CN102097154A - Back surface field aluminium paste for solar cells - Google Patents
Back surface field aluminium paste for solar cells Download PDFInfo
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- CN102097154A CN102097154A CN 201010560269 CN201010560269A CN102097154A CN 102097154 A CN102097154 A CN 102097154A CN 201010560269 CN201010560269 CN 201010560269 CN 201010560269 A CN201010560269 A CN 201010560269A CN 102097154 A CN102097154 A CN 102097154A
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- silicon
- powder
- back field
- aluminum paste
- aluminium powder
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Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 97
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000004411 aluminium Substances 0.000 title claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 73
- 239000000853 adhesive Substances 0.000 claims abstract description 35
- 230000001070 adhesive effect Effects 0.000 claims abstract description 35
- 239000003607 modifier Substances 0.000 claims abstract description 21
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 235000013339 cereals Nutrition 0.000 claims description 15
- 239000007822 coupling agent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000004364 calculation method Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 17
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007767 bonding agent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000001856 Ethyl cellulose Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 229920001249 ethyl cellulose Polymers 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- -1 silver-aluminum Chemical compound 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000004523 agglutinating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000005331 crown glasses (windows) Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention relates to a back surface field aluminium paste for solar cells. The aluminium paste comprises the following components in parts by weight: 65-80 parts of aluminium powder, 1-5 parts of inorganic adhesive, 10-30 parts of organic carrier and 1-2 parts of modifier. Sintered films with lower warpage can be obtained through the back surface field aluminium paste.
Description
Technical field
The present invention relates to the metallic pigments field, relate to a kind of used for solar batteries back field aluminum paste particularly.
Background technology
Back field aluminum paste plays an important role in the manufacturing of crystal silicon solar cell sheet, on the one hand, passivation the cell back face; On the other hand,, just tie, improved minority carrier life time thereby form P+/P because eutectic takes place in sintering process for aluminium and silicon; It is corresponding to increase ruddiness in addition.Improve open circuit voltage, short circuit current and the fill factor, curve factor of battery sheet, and then improved the transformation efficiency of battery.
Back field aluminum paste belongs to the high temperature conductor paste, is made up of conductive powder body-aluminium powder, inorganic adhesive-glass dust and organic carrier-mainly refer to solvent and organic resin and various additive usually.Mix above-mentioned each component, and through three-high mill rolling and a kind of paste material of forming repeatedly.This slurry is via silk screen printing and after the continuous tunnel furnace rapid thermal treatment, in the opaco formation aluminium back of the body field of silicon chip of solar cell.
Desirable back field aluminum paste need have very little angularity after forming rete, and rete is smooth, and the pill of aluminium that do not have, aluminium bud, part occur coming off and the dry linting phenomenon.Wherein angularity is to weigh a key factor of sintered membrane quality.Existing a large amount of research attempts to reduce and even eliminate the angularity of sintered membrane in the prior art, for example Chinese patent application CN200710042439.0 (a kind of silver-aluminum slurry material and preparation technology thereof who prepares used for solar batteries), (200810047523.6 a kind of environment protection type silicon solar cell back electric field aluminum pulp and preparation method thereof), (200810196407.0 solar silicon photovoltaic cell is formed and preparation method thereof with leadless electronic slurry), (200910027898.1 organic adhesive for aluminum paste of silicon solar cells and preparation method thereof), (200910027899.5 inorganic adhesive for aluminum paste of silicon solar cells and preparation method thereof), 200910115679.8 (electrode of solar battery forms with slurry and preparation method thereof, (200910115680.0 electrode of solar battery forms and uses slurry), 200910227211.8 (a kind of crystal silicon solar energy battery aluminium paste is formed and preparation method thereof, with 201010118869.8 (a kind of used for solar batteries lead-free aluminum slurries) etc., these documents all relate to the improvement to formula of size.
