CN106007390A - Lead-free glass composition for silicon solar cell front silver paste and preparation method thereof - Google Patents
Lead-free glass composition for silicon solar cell front silver paste and preparation method thereof Download PDFInfo
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- CN106007390A CN106007390A CN201610315725.9A CN201610315725A CN106007390A CN 106007390 A CN106007390 A CN 106007390A CN 201610315725 A CN201610315725 A CN 201610315725A CN 106007390 A CN106007390 A CN 106007390A
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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 invention relates to the technical field of lead-free glass compositions, in particular to a lead-free glass composition for silicon solar cell front silver paste and a preparation method thereof. The lead-free glass composition is prepared from, by mass, 30-80%wt% of TeO2, 7-25wt% of Bi2O3, 1-15wt% of ZnO, 1-15wt% of CaO, 0.1-10wt% of SiO2 and 0-5wt% of B2O3. The lead-free glass composition is low in softening temperature, and is high in adhesive force and low in RS after being used for crystalline silicon solar cell front silver paste and sintered.
Description
Technical field
The present invention relates to the technical field of Nonlead glass composition, more particularly it relates to silicon solar cell front side silver paste Nonlead glass composition and preparation method thereof.
Background technology
Solar energy power generating has become as the industry that after field of renewable energy relays wind-power electricity generation, industrialized development is the fastest, maximum.At present, the solaode in photovoltaic generation remains based on crystal-silicon solar cell, outshines othersOne branch of the tree is particularly thriving, the market share big 90%, and large area commercialization efficiency of solar cell is up to 18-19%.Silver slurry is the important materials of electrode of solar battery, it is exclusively used for above silicon chip of solar cell by the method for silk screen printing, covering on silica glass substrate, the conductive electrode of low ohm contact resistance strong at solar cell surface formation adhesive force, cell photoelectric conversion efficiency is high.Above-mentioned slurry is mainly made up of according to a certain percentage raw materials such as argentum powder, glass dust, organic carrier and modifying agent.Add after glass dust, can substantially reduce sintering peak temperature, make metal powder silver form silverskin after sintered peak temperature, and formed silverskin smooth surface, do not play ash, film and silicon chip have stronger adhesive force simultaneously.Additionally, glass dust has vital impact to the bending of silicon chip.There is the problem that fusion temperature is high, softening temperature is high and adhesive force is low in the glass dust used in crystal silicon solar batteries front side silver paste at present, for this problem, glass powder with low melting point is widely used, but, these type of glass powder with low melting point great majority contain lead oxide, lead is bigger to human health risk, it is possible to assembles in human body and causes lead poisoning.In order to preferably safeguard the living environment that the mankind depend on for existence, the U.S., European Union and Japan etc. have all formulated some environmental protection policies, produce it and the electronic product of import carries out environmental protection restriction.Electronic product is unleaded has become next step development trend of electronics manufacturing, and the photovoltaic solar cell as one of clean energy resource offer also should be unleaded during 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 composition and preparation method thereof, and described Nonlead glass composition softening temperature is low, and high for crystal silicon solar front side silver paste sintering postadhesion power, RS is low.
In order to realize foregoing invention purpose, this invention takes techniques below scheme:
Silicon solar cell front side silver paste Nonlead glass composition, on the basis of the weight/mass percentage composition of described Nonlead glass composition, described Nonlead glass composition comprises the TeO of following components: 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。
In one embodiment, described Nonlead glass composition also includes the additive of 1-5 wt%.
In one embodiment, one or more combinations during described additive is the metal simple-substance of lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, ferrum, ruthenium, cobalt, nickel, copper, stannum, cerium and gadolinium or its metal-oxide.
In one embodiment, described additive is Li2O、K2O、Na2One or more combinations in O.
In one embodiment, the particle diameter of described Nonlead glass composition is 0.1-3 micron.
In one embodiment, the softening temperature of described Nonlead glass composition is 350-450 DEG C.
Another object of the present invention is to provide the preparation method of described silicon solar cell front side silver paste Nonlead glass composition, including: according to described predetermined ratio, uniformly mixing, obtain mixing raw material, mixing raw material is loaded in platinum crucible, then platinum crucible is put into heat temperature raising in high temperature box furnace, at a temperature of 1100-1300 DEG C, be incubated 0.5-1 hour, fused mass is made to become homogeneous liquid, and the raw material analyte without any remnants completely；Pour described homogeneous liquid in deionized water shrend, take out glass particle after cooling, and put into forced air oven drying；The glass particle of described drying, abrading-ball and deionized water are loaded in ball grinder and seals, loading in ball mill and carry out ball milling, ball milling is after 2-5 hour, and sieve elimination abrading-ball, obtain glass slip and put into forced air oven and be dried, sieve, obtaining Nonlead glass composition.
