CN106328247A - Lead-free silver paste for solar cell and preparation method of lead-free silver paste - Google Patents
Lead-free silver paste for solar cell and preparation method of lead-free silver paste Download PDFInfo
- Publication number
- CN106328247A CN106328247A CN201510376375.2A CN201510376375A CN106328247A CN 106328247 A CN106328247 A CN 106328247A CN 201510376375 A CN201510376375 A CN 201510376375A CN 106328247 A CN106328247 A CN 106328247A
- Authority
- CN
- China
- Prior art keywords
- lead
- powder
- preparation
- parts
- organic
- 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.)
- Pending
Links
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses lead-free silver paste for a solar cell and a preparation method of the lead-free silver paste. The silver paste is prepared from the following raw materials in parts by weight: 60-70 parts of silver powder, 0.5-5 parts of glass powder, 1-6 parts of organic carriers and 12-20 parts of assistants, wherein the glass powder is a Bi-Ba-Ti-Zr-Si-Al-Mg-Zn-O system; the organic carriers are prepared from an organic solvent and an organic additive; and the assistants are prevented from the following raw materials in parts by weight: 3-4 parts of boron oxide, 0.1-0.2 part of lauryl sodium sulfate, 0.5-0.6 part of dimethyl phthalate, 0.1-0.2 part of lecithin, 0.4-0.7 part of polysiloxane and 26-28 parts of turpentine. The lead-free silver paste does not contain lead, completely meets the environmental protection requirements, can form a conducting electrode with high adhesive force and low ohm contact resistance on the surface of the solar cell, and is an ideal substituent of lead-bearing silver paste; and the photoelectric conversion efficiency of the cell is high.
Description
Technical field
The present invention relates to technical field of solar, a kind of lead-free silver slurry used for solar batteries and preparation method thereof.
Background technology
Lead is a kind of cumulative toxicant, and it is easy to by gastrointestinal absorption, and a portion destroys blood makes erythrocyte decompose, and part is diffused into systemic organs and tissue by blood, and enters skeleton.And the lead compound being deposited in internal organs and bone marrow is extremely slow by the speed of internal discharge, gradually form chronic poisoning.Chronic lead poisoning is the most only felt tired, inappetence, lose weight.When chronic poisoning developing deeply, headache, tinnitus, visual disorder, miscarriage, anemia, mental disorder will be presented, early wait indefinitely.Europe all proposes unleaded requirement to electronic product, toy and solder, and the legal provisions put into effect such as EU member country rise on July 1st, 2006, enters the electronic product of European Union, including electronic toy, must not contain the harmful substances such as lead, cadmium, hydrargyrum.The above regulation all promotes various countries to accelerate to develop crown glass, including leadless crystal glass, lead-free optic glass, unleaded electrovacuum and electronic glass, crown glass solder.
Solar energy is as a kind of green energy resource, inexhaustible with it, pollution-free, be not increasingly subject to people's attention by advantages such as resource advantage are limited.The back side of existing solaode is can be in the n-type region that silicon chip back side is formed, and making n-type silicon transoid is p-type silicon, and at photoirradiated surface, in order to allow light enter inside quasiconductor, electrode is usually made comb teeth-shaped.Its front electrode silver slurry printing forms, and backplate is formed by silver slurry, silver aluminium paste or aluminium paste printing.Front electrode is with silver slurry generally by argentum powder, organic solvent, and glass dust etc. forms.Front electrode of solar battery silver slurry usually requires that good silk screen printing performance, the front silver electrode fine rule printed to have fine processability, the depth-width ratio i.e. printed electrode to be got well, but, the front side silver paste thixotropy of prior art and stability still have much room for improvement, and making the silver-colored arrangement of conductors after silk screen printing the finest and close so that the transformation efficiency of solaode is low.Due to lead bearing glass have that resistance is big, dielectric loss is little, refractive index and dispersion high, and absorb the series of characteristics such as high-energy radiation, softening temperature is low, chemical stability is good, its application in silver slurry used for solar batteries is relatively broad, in view of the hazardness of lead, silver slurry is unleaded is the inexorable trend of social development.
Summary of the invention
It is an object of the invention to provide a kind of lead-free silver slurry used for solar batteries and preparation method thereof, the silver slurry prepared can form in solar cell surface that adhesive force is strong, the conductive electrode of low ohm contact resistance, cell photoelectric conversion efficiency is high, is the preferable substituent of leaded silver slurry.