In the above-mentioned background document, CN101789456A discloses a kind of used for solar batteries lead-free aluminum slurry, and is main as producing the solar cell conductive electrode.This lead-free aluminum slurry is that the aluminium powder of 70-80%, the organic bond of 19-30%, the unorganic glass powder of 0.1-5% and first additive of 0.1-2% are formed by mass percent mainly.Wherein organic bond comprises that mass percent is the terpinol of 40-60%, the ethyl cellulose of 1-5%, the lecithin of 1-5% and second additive of 20-50%.Existing used for solar batteries aluminium paste poorly conductive, technical problem that photoelectric conversion efficiency is low have mainly been solved.Have and conduct electricity very well the advantage that photoelectric conversion efficiency is high.CN200910227211.8 discloses a kind of crystal silicon solar energy battery aluminium paste and forms and preparation method thereof, its aluminium paste is formed the ball aluminum powder that comprises mass percent 50～85%, 2～15% crown glass bonding agent, 10～35% organic carrier, 0.5～6% metal or non-metal powder additive obtain aluminium paste after preparation.CN200910115680.0 discloses a kind of electrode of solar battery formation slurry, comprise: the aluminium powder of mass percent 65～75%, 20～30% organic carrier, 0.2～6% unorganic glass powder and 0.5～1% functional additive, described aluminium powder comprises at least two types, and wherein one type average grain diameter is less than 2 μ m and account for aluminium powder mass percent 1～10%.
Summary of the invention
The present invention proposes a kind of new used for solar batteries back field aluminum paste prescription, to improve and even to eliminate the warping phenomenon of aluminium paste sintered membrane.
The back field aluminum paste that is used for solar cell of the present invention is made up of following ingredients:
Aluminium powder 65-80 part
Inorganic adhesive 1-5 part
Organic carrier 10-30 part
Modifier 1-2 part
Wherein, modifier is that average grain diameter is no more than 5 microns simple substance silica flour or silicon-aluminum powder.Owing to introduced this modifier, the warpage properties of resulting battery sheet is significantly reduced.
In a kind of embodiment, modifier is the silicon-aluminum powder, mainly is made up of silicon and two kinds of elements of aluminium, and wherein the content of silicon suits between 10-80wt%.In a kind of execution mode more specifically, described silicon-aluminum powder is 1.5-2.0 part, and in the alloyed powder silicone content between 10-20wt%.
In a kind of optimal way, the average grain diameter of modifier is no more than 3 microns.
In another kind of preferred implementation, used aluminium powder lives through the surface treatment of the mixing coupling agent of being made up of titanate esters and borate, this mixing coupling agent does not contain phosphorus, and the amount ratio of titanate esters and borate is calculated by quality and is 20-80: 80-20, and the consumption that mixes coupling agent is the 0.5-3% of aluminium powder weight.
In another kind of preferred implementation, inorganic adhesive has following compositions:
Bi
2O
355-90 part
SiO
212-15 part
H
3BO
310-25 part
ZnO 4-25 part
Al
2O
30-10 part
ZrO
20-5 part
TiO
20-5 part
V
2O
51-5 part
BaCO
31-8 part
CaCO
31-8 part,
Wherein, ZnO and H
3BO
3Weight ratio between 1: 1 to 1: 4, V
2O
5, BaCO
3, CaCO
3Three's umber is no more than 20% of the total umber of described inorganic binder.As preferred mode, wherein Al
2O
3, ZrO
2, and TiO
2Umber be respectively 3-10 part, 1-5 part and 1-5 part.
In another kind of preferred implementation, inorganic adhesive is divided into A component and B component from particle diameter, and the D50 value of A component is the 1-2 micron, and the D50 value of B component is the 2-4 micron.The A component is identical with the constituent of B component, forms by weight the ratio of 20-80: 80-20.
