CN103514973A - Conductive slurry used for solar cell and method of preparing the same - Google Patents
Conductive slurry used for solar cell and method of preparing the same Download PDFInfo
- Publication number
- CN103514973A CN103514973A CN201210209770.8A CN201210209770A CN103514973A CN 103514973 A CN103514973 A CN 103514973A CN 201210209770 A CN201210209770 A CN 201210209770A CN 103514973 A CN103514973 A CN 103514973A
- Authority
- CN
- China
- Prior art keywords
- glass powder
- unorganic glass
- powder
- electrocondution slurry
- unorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides conductive slurry used for solar cells and a method of preparing the same. The conductive slurry comprises metal powder, an inorganic binder and an organic carrier. The inorganic binder contains at least two kinds of inorganic glass powder. The prepared aluminium back surface field conductive slurry is silk-screened on a silicon chip to obtain a metal film layer that is smooth and compact, has a nice appearance, is free of bubbles and metal particles, and is high in cell filling factor and high in photoelectric conversion efficiency. Meanwhile, the metal film layer is tightly adhered to the silicon chip, the warping degree of cells is low, and cells can stand a water boiling test.
Description
Technical field
The invention belongs to technical field of solar batteries, relate in particular to a kind of conductive paste for solar cell and preparation method thereof.
Background technology
Day by day the increasingly sharpening of exhaustion, problem of environmental pollution that is accompanied by traditional energy, the development and application of new forms of energy has become human research's focus.Solar energy inexhaustible, green non-pollution is one of emphasis of new energy development utilization.
Electrocondution slurry is the important materials of making silica-based solar cell.Silica-based solar cell is generally by being printed on electrocondution slurry on silicon substrate, and then electric field and electrode are carried on the back in dry and sintering preparation.Existing electrocondution slurry is mainly formed by functional powder (metal powder), unorganic glass powder, organic carrier mix and blend rolling.Wherein, metal powder, generally as conductive phase, is generally aluminium powder or silver powder, and unorganic glass powder as inorganic binder, strengthens the adhesion of metal powder and silicon base when sintered molten.
At present the glass dust of commercial solar cell electrocondution slurry generally by the oxide melt water quenching of bismuth oxide, boron oxide class again ball milling form, generally only use a kind of glass dust, the median particle diameter D of glass dust
50be generally 1.0 ~ 5.0 μ m, use amount accounts for 2 ~ 10wt% of whole formula conventionally, use amount is larger, and unorganic glass powder is non-conductor, thereby cause the sheet resistance of solar battery sheet larger, battery series resistance is large, has reduced the electricity conversion of battery, makes the photoelectric conversion efficiency of solar battery sheet not reach desirable requirement.
Summary of the invention
When the present invention is applied to solar cell in order to solve existing electrocondution slurry, the sheet resistance of solar battery sheet is still larger, the technical problem that electricity conversion is undesirable, a kind of electrocondution slurry that can prepare the solar battery sheet that sheet resistance is lower, fill factor, curve factor is high, electricity conversion is higher and preparation method thereof is provided, the metal film angularity that simultaneously prepared by electrocondution slurry is low, can test by water boiling resistance, the smooth densification of metallic diaphragm, with the strong adhesion of silicon chip, outward appearance is good.
First object of the present invention is to provide a kind of conductive paste for solar cell, comprises conductive metal powder, inorganic binder and organic carrier, and described inorganic binder comprises at least two kinds of unorganic glass powder.
Second object of the present invention is to provide the preparation method of above-mentioned electrocondution slurry, and step comprises: at least two kinds of unorganic glass powder and conductive metal powder are scattered in organic carrier, grind to obtain electrocondution slurry.
The present inventor surprisingly finds, adopt multiple different unorganic glass powder to mix the inorganic binder as conductive paste for solar cell, can reduce the total amount of glass dust, the metal film not only making and the strong adhesion of silicon base, and the metal film density making is high, outward appearance is good, without blistering phenomenon and metallic particles phenomenon.The sheet resistance of the solar battery sheet of preparation is lower simultaneously, fill factor, curve factor is high, electricity conversion is high.Infer reason may for current crystal-silicon solar cell metallization process generally: during the silicon chip Guo tunnel sintering furnace of screen printing sizing agent, whole continuous tunnel furnace has a plurality of (9 or more than) temperature province along the direct of travel of silicon chip, silicon chip advances to peak temperature (generally at 900 ~ 930 ℃) again to room temperature from room temperature, temperature gradient excursion is very large, and the time of whole process is also about 2 minutes, and the physical property of single glass powder is difficult to adapt to this temperature situation jumpy, for example single glass powder is just difficult to take into account aluminium powder and before with after fusion point aluminium powder is melted to erosion effect at fusion point (660 ℃ of left and right).In aluminium back surface field electrocondution slurry forms, (coefficient of expansion is 232 * 10 to single glass powder average coefficient of linear expansion with metallic aluminium simultaneously
-7/ ℃, 20 ~ 300 ℃) and silicon (coefficient of expansion is 26 * 10
-7/ ℃, 20 ~ 300 ℃) widely different, be difficult to the difference of balance metallic aluminium and silicon chip, adopt multiple hybrid glass powder, can effectively reduce thermal expansion gradient between silicon chip-glass dust-aluminium powder, thereby reduce the angularity of battery on a large scale.Research simultaneously also finds that a large amount of glass dust can cause the angularity of cell piece to increase, and fragmentation rate rises, and the present invention can reduce the total amount of glass dust greatly, also can further reduce the angularity of battery, improves yield, reduces costs.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of conductive paste for solar cell, comprise conductive metal powder, inorganic binder and organic carrier, described inorganic binder comprises at least two kinds of unorganic glass powder.Can reduce the total amount of glass dust, the metal film not only making and the strong adhesion of silicon base, and also the metal film density making is high, and outward appearance is good, without blistering phenomenon and metallic particles phenomenon.The sheet resistance of the solar battery sheet of preparation is lower simultaneously, fill factor, curve factor is high, electricity conversion is high.