In one embodiment, the temperature dried in described forced air oven is 120 DEG C.
In one embodiment, it is 120 DEG C that described glass slip puts into the temperature that forced air oven is dried, and the time is 12-24 hour.
Another object of the present invention is to provide described silicon solar cell front side silver paste Nonlead glass composition to be applied in conductive silver paste.
Compared with prior art, the invention have the benefit that the problems such as the Nonlead glass composition of the present invention solves that the fusion temperature that in prior art, lead-free glass powder exists is high, softening temperature is high and adhesive force is low and crown glass exist the high problem of Rs preparing solar energy front side silver paste.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Detailed description of the invention
Unless otherwise defined, all technology used herein and scientific terminology have the identical implication being generally understood that with one skilled in the art of the present invention.When there is contradiction, it is as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " including ", " having ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, comprise the compositions of listed elements, step, method, goods or device and be not necessarily solely those key elements, but other not expressly listed key element or the intrinsic key element of this kind of compositions, step, method, goods or device can be included.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If in claim, this phrase will make claim be closed so that it is does not comprise the material in addition to the material that those describe, but except relative customary impurities.When being rather than immediately following during phrase " Consists of " occurs in the clause of claim main body after theme, it is only limited to the key element described in this clause；Other key element is not excluded outside as overall described claim.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferred scope or a series of upper limit preferred value and lower preferable values, this is appreciated that and specifically discloses all scopes formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, regardless of whether whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc..When numerical range is described in this article, unless otherwise indicated, otherwise this scope is intended to include its end value and all integers within the range and mark.
Additionally, the indefinite article " a kind of " before key element of the present invention or component and " one " quantitative requirement (i.e. occurrence number) unrestriction to key element or component.Therefore " one " or " a kind of " should be read as including one or at least one, and the key element of singulative or component also include plural form, unless described quantity substantially refers to singulative.
Silicon solar cell front side silver paste Nonlead glass composition, on the basis of the weight/mass percentage composition of described Nonlead glass composition, described Nonlead glass composition comprises the TeO of following components: 30-80wt%2, the Bi of 7-25wt%2O3,
The B2O3 of the SiO2 of the CaO of the ZnO of 1-15wt%, 1-15wt%, 0.1-10wt%, 0-5wt%.
CaO in the component of heretofore described Nonlead glass composition can use CaF2Replace, it is achieved same technique effect.
In one is preferably carried out mode, described Nonlead glass composition also includes the additive of 1-5 wt%.
In one is preferably carried out mode, described additive is one or more combinations in the metal simple-substance of lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, ferrum, ruthenium, cobalt, nickel, copper, stannum, cerium and gadolinium or its metal-oxide.Described additive can also be any compound of the metal-oxide that can generate lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, ferrum, ruthenium, cobalt, nickel, copper, stannum, cerium and gadolinium when roasting.
In one is preferably carried out mode, described additive is Li2O、K2O、Na2One or more combinations in O.
Li in heretofore described additive2O can replace with LiF, Na2O can replace with NaF, K2O can replace with KF, it is achieved same technique effect.
In one is preferably carried out mode, the particle diameter of described Nonlead glass composition is 0.1-3 micron.
In one is preferably carried out mode, the softening temperature of described Nonlead glass composition is 350-450 DEG C.
Another object of the present invention is to provide the preparation method of described silicon solar cell front side silver paste Nonlead glass composition, including: according to described predetermined ratio, uniformly mixing, obtain mixing raw material, mixing raw material is loaded in platinum crucible, then platinum crucible is put into heat temperature raising in high temperature box furnace, at a temperature of 1100-1300 DEG C, be incubated 0.5-1 hour, fused mass is made to become homogeneous liquid, and the raw material analyte without any remnants completely；Pour described homogeneous liquid in deionized water shrend, take out glass particle after cooling, and put into forced air oven drying；The glass particle of described drying, abrading-ball and deionized water are loaded in ball grinder and seals, loading in ball mill and carry out ball milling, ball milling is after 2-5 hour, and sieve elimination abrading-ball, obtain glass slip and put into forced air oven and be dried, sieve, obtaining Nonlead glass composition.
