CN107689261A - A kind of crystal silicon solar energy battery positive silver paste - Google Patents

A kind of crystal silicon solar energy battery positive silver paste Download PDF

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Publication number
CN107689261A
CN107689261A CN201610645651.5A CN201610645651A CN107689261A CN 107689261 A CN107689261 A CN 107689261A CN 201610645651 A CN201610645651 A CN 201610645651A CN 107689261 A CN107689261 A CN 107689261A
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CN
China
Prior art keywords
silver paste
positive silver
silicon solar
crystal silicon
solar energy
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Pending
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CN201610645651.5A
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Chinese (zh)
Inventor
郭宏彬
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Jiangsu Zheng Neng Electronic Science And Technology Co Ltd
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Jiangsu Zheng Neng Electronic Science And Technology Co Ltd
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Priority to CN201610645651.5A priority Critical patent/CN107689261A/en
Publication of CN107689261A publication Critical patent/CN107689261A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022408Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The present invention relates to a kind of crystal silicon solar energy battery positive silver paste, a kind of crystal silicon solar energy battery positive silver paste, the positive silver paste includes silver powder, lead-free glass powder and organic carrier, also contain compositions of additives in the unleaded positive silver paste, the weight ratio between the lead-free glass powder and additive is 1: 0.1 5.Present invention reduces corrosion of the alkaline matter in lead-free glass powder to the encapsulating material EVA adhesive film of battery, avoid encapsulating material EVA adhesive film and protective effect to battery is lost because of delamination, improve the service life of battery.