Between different multiple unorganic glass powder, form different, can be that composition is completely different, select the glass dust of different series, such as selecting Pd system, Bi-B-Si glass frit etc., the present invention preferably different multiple unorganic glass powder is Bi-B-Si glass frit, but the component in Bi-B-Si glass frit is different, it can be contained inorganic oxide species difference, the percentage composition that can be also contained inorganic oxide is different, and the present invention preferably unorganic glass powder not of the same race is that inorganic oxide melting by different percentage compositions forms.
Preferably, the total amount of every kind of unorganic glass powder of take is benchmark, and multiple unorganic glass powder independently comprises respectively
The Bi of 40 ~ 60wt%
2o
3, the B of 15-25wt%
2o
3, the SiO of 10 ~ 20wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3.Inorganic oxide by different percentage compositions is smelted into different unorganic glass powder.Further preferably, inorganic binder comprises the first unorganic glass powder and the second unorganic glass powder, and wherein, the total amount of the first unorganic glass powder of take is benchmark, and the first unorganic glass powder comprises the Bi of 40 ~ 50wt%
2o
3, the B of 20 ~ 25wt%
2o
3, the SiO of 15 ~ 20wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3; The total amount of the second unorganic glass powder of take is benchmark, and the second unorganic glass powder comprises the Bi of 50 ~ 60wt%
2o
3, the B of 15 ~ 20wt%
2o
3, the SiO of 10 ~ 15wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3.Further preferably the weight ratio of above-mentioned the first unorganic glass powder and the second unorganic glass powder is 1:0.5 ~ 2.0.In better situation, also preferably inorganic binder comprises the first unorganic glass powder, the second unorganic glass powder and the 3rd unorganic glass powder, and wherein, the total amount of the first unorganic glass powder of take is benchmark, and the first unorganic glass powder comprises the Bi of 40 ~ 50wt%
2o
3, the B of 20 ~ 25wt%
2o
3, the SiO of 15 ~ 20wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3; The total amount of the second unorganic glass powder of take is benchmark, and the second unorganic glass powder comprises the Bi of 50 ~ 55wt%
2o
3, the B of 15 ~ 20wt%
2o
3, the SiO of 13 ~ 15wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3; The total amount of the 3rd unorganic glass powder of take is benchmark, and the 3rd unorganic glass powder comprises the Bi of 55 ~ 60wt%
2o
3, the B of 15 ~ 20wt%
2o
3, the SiO of 10 ~ 13wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3.Further preferably, the weight of the first unorganic glass powder: the weight of the second unorganic glass powder: the weight of the 3rd unorganic glass powder is 1:0.5 ~ 2.0:0.5 ~ 2.0.
Preferably, the median particle diameter D of multiple unorganic glass powder
50be independently 0.1 ~ 1.0 μ m respectively, the particle diameter of multiple unorganic glass powder can be the same or different, and the median particle diameter of preferred multiple unorganic glass powder is different, further improves the intergranular interactions such as conductive metal powder, glass dust, makes filling effect better.The present invention surprisingly finds to adopt particle diameter to be less than the mixed powder of the multiple glass dust of 1 micron, the metal film square resistance forming after silk-screen sintering is less, the series resistance of cell piece is lower, photoelectric conversion efficiency is higher, simultaneously, the adhesive force of metal film and silicon chip is fine, and the angularity of cell piece is little, can test by water boiling resistance.Infer that reason may be for being the relation of particle diameter cube according to spheroid mass, particle diameter diminishes, and powder number number becomes cube exponent increase.With glass dust molten corrosive, fall the aluminium oxide on aluminium powder surface, aluminium simple substance at high temperature being infiltrated and in silicon chip, form silicon-aluminum layer is example, in theory, glass dust spheroid can form effective corrosion to eight ball aluminum powder around, volume (the reducing particle diameter) scheme that reduces single glass dust can effectively reduce total consumption of glass dust, thereby reduce the impact of non-conductor glass dust on the sheet resistance of solar battery sheet, particle diameter of the present invention also can further avoid glass dust to exaggerate to the corrosion of aluminium oxide simultaneously, avoids aluminium film water only to boil.
Preferably, the softening point temperature Ts of multiple unorganic glass powder is independently 500 ~ 600 ℃ respectively, and average coefficient of linear expansion is independently respectively 50 * 10
-7~ 100 * 10
-7/ ℃, proportion is independently respectively 3.0 ~ 4.0g/cm
3the physical parameters such as the softening point temperature Ts of general unorganic glass powder not of the same race, average coefficient of linear expansion, proportion are different, the variation of the various situations when solar battery sheet sintering of the further balance electrocondution slurry of unorganic glass powder by preferred multiple softening point temperature Ts, average coefficient of linear expansion, proportion, makes the performance of solar battery sheet best.
Preferably, the total amount of electrocondution slurry of take is benchmark, and described electrocondution slurry comprises the conductive metal powder of 75 ~ 79wt%, the inorganic binder of 0.1 ~ 1.0wt% and the organic carrier of 20 ~ 24wt%.Wherein, the consumption of non-conductor inorganic binder is few, only need to can reach the preparation requirement of solar cell less than 1.0wt%, the metallic diaphragm strong adhesion of preparation, and metal film density is high, and outward appearance is good, without blistering phenomenon and metallic particles phenomenon.
Preferably, conductive metal powder is aluminium powder, and wherein, aluminium powder comprises the ball aluminum powder of two or more different median particle diameters, the median particle diameter D of the ball aluminum powder of multiple different median particle diameters
50be independently respectively 1.0 ~ 8.0 μ m.Not only further optimize density degree and the outward appearance of metal film, and can optimize the interaction between conducting metal powder, reduce volume resistance.
The preferred ball aluminum powder of the present invention is nucleocapsid structure, and kernel is aluminium simple substance, and shell is aluminium oxide.Under preferable case, the thickness of the surface alumina oxide of ball aluminum powder is 10-20nm, further optimizes the interaction between itself and glass dust, further optimizes the performance of solar battery sheet.
