CN106007390B - Silicon solar cell front side silver paste Nonlead glass composition and preparation method thereof - Google Patents
Silicon solar cell front side silver paste Nonlead glass composition and preparation method thereof Download PDFInfo
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- CN106007390B CN106007390B CN201610315725.9A CN201610315725A CN106007390B CN 106007390 B CN106007390 B CN 106007390B CN 201610315725 A CN201610315725 A CN 201610315725A CN 106007390 B CN106007390 B CN 106007390B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
The present invention relates to the technical fields of Nonlead glass composition, more particularly it relates to silicon solar cell front side silver paste Nonlead glass composition and preparation method thereof.On the basis of the mass percentage of the Nonlead glass composition, the Nonlead glass composition includes following components: the TeO of 30-80wt%2, the Bi of 7-25wt%2O3, the SiO of the CaO of the ZnO of 1-15wt%, 1-15wt%, 0.1-10wt%2, the B of 0-5wt%2O3, the softening temperature of the Nonlead glass composition is low, and high for adhesive force after the sintering of crystal silicon solar front side silver paste, RS is low.
Description
Technical field
The present invention relates to the technical fields of Nonlead glass composition, more particularly it relates to which silicon solar cell is just
Face silver paste Nonlead glass composition and preparation method thereof.
Background technique
It is most fast, most that solar energy power generating has become industrialized development after field of renewable energy relaying wind-power electricity generation
Big industry.Currently, the solar battery in photovoltaic power generation is still to be outshined othersOne branch of the tree is particularly thriving based on crystal-silicon solar cell, market
Share is big by 90%, and efficiency of solar cell is commercialized up to 18-19% in large area.Silver paste is the important materials of electrode of solar battery,
It is exclusively used for above silicon chip of solar cell, is covered on silica glass substrate, in solar battery by the method for silk-screen printing
Surface forms the conductive electrode of strong, the low ohm contact resistance of adhesive force, cell photoelectric high conversion efficiency.Above-mentioned slurry is mainly by silver
The raw materials such as powder, glass powder, organic carrier and modifying agent form according to a certain percentage.It is added after glass powder, can be substantially reduced
It is sintered peak temperature, so that metal powder silver is being formed silverskin after being sintered peak temperature, and the silverskin surface formed is smooth, does not play ash,
Film and silicon wafer have stronger adhesive force simultaneously.In addition, glass powder has vital influence to the bending of silicon wafer.Crystal silicon at present
Glass powder used in solar cell front side silver paste has that fusion temperature is high, softening temperature is high and adhesive force is low,
For this problem, glass powder with low melting point is widely used, however, most of such glass powder with low melting point contains lead oxide, lead pair
Human health risk is larger, can assemble in human body and cause lead poisoning.In order to preferably safeguard life for the survival of mankind
Environment living, the U.S., European Union and Japan etc. have formulated some environmental protection policies, produce to it and the electronic product of import carries out environmental protection
Limitation.The unleaded development trend for having become electronics manufacturing next step of electronic product, the light as one of clean energy resource offer
Lying prostrate solar battery also should be unleaded during the manufacturing.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of silicon solar cell front side silver paste Nonlead glass compositions
And preparation method thereof, the Nonlead glass composition softening temperature is low, for adhesive force after the sintering of crystal silicon solar front side silver paste
Height, RS are low.
In order to achieve the above-mentioned object of the invention, this invention takes following technical schemes:
Silicon solar cell front side silver paste Nonlead glass composition is contained with the quality percentage of the Nonlead glass composition
On the basis of amount, the Nonlead glass composition includes following components: the TeO of 30-80wt%2, the Bi of 7-25wt%2O3, 1-15wt%
ZnO, the SiO of the CaO of 1-15wt%, 0.1-10wt%2, the B of 0-5wt%2O3。
In one embodiment, the Nonlead glass composition further includes the additive of 1-5 wt%.
In one embodiment, the additive be lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten,
One of manganese, iron, ruthenium, cobalt, nickel, copper, tin, the metal simple-substance of cerium and gadolinium or its metal oxide or multiple combinations.
In one embodiment, the additive is Li2O、K2O、Na2One of O or multiple combinations.
In one embodiment, the partial size of the Nonlead glass composition is 0.1-3 microns.
In one embodiment, the softening temperature of the Nonlead glass composition is 350-450 DEG C.
