CN103000249B - A kind of solar cell front side silver paste and preparation method thereof - Google Patents
A kind of solar cell front side silver paste and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of solar cell front side silver paste and preparation method thereof, comprise the component of following percetage by weight: argentum powder 80%～90%, lead bearing glass powder 0.5%～5%, inorganic additive 0.05%～3%, organic carrier 5%～15%, in described lead bearing glass powder, the weight/mass percentage composition of lead is 30%～90%, and described inorganic additive comprises TeO2Micropowder, described organic carrier includes resin and organic solvent.The silver slurry of the present invention is applicable to the silica-based solar cell of surface height square resistance, good Ohmic contact can be formed on high square resistance silicon based cells, therefore solaode transformation efficiency is greatly improved, and maintain the welding pulling force after high lead silver slurry sintering on the solar cell, the preparation method of the cell front side silver paste of the present invention enormously simplify silver slurry preparation technology simultaneously, has saved production cost.
Description
Technical field
The present invention relates to technical field of solar batteries, particularly relate to a kind of solar cell front side silver paste and
Its preparation method.
Background technology
Along with shortage and people's concern to CO2 emission of the traditional energies such as coal, oil, natural gas,
Solar energy generation technology has obtained the development of saltatory.Wherein crystal silicon solar energy battery technology is as solar energy
The main body of generation technology, enjoys the concern of people always, continuous by crystal silicon solar energy battery technology
Research, its photoelectric transformation efficiency constantly promotes.
The quality of solaode except depend on carrier concentration in used crystal silicon material, distribution and
Beyond mobility, also affected by battery plus-negative plate electrode performance.Wherein front electrode directly affects and goes here and there
Connection resistance, shunt resistance, fill factor, curve factor and photoelectric transformation efficiency, therefore the quality of front electrode silver slurry determines
The performance of solaode.
Conductive silver paste mainly includes following ingredient: argentum powder, organic carrier, glass dust and inorganic add
Add agent.In front side silver paste, in addition to key component argentum powder, the composition of glass dust and inorganic additive and
Content plays vital effect to the impact of the final efficiency of cell piece.
At present, mostly the glass dust of preparation silver slurry is business-like high pbo glass powder, rotten by the lead in glass dust
The SiN anti-reflection layer of erosion silicon chip surface, and assist argentum powder to form secondary crystallization at silicon face, form effective Europe
Nurse contacts.Thus it is common to use high pbo glass powder is as the raw material preparing front side silver paste.But from the most silica-based
From the point of view of the trend of solar energy development, the square resistance that silicon chip surface is high will become main flow, because high square resistance silicon chip
Improve short wave response, photoelectric transformation efficiency can be effectively improved.And the PN junction of high square resistance silicon based cells is relatively low
The PN junction of sheet resistance is shallow, as gone high temperature corrosion with common high pbo glass powder, it is easy to puncture PN junction, it is difficult to
Reach due efficiency.It is thus desirable to find the comparatively gentle glass of novel corrosivity to reach appropriateness corrosion
Effect.By the interpolation of inorganic additive, neutralization lead corrosion performance can be played and promote argentalium alloy shape
The effect become.Therefore, by the selection of inorganic additive kind and content being expanded tradition front side silver paste
Range so that it is can not only be suitable on high square resistance silicon based cells sheet, moreover it is possible to be effectively improved silica-based
The efficiency of solaode.Solar cell front side silver paste patent and reported literature are more, as in patent at present
US20110308597, US20110232746, US20110308596 disclose and utilizes tellurate glass powder
Prepare solar cell front side silver paste.But, tellurate glass powder is relatively low because of lead content, the corruption to silicon chip
But erosion property is poor, although meets the demand of high square resistance but reduces the sintering degree of glass dust and silicon chip,
Thus reduce welding pulling force.One defect of the silver slurry that therefore prepared by tellurate glass powder is exactly grid line and silicon
The sintering character of sheet is poor.Use lead-free glass powder and inorganic additive is disclosed in patent US7935279
TeO2And Bi2O3Prepare solar cell front side silver paste, but the front side silver paste conversion efficiency prepared by this invention
Low, it is difficult to commercialization.
