CN102314958A - Conductive aluminum paste used for crystalline-silicon solar-battery back electrode and preparation method thereof - Google Patents
Conductive aluminum paste used for crystalline-silicon solar-battery back electrode and preparation method thereof Download PDFInfo
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Abstract
A conductive aluminum paste used for a crystalline-silicon solar-battery back electrode and a preparation method thereof are disclosed. The conductive aluminum paste comprises, by weight, 65%-80% of an aluminum powder, 15%-30% of an organic carrier, 1%-5% of an inorganic glass powder, 0.1%-1% of an additive, 0.1%-5% of a coupling agent. The organic carrier is made of a polymer and an organic solvent, wherein the organic carrier comprises, by weight, 5%-20% of the polymer and 80%-95% of the organic solvent. Under the condition of not increasing production costs, the conductive aluminum paste can form a good back field effect with a silicon chip, photoelectric conversion efficiency of a cell can be effectively raised and beading stress of the cell after sintering can be effectively inhibited.
Description
Technical field
The present invention relates to a kind of rear electrode for crystal silicon solar battery with conduction aluminium paste and preparation method thereof.
Background technology
Along with the develop rapidly of heliotechnics, the production cost that reduces solar cell has become the main target of present solar cell industry research and development.Wherein, the thickness that reduces silica-based sheet material be reduce cost, one of the important means of economical with materials.But along with the reduction of silicon chip thickness, the battery sheet causes the flexibility of battery sheet to increase, and finally causes the fragment rate of the battery sheet in the battery pack process of assembling significantly to increase owing to receive the stress in the sintering process, causes the increase of production cost.
At present, the method that solves battery bending tablet degree mainly contains the shrinkage that reduces glass dust and the print thickness of attenuate battery back electrode.But; Adopt the lower glass dust of shrinkage; Because higher, flowability of its softening point and wettability are poor, its protective capability to aluminium powder is not enough, and existence can cause that aluminum back electrode and silicon chip poor adhesive force, aluminum back electrode sheet resistance are big, the defective of reduction battery efficiency; Adopt the print thickness of attenuate battery back electrode, its back of the body electric field (BSF) forms effect and is affected, the defective that existence can cause the contact resistance between the reduction of battery conductive performance, aluminium electrode film and silicon chip to increase, cause open circuit voltage and conversion efficiency to reduce.Therefore, need provide and can form good back of the body field effect, have high photoelectric conversion efficiency with silicon chip, the battery back electrode that can alleviate the bending stress of silicon chip again forms uses slurry.
Summary of the invention
The technical problem that the present invention will solve is: provide a kind of rear electrode for crystal silicon solar battery with the conduction aluminium paste; Under the prerequisite that does not increase production cost; It can form good back of the body field effect with silicon chip; Effectively improve the photoelectric conversion efficiency of battery sheet, can suppress the bending stress of battery sheet behind the sintering again well.
Another technical problem that the present invention will solve is: the preparation method of a kind of crystal silicon solar energy battery with back electrode conduction aluminium paste is provided, and it is more even that this method can make aluminium powder in slurry, disperse.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is:
A kind of rear electrode for crystal silicon solar battery is with the conduction aluminium paste, and the component of said conduction aluminium paste and mass percent thereof are: aluminium powder 65～80%; Organic carrier 15～30%; Unorganic glass powder 1～5%; Additive 0.1～1%; Coupling agent 0.1～5%; Said organic carrier is mixed by polymer and organic solvent, and wherein the mass percentage content of polymer is 5～20%, and the mass percent of organic solvent is 80～95%.
Said coupling agent is selected from any in silane coupler, titanate coupling agent, the aluminate coupling agent.
Said coupling agent is selected from any in gamma-aminopropyl-triethoxy-silane, γ-(2, the 3-glycidoxy) propyl trimethoxy silicane, γ-(methacryloxy) propyl trimethoxy silicane, the gamma-mercaptopropyltriethoxysilane.
The average grain diameter of said aluminum particle is 2～8 μ m.
Said polymer is a kind of in ethyl cellulose, acetic acid butyl cellulose, hydroxy ethyl cellulose, the phenolic resins or their mixture.
Said organic solvent is a kind of in diethylene glycol butyl ether, terpinol, BC acetate, the ATBC or their mixture.
