CN101826564B - Solar cell back surface field aluminum paste - Google Patents

Solar cell back surface field aluminum paste Download PDF

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Publication number
CN101826564B
CN101826564B CN2010101679153A CN201010167915A CN101826564B CN 101826564 B CN101826564 B CN 101826564B CN 2010101679153 A CN2010101679153 A CN 2010101679153A CN 201010167915 A CN201010167915 A CN 201010167915A CN 101826564 B CN101826564 B CN 101826564B
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parts
back surface
glass
aluminum paste
surface field
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CN101826564A (en
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张艳
刘子英
王小记
任明淑
刘宁
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China Lucky Group Corporation
Lucky Film Co Ltd
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China Lucky Film Group Corp
Lucky Film Co Ltd
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Abstract

The invention relates to a solar cell back surface field aluminum paste, which consists of aluminum powder, organic bond, glass binder and additive, and the glass binder consists of the following components in part by weight: 30 to 60 parts of Bi2O3, 10 to 15 parts of B2O3, 30 to 45 parts of SiO2, 2 to 5 parts of Al2O3 and 0.1 to 5 parts of IrO2. The prepared aluminum paste has high heat resistance and sintering resistance, the surface curvature of a sintered silicon wafer is small, the tightness between an aluminum film and the surface of the silicon wafer is high, a back surface field cannot easily come off, moreover, the aluminum paste cannot be easily sintered into a continuous glass film, and the conductivity of the back surface field is excellent.

Description

A kind of back surface field aluminum paste of solar battery
Technical field
The present invention relates to a kind of aluminium paste, particularly a kind of crystal silicon solar batteries back field aluminum paste.
Background technology
Solar energy more and more is subject to people's attention as a kind of cleaning, nexhaustible green regenerative energy sources.Photovoltaic application is the key areas of Application of Solar Energy, crystal silicon solar batteries is to be the environmental type regenerative resource semiconductor device of electric energy with conversion of solar energy directly, business-like crystal silicon solar batteries, basically all adopt electric slurry by the front and rear surfaces of silk screen printing at crystal silicon, form electrode by co-sintering technology, used electric slurry is generally positive electrode and adopts the silver slurry, and back electrode adopts aluminum paste, and back of the body electric field adopts aluminium paste.Aluminium paste has low price, the advantage of electric performance stablity, and aluminium and silicon is easy to form PN junction, has the long wave response characteristic, has the good Ohmic contact characteristic with silicon wafer, has good ageing resistance.
The electrode of crystal silicon solar batteries generally is according to following method preparation: the slurry that will contain conductive metal powder, glass binder and organic bond is printed on the silicon substrate, carries out drying and high-temperature firing, forms electrode.Firing temperature generally is controlled at 850-900 ℃, because temperature is higher, causes back side slurry mechanical strength easily and back of the body electric field comes off when descending, firing back base material bending and forming electrode layer with the adaptation of base material problem.In addition, existing slurry also exists temperature too high or temperature retention time is long in sintering procedure, forms the continuous glass-film of one deck between metal and substrate, causes carrying on the back the problem that an electric conductivity reduces and cracks under stress.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of back surface field aluminum paste of solar battery, and the heat resistance of this aluminium paste and sintering resistance can be good, and the silicon face flexibility is little behind the sintering, and is good with the adaptation of silicon face, and back of the body power plant is difficult for breaking away from.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of back surface field aluminum paste of solar battery, it comprises aluminium powder, organic bond, glass binder and additive, the component of described glass binder and parts by weight thereof are: Bi 2O 330～60 parts, B 2O 310～15 parts, SiO 230～45 parts, Al 2O 32～5 parts, IrO 20.1～5 parts.
Above-mentioned back surface field aluminum paste of solar battery, the component of described glass binder and parts by weight thereof are: Bi 2O 330～50 parts, B 2O 310～15 parts, SiO 230～45 parts, Al 2O 32～part, IrO 20.1～2 parts.
Above-mentioned back surface field aluminum paste of solar battery, described aluminium powder are 1～7 micron spheric granules for surface parcel aln layer, average grain diameter.
Above-mentioned back surface field aluminum paste of solar battery, described additive are Si Ban and pump oil.
Aluminium powder is the important raw and processed materials in the solar energy back field aluminum paste, when high temperature, can form eutectic with silicon, simultaneously, metallic aluminium powder plays the effect of conduction in slurry, energy and Semiconducting Silicon Materials form good Ohmic contact, are most widely used metal materials during the silicon solar cell back electrode is made.