Another aspect of the present invention provides a kind of back field aluminum paste composition that is used for solar cell, and it comprises following ingredients:
Aluminium powder 65-80 part
Inorganic adhesive 1-5 part
Organic carrier 10-30 part
Additive 0.1-1 part,
Wherein, aluminium powder lives through the mixing coupling agent surface treatment of being made up of titanate esters and borate, and this mixing coupling agent does not contain phosphorus, and the amount ratio of titanate esters and borate is 20-80: 80-20 by the quality calculation.
The invention still further relates to a kind of method for preparing above-mentioned back field aluminum paste composition, may further comprise the steps:
1) needed aluminium powder raw material is added in the high-speed mixer, measure on demand, after liquid feeding finishes, continue to stir 2-10 minute, aluminium powder is taken out drying with atomizing type adding surface treatment liquid;
2) take by weighing each component of inorganic adhesive by the prescription requirement, after in mixer, mixing, melting under 1150 ℃ of-1250 ℃ of conditions, shrend, ball milling;
3) resin is joined be equipped with hot solvent in reactor, stir, after all resins dissolving, continue insulation and stirred at least 5 hours.
4) according to the prescription requirement, aluminium powder, inorganic adhesive, modifier, organic carrier (being made up of resin and organic solvent) and auxiliary agent (additive) are mixed, stirring becomes the paste shape semifluid of homogeneous, on three-high mill, carry out rolling then, up to the slurry of the good fluidity that becomes homogeneous, fineness is≤12 microns, and viscosity is 20,000-60 is between the 000mPa.s.
In said method, surface treatment liquid is the mixing coupling agent that contains titanate esters and borate, and described mixing coupling agent does not contain phosphorus, and the amount ratio of titanate esters and borate is 20-80: 80-20 by the quality calculation.
Back field aluminum paste provided by the invention can obtain the sintered membrane than low warpage, and other technologies advantage of the present invention can be readily appreciated that by the following detailed description to technical scheme in conjunction with the embodiments.
Embodiment
Among the present invention, unless stated otherwise, when mentioning component ratio all with listed as parts by weight.In a first aspect of the present invention, this back field aluminum paste is by mainly being made up of following ingredients:
Aluminium powder 65-80 part
Inorganic adhesive 1-5 part
Organic carrier 10-30 part
Modifier 1-2 part.
Aluminium powder
Used aluminium powder is the nitrogen atomization powder, has the average grain diameter of 1-10 micron, wherein preferred 2-6 micron, and perhaps average grain diameter meets the mixture of several aluminium powders of above-mentioned requirements, and D99 is no more than 25 microns.
As preferably, used aluminium powder is through surface treatment.Among the present invention, with titanate esters and borate Combined Treatment, wherein, these two kinds of coupling agents are not phosphorous coupling agent, because most battery sheet is the P matrix, have promptly passed through boron diffusion.The amount ratio of titanate esters and borate is 20-80: 80-20 by quality, is preferably 40-70: 60-30, for example can be 45: 55, and 50: 50, perhaps 55: 45.The consumption of inorganic agent is the 0.5-3% of aluminium powder weight, preferred 1-2%.Be used for titanate esters of the present invention and have following general formula:
ROO
(4-n)Ti(OX-R’Y)
n
Wherein, n is 2 or 3, and R is the straight or branched alkyl of C2-C20, and wherein preferred C14-C18, OX-can be the alkoxyls, sulfonic group of carboxyl, C1-C5 etc.R ' is the straight or branched alkyl of C2-C10.It is very useful adopting above-mentioned titanate esters, because these titanate esters have good dispersiveness.Concrete application examples has KR-TTS, KR-201 etc.The present invention does not have particular restriction to borate, occurs on the market all can using as the borate of coupling agent, and the example that for example can be used for borate of the present invention has: LD-100, TB60 etc.In use, inorganic agent can be dissolved with The suitable solvent, be made into treatment fluid, operable solvent includes but not limited to ethanol, ethylene glycol, ethyl acetate, acetone, toluene, dimethylbenzene, methylethylketone etc.