For achieving the above object, the present invention provides following technical scheme:
A kind of lead-free silver slurry used for solar batteries, according to mass fraction meter, is made up of following raw material: argentum powder 60-70 part, glass dust 0.5-5 part, organic carrier 1-6 part and auxiliary agent 12-20 part；Described glass dust is Bi-Ba-Ti-Zr-Si-Al-Mg-Zn-O system, according to mass percent, is made up of following raw material: Bi2O356-66%、BaCO32-3%、TiO26-8%、ZrO24-5%、SiO215-18%、Al2O33-3.5%, MgO3-3.5% and ZnO1-3%；Described organic carrier is made up of organic solvent and organic additive, and described organic solvent is one or more the mixture in terpineol and Oleum Terebinthinae, and described organic additive is one or more the mixture in ethyl cellulose and NC Nitroncellulose；Described auxiliary agent, according to mass fraction meter, is made up of following raw material: boron oxide 3-4 part, sodium lauryl sulphate 0.1-0.2 part, dimethyl phthalate 0.5-0.6 part, lecithin 0.1-0.2 part, polysiloxanes 0.4-0.7 part and Oleum Terebinthinae 26-28 part.
As the further scheme of the present invention: also include ultraviolet initiator 0.5-5 part and photosensitizer 0.5-4 part.
As the further scheme of the present invention: described ultraviolet initiator is one or both the mixture in benzophenone and 1-Phenylethanone., described photosensitizer is one or more mixture in camphorquinone, Benzoin derivative, acyl group phosphorous oxide, fluorination cyclopentadienyl titanium, diaryl group iodized salt, triaryl sulfonium salts and iron arene complexes.
The preparation method of described lead-free silver slurry used for solar batteries, comprises the following steps:
(1) preparation of glass dust, comprises the following steps:
11) dispensing: weigh Bi according to the above ratio2O3、BaCO3、TiO2、ZrO2、SiO2、Al2O3, MgO and ZnO, mix homogeneously；
12) preheating: put in corundum crucible by the powder after step 11) mix homogeneously, is then placed in the electric furnace of 350 DEG C insulation 45-60min；
13) sintering: the powder after step 12) being preheated puts into hot crucible, then puts in electric furnace by hot crucible, powder is warming up to 1120-1125 DEG C, constant temperature 1.2h；
14) shrend: take out the powder after step 13) sintering, carries out shrend, is then dried at a temperature of 85-90 DEG C, obtains frit；
15) grind: according to ball milling: water: the mass ratio of frit is that ball milling, water and frit are put in ball grinder by the ratio of 4:2:1, is put into by this ball grinder in ball mill and carries out ball milling, and Ball-milling Time is 8-12h, and drum's speed of rotation is 400r/min；
16) it is dried: by frit removal ground for step 15), be then dried at a temperature of 85-90 DEG C, obtain glass dust, standby；
(2) preparation of organic carrier: according to organic solvent: the mass ratio of organic additive is that the ratio of 6:1 weighs organic solvent and organic additive, and it is poured in the container of band agitating device respectively, at a temperature of 80-88 DEG C, blended stirring and dissolving, sieve, obtain organic carrier, standby；
(3) preparation of auxiliary agent: boron oxide is put in 550-580 DEG C of temperature lower calcination 2.5-3h in calcining furnace, take out and be cooled to room temperature, grind 60min；By dimethyl phthalate, Oleum Terebinthinae stirring and evenly mixing, at 150-170 DEG C, react 2.5-2.8h, after being cooled to 85-88 DEG C, add lecithin, polysiloxanes, sodium lauryl sulphate, insulated and stirred 5-5.5h, obtain product；By the boron oxide mixed grinding 3h after this product and calcining and grinding, crossing 350 mesh sieves, gained slurry is auxiliary agent, standby；
(4) preparation of silver slurry, comprises the following steps:
41) first the glass dust that argentum powder prepares with step (1) is added dehydrated alcohol to mix, at a temperature of 55 DEG C, stirring ultrasonic disperse 12min, obtain homodisperse solid fraction powder；
42) organic carrier and the step 41 then step (2) prepared) prepare solid fraction powder mix, stir and grind 15-25min, obtaining mixed slurry；
43) auxiliary agent and the step 42 finally prepared by step (3)) prepare mixed slurry mix, stir and grind 15-25min, prepare silver starch.
As the further scheme of the present invention: in described step (4), step 42) and step 43) between also include mixing mixed slurry with ultraviolet initiator and photosensitizer.
As the further scheme of the present invention: described ultraviolet initiator is one or both the mixture in benzophenone and 1-Phenylethanone.；Described photosensitizer is one or more mixture in camphorquinone, Benzoin derivative, acyl group phosphorous oxide, fluorination cyclopentadienyl titanium, diaryl group iodized salt, triaryl sulfonium salts and iron arene complexes.
