CN102855961A - Paste for formation of solar cell back electrodes and preparation method thereof - Google Patents
Paste for formation of solar cell back electrodes and preparation method thereof Download PDFInfo
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- CN102855961A CN102855961A CN2012103050893A CN201210305089A CN102855961A CN 102855961 A CN102855961 A CN 102855961A CN 2012103050893 A CN2012103050893 A CN 2012103050893A CN 201210305089 A CN201210305089 A CN 201210305089A CN 102855961 A CN102855961 A CN 102855961A
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Abstract
The invention discloses a paste for the formation of solar cell back electrodes, which comprises the following components in percentage by mass: 70-85% of aluminium powder, 14-24% of organic carriers, 0.2-6% of inorganic glass powder and 0.5-1% of a functional additive, wherein the inorganic glass powder contains middle-softening-point glass powder with a softening point of 400-550 DEG C, glass powder with a softening point of 370-400 DEG C and glass powder with a softening point of 550-590 DEG C. The paste for the formation of solar cell back electrodes disclosed by the invention can adapt to different sintering conditions, especially has an extremely wide high-temperature area sintering temperature range, and has the best matching characteristics with the sintering of various silver pastes.
Description
Technical field
The present invention relates to the slurry of electrode of solar battery, be specifically related to a kind of rear surface of solar cell paste for electrode forming and preparation method thereof.
Background technology
Along with the average efficiency of the improving constantly of the photoelectric conversion efficiency of solar cell, at present monocrystaline silicon solar cell large-scale production near 18.5%; solar battery electrode slurry also increases gradually on the impact of photoelectric conversion efficiency; especially the kind of solar cell front side silver paste is constantly updated; the sintering temperature optimum range constantly changes, and conclusive effect has been played in the raising of solar battery efficiency.At this moment, the sintering condition of back electrode of solar cell aluminium paste seems extremely important with cooperatively interacting of front side silver paste.
The biggest factor that determines aluminium paste sintering process window is glass dust binding agent wherein.The back electrode slurry of silicon solar cell in the past uses the glass dust binding agent of single softening point usually, and its typical range is between 450-550 ℃.Simultaneously, the softening point of General Requirements glass dust must be lower than 577 ℃ of degree of temperature spot that alusil alloy forms.Also Just because of this, the thermal characteristics of common aluminium paste in sintering process is very single, and the adaptability that sintering curre is changed is little.In actual applications, for different silver slurries, the variation of sintering condition is also very large, and this has just caused the sintering condition of silver-colored slurry inconsistent with the optimum sintering condition of aluminium paste.Therefore, when guaranteeing the silver electrode excellent in performance, reduce as far as possible the impact on the aluminium electrode performance, the aluminum electrode slurry that can adapt to different silver electrode sintering conditions need to be provided, could obtain sharpest edges in whole efficiency like this.Simultaneously, the stress bending of silicon chip has also obtained maximum reduction behind the electrode sintering.
Summary of the invention
The problems such as it is very single that first problem to be solved by this invention is to overcome in the prior art common aluminium paste thermal characteristics, and the adaptability that sintering curre is changed is little provide a kind of rear surface of solar cell paste for electrode forming that is applicable to super wide sintering range.
Another technical problem to be solved by this invention is to provide a kind of preparation method of rear surface of solar cell paste for electrode forming.
In order to solve these problems of the prior art, aspect first, technical scheme provided by the invention is: the rear surface of solar cell paste for electrode forming, comprise aluminium powder, organic carrier, unorganic glass powder and functional additive, it is 400 ~ 550 ℃ middle softening point glass dust that described unorganic glass powder comprises softening point, it is characterized in that described unorganic glass powder also comprises the glass dust of 370 ℃ ~ 400 and 550 ~ 590 ℃ of softening points.
Preferably, consisting of of described unorganic glass powder:
1. softening point is 370 ~ 400 ℃ low softening point glass dust, accounts for glass dust mass percent 0.5 ~ 10%;
2. softening point is 400 ~ 550 ℃ middle softening point glass dust, accounts for glass dust mass percent 80% ~ 98%;
3. softening point is 550 ~ 590 ℃ of high softening-point glass dust, accounts for glass dust mass percent 0.5 ~ 10%.
