CN104575685A - Crystal silicon solar cell high adhesive force back surface field aluminum electrocondution slurry and preparation method - Google Patents
Crystal silicon solar cell high adhesive force back surface field aluminum electrocondution slurry and preparation method Download PDFInfo
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- CN104575685A CN104575685A CN201510015499.8A CN201510015499A CN104575685A CN 104575685 A CN104575685 A CN 104575685A CN 201510015499 A CN201510015499 A CN 201510015499A CN 104575685 A CN104575685 A CN 104575685A
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Abstract
The invention discloses crystal silicon solar cell high adhesive force back surface field aluminum electrocondution slurry which comprises 68%-80% of aluminite powder, 1%-6% of glass powder, 16%-25% of organic bond and 1%-3% of auxiliaries. The auxiliaries are composed of 60% of wetting dispersant and 40% of diffusion pump oil. The aluminum electrocondution slurry is printed on the back surface of a crystal silicon solar cell piece. Aluminium-silicon alloy reaction is performed on aluminum and substrate silicon through infrared quick calcining technology. A preparation method for the aluminum electrocondution slurry comprises the following steps that the aluminite powder, the glass powder, the organic bond and the auxiliaries are put in a vacuum mixer to be mixed, and dispersed by a three-high mill to obtain aluminum electrocondution slurry with less than or equal to 15Mum of precision and 20-40 Pa.s viscosity. The aluminum electrocondution slurry is good in property, and suitable for the use of a crystal silicon solar cell back surface field. A calcined aluminum film and a silicon substrate have good adhesive force and water resistence, aluminium pills and aluminium blisters do not exist, the calcined cell piece is small in bending, and the conversion efficiency is higher.
Description
Technical field
The invention belongs to solar cell field of new, particularly a kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste 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.
Aluminum conductive electric slurry belongs to one of electronic information material, is also the main auxiliary material making solar cell simultaneously.In current crystal silicon solar batteries manufacture craft, aluminum conductive electric slurry is almost printed on the whole shady face of battery, and due to metallic aluminium, (coefficient of expansion is 232 × 10
-7/ DEG C, 20 ~ 300 DEG C) (coefficient of expansion is 26 × 10 with silicon
-7/ DEG C, 20 ~ 300 DEG C) the difference of thermal coefficient of expansion, causing aluminum conductive electric slurry when sintering, in silicon chip, producing stress, cause silicon chip to bend, directly affects the rate of finished products of solar cell and follow-up component process.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste, it is unleaded, without cadmium, without thallium, aluminum membranous layer after burning till and silicon substrate have adhesive force well, the cell piece utilizing it to prepare without aluminium pill, aluminium blister, bending little, EVA pulling force is strong, transformation efficiency is high.
Present invention also offers a kind of preparation method of described crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste.
The technical scheme that technical solution problem of the present invention adopts is: a kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste, and described aluminum conductive electric slurry is made primarily of following raw material by mass percentage: aluminium powder 68 ~ 80%, glass dust 1 ~ 6%, organic bond 16 ~ 25% and auxiliary agent 1 ~ 3%; The composition of described auxiliary agent comprises the wetting dispersing agent of 60% and the diffusion pump oil of 40% by mass percentage; Fineness≤15 μm of described aluminum conductive electric slurry, viscosity is 20 ~ 40Pas.
As preferably, the purity of described aluminium powder is greater than 99.9%, and the average laser particle diameter of described aluminium powder is 1.0 ~ 10 μm, and the surface of described aluminium powder is covered with pellumina, described pellumina is the ball aluminum powder that atomization is produced, and the thickness of described pellumina is 2.0 ~ 10.0nm.
Further preferably, the average laser particle diameter of described aluminium powder is 6.0 ~ 8.0 μm, and apparent density is 0.60 ~ 0.85g/cc, and specific area is 0.70 ~ 1.00m
2/ g.Generally, the aluminium powder purity selected can introduce impurity at the cell piece back side lower than 99.9%, increases Carrier recombination speed, thus reduces 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 but the thickness of oxide layer more than 10nm, in slurry sintering process, obstacle can be caused to the formation of silicon-aluminum, hinder the formation of P+ layer.