Organic carrier is organic system conventional in the electrocondution slurry of prior art, and the total amount of organic carrier of take is benchmark, specifically can be preferred, and organic carrier comprises the ethyl cellulose of 5.0 ~ 20wt%, the auxiliary agent of 0.1 ~ 5.0wt% and the mixed solvent of 75 ~ 90wt%; Described auxiliary agent is that one or more in polyamide powder, modified hydrogenated castor oil, hexadecanol or 18 alcohol mix; Two or more in terpinol, dibutyl phthalate (DBP), butyl carbitol, turpentine oil, butyl glycol ether, butyl carbitol acetate, ethylene glycol ether acetate, tributyl citrate and tributyl phosphate of described mixed solvent mixes.Also can contain other property-modifying additives, the present invention is not particularly limited, and can select according to actual conditions.Can commercially also can configure voluntarily, collocation method can be dissolved in ethyl cellulose and auxiliary agent in the mixed solvent being comprised of terpinol or other organic solvents, at 60 ~ 80 ℃, make it fully dissolve and stir, obtain the organic carrier of transparent homogeneous.
Meanwhile, the invention provides the preparation method of above-mentioned conductive paste for solar cell, step comprises: at least two kinds of unorganic glass powder and conductive metal powder are scattered in organic carrier, grind to obtain electrocondution slurry, method is simple and easy to realize.
Be scattered in organic carrier and adopt and well known to a person skilled in the art various process for dispersing, conductive metal powder and multiple glass dust can be added in organic carrier and mix respectively, also after can mixing in whole or in part, add in organic carrier and mix together, can once add, also can add in batches, the present invention is restriction not, the method adding and the method the present invention who mixes be restriction not, when conductive metal powder is selected the ball aluminum powder of multiple particle diameter, in better situation, be specifically as follows and adopt respectively V-Mixer to mix the ball aluminum powder of selected multiple glass dust and multiple particle diameter, obtain hybrid glass powder and mix aluminium powder, organic carrier is placed in to the stainless cylinder of steel of high speed dispersor, stir on one side, add hybrid glass powder on one side, stir evenly, add several times mixing aluminium powder, add first and stir evenly at every turn, then add next time, after all adding, stir evenly at a high speed, use again
three-roll grinder grind 15 ~ 20 times, fineness of grind, to < 20 μ m, can make aluminium back surface field electrocondution slurry.
Preferably, at least two kinds of unorganic glass powder are by forming the inorganic oxide melting that forms the different component of every kind of unorganic glass powder.In better situation, preferably the inorganic oxide that forms every kind of unorganic glass powder is mixed, at 550 ~ 600 ℃, is incubated 0.5 ~ 1h, after at 1250 ~ 1300 ℃, be incubated 1 ~ 2h, rear shrend obtains every kind of unorganic glass powder.Mix to adopt well known to a person skilled in the art various mixed methods, the oxide powder that for example adopts V-Mixer that each is formed to every kind of unorganic glass powder mixes.Insulation can adopt and well known to a person skilled in the art various sintering furnaces, for example, can put into corundum crucible, and be placed in silicon carbide rod furnace, by being warming up to 550 ~ 600 ℃ in silicon carbide rod furnace, is incubated 0.5 ~ 1h, then is warming up to 1250 ~ 1300 ℃, is incubated 1 ~ 2h.After general shrend, obtain bead, bead is separated, the rear glass dust of pulverizing to obtain, separated method adopts and well known to a person skilled in the art various separation methods, for example, filter.
Preferably, the method of pulverizing is dry grinding, in better situation, be specifically as follows and pack bead into ball grinder, zirconia ball in mass ratio: bead: deionized water=4:0.5 ~ 2:0.5 ~ 1.5,300 ~ 400 revs/min of tank speed, wet-milling 6 ~ 8h, filters post-drying, 0.5 ~ the 3h that dry grinds again, during dry grinding, the mass ratio of zirconia ball and glass dust is 1:1 ~ 3.Optimize the particle diameter of glass dust, improve sintering activity and softening point low.
Below by specific embodiment, the invention will be further described.
Embodiment 1
The present embodiment is used for preparing aluminium back surface field electrocondution slurry.
(1) preparation of unorganic glass powder
Get the Bi of 49wt%
2o
3, the B of 25wt%
2o
3, the SiO of 16wt%
2, the Sb of 4wt%
2o
3, the BaO of 2.0wt%, the MgO of 2.0wt%, the CaO of 1.0wt%, the Al of 1.0wt%
2o
3, adopt V-Mixer to mix, pack in porcelain crucible, put into silicon carbide rod furnace, intensification is preheating to 550 ℃, insulation 0.5h, then rise to 1250 ℃, melting 1.0h, shrend is filtered, and will obtain bead and pack ball grinder into, control mass ratio, zirconia ball: bead: deionized water=4:1:0.5, tank speed 100/ minute, wet-milling ball milling 7h, filters, and dries, the 2.5h that dry grinds again, during dry grinding, the mass ratio of zirconia ball and bead is 1:2, makes unorganic glass powder A11.
Adopt BT-2003 type laser fineness gage (Dandong Bai Te company produces, lower same), adopt water as decentralized medium, record the median particle diameter D of the unorganic glass powder A11 of above-mentioned preparation
50be 0.65 μ m, proportion (adopting the test of 10ml specific gravity bottle, lower same) is 3.65g/cm
3, softening point (adopt Germany to produce STA449PC/STA409PC simultaneous thermal analysis instrument and carry out DTA test, be lower same) is 588 ℃, average coefficient of linear expansion (adopts thermomechanical analyzer to test, temperature range: from 20 ℃, be warmed up to tested glass dust and melt, lower same) ℃) be 57 * 10
-7/ ℃.