A kind of rear electrode for crystal silicon solar battery is with the preparation method of conduction aluminium paste, and it may further comprise the steps:
A. the preliminary treatment of aluminium powder:
Coupling agent is joined in the organic solvent, join in the aluminium powder after mixing, stir, drying obtains pretreated aluminium powder;
B. the preparation of organic carrier:
Polymer and organic solvent mixed and be heated to polymer dissolve fully, obtain organic carrier;
C. unorganic glass powder and organic carrier are joined in the pretreated aluminium powder, mix back adding additive and stir, roll compacting, the rear electrode for crystal silicon solar battery that obtain below the fineness 20 μ m, viscosity is 25-35Pa.S is with the conduction aluminium paste.
Said organic solvent is any in methyl alcohol, ethanol, acetone, the ethyl acetate.
Compared with prior art, the present invention has following advantage:
1. after using coupling agent that aluminium powder is carried out preliminary treatment; Coupling agent is coated on the surface of aluminum particle equably; The gathering of alumina particles in the formula system and the rapid multiviscosisty of polymer so both can have been avoided; Can improve the wetability of polymer again, also can make aluminium powder and polymer realize firm bonding, aluminum particle is dispersed in the three-dimensional space net structure of organic carrier formation more uniformly and stably aluminium powder; The contact resistance of aluminium paste battery sheet behind sintering that this aluminium powder of usefulness makes is little, and conversion efficiency is high.
2. coupling agent is coated on the aluminum particle surface, has increased the non-oxidizability of aluminum particle, helps the raising of electrical property behind the aluminium paste sintering.
3. the silicon dioxide microparticle that silane coupler produces in the aluminium paste sintering process forms equally distributed superficial layer on aluminum particle, can significantly reduce intergranular cohesive force, improves the bending stress of battery sheet.
4. the aluminium paste that obtains according to the inventive method is through forming required back of the body field (BSF) effect of solar cell on silicon chip behind the sintering; And have conduct electricity very well, contact resistance is low, open circuit voltage and photoelectric conversion efficiency high, with the high advantage of adhesion strength of silicon chip, the aluminium electrode film smooth surface that forms behind the sintering, do not play ash, the no pill of aluminium.
Embodiment
Coupling agent among the present invention also is called a kind of " bridging agent ", and its end parent is inorganic, and other end parent is organic, between inorganic filler and organic resin, erects a bridge block.Inorganic filler is after with coupling agent treatment, and the surface reaches organic coating with the chemical b ` of the inorganic end of coupling agent parent, and when adding the organic resin blend, its intermiscibility and dispersiveness increase substantially.Utilized this effect of coupling agent among the present invention; After adding the silane coupler of certain content in the aluminium powder; Silane coupler evenly is coated on the surface of aluminum particle, can its hydrophilic surface be transformed into the organophilic solvent surface; Particle accumulation and the rapid multiviscosisty of polymer in the system both can have been avoided; Can improve the wetability of polymer again, also can make aluminium powder and polymer realize firm bonding, aluminum particle is dispersed in the three-dimensional space net structure of organic carrier formation more uniformly and stably through carbon functional group's silane coupler to aluminium powder.
Because the easy oxidation of aluminium powder, the inventor has also increased the non-oxidizability of aluminum particle through discovering that coupling agent is coated on the aluminum particle surface, helps the raising of electrical property behind the sintering.
In the present invention; The inventor is through discovering, in sintering process, silane coupler decomposes; Produce silicon dioxide microparticle; This finely disseminated silicon dioxide microparticle forms equally distributed superficial layer on aluminum particle, can significantly reduce intergranular cohesive force, improves the bending stress of silicon chip.Simultaneously; Coupling agent is in sintering process; Along with the volatilization gradually of organic solvent, between the aluminum particle of uniform and stable distribution and the particle, fully contact more easily between particle and the silicon chip, form conduction network chain and fine and close aluminium film; Improve its adhesive strength, reduce the contact resistance between aluminium electrode and the silicon chip.Therefore, add the contact resistance that an amount of coupling agent can reduce aluminium paste, improve the conversion efficiency of battery sheet, improved the flexibility of battery sheet simultaneously.Among the present invention, the addition of coupling agent is 0.1～5% (mass percent).If the addition of coupling agent less than 0.1%, then do not have to behind the even peptizaiton of aluminium powder and the sintering to the counter-bending effect of battery sheet, thereby to improve electrical property with improve crooked do not have significantly act on; If the addition of coupling agent surpasses at 5% o'clock, can make the surface of aluminum particle form thicker " coating layer ", hindered the formation of " conduction network chain " between the aluminum particle, contact resistance also increases thereupon.
Be fit to coupling agent among the present invention and can be selected from any in silane coupler, titanate coupling agent, the aluminate coupling agent; Preferred gamma-aminopropyl-triethoxy-silane (the trade name: KH-550), γ-(2, the 3-glycidoxy) propyl trimethoxy silicane (trade name: KH-560), γ-(methacryloxy) propyl trimethoxy silicane (trade name: HK-570), gamma-mercaptopropyltriethoxysilane (trade name: a kind of KH-580) of using.
