CN102855961B - 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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- CN102855961B CN102855961B CN201210305089.3A CN201210305089A CN102855961B CN 102855961 B CN102855961 B CN 102855961B CN 201210305089 A CN201210305089 A CN 201210305089A CN 102855961 B CN102855961 B CN 102855961B
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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 photoelectric conversion efficiency of solar cell, monocrystaline silicon solar cell large-scale production is at present close to 18.5%; the impact of solar battery electrode slurry on photoelectric conversion efficiency also increases gradually; especially the kind of solar cell front side silver paste is constantly updated; sintering temperature optimum range constantly changes, and serves conclusive effect to the raising of solar battery efficiency.Now, the sintering condition of back electrode of solar cell aluminium paste seems extremely important with cooperatively interacting of front side silver paste.
Determine that the biggest factor of 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 DEG C.Meanwhile, the softening point of General Requirements glass dust must lower than the temperature spot 577 DEG C degree of alusil alloy formation.Also Just because of this, the thermal characteristics of common aluminium paste in sintering process is very single, little to the adaptability of sintering curre change.In actual applications, for different silver slurry, the change of sintering condition is also very large, and the sintering condition which results in silver slurry is inconsistent with the optimum sintering condition of aluminium paste.Therefore, while guarantee silver electrode excellent in performance, the impact on aluminium electrode performance to be reduced as far as possible, need to provide the aluminum electrode slurry that can adapt to different silver electrode sintering conditions, sharpest edges could be obtained in whole efficiency like this.Meanwhile, after electrode sintering, the stress of silicon chip is bending have also been obtained maximum reduction.
Summary of the invention
It is very single that first problem to be solved by this invention is to overcome common aluminium paste thermal characteristics in prior art, to problems such as the adaptability of sintering curre change are little, provides a kind of rear surface of solar cell paste for electrode forming being applicable to ultra-wide sintering range.
Another technical problem to be solved by this invention is the preparation method providing a kind of rear surface of solar cell paste for electrode forming.
In order to solve these problems of the prior art, in first, technical scheme provided by the invention is: rear surface of solar cell paste for electrode forming, comprise aluminium powder, organic carrier, unorganic glass powder and functional additive, described unorganic glass powder comprises the middle softening point glass dust that softening point is 400 ~ 550 DEG C, it is characterized in that, described unorganic glass powder also comprises the glass dust of 370 DEG C ~ 400 and 550 ~ 590 DEG C of softening points.
Preferably, the consisting of of described unorganic glass powder:
1. softening point is the low softening point glass dust of 370 ~ 400 DEG C, accounts for glass dust mass percent 0.5 ~ 10%;
2. softening point is the middle softening point glass dust of 400 ~ 550 DEG C, accounts for glass dust mass percent 80% ~ 98%;
3. softening point is 550 ~ 590 DEG C 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 the low softening point glass dust of 370 ~ 400 DEG C, accounts for glass dust mass percent 3%-6%;
2. softening point is the middle softening point glass dust of 400 ~ 550 DEG C, accounts for glass dust mass percent 80% ~ 98%;
3. softening point is the high softening-point glass dust of 550 ~ 590 DEG C, accounts for glass dust content mass percent 3%-6%.
Preferably, described slurry comprise the aluminium powder of mass percent 70-85%, the organic carrier of 14-24%, the unorganic glass powder of 0.2 ~ 6% and 0.5 ~ 1% functional additive.
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 is 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, and 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
3one or both in P series glass, and small amounts thing additive; 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 be selected from ethyl cellulose, acrylic resin, NC Nitroncellulose, phenolic resins one or more; 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 solvent such as the polymer such as cellulose family and resinae and alcohols, ethers, lipid.Main Function is the printing performance regulating described slurry, improves the film forming of electrode slurry.Described organic carrier is mixed by the polymer of mass percent 5 ~ 20% and the organic solvent of 80 ~ 95%.
Preferably, described functional additive is selected from one or more in surfactant, thixotropic agent, sintering aids, sticky net preventing agent, dispersant and defoamer.