Therefore, how to obtain a kind of conversion efficiency high, welding pulling force is big, and preparation method step is few too simultaneously
Sun energy cell front side silver paste, is still worth people to be continually striving to explore.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide one to be applicable to height
Solar cell front side silver paste that sheet resistance is silica-based and preparation method thereof, this silver slurry transformation efficiency is high, welds pulling force
Greatly.
The purpose of the present invention can be achieved through the following technical solutions:
A first aspect of the present invention is to provide a kind of solar cell front side silver paste, comprises following percetage by weight
Component: argentum powder 80%～90%, lead bearing glass powder 0.5%～5%, inorganic additive 0.05%～3%, have
Airborne body 5%～15%, in described lead bearing glass powder, the weight/mass percentage composition of lead is 30%～90%, described nothing
Machine additive comprises TeO2Micropowder, described organic carrier includes resin and organic solvent.
The present invention comprises TeO by adding in front side silver paste2The inorganic additive of micropowder, plays neutralization lead rotten
The effect that erosion performance and promotion argentalium alloy are formed, makes the corrosivity of glass reach the effect that appropriateness is gentle, makes
The PN junction obtaining high square resistance silicon based cells is difficult to breakdown, makes inapplicable high lead silver slurry energy on high square resistance originally
Enough applicable, and solaode transformation efficiency is greatly improved, maintain primeval lead glass dust and silicon
The sintering character of sheet, maintains higher welding pulling force after making this silver slurry sintering on the solar cell.
Preferably, the percetage by weight of described inorganic additive is 0.1%～1.5%, more preferably 0.1%～
0.5%；The percetage by weight of lead bearing glass powder is 1%～4%, more preferably 2.5%～3%.
In described lead bearing glass powder, the weight/mass percentage composition of lead is preferably 70%～85%, described lead bearing glass powder
Particle mean size is preferably 0.1 μm～10 μm, more preferably 0.1 μm ~ 2 μm.
In order to make gained cell front side silver paste have more preferable conversion efficiency and welding pulling force, the present invention preferably,
Described TeO2The purity of micropowder is more than 99.9%, TeO2The particle mean size of micropowder is in 0.1 μm～10 μm, more
It is preferably 0.3 μm～3 μm.
Preferably, the purity of described argentum powder is 99.0%～99.999%, and described argentum powder is that particle mean size exists
0.5 μm～the spherical or flakey body of 10 μm.Described argentum powder is more preferably particle mean size in 0.5 μm～3 μm
Spheroid.
Preferably, described inorganic additive also comprises SeO2Micropowder.
Preferably, described organic carrier also includes plasticizer and/or surfactant.
Preferably, described resin one in ethyl cellulose resin, rosin resin, the phenolic resin or
Several, the more preferably mixing of ethyl cellulose resin, rosin resin and phenolic resin.
Preferably, described organic solvent is selected from terpineol, Oleum Terebinthinae, propylene glycol methyl ether acetate, butyl card
Must one or more in alcohol, ethylene glycol monomethyl ether acetate, petroleum ether, ether solvent, more preferably pine
The mixing of oleyl alcohol, ethylene glycol monomethyl ether acetate and propylene glycol methyl ether acetate.
A second aspect of the present invention is to provide the preparation method of a kind of solar cell front side silver paste, described method
Comprise the following steps:
(1) preparation of organic carrier: the resin that percetage by weight is 10%～20% is joined 80%～90%
Organic solvent in, stir 1～2 hour at 80～150 DEG C, after dissolving the organic carrier of homogeneous transparent.
(2) mixing of silver slurry: by argentum powder that percetage by weight is 80%～90%, 5%～15% step (1)
After the lead bearing glass powder mixing and stirring of gained organic carrier, 0.5%～5%, adding percetage by weight is
0.05%～3% inorganic additive stirring, obtains uniform combined silver slurry.
(3) dispersion of silver slurry: combined silver slurry step (2) prepared is put into three-roll grinder and fully ground
Grind 2～5 times, until slurry fineness is less than 15 μm, thus obtain silver slurry slurry.
