CN102324266A - Glass-powder-free crystalline silicon solar battery aluminum paste and preparation method thereof - Google Patents
Glass-powder-free crystalline silicon solar battery aluminum paste and preparation method thereof Download PDFInfo
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- CN102324266A CN102324266A CN 201110237170 CN201110237170A CN102324266A CN 102324266 A CN102324266 A CN 102324266A CN 201110237170 CN201110237170 CN 201110237170 CN 201110237170 A CN201110237170 A CN 201110237170A CN 102324266 A CN102324266 A CN 102324266A
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Abstract
The invention relates to a glass-powder-free crystalline silicon solar battery aluminum paste and a preparation method thereof. The aluminum paste consists of the following raw materials by mass portions: 70-80 portions of aluminum powder, 18-28 portions of organic bond, 0.5-1.5 portions of adhesive force additive and 0.5-1.5 portions of adjuvant, wherein the adhesive force additive is zinc decanoate, zinc naphthenate, zinc citrate or zirconium citrate. After the aluminum paste is screen-printed and dried, the aluminum paste can be sintered within a wider temperature range, a back surface field can be in good ohmic contact with a silicon wafer, the adhesive force is good, the conversion efficiency of cells is high and the warping degree of the cells is reduced.
Description
Technical field
The present invention relates to a kind of crystal silicon solar energy battery aluminum conductive electric slurry and preparation method thereof.
Background technology
Along with the development of human history, people are also more and more to demands for energy.Yet along with deepening continuously of traditional fossil energy exploitation, these energy have one day eventually can be exhausted.In addition, traditional fossil energy pollution on the environment is serious day by day, and the whole world is experiencing a series of disastrous effects that the greenhouse gas effect is brought, and this makes people show special preference to the demand of clean energy resource.The solar energy power generating industry obtains fast development under this background, over past ten years, be that the average annual growth rate of photovoltaic industry of representative surpasses 30 parts with the crystal silicon solar energy battery, becomes one of main clean energy resource developing direction in the whole world.
Aluminium paste is to make one of important former material of crystal silicon solar energy battery, has aluminium gettering and heavy doping double action, can significantly improve the electricity conversion of battery.In order to reduce the production cost of battery sheet, the thickness of crystal silicon chip constantly reduces.On the one hand when the thickness of minority carrierdiffusion length and silicon chip during quite or above the thickness of silicon chip, the back of the body electric field of sintering aluminium paste formation is just particularly evident to the influence of characteristic of solar cell; On the other hand, the continuous reduction of crystal silicon chip thickness will make the angularity of battery sheet increase gradually.Therefore, form effectively back of the body electric field, and the angularity of reduction battery sheet becomes the inevitable direction of aluminium paste development.
Traditional crystal silicon solar energy battery aluminium paste is made up of organic bond, inorganic bond glass dust, aluminium powder and other auxiliary agent.Organic bond plays a part wetting dispersion as the carrier of slurry to aluminium powder and glass dust, and the function of slurry printing film forming is provided.Auxiliary agent and organic bond are used, and regulate the rheological property of slurry, provide slurry better technological operation performance.Aluminium powder is as main function phase, when high temperature sintering and silicon can form eutectic, form the effective aluminium back of the body, simultaneously, the aluminium backing layer itself has excellent conducting performance, current delivery to back electrode.Glass dust melts in sintering process as high-temperature agglomerant, makes the aluminium powder sintering form the conducting film of an even compact, and makes the conducting film of formation and silicon chip form good adhering to.In Japan Patent JP2000090734, JP2001202822, JP2004134775, JP2005317898, JP2006278071, JP2007019069, JP2007115738, all mentioned one type of leaded low-melting glass material; But because lead has certain toxicity; Can cause very big pollution to environment; And be one of material of the RoHs of European Union explicit order restriction, therefore, all not leaded or lead tolerance of the used glass dust of existing market aluminium paste meets the RoHs standard.All narrate one type of crown glass system among China aluminium paste patent CN1877864A, CN1901234A, CN101425545A and the CN101582462A, met the environmental protection standard.But glass dust mainly is through high melt by the number of metal oxide; And process is broken, grinding forms, and its system and course of reaction are very complicated, and quality is difficult to be effectively controlled; Difference between batch makes that a back of the body pulling force is fluctuated, and a back of the body compactness also is affected; And; Glass dust belongs to inorganic insulating material; The glass-film that fusion forms in sintering process also has certain influence to the resistivity of aluminium backing layer; Must be controlled at that sintering just can reach effect preferably in the less temperature range, this makes the sintering window of aluminium paste narrow down greatly, the matching variation of burning altogether with positive silver.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency; A kind of no glass dust crystal silicon solar energy battery aluminium paste and preparation method thereof is provided; After this slurry process silk screen printing, the drying, can in wider temperature range, carry out sintering, back of the body field forms good Ohmic contact with silicon chip; Adhesive force is good, and battery sheet conversion efficiency is high, angularity is low.