Description

A kind of crystal silicon solar energy battery positive silver paste
Technical field
The present invention relates to a kind of crystal silicon solar energy battery positive silver paste, belong to technical field of solar batteries.
Background technology
Solar energy is a kind of green energy resource, because its is pollution-free, inexhaustible, do not limited by resource advantage the advantages that and it is more next More it is valued by people, so solar cell arises at the historic moment.Crystal silicon solar batteries are that one kind can respond simultaneously to luminous energy The device of electric energy can be converted light energy into, it can convert light energy into electric energy using photovoltaic effect.When sunlight arrives During cell panel, certain electrical potential difference is produced on battery the two poles of the earth surface, connects external circuitses, it is possible to produce electric current.Several Battery is connected by way of serial or parallel connection, then close by encapsulating material EVA adhesive film (ethylene-vinyl acetate copolymer) Envelope protection, with regard to battery component can be made, and then battery array is formed, match somebody with somebody with other electronic devices and be combined into autonomous system or be incorporated to Power network, there is provided the supply of electric power of cleaning.Crystal silicon solar batteries electrode includes positive silver electrode, back side silver electrode and Al-BSF electricity Pole, positive silver electrode are to be formed using front side silver paste by silk-screen printing, drying, high temperature sintering, and the performance of front side silver paste is direct The performance of solar battery sheet front silver electrode is determined, is the critical material in crystal silicon solar energy battery manufacture.
At present, crystal silicon solar batteries are generally prepared with positive silver paste by silver powder, lead-free glass powder and organic carrier, Most of positive silver pastes use the glass dust containing higher proportion lead oxide.In order to preferably safeguard life cycle for the survival of mankind Border, the unleaded development trend for turning into electronics manufacturing of electronic product, preparing lead-free silver slurry using lead-free glass powder also turns into Following developing direction.In existing positive silver paste technology, contained lead-free glass powder includes basic anhydride, in sintering process, just Silver paste is to SiNx:The corrosiveness of H antireflective coatings is completed mainly by alkali glass, and reacts mainly on silicon substrate surface to enter OK, simultaneously because the slurry thawing time is extremely short, viscosity is high, poor fluidity, and this can cause each material distribution in electrode material different. Glass in course of reaction close to silicon substrate body portion reacts and is consumed, but still there are a considerable amount of basic species on electrode top layer Matter remains, the alkaline matter of residual make under high temperature and hygrothermal environment the ester of the encapsulating material EVA adhesive film of battery it is strong occur fracture, Aging cracking denaturation occurs for polymer molecular chain, ultimately results in the delamination of encapsulating material EVA adhesive film and protection is lost to battery and is made With reducing the service life of battery.
The content of the invention
The primary and foremost purpose of the present invention is, overcomes problems of the prior art, there is provided a kind of crystal of superior performance Silicon solar cell positive silver paste.
To solve above technical problem, a kind of crystal silicon solar energy battery positive silver paste provided by the present invention, its feature It is:The raw material components and weight content of the positive silver paste are as follows:Silver powder 87-92 parts, organic carrier 5-10 parts, crown glass 0.1~2 part of 1~5 part of powder and additive, wherein the percetage by weight sum of each component are 100%.Described silver-colored part is high vibration density Silver powder is spent, it is per cubic centimeter that tap density is more than 6g.The composition and percetage by weight of the lead-free glass powder be:Bi2O340- 60%th, Pb3O4- 8-15%, TeO220-35%, SiO22-6%, ZnO3-8%, MgO3-8%, TiO20.5-2%, P2O5-0.5- 2%.The composition and percetage by weight of organic carrier be:Terpinol 40-65%, ethyl cellulose 5-10%, butyl carbitol 10- 15%th, butyl carbitol acetate 9-15%, n-butanol 10-15%, phenmethylol 10-15%, Span804-7%.
It is an advantage of the current invention that overcome problems of the prior art, there is provided a kind of crystal silicon solar energy battery is just The preparation method of silver paste, manufactured positive silver paste electricity conversion is high, and adhesive force is high, and adhesive force converts after high temperature ageing Efficiency decay is small, and compared with prior art, the present invention is applied in combination and controlled theirs by glass dust and organic additive Usage ratio, ensureing SiNx of the glass dust in sintering process to silicon chip surface:H antireflective coatings produce corrosiveness, realize silver While electrode contacts with the good conductive of silicon substrate, in sintering process and cooling stage, additive reacts with lead-free glass powder And positive silver electrode surface can be partly transferred to, consume the remaining alkaline matter of positive silver electrode surface so that positive silver electrode table Face reduces corrosion of the alkaline matter for the encapsulating material EVA adhesive film of battery, avoids package material in neutral or close neutrality Material EVA adhesive film loses the protective effect to battery because of delamination, improves the service life of battery.
Embodiment
Embodiment one
Positive silver paste provided by the invention is used for the positive silver electrode for making crystal silicon solar batteries, and the positive silver paste is by silver Powder, lead-free glass powder, organic carrier and compositions of additives are prepared.Lead-free glass powder liquefies in Fast Sintering, in silver Cementation is played between powder and silicon chip, while plays a part of penetrating antireflective coating, makes to be formed between silver powder and silicon chip Good Ohmic contact.The lead-free glass powder that the present invention uses is known to those skilled in the art, and it can be directly from market Purchase can also be prepared using method well known to those skilled in the art, and its softening temperature is 350 DEG C~600 DEG C.Because When its softening temperature is less than 350 DEG C, may be caused because of the excess flow of glass melt between positive silver electrode and silicon chip Glass film layers are blocked up, cause the contact resistance of positive silver electrode and silicon chip to rise;, may when its softening temperature is higher than 600 DEG C Cause glass dust and silver powder to sinter not exclusively, produce " raw burn " phenomenon, cause adhesive force to decline in the bulk resistor with positive silver electrode Rise.It is adapted to the lead-free glass powder of the present invention to can be selected by Bi2O3、Pb3O4、TeO2、SiO2、ZnO、MgO、TiO2、P2O5The nothing of composition Lead glass system, for the size controlling of glass dust below 10 microns, dosage is the 1~5% of silver paste weight.If glass dust Dosage less than 