Another object of the present invention is to provide the preparation of the silicon solar cell front side silver paste Nonlead glass composition
Method, comprising: according to the predetermined ratio, uniformly mixes, obtain mixed raw material, mixed raw material is fitted into platinum crucible,
Platinum crucible is put into heat temperature raising in high temperature box furnace again, 1100-1300 DEG C at a temperature of keep the temperature 0.5-1 hours so that
Fusant becomes homogeneous liquid completely, and is free of the raw material decomposes object of any remnants；By the homogeneous liquid pour into from
Water quenching in sub- water takes out glass particle after cooling, and is put into drying in forced air oven；By the glass particle of the drying, mill
Ball and deionized water are fitted into ball grinder and seal, and are fitted into ball mill and carry out ball milling, and after ball milling 2-5 hours, sieving filters off mill
Ball, obtains glass slurry and is put into forced air oven being dried, be sieved to get Nonlead glass composition.
In one embodiment, the temperature dried in the forced air oven is 120 DEG C.
In one embodiment, it is 120 DEG C that the glass slurry, which is put into the temperature that forced air oven is dried, the time
It is 12-24 hours.
Yet another object of that present invention is to provide the silicon solar cell front side silver paste Nonlead glass composition application
In conductive silver paste.
Compared with prior art, the invention has the benefit that Nonlead glass composition of the invention solves existing skill
It is prepared by the problems such as fusion temperature existing for lead-free glass powder is high in art, softening temperature is high and adhesive force is low and crown glass
Solar energy front side silver paste has Rs's high.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
Unless otherwise defined, all technologies used herein and scientific term have and the common skill of fields of the present invention
The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ",
" 1-3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range be intended to include its end value and
All integers and score in the range.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the quantity obviously refers to singular.
Silicon solar cell front side silver paste Nonlead glass composition is contained with the quality percentage of the Nonlead glass composition
On the basis of amount, the Nonlead glass composition includes following components: the TeO of 30-80wt%2, the Bi of 7-25wt%2O3, 1-15wt%
ZnO, the B2O3 of the SiO2 of the CaO of 1-15wt%, 0.1-10wt%, 0-5wt%.
CaO in the component of heretofore described Nonlead glass composition can use CaF2Replacement, realizes same technology
Effect.
It is preferably carried out in mode in one kind, the Nonlead glass composition further includes the additive of 1-5 wt%.
Be preferably carried out in mode in one kind, the additive be lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium,
One of molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, copper, tin, the metal simple-substance of cerium and gadolinium or its metal oxide or multiple combinations.
The additive be also possible to roasting when can generate lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese,
Iron, ruthenium, cobalt, nickel, copper, tin, cerium and gadolinium metal oxide any compound.
It is preferably carried out in mode in one kind, the additive is Li2O、K2O、Na2One of O or multiple combinations.
Li in heretofore described additive2O can be replaced with LiF, Na2O can be replaced with NaF, K2O can use KF
Replacement, realizes same technical effect.
It is preferably carried out in mode in one kind, the partial size of the Nonlead glass composition is 0.1-3 microns.
It is preferably carried out in mode in one kind, the softening temperature of the Nonlead glass composition is 350-450 DEG C.
Another object of the present invention is to provide the preparation of the silicon solar cell front side silver paste Nonlead glass composition
Method, comprising: according to the predetermined ratio, uniformly mixes, obtain mixed raw material, mixed raw material is fitted into platinum crucible,
Platinum crucible is put into heat temperature raising in high temperature box furnace again, 1100-1300 DEG C at a temperature of keep the temperature 0.5-1 hours so that
Fusant becomes homogeneous liquid completely, and is free of the raw material decomposes object of any remnants；By the homogeneous liquid pour into from
Water quenching in sub- water takes out glass particle after cooling, and is put into drying in forced air oven；By the glass particle of the drying, mill
Ball and deionized water are fitted into ball grinder and seal, and are fitted into ball mill and carry out ball milling, and after ball milling 2-5 hours, sieving filters off mill
Ball, obtains glass slurry and is put into forced air oven being dried, be sieved to get Nonlead glass composition.
It is preferably carried out in mode in one kind, the temperature dried in the forced air oven is 120 DEG C.
It is preferably carried out in mode in one kind, it is 120 that the glass slurry, which is put into the temperature that forced air oven is dried,
DEG C, the time is 12-24 hours.