The objective of the invention is to realize like this: a kind of no glass dust crystal silicon solar energy battery aluminium paste, said aluminium paste is made up of the raw material of following mass parts:
70 ~ 80 parts of aluminium powders
18 ~ 28 parts of organic bonds
0.5 ~ 1.5 part of adhesive force additive
0.5 ~ 1.5 part of auxiliary agent;
Said adhesive force additive is a metal salts of organic acids.
Said metal salts of organic acids is capric acid zinc, zinc naphthenate, zinc citrate or citric acid zirconium.
Said aluminium powder is the ball aluminum powder with certain grain size size distribution, and average grain diameter D50 is 4-8 μ m, and purity is greater than 99.8%, and active aluminium content is greater than 98.0%.More preferably, the particle diameter D10 of aluminium powder is less than 2 μ m, and D90 is less than 15 μ m.
Said organic bond is made up of high molecular polymer, organic solvent and organic additive; Three's quality proportioning is a high molecular polymer: organic solvent: organic additive=4 ~ 18:60 ~ 150:2.5 ~ 7.5, 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 BC, BC acetate, terpinol, TMPD isobutyrate, ATBC, ethylene glycol phenyl ether, the phenmethylol etc.; Organic additive 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: ethyl cellulose 3-8 part; Terpinol 20-50 part, BC 30-60 part, TMPD isobutyrate 10-40 part; Oleic acid 0.5-2.5 part, alkyd resins 1-10 part and pump oil 1-5 part.
Said adhesive force additive is a metal salts of organic acids; Comprise capric acid zinc, zinc naphthenate, zinc citrate or citric acid zirconium etc.; It is characterized in that can be miscible with above-mentioned organic bond; In aluminium paste, can reach other even dispersion of molecular level, form oxide crystal in the sintering process and can bond together the conducting film that forms densification to aluminium powder, thereby replace the glass dust in traditional aluminium paste as glue.
Said auxiliary agent is wetting dispersing agent BYK-108 of BIC Corp and the antifoaming agent KS-66 of Japan XINYUE.
The preparation method of above-mentioned no glass crystal aluminum paste of silicon solar cells may further comprise the steps:
1) preparation of organic bond
Component weighing in proportion that will be except that resin is heated to 80-100 ° of C, 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 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) replaces the glass dust component in traditional aluminium paste with the adhesive force additive, reduced this operation of glass dust preparation, realized the normal temperature process that aluminium paste is produced, more energy-conservation and environmental protection.
2) the adhesive force additive reaches the dispersion of molecule rank in slurry system; The oxide that forms in the sintering process " glue " forms fine and close aluminium back of the body field with the mode of interface bonding basically on silicon chip; The resistance of aluminium backing layer side is low, can obtain good Ohmic contact, has improved the conversion efficiency of battery sheet.
3) the preparation process of organic bond can make the dissolving resin time shorter, effectively reduces solvent evaporates; Filter efficiency is higher, avoids becoming sticky after the organic bond cooling and stops up mesh when filtering, thereby make that the quality of organic bond is more stable.
4) the preparation process of aluminium paste has increased each former material dispersed uniform property, has reduced the probability that occurs the aluminium paillette in the three roller process of lapping simultaneously, makes that the quality of aluminium paste product is more stable.