In the preparation process of solar cell front side silver paste of the present invention, it is not necessary to prepare glass dust separately, only need
Utilize existing business-like leaded be 30%～90%, granularity at 0.1 μm～the glass dust of 10 μm,
The method eliminates argentum powder and the preparation process of lead bearing glass powder in existing method, enormously simplify silver slurry preparation
Technique, has saved production cost.
The present invention compared with prior art has the advantage that
1) solar cell front side silver paste of the present invention uses TeO2Micropowder is as inorganic additive, by control
TeO processed2The content of micropowder and granularity, make script inapplicable high lead silver slurry on high square resistance to be suitable for, and
And solaode transformation efficiency is greatly improved, maintain the agglutinating property of primeval lead glass dust and silicon chip
Can, maintain higher welding pulling force after making this silver slurry sintering on the solar cell.
2) due to the fact that and directly use existing commercialization lead bearing glass powder as raw material, convert effect obtaining
While the silver slurry product that rate is high, welding pulling force is big, enormously simplify silver slurry preparation technology, saved production
Cost.
Detailed description of the invention
Used in embodiment, argentum powder orders finished product from the manufacturer of professional production silver slurry argentum powder；TeO2Micro-
The micropowder finished product that granularity is 0.1 μm～10 μm that powder is provided by domestic manufacturers.Lead bearing glass powder is import
Silver slurry special glass powder finished product.
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that retouched
The embodiment stated is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art obtained under not making creative work premise all its
His embodiment, broadly falls into the scope of protection of the invention.
Embodiment 1
A kind of solar cell front side silver paste, comprises the component of following percetage by weight: 87% particle mean size is
The argentum powder of 1.5 μm, 2.9% particle mean size be the lead bearing glass powder of 1.5 μm, 0.1% particle mean size be 1 μm TeO2
Micropowder, 10% organic carrier；Wherein organic carrier comprises the following components occupying airborne body weight percentage ratio: 10%
Ethyl cellulose resin, 4% rosin resin, 6% phenolic resin, 80% organic solvent (50% terpineol, 22%
Ethylene glycol monomethyl ether acetate, the mixture of 28% propylene glycol methyl ether acetate), lead in described lead bearing glass powder
Weight/mass percentage composition be 75%～80%.
The preparation method of the cell front side silver paste of described embodiment 1 comprises the following steps:
(1) preparation of organic carrier: by 10g ethyl cellulose resin, 4g rosin resin, 6g phenolic aldehyde tree
Fat, joins 80ml organic solvent (Oleum Terebinthinae, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate
Mixture) in, stir 2 hours at 100 DEG C, after dissolving the organic carrier of homogeneous transparent.
(2) selection of glass dust: select glass transformation temperature at the commercialization lead bearing glass powder of 360～380 DEG C,
In described lead bearing glass powder, the weight/mass percentage composition of lead is 75%～80%.
(3) mixing of silver slurry: by the argentum powder that 870g particle mean size is 1.5 μm, 100g step (1) gained
Organic carrier, 29g step (2) gained glass dust and 1g particle mean size are 1 μm TeO2Micropowder mix and blend,
Obtain homogeneous mixture.
(4) dispersion of silver slurry: step (3) gained mixture is put into three-roll grinder and is fully ground 5
Secondary, by Hegman fineness grind agent measurement fineness less than after 15 μm, i.e. prepare the front side silver paste slurry of the present invention.
Embodiment 2
A kind of solar cell front side silver paste, comprises the component of following percetage by weight: 89% particle mean size is
The argentum powder of 1 μm, 2.5% particle mean size be the lead bearing glass powder of 1.2 μm, 0.5% particle mean size be 0.3 μm TeO2
Micropowder, 8% organic carrier；Wherein said organic carrier comprises the following components occupying airborne body weight percentage ratio:
10% ethyl cellulose resin, 5% rosin resin, 2% phenolic resin, 83% organic solvent (50% terpineol,
22% ethylene glycol monomethyl ether acetate, the mixture of 28% propylene glycol methyl ether acetate), described lead bearing glass powder
The weight/mass percentage composition of middle lead is 80%～85%, described TeO2Micropowder purity is more than 99.9%.