Compared with prior art, the invention has the beneficial effects as follows: the present invention is the most leaded, comply fully with environmental requirement, can form in solar cell surface that adhesive force is strong, the conductive electrode of low ohm contact resistance, cell photoelectric conversion efficiency is high, is the preferable substituent of leaded silver slurry.The glass powder particles of the present invention is uniform, good dispersion, and softening point is between 350-400 DEG C；It is mainly composed of Bi2O3、SiO2、TiO2And ZrO2, and be equipped with remaining multiple a small amount of component and be combined with each other and be modified, promote the existing relatively low softening temperature of glass dust, have again reasonable sintering activating energy；Can promote that argentum powder preferably sinters, make electrode more closely knit, effectively reduce the oxidation of Argent grain, make solaode have high conversion efficiency, form good Ohmic contact, reduce series resistance.Silver of the present invention slurry can solidify to use heating or ultraviolet light irradiation mode；May be used for the structure of solaode and electron product circuit.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of lead-free silver slurry used for solar batteries, according to mass fraction meter, it is made up of following raw material: 60 parts of argentum powder, 0.5 part of glass dust, organic carrier 1 part and auxiliary agent 12 parts；Glass dust is Bi-Ba-Ti-Zr-Si-Al-Mg-Zn-O system, according to mass percent, is made up of following raw material: Bi2O356%、BaCO33%、TiO28%、ZrO25%、SiO218%、Al2O33.5%, MgO3.5% and ZnO3%；Organic carrier is made up of organic solvent and organic additive, and organic solvent is terpineol, and organic additive is ethyl cellulose；Auxiliary agent, according to mass fraction meter, is made up of following raw material: boron oxide 3 parts, sodium lauryl sulphate 0.1 part, dimethyl phthalate 0.5 part, 0.1 part of lecithin, polysiloxanes 0.4 part and Oleum Terebinthinae 26 parts.
The preparation method of described lead-free silver slurry used for solar batteries, comprises the following steps:
(1) preparation of glass dust, comprises the following steps:
11) dispensing: weigh Bi according to the above ratio2O3、BaCO3、TiO2、ZrO2、SiO2、Al2O3, MgO and ZnO, mix homogeneously；
12) preheating: put in corundum crucible by the powder after step 11) mix homogeneously, is then placed in the electric furnace of 350 DEG C insulation 60min；
13) sintering: the powder after step 12) being preheated puts into hot crucible, then puts in electric furnace by hot crucible, powder is warming up to 1120 DEG C, constant temperature 1.2h；
14) shrend: take out the powder after step 13) sintering, carries out shrend, is then dried at a temperature of 85 DEG C, obtains frit；
15) grind: according to ball milling: water: the mass ratio of frit is that ball milling, water and frit are put in ball grinder by the ratio of 4:2:1, is put into by this ball grinder in ball mill and carries out ball milling, and Ball-milling Time is 8h, and drum's speed of rotation is 400r/min；
16) it is dried: by frit removal ground for step 15), be then dried at a temperature of 85 DEG C, obtain glass dust, standby；
(2) preparation of organic carrier: according to organic solvent: the mass ratio of organic additive is that the ratio of 6:1 weighs organic solvent and organic additive, and it is poured in the container of band agitating device respectively, at a temperature of 88 DEG C, blended stirring and dissolving, sieve, obtain organic carrier, standby；
(3) preparation of auxiliary agent: boron oxide is put in 550 DEG C of temperature lower calcination 3h in calcining furnace, take out and be cooled to room temperature, grind 60min；By dimethyl phthalate, Oleum Terebinthinae stirring and evenly mixing, at 170 DEG C, react 2.5h, after being cooled to 85 DEG C, add lecithin, polysiloxanes, sodium lauryl sulphate, insulated and stirred 5.5h, obtain product；By the boron oxide mixed grinding 3h after this product and calcining and grinding, crossing 350 mesh sieves, gained slurry is auxiliary agent, standby；
(4) preparation of silver slurry, comprises the following steps:
41) first the glass dust that argentum powder prepares with step (1) is added dehydrated alcohol to mix, at a temperature of 55 DEG C, stirring ultrasonic disperse 12min, obtain homodisperse solid fraction powder；
42) organic carrier and the step 41 then step (2) prepared) prepare solid fraction powder mix, stir and grind 25min, obtaining mixed slurry；
43) auxiliary agent and the step 42 finally prepared by step (3)) prepare mixed slurry mix, stir and grind 15min, prepare silver starch.
Embodiment 2
In the embodiment of the present invention, a kind of lead-free silver slurry used for solar batteries, according to mass fraction meter, it is made up of following raw material: 70 parts of argentum powder, 5 parts of glass dust, organic carrier 6 parts, auxiliary agent 20 parts, ultraviolet initiator 0.5 part and photosensitizer 0.5 part；Glass dust is Bi-Ba-Ti-Zr-Si-Al-Mg-Zn-O system, according to mass percent, is made up of following raw material: Bi2O366%、BaCO32%、TiO26%、ZrO24%、SiO215%、Al2O33-%, MgO3% and ZnO1%；Organic carrier is made up of organic solvent and organic additive, and organic solvent is Oleum Terebinthinae, and organic additive is NC Nitroncellulose；Auxiliary agent, according to mass fraction meter, is made up of following raw material: boron oxide 4 parts, sodium lauryl sulphate 0.2 part, dimethyl phthalate 0.6 part, 0.2 part of lecithin, polysiloxanes 0.7 part and Oleum Terebinthinae 28 parts.Ultraviolet initiator is the mixture of benzophenone and 1-Phenylethanone., and photosensitizer is acyl group phosphorous oxide.