Preferably, described unorganic glass powder consists of:
1. softening point is 370 ~ 400 ℃ low softening point glass dust, accounts for glass dust mass percent 3%-6%;
2. softening point is 400 ~ 550 ℃ middle softening point glass dust, accounts for glass dust mass percent 80% ~ 98%;
3. softening point is 550 ~ 590 ℃ high softening-point glass dust, accounts for glass dust content mass percent 3%-6%.
Preferably, described slurry comprises organic carrier, 0.2 ~ 6% unorganic glass powder and 0.5 ~ 1% the functional additive of aluminium powder, the 14-24% of mass percent 70-85%.
Preferably, described high softening-point glass dust, its average grain diameter is at 0.4 ~ 1.5 micron, and the largest particles diameter is less than 2.5 microns; Described middle softening point and low softening point glass dust, its average grain diameter are 1 ~ 2.5 micron, and maximum particle diameter is below 3.5 microns.
Preferably, described high softening-point glass dust, average grain diameter is 0.4 ~ 1.2 micron, the scope of described aluminium powder average grain diameter is 1 ~ 10 micron.
Preferably, described glass dust comprises B
2O
3-SiO
2-PbO P series glass, unleaded Bi
2O
3-SiO
2-ZnO-B
2O
3In the P series glass one or both, and a small amount of oxide addition; Described oxide addition comprises MgO, CaO, V
2O
5, ZnO one or more.
Preferably, described organic carrier is mixed by polymer and organic solvent; Described polymer is selected from one or more in ethyl cellulose, acrylic resin, NC Nitroncellulose, the phenolic resins; Described organic solvent is selected from one or more mixing such as terpinol, carbitol, tributyl citrate, lecithin, diethylene glycol ether.Organic carrier is the mixture of the organic solvents such as the polymer such as cellulose family and resinae and alcohols, ethers, lipid.Main Function is the printing performance of regulating described slurry, improves the film forming of electrode slurry.Described organic carrier is mixed by the polymer of mass percent 5 ~ 20% and 80 ~ 95% organic solvent.
Preferably, described functional additive is selected from one or more in surfactant, thixotropic agent, sintering aids, sticky net preventing agent, dispersant and the defoamer.
Electrode of solar battery of the present invention forms with the glass dust that contains mass percent 0.2 ~ 6% in the slurry, and this glass dust is made of the glass dust of multiple softening point, greatly widen the softening range of glass dust, when sintering temperature is too high or too low, can both have the segment glass powder to work.In the design of the glass dust of routine, because the formation initial temperature of alusil alloy at 577 ℃, therefore requires the softening point temperature of glass dust will be well below 577 ℃, generally below 550 ℃.Yet, we find, peak temperature during sintering generally can be more than 700 ℃, because the effect of glass dust is not only on aluminium silicon formation face, but also act directly between the aluminum particle, a small amount of add that softening point approaches or the glass dust of a little higher than alusil alloy formation temperature, glass dust excessively infiltrates aluminium powder and silicon chip after softening and crooked increase of silicon chip that cause in the time of can avoiding the higher temperature sintering.On the other hand, during the design of conventional glass dust since between 300 ~ 400 ℃ organic resin will volatilize fully, so the glass dust softening point generally is not less than 400 degree.Yet, we find the very glass dust of low softening point (370 ~ 400 ℃) of suitable interpolation, can't affect the volatilization of organic carrier, and because addition is considerably less, can guarantee in sintering process the pre-infiltration of aluminium powder and silicon chip is conducive to final battery performance.