Modifier
In above-mentioned composition, modifier is that average grain diameter is no more than 5 microns simple substance silica flour or silicon-aluminum powder.The inventor finds, when introducing this modifier in aluminium paste, can alleviate the warpage of sintered membrane well.The introducing amount of modifier is a key character, should not be too high, otherwise can the agglutinating property of slurry be had a negative impact.Use the silicon-aluminum powder mainly to be made up of silicon and two kinds of elements of aluminium among the present invention, wherein the content of silicon suits between 10-80%.When alloyed powder introducing amount is low, can adopt the higher silicon-aluminum powder of silicone content, measure when higher when introducing, can adopt the lower alloyed powder of silicone content.In a kind of preferred implementation of the present invention, introduce the alloyed powder of 1.5-2.0 part silicone content between 10-20% based on 65-80 part aluminium powder.The important prerequisite that modifier among the present invention can play a role is to have to be no more than 5 microns average grain diameter.The inventor finds that smaller particle size can provide suitable agglutinating property.If particle diameter is too high, for example be higher than 6 microns, then be difficult to realize anti-warpage function.Preferred average grain diameter is no more than 3 microns modifier among the present invention.
Inorganic adhesive
All inorganic compositions that can be used for electric slurry in the prior art all can be used for the present invention.Be in environmental protection and consider, should not in bonding agent, introduce plumbous.As an example, following various prescription all can be used for the present invention:
Prescription 1
Bi
2O
330-60 part
SiO
220-50 part
B
2O
31-4 part
TiO
23-10 part
ZnO 0-3 part
MgO 0-2 part
Prescription 2
CaO 1-20 part
SiO
21-20 part
B
2O
33-20 part
ZnO 1-15 part
MnO
22-5 part
Bi
2O
30-82 part
Al
2O
30-10 part
ZrO
20-5 part
Li
2O 0-5 part
BaO 0-40 part
MgO 0-5 part
Prescription 3
SiO
210-20 part
B
2O
315-30 part
Al
2O
35-15 part
Bi
2O
315-35 part
ZrO
215-18 part
ZnO 10-25 part
MoO
31-8 part
Of the present invention one preferred aspect, adopt prescription with following ratio:
Prescription 4
Bi
2O
355-90 part
SiO
212-15 part
H
3BO
310-25 part
ZnO 4-25 part
Al
2O
30-10 part
ZrO
20-5 part
TiO
20-5 part
V
2O
50-5 part
BaCO
30-8 part
CaCO
30-8 part,
Wherein, ZnO and H
3BO
3Weight ratio between 1: 1 to 1: 4, V
2O
5+ BaCO
3+ CaCO
3Three's umber is no more than 20% of total umber.As preferably, in this inorganic adhesive, contain the following various materials of 1 weight portion: ZrO at least
2, TiO
2, V
2O
5, BaCO
3, CaCO
3
The characteristics of this prescription are the alkali-free metals, to avoid damaging semi-conducting material, because alkali metal easily deposit in p-n junction under electric field action is degenerated knot, cause puncturing creep.
Another advantage of this prescription is that the softening point of inorganic binder is between 500-600 ℃.Both easy sintering between this softened zone can not cause rete defective to occur again, as the pill of aluminium, aluminium bud, come off etc.
As further preferred, the present invention has adopted unique particle diameter to select.Particularly, be used for glass dust of the present invention and be divided into A component and B component from particle diameter, the D50 value of A component is the 1-2 micron, and the D50 value of B component is the 2-4 micron.The A component is identical with the constituent of B component, forms inorganic adhesive by weight the ratio of 20-80: 80-20.Adopt this prescription, softening point is between 530-570 ℃.Employing has the glass dust of this grain diameter characteristic, makes powder have bigger span, can form fine and close more baked film, thereby has guaranteed the compactness of sintered membrane, and this can its resistance to water of corresponding raising.