The preparation method of described lead-free silver slurry used for solar batteries, comprises the following steps:
(1) preparation of glass dust, comprises the following steps:
11) dispensing: weigh Bi according to the above ratio2O3、BaCO3、TiO2、ZrO2、SiO2、Al2O3, MgO and ZnO, mix homogeneously；
12) preheating: put in corundum crucible by the powder after step 11) mix homogeneously, is then placed in the electric furnace of 350 DEG C insulation 45min；
13) sintering: the powder after step 12) being preheated puts into hot crucible, then puts in electric furnace by hot crucible, powder is warming up to 1125 DEG C, constant temperature 1.2h；
14) shrend: take out the powder after step 13) sintering, carries out shrend, is then dried at a temperature of 85-90 DEG C, obtains frit；
15) grind: according to ball milling: water: the mass ratio of frit is that ball milling, water and frit are put in ball grinder by the ratio of 4:2:1, is put into by this ball grinder in ball mill and carries out ball milling, and Ball-milling Time is 12h, and drum's speed of rotation is 400r/min；
16) it is dried: by frit removal ground for step 15), be then dried at a temperature of 90 DEG C, obtain glass dust, standby；
(2) preparation of organic carrier: according to organic solvent: the mass ratio of organic additive is that the ratio of 6:1 weighs organic solvent and organic additive, and it is poured in the container of band agitating device respectively, at a temperature of 88 DEG C, blended stirring and dissolving, sieve, obtain organic carrier, standby；
(3) preparation of auxiliary agent: boron oxide is put in 580 DEG C of temperature lower calcination 2.5h in calcining furnace, take out and be cooled to room temperature, grind 60min；By dimethyl phthalate, Oleum Terebinthinae stirring and evenly mixing, at 150 DEG C, react 2.8h, after being cooled to 88 DEG C, add lecithin, polysiloxanes, sodium lauryl sulphate, insulated and stirred 5h, obtain product；By the boron oxide mixed grinding 3h after this product and calcining and grinding, crossing 350 mesh sieves, gained slurry is auxiliary agent, standby；
(4) preparation of silver slurry, comprises the following steps:
41) first the glass dust that argentum powder prepares with step (1) is added dehydrated alcohol to mix, at a temperature of 55 DEG C, stirring ultrasonic disperse 12min, obtain homodisperse solid fraction powder；
42) organic carrier and the step 41 then step (2) prepared) prepare solid fraction powder mix, stir and grind 15min, obtaining mixed slurry；
43) by step 42) after the mixed slurry for preparing mix with ultraviolet initiator and photosensitizer, the auxiliary agent finally step (3) prepared adds mixing, stirs and grinds 25min, prepares silver-colored slurry.
Embodiment 3
In the embodiment of the present invention, a kind of lead-free silver slurry used for solar batteries, according to mass fraction meter, it is made up of following raw material: 70 parts of argentum powder, 0.5 part of glass dust, organic carrier 1 part and auxiliary agent 12 parts；Glass dust is Bi-Ba-Ti-Zr-Si-Al-Mg-Zn-O system, according to mass percent, is made up of following raw material: Bi2O356%、BaCO33%、TiO28%、ZrO25%、SiO218%、Al2O33.5%, MgO3.5% and ZnO3%；Organic carrier is made up of organic solvent and organic additive, and organic solvent is terpineol, and organic additive is NC Nitroncellulose；Auxiliary agent, according to mass fraction meter, is made up of following raw material: boron oxide 3 parts, sodium lauryl sulphate 0.2 part, dimethyl phthalate 0.6 part, 0.1 part of lecithin, polysiloxanes 0.7 part and Oleum Terebinthinae 26 parts.