Glass dust containing mass percent 0.2 ~ 6% in electrode of solar battery formation slurry of the present invention, and this glass dust is made up of the glass dust of multiple softening point, greatly widen the softening range of glass dust, segment glass powder can both be had when sintering temperature is too high or too low to work.In the glass dust design of routine, because the formation initial temperature of alusil alloy is at 577 DEG C, therefore require that the softening point temperature of glass dust will well below 577 DEG C, generally below 550 DEG C.But, we find, peak temperature during sintering generally can more than 700 DEG C, because the effect of glass dust is not only in aluminium silicon forming surface, but also act directly between aluminum particle, a small amount of interpolation softening point close to or the glass dust of a little higher than alusil alloy formation temperature, when higher temperature can be avoided sinter, glass dust softens rear excessive infiltration aluminium powder and silicon chip and the bending increase of silicon chip that causes.On the other hand, because organic resin between 300 ~ 400 DEG C will volatilize completely during conventional glass frit design, therefore glass dust softening point is generally not less than 400 degree.But, we find the glass dust of the unusual low softening point (370 ~ 400 DEG C) of suitable interpolation, can't affect the volatilization of organic carrier, and due to addition considerably less, the pre-invasion to aluminium powder and silicon chip in sintering process can be ensured, be conducive to final battery performance.
In the present invention, the low softening point in glass dust and high softening-point glass dust play to widening of sintering condition the effect of supplying.Low softening point glass dust accounts for glass dust content mass percent 0.5 ~ 10%, if if its mass percent is too much, is greater than 10%, then glass melting liquid overall viscosity can be caused too low, increase the rear silicon chip degree of crook of sintering, electrode silicon chip contact resistance increases; If low softening point glass dust does not contain or amount is too low, then when under the sintering condition that electrode sintering temperature reduces or sintering furnace belt speed is accelerated, glass dust cementation can not be not fully exerted, 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%.In glass dust, the middle softening point glass dust of mass percent 80 ~ 98%, softening point 400 ~ 550 DEG C plays the effect of normal inorganic binder.Secondly, the high softening-point glass dust in glass dust, accounts for glass dust content mass percent 0.5 ~ 10%; High softening-point glass dust is in order to need the sintering condition of higher temperature to add when coordinating some silver electrode paste to sinter, when its content is too low, then do not have the effect of expanding sintering range, too high levels, such as be greater than 10%, can cause in sintering process and melt not exclusively, the residual conductivity too much affecting electrode film; General preferable range is between 3-6%.
Simultaneously, the feature of electrode of solar battery formation slurry of the present invention is also in three described kind glass dust, high softening-point glass dust, its average grain diameter must below 1.5 microns (preferable range is at 0.4 ~ 1.5 micron), and maximum gauge must be less than 2.5 microns.Low softening point and middle softening point glass dust, its average grain diameter can below 3.5 microns (preferable range 1 ~ 2.5 micron).Wherein average grain diameter can be single, also can be different multiple mixing.
In 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 are heated to 60-90 DEG C, until dissolution of polymer, form clear viscous liquids, obtain organic carrier;
(2) put into mixer after aluminium powder and glass dust being mixed in proportion, add aforesaid organic carrier, and functional additive stirs in advance;
(3) mixed material after above-mentioned stirring is ground on grinder, obtain finely dispersed slurry, then carry out vacuum defoamation process, slurry fineness <15 μm, viscosity 3.5 ~ 4.5 ten thousand mPa.s;
(4) after 650 ~ 800 DEG C of high temperature sinterings, formation bending stress is low, same substrate compact solar battery back aluminium electrode.
In the present invention, term " aluminium powder ", its grain shape is spherical or closely spherical, aluminium powder purity >=99.97%, and mixed by aluminium powder that is a kind of, two or more average grain diameter and form, the preferable range of its average grain diameter is at 1 ~ 10 micron.
In the present invention, term " high softening-point glass dust ", refers to that softening point is the glass dust of 550 ~ 590 DEG C.
In the present invention, term " middle softening point glass dust ", refers to that softening point is the glass dust of 400 ~ 550 DEG C.
In the present invention, term " low softening point glass dust ", refers to that softening point is the glass dust of 370 DEG C-400 DEG C.
Relative to scheme of the prior art, advantage of the present invention is:
1. electrode of solar battery formation slurry of the present invention, do not affect slurry thermal characteristic when ordinary sinter, avoid glass solution interface aggregates that low softening point glass dust too much causes, shortcoming that silicon chip stress increases, also avoid the disadvantage of the not enough skewness of glass dust melting that high softening-point glass dust too much causes simultaneously, to the sintering condition adaptability improving aluminium paste, to the matching improved with front silver electrode paste, finally to raising battery electrical property, open circuit voltage, photoelectric conversion efficiency, and suppress that silicon chip is bending serves positive role.
2. slurry of the present invention can adapt to different sintering conditions, especially has the high-temperature region sintering range of non-constant width, and the sintering with multiple silver slurry all has optimum Match characteristic, ensures the stability of battery conversion efficiency.