The aluminium powder that uses among the present invention can be sheet or spherical particle, preferably uses spherical particle, most preferably uses the spheric granules of surface parcel aln layer.Aluminium powder surface parcel aln layer guarantees the not oxidized blackening of aluminium powder when grinding, the generation of avoiding playing aluminium blister, the pill of aluminium in the aluminium paste sintering procedure and falling grey phenomenon, the electric conductivity of assurance aluminium powder.Aluminium powder among the present invention can use 1～10 micron spheric granules of average grain diameter, preferably uses the spheric granules of 1～7 micron of average grain diameter.When average grain diameter during, cause easily that aluminium powder melts too early, temperature retention time prolongs in sintering process, make that the sintered aluminium film is too fine and close, the surperficial easy bending of crystal silicon less than 1 micron; When average grain diameter during greater than 7 microns, aluminium powder is difficult for melting when sintering, and formed aluminium film is too loose, can not fully contact between the ball aluminum powder particle to fuse together and form path, influences electric conductivity, thereby influences the transformation efficiency of solar cell.
Glass binder is glass dust again, and it is fusion after sintering processes, and aluminium powder attached to silicon chip surface, is formed continuous uniform conductive film, and it also is the major reason that influences the crystal silicon surface curvature.
The bending of silicon is relevant with the coefficient of linear expansion of glass, and the coefficient of linear expansion of silicon and the coefficient of linear expansion of glass are approaching more, and the surface curvature degree of crystal silicon is more little, and the aluminium paste that obtains adaptation with the crystal silicon surface behind sintering is good more, back of the body power plant difficult drop-off.
In order to obtain being fit to the glass binder of the present invention's needs, glass binder of the present invention contains Bi 2O 3, B 2O 3, SiO 2, Al 2O 3And IrO 2Wherein: Bi 2O 3Be the main body composition of glass, it has the reduction glass softening point, makes glass have the effect of suitable mobile and adjusting thermal expansion coefficient of glass when fusing, and in addition, it can also increase the proportion of glass.Bi in the glass 2O 3If content very little, above-mentioned these effects can become not enough; If this content is too high, it is too high that thermal coefficient of expansion may become, the Bi among the present invention 2O 3Parts by weight be 30～60 parts, preferred 30～50 parts.SiO 2Also be the important component that forms glass, it is a crux to forming stable glass, SiO in the glass 2Content very little, it is unstable that glass can become, in rational content range, along with SiO 2The increase of content, the softening point of glass can uprise, and it is big that viscosity becomes, and the chemical stability of glass and thermal stability increase, and acid resistance strengthens, and mechanical strength increases, and smelting temperature increases, the SiO among the present invention 2Parts by weight be 30～45 parts.B 2O 3Be to be similar to SiO 2The component of formation glass, it can make very that glass melts easily, and suppresses the undue increase of thermal expansion coefficient of glass, and makes glass have suitable flowability when roasting, along with B 2O 3The increase of content, glass softening point reduces, the B in the glass 2O 3If content very little, it is unstable that glass can become, the B among the present invention 2O 3Parts by weight be 10～15 parts.Al 2O 3Replaceable part Si O 2, increase chemical stability, thermal stability and the acid resistance of glass, reduce crystallization, the Al among the present invention 2O 3Parts by weight be 2～5 parts.IrO 2Be added in and introduced iridium in the glass binder, it makes glass have good wettability, plays the effect of the coefficient of linear expansion of adjusting glass simultaneously, by regulation and control IrO 2Consumption make glass coefficient of linear expansion more near the coefficient of linear expansion of crystal silicon, the IrO among the present invention 2Parts by weight be 0.1～5 part, preferred 0.1～2 part.Simultaneously, add IrO in the glass binder 2, can also make aluminium paste fine and smooth more evenly, improve the thermal endurance and the control sintering character of aluminium paste, make the aluminium film behind the aluminium paste sintering more firm to adhering to of silicon chip, form good Ohmic contact, improved the photoelectric conversion efficiency of battery.
Glass binder among the present invention can prepare according to following method, but is not limited thereto.
With frit according to the parts by weight weighing, put into the high alumina crucible after mixing, in resistance furnace, melted 1～2 hour in 850～1100 ℃, be cooled to about 850 ℃, cold pressing by force and make frit, adopt the Hang Xingshi ball mill with about about 2.5 hours of glass binder breakdown mill, preparation glass binder.