In one is preferably carried out mode, the temperature dried in described forced air oven is 120 DEG C.
In one is preferably carried out mode, it is 120 DEG C that described glass slip puts into the temperature that forced air oven is dried, and the time is 12-24 hour.
Another object of the present invention is to provide described silicon solar cell front side silver paste Nonlead glass composition to be applied in conductive silver paste.
Embodiment:
Embodiment 1, silicon solar cell front side silver paste Nonlead glass composition, on the basis of the weight/mass percentage composition of described Nonlead glass composition, described Nonlead glass composition comprises the TeO of following components: 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。
Embodiment 2, identical with embodiment 1, different places is, described Nonlead glass composition also includes the additive of 1-5 wt%.
Embodiment 3, identical with embodiment 2, different places is, described additive is one or more combinations in the metal simple-substance of lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, ferrum, ruthenium, cobalt, nickel, copper, stannum, cerium and gadolinium or its metal-oxide.
Embodiment 4, identical with embodiment 3, different places is, described additive is Li2O、K2O、Na2One or more combinations in O.
Embodiment 5, identical with embodiment 1, different places is, the particle diameter of described Nonlead glass composition is 0.1-3 micron.
Embodiment 6, identical with embodiment 1, different places is, the softening temperature of described Nonlead glass composition is 350-450 DEG C.
Embodiment 7, the preparation method of silicon solar cell front side silver paste Nonlead glass composition, it is characterized in that, including: according to described predetermined ratio, uniformly mix, obtain mixing raw material, mixing raw material is loaded in platinum crucible, then platinum crucible is put into heat temperature raising in high temperature box furnace, at a temperature of 1100-1300 DEG C, be incubated 0.5-1 hour, fused mass is made to become homogeneous liquid, and the raw material analyte without any remnants completely；Pour described homogeneous liquid in deionized water shrend, take out glass particle after cooling, and put into forced air oven drying；The glass particle of described drying, abrading-ball and deionized water are loaded in ball grinder and seals, loading in ball mill and carry out ball milling, ball milling is after 2-5 hour, and sieve elimination abrading-ball, obtain glass slip and put into forced air oven and be dried, sieve, obtaining Nonlead glass composition.
Embodiment 8, identical with embodiment 7, different places is, the temperature dried in described forced air oven is 120 DEG C.Embodiment 9, identical with embodiment 7, different places is, it is 120 DEG C that described glass slip puts into the temperature that forced air oven is dried, and the time is 12-24 hour.
Embodiment 10, described silicon solar cell front side silver paste Nonlead glass composition is applied in conductive silver paste.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that be; following example are served only for that the invention will be further described; it is not intended that limiting the scope of the invention, some nonessential improvement and adjustment that professional and technical personnel in the field makes according to the content of foregoing invention, still fall within protection scope of the present invention.
It addition, illustrate without other, raw materials used is all commercially available.
Silicon solar cell front side silver paste Nonlead glass composition component and proportioning, according to described predetermined ratio, uniformly mixing, obtain mixing raw material, mixing raw material is loaded in platinum crucible, then platinum crucible is put into heat temperature raising in high temperature box furnace, at a temperature of 1100-1300 DEG C, be incubated 0.5-1 hour, fused mass is made to become homogeneous liquid, and the raw material analyte without any remnants completely；Pour described homogeneous liquid in deionized water shrend, take out glass particle after cooling, and put into 120 DEG C of forced air oven drying；The glass particle of described drying, abrading-ball and deionized water are loaded in ball grinder and seals, load in ball mill and carry out ball milling, after ball milling 2-5 hour, sieve elimination abrading-ball, obtain glass slip and put into 120 DEG C of forced air oven and be dried 12-24 hour, sieve, obtaining Nonlead glass composition.
First-selected, sketch the basic scheme of material prescription of the present invention: silicon solar cell front side silver paste Nonlead glass composition, it is characterized in that, on the basis of the weight/mass percentage composition of described Nonlead glass composition, described Nonlead glass composition comprises the TeO of following components: 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。
Embodiment 1-6
Silicon solar cell front side silver paste Nonlead glass composition, its formula is according to the 1-6 formula (the most corresponding 1-6 embodiment) of table 1, adjust through component, melted, shrend, drying, ball milling, that the operation such as sieve obtains softening temperature after processing is low, high for crystal silicon solar front side silver paste sintering postadhesion power, the Nonlead glass composition that RS is low.Nonlead glass composition described in formula also includes the additive of 1-5 wt%；Described additive is one or more combinations in the metal simple-substance of lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, ferrum, ruthenium, cobalt, nickel, copper, stannum, cerium and gadolinium or its metal-oxide；Described additive is Li2O、K2O、Na2One or more combinations in O.
The Nonlead glass composition prepared by above-mentioned formula, the particle diameter of described Nonlead glass composition is 0.1-3 micron, and softening temperature is 350-450 DEG C.Being formed the back electric field silver electrodes of crystal silicon solar energy battery cell piece (156mm × 156mm specification) by silk-screen printing technique, and carry out performance test, the silicon solar cell of gained is functional, and test result is shown in Table 2.
Table 1
Table 2
Aforesaid example is merely illustrative, for explaining some features of inventive feature.Appended claim is intended to the widest scope that requirement it is contemplated that, and embodiments as presented herein is only the explanation of embodiment of selection of combination according to all possible embodiment.Therefore, the purpose of applicant is that appended claim is not by the selectional restriction of the example of explanation inventive feature.And the progress in science and technology will form the possible equivalent not being presently considered due to the inaccurate reason of language performance or son replacement, and these changes also should be interpreted to be covered by appended claim in the conceived case.
Claims (10)
1. silicon solar cell front side silver paste Nonlead glass composition, it is characterised in that on the basis of the weight/mass percentage composition of described Nonlead glass composition, described Nonlead glass composition comprises the TeO of following components: 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。
Silicon solar cell front side silver paste Nonlead glass composition the most according to claim 1, it is characterised in that described Nonlead glass composition also includes 1-5
The additive of wt%.
Silicon solar cell front side silver paste Nonlead glass composition the most according to claim 2, it is characterized in that, described additive is one or more combinations in the metal simple-substance of lithium, sodium, potassium, magnesium, strontium, barium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, ferrum, ruthenium, cobalt, nickel, copper, stannum, cerium and gadolinium or its metal-oxide.
Silicon solar cell front side silver paste Nonlead glass composition the most according to claim 3, it is characterised in that described additive is Li2O、K2O、Na2One or more combinations in O.
Silicon solar cell front side silver paste Nonlead glass composition the most according to claim 1, it is characterised in that the particle diameter of described Nonlead glass composition is 0.1-3 micron.
Silicon solar cell front side silver paste Nonlead glass composition the most according to claim 1, it is characterised in that the softening temperature of described Nonlead glass composition is 350-450 DEG C.
7. the preparation method of the silicon solar cell front side silver paste Nonlead glass composition of claim 1, it is characterized in that, including: according to described predetermined ratio, uniformly mixing, obtains mixing raw material, loads in platinum crucible by mixing raw material, platinum crucible is put into heat temperature raising in high temperature box furnace again, it is incubated 0.5-1 hour so that fused mass becomes homogeneous liquid, and the raw material analyte without any remnants completely at a temperature of 1100-1300 DEG C；Pour described homogeneous liquid in deionized water shrend, take out glass particle after cooling, and put into forced air oven drying；The glass particle of described drying, abrading-ball and deionized water are loaded in ball grinder and seals, loading in ball mill and carry out ball milling, ball milling is after 2-5 hour, and sieve elimination abrading-ball, obtain glass slip and put into forced air oven and be dried, sieve, obtaining Nonlead glass composition.
The preparation method of silicon solar cell front side silver paste Nonlead glass composition the most according to claim 7, it is characterised in that the temperature dried in described forced air oven is 120 DEG C.
The preparation method of silicon solar cell front side silver paste Nonlead glass composition the most according to claim 7, it is characterised in that it is 120 DEG C that described glass slip puts into the temperature of forced air oven drying, and the time is 12-24 hour.
10. the application in conductive silver paste of the silicon solar cell front side silver paste Nonlead glass composition described in any one of claim 1 to 9.
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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 |
| CN116332520A (en) * | 2023-03-27 | 2023-06-27 | 昆明理工大学 | Leadless glass powder and preparation method and application thereof |
| CN116543947A (en) * | 2023-06-26 | 2023-08-04 | 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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Cited By (7)
| 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 |
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| 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 |
| CN116543947A (en) * | 2023-06-26 | 2023-08-04 | 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 |
| 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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