3. slurry of the present invention can fully form back surface field effect (BSF) required by solar cell with silicon substrate, there is open circuit voltage and photoelectric conversion efficiency is high, conductivity is good, contact resistance is low, the stress of silicon chip bends little, to silicon chip adhesion-tight feature, 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 embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Material source or source: aluminium powder is common commercially available prod, can purchased from ocean Aluminum, Anshan Aluminum, the aluminium powder of Kingsoft Aluminum etc.In the present embodiment, high softening-point glass dust used, middle softening point glass dust and low softening point glass dust are ordered from Xi'an Wanda's photoelectricity, also can from Red Star electronics, and the companies such as Kunshan English Fitow photoelectricity and Foshan Dong Gu order.In the present embodiment, the material such as polymer used and organic solvent is common commercially available prod.
Embodiment
The 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
By the average grain diameter of mass percent 1% be 0.91 μm of spherical aluminium powder and 95% average grain diameter be the spherical aluminium powder Homogeneous phase mixing of 6.12 μm, manufacture 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 70-90 degree, and cellulose and resin are dissolved completely, forms transparent organic carrier B
Glass dust 1-C
Glass dust composition selects B
2o
3-SiO
2-PbO P series glass powder.The softening point of glass dust can control by regulating the proportioning of each component and the content of trace element in composition.The glass dust of the basic, normal, high softening point used in this patent proposes softening point and size distribution requirements by us, entrusts specialized factory to be prepared.The average fineness of various types of glass dust is 1.9 μm.The set-up procedure of glass dust C is as follows: by the glass dust of the softening point 395 DEG C of mass percent 6%, the glass dust of mass percent 88% softening point 495 DEG C, and the glass dust Homogeneous phase mixing of the softening point 555 DEG C of mass percent 6%, formed and manufacture electrode of solar battery formation slurry glass dust 1-C.
Get electrode of solar battery by mass percentage 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 preparation material, is then less than 15m by the mixing one-tenth fineness of three-roll grinder, 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
By the average grain diameter of mass percent 1% be 0.91 μm of spherical aluminium powder and 95% average grain diameter be the spherical aluminium powder Homogeneous phase mixing of 6.12 μm, manufacture 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 70-90 degree, and cellulose and resin are dissolved completely, forms transparent organic carrier F.
3. glass dust 2-C
Glass dust composition selects B
2o
3-SiO
2-PbO P series glass powder.The softening point of glass dust can control by regulating the proportioning of each component and the content of trace element in composition.The glass dust of the basic, normal, high softening point used in this patent proposes softening point and size distribution requirements by us, entrusts specialized factory to be prepared.The average fineness of various types of glass dust is 1.9 μm.The set-up procedure of glass dust C is as follows: by the glass dust of the softening point 370 DEG C of mass percent 3%, the glass dust of mass percent 94% softening point 495 DEG C, and the glass dust Homogeneous phase mixing of the softening point 590 DEG C of mass percent 3%, formed and manufacture electrode of solar battery formation slurry glass dust 2-C.
Get electrode of solar battery by mass percentage 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 preparation material, is then less than 15 μm by the mixing one-tenth fineness of three-roll grinder, the paste for electrode forming of viscosity 3.5 ~ 4.5 ten thousand mPas.
Reference examples
Adopt average fineness to be 1.9 μm, softening point is the single softening point glass dust of 495 DEG C.The each composition of all the other slurries and preparation method are with embodiment 1.
Above-mentioned the electrode obtained formation slurry is passed through silk screen printing, the monocrystalline silicon substrate (thickness about 180 microns) of specification 125mmx125mm two sides making herbs into wool forms electrode film, and try out on a production line, print thickness is every sheet slurry 0.8g, enter continuous tunnel furnace to dry, temperature 200 DEG C.After drying, aluminum film electrode is without obscission, then changes another side printing front side silver paste, dries laggard continuous tunnel furnace sintering.Often kind of aluminum electrode slurry carries out three contrast tests, and the peak temperature of sintering is respectively 740 DEG C, 760 DEG C, and 780 DEG C, front silver electrode paste all adopts same commodity.Electrical property, substrate camber, electrodes and outward appearance is measured after coming out of the stove.The properties mean value measured is as shown in table 1.
As shown in table 1, performance comparison with the solar cell formation aluminum slurry not adopting multiple softening point glass dust to mix can find, under suitable sintering temperature, aluminum electrode slurry can obtain an extraordinary photoelectric conversion efficiency substantially, more than 18.02%.But, for the aluminium paste not adopting multiple softening point glass to mix, when sintering temperature significantly off-target value time, photoelectric conversion efficiency decline amplitude maximum.Although silver slurry plays larger effect affecting on conversion efficiency of solar cell, the result of table 1 still can be found out, have employed the aluminum electrode slurry of the basic, normal, high softening point glass mixing that this patent proposes, although conversion efficiency declines to some extent, but fall is reduced, illustrate that the slurry that this patent proposes has with powerful sintering condition adaptability.