As preferably, the composition of described glass dust is as follows by mass percentage: SiO
21 ~ 10%, ZnO 10 ~ 30%, B
2o
310 ~ 40%, Bi
2o
330 ~ 50%, Al
2o
35 ~ 10% and 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
3glass softening point and the rear silicon warp degree of slurry sintering can be controlled, reduce glass expansion coefficient, after slurry is sintered, reach suitable angularity.V
2o
5be used for controlling the mobility of glass, make there is suitable flow regime in slurry sintering.B
2o
3play the effect of flux, can reduce the melt temperature of glass, and at high temperature reduce glass viscosity, 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.
As preferably, the composition of described organic bond is as follows by mass percentage: 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% and butyl carbitol 20 ~ 40%.Ethyl cellulose is the main component of adhesive; Rosin can prevent 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, thus reaches desirable printing effect.BS can increase lubrification and the dispersiveness of slurry, reaches better printing effect, and after phenolic resins or novolac epoxy resin can make oven dry, aluminum membranous layer is finer and close, makes it have better adhesive force.
Described aluminum conductive electric slurry is printed in the back side of crystal silicon solar batteries sheet, through infrared fast-firing technique (silicon chip surface true peak temperature 780 ~ 810 DEG C, 1 ~ 2 second), aluminium and the reaction of matrix silicon generation alusil alloy, realize ohmic contact thus 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, ensure that the reliability of cell piece.
A preparation method for described crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry, described preparation method comprises the preparation of inorganic bond phase glass dust, the preparation of organic bond; According to described pulp furnish, aluminium powder, glass dust and organic bond, auxiliary agent are put into de-airing mixer and stirred, then through three-high mill dispersion, controls 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.Above-mentioned each raw material stirs in de-airing mixer, and object promotes that organic carrier is to the infiltration of powder, makes powder fully disperse in the carrier simultaneously, reduces the difficulty that powder disperses on three-roll grinder.The reaction of scraper plate fineness be the aggregation extent of particle in slurry, control, below 15 μm, slurry fully to be disperseed, if granularity is greater than 15 μm, just to there will be uniformity inadequate, the phenomenon of network blocking during printing.Viscosity controls to contribute to obtaining good printing effect at 20 ~ 40Pas, and viscosity is higher than 40Pas, and the printing weight of slurry is excessive, slurry haftplatte impact printing; Viscosity is too low lower than the viscosity of 20Pas slurry, and printing weight is partially light, spillage, can affect the open circuit voltage of battery.
As preferably, the preparation method of described glass dust is as follows: the composition of glass dust is as follows by mass percentage: SiO
21 ~ 10%, ZnO 10 ~ 30%, B
2o
310 ~ 40%, Bi
2o
330 ~ 50%, Al
2o
35 ~ 10% and V
2o
51 ~ 7%.Weighed by mass percentage by above-mentioned oxide, Homogeneous phase mixing, in crucible, is founded in Muffle furnace, is warming up to 600 DEG C, is incubated 0.5 hour, continues to be warming up to 1200 DEG C, melting 1 ~ 2 hour; After the glass shrend of uniform melt, be added in polyurethane tank, using pure water as medium, 6mm zirconia ball is that ball milling ball carries out ball milling; Wherein zirconia ball: glass: the mass ratio of pure water is 3:1:1; Loading is 1/3 ~ 2/3 of ball grinder cumulative volume, and Ball-milling Time is 24 hours, and tank speed is 100 ~ 150/ points, obtains the unorganic glass powder of average grain diameter≤10.0 μm.
As preferably, the preparation method of described organic bond is as follows: the composition of organic bond is as follows by mass percentage: 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% and butyl carbitol 20 ~ 40%.Above-mentioned component is weighed up by mass percentage and puts into container, mix and be heated to 80 DEG C ~ 160 DEG C, add solid ethyl cellulose and rosin powder under stirring, continue to be stirred to pressed powder and dissolve completely, the transparent uniform solution of formation is organic bond.