Organic carrier is mixed by polymer and organic solvent, and wherein the 5-20% of organic carrier is that polymer, 80-95% are organic solvent (mass percent).
Polymer can adopt one or more in ethyl cellulose, acetic acid butyl cellulose, hydroxy ethyl cellulose, the phenolic resins; Said organic solvent can adopt one or more in diethylene glycol butyl ether, terpinol, BC acetate, the ATBC.
The main effect of organic carrier is a printing performance of regulating slurry, improves the film forming of electrode slurry.The addition of organic carrier is 15-30% (mass percent) among the present invention.If the content of organic carrier is less than 15%, then the slurry thixotropy reduces, and printing performance is influenced; If the content of organic carrier is greater than 30%, then slurry viscosity is low excessively, is unfavorable for the raising of conductivity.
The unorganic glass powder can be selected B for use
2O
3-SiO
2-Bi
2O
3System, B
2O
3-SiO
2-PbO system, Bi
2O
3-SiO
2A kind of and oxide addition in-the ZnO system constitutes, and affiliated oxide addition comprises Al
2O
3, ZrO
2, Sb
2O
3, V
2O
5, TiO
2In one or more.The softening point of glass dust is 400-600 ℃, and diameter is controlled at 1-10 μ m.The unorganic glass powder bonds together aluminium electrode film and silicon chip when high temperature sintering, and can promote the fusion of alumina particles, strengthens the mechanical strength and the surface property of aluminium electrode film.Among the present invention, the content of glass dust is 1-5% (mass percent).If the content of glass dust is less than 1%, the cohesive force of aluminium electrode film and silicon chip is low behind the sintering, and battery sheet surface the pill of aluminium occurs, plays ash, and the mechanical strength of aluminium electrode film reduces simultaneously; If content greater than 5%, forms one deck glaze on the silicon chip surface after the glass dust fusing easily, influence electric conductivity.
Said additive comprises one or more in anti-settling agent, levelling agent, antifoaming agent, wetting agent, the thixotropic agent.Main effect is storing performance and the printing performance that guarantees slurry.
The concrete manufacture method of above-mentioned slurry is following:
A. the preliminary treatment of aluminium powder:
Coupling agent is joined in the organic solvent, join in the aluminium powder after mixing, stir, drying obtains pretreated aluminium powder;
B. the preparation of organic carrier:
Polymer and organic solvent mixed and be heated to polymer dissolve fully, obtain organic carrier;
C. unorganic glass powder and organic carrier are joined in the preprocessed silver powder, mix back adding additive and stir, roll compacting, the rear electrode for crystal silicon solar battery that obtain below the fineness 20 μ m, viscosity is 25-35Pa.S is with the conduction aluminium paste.
Above-mentioned slurry is with 200-400 order web plate, and the mode through silk screen printing forms film on the solar cell silicon chip, and the slurry after the printing is through 160-270 ℃ of oven dry, and sintering forms a back of the body aluminium electrode under 650-950 ℃ high temperature then.
Below in conjunction with specific embodiment the present invention is described further.
Embodiment 1
1), the preliminary treatment of aluminium powder:
Take by weighing 0.1g silane coupler KH570, join in the 100ml absolute ethyl alcohol, after mixing, mixed liquor is joined in the 65g aluminium powder dispersed with stirring 20 minutes; The dispersion liquid of aluminium powder is put into 80 ℃ dry 3 hours of vacuum drying chamber, obtain pretreated aluminium powder.
2), the preparation of organic carrier:
Take by weighing 3g ethyl cellulose, 2g cellaburate, add 10g terpinol, 5g ATBC, 10g diethylene glycol butyl ether, the two mixing also is heated to 60 ℃, dissolves fully up to polymer, forms transparent thick liquid, obtains said organic carrier.
3), glass dust C
Adopt B
2O
3-SiO
2-Bi
2O
3System glass dust, average fineness 2.5 μ m, 500 ℃ of softening points.
Organic carrier, the glass dust 5g of preparation are joined in the above-mentioned pretreated aluminium powder that obtains; After mixing; Adding the high wetting agent D655 of 0.1g enlightening stirs in advance; Grind with three-roll grinder then, roll compacting, the rear electrode for crystal silicon solar battery that obtains fineness 20 μ m, viscosity 25Pa.S is with the conduction aluminium paste.