Among the present invention, the low softening point in the glass dust and high softening-point glass dust will play the effect of supplying to widening of sintering condition.Low softening point glass dust accounts for glass dust content mass percent 0.5 ~ 10%, if if its mass percent is too much, greater than 10%, then can cause glass melting liquid overall viscosity excessively low, and silicon chip degree of crook behind the increase sintering, electrode silicon chip contact resistance increases; If low softening point glass dust does not contain or amount is excessively low, then under the sintering condition that the electrode sintering temperature reduces or the sintering furnace belt speed is accelerated, the glass dust cementation can not be not fully exerted, the aluminum back electrode hydraulic performance decline; Consider, described low-melting glass powder content changes in mass percent 0.5 ~ 10% scope, preferable range 3 ~ 6%.The middle softening point glass dust that mass percent 80 ~ 98% in the glass dust, softening point are 400 ~ 550 ℃ plays the effect of normal inorganic binder.Secondly, the high softening-point glass dust in the glass dust accounts for glass dust content mass percent 0.5 ~ 10%; High softening-point glass dust needs the sintering condition of higher temperature to add when cooperating some silver electrode paste sintering, when its content excessively low, then do not have the effect of expanding sintering range, too high levels, for example greater than 10%, in sintering process, can cause and melt not exclusively the residual too much conductivity that affects electrode film; General preferable range is between 3-6%.
Simultaneously, the feature that electrode of solar battery of the present invention forms with slurry also is in the described three kind glass dust, high softening-point glass dust, its average grain diameter must be at (preferable range be at 0.4 ~ 1.5 micron) below 1.5 microns, and maximum gauge must be less than 2.5 microns.Low softening point and middle softening point glass dust, its average grain diameter can be in (1 ~ 2.5 micron of preferable range) below 3.5 microns.Wherein average grain diameter can be single, also can be different multiple mixing.
Aspect second, the invention provides the preparation method of rear surface of solar cell paste for electrode forming, it is characterized in that, said method comprising the steps of:
(1) polymer and organic solvent are mixed with organic carrier: polymer and organic carrier are mixed in proportion and be heated to 60-90 ℃, until polymer dissolution forms transparent thick liquid, obtain organic carrier;
(2) put into mixer after aluminium powder and glass dust are mixed in proportion, add aforesaid organic carrier, and functional additive stirs in advance;
(3) mixed material after the above-mentioned stirring is ground at grinder, obtain finely dispersed slurry, then carry out vacuum defoamation and process slurry fineness＜15 μ m, viscosity 3.5 ~ 4.5 ten thousand mPa.s;
(4) through behind 650 ~ 800 ℃ of high temperature sinterings, form low, the compact solar battery back aluminium of the same substrate electrode of bending stress.
Among the present invention, term " aluminium powder ", its grain shape is spherical or closely spherical, and aluminium powder purity 〉=99.97% is made of aluminium powder mixing a kind of, two or more average grain diameter, and the preferable range of its average grain diameter is at 1 ~ 10 micron.
Among the present invention, term " high softening-point glass dust " refers to that softening point is 550 ~ 590 ℃ glass dust.
Among the present invention, term " middle softening point glass dust " refers to that softening point is 400 ~ 550 ℃ glass dust.
Among the present invention, term " low softening point glass dust " refers to that softening point is 370 ℃-400 ℃ glass dust.
With respect to scheme of the prior art, advantage of the present invention is:
1. electrode of solar battery of the present invention forms and uses slurry, slurry thermal characteristic when not affecting ordinary sinter, the shortcoming that assemble at the glass solution interface, silicon chip stress increases of having avoided low softening point glass dust too much to cause, also avoided simultaneously the disadvantage of the not enough skewness of glass dust melting that high softening-point glass dust too much causes, to improving the sintering condition adaptability of aluminium paste, to improving the matching with the front silver electrode paste, finally to improving battery electrical property, open circuit voltage, photoelectric conversion efficiency, and suppress the silicon chip bending and played positive role.
2. slurry of the present invention can adapt to different sintering conditions, and the high-temperature region sintering range of non-constant width is especially arranged, and the sintering of starching with multiple silver all has the optimum Match characteristic, guarantees the stability of battery conversion efficiency.
