CN102324267A - High-photoelectric-conversion-efficiency crystalline silicon solar battery aluminum paste and preparation method thereof - Google Patents
High-photoelectric-conversion-efficiency crystalline silicon solar battery aluminum paste and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-photoelectric-conversion-efficiency crystalline silicon solar battery aluminum paste, which consists of the following raw materials by mass percent: 60-70 percent of aluminum powder, 20-35 percent of organic bond, 1-10 percent of aluminum-silicon alloy powder, 0.2-2 percent of glass powder and 0.1 to 1.5 percent of adjuvant, wherein the sum of the mass percent of the raw materials is 100 percent, the content of aluminum contained in the aluminum-silicon alloy powder is 8-15 percent and the average grain size of the aluminum-silicon alloy powder is small than 2mum. The invention additionally provides a preparation method for the crystalline silicon solar battery aluminum paste. After the paste is screen-printed, dried and sintered, an aluminum back surface field is formed on a silicon wafer. The adhesive force of the aluminum back surface field is high, the warping degree of cells is low, the photoelectric conversion efficiency is high, the cost is low and the aluminum paste is nontoxic.
Description
Technical field
The present invention relates to a kind of high electricity conversion crystal silicon solar energy battery aluminium paste and preparation method thereof.The solar cell aluminium paste is mainly used in and forms an aluminium back of the body BSF in the crystal silicon solar energy battery manufacturing, improves the efficient of solar cell, belongs to technical field of electronic materials.
Background technology
Along with the development of human history, people are more and more to the consumption of the energy.People recognize that traditional fossil energy has one day eventually can be exhausted, and traditional fossil energy pollution on the environment is serious day by day in the reality, and this makes people show special preference to the demand of clean energy resource.Solar energy comes into one's own as a kind of cleaning and inexhaustible, nexhaustible energy day by day, and the widely-used people of making of solar water heater are filled with unbounded confidence to the utilization of solar energy.The solar energy power generating industry obtains fast development under this background, in recent ten years, be that the average annual growth rate of photovoltaic industry of representative surpasses 30% with the crystal silicon solar energy battery, becomes one of main clean energy resource developing direction in the whole world.
In the photovoltaic industry; The effect of aluminium paste is to form back of the body electric field in the burning process altogether at battery; Be the BSF layer, just form one deck heavily doped region identical, can effectively improve the photoelectric conversion efficiency of solar cell with the matrix conduction type at the back side of solar cell.In the aluminium paste sintering process, when the temperature of aluminium silicon interface reached more than 577 ℃, aluminium and silicon can form the molten state alloy in certain proportion; When temperature reduces, the alusil alloy cooling, the ratio of silicon in alloy reduces gradually; From alloy, separate out, formed the heavily doped layer that one deck is mixed aluminium, i.e. p
+Layer has just formed p-p with p type silicon substrate
+Knot.At p-p
+Near interface, the p district forms hole accumulation layer, p
+The district forms depletion layer, points to p so formed in the space charge region by the p district
+The internal electric field in district, the electronics that can stop the p district is to p
+District's motion promptly forms a height knot.This is just tied and makes photoelectron can not overflow from the back side, be collected but be reflected back again, and this internal electric field can produce acceleration to photo-generated carrier, has increased the active diffusion length of charge carrier, has improved the short circuit current of battery.Along with the continuous attenuation of crystal silicon chip, the effect of aluminium back of the body field in crystal silicon solar energy battery is more remarkable.While p-p
+The photovoltage and the n at knot two ends
+The photovoltage stack at-p two ends makes the open circuit voltage of battery improve.
In addition, in the formation of the aluminium back of the body, because the stress that aluminium silicon atom lattice mismatch produces, beavy metal impurity in the crystalline silicon or room diffuse to the interface and are effectively absorbed by aluminium, thereby play the effect of aluminium gettering.The aluminium gettering can significantly improve open circuit voltage, fill factor, curve factor and the conversion efficiency of crystal silicon solar energy battery.