Organic carrier
There is not strict restriction to being used for organic carrier of the present invention.In principle, be used for all electric slurry organic carriers of the prior art and all can be used for the present invention.Organic carrier is made up of organic resin and organic solvent usually.Operable organic resin comprises ethyl cellulose, rosin, newtrex, solid propenoic acid resin, perhaps their mixture.Operable organic solvent comprises terpinol, butyl carbitol, butyl carbitol acetate, alcohol ester-12, octanol, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether, propylene glycol monobutyl ether or their mixture, it is preferred wherein using mixed solvent, this makes dicyandiamide solution not possess constant boiling point, is beneficial to volatilization uniformly in drying course.
Aluminum paste composition of the present invention also contains the auxiliary additive of convention amount usually, for example rheological agent, defoamer, lubricant or the like, and their total weight is generally between 0.1-1 part.
Preparation back field aluminum paste according to the present invention generally comprises following step:
1) surface treatment of aluminium powder
Needed aluminium powder raw material is added in the high-speed mixer, measure on demand with atomizing type and add above-mentioned Combined Treatment liquid, after liquid feeding finishes, continue to stir 2-10 minute, aluminium powder is taken out drying.
2) preparation of inorganic adhesive
Take by weighing each component of inorganic adhesive by the prescription requirement, in high-speed mixer, mix melting under 1150 ℃ of-1250 ℃ of conditions then, shrend, ball milling.Under the situation of using the different-grain diameter bonding agent, obtain the glass dust of different-grain diameter by different milling times.In a kind of embodiment of the present invention, be 30-50rpm with the speed setting of ball mill, ball milling obtained the inorganic adhesive B of D50 value for the 2-4 micron in 48 hours, and ball milling obtained the inorganic adhesive A of D50 value between the 1-2 micron in 72 hours.
3) preparation of organic carrier
Take by weighing solvent and resin by the prescription requirement, in reactor, mixing, normally under the temperature that improves, mix, for example under 50-80 ℃ temperature, with needed resin, slowly join in the solvent of heat, after all resins dissolving, preferably continue insulation and stirring a period of time, so that form the resin dispersion of homogeneous.
4) according to the prescription requirement, taking by weighing aluminium powder, inorganic adhesive, modifier, organic carrier and auxiliary agent etc. is mixed together, stirring becomes the paste shape semifluid of homogeneous, on three-high mill, carry out rolling then, up to the slurry of the good fluidity that becomes homogeneous, fineness is≤12 microns, and viscosity is 20,000-60 is between the 000mPa.s.
Embodiment 1:
The processing of aluminium powder: will add in the high-speed mixer available from the aluminium powder 50kg (KY523, KY445, KY456, KY467 respectively account for 25%) of gold source, Luxi County powder body material Co., Ltd, measure on demand with atomizing type adding 3kg Combined Treatment liquid.Contain 0.3kg titanate esters (KR-201, two isostearoyl base tetraethyl titanates), 0.2kg borate (LD-100P, Yangzhou Lida Resin Co., Ltd. produces) and 2.5kg ethanol in the Combined Treatment liquid, the ratio of titanate esters and borate is 3 to 2, and consumption is 1% of an aluminium powder.After liquid feeding finishes, continue to mix 3 minutes, aluminium powder is taken out, it is dry down to be placed at 50-70 ℃, vacuum condition, 6-8 hour, obtains disposing the required aluminium powder of slurry.
The preparation of inorganic adhesive: by 20 parts of SiO
2, 18 parts of B
2O
3, 13 parts of Al
2O
3, 15 parts of Bi
2O
3, 16 parts of ZrO
2With the ratio preparation bonding agent of 10 parts of ZnO, after mixing, melting is 1 hour under 1150 ℃ of-1250 ℃ of conditions, shrend, ball milling to D50 value is 3.0 ± 0.5 microns then, after Separation of Solid and Liquid and the washing, and the oven dry solid constituent, through high-speed breakage, dry state was descended 500 sieves, obtained inorganic adhesive.
