CN103762249B - Crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry and preparation method - Google Patents
Crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry and preparation method Download PDFInfo
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Abstract
The invention belongs to solar cell field of new, particularly a kind of crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry and preparation method.Crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry mixes primarily of following raw material by mass percentage: aluminium powder 60-75%, silicon aluminium alloy powder 5-10%, glass dust 1-10%, organic bond 15-30%.This back surface field passivation aluminum conductive electric slurry is for being printed on the back side of crystal silicon solar batteries sheet, through infrared fast-firing technique (silicon chip surface true peak temperature 780 DEG C-810 DEG C, 1-2 second), aluminium and the reaction of matrix silicon generation alusil alloy, realize ohmic contact and form back surface field, guarantee the high transformation efficiency of cell piece, aluminum conductive electric slurry sintered membrane and sill adhesive force good, do not play aluminium pill, aluminium blister, water-tolerant, do not affect the production of assembly and ensure that the reliability of cell piece.
Description
Technical field
The invention belongs to solar cell field of new, particularly a kind of crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry and preparation method.
Background technology
Crystal silicon solar batteries is a kind of semipermanent physical battery solar energy being converted into electric energy, along with fossil (oil, coal, natural gas etc.) the extreme consumption of the energy, the lack of energy produced and day by day serious greenhouse effect, the demand of the mankind to new cleaning fuel becomes more and more urgent.In the time that future is very long, the sun will be effective supplier of mankind's clean energy resource, at present, crystal silicon solar batteries converts solar energy into one of domestic energy active parts, its range of application just expands to daily life from space flight, military affairs, while not producing new pollution, the reduction of cost will make solar cell obtain applying more widely.
According to International Energy Agency's prediction, whole world coal can only with 220 years, and oil exploitation peak value is positioned at 2012, and will at 30-60 years post consumptions to the greatest extent.And solar radiant energy estimates can keep the radiant output of approximately constant in 10,000,000,000 years, it is predicted, the year two thousand fifty the solar energy ratio that will occupy 20% in whole energy resource structure, and will 70% be reached to 2100 years these ratios.Obviously, there is basic change by this century in mankind's energy resource structure, and solar energy will become the most important energy.
Aluminium back surface field is that crystalline silicon modern solar cell generally adopts, typical back surface passivation structure, through development for many years, the production technology of aluminium back surface field has tended to ripe, stable, also day by day deepen every research of aluminium back surface field, these all determine aluminium back surface field within the quite a while from now on will be widely used in crystal-silicon solar cell production.But along with the development of technique, thinner solar cell is about to occur, this has higher requirement to the passivation of aluminium back surface field, further research aluminium back surface field passivation is efficient solar battery research and a very important important step in producing.The surface passivation of aluminium back surface field, back surface recombination rate can be reduced, improve the collection rate of minority carrier, thus improve open circuit voltage, aluminium is easy to form good ohmic with P-type silicon and contacts simultaneously, alusil alloy structure for this reason, not only there is the effect of back surface field, but also back surface ohmic contacts can be formed well, as the output electrode of electric current, reduce contact resistance, improve the electric property of battery.
Summary of the invention
The invention provides a kind of crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry, it is unleaded, without cadmium, without thallium, the cell piece utilizing it to prepare is without aluminium pill, aluminium blister, bending little, forms BSF layer well.
The present invention also provides a kind of preparation method of described crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry, this slurry mixes primarily of following raw material by mass percentage: aluminium powder 60-75%, silicon aluminium alloy powder 5-10%, glass dust 1-10%, organic bond 16-22%.This back surface field passivation aluminum conductive electric slurry is for being printed on the back side of crystal silicon solar batteries sheet, through infrared fast-firing technique (silicon chip surface true peak temperature 780 DEG C-810 DEG C, 1-2 second), aluminium and the reaction of matrix silicon generation alusil alloy, realize ohmic contact and form back surface field, guarantee the high transformation efficiency of cell piece, aluminum conductive electric slurry sintered membrane and sill adhesive force good, do not play aluminium pill, aluminium blister, water-tolerant, do not affect the production of assembly and ensure that the reliability of cell piece.