The preparation method of the cell front side silver paste of described embodiment 2 comprises the following steps:
(1) preparation of organic carrier: by 10g ethyl cellulose resin, 5g rosin resin, 2g phenolic aldehyde
Resin, joins 83ml organic solvent (Oleum Terebinthinae, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetic acid
The mixture of ester) in, stir 2 hours at 100 DEG C, after dissolving, obtain the organic carrier of homogeneous transparent.
(2) selection of glass dust: select glass transformation temperature at the commercialization lead bearing glass powder of 360～380 DEG C,
In described lead bearing glass powder, the weight/mass percentage composition of lead is 80%～85%.
(3) mixing of silver slurry: by the argentum powder that 890g particle mean size is 1 μm, 80g step (1) gained has
Airborne body, 25g step (2) gained glass dust and 5g particle mean size are 0.3 μm TeO2Micropowder mix and blend,
Obtain homogeneous mixture.
(4) dispersion of silver slurry: step (3) gained mixture is put into three-roll grinder and is fully ground 5
Secondary, by Hegman fineness grind agent measurement fineness less than after 15 μm, i.e. prepare the front side silver paste slurry of the present invention.
Embodiment 3
A kind of solar cell front side silver paste, comprises the component of following percetage by weight: 87% particle mean size is
The argentum powder of 3 μm, 3% particle mean size be the lead bearing glass powder of 5 μm, 3% particle mean size be 2 μm TeO2Micropowder,
7% organic carrier；Wherein said organic carrier comprises the following components occupying airborne body weight percentage ratio: 7% second
Base celluosic resin, 5% rosin resin, 88% organic solvent (50% terpineol, 22% ethylene glycol monobutyl ether vinegar
Acid esters, the mixture of 28% propylene glycol methyl ether acetate), the weight/mass percentage composition of lead in described lead bearing glass powder
It is 70%～75%, described TeO2Micropowder purity is more than 99.9%.
The preparation method of the cell front side silver paste of described embodiment 3 comprises the following steps:
(1) preparation of organic carrier: by 7g ethyl cellulose resin, 5g rosin resin, join 88ml
Organic solvent (50% terpineol, 22% ethylene glycol monomethyl ether acetate, 28% propylene glycol methyl ether acetate mixed
Compound) in, stir 2 hours at 100 DEG C, after dissolving, obtain the organic carrier of homogeneous transparent.
(2) selection of glass dust: select glass transformation temperature at the commercialization lead bearing glass powder of 360～380 DEG C,
In described lead bearing glass powder, the weight/mass percentage composition of lead is 70%～75%.
(3) mixing of silver slurry: by the argentum powder that 870g particle mean size is 3 μm, 70g step (1) gained has
Airborne body, 30g step (2) gained glass dust and 30g particle mean size are 2 μm TeO2Micropowder mix and blend,
Obtain homogeneous mixture.
(4) dispersion of silver slurry: step (3) gained mixture is put into three-roll grinder and is fully ground 5
Secondary, by Hegman fineness grind agent measurement fineness less than after 15 μm, i.e. prepare the front side silver paste slurry of the present invention.
Comparative example:
Comparative example is a kind of solar cell front side silver paste, comprises the component of following percetage by weight: 89%
Particle mean size be the argentum powder of 1 μm, 3% particle mean size be the lead bearing glass powder of 1.2 μm, 8% organic carrier；
Wherein said organic carrier comprises the following components occupying airborne body weight percentage ratio: 10% ethyl cellulose tree
Fat, 5% rosin resin, 2% phenolic resin, 83% organic solvent (50% terpineol, 22% ethylene glycol only son
Ether acetate, the mixture of 28% propylene glycol methyl ether acetate), the percent mass of lead in described lead bearing glass powder
Content is 80%～85%.
The preparation method of the cell front side silver paste of described comparative example comprises the following steps:
(1) preparation of organic carrier: by 10g ethyl cellulose resin, 5g rosin resin, 2g phenolic aldehyde
Resin, join 83ml organic solvent (50% terpineol, 22% ethylene glycol monomethyl ether acetate, 28% the third
The mixture of glycol methyl ether acetate) in, stir 2 hours at 100 DEG C, after dissolving, obtain having of homogeneous transparent
Airborne body.