0.5%, can influence antireflective coating etching and silicon substrate and silver electrode between adhesive force;If dosage more than 5%, The electrical property of cell piece can be reduced.Lead-free glass powder mainly exists in sintering process to the corrosiveness of silicon nitride anti-reflecting film Silicon substrate surface is carried out, simultaneously as the thawing time of positive silver paste is extremely short, viscosity is high, poor fluidity, causes in positive silver electrode The distribution of each material is different, causes the lead-free glass powder close to silicon substrate to be consumed, and the top layer of positive silver electrode still has and quite counted The alkaline matter residual of amount, the alkaline matter of these residuals make the encapsulating material EVA adhesive film of battery under high temperature and hygrothermal environment Ester it is strong fracture occurs, aging cracking denaturation occurs for polymer molecular chain, ultimately result in the delamination of encapsulating material EVA adhesive film and right Battery loses protective effect, reduces the service life of battery.In order to consume the remaining alkaline matter of positive silver electrode surface so that Positive silver electrode surface is in neutral or close neutrality, reduces corrosion of the alkaline matter for the encapsulating material EVA adhesive film of battery, this Invent in the positive silver paste provided and used additive.In sintering process, additive melts and occurred with lead-free glass powder anti- Should, produce the neutral substance harmless to encapsulating material;In the cooling stage of sintering process back segment, due to lead-free glass powder molten mass Cooling meat, the additive of melting state are transferred to positive silver electrode surface so that its further alkaline matter with electrode surface Reaction, consumes remaining alkali compounds, positive silver electrode surface is caused in neutral or close neutrality, so as to eliminate alkaline matter pair The influence of EVA layer.The fusing point for the additive that the present invention uses is lower than the softening temperature of glass dust 10 DEG C~260 DEG C, it is therefore an objective to profit With the distribution of the fusing point difference control additive of the two.The fusing point of additive is higher than glass dust softening point, or the two difference less than 10 DEG C, After sintering cooling, additive may be retained inside positive silver electrode without migrating to surface.The fusing point and glass dust of additive Softening point difference is more than 260 DEG C, and its fusing point and volatilization temperature are too low, cause additive in sintering process excess flow or volatilization, shadow Ring electrode outward appearance.Additive amount is the 0.1~2% of silver paste gross weight, if dosage is too low, it is unnecessary can not to play consumption The effect of alkaline matter, can not solve EVA aging delaminations:If dosage is too high, electrode bulk resistor may be increased.In order to Both can guarantee that has good Ohmic contact between silver powder and silicon chip, and can prevents the alkaline matter in slurry for battery The corrosion of encapsulating material EVA adhesive film, present invention employs additive and lead-free glass powder to be applied in combination, and controls its amount ratio Example, the weight between lead-free glass powder and additive, can be right less than the proportion than controlling in the range of 1: 0.1~5.0 The corrosive nature of positive silver paste has an impact, and causes positive silver paste contact resistance to rise;Higher than the proportion, it is impossible to prevent nothing The corrosiveness of alkaline matter in lead glass powder to EVA.
The silver powder used in the present invention can select silver powder well known in the art, preferably 0.2~2 micron of average grain diameter, shake Real density is more than 4.5g/cc silver powder.
The organic carrier that the present invention uses can select resin well known in the art and solvent to prepare, preferably following method systems Standby organic carrier:By terpinol 40-65%, ethyl cellulose 5-10%, butyl carbitol 10-15%, want base carbitol vinegar Acid esters 9-15%, n-butanol 10-15%, phenmethylol 10-15% and Span804-7% organic solvent is mixed evenly and added Heat arrives 60-90 DEG C, until polymer is completely dissolved, forms clear viscous liquids, impurity screening, obtains the organic carrier.
Crystal silicon solar energy battery provided by the invention can be prepared with unleaded positive silver paste using following methods:
Lead-free glass powder, 8~20% organic carrier of positive silver paste weight 0.5~5% will be accounted for, 0.3~4.5% adds After adding agent well mixed, 75~90% silver powder is added, is ground after stirring, obtain crystal silicon solar energy battery with unleaded positive silver Slurry.
By above-mentioned slurry with 280~400 mesh web plates, crystal silicon solar batteries silicon substrate is printed on by way of silk-screen printing On piece front, the slurry after printing is by 160~270 DEG C of drying, and sintering forms front silver electricity at a high temperature of 650~950 DEG C Pole.
With reference to specific embodiment, the invention will be further described.
The preparation of organic carrier:
Weigh terpinol 40, ethyl cellulose 5, butyl carbitol 10, want base carbitol acetate 9, n-butanol 10, benzene first Alcohol 10 and Span804, it is mixed and heated to 60~90 DEG C, dissolves, obtain organic binder bond, it is standby.
Embodiment 1
The ultra-fine softening temperatures of 5g are weighed as 560 DEG C of lead-free glass powders, 75g silver powder, 19g organic carriers, 1g diboron trioxides, Well mixed, three-roller rolling fineness is less than 10 microns, adjusts viscosity to 280~400Pa.s with terpinol, obtains crystalline silicon too The positive energy unleaded positive silver paste of battery.
Embodiment 2
The ultra-fine softening temperatures of 3g are weighed as 600 DEG C of lead-free glass powders, 75g silver powder, 20g organic carriers, the oxidations of 0.3g five two Phosphorus, 1g tellurium dioxide, be well mixed, three-roller rolling fineness is less than 10 microns, with terpinol adjust viscosity to 280~ 400Pa.s, crystal silicon solar energy battery is obtained with unleaded positive silver paste.
Embodiment 3
The ultra-fine softening temperatures of 0.5g are weighed to aoxidize for 350 DEG C of lead-free glass powders, 90g silver powder, 9.2g organic carriers, 0.3g five Two phosphorus, it is well mixed, three-roller rolling fineness is less than 10 microns, adjusts viscosity to 280~400Pa.s with terpinol, obtains crystalline substance The unleaded positive silver paste of body silicon solar cell.
Embodiment 4
The ultra-fine softening temperatures of 0.9g are weighed as 435 DEG C of lead-free glass powders, 86.6g silver powder, 8g organic carriers, 4.5 titanium dioxides Selenium, it is well mixed, three-roller rolling fineness is less than 10 microns, adjusts viscosity to 280~400Pa.s with terpinol, obtains crystal The unleaded positive silver paste of silicon solar cell.
Embodiment 5
The ultra-fine softening temperatures of 2g are weighed as 480 DEG C of lead-free glass powders, 85g silver powder, 9.5g organic carriers, 4.5 selenium dioxide, Well mixed, three-roller rolling fineness is less than 10 microns, adjusts viscosity to 280~400Pa.s with terpinol, obtains crystalline silicon too The positive energy unleaded positive silver paste of battery.

