raw material according to the above ratio;
Second step: raw material described in the first step is fully mixed;
The 3rd step: the mixture of the second step gained is added in the crucible, crucible is placed High Temperature Furnaces Heating Apparatus, the stage is warming up to 1350～1400 ℃, is incubated 60 minutes;
The 4th step: pour the glass metal of the 3rd step gained into the de-ionized quenching-in water;
The 5th step: the frit after will quenching is put into the ball mill ball milling;
The 6th step: the frit behind the ball milling is dry, sieve, promptly obtain lead-free glass powder.
Wherein, the stage heats up at first being warming up to 325～350 ℃ and be incubated 20 minutes, is incubated 40 minutes after being heated to 750～800 ℃ then, is heated to 1300～1350 ℃ once more.
Wherein, the 16 hours time of ball milling.
More than the sun power electrode slurry of four embodiment see the following form concrete the composition with lead-free glass powder:
More than the sun power electrode slurry of four embodiment gained see the following form with the performance of lead-free glass powder:
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (6)
1. a sun power electrode slurry is used lead-free glass powder, it is characterized in that the component of said lead-free glass powder comprises: the Bi of 50～80wt%
2O
3, 1～20wt% SiO
2, the ZnO of 5～30wt%, the Al of 1～5wt%
2O
3, the CaO of 0.1～10wt%, the MgO of 0.1～5wt% and the Sb of 0.1～5wt%
2O
3
2. lead-free glass powder as claimed in claim 1 is characterized in that, the component of said lead-free glass powder comprises: the Bi of 65～80wt%
2O
3, 5～20wt% SiO
2, the ZnO of 5～20wt%, the Al of 2～5wt%
2O
3, the CaO of 1～2wt%, the MgO of 0.1～2wt%, the Sb of 0.5～2wt%
2O
3
3. lead-free glass powder as claimed in claim 2 is characterized in that, the granularity of said lead-free glass powder is not more than 5 μ m.
4. a sun power electrode slurry is characterized in that with the preparation method of lead-free glass powder said preparation method may further comprise the steps:
The first step: press following proportional arrangement raw material: the Bi of 50～80wt%
2O
3, 1～20wt% SiO
2, the ZnO of 5～30wt%, the Al of 1～5wt%
2O
3, the CaO of 0.1～10wt%, the MgO of 0.1～5wt% and the Sb of 0.1～5wt%
2O
3
Second step: raw material described in the first step is fully mixed;
The 3rd step: the mixture of the second step gained is added in the crucible, crucible is placed High Temperature Furnaces Heating Apparatus, the stage is warming up to 1250～1400 ℃, is incubated 30～60 minutes;
The 4th step: pour the glass metal of the 3rd step gained into the de-ionized quenching-in water;
The 5th step: the frit after will quenching is put into the ball mill ball milling;
The 6th step: the frit behind the ball milling is dry, sieve, promptly obtain lead-free glass powder.
5. the preparation method of lead-free glass powder as claimed in claim 4; It is characterized in that; Said stage heats up at first being warming up to 300～350 ℃ and be incubated 10～20 minutes, is incubated 30～40 minutes after being heated to 700～800 ℃ then, is heated to 1250～1400 ℃ once more.
6. the preparation method of lead-free glass powder as claimed in claim 5 is characterized in that, the time of said ball milling was at least 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100302727A CN102603195A (en) | 2012-02-13 | 2012-02-13 | Lead-free glass powder for solar electrode sizing agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100302727A CN102603195A (en) | 2012-02-13 | 2012-02-13 | Lead-free glass powder for solar electrode sizing agent and preparation method thereof |
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| CN102603195A true CN102603195A (en) | 2012-07-25 |
Family
ID=46521055
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|---|---|---|---|
| CN2012100302727A Pending CN102603195A (en) | 2012-02-13 | 2012-02-13 | Lead-free glass powder for solar electrode sizing agent and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838284A (en) * | 2012-09-13 | 2012-12-26 | 上海交通大学 | Medium temperature sintering glass powder and preparation method thereof |
| CN103193391A (en) * | 2013-04-16 | 2013-07-10 | 江苏太阳新材料科技有限公司 | Lead-free glass powder for silver paste on back of crystalline silicon solar cell and preparation method thereof |
| CN104118992A (en) * | 2014-07-22 | 2014-10-29 | 江苏欧耐尔新型材料有限公司 | Glass powder for solar high-sheet-resistance paste and preparation method thereof |
| CN106242304A (en) * | 2016-08-31 | 2016-12-21 | 安徽斯迈尔电子科技有限公司 | A kind of preparation method of the glass dust for thick-film resistor |
| CN106946463A (en) * | 2017-02-20 | 2017-07-14 | 江苏瑞德新能源科技有限公司 | It is a kind of for glass dust of back silver paste of solar cell and preparation method thereof |
| CN107759092A (en) * | 2017-09-28 | 2018-03-06 | 浙江光达电子科技有限公司 | It is a kind of to be used to carry on the back lead-free glass powder of passivation crystal silicon solar battery back face silver paste and preparation method thereof |
| CN110950537A (en) * | 2018-09-27 | 2020-04-03 | 湖南嘉业达电子有限公司 | Preparation method of low-expansion low-temperature environment-friendly glass glaze |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838284A (en) * | 2012-09-13 | 2012-12-26 | 上海交通大学 | Medium temperature sintering glass powder and preparation method thereof |
| CN102838284B (en) * | 2012-09-13 | 2015-07-08 | 上海交通大学 | Medium temperature sintering glass powder and preparation method thereof |
| CN103193391A (en) * | 2013-04-16 | 2013-07-10 | 江苏太阳新材料科技有限公司 | Lead-free glass powder for silver paste on back of crystalline silicon solar cell and preparation method thereof |
| CN104118992A (en) * | 2014-07-22 | 2014-10-29 | 江苏欧耐尔新型材料有限公司 | Glass powder for solar high-sheet-resistance paste and preparation method thereof |
| CN106242304A (en) * | 2016-08-31 | 2016-12-21 | 安徽斯迈尔电子科技有限公司 | A kind of preparation method of the glass dust for thick-film resistor |
| CN106946463A (en) * | 2017-02-20 | 2017-07-14 | 江苏瑞德新能源科技有限公司 | It is a kind of for glass dust of back silver paste of solar cell and preparation method thereof |
| CN107759092A (en) * | 2017-09-28 | 2018-03-06 | 浙江光达电子科技有限公司 | It is a kind of to be used to carry on the back lead-free glass powder of passivation crystal silicon solar battery back face silver paste and preparation method thereof |
| CN110950537A (en) * | 2018-09-27 | 2020-04-03 | 湖南嘉业达电子有限公司 | Preparation method of low-expansion low-temperature environment-friendly glass glaze |
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Application publication date: 20120725 |