(2) selection of glass dust: select glass transformation temperature at the commercialization lead bearing glass powder of 360～380 DEG C,
In described lead bearing glass powder, the weight/mass percentage composition of lead is 80%～85%.
(3) mixing of silver slurry: by the argentum powder that 890g particle mean size is 1 μm, 80g step (1) gained has
Airborne body, 30g step (2) gained glass dust mix and blend, obtain homogeneous mixture.
(4) dispersion of silver slurry: step (3) gained mixture is put into three-roll grinder and is fully ground 5
Secondary, by Hegman fineness grind agent measurement fineness less than after 15 μm, i.e. prepare comparative example tradition front side silver paste slurry.
The performance test results and evaluation:
By the silver slurry front electrode slurry of embodiment 1-3 and comparative example gained, with 400 mesh silk screen printings in thickness
Being on the 125*125 monocrystalline silicon piece of 175 μm～185 μm, the sheet resistance of monocrystalline silicon sheet surface is all higher than 80 ohm
/ side, makes test material after drying, sintering.Silver slurry in comparative example is also at 125*125, monocrystalline silicon piece
The sheet resistance on surface is on the monocrystalline silicon piece of 60～65 ohm/side and has carried out contrast experiment.
The method of testing used and gained test result are all from solar energy research institute of Shanghai Communications University.
The silver slurry every test result of slurry of embodiment 1-3 and comparative example is shown in Table 1-2.
Table 1 is silver slurry slurry every electrical property average
Wherein, Model: sample；Voc: open-circuit voltage；Isc: short circuit current；Vmax: best effort electricity
Pressure；Imax: recommended current；Pmax: peak power；Eff: conversion efficiency；FF: fill factor, curve factor；
Rs: series resistance；Rsh: parallel resistance；Irev: reverse leakage；EnuTemp: ambient temperature；Sun:
Sun light intensity.
Table 2 is cell piece pulling force meansigma methods
| Sample | Pulling force meansigma methods (N) |
| 1 | 3.2 |
| 2 | 3.5 |
| 3 | 3.8 |
| Comparative example | 3.2 |
From the test result of table 1 it can be seen that by the present invention in that and use TeO2Micropowder as inorganic additive,
And by controlling TeO2The content of micropowder and granularity, ensure that silicon chip surface SiN anti-reflection layer corrodes, and promotes
While argentalium alloy is formed, slow down the lead corrosion to silicon chip so that gained silver slurry slurry can be at height
Apply on the silicon based cells of sheet resistance, and every electrical property all reaches the light of higher level, particularly battery
Photoelectric transformation efficiency (Eff) value, has reached 18.24%, thus has been effectively improved solaode transformation efficiency.
And by comparative example it will be seen that although traditional high lead silver slurry can be at low square resistance (less than 70 ohm/side)
Silica-based solar cell on be suitable for, but efficiency is obviously high not as the silicon based cells of high square resistance.And high lead silver
Slurry obviously cannot form good Ohmic contact on the silica-based solar cell sheet of high square resistance, therefore can not fit
With.
From table 2 it can be seen that the present invention is while improving the efficiency of silica-based solar cell, do not make
Welding pulling force declines, and efficiently avoid the tellurate glass welding low defect of pulling force, its meansigma methods up to
3.8N, good welding pulling force ensure that the permanent service life of silica-based solar cell.
The above, the only preferable detailed description of the invention of the present invention, but protection scope of the present invention is not limited to
With this, any those familiar with the art, in the technical scope that the invention discloses, can think easily
The change arrived or replacement, all should contain within protection scope of the present invention.