The invention has the beneficial effects as follows: compared with prior art, the present invention, by the optimization to electrocondution slurry component and preparation technology, provides a kind of function admirable, and is more suitable for the passivation aluminum conductive electric slurry of crystal silicon solar batteries back surface field use.Aluminum membranous layer after burning till and silicon substrate have adhesive force and resistance to water well, and without aluminium pill, aluminium blister, the cell piece burnt till bends little, and transformation efficiency is higher.Be embodied as following some:
(1) glass dust is the inorganic bond phase of aluminum conductive electric slurry, glass within the scope of optimized proportion can make aluminium fully melt in sintering process, infiltrates silicon face, makes aluminium back surface field uniform and stable, thus effectively reduce silicon chip surface recombination rate, make back surface field firm adhesion after sintering simultaneously;
(2) aluminium powder is the critical function phase of aluminum conductive electric slurry, and the present invention uses spherical atomizing aluminium powder to meet requirement on electric performance, except can obtaining desirable back surface field effect, also there is substrate deformation little, do not play aluminium pill, aluminium blister, the advantages such as back surface field is uniform and smooth, and outward appearance is good;
(3) combination of different solvents in organic bond, aluminium powder oxidation degree in drying course is reduced, and aluminum conductive electric slurry and base material invade profit well, and slowly, printing performance is good for the rate of settling;
(4) auxiliary agent can suppress aluminium powder premature oxidation, and make aluminum membranous layer smooth, smooth, compactness is better.
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 ~ 5:
A kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste, described aluminum conductive electric slurry is mixed (by mass percentage) by raw material as shown in table 1 below.
In table 1. embodiment 1 ~ 5, the composition of aluminum conductive electric slurry is detailed
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Aluminium powder | 68 | 75 | 71 | 80 | 78 |
| Glass dust | 6 | 4 | 3 | 1 | 2 |
| Organic bond | 25 | 19 | 24.5 | 16 | 17.5 |
| Auxiliary agent | 1 | 2 | 2.5 | 3 | 2.5 |
The preparation method of described crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste is as follows: raw material aluminium powder, silicon aluminium alloy powder, glass dust and organic bond are put into de-airing mixer by the proportioning in upper 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.
In the preparation method of above-mentioned electrocondution slurry; 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, the average grain diameter 6.0 ~ 8.0 μm (laser particle) of aluminium powder; apparent density is 0.60 ~ 0.85g/cc, and specific area is 0.70 ~ 1.00m
2/ g.
In the preparation method of above-mentioned electrocondution slurry, glass dust is crown glass, and the proportioning of its inorganic constituents and each component is in table 2.Raw material is weighed by the proportioning in table 2, after Homogeneous phase mixing, puts into porcelain crucible, 1200 DEG C of meltings 1 hour in Muffle furnace; Add in polyurethane tank by after the glass shrend of uniform melt, using pure water as medium, 6mm zirconia ball is ball milling ball, wherein zirconia ball: glass: the mass ratio of pure water is 3:1:1; Loading is 1/3 ~ 2/3 of ball grinder cumulative volume, and Ball-milling Time is 24 hours, and tank speed is 100 ~ 150/ points, and obtain the unorganic glass powder of average grain diameter≤10.0 μm, this glass dust is as the inorganic bond of aluminum conductive electric slurry.
In table 2. embodiment 1 ~ 5, the composition of glass dust is detailed
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| SiO 2 | 10 | 5 | 1 | 6 | 2 |
| ZnO | 22 | 18 | 30 | 20 | 13 |
| B 2O 3 | 25 | 15 | 10 | 35 | 40 |
| Bi 2O 3 | 33 | 47 | 48 | 30 | 32 |
| Al 2O 3 | 5 | 8 | 10 | 6 | 9 |
| V 2O 5 | 5 | 7 | 1 | 3 | 4 |
In the preparation method of above-mentioned electrocondution slurry, organic bond is by as the component of 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 80 DEG C ~ 160 DEG C, add solid ethyl cellulose and rosin powder under stirring, stir 1 ~ 2 hour, now pressed powder dissolves completely, and form completely transparent homogeneous solution, as the organic bond of aluminum conductive electric slurry.
In table 3. embodiment 1 ~ 5, the composition of organic bond is detailed
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Ethyl cellulose | 5.5 | 5 | 1 | 8 | 6 |
| Phenolic resins | 6 | 2 | 10 | 9 | 5 |
| Rosin | 1.5 | 1.2 | 0.8 | 0.5 | 2 |
| Terpinol | 45 | 50 | 40 | 20.5 | 27 |
| Phenmethylol | 11 | 11.8 | 10 | 15 | 30 |
| BS | 9 | 5 | 14.2 | 20 | 10 |
| Butyl carbitol | 22 | 25 | 24 | 27 | 20 |
The aluminum conductive electric slurry performance that embodiment 1 ~ 5 obtains in table 4, and compares with the use result of conventional aluminium paste.
