CN103000251B - Solar cell silver-backed slurry with wide sintering process window - Google Patents
Solar cell silver-backed slurry with wide sintering process window Download PDFInfo
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- CN103000251B CN103000251B CN201210446522.5A CN201210446522A CN103000251B CN 103000251 B CN103000251 B CN 103000251B CN 201210446522 A CN201210446522 A CN 201210446522A CN 103000251 B CN103000251 B CN 103000251B
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Abstract
The invention relates to solar cell silver-backed slurry with a wide sintering process window. The slurry is composed of, by weight, 45-55% of silver powder, 3-7% of lead-free silicon-free glass powder, 10-15% of organic binder, 20-40% of solvent, 0.1-5% of sintering promoter and balance of auxiliaries, wherein, the sliver powder is composed of, by weight, 50-80% of spherical silver powder and 20-50% of schistose silver powder. The silver-backed slurry adopts the silver powder with different sintering activities to be used with the lead-free silicon-free glass powder, and small amount of the sintering promoter is added, so that the silver powder of different sintering activities can realize forming of a compact silver-film structure within a wider sintering temperature range; the lead-free silicon-free glass powder is low in crystallization degree, so that dissolving, of the sliver powder, in a glass phase, within the wide sintering temperature range is promoted; and adding of certain amount of the sintering promoter can effectively avoid the sliver powder from self-coagulation to form silver bar, so that the silver-backed slurry has the wide sintering process window.
Description
Technical field
The present invention relates to a kind of electrocondution slurry, be specifically related to a kind of have wide sintering process window back silver paste of solar cell.
Background technology
Solar cell is a kind of semiconductor device that can convert solar energy into electrical energy.Back silver paste of solar cell is the chief component of solar cell electric slurry, and it is mainly used for making back side main grid in manufacture of solar cells, plays the effect of deriving of being confluxed by the electric current that aluminium back surface field is collected.Rear surface of solar cell silver slurry forms primarily of silver powder, organic bond, inorganic bond, solvent and auxiliary agent.Except the performance index such as cost, conductivity of back silver paste, the width of sintering process window is also the key index investigating back silver paste, because it affects the processing quality of cell piece production and the yields of final finished solar battery sheet.Therefore, prepare a kind of excellent performance, there is the back silver paste of wide sintering process window constitute key technology main points in manufacture of solar cells.
At present, back silver paste of solar cell uses the spherical of single shape or flake silver powder as the electric conductor of back silver paste.As application number a kind of back silver paste of solar cell using single flake silver powder to be electric conductor disclosed in the Chinese patent of 201110200935.0, and application number is a kind of disclosed in the Chinese patent of 201110297031.4 uses the spherical silver powder of 0.5-2 μm as the back silver paste of solar cell of electric conductor, silver powder sintering activity contained by it is single, and the sintering process window of this kind of back silver paste is often narrower.By contrast, the electric conductor that solar cell positive silver paste has gradually adopted mixture that is spherical or flake silver powder to starch as silver, as application number a kind of mixture solar cell positive silver paste as electric conductor using the granular silver powder of 0.1-2 μm and the flake silver powder of 3-10 μm disclosed in the Chinese patent of 201110201638.8, wherein, spherical and flake silver powder has different sintering activities, and corresponding gained silver slurry has wider sintering process window.But the glass dust adopted in current this kind of positive silver paste mostly still is siliceous glass dust, this kind of siliceous glass dust thermal coefficient of expansion is lower, but crystallization degree is high.This crystallization can make the sintering process windows narrow of silver slurry, namely the parameter variations of sintering process easily causes the minimizing that silver powder dissolves in glassy phase, and then causing the generation of block silver, the characteristic making the silver of the silver powder containing different sintering activity starch its wide sintering process window cannot embody.Therefore, prepare a kind of excellent performance, there is the back silver paste of solar cell of wide sintering process window, at least need to carry out integrated survey from the sintering activity of silver powder and these two angles of sintering process performance of glass dust.
Summary of the invention
The technical issues that need to address of the present invention are to overcome the deficiencies in the prior art, provide a kind of excellent performance, have the back silver paste of solar cell of wide sintering process window.
The technical issues that need to address of the present invention are achieved through the following technical solutions:
A kind of back silver paste of solar cell with wide sintering process window, its composition and percetage by weight thereof are: silver powder 45-55%, unleaded be auxiliary agent without silex glass powder 3-7%, organic bond 10-15%, solvent 20-40%, sintering aids 0.1-5%, surplus, and the percetage by weight sum of each component is 100%.
Above-mentioned silver powder is that 50-80% ball shape silver powder and 20-50% flake silver powder form by percetage by weight, the tap density >5g/cm of ball shape silver powder
3, average grain diameter is 0.2-1.5 μm; The tap density >4.5g/cm of flake silver powder
3, average thickness is 0.1-0.2 μm, and average transverse is 0.5-3 μm.