Claims (7)
1. a solar cell front side silver paste, it is characterised in that comprise following weight percent
The component of number: argentum powder 80%～90%, lead bearing glass powder 0.5%～5%, inorganic additive
0.05%～3%, organic carrier 5%～15%, the percent mass of lead in described lead bearing glass powder
Content is 30%～90%, and described inorganic additive is TeO2 micropowder, described organic carrier bag
Include resin and organic solvent；Described resin is selected from ethyl cellulose resin, rosin resin, phenolic aldehyde
One or more in resin；Described organic solvent is selected from terpineol, Oleum Terebinthinae, propylene glycol first
In ether acetate, butyl carbitol, ethylene glycol monomethyl ether acetate, petroleum ether, ether solvent
One or more；The particle mean size of described TeO2 micropowder is in 0.1 μm～10 μm.
2. solar cell front side silver paste as claimed in claim 1, it is characterised in that institute
The percetage by weight stating inorganic additive is 0.1%～1.5%, the weight percent of lead bearing glass powder
Number is 1%～4%.
3. solar cell front side silver paste as claimed in claim 1, it is characterised in that institute
State the purity of TeO2 micropowder more than 99.9%.
4. solar cell front side silver paste as claimed in claim 1, it is characterised in that institute
State the particle mean size of TeO2 micropowder in 0.3 μm～3 μm.
5. solar cell front side silver paste as claimed in claim 1 or 2, it is characterised in that
The purity of described argentum powder is 99.0%～99.999%, described argentum powder be particle mean size in 0.5 μm～
Spherical or the flakey body of 10 μm.
6. solar cell front side silver paste as claimed in claim 1 or 2, it is characterised in that
Described organic carrier also includes plasticizer and/or surfactant.
7. a preparation method for solar cell front side silver paste as claimed in claim 1,
It is characterized in that, said method comprising the steps of:
(1) preparation of organic carrier: the resin that percetage by weight is 10%～20% is added
In organic solvent to 80%～90%, stir 1～2 hour at 80～150 DEG C, dissolve
After the organic carrier of homogeneous transparent；
(2) mixing of silver slurry: by argentum powder that percetage by weight is 80%～90%, 5%～
The lead bearing glass powder mix and blend of 15% step (1) gained organic carrier, 0.5%～5% is equal
After even, adding percetage by weight is 0.05%～3% inorganic additive stirring, obtains and mixes uniformly
Close silver slurry；
(3) dispersion of silver slurry: three-roll grinder put into by combined silver slurry step (2) prepared
Inside it is fully ground 2～5 times, until slurry fineness is less than 15 μm, thus obtains silver slurry slurry.
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| CN103617824B (en) * | 2013-12-06 | 2016-10-05 | 苏州柏特瑞新材料有限公司 | A kind of high adhesion force solar cell front side silver paste and preparation method thereof |
| CN103951262B (en) * | 2014-04-15 | 2017-01-25 | 江苏欧耐尔新型材料有限公司 | Lead-tellurium-bismuth-containing glass paste for positive electrodes of solar cells as well as preparation and application methods of glass paste |
| CN106816203A (en) * | 2017-03-20 | 2017-06-09 | 北京市合众创能光电技术有限公司 | Crystal silicon solar energy battery high-tensile strength positive silver paste and preparation method thereof |
| CN107195355B (en) * | 2017-04-21 | 2019-11-08 | 昆明理工大学 | A kind of front side silver paste suitable on high square resistance shallow junction solar battery |
| CN110648781B (en) * | 2019-09-10 | 2021-07-16 | 广州市儒兴科技开发有限公司 | Main grid front silver paste suitable for step-by-step screen printing |
| CN110942841A (en) * | 2019-12-13 | 2020-03-31 | 新昌中国计量大学企业创新研究院有限公司 | Lead-free silver conductor slurry and preparation process thereof |
| CN111732337B (en) * | 2020-08-07 | 2023-02-10 | 上海银浆科技有限公司 | Lead-free glass component and high-welding-tension crystalline silicon solar cell conductive silver paste containing same |
| CN113053583B (en) * | 2021-03-02 | 2021-11-16 | 福建钰辰微电子有限公司 | Silver paste for roll-to-roll production process of flexible circuit board and preparation thereof |
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| JP6043291B2 (en) * | 2010-10-28 | 2016-12-14 | ヘレウス プレシャス メタルズ ノース アメリカ コンショホーケン エルエルシー | Solar cell metallization materials containing metal additives |
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