The preparation method of described lead-free silver slurry used for solar batteries, comprises the following steps:
(1) preparation of glass dust, comprises the following steps:
11) dispensing: weigh Bi according to the above ratio2O3、BaCO3、TiO2、ZrO2、SiO2、Al2O3, MgO and ZnO, mix homogeneously；
12) preheating: put in corundum crucible by the powder after step 11) mix homogeneously, is then placed in the electric furnace of 350 DEG C insulation 50min；
13) sintering: the powder after step 12) being preheated puts into hot crucible, then puts in electric furnace by hot crucible, powder is warming up to 1120 DEG C, constant temperature 1.2h；
14) shrend: take out the powder after step 13) sintering, carries out shrend, is then dried at a temperature of 90 DEG C, obtains frit；
15) grind: according to ball milling: water: the mass ratio of frit is that ball milling, water and frit are put in ball grinder by the ratio of 4:2:1, is put into by this ball grinder in ball mill and carries out ball milling, and Ball-milling Time is 8h, and drum's speed of rotation is 400r/min；
16) it is dried: by frit removal ground for step 15), be then dried at a temperature of 85 DEG C, obtain glass dust, standby；
(2) preparation of organic carrier: according to organic solvent: the mass ratio of organic additive is that the ratio of 6:1 weighs organic solvent and organic additive, and it is poured in the container of band agitating device respectively, at a temperature of 80 DEG C, blended stirring and dissolving, sieve, obtain organic carrier, standby；
(3) preparation of auxiliary agent: boron oxide is put in 580 DEG C of temperature lower calcination 2.5h in calcining furnace, take out and be cooled to room temperature, grind 60min；By dimethyl phthalate, Oleum Terebinthinae stirring and evenly mixing, at 170 DEG C, react 2.8h, after being cooled to 88 DEG C, add lecithin, polysiloxanes, sodium lauryl sulphate, insulated and stirred 5.5h, obtain product；By the boron oxide mixed grinding 3h after this product and calcining and grinding, crossing 350 mesh sieves, gained slurry is auxiliary agent, standby；
(4) preparation of silver slurry, comprises the following steps:
41) first the glass dust that argentum powder prepares with step (1) is added dehydrated alcohol to mix, at a temperature of 55 DEG C, stirring ultrasonic disperse 12min, obtain homodisperse solid fraction powder；
42) organic carrier and the step 41 then step (2) prepared) prepare solid fraction powder mix, stir and grind 25min, obtaining mixed slurry；
43) auxiliary agent and the step 42 finally prepared by step (3)) prepare mixed slurry mix, stir and grind 25min, prepare silver starch.
Embodiment 4
In the embodiment of the present invention, a kind of lead-free silver slurry used for solar batteries, according to mass fraction meter, it is made up of following raw material: 60 parts of argentum powder, 5 parts of glass dust, organic carrier 6 parts, auxiliary agent 20 parts, ultraviolet initiator 5 parts and photosensitizer 4 parts；Glass dust is Bi-Ba-Ti-Zr-Si-Al-Mg-Zn-O system, according to mass percent, is made up of following raw material: Bi2O366%、BaCO32%、TiO26%、ZrO24%、SiO215%、Al2O33%, MgO3% and ZnO1%；Organic carrier is made up of organic solvent and organic additive, and organic solvent is Oleum Terebinthinae, and organic additive is ethyl cellulose；Auxiliary agent, according to mass fraction meter, is made up of following raw material: boron oxide 4 parts, sodium lauryl sulphate 0.1 part, dimethyl phthalate 0.5 part, 0.2 part of lecithin, polysiloxanes 0.4 part and Oleum Terebinthinae 28 parts.Ultraviolet initiator is 1-Phenylethanone., and photosensitizer is Benzoin derivative.
The preparation method of described lead-free silver slurry used for solar batteries, comprises the following steps:
(1) preparation of glass dust, comprises the following steps:
11) dispensing: weigh Bi according to the above ratio2O3、BaCO3、TiO2、ZrO2、SiO2、Al2O3, MgO and ZnO, mix homogeneously；
12) preheating: put in corundum crucible by the powder after step 11) mix homogeneously, is then placed in the electric furnace of 350 DEG C insulation 60min；
13) sintering: the powder after step 12) being preheated puts into hot crucible, then puts in electric furnace by hot crucible, powder is warming up to 1125 DEG C, constant temperature 1.2h；
14) shrend: take out the powder after step 13) sintering, carries out shrend, is then dried at a temperature of 90 DEG C, obtains frit；
15) grind: according to ball milling: water: the mass ratio of frit is that ball milling, water and frit are put in ball grinder by the ratio of 4:2:1, is put into by this ball grinder in ball mill and carries out ball milling, and Ball-milling Time is 12h, and drum's speed of rotation is 400r/min；
16) it is dried: by frit removal ground for step 15), be then dried at a temperature of 85-90 DEG C, obtain glass dust, standby；
(2) preparation of organic carrier: according to organic solvent: the mass ratio of organic additive is that the ratio of 6:1 weighs organic solvent and organic additive, and it is poured in the container of band agitating device respectively, at a temperature of 80-88 DEG C, blended stirring and dissolving, sieve, obtain organic carrier, standby；
(3) preparation of auxiliary agent: boron oxide is put in 560 DEG C of temperature lower calcination 2.8h in calcining furnace, take out and be cooled to room temperature, grind 60min；By dimethyl phthalate, Oleum Terebinthinae stirring and evenly mixing, at 160 DEG C, react 2.5h, after being cooled to 85 DEG C, add lecithin, polysiloxanes, sodium lauryl sulphate, insulated and stirred 5h, obtain product；By the boron oxide mixed grinding 3h after this product and calcining and grinding, crossing 350 mesh sieves, gained slurry is auxiliary agent, standby；
(4) preparation of silver slurry, comprises the following steps:
41) first the glass dust that argentum powder prepares with step (1) is added dehydrated alcohol to mix, at a temperature of 55 DEG C, stirring ultrasonic disperse 12min, obtain homodisperse solid fraction powder；
42) organic carrier and the step 41 then step (2) prepared) prepare solid fraction powder mix, stir and grind 15min, obtaining mixed slurry；
43) by step 42) after the mixed slurry for preparing mix with ultraviolet initiator and photosensitizer, the auxiliary agent finally step (3) prepared adds mixing, stirs and grinds 15min, prepares silver-colored slurry.