Embodiment
Embodiment 1:
Aluminium powder: used aluminium powder particle diameter D50 is 4.8 μ m, and D10 is 1.2 μ m, and D90 is 13.5 μ m.
Organic bond: by 2 parts of mass parts alkyd resins, 35 parts of terpinols, 35 parts of BCs; 20 parts of TMPD isobutyrates, 2 parts of oleic acid, 2.5 parts of pump oil; Mix to add in the agitated reactor and be heated to 80-100 ℃; The ethyl cellulose that stir to add 3.5 parts then, filter the dissolving back, is clarified, transparent organic bond.
Aluminium paste: get 74 parts of aluminium powders by mass parts, 24 parts of above-mentioned organic bonds, 1 part on capric acid zinc; 0.5 part of wetting dispersing agent (BYK-108), 0.5 part of antifoaming agent (KS-66) stirs 30min with homogenizer (1000r/min); The slurry fineness reaches 40-50 μ m, grinds 30000-45000 mPas during 25 ℃ of control slurry viscosities with three-roll grinder; < 20 μ m process the present invention and do not have glass dust crystal silicon solar energy battery aluminium paste 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; Just silver of Li Shi 9235 is congratulated in the printing of dry back, tests correlated performance through oven dry, tunnel sintering furnace co-sintering (778 ℃ of peak temperatures, 6.4s more than 600 ℃) back: open circuit voltage (mean value) 628mv; Short circuit current (mean value) 5.66A; The average light photoelectric transformation efficiency reaches 17.91%, and the angularity of battery sheet is 1.15mm, and a back of the body EVA peels off pulling force>10N.
Embodiment 2:
Aluminium powder: used aluminium powder particle diameter D50 is 5.6 μ m, and D10 is 1.4 μ m, and D90 is 14.7 μ m.
Organic bond: by 2 parts of mass parts alkyd resins, 30 parts of terpinols, 30 parts of BCs; 30 parts of TMPD isobutyrates, 1.5 parts of oleic acid, 2.5 parts of pump oil; Mix to add in the agitated reactor and be heated to 80-100 ℃; The ethyl cellulose that stir to add 4.0 parts then, filter the dissolving back, is clarified, transparent organic bond.
Aluminium paste: get 76 parts of aluminium powders by mass parts, 22 parts of above-mentioned organic bonds, 0.8 part of zinc naphthenate; 0.6 part of wetting dispersing agent (BYK-108), 0.6 part of antifoaming agent (KS-66) stirs 30min with homogenizer (1000r/min); The slurry fineness reaches 40-50 μ m, grinds 30000-45000 mPas during 25 ℃ of control slurry viscosities with three-roll grinder; < 20 μ m process the present invention and do not have glass dust crystal silicon solar energy battery aluminium paste 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; Just silver of Li Shi 9235 is congratulated in the printing of dry back, tests correlated performance through oven dry, tunnel sintering furnace co-sintering (785 ℃ of peak temperatures, 6.6s more than 600 ℃) back: open circuit voltage (mean value) 627mv; Short circuit current (mean value) 5.63A; The average light photoelectric transformation efficiency reaches 17.80%, and the angularity of battery sheet is 0.95mm, and a back of the body EVA peels off pulling force>10N.
Embodiment 3:
Aluminium powder: used aluminium powder particle diameter specification is identical with embodiment 1.
Organic bond: by 3 parts of mass parts alkyd resins, 35 parts of terpinols, 30 parts of BCs; 25 parts of TMPD isobutyrates, 1 part of oleic acid, 2.5 parts of pump oil; Mix to add in the agitated reactor and be heated to 80-100 ℃; The ethyl cellulose that stir to add 3.5 parts then, filter the dissolving back, is clarified, transparent organic bond.