Tradition aluminium paste composition is generally organic bond, inorganic bond, aluminium powder and auxiliary agent.The quality of size performance is directly related with used aluminium powder characteristic such as purity, size and particle size distribution etc.The aluminium powder that present preparation aluminium paste is used can form one deck aluminium nitride ceramics layer all by the preparation of nitrogen atomization method on the surface of aluminium powder, has restricted the formation of BSF layer to a certain extent.Publication number is to have mentioned in the patent of CN101425545A, CN101651155A etc. adding the formation that III main group material (boron, gallium, indium, thallium) improves the BSF layer; But these materials or cost are very high; Reserves are less, or toxicity is very big, and imperfect additive.And except that boron, these additives all belong to the soft metal, and compactness and the adhesive force to aluminium back of the body field all has harmful effect to a certain extent.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency; A kind of crystal silicon solar energy battery aluminium paste and preparation method thereof is provided, on silicon wafer, forms aluminium back of the body field behind this slurry process silk screen printing, drying, the sintering, aluminium back of the body field adhesive force is high; Battery sheet angularity is low; Photoelectric conversion efficiency is high, and cost is lower, avirulence.
Technical scheme provided by the invention is: in the conventional aluminum slurry system, add the alusil alloy powder of certain proportion, certain grain size scope, when improving aluminium back of the body field, can effectively reduce the consumption of aluminium powder and glass dust.
The objective of the invention is to realize like this: a kind of high electricity conversion crystal silicon solar energy battery aluminium paste, said aluminium paste mainly is made up of the raw material of following mass percent:
Aluminium powder 60 ~ 75%
Organic bond 20 ~ 35%
Alusil alloy powder 1 ~ 10%
Glass dust 0.2 ~ 2%
Auxiliary agent 0.1 ~ 1.5%
The mass percent sum of each raw material is 100%.
Said aluminium powder is a ball aluminum powder, and average grain diameter is 4 ~ 8 μ m, and tap density is greater than 1.5g/cm
3, aluminium content is greater than 99.8%, and active aluminium content is greater than 98%.Particle diameter is too big, and the aluminium back of the body field that sintering forms is fine and close inadequately; Particle diameter is too little, and a back of the body sintering plays the aluminium bud easily, and periphery is prone to come off grey.Tap density is too little, also can cause a back of the body sintering fine and close inadequately.Impurity causes pollution too much easily, makes to carry on the back a deleterious.Active aluminium content is too low, just can not form enough thick back of the body electric field.
Said organic bond is made up of high molecular polymer, organic solvent and auxiliary agent, and wherein high molecular polymer is one or more in ethyl cellulose, phenolic resins, epoxy resin, the alkyd resins etc.Organic solvent is one or more in higher boiling point alcohols or the ester class, like terpinol, BC, phenmethylol, ethylene glycol phenyl ether, BC acetate, TMPD isobutyrate, ATBC etc.Auxiliary agent is one or more in oleic acid, castor oil acid, stearic acid, silicone oil, castor oil, pump oil, sapn, tween, diethyl phthalate, dibutyl phthalate, the dioctyl phthalate etc.More preferably, said organic bond by the proportioning of mass parts is: 3 ~ 8 parts of ethyl celluloses; 1 ~ 5 part in phenolic resins, 20 ~ 50 parts of terpinols, 30 ~ 60 parts of BC acetates; 20 ~ 40 parts of TMPD isobutyrates, 1 ~ 5 part of 0.5 ~ 2.5 part of sapn and pump oil.
Said alusil alloy powder has certain element to be formed, and the content of silicon in the alusil alloy powder is 8 ~ 15%, and the average grain diameter of alusil alloy powder is less than 2 μ m.Cross when low when silicone content, during alusil alloy fusion cooling, can not separate out for silica-based, do not have facilitation forming aluminium back of the body field; And when silicone content was too high, the speed of separating out silicon during alusil alloy fusion cooling was fast, and the silicon that richness is gathered can influence the conductivity of aluminium backing layer.When the particle diameter of alusil alloy powder is too big, in the Fast Sintering process, be difficult to complete fusion, can not give full play to the effect of alloyed powder.