3. slurry of the present invention can fully form the desired back surface field effect of solar cell (BSF) with silicon substrate, have that open circuit voltage and photoelectric conversion efficiency are high, conductivity is good, contact resistance is low, the stress bending of silicon chip is little, to the characteristics of silicon chip adhesion-tight, aluminium electrode film smooth surface, non-foaming, do not fall ash, do not play aluminium pill.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Material source or source: aluminium powder is common commercially available prod, can be available from the ocean Aluminum, and Anshan Aluminum, the aluminium powder of Kingsoft Aluminum etc.Used high softening-point glass dust, middle softening point glass dust and low softening point glass dust are ordered from Xi'an Wanda's photoelectricity in the present embodiment, also can be from the Red Star electronics, and the companies such as Kunshan English Fitow photoelectricity and Foshan Dong Gu order.The materials such as used polymer and organic solvent are common commercially available prod in the present embodiment.
Embodiment
Present embodiment describes composition and the preparation method of electrode slurry of the present invention in detail.Following embodiment is used for example the present invention, and scope of the present invention is not limited to following embodiment.
Embodiment 1: electrode of solar battery forms slurry
Aluminium powder 1-A
Be the spherical aluminium powder of 0.91 μ m with 95% average grain diameter with the average grain diameter of mass percent 1% be that the spherical aluminium powder of 6.12 μ m evenly mixes, make electrode of solar battery and form slurry aluminium powder A, aluminium powder purity 99.97%
Organic carrier 1-B
According to mass percent ethyl cellulose 2.5%, resin 2%, terpinol 60%, diethylene glycol dimethyl ether 20%, butyl carbitol acetate 14.5%, lecithin 1% mixes, and is heated to the 70-90 degree, and cellulose and resin are dissolved fully, forms transparent organic carrier B
Glass dust 1-C
Glass dust forms selects B
2O
3-SiO
2-PbO P series glass powder.The softening point of glass dust can be controlled by proportioning and the micro-content of regulating each component in the composition.The glass dust of the basic, normal, high softening point that uses in this patent proposes softening point and particle size distribution requirement by us, entrusts specialized factory to be prepared.The average fineness of various types of glass dust is 1.9 μ m.The set-up procedure of glass dust C is as follows: with the glass dust of 395 ℃ of the softening points of mass percent 6%, the glass dust that mass percent 88% softening point is 495 ℃, and the glass dust of 555 ℃ of the softening points of mass percent 6% evenly mixes, and forms to make electrode of solar battery and form slurry glass dust 1-C.
Get by mass percentage electrode of solar battery and form slurry aluminium powder 1-A77.5%, organic carrier 1-B19.5%, glass dust 1-C1.5%, and thixotropic agent 0.5%, defoamer 0.5%, dispersant 0.5% adds stirrer for mixing and becomes the preparation material, then uses the mixing one-tenth fineness of three-roll grinder less than 15m, the paste for electrode forming of viscosity 3.5 ~ 4.5 ten thousand mPas.
Embodiment 2
Electrode of solar battery forms slurry aluminium powder 2-A
Be the spherical aluminium powder of 0.91 μ m with 95% average grain diameter with the average grain diameter of mass percent 1% be that the spherical aluminium powder of 6.12 μ m evenly mixes, make electrode of solar battery and form slurry aluminium powder A, aluminium powder purity 99.97%.
2. organic carrier 2-B
According to mass percent ethyl cellulose 2.5%, resin 2%, terpinol 60%, diethylene glycol dimethyl ether 20%, butyl carbitol acetate 14.5%, lecithin 1% mixes, and is heated to the 70-90 degree, and cellulose and resin are dissolved fully, forms transparent organic carrier F.
3. glass dust 2-C
Glass dust forms selects B
2O
3-SiO
2-PbO P series glass powder.The softening point of glass dust can be controlled by proportioning and the micro-content of regulating each component in the composition.The glass dust of the basic, normal, high softening point that uses in this patent proposes softening point and particle size distribution requirement by us, entrusts specialized factory to be prepared.The average fineness of various types of glass dust is 1.9 μ m.The set-up procedure of glass dust C is as follows: with the glass dust of 370 ℃ of the softening points of mass percent 3%, the glass dust that mass percent 94% softening point is 495 ℃, and the glass dust of 590 ℃ of the softening points of mass percent 3% evenly mixes, and forms to make electrode of solar battery and form slurry glass dust 2-C.