Get the Bi of 59wt%
2o
3, the B of 19wt%
2o
3, the SiO of 12wt%
2, the Sb of 5wt%
2o
3, the BaO of 3.0wt%, the MgO of 1.0wt% and the CaO of 1.0wt%.The manufacture craft of glass dust is identical with A11 unorganic glass powder, makes unorganic glass powder A12.Record its median particle diameter D
50be 0.64 μ m, proportion is 3.23g/cm
3, softening point is 532 ℃, average coefficient of linear expansion is 84 * 10
-7/ ℃.
Adopt V-Mixer by unorganic glass powder A11 and A12,1:1 mixes in mass ratio, obtains hybrid glass powder A1.
(2) configuration of organic carrier
According to quality than terpinol: butyl carbitol: butyl carbitol acetate=50:40:10 mixes organic solvent, forms the mixed solvent of electrocondution slurry.Take organic carrier total amount as benchmark, get the mixed solvent of 89.5wt%, (Tao Shi produces to add 8.8wt% ethyl cellulose STD-4, viscosity is 4), the rilanit special of 1.2wt%, 0.5wt% 18 alcohol, be heated to 65 ℃, it is fully dissolved, and stir, obtain the organic carrier solution of homogeneous clarification.
(3) preparation of electrocondution slurry
Get and account for electrocondution slurry total amount 63wt%, median particle diameter D
50be 5.0 ~ 6.0 μ m and account for slurry total amount 15wt%, middle particle diameter D
50the ball aluminum powder (ocean, Henan Chinalco produces common aluminium powder, and aluminium oxide thickness is at 13 ~ 15nm) that is two kinds of different median particle diameters of 1.0 ~ 2.0 μ m is mixed to get mixing aluminium powder.Get again the above-mentioned organic carrier solution that accounts for electrocondution slurry total amount 21.40wt%, be placed in the stainless cylinder of steel of high speed dispersor, stir on one side, add the above-mentioned hybrid glass powder A1 making that accounts for total amount 0.60wt% on one side, stir, then add mixing aluminium powder obtained above, wherein aluminium powder adds several times, add first and stir evenly at every turn, then add next time; After all adding, stir evenly at a high speed; With three-roll grinder, grind 15 times again, detect and make its fineness be less than 20 μ m, obtain aluminium back surface field electrocondution slurry sample S1.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S2, the mass ratio of different is unorganic glass powder A11 and unorganic glass powder A12 is 1:0.5, makes hybrid glass powder A2, adopts hybrid glass powder A2 to make aluminium back surface field electrocondution slurry S2.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S3, the mass ratio of different is unorganic glass powder A11 and unorganic glass powder A12 is 1:2, makes hybrid glass powder A3, adopts hybrid glass powder A3 to make aluminium back surface field electrocondution slurry S3.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S4, the mass ratio of different is unorganic glass powder A11 and unorganic glass powder A12 is 1:4, makes hybrid glass powder A4, adopts hybrid glass powder A4 to make aluminium back surface field electrocondution slurry S4.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S5, the amount of the hybrid glass powder A1 that different is adds in the preparation of electrocondution slurry is 1.00wt%, and the amount of organic carrier is 21.00wt%.
Embodiment 6
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S6, the amount of the hybrid glass powder A1 that different is adds in the preparation of electrocondution slurry is 0.10wt%, and the amount of organic carrier is 21.90wt%.
Embodiment 7
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S7, in the preparation of different is two kinds of unorganic glass powder, the dry grinding time is 1.5h, make unorganic glass powder A71, A72, the particle diameter that adopts the method identical with embodiment 1 to record unorganic glass powder A71, A72 is 0.96 μ m, by unorganic glass powder A71 and A72 in mass ratio 1:1 be mixed to get hybrid glass powder A7, adopt hybrid glass powder A7 to make aluminium back surface field electrocondution slurry S7.
Embodiment 8
Adopt the method identical with embodiment 1 to prepare aluminium back surface field electrocondution slurry S8, different employing hybrid glass powder A8 make aluminium back surface field electrocondution slurry S8, wherein hybrid glass powder A8 adopts V-Mixer by unorganic glass powder A81, A82 and A83, and 1:1:1 mixes and makes in mass ratio.
Wherein, get the Bi of 47wt%
2o
3, the B of 24wt%
2o
3, the SiO of 17wt%
2, the Sb of 5.0wt%
2o
3, the BaO of 3.0wt%, the MgO of 2.0wt% and the CaO of 2.0wt%.The manufacture craft of glass dust is identical with A11 unorganic glass powder, and wet-milling Ball-milling Time is 8h, makes unorganic glass powder A81.Record its median particle diameter D
50be 0.48 μ m, proportion is 3.28g/cm
3, softening point is 582 ℃, average coefficient of linear expansion is 51 * 10
-7/ ℃.
Get the Bi of 53.5wt%
2o
3, the B of 19wt%
2o
3, the SiO of 14.5wt%
2, the Sb of 6.0wt%
2o
3, the BaO of 3.0wt%, the MgO of 2.0wt% and the CaO of 1.0wt%, the Al of 1.0wt%
2o
3.The manufacture craft of glass dust is identical with inorganic A11 glass dust, and wet-milling Ball-milling Time is 7h, makes unorganic glass powder A82.Record its median particle diameter D
50be 0.65 μ m, proportion is 3.64g/cm
3, softening point is 550 ℃, average coefficient of linear expansion is 65 * 10
-7/ ℃.