The preparation of organic carrier: 30kg terpinol solvent is joined in the reactor, stir and be no more than 100rpm, simultaneously, be heated to 70 ℃; With needed resin ethyl cellulose 3kg, slowly join in the solvent of heat, stirring aggravates to 500rpm, after all resins dissolving, continue to keep temperature and stirring condition, stop to stir cooling at least after 5 hours, store in the transfer vector special container, cool off fully, obtain organic carrier 33kg.
With 7500g aluminium powder, 150g inorganic adhesive, the 100g average grain diameter of above-mentioned processing is that 5 microns simple substance silica flour, the above-mentioned organic carrier 2000g that makes, auxiliary agent 250g (levelling agent, defoamer, lubricant) etc. are mixed together, stirring becomes the paste shape semifluid of homogeneous, on three-high mill, carry out rolling then, slurry up to the good fluidity that becomes homogeneous, fineness is≤12 microns, viscosity is 20, and 000-60 is between the 000mPa.s.
Comparative Examples 1
Repeat the operation of embodiment 1, difference is not introduce the simple substance silica flour modifier among the embodiment 1.
It in the table 1 test result of each embodiment gained slurry.As can be seen from Table 1, the angularity of embodiment 1 gained slurry is significantly less than Comparative Examples.Can draw thus, be better than having adopted modifier of the present invention, reduce the angularity of battery sheet.
Embodiment 2:
The processing of aluminium powder: will add in the high-speed mixer available from the aluminium powder 50kg (KY523, KY445, KY456, KY467 respectively account for 25%) of gold source, Luxi County powder body material Co., Ltd, measure on demand with atomizing type adding 5kg Combined Treatment liquid.Contain 0.2kg titanate esters KR-201,0.3kg borate (LD-100P, Yangzhou Lida Resin Co., Ltd. produces) and 4.5kg ethanol in the Combined Treatment liquid, the ratio of titanate esters and borate is 2 to 3, and consumption is 1% of an aluminium powder.After liquid feeding finishes, continue to mix 3 minutes, aluminium powder is taken out, it is dry down to be placed at 50-70 ℃, vacuum condition, 6-8 hour, obtains disposing the required aluminium powder of slurry.
The preparation of inorganic adhesive: prepare bonding agent in following ratio:
Bi
2O
355 parts
SiO
215 parts
H
3BO
320 parts
5 parts of ZnO
Al
2O
32 parts
ZrO
21 part
TiO
25 parts
V
2O
55 parts
BaCO
32 parts
CaCO
31 part,
ZnO and H
3BO
3Weight ratio be 1: 4, V
2O
5, BaCO
3, CaCO
3Three's umber is 7% of an inorganic binder total amount.
After mixing, melting is 1 hour under 1150 ℃ of-1250 ℃ of conditions, shrend, and ball milling is 48 hours then, after Separation of Solid and Liquid and the washing, the oven dry solid constituent, through high-speed breakage, dry state was descended 500 sieves, obtained inorganic adhesive B; The ball milling time should be 72 hours, obtained inorganic adhesive A.
The preparation of organic carrier: the 30kg terpinol is joined in the reactor, stir and be no more than 100rpm, simultaneously, be heated to 70 ℃; With needed resin-ethyl cellulose 3kg, slowly join in the solvent of heat, stir and aggravate to 500rpm, after all resins dissolving, continue to keep temperature and stirring condition, stop after 8 hours stirring, cooling is stored in the transfer vector special container, is cooled off fully, obtains organic carrier 33kg.
Aluminium powder 7500g, the inorganic adhesive 100g (A and B respectively account for 50%) of above-mentioned processing, simple substance silica flour, the above-mentioned organic carrier 2000g that makes, other auxiliary agents 250g etc. that the 150g average grain diameter is 5 microns are mixed together, stirring becomes the paste shape semifluid of homogeneous, on three-high mill, carry out rolling then, slurry up to the good fluidity that becomes homogeneous, fineness is≤12 microns, viscosity is 20, and 000-60 is between the 000mPa.s.