Said glass dust is a kind of lead-free glass powder with low melting point, and this glass dust is B (boron)-Bi (bismuth)-Si (silicon)-Zn (zinc) system, and has added a certain amount of aluminium oxide; Zirconia; Vanadium oxide, molybdenum oxide, said glass dust mainly is made up of the raw material of following mass percent:
Boron oxide 10 ~ 30%
Bismuth oxide 50 ~ 80%
Silica 1 ~ 10%
Zinc oxide 1 ~ 10%
Aluminium oxide 0.5 ~ 5%
Zirconia 0.5 ~ 5%
Vanadium oxide 0.5 ~ 5%
Molybdenum oxide 0.5 ~ 5%
The mass percent sum of each raw material is 100%.
Said auxiliary agent is the antifoaming agent KS-66 of Japan XINYUE.
The preparation method of above-mentioned aluminium paste comprises following processing step:
1) preparation of organic bond
Component weighing in proportion that will be except that resin is heated to 80 ~ 100 ℃, while stir the resin that slowly adds ormal weight then, after resin dissolves fully, filters while hot, promptly obtains transparent organic bond.
2) preparation of glass dust
Metal oxide weighing in proportion with all components; Mix with three-dimensional mixer, 95 ~ 105 ℃ of dryings are 1 ~ 2 hour then, 1050 ~ 1150 ℃ of meltings in dry back 1 ~ 1.5 hour; Pour melted glass precursor solution in pure water shrend; Use the ball mill ball milling regular hour again, sieving obtains the glass dust that particle diameter is 0.5 ~ 2.5 μ m, glass dust dry for standby.
3) preparation of slurry
Take by weighing each component of aluminium paste in proportion and mix, stir, make slurry reach certain fineness 40 ~ 50 μ m with the high speed dispersion mixer; On three-roll grinder, grind then; Make slurry reach homogeneously dispersed state, slurry fineness < 20 μ m, viscosity 30000 ~ 45000mPas (25 ℃).
The invention has the beneficial effects as follows:
1) the alusil alloy powder of extra interpolation, its fusing point can partly play the effect of glass dust about 580 ℃, can significantly reduce the addition of glass dust.
2) the alusil alloy powder of extra interpolation; Fusion directly forms aluminium silicon eutectic in sintering process, has effectively increased the amount of aluminium silicon interface place formation aluminium silicon eutectic, and silicon is separated out the heavily doped layer thickness increase of formation in the cooling procedure; Strengthen a back of the body effect, improved the electrical property of battery sheet.
3) the alusil alloy powder of extra interpolation, the aluminium silicon congruent melting scale of construction of having replenished aluminium silicon interface place makes that the requirement to content of aluminium powder reduces in the slurry system; Can effectively reduce aluminium powder ratio in the aluminium paste; The cost that saves material, simultaneously, the result that the aluminium powder ratio reduces is that the aluminium paste solid content reduces; Can reduce the aluminium paste number to be printed of client's monolithic battery to a certain extent, reduce battery sheet manufactured materials cost.
Embodiment
Embodiment 1:
Aluminium powder: used aluminium powder average grain diameter is 5.3, and tap density is 1.57g/cm
3
Organic bond:
By 30 parts of mass parts terpinols, 40 parts of BC acetates, 20 parts of TMPD isobutyrates; 2.5 parts of 1 part of sapn and pump oil; Mix to add in the agitated reactor being heated to 80 ~ 100 ℃, stir the ethyl cellulose that adds 4.5 parts, 2 parts phenolic resins then; Filter dissolving back, is clarified, transparent organic bond.