Above-mentioned unleaded without silex glass powder composition and percetage by weight be: 65-85% bismuth oxide, 3-15% boron oxide, 1-10% zinc oxide, 1-10% aluminium oxide, 3-15% barium monoxide, 0.1-5% calcium oxide, 0.5-5% vanadium oxide and 0-3% property-modifying additive, wherein property-modifying additive is the one in zirconium dioxide, phosphorus pentoxide, titanium dioxide and cobalt sesquioxide, and the percetage by weight sum of each component of glass dust is 100%.Preferred technical scheme is: unleaded without silex glass powder composition and percetage by weight be: 72% bismuth oxide, 8% boron oxide, 5% zinc oxide, 5% aluminium oxide, 4% barium monoxide, 3% calcium oxide and 3% vanadium oxide.
Above-mentioned sintering aids is silver oxide or silver carbonate.
Above-mentioned organic bond, solvent and auxiliary agent are organic bond, solvent and auxiliary agent general in electric slurry used for solar batteries.
Compared with prior art, advantage of the present invention and beneficial effect are: the silver powder of different sintering activity and unleaded to arrange in pairs or groups without silex glass powder use by the present invention on formula, and add a small amount of sintering aids; Wherein, the silver powder mixture of different sintering activity is as the electric conductor of back silver paste, can make silver powder in wider sintering range, form fine and close silverskin structure, unleaded low without silex glass powder crystallization degree, be conducive to promoting the dissolving of silver powder in wide sintering range in glassy phase, effectively avoid silver powder to melt cohesion and form block silver, ensure that silver layer has high conductance; A certain amount of sintering aids can avoid the self-coagulation of silver powder further; Used by the silver powder of different sintering activity, the unleaded collocation without silex glass powder and a small amount of sintering aids, make this back silver paste of solar cell have wide sintering process window.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described further.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
Embodiment 1
Have a back silver paste of solar cell for wide sintering process window, its component and percetage by weight thereof are: 55% silver powder, 7% unleaded without silex glass powder, 10% acrylic resin, 20% terpinol, 5% silver oxide, 3% for BYK-110.Wherein, silver powder is that 80% ball shape silver powder and 20% flake silver powder form by percetage by weight, the tap density >5g/cm of ball shape silver powder
3, average grain diameter is the tap density >4.5g/cm of 0.2-1.5 μm, flake silver powder
3, average thickness is 0.1-0.2 μm, and average transverse is 0.5-3 μm; Unleaded without silex glass powder composition and percetage by weight be: 85% bismuth oxide, 3% boron oxide, 1% zinc oxide, 1% aluminium oxide, 3% barium monoxide, 5% calcium oxide, 0.5% vanadium oxide and 1.5% zirconium dioxide.
Embodiment 2
A kind of back silver paste of solar cell with wide sintering process window, its component and percetage by weight thereof are: 45% silver powder, 3% unleaded without silex glass powder, 11% ethyl cellulose, 40% solvent, 0.1% silver carbonate, 0.9%BYK-110, wherein, silver powder is that 50% ball shape silver powder and 50% flake silver powder form by percetage by weight, the tap density >5g/cm of ball shape silver powder
3, average grain diameter is the tap density >4.5g/cm of 0.2-1.5 μm, flake silver powder
3, average thickness is 0.1-0.2 μm, and average transverse is 0.5-3 μm; Unleaded without silex glass powder composition and percetage by weight be: 65% bismuth oxide, 15% boron oxide, 4.9% zinc oxide, 2% aluminium oxide, 5% barium monoxide, 0.1% calcium oxide, 5% vanadium oxide and 3% phosphorus pentoxide.
Embodiment 3
Have a back silver paste of solar cell for wide sintering process window, its component and percetage by weight thereof are: 50% silver powder, 5% unleaded without silex glass powder, 10% methacrylic resin, 30% butyl carbitol acetate, 3% silver oxide, 2%BYK-110; Wherein, silver powder is that 70% ball shape silver powder and 30% flake silver powder form by percetage by weight, the tap density >5g/cm of ball shape silver powder
3, average grain diameter is the tap density >4.5g/cm of 0.2-1.5 μm, flake silver powder
3, average thickness is 0.1-0.2 μm, and average transverse is 0.5-3 μm; Unleaded without silex glass powder composition and percetage by weight be: 67% bismuth oxide, 5% boron oxide, 10% zinc oxide, 10% aluminium oxide, 4% barium monoxide, 0.5% calcium oxide, 1.5% vanadium oxide and 2% titanium dioxide.
Embodiment 4
Have a back silver paste of solar cell for wide sintering process window, its component and percetage by weight thereof are: 54% silver powder, 6.5% unleaded without silex glass powder, 12% modified hydrogenated castor oil, 24% turpentine oil, 2.5% silver oxide, 1%BYK-110; Wherein, silver powder is that 60% ball shape silver powder and 40% flake silver powder form by percetage by weight, the tap density >5g/cm of ball shape silver powder
3, average grain diameter is the tap density >4.5g/cm of 0.2-1.5 μm, flake silver powder
3, average thickness is 0.1-0.2 μm, and average transverse is 0.5-3 μm; Unleaded without silex glass powder composition and percetage by weight be: 70% bismuth oxide, 8% boron oxide, 8% zinc oxide, 2% aluminium oxide, 3% barium monoxide, 3% calcium oxide, 4% vanadium oxide and 2% cobalt sesquioxide.