Embodiment 5
In the embodiment of the present invention, a kind of lead-free silver slurry used for solar batteries, according to mass fraction meter, it is made up of following raw material: 65 parts of argentum powder, 2.5 parts of glass dust, organic carrier 4 parts, auxiliary agent 16 parts, ultraviolet initiator 2 parts and photosensitizer 2 parts；Glass dust is Bi-Ba-Ti-Zr-Si-Al-Mg-Zn-O system, according to mass percent, is made up of following raw material: Bi2O361%、BaCO32.5%、TiO27%、ZrO24.5%、SiO217%、Al2O33.5%, MgO3% and ZnO2%；Organic carrier is made up of organic solvent and organic additive, and organic solvent is terpineol and terebinthine mixture, and organic additive is the mixture of ethyl cellulose and NC Nitroncellulose；Auxiliary agent, according to mass fraction meter, is made up of following raw material: boron oxide 3.5 parts, sodium lauryl sulphate 0.15 part, dimethyl phthalate 0.55 part, 0.15 part of lecithin, polysiloxanes 0.5 part and Oleum Terebinthinae 27 parts.Ultraviolet initiator is benzophenone, and photosensitizer is camphorquinone.
The preparation method of described lead-free silver slurry used for solar batteries, comprises the following steps:
(1) preparation of glass dust, comprises the following steps:
11) dispensing: weigh Bi according to the above ratio2O3、BaCO3、TiO2、ZrO2、SiO2、Al2O3, MgO and ZnO, mix homogeneously；
12) preheating: put in corundum crucible by the powder after step 11) mix homogeneously, is then placed in the electric furnace of 350 DEG C insulation 55min；
13) sintering: the powder after step 12) being preheated puts into hot crucible, then puts in electric furnace by hot crucible, powder is warming up to 1125 DEG C, constant temperature 1.2h；
14) shrend: take out the powder after step 13) sintering, carries out shrend, is then dried at a temperature of 85 DEG C, obtains frit；
15) grind: according to ball milling: water: the mass ratio of frit is that ball milling, water and frit are put in ball grinder by the ratio of 4:2:1, is put into by this ball grinder in ball mill and carries out ball milling, and Ball-milling Time is 12h, and drum's speed of rotation is 400r/min；
16) it is dried: by frit removal ground for step 15), be then dried at a temperature of 85 DEG C, obtain glass dust, standby；
(2) preparation of organic carrier: according to organic solvent: the mass ratio of organic additive is that the ratio of 6:1 weighs organic solvent and organic additive, and it is poured in the container of band agitating device respectively, at a temperature of 88 DEG C, blended stirring and dissolving, sieve, obtain organic carrier, standby；
(3) preparation of auxiliary agent: boron oxide is put in 560 DEG C of temperature lower calcination 2.8h in calcining furnace, take out and be cooled to room temperature, grind 60min；By dimethyl phthalate, Oleum Terebinthinae stirring and evenly mixing, at 160 DEG C, react 2.8h, after being cooled to 85 DEG C, add lecithin, polysiloxanes, sodium lauryl sulphate, insulated and stirred 5.5h, obtain product；By the boron oxide mixed grinding 3h after this product and calcining and grinding, crossing 350 mesh sieves, gained slurry is auxiliary agent, standby；
(4) preparation of silver slurry, comprises the following steps:
41) first the glass dust that argentum powder prepares with step (1) is added dehydrated alcohol to mix, at a temperature of 55 DEG C, stirring ultrasonic disperse 12min, obtain homodisperse solid fraction powder；
42) organic carrier and the step 41 then step (2) prepared) prepare solid fraction powder mix, stir and grind 15min, obtaining mixed slurry；
43) by step 42) after the mixed slurry for preparing mix with ultraviolet initiator and photosensitizer, the auxiliary agent finally step (3) prepared adds mixing, stirs and grinds 25min, prepares silver-colored slurry.
The present invention is the most leaded, complies fully with environmental requirement, can form in solar cell surface that adhesive force is strong, the conductive electrode of low ohm contact resistance, and cell photoelectric conversion efficiency is high, is the preferable substituent of leaded silver slurry.The glass powder particles of the present invention is uniform, good dispersion, and softening point is between 350-400 DEG C；It is mainly composed of Bi2O3、SiO2、TiO2And ZrO2, and be equipped with remaining multiple a small amount of component and be combined with each other and be modified, promote the existing relatively low softening temperature of glass dust, have again reasonable sintering activating energy；Can promote that argentum powder preferably sinters, make electrode more closely knit, effectively reduce the oxidation of Argent grain, make solaode have high conversion efficiency, form good Ohmic contact, reduce series resistance.Silver of the present invention slurry can solidify to use heating or ultraviolet light irradiation mode；May be used for the structure of solaode and electron product circuit.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, and without departing from the spirit or essential characteristics of the present invention, it is possible to realize the present invention in other specific forms.Therefore, no matter from the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is limited by claims rather than described above, it is intended that all changes fallen in the implication of equivalency and scope of claim included in the present invention.