Glass dust: by 12 parts of mass parts boron oxides, 65 parts of bismuth oxides, 8 parts of silica; 8 parts in zinc oxide, 3 parts in aluminium oxide, 2 parts of zirconias; 1 part of 1 part of vanadium oxide and molybdenum oxide mixed back 100 ℃ of dryings 1.5 hours, then 1100 ℃ of meltings 1.2 hours; With planetary ball mill ball milling 1 hour, cross behind 500 mesh sieves to such an extent that particle diameter be the glass dust of 1.8 μ m, dry for standby after the shrend.
Aluminium paste: get 71 parts of aluminium powders by mass parts, 25 parts of above-mentioned organic bonds, 3 parts in alusil alloy powder; 0.6 part in glass dust, 0.4 part of antifoaming agent (KS-66) stirs 30min with homogenizer (1000r/min); The slurry fineness reaches 40 ~ 50 μ m, grinds 25000 ~ 40000 mPas during 25 ℃ of control slurry viscosities with three-roll grinder; < 20 μ m process the high electricity conversion crystal silicon solar energy battery of the present invention aluminium paste to the slurry fineness.
The printed battery sheet is also tested correlated performance: 125 * 125mm (thickness 180 ± 20 μ m) monocrystalline silicon piece; With the above-mentioned aluminium paste of 250 order silk screen printings, average quantity used in unit volume blasted 0.91g, Li Shi 9235 positive silver are congratulated in the printing of dry back; Through oven dry, tunnel sintering furnace co-sintering (775 ℃ of peak temperatures; 6.1s more than 600 ℃) back test correlated performance: open circuit voltage (mean value) 632mv, short circuit current (mean value) 5.66A, the average light photoelectric transformation efficiency reaches 18.16%; The angularity of battery sheet is 1.00mm, and a back of the body EVA peels off pulling force>10N.
Embodiment 2:
Aluminium powder: used aluminium powder average grain diameter is 5.5, and tap density is 1.59g/cm
3
Organic bond: by 35 parts of mass parts terpinols, 35 parts of BC acetates, 20 parts of TMPD isobutyrates, 2 parts of 1.5 parts of sapns and pump oil,
Mix to add in the agitated reactor and being heated to 80 ~ 100 ℃, stir the ethyl cellulose that adds 3.5 parts then, 3 parts phenolic resins, filter the dissolving back, is clarified, transparent organic bond.
Glass dust: by 10 parts of mass parts boron oxides, 70 parts of bismuth oxides, 6 parts of silica; 6 parts in zinc oxide, 2 parts in aluminium oxide, 2 parts of zirconias; 3 parts of 1 part of vanadium oxide and molybdenum oxides mixed back 100 ℃ of dryings 1.5 hours, then 1100 ℃ of meltings 1.2 hours; With planetary ball mill ball milling 1 hour, cross behind 500 mesh sieves to such an extent that particle diameter be the glass dust of 1.7 μ m, dry for standby after the shrend.
Aluminium paste: get 68 parts of aluminium powders by mass parts, 26 parts of above-mentioned organic bonds, 5 parts in alusil alloy powder; 0.5 part of 0.5 part in glass dust and antifoaming agent (KS-66) stir 30min with homogenizer (1000r/min), and the slurry fineness reaches 40-50 μ m; Grind with three-roll grinder; 25000 ~ 40000 mPas during 25 ℃ of slurry viscosities of control, < 20 μ m process the high electricity conversion crystal silicon solar energy battery of the present invention aluminium paste to the slurry fineness.
The printed battery sheet is also tested correlated performance: 125 * 125mm (thickness 180 ± 20 μ m) monocrystalline silicon piece; With the above-mentioned aluminium paste of 250 order silk screen printings, average quantity used in unit volume blasted 0.88g, Li Shi 9235 positive silver are congratulated in the printing of dry back; Through oven dry, tunnel sintering furnace co-sintering (780 ℃ of peak temperatures; 5.6s more than 600 ℃) back test correlated performance: open circuit voltage (mean value) 633mv, short circuit current (mean value) 5.65A, the average light photoelectric transformation efficiency reaches 18.18%; The angularity of battery sheet is 1.05mm, and a back of the body EVA peels off pulling force>10N.