As preferably, described aluminium powder is purity more than 99.9%, average grain diameter 1.0-10 μm, and the ball aluminum powder that the atomization that surface is covered with pellumina is produced, the thickness of pellumina is 2.0-10.0nm.Further preferably, average grain diameter 6.0-8.0 μm (laser particle) of described aluminium powder, apparent density 0.60-0.85g/cc, specific area is 0.70-1.00m
2/ g.Realize back surface field surface passivation and mainly reduce semiconductor surface activity, thus reduce recombination rate, once added the cleaning procedure on surface, and made gettering more thorough.Generally select aluminium powder purity can introduce impurity level at the cell piece back side lower than 99.9%, increase Carrier recombination speed, thus reduce electric current and the open circuit voltage of battery, select purity higher than 99.9% aluminium powder contribute to the formation of back surface field P+ layer.Aluminium powder top layer is easily oxidized, if thickness is more than 10nm, in slurry sintering process, can form alloy and cause obstacle, hinder the formation of P+ layer to the contact of silicon and aluminium.The present invention effectively improves P+ layer thickness by adding silicon aluminium alloy powder, reduces Carrier recombination speed, forms better aluminium back surface field passivation effect.
As preferably, its inorganic constituents of described glass dust and respective quality percentage as follows: SiO
21-10%, ZnO10-30%, B
2o
310-40%, Bi
2o
330-50%, Al
2o
35-10%, V
2o
51-7%.Wherein B
2o
3, Bi
2o
3, SiO
2be the material of main part forming glass, the vitreum of stable homogeneous can be formed.ZnO, Al
2o
3reach and control glass softening point and the rear silicon warp degree of slurry sintering, reduce after glass expansion coefficient makes slurry sinter and reach suitable angularity.V
2o
5the mobility being used for controlling glass makes there is suitable flow regime in slurry sintering.Wherein B
2o plays the effect of flux, can reduce the melt temperature of glass, and at high temperature reduce glass viscosity, and its content does not have effective fluxing action lower than 10%, weakens rapidly higher than 60% strength of glass; SiO
2play bridging action in glass, form glass network together with oxide, contribute to the stability of raising glass and improve intensity, its content can increase higher than the fusing point of 30% glass, is unfavorable for the formation of back surface field layer; B
2o
3act on SiO
2similar, B in addition
2o
3can reduce glass melting point, the sintering temperature of adjustment slurry and thermal coefficient of expansion, Boron contents is high lower than 10% system fusing point, and Boron contents is large higher than 30% system thermal coefficient of expansion, increases the angularity of aluminium paste; ZnO be used for the thermal coefficient of expansion and the cooling that adjust glass time crystallization rate, the thermal coefficient of expansion of content height glass is little, contributes to reducing the warpage degree of cell piece after sintering.
As preferably, the preparation method of described glass dust is as follows: mixed in proportion by oxide, puts into crucible, and 600 DEG C of insulations 0.5 hour, be then warming up to 1200 DEG C of meltings 2 hours, after shrend, ball milling makes glass dust average grain diameter≤10 μm.
As preferably, described organic bond by mass percentage composed as follows: ethyl cellulose 1-10%, phenolic resins or novolac epoxy resin 1-10%, rosin 0.5-2%, terpinol 20-50%, phenmethylol 10-30%, BS 5-20%, butyl carbitol 20-40%.Ethyl cellulose is the main component of adhesive; Rosin prevents aluminium paste degree of oxidation in oven dry from increasing, and plays anti-settling effect in the slurry; Terpinol, butyl carbitol, phenmethylol are the main components of solvent, and three is mixed for adjusting rate of volatilization when solvent is dried, and makes slurry reach suitable mobility and thixotropy, reaches desirable printing effect.Lubrification and the dispersiveness of BS increase slurry reach better printing effect, and after phenolic resins or novolac epoxy resin can make oven dry, aluminum membranous layer is finer and close, has better adhesive force.
As preferably, the preparation method of described organic bond is as follows: the preparation method of described organic bond is as follows: described phenolic resins or novolac epoxy resin, terpinol, phenmethylol, BS and butyl carbitol are weighed up by mass percentage and put into container, mix and be heated to 80 DEG C-160 DEG C, solid ethyl cellulose and rosin powder is added under stirring, until pressed powder dissolves completely, form transparent uniform solution and namely obtain organic bond.
As preferably, fineness≤15 μm of described aluminum conductive electric slurry, viscosity is 20-40Pas.
As preferably, silicon aluminium alloy powder average grain diameter is 1-10 μm, and purity is the alloy powder of silicon 15%, aluminium 85%.