Embodiment 2
1), the preliminary treatment of aluminium powder
Take by weighing 5g silane coupler KH550, join in the 150ml methyl alcohol, mix, mixed liquor is joined in the 80g aluminium powder, dispersed with stirring 20 minutes; The dispersion liquid of aluminium powder is put into 80 ℃ dry 4 hours of vacuum drying chamber, obtain pretreated aluminium powder.
2), the preparation of organic carrier
Take by weighing 0.5g ethyl cellulose, 0.5g cellaburate, add 10g terpinol, 5g diethylene glycol butyl ether, the two mixing also is heated to 80 ℃, dissolves fully up to polymer, forms transparent thick liquid, obtains said organic carrier.
3), glass dust
Adopt B
2O
3-SiO
2-Bi
2O
3System glass dust, average fineness 2.5 μ m, 500 ℃ of softening points.
Organic carrier, the glass dust 1g of above-mentioned preparation are joined in the above-mentioned pretreated aluminium powder; Mixing the back high wetting agent D655 of adding 1g enlightening stirs in advance; Then with grinding on the three-roll grinder; Roll compacting, the rear electrode for crystal silicon solar battery that obtains fineness 20 μ m, viscosity 30Pa.S is with the conduction aluminium paste.
Embodiment 3
1), the preliminary treatment of aluminium powder
Take by weighing 3g silane coupler KH560, join in 120ml 95% ethanol, after mixing, mixed liquor is joined in the 70g aluminium powder dispersed with stirring 20 minutes; The dispersion liquid of aluminium powder is put into 80 ℃ dry 3 hours of vacuum drying chamber, obtain pretreated aluminium powder.
2), the preparation of organic carrier
Take by weighing 3g ethyl cellulose, 0.5g phenolic resins, add 15g BC acetate, 5g ATBC, the two mixing also is heated to 90 ℃, dissolves fully up to polymer, forms transparent thick liquid, obtains said organic carrier.
3), glass dust
Adopt B
2O
3-SiO
2-PbO system glass dust, average fineness 3.9 μ m, 450 ℃ of softening points.
The above-mentioned organic carrier that obtains, glass dust 3g are joined in the above-mentioned pretreated aluminium powder; Mixing back adding 0.5g castor oil thixotropic agent stirs in advance; Then with grinding on the three-roll grinder; Roll compacting obtains fineness 20 μ m, and the rear electrode for crystal silicon solar battery of viscosity 28Pa.S is with the conduction aluminium paste.
Embodiment 4
1), the preliminary treatment of aluminium powder
Take by weighing 3g silane coupler KH560, join in the 120ml ethyl acetate, after mixing, mixed liquor is joined in the 70g aluminium powder dispersed with stirring 20 minutes; The dispersion liquid of aluminium powder is put into 80 ℃ dry 3 hours of vacuum drying chamber, obtain pretreated aluminium powder.
2), the preparation of organic carrier
Take by weighing 2g ethyl cellulose, 0.5g cellaburate, add 15g BC acetate, 5g terpinol, the two mixing also is heated to 70 ℃, dissolves fully up to polymer, forms transparent thick liquid, obtains said organic carrier.
3), glass dust
Adopt B
2O
3-SiO
2-PbO system glass dust, average fineness 3.9 μ m, 450 ℃ of softening points.
The above-mentioned organic carrier that obtains, glass dust 4g are joined in the above-mentioned pretreated aluminium powder; Mixing back adding 0.5g levelling agent BYK-306 stirs in advance; Then with grinding on the three-roll grinder; Roll compacting, the rear electrode for crystal silicon solar battery that obtains fineness 20 μ m, viscosity 28Pa.S is with the conduction aluminium paste.
Embodiment 5
1), the preliminary treatment of aluminium powder
Take by weighing 2g silane coupler KH580, join in the 120ml acetone, after mixing, mixed liquor is joined in the 75g aluminium powder dispersed with stirring 20 minutes; The dispersion liquid of aluminium powder is put into 80 ℃ dry 3 hours of vacuum drying chamber, obtain pretreated aluminium powder.
2), organic carrier, glass dust are with embodiment 3
Organic carrier 20g, glass dust 3g are joined in the above-mentioned pretreated aluminium powder; Mixing back adding 0.5g castor oil thixotropic agent stirs in advance; Then with grinding on the three-roll grinder; Roll compacting, the rear electrode for crystal silicon solar battery that obtains fineness 20 μ m, viscosity 28Pa.S is with the conduction aluminium paste.
Comparative example 1
Take by weighing 70g aluminium powder, 3g silane coupler KH560, aluminium powder is not anticipated, and silane coupler directly adds in the slurry, and all the other each paste compositions and preparation method obtain solar energy back of the body electric field and use aluminium paste with embodiment 3.