Get by mass percentage electrode of solar battery and form slurry aluminium powder 2-A77.5%, organic carrier 2-B19.5%, glass dust 2-C1.5%, and thixotropic agent 0.5%, defoamer 0.5%, dispersant 0.5% adds stirrer for mixing and becomes the preparation material, then uses the mixing one-tenth fineness of three-roll grinder less than 15 μ m, the paste for electrode forming of viscosity 3.5 ~ 4.5 ten thousand mPas.
Reference examples
Adopting average fineness is 1.9 μ m, and softening point is 495 ℃ single softening point glass dust.Each composition of all the other slurries and preparation method are with embodiment 1.
Above-mentioned the electrode obtained is formed with slurry by silk screen printing, monocrystalline silicon substrate (about 180 microns of thickness) in specification 125mmx125mm two sides making herbs into wool forms electrode film, tries out at production line, and print thickness is every and uses slurry 0.8g, advance the continuous tunnel furnace oven dry, 200 ℃ of temperature.Then aluminum film electrode changes another side printing front side silver paste without obscission after the oven dry, dries laggard continuous tunnel furnace sintering.Every kind of aluminum electrode slurry carries out contrast test three times, and the peak temperature of sintering is respectively 740 ℃, and 760 ℃, and 780 ℃, the front silver electrode paste all adopts same commodity.Come out of the stove rear measurement electrical property, substrate flexibility, electrodes and outward appearance.The properties mean value of measuring is as shown in table 1.
As shown in table 1, can find with the performance comparison of aluminum slurry with the solar cell formation of not adopting multiple softening point glass dust to mix, under suitable sintering temperature, aluminum electrode slurry can obtain an extraordinary photoelectric conversion efficiency substantially, more than 18.02%.Yet for the aluminium paste that does not adopt multiple softening point glass to mix, in the time of the significant off-target value of sintering temperature, the amplitude that photoelectric conversion efficiency descends is maximum.Although silver slurry has play a part larger affecting conversion efficiency of solar cell, the result of table 1 still can find out, the aluminum electrode slurry that the basic, normal, high softening point glass that has adopted this patent to propose mixes, although conversion efficiency descends to some extent, but fall is reduced, and illustrates that the slurry that this patent proposes has with powerful sintering condition adaptability.
In addition, the aluminium electrode electrode surface that the electrode slurry that patent of the present invention proposes forms in order, flexibility is very low, has embodied simultaneously very excellent electrical property and mechanical performance.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with technique can understand content of the present invention and according to this enforcement, can not limit protection scope of the present invention with this.All equivalent transformations that Spirit Essence is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (10)
1. rear surface of solar cell paste for electrode forming, comprise aluminium powder, organic carrier, unorganic glass powder and functional additive, it is 400 ~ 550 ℃ middle softening point glass dust that described unorganic glass powder comprises softening point, it is characterized in that described unorganic glass powder also comprises the glass dust of 370 ℃ ~ 400 and 550 ~ 590 ℃ of softening points.
2. rear surface of solar cell paste for electrode forming according to claim 1 is characterized in that, the consisting of of described unorganic glass powder:
1. softening point is 370 ~ 400 ℃ low softening point glass dust, accounts for glass dust mass percent 0.5 ~ 10%;
2. softening point is 400 ~ 550 ℃ middle softening point glass dust, accounts for glass dust mass percent 80% ~ 98%;
3. softening point is 550 ~ 590 ℃ of high softening-point glass dust, accounts for glass dust mass percent 0.5 ~ 10%.
3. rear surface of solar cell paste for electrode forming according to claim 2 is characterized in that, the consisting of of described unorganic glass powder:
1. softening point is 370 ~ 400 ℃ low softening point glass dust, accounts for glass dust mass percent 3%-6%;
2. softening point is 400 ~ 550 ℃ middle softening point glass dust, accounts for glass dust mass percent 80% ~ 98%;
3. softening point is 550 ~ 590 ℃ high softening-point glass dust, accounts for glass dust content mass percent 3%-6%.