A kind of preparation method of described crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry, according to described pulp furnish, aluminium powder, silicon aluminium alloy powder, glass dust and organic bond are put into de-airing mixer stir, disperse through three-high mill again, control scraper plate fineness≤15 μm, make mixture form the slurry evenly with lasting rheological behavior, obtain aluminum conductive electric slurry.Fineness≤15 μm of described aluminum conductive electric slurry, viscosity is 20-40Pas.Raw material stirs in de-airing mixer, and object reaches organic carrier to the more effective infiltration of powder, makes powder fully disperse in the carrier simultaneously, reduces the difficulty that powder disperses on three-roll grinder.Scraper plate fineness is the aggregation extent of particle in reaction paste, controls, below 15 μm, slurry fully to be disperseed, and granularity is greater than 15 μm and just there will be uniformity not, the phenomenon of network blocking during printing.Viscosity controls to contribute to obtaining good printing effect at 25-45Pas, and viscosity is higher than 45Pas, and the printing weight of slurry is excessive, slurry haftplatte impact printing; Viscosity is too low lower than the viscosity of 25Pas slurry, and printing weight is partially light, and spillage etc., can affect the open circuit voltage of battery.
1. the preparation of inorganic bond phase glass dust
Component and the content of glass dust are respectively: silicon dioxide (SiO
2) 1-10%, diboron trioxide (B
2o
3) 10-40%, zinc oxide (ZnO) 10-30%, bismuth oxide (Bi
2o
3) 30-50%, aluminium oxide (Al
2o
3) 5-10%, vanadic oxide (V
2o
5) 1-7%.
Weighed by mass percentage by above-mentioned raw materials, Homogeneous phase mixing, in porcelain crucible, is founded in Muffle furnace, is warming up to 600 degree, is incubated 0.5 hour, is warming up to 1200 DEG C of meltings 2 hours, by the glass shrend of fusing, and makes glass dust average grain diameter be≤10 μm with ball milling.
2. the preparation of organic bond
The component of organic bond and content are distinguished as follows: ethyl cellulose 1-10%, phenolic resins or novolac epoxy resin 1-10%, rosin 0.5-2%, terpinol 20-50%, phenmethylol 10-30%, BS 5-20%, butyl carbitol 20-40%, weigh up above-mentioned by mass percentage and put into rustless steel container, mix and heat 80 DEG C-160 DEG C, under agitation add ethyl cellulose and rosin, Keep agitation, until become completely transparent homogeneous solution as organic bond.
3. the configuration of aluminum conductive electric slurry
Aluminium powder 60-75% quality, silicon aluminium alloy powder 5-10%, glass dust 1-10% quality, organic thing 16-22% quality are pressed electrocondution slurry proportion of composing, after total amount 100% mixes, with three-high mill, shearing dispersion is carried out to mixture again, the slurry (fineness < 15 μm, viscosity 20-40Pa.s) mixture being formed evenly have lasting rheological behavior is target product aluminum conductive electric slurry.
The present invention, by the optimization of component and technique, has manufactured a kind of function admirable, is more suitable for the passivation aluminum conductive electric slurry that crystal silicon solar batteries back surface field uses.Aluminum membranous layer after burning till and silicon substrate have well adhesive force, resistance to water, without aluminium pill, aluminium blister, the cell piece burnt till bends little, and transformation efficiency is higher.Compared with prior art, advantage of the present invention is:
1. unorganic glass is the Binder Phase of aluminum conductive electric slurry mutually, and the glass within the scope of optimized proportion makes aluminium fully melt in sintering process, infiltrate silicon face, aluminium back surface field is uniform and stable thus effectively reduce silicon chip surface recombination rate, makes it back surface field firm adhesion after sintering simultaneously.
2. aluminium powder is aluminium paste critical function phase, and the present invention uses spherical atomizing aluminium powder to meet requirement on electric performance, and obtain outside desirable back surface field effect, substrate deformation is little, does not play aluminium pill, aluminium blister.Back surface field is uniform and smooth, and outward appearance is good.
3. the combination of different solvents in organic bond, ensure that and clap dissolution characteristics and when rate of volatilization, aluminium powder oxidation degree in drying course is reduced, and aluminum conductive electric slurry and base material infiltrate, and the rate of settling is slow, while printing performance good.
4. silicon aluminium alloy powder is effective powder filler, impels and forms even aluminium back surface field, increases BSF layer thickness, thus promotes electrical property.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.
In the present invention, if not refer in particular to, all parts, percentage are unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is conventional.
Embodiment 1-6:
A kind of crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry is mixed by raw material by mass percentage as shown in table 1.Aluminium powder, silicon aluminium alloy powder, glass dust and organic bond are put into de-airing mixer by the proportioning of table 1, Keep agitation 2 hours, form homogeneous mixture, disperse through three-high mill again, grind to form homogeneous slurry, scraper plate fineness≤15 μm, finally obtain having lasting rheological behavior, fineness≤15 μm, viscosity is the aluminum conductive electric slurry of 20-40Pas.