Yet another object of that present invention is to provide the silicon solar cell front side silver paste Nonlead glass composition application
In conductive silver paste.
Embodiment:
Embodiment 1, silicon solar cell front side silver paste Nonlead glass composition, with the Nonlead glass composition
On the basis of mass percentage, the Nonlead glass composition includes following components: the TeO of 30-80wt%2, 7-25wt%'s
Bi2O3, the SiO of the CaO of the ZnO of 1-15wt%, 1-15wt%, 0.1-10wt%2, the B of 0-5wt%2O3。
Embodiment 2, identical as embodiment 1, different places are that the Nonlead glass composition further includes 1-5
The additive of wt%.
Embodiment 3, identical as embodiment 2, different places are, the additive be lithium, sodium, potassium, magnesium, strontium, barium,
Titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, copper, tin, cerium and gadolinium metal simple-substance or its metal oxide in
One or more combinations.
Embodiment 4, identical as embodiment 3, different places are that the additive is Li2O、K2O、Na2One in O
Kind or multiple combinations.
Embodiment 5, identical as embodiment 1, different places are that the partial size of the Nonlead glass composition is 0.1-
3 microns.
Embodiment 6, identical as embodiment 1, different places are that the softening temperature of the Nonlead glass composition is
350-450℃。
Embodiment 7, the preparation method of silicon solar cell front side silver paste Nonlead glass composition, which is characterized in that
It include: uniformly to mix, obtain mixed raw material, mixed raw material is fitted into platinum crucible according to the predetermined ratio, then by platinum
Golden crucible is put into heat temperature raising in high temperature box furnace, 1100-1300 DEG C at a temperature of keep the temperature 0.5-1 hours so that fusant
Become homogeneous liquid completely, and is free of the raw material decomposes object of any remnants；The homogeneous liquid is poured into deionized water
Water quenching takes out glass particle after cooling, and is put into drying in forced air oven；By the glass particle of the drying, abrading-ball and go
Ionized water is fitted into ball grinder and seals, and is fitted into ball mill and carries out ball milling, and after ball milling 2-5 hours, sieving filters off abrading-ball, obtains
Glass slurry is simultaneously put into forced air oven and is dried, is sieved to get Nonlead glass composition.
Embodiment 8, identical as embodiment 7, different places are that the temperature dried in the forced air oven is
120℃.Embodiment 9, identical as embodiment 7, different places are that the glass slurry is put into forced air oven and is done
Dry temperature is 120 DEG C, and the time is 12-24 hours.
Embodiment 10, the silicon solar cell front side silver paste are applied to conductive silver paste with Nonlead glass composition
In.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of foregoing invention, still fall within protection scope of the present invention.
In addition, if illustrated without other, it is raw materials used to be all commercially available.
Silicon solar cell front side silver paste Nonlead glass composition component and proportion, according to the predetermined ratio,
Even mixing, obtains mixed raw material, and mixed raw material is fitted into platinum crucible, then platinum crucible is put into high temperature box furnace and is heated
Heating, 1100-1300 DEG C at a temperature of keep the temperature 0.5-1 hour so that fusant becomes homogeneous liquid completely, and without times
What remaining raw material decomposes object；The homogeneous liquid is poured into water quenching in deionized water, takes out glass particle after cooling, and put
Enter drying in 120 DEG C of forced air ovens；The glass particle, abrading-ball and deionized water of the drying are fitted into ball grinder and close
Envelope, is fitted into ball mill and carries out ball milling, and after ball milling 2-5 hours, sieving filters off abrading-ball, obtains glass slurry and is put into 120 DEG C of drums
Wind formula baking oven is dried 12-24 hours, is sieved to get Nonlead glass composition.
First choice, sketch the basic scheme of material prescription of the present invention: silicon solar cell front side silver paste is combined with crown glass
Object, which is characterized in that on the basis of the mass percentage of the Nonlead glass composition, the Nonlead glass composition includes
Following components: the TeO of 30-80wt%2, the Bi of 7-25wt%2O3, the CaO of the ZnO of 1-15wt%, 1-15wt%, 0.1-10wt%'s
SiO2, the B of 0-5wt%2O3。
Embodiment 1-6
Silicon solar cell front side silver paste Nonlead glass composition, it is (right respectively according to No. 1-6 formula of table 1 to be formulated
Answer 1-6 embodiment), acquisition softening temperature is low after the processing of the processes such as component adjustment, melting, water quenching, drying, ball milling, sieving,
The Nonlead glass composition high, RS low for adhesive force after the sintering of crystal silicon solar front side silver paste.Crown glass described in formula
Composition further includes the additive of 1-5 wt%；The additive be lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum,
One of tungsten, manganese, iron, ruthenium, cobalt, nickel, copper, tin, the metal simple-substance of cerium and gadolinium or its metal oxide or multiple combinations；It is described
Additive is Li2O、K2O、Na2One of O or multiple combinations.