Claims (4)

  1. A kind of 1. crystal silicon solar energy battery positive silver paste, it is characterised in that:The raw material components and weight of the positive silver paste contain Amount is as follows:0.1~2 part of silver powder 87-92 parts, organic carrier 5-10 parts, 1~5 part of lead-free glass powder and additive, wherein each component Percetage by weight sum be 100%.
  2. A kind of 2. crystal silicon solar energy battery positive silver paste according to right 1, it is characterised in that:Described silver-colored part is high jolt ramming Density silver powder, it is per cubic centimeter that tap density is more than 6g.
  3. A kind of 3. crystal silicon solar energy battery positive silver paste according to right 1, it is characterised in that:The lead-free glass powder Composition and percetage by weight are:Bi2O340-60%, Pb3O4- 8-15%, TeO220-35%, SiO22-6%, ZnO3-8%, MgO3-8%, TiO20.5-2%, P2O50.5-2%.
  4. A kind of 4. crystal silicon solar energy battery positive silver paste according to right 1, it is characterised in that:The composition of organic carrier and Percetage by weight is:Terpinol 40-65%, ethyl cellulose 5-10%, butyl carbitol 10-15%, butyl carbitol acetic acid Ester 9-15%, n-butanol 10-15%, phenmethylol 10-15%, Span804-7%.
CN201610645651.5A 2016-08-04 2016-08-04 A kind of crystal silicon solar energy battery positive silver paste Pending CN107689261A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110174412A (en) * 2019-05-21 2019-08-27 常州聚和新材料股份有限公司 A kind of method of glass in test silver paste to silicon chip surface corrosion depth

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120097237A1 (en) * 2009-04-07 2012-04-26 Lg Innotek Co., Ltd. Paste and Solar Cell Using the Same
CN103208321A (en) * 2013-04-16 2013-07-17 江苏太阳新材料科技有限公司 Crystalline silicon solar cell back surface field aluminum paste and preparation method thereof
CN106328246A (en) * 2015-06-19 2017-01-11 江苏正能电子科技有限公司 Positive silver paste for crystalline silicon solar cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120097237A1 (en) * 2009-04-07 2012-04-26 Lg Innotek Co., Ltd. Paste and Solar Cell Using the Same
CN103208321A (en) * 2013-04-16 2013-07-17 江苏太阳新材料科技有限公司 Crystalline silicon solar cell back surface field aluminum paste and preparation method thereof
CN106328246A (en) * 2015-06-19 2017-01-11 江苏正能电子科技有限公司 Positive silver paste for crystalline silicon solar cell

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110174412A (en) * 2019-05-21 2019-08-27 常州聚和新材料股份有限公司 A kind of method of glass in test silver paste to silicon chip surface corrosion depth

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