Table 1(weight: g)
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Aluminium powder | 70 | 68 | 60 | 75 | 65 | 72 |
| Silicon aluminium alloy powder | 6 | 10 | 8 | 7 | 9 | 5 |
| Glass dust | 3 | 1 | 10 | 2 | 7 | 6 |
| Organic bond | 21 | 21 | 22 | 16 | 19 | 17 |
1. aluminium powder
Aluminium powder is the atomizing aluminium powder that commercially available nitrogen protection method is produced, and aluminium powder is aluminium nitride passivation ball aluminum powder, average grain diameter 6.0-8.0 μm (laser particle) of aluminium powder, and apparent density 0.60-0.85g/cc, specific area is 0.70-1.00m
2/ g.Silicon aluminium alloy powder average grain diameter is 1-10 μm, and purity is the alloy powder of silicon 15%, aluminium 85%.
2. silicon aluminium alloy powder
Silicon aluminium alloy powder average grain diameter is 5-6 μm, and purity is the alloy powder of silicon 15%, aluminium 85%.
3. inorganic bond phase---the preparation of glass dust
The homemade glass dust of the present invention is crown glass, and its inorganic constituents and corresponding proportioning are in table 2.Above-mentioned raw materials is weighed, porcelain crucible is put into after Homogeneous phase mixing, melting in 1200 DEG C/1 hour in Muffle furnace, use pure water as medium using adding after the glass shrend of uniform melt in polyurethane tank, 6mm zirconia ball is ball milling ball, by zirconia ball: glass: pure water mass ratio is 3:1:1, loading is 2/1 to three/3rds of ball grinder cumulative volume, be 24 hours during ball milling, tank speed 100-150/ divides, obtain average grain diameter≤10.0 μm unorganic glass powder, this glass dust is as the inorganic bond of aluminum conductive electric slurry of the present invention.
Table 2(weight: g)
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| SiO 2 | 10 | 5 | 1 | 6 | 2 | 8 |
| ZnO | 22 | 18 | 30 | 20 | 13 | 10 |
| B 2O 3 | 25 | 15 | 10 | 35 | 40 | 19 |
| Bi 2O 3 | 33 | 47 | 48 | 30 | 32 | 50 |
| Al 2O 3 | 5 | 8 | 10 | 6 | 9 | 7 |
| V 2O 5 | 5 | 7 | 1 | 3 | 4 | 6 |
4. the preparation of organic bond
Press the component as table 3 and weight proportion, terpinol, butyl carbitol and tributyl phosphate are weighed up by mass percentage and puts into rustless steel container, mix and be heated to 60-80 DEG C, solid ethyl cellulose and rosin powder is added under stirring, stir 1-2 hour, now pressed powder dissolves completely, and forms completely transparent homogeneous solution, and the present invention it can be used as the organic bond of aluminum conductive electric slurry.
Table 3(weight: g)
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Ethyl cellulose | 5.5 | 5 | 1 | 8 | 6 | 10 |
| Phenolic resins | 6 | 2 | 10 | 9 | 5 | 1 |
| Rosin | 1.5 | 1.2 | 0.8 | 0.5 | 2 | 1 |
| Terpinol | 45 | 50 | 40 | 20.5 | 27 | 20 |
| Phenmethylol | 11 | 11.8 | 10 | 15 | 30 | 15 |
| BS | 9 | 5 | 14.2 | 20 | 10 | 13 |
| Butyl carbitol | 22 | 25 | 24 | 27 | 20 | 40 |
The aluminum conductive electric slurry performance that embodiment 1-6 obtains in table 4, and compares with the use result of conventional aluminium paste.
Table 4
Viscosity: VT-04E60rpm2#spindle25 DEG C.
With the bent 1.0-1.5mm of vernier caliper lateral bending, smooth in appearance, without aluminium pill, aluminium blister, bonds aluminium film without peeling with EVA.
As can be seen from Table 4, above 1-6 embodiment data result can meet existing market requirement, the highest with embodiment 1 data.Embodiment 1-6 all has printing capability relatively preferably, and viscosity controls at about 30Pas.After 780 DEG C of sintering, outward appearance aspect, aluminium lamination smooth surface is without blister, adhesive force reaches more than 25N, and warpage is little, under similarity condition in electrical property, back surface field passivation aluminium paste, than common aluminium paste high 0.02-0.05% on electricity conversion, realizes the optimum efficiency of surface passivation.