Get the Bi of 59wt%
2o
3, the B of 17wt%
2o
3, the SiO of 12wt%
2, the Sb of 5wt%
2o
3, the BaO of 3.0wt%, the MgO of 2.0wt%, the CaO of 2.0wt%.The manufacture craft of glass dust is identical with inorganic A11 glass dust, and wet-milling Ball-milling Time is 6h, makes unorganic glass powder A83.Record its median particle diameter D
50be 0.87 μ m, proportion is 3.87g/cm
3, softening point is 522 ℃, average coefficient of linear expansion is 83 * 10
-7/ ℃.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare unorganic glass powder A11, organic carrier, different is the preparation of electrocondution slurry: get and account for electrocondution slurry total amount 63wt%, median particle diameter D
50be 5.0 ~ 6.0 μ m and account for slurry total amount 15wt%, middle particle diameter D
50the ball aluminum powder (ocean, Henan Chinalco produces common aluminium powder, and aluminium oxide thickness is at 13 ~ 15nm) that is two kinds of different median particle diameters of 1.0 ~ 2.0 μ m is mixed to get mixing aluminium powder.Get again the above-mentioned organic carrier solution that accounts for electrocondution slurry total amount 20.70wt%, be placed in the stainless cylinder of steel of high speed dispersor, stir on one side, add the unorganic glass powder A11 that accounts for total amount 1.30wt% on one side, stir, then add mixing aluminium powder obtained above, wherein aluminium powder adds several times, add first and stir evenly at every turn, then add next time; After all adding, stir evenly at a high speed; With three-roll grinder, grind 15 times again, detect and make its fineness be less than 20 μ m, obtain aluminium back surface field electrocondution slurry sample DS1.
Comparative example 2
(1) preparation of unorganic glass powder
Get the Bi of 55wt%
2o
3, the B of 22wt%
2o
3, the SiO of 17wt%
2, the Sb of 2.0wt%
2o
3, the Al of 2.0wt%
2o
3, the ZnO of 1.0wt%, the CaO of 1wt%, employing V-Mixer mixes, pack in porcelain crucible, put into silicon carbide rod furnace, heat up and be preheating to 550 ℃, insulation 0.5h, rise to again 1250 ℃, melting 1.0h, shrend is filtered, to obtain bead and pack ball grinder into, control mass ratio, zirconia ball: bead: deionized water=4:1:0.5, tank speed 100/ minute, wet-milling ball milling 5.5h, filter, dry, then the 1.0h that dry grinds, during dry grinding, the mass ratio of zirconia ball and bead is 1:2, makes unorganic glass powder D2.
Record the median particle diameter D of the unorganic glass powder D2 of above-mentioned preparation
50be 1.45 μ m, proportion is 3.47g/cm
3, softening point is 605 ℃, average coefficient of linear expansion is 43 * 10
-7/ ℃.
(2) configuration of organic carrier
Adopt the method identical with embodiment 1 to prepare organic carrier.
(3) preparation of electrocondution slurry
Get and account for electrocondution slurry total amount 76wt%, median particle diameter D
50be that (ocean, Henan Chinalco produces common aluminium powder for the ball aluminum powder of 4.0 ~ 5.0 μ m, aluminium oxide thickness is at 13 ~ 15nm), get again the above-mentioned organic carrier solution that accounts for electrocondution slurry total amount 21.5wt%, be placed in the stainless cylinder of steel of high speed dispersor, stir on one side, add the above-mentioned unorganic glass powder D2 making that accounts for total amount 2.5wt% on one side, stir, then add aluminium powder above, wherein aluminium powder adds several times, add first and stir evenly at every turn, then add next time; After all adding, stir evenly at a high speed; With three-roll grinder, grind 15 times again, detect and make its fineness be less than 20 μ m, obtain aluminium back surface field electrocondution slurry sample DS2.
Comparative example 3
Adopt the method identical with comparative example 2 to prepare unorganic glass powder D2, organic carrier, different is the preparation of electrocondution slurry: get and account for electrocondution slurry total amount 63wt%, median particle diameter D
50be 5.0 ~ 6.0 μ m and account for slurry total amount 15wt%, middle particle diameter D
50the ball aluminum powder (ocean, Henan Chinalco produces common aluminium powder, and aluminium oxide thickness is at 13 ~ 15nm) that is two kinds of different median particle diameters of 1.0 ~ 2.0 μ m is mixed to get mixing aluminium powder.Get again the above-mentioned organic carrier solution that accounts for electrocondution slurry total amount 21.40wt%, be placed in the stainless cylinder of steel of high speed dispersor, stir on one side, add the unorganic glass powder D2 that accounts for total amount 0.60wt% on one side, stir, then add mixing aluminium powder obtained above, wherein aluminium powder adds several times, add first and stir evenly at every turn, then add next time; After all adding, stir evenly at a high speed; With three-roll grinder, grind 15 times again, detect and make its fineness be less than 20 μ m, obtain aluminium back surface field electrocondution slurry sample DS3.
Performance test
The solar battery aluminum back of the body electric field that above-described embodiment 1-8 and comparative example 1-3 are made is used for respectively preparing solar battery sheet with electrocondution slurry S1-S8 and DS1-DS3.Polysilicon chip specification: 156 * 156mm, before thickness is 200 μ m(corrosion), before printing, thickness is 180 μ m.First adopt 200 object silk screen printing back silver electrode slurrys (PV505 of Du Pont), dry, adopt again 280 object meshcounts to print respectively S1-S8 and DS1-DS3, printing weight be every with slurry 1.5 grams, bake out temperature is 125 ℃, drying time is 4min, adopt again 200 object silk screen printing front silver electrode pastes (16C of Du Pont), cross continuous tunnel furnace and dry sintering, continuous tunnel furnace temperature gradient distribution, the time that crosses continuous tunnel furnace is 2min, sintering peak temperature is 910 ± 10 ℃, time is 1s left and right, after coming out of the stove, obtain corresponding cell piece and be designated as respectively S10-S80 and DS10-DS30.
Adopt respectively 200 cell pieces to test, test obtains data and gets its mean value.
Surface appearance: estimate the back surface field surface appearance of each solar cell piece, smooth, without aluminium pill or metallic particles, without blistering, be designated as OK, otherwise be designated as NG.
Water boiling resistance test: cell piece dropped in the hot water of 70 ~ 80 ℃ and stop 10 ~ 15min, observing aluminium film surface and whether react with water and produce bubble, and observing poach front and back aluminium film outward appearance and whether have significant change.If do not produced bubble, and outward appearance is without significant change, is designated as OK, otherwise is designated as NG.