Claims (5)
1. one kind high electricity conversion crystal silicon solar energy battery aluminium paste, it is characterized in that: said aluminium paste is made up of the raw material of following mass percent:
Aluminium powder 60 ~ 75%
Organic bond 20 ~ 35%
Alusil alloy powder 1 ~ 10%
Glass dust 0.2 ~ 2%
Auxiliary agent 0.1 ~ 1.5%
The mass percent sum of each raw material is 100%,
Said alusil alloy powder, the content of silicon in the alusil alloy powder is 8 ~ 15%, the average grain diameter of alusil alloy powder is less than 2 μ m.
2. a kind of high electricity conversion crystal silicon solar energy battery aluminium paste according to claim 1, it is characterized in that: said aluminium powder is a ball aluminum powder, and its average grain diameter is 4 ~ 8 μ m, and tap density is greater than 1.5g/cm
3, aluminium content is greater than 99.8%, and active aluminium content is greater than 98%.
3. a kind of high electricity conversion crystal silicon solar energy battery aluminium paste according to claim 1 and 2 is characterized in that:
Said organic bond is made up of high molecular polymer, organic solvent and auxiliary agent; Wherein high molecular polymer is one or more in ethyl cellulose, phenolic resins, epoxy resin, the alkyd resins; Said organic solvent is one or more in terpinol, BC, phenmethylol, ethylene glycol phenyl ether, BC acetate, TMPD isobutyrate, the ATBC, and said auxiliary agent is one or more in oleic acid, castor oil acid, stearic acid, silicone oil, castor oil, pump oil, sapn, tween, diethyl phthalate, dibutyl phthalate, the dioctyl phthalate;
Said glass dust is made up of the raw material of following mass percent:
Boron oxide 10 ~ 30%
Bismuth oxide 50 ~ 80%
Silica 1 ~ 10%
Zinc oxide 1 ~ 10%
Aluminium oxide 0.5 ~ 5%
Zirconia 0.5 ~ 5%
Vanadium oxide 0.5 ~ 5%
Molybdenum oxide 0.5 ~ 5%
The mass percent sum of each raw material is 100%;
Said auxiliary agent is the antifoaming agent KS-66 of Japan XINYUE.
4. a kind of high electricity conversion crystal silicon solar energy battery aluminium paste according to claim 1 and 2; It is characterized in that: said organic bond by the proportioning of mass parts is: 3 ~ 8 parts of ethyl celluloses; 1 ~ 5 part in phenolic resins, 20 ~ 50 parts of terpinols, 30 ~ 60 parts of BC acetates; 20 ~ 40 parts of TMPD isobutyrates, 1 ~ 5 part of 0.5 ~ 2.5 part of sapn and pump oil.
5. the preparation method of one kind high according to claim 1 electricity conversion crystal silicon solar energy battery aluminium paste, it is characterized in that: said method comprises following processing step:
1) preparation of organic bond
Each component of organic bond weighing in proportion that will be except that resin is heated to 80 ~ 100 ℃, while stir the resin that slowly adds ormal weight then, after resin dissolves fully, filters while hot, promptly obtains transparent organic bond,
2) preparation of glass dust
Each raw material of glass dust weighing in proportion with all components mixes with three-dimensional mixer, and 95 ~ 105 ℃ of dryings are 1 ~ 2 hour then; 1050 ~ 1150 ℃ of meltings in dry back 1 ~ 1.5 hour; Pour melted glass precursor solution in pure water shrend, use the ball mill ball milling regular hour again, sieving obtains the glass dust that particle diameter is 0.5 ~ 2.5 μ m; The glass dust dry for standby
3) preparation of slurry
Take by weighing each component of aluminium paste in proportion and mix, stir, make slurry reach certain fineness 40 ~ 50 μ m with the high speed dispersion mixer; On three-roll grinder, grind then; Make slurry reach homogeneously dispersed state, slurry fineness < 20 μ m, 25 ℃ of viscosity 30000 ~ 45000mPas.
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