Embodiment 5
Have a back silver paste of solar cell for wide sintering process window, its component and percetage by weight thereof are: 52% silver powder, 6% unleaded without silex glass powder, 13% acrylic resin, 27% terpinol, 1% silver carbonate, 1%BYK-110; Wherein, silver powder is that 55% ball shape silver powder and 45% flake silver powder form by percetage by weight, the tap density >5g/cm of ball shape silver powder
3, average grain diameter is the tap density >4.5g/cm of 0.2-1.5 μm, flake silver powder
3, average thickness is 0.1-0.2 μm, and average transverse is 0.5-3 μm; Unleaded without silex glass powder composition and percetage by weight be: 72% bismuth oxide, 8% boron oxide, 5% zinc oxide, 5% aluminium oxide, 4% barium monoxide, 3% calcium oxide and 3% vanadium oxide.
Above-mentioned each embodiment is further illustrating of making foregoing of the present invention, but the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to above-described embodiment.It should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (4)
1. there is a back silver paste of solar cell for wide sintering process window, it is characterized in that: the composition of this back silver paste and percetage by weight thereof are: silver powder 45-55%, unleaded be auxiliary agent without silex glass powder 3-7%, organic bond 10-15%, solvent 20-40%, sintering aids 0.1-5%, surplus; And the percetage by weight sum of each component is 100%; Wherein, described sintering aids is silver oxide or silver carbonate; Described silver powder is that 50-80% ball shape silver powder and 20-50% flake silver powder form by percetage by weight, the tap density >5g/cm of ball shape silver powder
3, average grain diameter is 0.2-1.5 μm; The tap density >4.5g/cm of flake silver powder
3, average thickness is 0.1-0.2 μm, and average transverse is 0.5-3 μm.
2. the back silver paste of solar cell with wide sintering process window according to claim 1, it is characterized in that: describedly unleadedly without silex glass powder composition and percetage by weight thereof be: bismuth oxide 65-85%, boron oxide 3-15%, zinc oxide 1-10%, aluminium oxide 1-10%, barium monoxide 3-15%, calcium oxide 0.1-5%, vanadium oxide 0.5-5% and property-modifying additive 0-3%, and the percetage by weight sum of each component of glass dust is 100%.
3. the back silver paste of solar cell with wide sintering process window according to claim 2, is characterized in that: described unleaded without silex glass powder composition and percetage by weight be: 72% bismuth oxide, 8% boron oxide, 5% zinc oxide, 5% aluminium oxide, 4% barium monoxide, 3% calcium oxide and 3% vanadium oxide.
4. the back silver paste of solar cell with wide sintering process window according to claim 2, is characterized in that: described property-modifying additive is the one in zirconium dioxide, phosphorus pentoxide, titanium dioxide and cobalt sesquioxide.
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| KR102032280B1 (en) * | 2013-04-25 | 2019-10-15 | 엘지전자 주식회사 | Paste composition for forming electrode of solar cell |
| CN103440901B (en) * | 2013-09-10 | 2016-08-24 | 乐凯胶片股份有限公司 | Low cost crystal silicon solar energy battery unleaded back silver paste and preparation method |
| EP2896602B1 (en) * | 2014-01-16 | 2017-08-09 | Heraeus Precious Metals North America Conshohocken LLC | Low-silver electroconductive paste |
| US20150194546A1 (en) * | 2014-01-09 | 2015-07-09 | Heraeus Precious Metals North America Conshohocken Llc | Low-silver electroconductive paste |
| CN104778988B (en) * | 2014-01-09 | 2017-10-24 | 上海贺利氏工业技术材料有限公司 | Low conductive silver slurry |
| CN104465875B (en) * | 2014-12-05 | 2016-09-21 | 清华大学 | A kind of preparation method of photovoltaic cell silver grating line |
| JP2016213284A (en) * | 2015-05-01 | 2016-12-15 | 東洋アルミニウム株式会社 | Aluminum paste composition for PERC type solar cell |
| CN104934104B (en) * | 2015-06-24 | 2017-05-31 | 东方电气集团东方汽轮机有限公司 | A kind of low silver content crystal silicon solar batteries back side silver paste and preparation method |
| CN105185429B (en) * | 2015-08-07 | 2019-01-18 | 昆明贵信凯科技有限公司 | Base metal electric slurry encasement medium slurry and its application |
| CN107424660A (en) * | 2017-02-20 | 2017-12-01 | 江苏瑞德新能源科技有限公司 | A kind of back silver paste used for solar batteries and preparation method thereof |
| CN107068240A (en) * | 2017-02-20 | 2017-08-18 | 江苏瑞德新能源科技有限公司 | A kind of back silver paste |
| CN107093489B (en) * | 2017-05-05 | 2019-04-05 | 肇庆市辰业电子有限公司 | A kind of inductance silver paste of inner electrode and preparation method thereof |
| CN108695009A (en) * | 2018-05-21 | 2018-10-23 | 江苏昊科汽车空调有限公司 | Modified high-efficient crystal silicon solar batteries and preparation method thereof |
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