In addition, it is to be understood that, although this specification is been described by according to embodiment, but the most each embodiment only comprises an independent technical scheme, this narrating mode of description is only for clarity sake, description should can also be formed, through appropriately combined, other embodiments that it will be appreciated by those skilled in the art that as an entirety, the technical scheme in each embodiment by those skilled in the art.
Claims (6)
1. a lead-free silver slurry used for solar batteries, it is characterised in that according to mass fraction meter, be made up of following raw material: argentum powder 60-70 part, glass dust 0.5-5 part, organic carrier 1-6 part and auxiliary agent 12-20 part；Described glass dust is Bi-Ba-Ti-Zr-Si-Al-Mg-Zn-O system, according to mass percent, is made up of following raw material: Bi2O356-66%、BaCO32-3%、TiO26-8%、ZrO24-5%、SiO215-18%、Al2O33-3.5%, MgO3-3.5% and ZnO1-3%；Described organic carrier is made up of organic solvent and organic additive, and described organic solvent is one or more the mixture in terpineol and Oleum Terebinthinae, and described organic additive is one or more the mixture in ethyl cellulose and NC Nitroncellulose；Described auxiliary agent, according to mass fraction meter, is made up of following raw material: boron oxide 3-4 part, sodium lauryl sulphate 0.1-0.2 part, dimethyl phthalate 0.5-0.6 part, lecithin 0.1-0.2 part, polysiloxanes 0.4-0.7 part and Oleum Terebinthinae 26-28 part.
Lead-free silver slurry used for solar batteries the most according to claim 1, it is characterised in that also include ultraviolet initiator 0.5-5 part and photosensitizer 0.5-4 part.
Lead-free silver slurry used for solar batteries the most according to claim 2; it is characterized in that; described ultraviolet initiator is one or both the mixture in benzophenone and 1-Phenylethanone., and described photosensitizer is one or more mixture in camphorquinone, Benzoin derivative, acyl group phosphorous oxide, fluorination cyclopentadienyl titanium, diaryl group iodized salt, triaryl sulfonium salts and iron arene complexes.
4. the preparation method of a lead-free silver slurry used for solar batteries as claimed in claim 1, it is characterised in that comprise the following steps:
(1) preparation of glass dust, comprises the following steps:
11) dispensing: weigh Bi according to the above ratio2O3、BaCO3、TiO2、ZrO2、SiO2、Al2O3, MgO and ZnO, mix homogeneously；
12) preheating: put in corundum crucible by the powder after step 11) mix homogeneously, is then placed in the electric furnace of 350 DEG C insulation 45-60min；
13) sintering: the powder after step 12) being preheated puts into hot crucible, then puts in electric furnace by hot crucible, powder is warming up to 1120-1125 DEG C, constant temperature 1.2h；
14) shrend: take out the powder after step 13) sintering, carries out shrend, is then dried at a temperature of 85-90 DEG C, obtains frit；
15) grind: according to ball milling: water: the mass ratio of frit is that ball milling, water and frit are put in ball grinder by the ratio of 4:2:1, is put into by this ball grinder in ball mill and carries out ball milling, and Ball-milling Time is 8-12h, and drum's speed of rotation is 400r/min；
16) it is dried: by frit removal ground for step 15), be then dried at a temperature of 85-90 DEG C, obtain glass dust, standby；
(2) preparation of organic carrier: according to organic solvent: the mass ratio of organic additive is that the ratio of 6:1 weighs organic solvent and organic additive, and it is poured in the container of band agitating device respectively, at a temperature of 80-88 DEG C, blended stirring and dissolving, sieve, obtain organic carrier, standby；
(3) preparation of auxiliary agent: boron oxide is put in 550-580 DEG C of temperature lower calcination 2.5-3h in calcining furnace, take out and be cooled to room temperature, grind 60min；By dimethyl phthalate, Oleum Terebinthinae stirring and evenly mixing, at 150-170 DEG C, react 2.5-2.8h, after being cooled to 85-88 DEG C, add lecithin, polysiloxanes, sodium lauryl sulphate, insulated and stirred 5-5.5h, obtain product；By the boron oxide mixed grinding 3h after this product and calcining and grinding, crossing 350 mesh sieves, gained slurry is auxiliary agent, standby；
(4) preparation of silver slurry, comprises the following steps:
41) first the glass dust that argentum powder prepares with step (1) is added dehydrated alcohol to mix, at a temperature of 55 DEG C, stirring ultrasonic disperse 12min, obtain homodisperse solid fraction powder；
42) organic carrier and the step 41 then step (2) prepared) prepare solid fraction powder mix, stir and grind 15-25min, obtaining mixed slurry；
43) auxiliary agent and the step 42 finally prepared by step (3)) prepare mixed slurry mix, stir and grind 15-25min, prepare silver starch.