Among the present invention, the effect of organic bond is to make the solid powder art in the aluminium paste have good adhesion strength and silicon chip is produced little stress after aluminium paste has even coating, drying when making aluminium paste have the not stratified not sedimentation of aluminium paste, the printing of good dispersiveness or suspension, postpone for a long time.Organic bond is made up of binder resin, organic solvent and auxiliary agent, and wherein, binder resin generally is selected from ethyl cellulose, cellaburate, turpentine wet goods, preferably uses ethyl cellulose, and addition is the 3-10% of organic bond total amount; Organic solvent can use one or more in methyl alcohol, ethanol, phenmethylol, n-butanol, hexadecanol, n-butanol, terpinol, ether, the diethylene glycol dimethyl ether diethylene glycol ether etc., the pure ethers organic solvent of preferred use, addition is the 80-90% of organic bond total amount; Auxiliary agent can use wetting dispersing agent, defoamer and levelling agent, and addition is 0.5～5% of an organic bond total amount.Organic bond mixes by mass percentage, and dissolving stirs and gets final product.
Additive among the present invention is used for improving the net performance excessively of aluminium paste, is fit to additive of the present invention and can selects sintering aid, tackifier, stabilizer, dispersant or surfactant for use, class of preferred use department and pump oil.
Back surface field aluminum paste of solar battery is formulated by aluminium powder, organic bond, glass binder and additive, is applicable to that the prescription of back surface field aluminum paste of solar battery of the present invention includes but not limited to following prescription:
Aluminium powder 70-85 weight portion;
Organic bond 10-25 weight portion;
Glass binder 1-10 weight portion;
Additive 1-5 weight portion.
After aluminium powder, organic bond, glass binder and additive mixed, be ground to fineness smaller or equal to 20 μ m, obtain back surface field aluminum paste of solar battery with three-roll grinder.
Back surface field aluminum paste of solar battery of the present invention makes slurry evenly be attached to silicon chip surface by screen printing mode.
Compared with prior art, the present invention has following advantage:
1. the glass binder that uses in the back surface field aluminum paste of solar battery is not leaded, and has lower softening point, is the ideal substitute of leaded low-melting-point glass, and environmentally friendly.
2. add IrO in the glass binder 2, glass has good wettability, by regulation and control IrO 2Consumption make glass coefficient of linear expansion more near the coefficient of linear expansion of crystal silicon, reduce the bending of silicon.Simultaneously, make aluminium paste fine and smooth more evenly, improved the thermal endurance and the control sintering character of aluminium paste, make the aluminium film behind the aluminium paste sintering more firm, form good Ohmic contact, improved the photoelectric conversion efficiency of battery adhering to of silicon chip.
3. the ball aluminum powder particle of use surface parcel aln layer guarantees aluminium powder not oxidized blackening when grinding, the generation of having avoided playing aluminium blister, the pill of aluminium in the aluminium paste sintering procedure and having fallen grey phenomenon, the electric conductivity of assurance aluminium powder.
4. class of use department and pump oil have improved the printability of aluminium paste as additive in the aluminium paste, have improved the net performance excessively of aluminium paste.
5. aluminium paste makes slurry evenly be attached to silicon chip surface through screen printing mode, and smooth, the no aluminium blister of the product surface that obtains after the sintering drying, the no pill of aluminium are peeled off, and heat resistance is good, the EVA bonding does not come off, good to silicon chip adhesive force, conductivity improves, long service life.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but be not limited thereto.
1. the preparation of organic bond: (total amount 200g)
Take by weighing by mass percentage: ethyl cellulose 18g, hexadecanol 4g, diethylene glycol dimethyl ether 12g, diethylene glycol ether 8g, terpinol 130g, n-butanol 26g mixes, 100～130 ℃ of dissolvings, stirring gets final product, standby.
2. the preparation of aluminium paste: (total amount 1000g)
Aluminium powder 750g;
Organic bond 200g;
Glass binder 30g;
The 8g of class of department;
Pump oil 12g;
Aluminium powder, glass binder, organic bond, additive by above mixed, are ground with three-roll grinder, obtain back surface field aluminum paste of solar battery, standby.
Embodiment 1
The preparation of glass binder:
Bi 2O 360 parts;
B 2O 310 parts;
SiO 235 parts;
Al 2O 32.9 part;
IrO 20.1 part;
Take by weighing each component of corresponding parts by weight according to above-mentioned prescription, mixing the back is 3 hours 140 ℃ of drying times, put into the high alumina crucible, in resistance furnace, melted 1.5 hours in 850 ℃, cooling, cold pressing by force and make frit, adopted the Hang Xingshi ball mill grinding about 2.5 hours, obtain glass binder.