In addition, the aluminium electrodes Apparently in Good Order& Condition that the electrode slurry that patent of the present invention proposes is formed, flexibility is very low, embodies very excellent electrical property and mechanical performance simultaneously.
Above-mentioned example, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to Spirit Essence of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (8)
1.
rear surface of solar cell paste for electrode forming, comprise aluminium powder, organic carrier, unorganic glass powder and functional additive, described unorganic glass powder comprises the middle softening point glass dust that softening point is 400 ~ 550 DEG C, it is characterized in that, described unorganic glass powder also comprises the glass dust of 370 DEG C ~ 400 and 550 ~ 590 DEG C of softening points; Wherein, the consisting of of described unorganic glass powder:
1. softening point is the low softening point glass dust of 370 ~ 400 DEG C, accounts for glass dust mass percent 0.5 ~ 10%;
2. softening point is the middle softening point glass dust of 400 ~ 550 DEG C, accounts for glass dust mass percent 80% ~ 98%;
3. softening point is 550 ~ 590 DEG C of high softening-point glass dust, accounts for glass dust mass percent 0.5 ~ 10%.
2.
rear surface of solar cell paste for electrode forming according to claim 1, is characterized in that, described slurry comprise the aluminium powder of mass percent 70-85%, the organic carrier of 14-24%, the unorganic glass powder of 0.2 ~ 6% and 0.5 ~ 1% functional additive.
3.
rear surface of solar cell paste for electrode forming according to claim 2, 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 is 1 ~ 2.5 micron, and maximum particle diameter is below 3.5 microns.
4.
rear surface of solar cell paste for electrode forming according to claim 3, is characterized in that, described high softening-point glass dust, and average grain diameter is 0.4 ~ 1.2 micron, and the scope of described aluminium powder average grain diameter is 1 ~ 10 micron.
5.
rear surface of solar cell paste for electrode forming according to claim 1, is characterized in that, described glass dust comprises B 2 o 3 -SiO 2 -PbO P series glass, unleaded Bi 2 o 3 -SiO 2 -ZnO-B 2 o 3 one or both in P series glass, and small amounts thing additive; Described oxide addition comprises MgO, CaO, V 2 o 5 , ZnO one or more.
6.
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 the organic solvent of 80 ~ 95%; Described polymer be selected from ethyl cellulose, acrylic resin, NC Nitroncellulose, phenolic resins one or more; Described organic solvent is selected from one or more mixing such as terpinol, carbitol, tributyl citrate, lecithin, diethylene glycol ether.
7.
rear surface of solar cell paste for electrode forming according to claim 1, is characterized in that, described functional additive be selected from surfactant, thixotropic agent, sintering aids, sticky net preventing agent, dispersant and defoamer one or more.
8.
the method of the rear surface of solar cell paste for electrode forming described in any one of preparation claim 1-7, comprises the following steps:
(1) polymer and organic solvent are mixed with organic carrier: polymer and organic solvent are mixed in proportion and are heated to 60-90 DEG C, until dissolution of polymer, form clear viscous liquids, obtain organic carrier;
(2) put into mixer after aluminium powder and glass dust being mixed in proportion, add aforesaid organic solvent, and functional additive stirs in advance;
(3) mixed material after above-mentioned stirring is ground on grinder, obtain finely dispersed slurry, then carry out vacuum defoamation process, slurry fineness <15 μm, viscosity 3.5 ~ 4.5 ten thousand mPa.s;
(4) after 650 ~ 800 DEG C of high temperature sinterings, formation bending stress is low, same substrate compact solar battery back aluminium electrode.
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| CN103559957B (en) * | 2013-09-22 | 2016-11-23 | 江苏瑞德新能源科技有限公司 | A kind of preparation method of positive silver paste |
| CN103762249B (en) * | 2013-10-16 | 2016-03-02 | 杭州正银电子材料有限公司 | Crystal silicon solar batteries back surface field passivation aluminum conductive electric slurry and preparation method |
| 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 |
| KR102007858B1 (en) * | 2017-11-06 | 2019-08-06 | 엘에스니꼬동제련 주식회사 | Electrode Paste For Solar Cell's Electrode And Solar Cell using the same |
| TWI688551B (en) * | 2018-06-25 | 2020-03-21 | 優陽材料科技股份有限公司 | Paste for forming a solar cell electrode and method for making the same, and method for making an electrode of high sheet-resistance solar cell |
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