The preparation method of lead-free silver slurry used for solar batteries the most according to claim 4, it is characterised in that in described step (4), step 42) and step 43) between also include mixing mixed slurry with ultraviolet initiator and photosensitizer.
The preparation method of lead-free silver slurry used for solar batteries the most according to claim 5, it is characterised in that described ultraviolet initiator is one or both the mixture in benzophenone and 1-Phenylethanone.；Described photosensitizer is one or more mixture in camphorquinone, Benzoin derivative, acyl group phosphorous oxide, fluorination cyclopentadienyl titanium, diaryl group iodized salt, triaryl sulfonium salts and iron arene complexes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510376375.2A CN106328247A (en) | 2015-07-01 | 2015-07-01 | Lead-free silver paste for solar cell and preparation method of lead-free silver paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510376375.2A CN106328247A (en) | 2015-07-01 | 2015-07-01 | Lead-free silver paste for solar cell and preparation method of lead-free silver paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106328247A true CN106328247A (en) | 2017-01-11 |
Family
ID=57722116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510376375.2A Pending CN106328247A (en) | 2015-07-01 | 2015-07-01 | Lead-free silver paste for solar cell and preparation method of lead-free silver paste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106328247A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113113170A (en) * | 2021-04-14 | 2021-07-13 | 上海日御新材料科技有限公司 | Front electrode for battery |
| CN113161035A (en) * | 2021-04-28 | 2021-07-23 | 佛山市顺德区百锐新电子材料有限公司 | General silver paste for lead-free piezoelectric ceramic and preparation method thereof |
-
2015
- 2015-07-01 CN CN201510376375.2A patent/CN106328247A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113113170A (en) * | 2021-04-14 | 2021-07-13 | 上海日御新材料科技有限公司 | Front electrode for battery |
| CN113161035A (en) * | 2021-04-28 | 2021-07-23 | 佛山市顺德区百锐新电子材料有限公司 | General silver paste for lead-free piezoelectric ceramic and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102136308B (en) | Organic carrier for silver paste and preparation method thereof as well as silver paste containing organic carrier and solar cell manufactured from silver paste | |
| CN102126829B (en) | Lead-free glass powder, preparation method thereof, silver paste containing glass powder and crystal silicon solar cell manufactured by using silver paste | |
| CN104979035B (en) | Lead-free composite glass adhesive solar battery positive silver paste | |
| CN104064286B (en) | A kind of preparation method of silver slurry used for solar batteries | |
| CN104505139B (en) | Low-resistance high-efficiency lead-free back silver pulp for amorphous silicon solar battery | |
| CN105097071B (en) | Positive conductive silver paste of silicon solar cell and preparation method of positive conductive silver paste | |
| CN101609724A (en) | A kind of electrode thick liquid without lead and silver and preparation method thereof | |
| CN101931014A (en) | Conductive slurry for solar battery and preparation method | |
| CN103295659B (en) | Conductive paste for solar cell and preparation method thereof | |
| CN103137239B (en) | A kind of front electrode of solar battery silver slurry and preparation method thereof and a kind of solar battery sheet | |
| CN106887271B (en) | Modified lead-free silver slurry of a kind of graphene and preparation method thereof | |
| CN102674696B (en) | A kind of glass powder and preparation method thereof and a kind of conductive silver paste and preparation method thereof | |
| CN106098144A (en) | A kind of glass dust and with its solar cell front side silver paste prepared and preparation method thereof | |
| CN103165214B (en) | A kind of aluminum conductive electric slurry used for solar batteries and preparation method thereof | |
| CN105321594B (en) | Positive silver paste of silicon solar cell and preparation method of positive silver paste | |
| CN102436865B (en) | High-photo-electricity environment-friendly type crystalline silicon solar battery aluminum paste | |
| CN105000806A (en) | Lead-free glass powder for back silver paste of silicon-based solar battery and preparation method of lead-free glass powder | |
| CN103310868B (en) | A kind of electronic devices and components silver slurry and preparation method thereof | |
| CN106328247A (en) | Lead-free silver paste for solar cell and preparation method of lead-free silver paste | |
| CN106504814A (en) | Glass dust, positive silver paste and preparation method thereof | |
| CN101931013A (en) | Solar cell conductive paste and preparation method thereof | |
| CN103177792A (en) | Lead-free aluminum paste for solar cell and preparation method thereof | |
| CN104318978B (en) | Electro-conductive paste with core shell conductive particles and preparation method thereof | |
| CN104058595B (en) | A kind of lead-free glass powder of silver paste of solar cells | |
| CN106448802A (en) | Conductive paste composition and semiconductor devices made therewith |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170111 |
|
| WD01 | Invention patent application deemed withdrawn after publication |