By Nonlead glass composition made from above-mentioned formula, the partial size of the Nonlead glass composition is 0.1-3 microns, soft
Changing temperature is 350-450 DEG C.Crystal silicon solar energy battery cell piece (156mm × 156mm rule are formed by silk-screen printing technique
Lattice) back electric field silver electrodes, and be tested for the property, resulting silicon solar cell is functional, and test result is shown in
Table 2.
Table 1
Table 2
Example above-mentioned is merely illustrative, some features of feature for explaining the present invention.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combined selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express it is inaccurate due to and not
The possible equivalent being presently considered or son replacement, and these variations should also be interpreted in the conceived case by appended
Claim covering.
Claims (7)
1. silicon solar cell front side silver paste Nonlead glass composition, which is characterized in that with the Nonlead glass composition
On the basis of mass percentage, the Nonlead glass composition includes following components: the TeO of 53.80wt%2, 5.98wt%'s
Bi2O3, the SiO of the CaO of the ZnO of 28.51wt%, 3.58wt%, 2.23wt%2, the B of 1.07wt%2O3, 4.46wt%'s
Li2The K of O, 0.37wt%2O。
2. silicon solar cell front side silver paste Nonlead glass composition according to claim 1, which is characterized in that described
The partial size of Nonlead glass composition is 0.1-3 microns.
3. silicon solar cell front side silver paste Nonlead glass composition according to claim 1, which is characterized in that described
The softening temperature of Nonlead glass composition is 350-450 DEG C.
4. the preparation method of the silicon solar cell front side silver paste Nonlead glass composition of claim 1, which is characterized in that packet
It includes: according to the predetermined ratio, uniformly mixing, obtain mixed raw material, mixed raw material is fitted into platinum crucible, then by platinum
Crucible is put into heat temperature raising in high temperature box furnace, 1100-1300 DEG C at a temperature of keep the temperature 0.5-1 hours so that fusant is complete
Become homogeneous liquid entirely, and is free of the raw material decomposes object of any remnants；The homogeneous liquid is poured into water in deionized water
It quenches, takes out glass particle after cooling, and be put into drying in forced air oven；By the glass particle of the drying, abrading-ball and go from
Sub- water is fitted into ball grinder and seals, and is fitted into ball mill and carries out ball milling, and after ball milling 2-5 hours, sieving filters off abrading-ball, obtains glass
Glass slurry is simultaneously put into forced air oven and is dried, is sieved to get Nonlead glass composition.
5. the preparation method of silicon solar cell front side silver paste Nonlead glass composition according to claim 4, special
Sign is that the temperature dried in the forced air oven is 120 DEG C.
6. the preparation method of silicon solar cell front side silver paste Nonlead glass composition according to claim 4, special
Sign is that the temperature that the glass slurry is put into forced air oven drying is 120 DEG C, and the time is 12-24 hours.
7. silicon solar cell front side silver paste Nonlead glass composition as claimed in any one of claims 1 to 6 is in conductive silver paste
Application in material.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10134925B2 (en) | 2016-04-13 | 2018-11-20 | E I Du Pont De Nemours And Company | Conductive paste composition and semiconductor devices made therewith |
| CN107068243A (en) * | 2017-04-21 | 2017-08-18 | 绵阳市奇帆科技有限公司 | A kind of preparation method of lead free solar front side silver paste material |
| CN108609856A (en) * | 2018-05-29 | 2018-10-02 | 北京北旭电子材料有限公司 | A kind of barium crown sealed glass, packaging system and preparation method thereof |
| CN116332520A (en) * | 2023-03-27 | 2023-06-27 | 昆明理工大学 | Leadless glass powder and preparation method and application thereof |
| CN116543947B (en) * | 2023-06-26 | 2023-10-31 | 浙江晶科新材料有限公司 | Additive of silver-aluminum paste of N-type solar cell, preparation method of additive and silver-aluminum paste |
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