Get 750g, 4 microns the above-mentioned organic bond, above-mentioned glass binder, class of 8g department and the 12g pump oil of 30g of aluminium powder, 200g mixes, and grinds with three-roll grinder, obtains back surface field aluminum paste of solar battery.
Pass through to use 280 purpose silk screen printings on 125mm*125mm (thickness 180+20 micron) monocrystalline silicon piece the aluminium paste that obtains, oven dry, sintering are tested its relevant performance.
Embodiment 2
The preparation of glass binder:
Bi 2O 345 parts;
B 2O 315 parts;
SiO 237 parts;
Al 2O 32.7 part;
IrO 20.5 part;
Take by weighing each component of corresponding parts by weight according to above-mentioned prescription, mixing the back is 3.5 hours 136 ℃ of drying times, put into the high alumina crucible, in resistance furnace, melted 2 hours in 900 ℃, cooling, cold pressing by force and make frit, adopted the Hang Xingshi ball mill grinding about 2 hours, obtain glass binder.
Get 750g, 6.5 microns the above-mentioned organic bond, above-mentioned glass binder, class of 8g department and the 12g pump oil of 30g of aluminium powder, 200g mixes, and grinds with three-roll grinder, obtains back surface field aluminum paste of solar battery.
Pass through to use 280 purpose silk screen printings on 125mm*125mm (thickness 180+20 micron) monocrystalline silicon piece the aluminium paste that obtains, oven dry, sintering are tested its relevant performance.
Embodiment 3
The preparation of glass binder:
Bi 2O 340 parts;
B 2O 312 parts;
SiO 242 parts;
Al 2O 34 parts;
IrO 22 parts;
Take by weighing each component of corresponding parts by weight according to above-mentioned prescription, mixing the back is 3.5 hours 135 ℃ of drying times, put into the high alumina crucible, in resistance furnace, melted 1.5 hours in 1000 ℃, cooling, cold pressing by force and make frit, adopted the Hang Xingshi ball mill grinding about 3 hours, obtain glass binder.
Get 750g, 1.0 microns the above-mentioned organic bond, above-mentioned glass binder, class of 8g department and the 12g pump oil of 30g of aluminium powder, 200g mixes, and grinds with three-roll grinder, obtains back surface field aluminum paste of solar battery.
Pass through to use 280 purpose silk screen printings on 125mm*125mm (thickness 180+20 micron) monocrystalline silicon piece the aluminium paste that obtains, oven dry, sintering are tested its relevant performance.
Embodiment 4
The preparation of glass binder:
Bi 2O 330 parts;
B 2O 314 parts;
SiO 245 parts;
Al 2O 335 parts;
IrO 25 parts;
Take by weighing each component of corresponding parts by weight according to above-mentioned prescription, mixing the back is 4 hours 130 ℃ of drying times, put into the high alumina crucible, in resistance furnace, melted 1 hour in 1100 ℃, cooling, cold pressing by force and make frit, adopted the Hang Xingshi ball mill grinding about 2.5 hours, obtain glass binder.
Get 750g, 2.5 microns the above-mentioned organic bond, above-mentioned glass binder, class of 8g department and the 12g pump oil of 30g of aluminium powder, 200g mixes, and grinds with three-roll grinder, obtains back surface field aluminum paste of solar battery.
Pass through to use 280 purpose silk screen printings on 125mm*125mm (thickness 180+20 micron) monocrystalline silicon piece the aluminium paste that obtains, oven dry, sintering are tested its relevant performance.
Embodiment 5
The preparation of glass binder:
Bi 2O 350 parts;
B 2O 312 parts;
SiO 230 parts;
Al 2O 332 parts;
IrO 23 parts;
Take by weighing each component of corresponding parts by weight according to above-mentioned prescription, mixing the back is 2 hours 130 ℃ of drying times, put into the high alumina crucible, in resistance furnace, melted 1.5 hours in 900 ℃, cooling, cold pressing by force and make frit, adopted the Hang Xingshi ball mill grinding about 2 hours, obtain glass binder.
Get 750g, 7.0 microns the above-mentioned organic bond, above-mentioned glass binder, class of 8g department and the 12g pump oil of 30g of aluminium powder, 200g mixes, and grinds with three-roll grinder, obtains back surface field aluminum paste of solar battery.
Pass through to use 280 purpose silk screen printings on 125mm*125mm (thickness 180+20 micron) monocrystalline silicon piece the aluminium paste that obtains, oven dry, sintering are tested its relevant performance.
Comparative Examples
The preparation of glass binder:
Bi 2O 335 parts;
B 2O 315 parts;
SiO 245 parts;
Al 2O 335 parts;
Take by weighing each component of corresponding parts by weight according to above-mentioned prescription, mixing the back is 4 hours 130 ℃ of drying times, put into the high alumina crucible, in resistance furnace, melted 1 hour in 1000 ℃, cooling, cold pressing by force and make frit, adopted the Hang Xingshi ball mill grinding about 2 hours, obtain glass binder.
Get 750g, 10.0 microns the above-mentioned organic bond, above-mentioned glass binder, class of 8g department and the 12g pump oil of 30g of aluminium powder, 200g mixes, and grinds with three-roll grinder, obtains back surface field aluminum paste of solar battery.
Pass through to use 280 purpose silk screen printings on 125mm*125mm (thickness 180+20 micron) monocrystalline silicon piece the aluminium paste that obtains, oven dry, sintering are tested its relevant performance.
Table 1: each embodiment performance data
In the table:
The method of testing of peel strength:
At stacked EVA on glass and TPT, the battery sheet is put into EVA, use laminating machine to encapsulate.Encapsulation back sample was placed 24 hours, with icking tool the EVA glue of sample surfaces was cut out little that is slit into 1cm*30cm, used cupping machine to carry out peel strength test.
Data adopt the aluminium paste of glass glue preparation of the present invention as can be seen from table, and the photoelectric conversion efficiency of solar cell obviously increases, and the silicon chip amount of bow obviously diminishes, and peel strength obviously increases.
This shows, add IrO in the glass binder 2, not only can improve open circuit voltage, short circuit current, and significantly improve electricity conversion, reduce the amount of bow of silicon chip, thereby improved the rate of finished products of monocrystalline silicon greatly.Smooth, the no aluminium blister of aluminium film surface, the pill of aluminium are peeled off, and be good to silicon chip adhesive force, and the EVA bonding does not come off.

Claims (4)

1. a back surface field aluminum paste of solar battery comprises aluminium powder, organic bond, and glass binder and additive is characterized in that, the component of described glass binder and parts by weight thereof are: Bi 2O 330～60 parts, B 2O 310～15 parts, SiO 230～45 parts, Al 2O 32～5 parts, IrO 20.1～5 parts.
2. back surface field aluminum paste of solar battery according to claim 1 is characterized in that the component of described glass binder and parts by weight thereof are: Bi 2O 330～50 parts, B 2O 310～15 parts, SiO 230～45 parts, Al 2O 32～5 parts, IrO 20.1～2 parts.
3. back surface field aluminum paste of solar battery according to claim 1 and 2 is characterized in that, described aluminium powder is 1～7 micron spheric granules for surface parcel aln layer, average grain diameter.
4. back surface field aluminum paste of solar battery according to claim 3 is characterized in that, described additive is Si Ban or pump oil.
CN2010101679153A 2010-05-11 2010-05-11 Solar cell back surface field aluminum paste Active CN101826564B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102097154B (en) * 2010-11-25 2012-07-25 长沙族兴新材料股份有限公司 Back surface field aluminium paste for solar cells
CN102314958A (en) * 2011-08-31 2012-01-11 乐凯胶片股份有限公司 Conductive aluminum paste used for crystalline-silicon solar-battery back electrode and preparation method thereof
CN104952512B (en) * 2014-03-28 2017-08-25 比亚迪股份有限公司 A kind of crystal silicon solar energy battery Al-BSF electrocondution slurry and preparation method thereof
CN104637568B (en) 2015-02-02 2017-02-01 南通天盛新能源股份有限公司 Aluminum paste for all-aluminum back surface field crystalline silicon solar cell and preparation method thereof
CN107689263B (en) * 2016-05-20 2019-02-15 浙江光隆能源科技股份有限公司 A kind of preparation method for the aluminium paste that back polishing polycrystalline solar cell uses

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CN1944310A (en) * 2006-10-19 2007-04-11 福耀集团双辽有限公司 Sunlight controlled self cleaning glass and its producing method
CN101345263A (en) * 2008-09-09 2009-01-14 季福根 Leadless electronic slurry composition for solar silicon photovoltaic cell and preparation method thereof
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