Aluminium paste: get 75 parts of aluminium powders by mass parts, 23 parts of above-mentioned organic bonds, 0.8 part of zinc citrate; 0.7 part of wetting dispersing agent (BYK-108), 0.5 part of antifoaming agent (KS-66) stirs 30min with homogenizer (1000r/min); The slurry fineness reaches 40-50 μ m, grinds 30000-45000 mPas during 25 ℃ of control slurry viscosities with three-roll grinder; < 20 μ m process the present invention and do not have glass dust crystal silicon solar energy battery aluminium paste 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; Just silver of Li Shi 9235 is congratulated in the printing of dry back, tests correlated performance through oven dry, tunnel sintering furnace co-sintering (778 ℃ of peak temperatures, 6.4s more than 600 ℃) back: open circuit voltage (mean value) 628mv; Short circuit current (mean value) 5.65A; The average light photoelectric transformation efficiency reaches 17.87%, and the angularity of battery sheet is 1.15mm, and a back of the body EVA peels off pulling force>10N.
Embodiment 4:
Aluminium powder: used aluminium powder particle diameter particle diameter specification is identical with embodiment 2.
Organic bond: by 4 parts of mass parts alkyd resins, 30 parts of terpinols, 35 parts of BCs; 22 parts of TMPD isobutyrates, 0.5 part of oleic acid, 4.5 parts of pump oil; Mix to add in the agitated reactor and be heated to 80-100 ℃; The ethyl cellulose that stir to add 4 parts then, filter the dissolving back, is clarified, transparent organic bond.
Aluminium paste: get 76 parts of aluminium powders by mass parts, 22 parts of above-mentioned organic bonds, 0.8 part of citric acid zirconium; 0.6 part of wetting dispersing agent (BYK-108), 0.6 part of antifoaming agent (KS-66) stirs 30min with homogenizer (1000r/min); The slurry fineness reaches 40-50 μ m, grinds 30000-45000 mPas during 25 ℃ of control slurry viscosities with three-roll grinder; < 20 μ m process the present invention and do not have glass dust crystal silicon solar energy battery aluminium paste 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; Just silver of Li Shi 9235 is congratulated in the printing of dry back, tests correlated performance through oven dry, tunnel sintering furnace co-sintering (780 ℃ of peak temperatures, 6.6s more than 600 ℃) back: open circuit voltage (mean value) 629mv; Short circuit current (mean value) 5.63A; The average light photoelectric transformation efficiency reaches 17.92%, and the angularity of battery sheet is 1.10mm, and a back of the body EVA peels off pulling force>10N.
Claims (6)
1. no glass dust 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 parts:
70 ~ 80 parts of aluminium powders
18 ~ 28 parts of organic bonds
0.5 ~ 1.5 part of adhesive force additive
0.5 ~ 1.5 part of auxiliary agent;
Said adhesive force additive is capric acid zinc, zinc naphthenate, zinc citrate or citric acid zirconium.
2. a kind of no glass dust crystal silicon solar energy battery aluminium paste according to claim 1, it is characterized in that: said aluminium powder average grain diameter D50 is 4-8 μ m, and purity is greater than 99.8%, and active aluminium content is greater than 98.0%.
3. a kind of no glass dust crystal silicon solar energy battery aluminium paste according to claim 1, it is characterized in that: the particle diameter D10 of said aluminium powder is less than 2 μ m, and particle diameter D90 is less than 15 μ m.
4. according to claim 1 or 2 or 3 described a kind of no glass dust crystal silicon solar energy battery aluminium pastes; It is characterized in that: said organic bond is made up of high molecular polymer, organic solvent and organic additive; Three's quality proportioning is a high molecular polymer: organic solvent: organic additive=4 ~ 18:60 ~ 150:2.5 ~ 7.5, and wherein high molecular polymer is one or more in ethyl cellulose, phenolic resins, epoxy resin, the alkyd resins; Organic solvent is one or more in BC, BC acetate, terpinol, TMPD isobutyrate, ATBC, ethylene glycol phenyl ether, the phenmethylol; Organic additive 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 auxiliary agent is wetting dispersing agent BYK-108 and antifoaming agent KS-66.
5. a kind of no glass dust crystal silicon solar energy battery aluminium paste according to claim 4; It is characterized in that: said organic bond by the proportioning of mass parts is: 3 ~ 8 parts of ethyl celluloses, 20 ~ 50 parts of terpinols; 30 ~ 60 parts of BCs; 10 ~ 40 parts of TMPD isobutyrates, 0.5 ~ 2.5 part of oleic acid, 1 ~ 5 part of 1 ~ 10 part of alkyd resins and pump oil.