Adhesive force: photovoltaic glass, EVA, cell piece, EVA and TPT are stacked in order, and carry out lamination, with wide rectangular of graduating with cutter 1cm, use mountain degree SH-100 pull and push dynamometer, along 45 ° of directions, it is carried out to tensile test, survey the average peeling force on its unit width, unit is N/cm.
Flexibility: by each solar cell piece degree of crook vernier caliper measurement, unit is mm.
Fill factor, curve factor, electricity conversion: adopt single flash operation simulator, according to the disclosed method of IEC904-1, each cell piece is carried out to electrochemical property test.Test condition is standard test condition (STC): light intensity: 1000W/m
2; Spectrum: AM1.5; Temperature: 25 ℃.
Test result is as table 1.
Table 1
As can be seen from the table, the aluminium back surface field electrocondution slurry that adopts hybrid glass powder of the present invention to prepare, silk-screen on silicon chip and sintering after, the smooth densification of metallic diaphragm obtaining, outward appearance is good, without blistering phenomenon and metallic particles phenomenon, the fill factor, curve factor of battery is high, and photoelectric conversion efficiency is high, simultaneously, the strong adhesion of metal film and silicon chip, cell piece angularity is low, can test by water boiling resistance.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (18)
1. a conductive paste for solar cell, is characterized in that, comprises conductive metal powder, inorganic binder and organic carrier, and described inorganic binder comprises at least two kinds of unorganic glass powder.
2. electrocondution slurry according to claim 1, is characterized in that, the composition between multiple described unorganic glass powder is different.
3. electrocondution slurry according to claim 1, is characterized in that, multiple described unorganic glass powder is Bi-B-Si glass frit, and unorganic glass powder not of the same race is prepared from by the inorganic oxide of different component.
4. electrocondution slurry according to claim 3, is characterized in that, the total amount of every kind of unorganic glass powder of take is benchmark, and multiple unorganic glass powder independently comprises respectively the Bi of 40 ~ 60wt%
2o
3, the B of 15 ~ 25wt%
2o
3, the SiO of 10 ~ 20wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3.
5. electrocondution slurry according to claim 3, is characterized in that, the median particle diameter D of multiple unorganic glass powder
50be independently respectively 0.1 ~ 1.0 μ m.
6. electrocondution slurry according to claim 3, is characterized in that, the softening point temperature Ts of multiple unorganic glass powder is independently 500 ~ 600 ℃ respectively, and average coefficient of linear expansion is independently respectively 50 * 10
-7~ 100 * 10
-7/ ℃, proportion is independently respectively 3.0 ~ 4.0g/cm
3.
7. electrocondution slurry according to claim 3, is characterized in that, described inorganic binder comprises the first unorganic glass powder and the second unorganic glass powder,
The total amount of the first unorganic glass powder of take is benchmark, and described the first unorganic glass powder comprises the Bi of 40 ~ 50wt%
2o
3, the B of 20 ~ 25wt%
2o
3, the SiO of 15 ~ 20wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3.
The total amount of the second unorganic glass powder of take is benchmark, and described the second unorganic glass powder comprises the Bi of 50 ~ 60wt%
2o
3, the B of 15 ~ 20wt%
2o
3, the SiO of 10 ~ 15wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3.
8. electrocondution slurry according to claim 7, is characterized in that, the weight ratio of described the first unorganic glass powder and the second unorganic glass powder is 1:0.5 ~ 2.0.
9. electrocondution slurry according to claim 3, is characterized in that, described inorganic binder comprises the first unorganic glass powder, the second unorganic glass powder and the 3rd unorganic glass powder,
The total amount of the first unorganic glass powder of take is benchmark, and described the first unorganic glass powder comprises the Bi of 40 ~ 50wt%
2o
3, the B of 20 ~ 25wt%
2o
3, the SiO of 15 ~ 20wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3.
The total amount of the second unorganic glass powder of take is benchmark, and described the second unorganic glass powder comprises the Bi of 50 ~ 55wt%
2o
3, the B of 15 ~ 20wt%
2o
3, the SiO of 13 ~ 15wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3,
The total amount of the 3rd unorganic glass powder of take is benchmark, and described the 3rd unorganic glass powder comprises the Bi of 55 ~ 60wt%
2o
3, the B of 15 ~ 20wt%
2o
3, the SiO of 10 ~ 13wt%
2, the Sb of 1 ~ 8wt%
2o
3, the BaO of 1.0 ~ 5.0wt%, the MgO of 0.5 ~ 5.0wt%, the CaO of 0.2 ~ 3.0wt% and the Al of 0 ~ 3.0wt%
2o
3
10. electrocondution slurry according to claim 9, is characterized in that, the weight of described the first unorganic glass powder: the weight of the second unorganic glass powder: the weight of the 3rd unorganic glass powder is 1:0.5 ~ 2.0:0.5 ~ 2.0
11. electrocondution slurries according to claim 1, is characterized in that, the total amount of electrocondution slurry of take is benchmark, and described electrocondution slurry comprises the conductive metal powder of 75 ~ 79wt%, the inorganic binder of 0.1 ~ 1.0wt% and the organic carrier of 20 ~ 24wt%.
12. electrocondution slurries according to claim 1, is characterized in that, described conductive metal powder is aluminium powder, and described aluminium powder comprises the ball aluminum powder of two or more different median particle diameters, the median particle diameter D of the ball aluminum powder of multiple different median particle diameters
50be independently respectively 1.0 ~ 8.0 μ m.
13. electrocondution slurries according to claim 12, is characterized in that, described ball aluminum powder is nucleocapsid structure, and kernel is aluminium simple substance, and shell is aluminium oxide, and the thickness of described aluminium oxide is 10 ~ 20nm.