The performance test results of table 4. embodiment 1 ~ 5 aluminum conductive electric slurry and conventional aluminium paste
Viscosity test condition: VT-04E 60rpm 2#spindle 25 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 ~ 5 embodiment data result can meet existing market requirement, wherein the highest with embodiment 1 data.
Embodiment 1 ~ 5 all has printing capability relatively preferably, and viscosity controls at about 30Pas; After 780 DEG C of sintering, aluminium lamination smooth surface is without blister, and adhesive force reaches more than 25N, and warpage is little.
The back surface field passivation aluminum conductive electric slurry of the present embodiment 1 ~ 5 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 rise aluminium pill, aluminium blister, water-tolerant, do not affect assembly production and ensure that the reliability of cell piece.
Above-described embodiment is one or more preferably schemes of the present invention, 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 (9)
1. a crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste, is characterized in that: the component of described aluminum conductive electric slurry comprises aluminium powder, inorganic bond phase, organic bond and auxiliary agent, and described inorganic bond is glass dust mutually; The content of each component of described aluminum conductive electric slurry is by percentage to the quality: aluminium powder 68 ~ 80%, glass dust 1 ~ 6%, organic bond 16 ~ 25% and auxiliary agent 1 ~ 3%; The composition of described auxiliary agent comprises the wetting dispersing agent of 60% and the diffusion pump oil of 40% by mass percentage; Fineness≤15 μm of described aluminum conductive electric slurry, viscosity is 20 ~ 40Pas.
2. a kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste according to claim 1, it is characterized in that: the purity of described aluminium powder is greater than 99.9%, the average laser particle diameter of described aluminium powder is 1.0 ~ 10 μm, the surface of described aluminium powder is covered with pellumina, described pellumina is the ball aluminum powder that atomization is produced, and the thickness of described pellumina is 2.0 ~ 10.0nm.
3. a kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste according to claim 2, is characterized in that: the average laser particle diameter of described aluminium powder is 6.0 ~ 8.0 μm, and apparent density is 0.60 ~ 0.85g/cc, and specific area is 0.70 ~ 1.00m
2/ g.
4. a kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste according to claim 1, is characterized in that: the composition of described glass dust is as follows by mass percentage: SiO
21 ~ 10%, ZnO 10 ~ 30%, B
2o
310 ~ 40%, Bi
2o
330 ~ 50%, Al
2o
35 ~ 10% and V
2o
51 ~ 7%.
5. a kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste according to claim 1, is characterized in that: the composition of described organic bond is as follows by mass percentage: 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% and butyl carbitol 20 ~ 40%.
6. a kind of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste as claimed in any of claims 1 to 5, it is characterized in that: described aluminum conductive electric slurry is printed in the back side of crystal silicon solar batteries sheet, through infrared fast-firing technique, aluminium and the reaction of matrix silicon generation alusil alloy, realize ohmic contact thus form back surface field.
7. the preparation method of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste as claimed in any of claims 1 to 5, is characterized in that: described preparation method comprises the preparation of inorganic bond phase glass dust, the preparation of organic bond; According to described pulp furnish, aluminium powder, glass dust and organic bond, auxiliary agent are put into de-airing mixer and stirred, then through three-high mill dispersion, controls 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.
8. the preparation method of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste according to claim 7, it is characterized in that: the preparation method of described glass dust is as follows: mixed in proportion by oxide, put into crucible, found in Muffle furnace, be warming up to 600 DEG C, be incubated 0.5 hour, continue to be warming up to 1200 DEG C, melting 2 hours, by the glass shrend of fusing, and makes glass dust average grain diameter≤10 μm with ball milling.
9. the preparation method of crystal silicon solar batteries high adhesion force aluminum back-surface-field conductive paste according to claim 7, it is characterized in that: 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 puts into container, mix and be heated to 80 DEG C ~ 160 DEG C, solid ethyl cellulose and rosin powder is added under stirring, continue to be stirred to pressed powder to dissolve completely, the transparent uniform solution of formation is organic bond.
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| CN107331436A (en) * | 2017-07-05 | 2017-11-07 | 四川银河星源科技有限公司 | Conducting aluminum paste for carrying on the back passivation solar cell and preparation method thereof |
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| CN110689991A (en) * | 2018-07-04 | 2020-01-14 | 白金科技股份有限公司 | Conductive paste |
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Application publication date: 20150429 |