6. the preparation method of a no glass dust crystal silicon solar energy battery aluminium paste as claimed in claim 1 is characterized in that: said method comprising the steps of:
1) preparation of organic bond
The component weighing in proportion of organic bond that will be except that resin is heated to 80-100 ℃, while stir the resin that adds ormal weight then, after resin dissolves fully, filters while hot, promptly obtains transparent organic bond;
2) preparation of slurry
Take by weighing each component of aluminium paste in proportion and mix, stir, make slurry reach fineness 40-50 μ m, 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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| CN103295660A (en) * | 2012-02-28 | 2013-09-11 | 勤凯科技股份有限公司 | Electrode slurry composition of solar cell |
| CN103886931A (en) * | 2014-01-27 | 2014-06-25 | 无锡光富光伏材料有限公司 | Aluminum paste for upconversion solar cell |
| CN103972308A (en) * | 2014-04-30 | 2014-08-06 | 湖南红太阳光电科技有限公司 | High-adhesion industrialization crystalline silicon solar cell aluminium paste |
| CN104240842A (en) * | 2013-06-21 | 2014-12-24 | 中国钢铁股份有限公司 | Method for preparing modified silver powder and glass powder-free sintered silver colloid |
| CN104575685A (en) * | 2015-01-12 | 2015-04-29 | 浙江光隆能源科技股份有限公司 | Crystal silicon solar cell high adhesive force back surface field aluminum electrocondution slurry and preparation method |
| 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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| CN108511107A (en) * | 2018-02-28 | 2018-09-07 | 江苏国瓷泓源光电科技有限公司 | A kind of back of the body passivation aluminium paste and preparation method thereof containing porous structure powder |
| CN110045864A (en) * | 2019-03-06 | 2019-07-23 | 苏州蓝沛光电科技有限公司 | The preparation method of seed layer |
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| CN103295660A (en) * | 2012-02-28 | 2013-09-11 | 勤凯科技股份有限公司 | Electrode slurry composition of solar cell |
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| CN103886931B (en) * | 2014-01-27 | 2017-06-16 | 无锡光富光伏材料有限公司 | A kind of up-conversion solar cell aluminium paste |
| CN103886931A (en) * | 2014-01-27 | 2014-06-25 | 无锡光富光伏材料有限公司 | Aluminum paste for upconversion solar cell |
| CN103972308A (en) * | 2014-04-30 | 2014-08-06 | 湖南红太阳光电科技有限公司 | High-adhesion industrialization crystalline silicon solar cell aluminium paste |
| CN104575685A (en) * | 2015-01-12 | 2015-04-29 | 浙江光隆能源科技股份有限公司 | Crystal silicon solar cell high adhesive force back surface field aluminum electrocondution slurry and preparation method |
| CN107778764A (en) * | 2016-08-26 | 2018-03-09 | 湖南利德电子浆料股份有限公司 | A kind of solar cell size organic carrier and preparation method thereof |
| 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 |
| CN107331436B (en) * | 2017-07-05 | 2019-04-16 | 四川省银河化学股份有限公司 | For carrying on the back the conducting aluminum paste and preparation method thereof of passivation solar battery |
| CN108511107A (en) * | 2018-02-28 | 2018-09-07 | 江苏国瓷泓源光电科技有限公司 | A kind of back of the body passivation aluminium paste and preparation method thereof containing porous structure powder |
| CN110045864A (en) * | 2019-03-06 | 2019-07-23 | 苏州蓝沛光电科技有限公司 | The preparation method of seed layer |
| CN117059303A (en) * | 2023-09-05 | 2023-11-14 | 江苏飞特尔通信有限公司 | Conductive aluminum paste for external electrode of LTCC filter and preparation method of conductive aluminum paste |
| CN117059303B (en) * | 2023-09-05 | 2024-04-16 | 江苏飞特尔通信有限公司 | Conductive aluminum paste for external electrode of LTCC filter and preparation method of conductive aluminum paste |
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