As can be seen from Table 4, above 1-6 embodiment data result can meet existing market requirement, the highest with embodiment 1 data.
Back surface field passivation aluminum conductive electric slurry of the present invention is for being printed on the back side of crystal silicon solar batteries sheet, through infrared fast-firing technique (silicon chip surface true peak temperature 780 DEG C-810 DEG C, 1-2 second), aluminium and the reaction of matrix silicon generation alusil alloy, realize ohmic contact and form back surface field, guarantee the high transformation efficiency of cell piece, aluminum conductive electric slurry sintered membrane and sill adhesive force good, do not play aluminium pill, aluminium blister, water-tolerant, do not affect the production of assembly and ensure that the reliability of cell piece.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (8)
1. a crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry, is characterized in that: this slurry mixes primarily of following raw material by mass percentage:
Aluminium powder 60-75%,
Silicon aluminium alloy powder 5-10%,
Glass dust 1-10%,
Organic bond 16-22%, described organic bond by mass percentage composed as follows:
Ethyl cellulose 1-10%,
Phenolic resins or novolac epoxy resin 1-10%,
Rosin 0.5-2%,
Terpinol 20-50%,
Phenmethylol 10-30%,
BS 5-20%,
Butyl carbitol 20-40%, the preparation method of described organic bond is as follows: described phenolic resins or novolac epoxy resin, terpinol, phenmethylol, BS and butyl carbitol are weighed up by mass percentage and put into container, mix and be heated to 80 DEG C-160 DEG C, solid ethyl cellulose and rosin powder is added under stirring, until pressed powder dissolves completely, form transparent uniform solution and namely obtain organic bond.
2. aluminum conductive electric slurry according to claim 1, is characterized in that: described aluminium powder is purity more than 99.9%, average grain diameter 1.0-10 μm, and the ball aluminum powder that the atomization that surface is covered with pellumina is produced, the thickness of pellumina is 2.0-10.0nm.
3. aluminum conductive electric slurry according to claim 2, is characterized in that: the average grain diameter 6.0-8.0 μm of described aluminium powder, apparent density 0.60-0.85g/cc, and specific area is 0.70-1.00m
2/ g.
4. aluminum conductive electric slurry according to claim 1 and 2, is characterized in that: its inorganic constituents of described glass dust and respective quality percentage as follows: SiO
21-10%, ZnO10-30%, B
2o
310-40%, Bi
2o
330-50%, Al
2o
35-10%, V
2o
51-7%.
5. aluminum conductive electric slurry according to claim 4, it is characterized in that the preparation method of described glass dust is as follows: mixed in proportion by oxide, put into crucible, 600 DEG C are incubated 0.5 hour, then be warming up to 1200 DEG C of meltings 2 hours, after shrend, ball milling makes glass dust average grain diameter≤10 μm.
6. aluminum conductive electric slurry according to claim 1 and 2, is characterized in that: fineness≤15 μm of described aluminum conductive electric slurry, and viscosity is 20-40Pas.
7. aluminum conductive electric slurry according to claim 1 and 2, is characterized in that: silicon aluminium alloy powder average grain diameter is 1-10 μm, and purity is the alloy powder of silicon 15%, aluminium 85%.
8. the preparation method of a crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry, it is characterized in that: according to pulp furnish as claimed in claim 1, aluminium powder, silicon aluminium alloy powder, glass dust and organic bond are put into de-airing mixer stir, disperse through three-high mill again, control scraper plate fineness≤15 μm, make mixture form the slurry evenly with lasting rheological behavior, obtain aluminum conductive electric slurry.
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| CN103204632A (en) * | 2012-01-14 | 2013-07-17 | 比亚迪股份有限公司 | Conductive glass powder and its preparation method, crystalline silicon solar battery aluminum conductive paste and preparation method |
| CN102760511A (en) * | 2012-05-28 | 2012-10-31 | 杭州正银电子材料有限公司 | Crystalline silicon solar cell BSF (back surface field) lead-free aluminum electroconductive slurry and preparation method thereof |
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Denomination of invention: Back-field passivated-aluminum conductive slurry for crystalline-silicon solar cell and preparation method Effective date of registration: 20181221 Granted publication date: 20160302 Pledgee: Hangzhou United Rural Commercial Bank, Limited by Share Ltd branch of science and technology Pledgor: Hangzhou Right Silver Electronic Material Material Co., Ltd. Registration number: 2018330000505 |
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