4. each described rear surface of solar cell paste for electrode forming according to claim 1-3, it is characterized in that described slurry comprises organic carrier, 0.2 ~ 6% unorganic glass powder and 0.5 ~ 1% the functional additive of aluminium powder, the 14-24% of mass percent 70-85%.
5. rear surface of solar cell paste for electrode forming according to claim 4 is characterized in that, described high softening-point glass dust, and its average grain diameter is at 0.4 ~ 1.5 micron, and the largest particles diameter is less than 2.5 microns; Described middle softening point and low softening point glass dust, its average grain diameter are 1 ~ 2.5 micron, and maximum particle diameter is below 3.5 microns.
6. rear surface of solar cell paste for electrode forming according to claim 4 is characterized in that, described high softening-point glass dust, and average grain diameter is 0.4 ~ 1.2 micron, the scope of described aluminium powder average grain diameter is 1 ~ 10 micron.
7. rear surface of solar cell paste for electrode forming according to claim 1 is characterized in that, described glass dust comprises B
2O
3-SiO
2-PbO P series glass, unleaded Bi
2O
3-SiO
2-ZnO-B
2O
3In the P series glass one or both, and a small amount of oxide addition; Described oxide addition comprises MgO, CaO, V
2O
5, ZnO one or more.
8. rear surface of solar cell paste for electrode forming according to claim 1 is characterized in that, described organic carrier is mixed by the polymer of mass percent 5 ~ 20% and 80 ~ 95% organic solvent; Described polymer is selected from one or more in ethyl cellulose, acrylic resin, NC Nitroncellulose, the phenolic resins; Described organic solvent is selected from one or more mixing such as terpinol, carbitol, tributyl citrate, lecithin, diethylene glycol ether.
9. rear surface of solar cell paste for electrode forming according to claim 1 is characterized in that, described functional additive is selected from one or more in surfactant, thixotropic agent, sintering aids, sticky net preventing agent, dispersant and the defoamer.
10. prepare the method for the described rear surface of solar cell paste for electrode forming of claim 1-9, may further comprise the steps:
(1) polymer and organic solvent are mixed with organic carrier: polymer and organic carrier are mixed in proportion and be heated to 60-90 ℃, until polymer dissolution forms transparent thick liquid, obtain organic carrier;
(2) put into mixer after aluminium powder and glass dust are mixed in proportion, add aforesaid organic carrier, and functional additive stirs in advance;
(3) mixed material after the above-mentioned stirring is ground at grinder, obtain finely dispersed slurry, then carry out vacuum defoamation and process slurry fineness＜15 μ m, viscosity 3.5 ~ 4.5 ten thousand mPa.s;
(4) through behind 650 ~ 800 ℃ of high temperature sinterings, form low, the compact solar battery back aluminium of the same substrate electrode of bending stress.
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| CN106328726B (en) * | 2016-08-30 | 2018-06-29 | 南通天盛新能源股份有限公司 | High-efficiency crystal silicon solar battery local contact back field aluminum paste of two sides light and preparation method thereof |
| CN106847366A (en) * | 2017-01-18 | 2017-06-13 | 广州市儒兴科技开发有限公司 | A kind of electrical crystal silicon solar battery back aluminum slurry high and preparation method thereof |
| CN111557036A (en) * | 2017-11-06 | 2020-08-18 | LS-Nikko铜制炼株式会社 | Conductive paste for solar cell electrode and solar cell manufactured using same |
| CN110634618A (en) * | 2018-06-25 | 2019-12-31 | 优阳材料科技股份有限公司 | Method for manufacturing solar cell electrode, conductive paste and method for manufacturing conductive paste |
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Effective date of registration: 20210210 Address after: Suzhou Research Institute of Xi'an Jiaotong University, No.7, Xionghua Road, Tangqiao town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee after: Zhangjiagang Boyou Photoelectric Technology Co.,Ltd. Address before: No. 99, benevolent Road, Suzhou Industrial Park, Jiangsu Province Patentee before: XI'AN JIAOTONG University SUZHOU ACADEMY |