Comparative example 2
Take by weighing aluminium powder 70g, do not add silane coupler, all the other each paste compositions and preparation method obtain solar energy back of the body electric field and use aluminium paste with embodiment 3.
The aluminium paste that the foregoing description 1～5 and Comparative Examples are obtained is applied to following prescription:
With above-mentioned gained slurry through silk screen printing on the monocrystalline silicon substrate (about 180 microns of thickness) of 125*125mm two sides making herbs into wool, form electrode film, print thickness is every and uses slurry 0.7g, advances 200 ℃ of oven dry of continuous tunnel furnace.Change another side printing front side silver paste then, oven dry back sintering, 890 ℃ of peak temperatures, the back of coming out of the stove is with silicon solar cell efficiency test measurement device electrical property, substrate flexibility.Each item performance mean value of measuring is following:
| ? | Isc（A） | Voc(V) | FF | Conversion efficiency (%) | Flexibility |
| Embodiment 1 | 5.30 | 0.608 | 0.74 | 16.40 | 2.0mm |
| Embodiment 2 | 5.42 | 0.612 | 0.75 | 16.68 | 1.0mm |
| Embodiment 3 | 5.45 | 0.613 | 0.76 | 16.79 | 0.8mm |
| Embodiment 4 | 5.41 | 0.613 | 0.75 | 16.65 | 0.8mm |
| Embodiment 5 | 5.43 | 0.612 | 0.74 | 16.70 | 1.0mm |
| Comparative example 1 | 5.35 | 0.610 | 0.74 | 16.60 | 1.2mm |
| Comparative example 2 | 5.20 | 0.606 | 0.75 | 16.23 | 2.2mm |
Annotate: Isc is a short circuit current;
Voc is an open circuit voltage;
FF is a fill factor, curve factor.
Claims (8)
1. a rear electrode for crystal silicon solar battery is characterized in that the component of said conduction aluminium paste and mass percent thereof are: aluminium powder 65～80% with the conduction aluminium paste; Organic carrier 15～30%; Unorganic glass powder 1～5%; Additive 0.1～1%; Coupling agent 0.1～5%; Said organic carrier is mixed by polymer and organic solvent, and wherein the mass percentage content of polymer is 5～20%, and the mass percent of organic solvent is 80～95%.
2. according to the said conduction aluminium paste of claim 1, it is characterized in that said coupling agent is selected from any in silane coupler, titanate coupling agent or the aluminate coupling agent.
3. according to the said conduction aluminium paste of claim 2; It is characterized in that; Said coupling agent is selected from any in gamma-aminopropyl-triethoxy-silane, γ-(2, the 3-glycidoxy) propyl trimethoxy silicane, γ-(methacryloxy) propyl trimethoxy silicane or the gamma-mercaptopropyltriethoxysilane.
4. according to the said conduction aluminium paste of claim 3, it is characterized in that the particle diameter of said aluminum particle is 2～8 μ m.
5. according to the said conduction aluminium paste of claim 4, it is characterized in that said polymer is a kind of in ethyl cellulose, acetic acid butyl cellulose, hydroxy ethyl cellulose or the phenolic resins or their mixture.
6. according to the said conduction aluminium paste of claim 5, it is characterized in that said organic solvent is a kind of in diethylene glycol butyl ether, terpinol, BC acetate or the ATBC or their mixture.
7. one kind prepares the method for using the conduction aluminium paste like claim 1,2,3,4,5 or 6 said rear electrode for crystal silicon solar battery, it is characterized in that it carries out according to the following steps:
A. the preliminary treatment of aluminium powder:
Coupling agent is joined in the organic solvent, join in the aluminium powder after mixing, stir, drying obtains pretreated aluminium powder;
B. the preparation of organic carrier:
Polymer and organic solvent mixed and be heated to polymer dissolve fully, obtain organic carrier;
C. unorganic glass powder and organic carrier are joined in the preprocessed silver powder, mix back adding additive and stir, roll compacting, the rear electrode for crystal silicon solar battery that obtain below the fineness 20 μ m, viscosity is 25-35Pa.S is with the conduction aluminium paste.
8. according to the said preparation method of claim 7, it is characterized in that said organic solvent is any in methyl alcohol, ethanol, acetone or the ethyl acetate.
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| CN103354940B (en) * | 2010-12-17 | 2016-05-04 | 太阳化学公司 | Composition based on aluminium and the solar cell that comprises the composition based on aluminium |
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Application publication date: 20120111 |