Embodiment 3:
The processing of aluminium powder: will add in the high-speed mixer available from the aluminium powder 50kg (KY523, KY445, KY456, KY467 respectively account for 25%) of gold source, Luxi County powder body material Co., Ltd, measure on demand with atomizing type adding 5kg Combined Treatment liquid.Contain 0.3kg titanate esters KR-TTS (isopropyl triisostearoyltitanate), 0.7kg borate (LD-100) and 4kg ethanol in the Combined Treatment liquid, the ratio of titanate esters and borate is 3 to 7, and consumption is 2% of an aluminium powder.After liquid feeding finishes, continue to mix 3 minutes, aluminium powder is taken out, it is dry down to be placed at 50-70 ℃, vacuum condition, 6-8 hour, obtains disposing the required aluminium powder of slurry.
The preparation of inorganic adhesive: prepare bonding agent in following ratio:
Bi
2O
390 parts
SiO
212 parts
H
3BO
310 parts
10 parts of ZnO
Al
2O
39 parts
ZrO
25 parts
TiO
21 part
V
2O
51 part
BaCO
38 parts
CaCO
38 parts,
ZnO and H
3BO
3Weight ratio be 1: 1, V
2O
5, BaCO
3, CaCO
3Three's umber is 11% of an inorganic binder total amount.
After mixing, melting is 1 hour under 1150 ℃ of-1250 ℃ of conditions, shrend, and ball milling is 3.0 ± 0.5 microns to D50 then, after Separation of Solid and Liquid and the washing, the oven dry solid constituent, through high-speed breakage, dry state was descended 500 sieves, obtained inorganic adhesive B; Ball milling to D50 be 1.5 ± 0.3 microns, obtain inorganic adhesive A.
The preparation of organic carrier: the 30kg terpinol is joined in the reactor, stir and be no more than 100rpm, simultaneously, be heated to 70 ℃; With ethyl cellulose 3kg, slowly join in the solvent of heat, stir and aggravate to 500rpm, after all resins dissolving, continue to keep temperature and stirring condition, stop after 8 hours stirring, cooling is stored in the transfer vector special container, is cooled off fully, obtains organic carrier 30kg.
With the aluminium powder 7500g of above-mentioned processing, (100gA accounts for 60% to the 150g inorganic adhesive, B accounts for 40%), the 150g average grain diameter is that 5 microns silicon-aluminum powder (silicone content is 15% in the alloyed powder), the above-mentioned organic carrier 2000g that makes, auxiliary agent 200g etc. are mixed together, stirring becomes the paste shape semifluid of homogeneous, on three-high mill, carry out rolling then, up to the slurry of the good fluidity that becomes homogeneous, fineness is≤12 microns, and viscosity is 20,000-60 is between the 000mPa.s.
Result from table 1 as can be seen, embodiment 2 and 3 adopts the inorganic adhesive of special components and ratio, and adopts the mixture of A and B component, the battery sheet of gained shows the water resistance that is higher than embodiment 1, wherein the resistance to water of embodiment 3 is better.
Embodiment 4
Substantially the same manner as Example 3, difference is that the average grain diameter of modifier is no more than 3 microns.
As can be seen from Table 1, the battery sheet of embodiment 4 gained has high conversion rate, preferable anti-warpage properties and preferable resistance to water.
Result's test
Aluminium paste with above-mentioned experiment preparation is printed the solar cell back field, and printing adopts automatic screen printer to finish, and the battery sheet adopts 125 * 125 monocrystalline silicon pieces, radix is 200, finish Fast Sintering in the despatch sintering furnace, measure relevant parameter then, the data that provide are average.
Water resistance test: the battery sheet that sinters, be soaked in the deionized water of room temperature, take out after 12 hours, dry gravimetry.Weight * 100% before resistance to water=immersion back weight/immersion.Gained the results are shown in the table 1.