14. electrocondution slurries according to claim 1, is characterized in that, the total amount of organic carrier of take is benchmark, and described organic carrier comprises the ethyl cellulose of 5.0 ~ 20wt%, the auxiliary agent of 0.1 ~ 5.0wt% and the mixed solvent of 75 ~ 90wt%; Described auxiliary agent is that one or more in polyamide powder, modified hydrogenated castor oil, hexadecanol or 18 alcohol mix; Two or more in terpinol, dibutyl phthalate (DBP), butyl carbitol, turpentine oil, butyl glycol ether, butyl carbitol acetate, ethylene glycol ether acetate, tributyl citrate and tributyl phosphate of described mixed solvent mixes.
The preparation method of 15. 1 kinds of conductive paste for solar cell as claimed in claim 1, is characterized in that, step comprises: at least two kinds of unorganic glass powder and conductive metal powder are scattered in organic carrier, grind to obtain electrocondution slurry.
16. preparation methods according to claim 15, is characterized in that, described at least two kinds of unorganic glass powder are by forming the inorganic oxide melting that forms the different component of every kind of unorganic glass powder.
17. preparation methods according to claim 16, it is characterized in that, the inorganic oxide that forms every kind of unorganic glass powder is mixed, at 550 ~ 600 ℃, be incubated 0.5 ~ 1h, after at 1250 ~ 1300 ℃, be incubated 1 ~ 2h, rear shrend, pulverize to obtain every kind of unorganic glass powder.
18. preparation methods according to claim 17, is characterized in that, the method for described pulverizing is dry grinding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210209770.8A CN103514973B (en) | 2012-06-25 | 2012-06-25 | Conductive paste for solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210209770.8A CN103514973B (en) | 2012-06-25 | 2012-06-25 | Conductive paste for solar cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103514973A true CN103514973A (en) | 2014-01-15 |
| CN103514973B CN103514973B (en) | 2016-05-11 |
Family
ID=49897550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210209770.8A Active CN103514973B (en) | 2012-06-25 | 2012-06-25 | Conductive paste for solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103514973B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104157949A (en) * | 2014-08-20 | 2014-11-19 | 苏州艾福电子通讯有限公司 | Sintering method of printing conductive silver paste and silver layer surface treatment method |
| CN104952512A (en) * | 2014-03-28 | 2015-09-30 | 比亚迪股份有限公司 | Al-ABSF (aluminum back surface field) conductive slurry for crystalline silicon solar cell, and manufacturing method for Al-ABSF conductive slurry |
| CN105761777A (en) * | 2014-12-18 | 2016-07-13 | 上海宝银电子材料有限公司 | Filament silver paste for automobile glass and preparation method of filament silver paste |
| CN106876067A (en) * | 2015-12-11 | 2017-06-20 | 李文熙 | The manufacture method of high conductivity thick film aluminium cream |
| CN109166646A (en) * | 2018-08-14 | 2019-01-08 | 华中科技大学 | It is a kind of for carry on the back passivation silicon solar cell environment-friendly type aluminum electrode slurry |
| CN110044509A (en) * | 2019-04-30 | 2019-07-23 | 东莞珂洛赫慕电子材料科技有限公司 | A method of realizing thick film heating body surface temperature comprehensive monitoring |
| 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 |
| CN114360762A (en) * | 2022-03-14 | 2022-04-15 | 西安拓库米电子科技有限公司 | Silver migration resistant silver conductor paste for sheet resistor and preparation method thereof |
| CN114822910A (en) * | 2022-05-20 | 2022-07-29 | 上海银浆科技有限公司 | Conductive silver-aluminum paste, preparation method, electrode and battery |
| CN115716711A (en) * | 2022-10-28 | 2023-02-28 | 广州市儒兴科技股份有限公司 | Glass powder, conductive paste, and preparation method and application thereof |
| CN115772005A (en) * | 2021-09-06 | 2023-03-10 | 长春理工大学 | Preparation method of lead-free glass powder for silver paste of solar cell |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060102228A1 (en) * | 2004-11-12 | 2006-05-18 | Ferro Corporation | Method of making solar cell contacts |
| CN101345263A (en) * | 2008-09-09 | 2009-01-14 | 季福根 | Leadless electronic slurry composition for solar silicon photovoltaic cell and preparation method thereof |
| CN101789456A (en) * | 2010-03-05 | 2010-07-28 | 西安宏星电子浆料科技有限责任公司 | Lead-free aluminum paste for solar battery |
| CN101866705A (en) * | 2010-06-22 | 2010-10-20 | 彩虹集团公司 | Back aluminum slurry for environment-friendly silicon-based solar battery and preparation method thereof |
| CN102081988A (en) * | 2010-12-27 | 2011-06-01 | 张振中 | Reinforced back electric field A1 slurry of silicon solar battery |
| CN102142467A (en) * | 2010-01-29 | 2011-08-03 | 比亚迪股份有限公司 | Solar cell back electric field aluminium paste and preparation method thereof |
| CN102214704A (en) * | 2006-03-20 | 2011-10-12 | 费罗公司 | Aluminum-boron solar cell contacts |
| CN102244112A (en) * | 2011-07-19 | 2011-11-16 | 彩虹集团公司 | Aluminium paste for silicon solar battery |
-
2012
- 2012-06-25 CN CN201210209770.8A patent/CN103514973B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060102228A1 (en) * | 2004-11-12 | 2006-05-18 | Ferro Corporation | Method of making solar cell contacts |
| CN102214704A (en) * | 2006-03-20 | 2011-10-12 | 费罗公司 | Aluminum-boron solar cell contacts |
| CN101345263A (en) * | 2008-09-09 | 2009-01-14 | 季福根 | Leadless electronic slurry composition for solar silicon photovoltaic cell and preparation method thereof |
| CN102142467A (en) * | 2010-01-29 | 2011-08-03 | 比亚迪股份有限公司 | Solar cell back electric field aluminium paste and preparation method thereof |
| CN101789456A (en) * | 2010-03-05 | 2010-07-28 | 西安宏星电子浆料科技有限责任公司 | Lead-free aluminum paste for solar battery |