The test result of each embodiment slurry gained battery sheet of table 1.
Abovely embodiments of the present invention are described, but these execution modes only are for exemplary purposes rather than restriction the present invention in conjunction with preferred embodiment.It should be understood that those skilled in the art can be under the prerequisite that does not deviate from scope and spirit of the present invention, change and revise for embodiment.Similarly, except above-mentioned execution mode, can also find many embodiments in the appended claims.
Claims (9)
1. be used for the back field aluminum paste of solar cell, it is characterized in that, form by following ingredients:
Aluminium powder 65-80 part
Inorganic adhesive 1-5 part
Organic carrier 10-30 part
Modifier 1-2 part,
Wherein, described modifier is that average grain diameter is no more than 5 microns simple substance silica flour or silicon-aluminum powder.
2. back field aluminum paste according to claim 1, wherein, described silicon-aluminum powder mainly is made up of silicon and two kinds of elements of aluminium, and wherein the content of silicon is between 10-80%.
3. back field aluminum paste according to claim 2, wherein, described silicon-aluminum powder is 1.5-2.0 part, and in the described silicon-aluminum powder content of silicon between 10-20%.
4. back field aluminum paste according to claim 1, wherein, the average grain diameter of described modifier is no more than 3 microns.
5. back field aluminum paste according to claim 1, wherein, described aluminium powder passes through the surface treatment of the mixing coupling agent of being made up of titanate esters and borate, described mixing coupling agent does not contain phosphorus, and the amount ratio of titanate esters and borate is 20-80: 80-20 by weight, and the consumption of described mixing coupling agent is the 0.5-3% of aluminium powder weight.
6. back field aluminum paste according to claim 1, wherein, described inorganic adhesive has following compositions:
Bi
2O
355-90 part
SiO
212-15 part
H
3BO
310-25 part
ZnO 4-25 part
Al
2O
30-10 part
ZrO
20-5 part
TiO
20-5 part
V
2O
50-5 part
BaCO
30-8 part
CaCO
30-8 part, and
ZnO and H
3BO
3Weight ratio between 1: 1 to 1: 4, V
2O
5, BaCO
3, CaCO
3Three's umber is no more than 20% of the total umber of described inorganic binder.
7. back field aluminum paste according to claim 6, wherein, described inorganic adhesive contains 1 part of ZrO at least
2, 1 part of TiO
2, 1 part of V
2O
5, 1 part of BaCO
3, and 1 part of CaCO
3
8. back field aluminum paste according to claim 1, wherein, described inorganic adhesive is divided into A component and B component from particle diameter, the D50 value of A component is the 1-2 micron, the D50 value of B component is the 2-4 micron, and the A component is identical with the constituent of B component, forms by weight the ratio of 20-80: 80-20.
9. be used for the back field aluminum paste of solar cell, it is characterized in that, comprise following ingredients:
Aluminium powder 65-80 part
Inorganic adhesive 1-5 part
Organic carrier 10-30 part
Additive 0.1-1 part,
Wherein, the mixing coupling agent surface treatment of described aluminium powder through forming by titanate esters and borate, described mixing coupling agent does not contain phosphorus, and the amount ratio of titanate esters and borate is 20-80: 80-20 by the quality calculation.
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Application publication date: 20110615 Assignee: LUXI JINYUAN POWDER MATERIAL CO.,LTD. Assignor: ZUXING NEW MATERIAL CO.,LTD. Contract record no.: 2013430000167 Denomination of invention: Back surface field aluminium paste for solar cells Granted publication date: 20120725 License type: Exclusive License Record date: 20131016 |
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Denomination of invention: Backfield aluminum paste for solar cells Granted publication date: 20120725 Pledgee: Ningxiang sub branch of Bank of Changsha Co.,Ltd. Pledgor: ZUXING NEW MATERIAL CO.,LTD. Registration number: Y2024980013898 |