| CN101866705A (en) * | 2010-06-22 | 2010-10-20 | 彩虹集团公司 | Back aluminum slurry for environment-friendly silicon-based solar battery and preparation method thereof |
| CN102081988A (en) * | 2010-12-27 | 2011-06-01 | 张振中 | Reinforced back electric field A1 slurry of silicon solar battery |
| CN102244112A (en) * | 2011-07-19 | 2011-11-16 | 彩虹集团公司 | Aluminium paste for silicon solar battery |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104952512A (en) * | 2014-03-28 | 2015-09-30 | 比亚迪股份有限公司 | Al-ABSF (aluminum back surface field) conductive slurry for crystalline silicon solar cell, and manufacturing method for Al-ABSF conductive slurry |
| CN104952512B (en) * | 2014-03-28 | 2017-08-25 | 比亚迪股份有限公司 | A kind of crystal silicon solar energy battery Al-BSF electrocondution slurry and preparation method thereof |
| CN104157949A (en) * | 2014-08-20 | 2014-11-19 | 苏州艾福电子通讯有限公司 | Sintering method of printing conductive silver paste and silver layer surface treatment method |
| CN105761777A (en) * | 2014-12-18 | 2016-07-13 | 上海宝银电子材料有限公司 | Filament silver paste for automobile glass and preparation method of filament silver paste |
| CN105761777B (en) * | 2014-12-18 | 2017-12-01 | 上海宝银电子材料有限公司 | A kind of vehicle glass fine rule silver paste and preparation method thereof |
| CN106876067A (en) * | 2015-12-11 | 2017-06-20 | 李文熙 | The manufacture method of high conductivity thick film aluminium cream |
| 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 |
| CN109166646A (en) * | 2018-08-14 | 2019-01-08 | 华中科技大学 | It is a kind of for carry on the back passivation silicon solar cell environment-friendly type aluminum electrode slurry |
| CN110044509A (en) * | 2019-04-30 | 2019-07-23 | 东莞珂洛赫慕电子材料科技有限公司 | A method of realizing thick film heating body surface temperature comprehensive monitoring |
| CN115772005A (en) * | 2021-09-06 | 2023-03-10 | 长春理工大学 | Preparation method of lead-free glass powder for silver paste of solar cell |
| CN114360762A (en) * | 2022-03-14 | 2022-04-15 | 西安拓库米电子科技有限公司 | Silver migration resistant silver conductor paste for sheet resistor and preparation method thereof |
| CN114822910A (en) * | 2022-05-20 | 2022-07-29 | 上海银浆科技有限公司 | Conductive silver-aluminum paste, preparation method, electrode and battery |
| CN114822910B (en) * | 2022-05-20 | 2022-12-06 | 上海银浆科技有限公司 | Conductive silver-aluminum paste, preparation method, electrode and battery |
| US11756699B1 (en) | 2022-05-20 | 2023-09-12 | Shanghai Silver Paste Sci. & Tech. Co., Ltd. | Conductive silver aluminum paste, preparation method, electrode and cell |
| CN115716711A (en) * | 2022-10-28 | 2023-02-28 | 广州市儒兴科技股份有限公司 | Glass powder, conductive paste, and preparation method and application thereof |
| CN115716711B (en) * | 2022-10-28 | 2023-12-15 | 广州市儒兴科技股份有限公司 | Glass powder, conductive paste and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103514973B (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103514973B (en) | Conductive paste for solar cell and preparation method thereof | |
| CN102157219B (en) | Silver paste for positive electrode of crystalline silicon solar cell and preparation method thereof | |
| CN101820002B (en) | Conductive paste for solar cell and preparation method thereof | |
| CN101609850B (en) | Lead-free silver conductive paste used for positive electrode of solar battery and preparation technique thereof | |
| CN102629496B (en) | Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry | |
| CN101931014B (en) | Conductive slurry for solar battery and preparation method | |
| CN105825913A (en) | Anti-aging back silver pulp used in crystalline silicon solar cell and preparation method for same | |
| CN102456427A (en) | Conductive paste and preparation method thereof | |
| CN104681122B (en) | Silver paste for front surface of solar battery and preparation method of silver paste | |
| CN103177791B (en) | A kind of aluminum conductive electric slurry used for solar batteries and preparation method thereof | |
| CN104979035A (en) | Lead-free composite glass adhesive solar battery positive silver paste | |
| CN101555388A (en) | Inorganic adhesive for aluminum paste of silicon solar cells and preparation method thereof | |
| CN103310871A (en) | Slurry for solar cells and preparation methods of slurry | |
| CN103183474B (en) | A kind of unorganic glass powder and preparation method thereof, a kind of electrocondution slurry and preparation method thereof | |
| CN110289121B (en) | Alloy aluminum paste for back of PERC solar cell | |
| CN102760511B (en) | Crystalline silicon solar cell BSF (back surface field) lead-free aluminum electroconductive slurry and preparation method thereof | |
| CN103165214A (en) | Solar cell aluminum electric-conduction slurry and preparation method thereof | |
| CN104751937A (en) | Aluminum conductive paste for solar cell and preparation method thereof | |
| CN101826564B (en) | Solar cell back surface field aluminum paste | |
| CN103426496A (en) | Aluminum back field slurry applied to solar battery, preparation method thereof, preparation method of solar battery piece and solar battery piece | |
| CN104751939B (en) | A kind of crystal silicon solar energy battery aluminum conductive electric slurry | |
| CN102651247B (en) | Novel conductive sizing agent for front-electrode of solar photovoltaic cell | |
| CN103177790B (en) | The preparation method of solar cell back surface field transition slurry and preparation method thereof and solar battery sheet and solar battery sheet | |
| CN114999704A (en) | Auxiliary glass powder additive for silver paste and preparation method thereof | |
| CN103366860A (en) | Solar cell used conductive slurry, preparation method thereof, and method for preparing solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |