CN102103895B - Silver paste used for positive electrodes of solar batteries and grid lines, preparation method thereof and solar battery containing same - Google Patents
Silver paste used for positive electrodes of solar batteries and grid lines, preparation method thereof and solar battery containing same Download PDFInfo
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- CN102103895B CN102103895B CN2010105553192A CN201010555319A CN102103895B CN 102103895 B CN102103895 B CN 102103895B CN 2010105553192 A CN2010105553192 A CN 2010105553192A CN 201010555319 A CN201010555319 A CN 201010555319A CN 102103895 B CN102103895 B CN 102103895B
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Abstract
The invention discloses a silver paste used for positive electrodes of solar batteries and grid lines, which comprises silver powder, glass powder, additive and an organic carrier. The silver paste is prepared by the following steps of: preparing a highly dispersed superfine silver grout used as the silver powder through a chemical liquid phase reduction method, then obtaining wet silver powder through solid-liquid separation, and preparing the agglomerate-free silver paste through direct mixing of the wet silver powder and the glass powder, the additive and the organic carrier according to the specified proportion without drying. The method for preparing the positive silver paste directly by using the wet silver powder comprises the steps of: preparation of the superfine silver powder through the chemical liquid phase reduction method, solid-liquid separation, washing, and direct preparation of the silver paste without a drying procedure in which the silver powder is easily agglomerated. The silver paste is characterized by high dispersity, no agglomeration and smaller fineness; and positive electrodes of solar batteries and grid lines, prepared through the screen printing and fast sintering process, have high definition, high evenness, high electrical conductivity and excellent photoelectric conversion efficiency.
Description
Technical field
The invention belongs to technical field of solar batteries, relate to a kind of front electrode of solar battery and grid line by hygrometric state silver powder preparation with conductive silver paste and preparation method thereof with contain the solar cell that this silver paste prepares.
Background technology
Solar energy is a kind of green energy resource, and is pollution-free, inexhaustible because of it, do not receive advantages such as region resource limit more and more to receive people's attention, so solar cell has arisen at the historic moment.Solar cell is a kind of semiconductor device that can solar energy converting be become electric energy, and solar cell can produce electric current under the condition of illumination, electric collecting is got up and transfers out through grid line and electrode.Front electrode of solar battery and grid line all are to be processed by technologies such as the silk screen printing of conductive silver paste through high-speed, high precision, low temperature drying, high temperature sinterings.
Solar cell front side silver paste mainly is made up of silver powder, glass dust, additive and organic carrier four parts.
Method to the silver powder preparation has many reports at present; Main method has spray heating decomposition, electrolysis, microwave plasma method, direct-current arc heat plasma method, mechanochemical synthesis, electron beam irradiation method etc.; But all there is weak point in these methods; Need the special atmosphere environment such as what have, the equipment of the needs that have specialty, the power consumption that has is big.The liquid phase chemical reduction method becomes the main method of present preparation silver powder because of advantages such as its experimental facilities are simple, easy to operate, cost is low, energy-conservation.Its method is in the aqueous solution, to reduce silver nitrate with reducing agent, after Separation of Solid and Liquid, wash, dry, sieve, obtain silver powder.
The patent application of chemical liquid phase reduction legal system silver powder is more; Like one Chinese patent application " preparation method of high dispersed superfine spherical silver powder for conductive silver slurry " (application number 200810097399.4); Its method is that silver ammino solution is added drop-wise in the reduction system of being made up of reducing agent formaldehyde, polyethylene of dispersing agent alcohol PVA and sodium hydroxide solution; Obtain the super fine silver powder slurries of high dispersive,, obtain particle size range at 0.3～1.0 micron polymolecularity superfine spherical silver powder again through Separation of Solid and Liquid and drying.Similarly also such as European patent EP 1930104A1, U.S. Pat 20090116998A1 and US20100065789A1 etc.The technology of above patent is greatly improved to the dispersiveness of silver powder, but in dry run, still has agglomeration to exist.Usually, super fine silver powder is easy to form aggregate in dry run.Agglomeration can be divided into soft-agglomerated and hard aggregation by the form of bonding.If it is soft-agglomerated that the reunion that the bonding on the Chemical Physics such as Van der Waals force causes is called, and soft-agglomerated available mechanical means is broken up; If the reunion by bondings chemically such as hydrogen bond, bridging oxygen key cause is called hard aggregation, hard aggregation then is difficult to break up with mechanical means, so in the preparation process, will reduce or avoid the generation of hard aggregation as far as possible.The reunion that silver powder forms in dry run often belongs to the latter, is difficult to break up with mechanical means.Big aggregate is after being mixed with the silver slurry, though grind through three rollers, fineness still is difficult to reduce; Thereby in screen printing process, be difficult to, stop up silk screen through silk screen; Accurate electrode and grid line will form breakpoint and broken string, and the electric current of battery sheet generation is difficult to effective transmission like this, has finally influenced the electrical property of battery; Electricity conversion is reduced, be difficult to satisfy the requirement of high performance solar batteries.
Summary of the invention
Technical problem to be solved by this invention is in dry run, to be prone to form reunite to existing silver powder in the prior art, and particularly hard aggregation makes the silver paste that is made in screen printing process; Be difficult to through silk screen, stop up silk screen, make electrode and grid line form breakpoint and broken string; And then the electric current that the battery sheet is produced is difficult to effective transmission, finally makes electricity conversion hang down these defectives, provides a kind of front electrode of solar battery and grid line of preparing with silver paste and preparation method thereof with contain the solar cell that this silver paste prepares; Silver powder in this silver paste adopts hygrometric state silver powder; This hygrometric state silver powder does not have agglomeration to take place, and the silver paste of being prepared does not have hard agglomeration, not or be not easy to occur soft aggregate yet; In screen printing process; Silk screen can not occur stopping up, make electrode and grid line not have breakpoint and broken string, obtain excellent solar cell.
Solving the technical scheme that technical problem of the present invention adopted is that this preparation front electrode of solar battery and grid line comprise silver powder, glass dust, additive and organic carrier with silver paste; Described silver powder is through the chemical liquid phase reducing process: silver ammino solution is joined the super fine silver powder slurries that prepared in reaction in the reduction system obtains high dispersive; Obtain hygrometric state silver powder through Separation of Solid and Liquid then; Without drying, the silver paste that directly is mixed with in the ratio of stipulating with this hygrometric state silver powder and glass dust, additive and organic carrier.
Preferably said process Separation of Solid and Liquid obtains hygrometric state silver powder again through washing.
Further preferably described washing is with washing several times, and preferred deionized water wash hygrometric state silver powder makes the resistivity of washing lotion reach 0.8-1.2M Ω cm, preferred 1M Ω cm, centrifugation then;
Further preferably adopt alcohols material again after the washing, preferred BC (being that viscosity, boiling point according to solvent is well-chosen with BC preferably) washing 1-4 time is preferably washed 3 times, and centrifugation obtains hard aggregation-free body hygrometric state silver powder again;
The silver paste of preferably preparing in the ratio of regulation with hygrometric state silver powder and glass dust, additive and organic carrier; Be that hygrometric state silver powder, glass dust, additive and organic carrier are measured; Its concrete metering method is: hygrometric state silver powder is carried out solid content in advance measure, prepare resulting silver paste by the amount of the required silver powder of actual proportioning according to the amount that solid content calculates required hygrometric state silver powder then.Can account for the 65-85% of slurry gross weight by the silver powder butt with hygrometric state silver powder and glass dust, additive and organic carrier preparation silver paste; Glass dust accounts for the 1-10% of slurry gross weight; Organic carrier accounts for the 10-20% of slurry gross weight; Additive accounts for the 0.1-2% of slurry gross weight, calculates the amount of required hygrometric state silver powder according to the solid content in the hygrometric state silver powder, substitutes the amount of required butt silver powder with this.
A kind of above-described front electrode of solar battery and grid line of preparing may further comprise the steps with the method for silver paste:
1. prepare the super fine silver powder slurries of high dispersive through the chemical liquid phase reducing process: silver ammino solution is joined react the super fine silver powder slurries that make high dispersive in the reduction system; Described reduction system refers to comprise the reduction system of reducing agent, dispersant formation, also can comprise sodium hydroxide solution as required.Reducing agent can adopt formaldehyde, hydrazine hydrate or ascorbic acid etc., and dispersant can adopt polyvinylpyrrolidone, polyvinyl alcohol or gelatin etc.;
2. obtain hygrometric state silver powder through Separation of Solid and Liquid;
3. can wash hygrometric state silver powder
4. without drying, directly be mixed with the silver paste of hard aggregation-free body in the ratio of regulation with this hygrometric state silver powder and glass dust, additive and organic carrier.
Washing is with washing several times in the preferably said step 3, and preferred deionized water wash hygrometric state silver powder makes the resistivity of washing lotion reach 0.8-1.2M Ω cm, preferred 1M Ω cm, centrifugation then.
Further preferably adopt alcohols material again after the washing, preferred BC washing 1-4 time is preferably washed 3 times, and centrifugation obtains hygrometric state silver powder again.
Preferably prepare silver paste with hygrometric state silver powder and glass dust, additive and organic carrier in the ratio of regulation in the above step (4); Be that hygrometric state silver powder, glass dust, additive and organic carrier are measured; Its concrete metering method is: measure hygrometric state silver powder solid content earlier; Calculate the amount of required hygrometric state silver powder then according to hygrometric state silver powder solid content by the amount of the required silver powder of actual proportioning; Account for the 65-85% of slurry gross weight with hygrometric state silver powder and glass dust, additive and organic carrier preparation silver paste by the silver powder butt, glass dust accounts for the 1-10% of slurry gross weight, and organic carrier accounts for the 10-20% of slurry gross weight; Additive accounts for the 0.1-2% of slurry gross weight; Calculate the amount of required hygrometric state silver powder according to the solid content in the hygrometric state silver powder, substitute the amount of required butt silver powder, obtain silver paste with glass dust, additive and organic carrier preparation again with this.Can account for the 65-85% of slurry gross weight by the silver powder butt with hygrometric state silver powder and glass dust, additive and organic carrier preparation silver paste; Glass dust accounts for the 1-10% of slurry gross weight; Organic carrier accounts for the 10-20% of slurry gross weight; Additive accounts for the 0.1-2% of slurry gross weight, calculates the amount of required hygrometric state silver powder according to the solid content in the hygrometric state silver powder, substitutes the amount of required butt silver powder with this.
Each component of hygrometric state silver powder, glass dust, additive and organic carrier after further preferably will accurately measuring stirs in advance, three-roll grinder grind 3～5 times to the slurry fineness be below the 8 μ m.
The present invention also provides the solar cell of the silver paste manufacturing of the above method preparation of a kind of usefulness; Promptly the silver paste with the above method preparation makes solar panel front electrode and grid line with conductive silver paste through the silk screen printing sintering on cell substrates, obtains required solar cell.
The present invention prepares super fine silver powder without the dry run that is prone to make silver powder to produce to reunite and directly prepare silver paste with hygrometric state silver powder through the chemical liquid phase reducing process; The silver paste of this abbreviated system preparation has been avoided the hard aggregation that occurs in the dry run; Suppressed the tendency that the produced in conventional processes super fine silver powder is easy to reunite to greatest extent; Significantly improved the dispersiveness of silver powder; And then reduced the fineness of slurry, and to compare with the positive silver paste (fineness 12～15 μ m) of common preparation, fineness can be decreased to below the 8 μ m greatly.Silver paste fineness by its preparation is little; In screen printing process, can see through silk screen easily; Behind the silk screen printing sintering, electrode and grid line do not have defectives such as breakpoint, accumulation and broken string, and weight in wet base is big after the battery printing; Sintering rear electrode line has bigger depth-width ratio (can reach 0.25～0.30); Both shortened the technological process of preparation silver paste, improved the electric conductivity of silver paste greatly again and the monocrystaline silicon solar cell sheet that makes thus has high-resolution, high-flatness, high conductivity and an excellent photoelectric transformation efficiency, reached more than 17.3%.The present invention is used to prepare the method for the conductive silver paste of front electrode of solar battery and grid line; Prepare the super fine silver powder slurries through the chemical liquid phase reducing process; Through after Separation of Solid and Liquid, the washing, directly prepare silver paste, the silver powder good dispersion that obtains then with hygrometric state silver powder without dry run; Alleviate the degree that silver powder is in the past reunited through super-dry, thereby improved the electricity conversion of solar cell.In addition, also reduce processing step, thereby saved the production time, save the energy and production cost and manpower, had tangible beneficial effect.
Description of drawings
Fig. 1 is the SEM comparison diagram of silver paste thick film after the printing oven dry, and left figure is that comparative example 1 usefulness dry state silver powder is made, and right figure is that embodiment 1 usefulness hygrometric state silver powder is made
Embodiment
Prepare front electrode of solar battery of the present invention and grid line and comprise silver powder, glass dust, additive and organic carrier with silver paste, described silver powder is through the chemical liquid phase reducing process silver ammino solution to be joined to react the super fine silver powder slurries that make high dispersive in the reduction system; Described reduction system refers to comprise the reduction system of reducing agent, dispersant formation, also can comprise sodium hydroxide solution as required.Reducing agent can adopt formaldehyde, hydrazine hydrate or ascorbic acid etc., and dispersant can adopt polyvinylpyrrolidone, polyvinyl alcohol or gelatin etc.; Obtain hygrometric state silver powder through Separation of Solid and Liquid then, after hygrometric state silver powder is washed,, directly be mixed with the silver paste of hard aggregation-free body in the ratio of regulation with this hygrometric state silver powder and glass dust, additive and organic carrier without drying.
Can be with hygrometric state silver powder and glass dust, additive and organic carrier preparation silver paste by one Chinese patent application numbers 200910304311.6; Denomination of invention: disclosed scheme in " front electrode of solar battery is with electric conductor slurry and preparation technology thereof ", silver powder (butt) accounts for the 65-85% of slurry gross weight; Glass dust is the Pb-B-Si-Zn-Ti-Al-O glass frit, accounts for the 1-10% of slurry gross weight; Organic carrier accounts for the 10-20% of slurry gross weight; Additive accounts for the 0.1-2% of slurry gross weight.The main component of glass dust shared percentage by weight in glass dust is: PbO 50-70%, B
2O
32-5%, SiO
220-30%, ZnO 1-5%, TiO 0.1-3%, Al
2O
32-5%; Organic carrier comprises organic solvent, thickener, surfactant and diluent: organic solvent occupies the 60-80% of airborne body gross weight, is a kind of in terpinol, ATBC, pine wood oil, the carbitol or any multiple mixture; Thickener occupies the 5-20% of airborne body gross weight; Be a kind of or any multiple mixture in ethyl cellulose, acrylic acid ester, the NC Nitroncellulose; Surfactant is hard acid ester salt; The 1-10% that occupies airborne body gross weight, diluent is ethanol, acetate or terpenes, occupies the 0.5-10% of airborne body gross weight; Additive comprises BaO and CaO powder, and the weight ratio of BaO and CaO powder is 0.5-1.5, and particle size range is the 1-5 micron.
Calculate the amount of required hygrometric state silver powder according to the solid content in the hygrometric state silver powder, substitute the amount of required butt silver powder with this.
Below in conjunction with non-limiting examples of the present invention, the present invention is made further detailed description.Table 1 is the electrical performance data of the battery of embodiment and comparative example.
Embodiment 1
Preparation front electrode of solar battery and grid line are used silver paste, may further comprise the steps:
1. prepare the super fine silver powder slurries of high dispersive through the chemical liquid phase reducing process: the solution 20L that silver nitrate is mixed with 0.15mol/L; With ammoniacal liquor and nitric acid its pH value is transferred to 7, forms silver ammino solution, again the reducing agent hydrazine hydrate is made into the solution 20L of 0.30mol/L; In reductant solution, add 100g polyethylene of dispersing agent pyrrolidones again; With ammoniacal liquor and nitric acid its pH value is transferred to 8, silver ammino solution liquid droping speed with 2L/min under 300 rev/mins electronic stirring is added drop-wise in reducing agent and the dispersant solution, after dropwising; Reacted again 10 minutes, and obtained the super fine silver powder slurries of high dispersive;
2. the super fine silver powder slurries are obtained hygrometric state silver powder through Separation of Solid and Liquid: make Separation of Solid and Liquid with centrifuge, the solid that obtains is a hygrometric state silver powder;
3. hygrometric state silver powder is washed: use the deionized water wash solid, make the resistivity of washing lotion reach 1M Ω cm, centrifugation then, with 4L BC washing 3 times, centrifugation obtains hygrometric state silver powder more at last;
4. without drying; Directly be mixed with positive silver paste by the following stated: at first 100 gram hygrometric state silver powder are carried out the solid content test with this hygrometric state silver powder and glass dust, additive and organic carrier; The test solid content is 95%; With 100g hygrometric state silver powder and 5g glass dust (press application number: 200910304311.6, the shared percentage by weight of its main component is in this glass dust: PbO 64.9%, B
2O
33.5%, SiO
224.8%, ZnO 2.7%, TiO 0.7%, Al
2O
33.4%), the 1g additive (adopts BaO and CaO powder; The weight ratio of BaO and CaO powder is 1; Particle size range is the 1-5 micron) (adopt terpinol to occupy 70% of airborne body gross weight with the 13g organic carrier as organic solvent; Ethyl cellulose occupies 15% of airborne body gross weight as thickener, and hard acid ester salt occupies 10% of airborne body gross weight as surfactant, ethanol as diluent occupy airborne body gross weight 5%); Mix stirring, three-roll grinder grind 3～5 times to the slurry fineness be below the 8 μ m, obtain required silver paste.
This silver paste is printed on the solar cell substrate behind the sintering; Obtain front electrode of solar battery and grid line, electrode and grid line do not have defectives such as breakpoint, accumulation and broken string, and the monocrystaline silicon solar cell sheet that makes thus can obtain the excellent photoelectric transformation efficiency; Reach 17.324% through test; Other electric properties are seen table 1, are 16.832% by 1 electricity conversion of comparative example in the table 1, and embodiment 1 is than about 0.5 percentage point of comparative example 1 height; Its performance obviously is superior to comparative example 1, and general electricity conversion all is very big progress for every high 0.1 percentage point.Fig. 1 is the SEM comparison diagram of prepared silver paste thick film after the printing oven dry, and left figure is that comparative example 1 usefulness dry state silver powder is made, and right figure is that present embodiment 1 usefulness hygrometric state silver powder is made.Left figure by Fig. 1 can find out that the made silver paste of dry state silver powder obviously has hard agglomeration (being the white agglomerate among the figure), and does not have aggregate among the right figure, and even particle distribution.Behind sintering, the battery sheet electricity conversion that the slurry printing that the hygrometric state silver powder of test proof embodiment 1 usefulness hard aggregation-free body is done is burnt till is apparently higher than the comparative example that hard agglomeration is arranged 1.
Embodiment 2
Preparation front electrode of solar battery and grid line are used silver paste, may further comprise the steps:
1. prepare the super fine silver powder slurries of high dispersive through the chemical liquid phase reducing process: the solution 20L that silver nitrate is mixed with 0.15mol/L; With ammoniacal liquor and nitric acid its pH value is transferred to 7, forms silver ammino solution, again reducing agent formaldehyde is made into the solution 20L of 0.30mol/L; In reductant solution, add 100g polyethylene of dispersing agent alcohol again; With ammoniacal liquor and nitric acid its pH value is transferred to 8, silver ammino solution liquid droping speed with 2L/min under 300 rev/mins electronic stirring is added drop-wise in reducing agent and the dispersant solution, after dropwising; Reacted again 10 minutes, and obtained the super fine silver powder slurries of high dispersive;
2. the super fine silver powder slurries are obtained hygrometric state silver powder through Separation of Solid and Liquid: make Separation of Solid and Liquid with centrifuge, the solid that obtains is a hygrometric state silver powder;
3. hygrometric state silver powder is washed: use deionized water wash, make the resistivity of washing lotion reach 1M Ω cm, centrifugation then, with 4L BC washing 3 times, centrifugation obtains hygrometric state silver powder more at last;
4. without drying; Directly be mixed with positive silver paste by the following stated: at first 100 gram hygrometric state silver powder are carried out the solid content test with this hygrometric state silver powder and glass dust, additive and organic carrier; The test solid content is 95%; With 100g hygrometric state silver powder and 5g glass dust, 1g additive and 13g organic carrier (glass dust, additive and organic carrier prescription with embodiment 1 in identical) mix stirring, three-roll grinder grind 3～5 times to the slurry fineness be below the 8 μ m, obtain required silver paste.
This silver paste is printed on the solar cell substrate behind the sintering; Obtain front electrode of solar battery and grid line; Electrode and grid line do not have defectives such as breakpoint, accumulation and broken string; The monocrystaline silicon solar cell sheet that makes thus can obtain the excellent photoelectric transformation efficiency, reaches 17.683% through test, and other electric properties are seen table 1.Close among the SEM figure of its prepared silver paste thick film after the printing oven dry and the right figure of Fig. 1, there is not aggregate, and even particle distribution.
Embodiment 3
Preparation front electrode of solar battery and grid line are used silver paste, may further comprise the steps:
1. prepare the super fine silver powder slurries of high dispersive through the chemical liquid phase reducing process: the solution 20L that silver nitrate is mixed with 0.15mol/L; With ammoniacal liquor and nitric acid its pH value is transferred to 7, forms silver ammino solution, again the reducing agent ascorbic acid is made into the solution 20L of 0.30mol/L; In reductant solution, add 100g dispersant gelatin again; With ammoniacal liquor and nitric acid its pH value is transferred to 8, silver ammino solution liquid droping speed with 2L/min under 300 rev/mins electronic stirring is added drop-wise in reducing agent and the dispersant solution, after dropwising; Reacted again 10 minutes, and obtained the super fine silver powder slurries of high dispersive;
2. the super fine silver powder slurries are obtained hygrometric state silver powder through Separation of Solid and Liquid: make Separation of Solid and Liquid with centrifuge, the solid that obtains is a hygrometric state silver powder;
3. hygrometric state silver powder is washed: use deionized water wash, make the resistivity of washing lotion reach 1M Ω cm, then centrifugation; At last with 4L BC washing 3 times; Centrifugation obtains hygrometric state silver powder again, prepares positive silver paste then; At first 100 gram hygrometric state silver powder are carried out the solid content test; The test solid content is 95%, and it is below the 8 μ m that 100g hygrometric state silver powder and 5g glass dust, 1g additive and 13g organic carrier (glass dust, additive and organic carrier prescription with embodiment 1 in identical) are mixed stirring, three-roll grinder grinding 3～5 times to slurry fineness, obtains required silver paste.
This silver paste is printed on the solar cell substrate behind the sintering; Obtain front electrode of solar battery and grid line; Electrode and grid line do not have defectives such as breakpoint, accumulation and broken string; The monocrystaline silicon solar cell sheet that makes thus can obtain the excellent photoelectric transformation efficiency, reaches 17.801% through test, and other electric properties are seen table 1.Close among the SEM figure of its prepared silver paste thick film after the printing oven dry and the right figure of Fig. 1, there is not aggregate, and even particle distribution.
Comparative example 1
Silver nitrate is mixed with the solution 20L of 0.15mol/L, its pH value is transferred to 7, form silver ammino solution with ammoniacal liquor and nitric acid; Again the reducing agent ascorbic acid is made into the solution 20L of 0.30mol/L, in reductant solution, adds 100g dispersant gelatin again, its pH value is transferred to 8 with ammoniacal liquor and nitric acid; Silver ammino solution liquid droping speed with 2L/min under 300 rev/mins electronic stirring is added drop-wise in reducing agent and the dispersant solution, after dropwising, reacted again 10 minutes; Make Separation of Solid and Liquid with centrifuge then, use deionized water wash, make the resistivity of washing lotion reach 1M Ω cm; Centrifugation then; With 4L BC washing 3 times, centrifugation obtains hygrometric state silver powder more at last.In 60 ℃ of vacuumizes 12 hours, obtain dried silver powder then.With the dried silver powder of 100g and 5.26g glass dust, 1.05g additive and 18.95g organic carrier mixing stirring, after three-roll grinder ground 3～5 times, the slurry fineness was 15 μ m.Behind the printing sintering, electrode and grid line have defectives such as breakpoint, accumulation and broken string with this slurry, and the electricity conversion of the monocrystaline silicon solar cell sheet that makes thus is 16.832%.Fig. 1 is the SEM comparison diagram of prepared silver paste thick film after the printing oven dry, and left figure is that comparative example 1 usefulness dry state silver powder is made.Left figure by Fig. 1 can find out that the made silver paste of dry state silver powder obviously has hard agglomeration (being the white agglomerate among the figure).
The electrical performance data of the battery of table 1 embodiment and comparative example
Claims (10)
1. one kind prepares front electrode of solar battery and grid line is used silver paste; Comprise silver powder, glass dust, additive and organic carrier, it is characterized in that described silver powder is through the chemical liquid phase reducing process: silver ammino solution is joined the super fine silver powder slurries that prepared in reaction obtains high dispersive in the reduction system, pass through Separation of Solid and Liquid then and obtain hygrometric state silver powder; Hygrometric state silver powder is again through washing; Described washing is with washing several times, makes the resistivity of washing lotion reach 0.8-1.2M Ω cm, then centrifugation; Without drying; The silver paste that directly is mixed with in the ratio of stipulating with this hygrometric state silver powder and glass dust, additive and organic carrier; Promptly account for the 65-85% of slurry gross weight by the silver powder butt with hygrometric state silver powder and glass dust, additive and organic carrier preparation silver paste; Glass dust accounts for the 1-10% of slurry gross weight, and organic carrier accounts for the 10-20% of slurry gross weight, and additive accounts for the 0.1-2% of slurry gross weight; Calculate the amount of required hygrometric state silver powder according to the solid content in the hygrometric state silver powder; Substitute the amount of required butt silver powder with this, adopt BaO and CaO powder as additive, the slurry fineness that each set of dispense of hygrometric state silver powder, glass dust, additive and organic carrier is processed is below the 8 μ m.
2. silver paste according to claim 1 is characterized in that said hygrometric state silver powder is with deionized water wash hygrometric state silver powder with water washing, makes the resistivity of washing lotion reach 1M Ω cm, and centrifugation obtains hard aggregation-free body hygrometric state silver powder then.
3. silver paste according to claim 1 and 2 is characterized in that adopting alcohols material washing 1-4 time again after the washing of hygrometric state silver powder, and centrifugation obtains hard aggregation-free body hygrometric state silver powder again;
4. silver paste according to claim 3 is characterized in that said employing alcohols material washing is to adopt BC washing 3 times.
5. silver paste according to claim 1; It is characterized in that with hygrometric state silver powder and glass dust, additive and organic carrier silver paste in the ratio preparation of regulation; Be that hygrometric state silver powder, glass dust, additive and organic carrier are measured; Its concrete metering method is: hygrometric state silver powder is carried out solid content in advance measure, prepare resulting silver paste by the amount of the required silver powder butt of actual proportioning according to the amount that solid content calculates required hygrometric state silver powder then.
6. one kind prepares front electrode of solar battery and grid line with the method for silver paste, may further comprise the steps:
(1) prepares the super fine silver powder slurries of high dispersive through the chemical liquid phase reducing process: silver ammino solution is joined the super fine silver powder slurries that reaction in the reduction system makes high dispersive;
(2) obtain hygrometric state silver powder through Separation of Solid and Liquid;
(3) hygrometric state silver powder water is washed several times, make the resistivity of washing lotion reach 0.8-1.2M Ω cm, then centrifugation;
(4) without drying; Directly be mixed with the silver paste of hard aggregation-free body in the ratio of regulation with this hygrometric state silver powder and glass dust, additive and organic carrier; Promptly account for the 65-85% of slurry gross weight by the silver powder butt with hygrometric state silver powder and glass dust, additive and organic carrier preparation silver paste; Glass dust accounts for the 1-10% of slurry gross weight, and organic carrier accounts for the 10-20% of slurry gross weight, and additive accounts for the 0.1-2% of slurry gross weight; Calculate the amount of required hygrometric state silver powder according to the solid content in the hygrometric state silver powder; Substitute the amount of required butt silver powder with this, adopt BaO and CaO powder as additive, it is below the 8 μ m that each component of hygrometric state silver powder, glass dust, additive and organic carrier is ground to form the slurry fineness.
7. the method for preparing front electrode of solar battery and grid line with silver paste according to claim 6 is characterized in that adopting alcohols material BC washing 1-4 time again after said step (3) washing, and centrifugation obtains hygrometric state silver powder again.
8. according to claim 6 or the 7 described methods that prepare front electrode of solar battery and grid line with silver paste; It is characterized in that preparing silver paste with hygrometric state silver powder and glass dust, additive and organic carrier in the ratio of regulation in the said step (4); Be that hygrometric state silver powder, glass dust, additive and organic carrier are measured; Its concrete metering method is: measure hygrometric state silver powder solid content earlier, calculate the amount of required hygrometric state silver powder then by the amount of the required silver powder butt of actual proportioning according to hygrometric state silver powder solid content.
9. the method for preparing front electrode of solar battery and grid line with silver paste according to claim 6, it is characterized in that in the step (4) with each component of hygrometric state silver powder, glass dust, additive and organic carrier grind be with each component of hygrometric state silver powder, glass dust, additive and organic carrier after the accurate metering stir in advance, three-roll grinder grinding 3～5 times to slurry fineness is below the 8 μ m.
10. solar cell with the silver paste manufacturing of the said method of one of claim 6-9 preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105553192A CN102103895B (en) | 2010-11-23 | 2010-11-23 | Silver paste used for positive electrodes of solar batteries and grid lines, preparation method thereof and solar battery containing same |
Applications Claiming Priority (1)
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| CN104217783A (en) * | 2014-09-19 | 2014-12-17 | 无锡光富光伏材料有限公司 | Reduced graphene oxide nano-silver paste and preparation method and application thereof |
| CN104505140B (en) * | 2014-12-16 | 2017-06-23 | 安徽凤阳德诚科技有限公司 | A kind of conductive silver paste of effective thickening |
| CN105798327B (en) * | 2016-05-13 | 2018-06-26 | 浙江光达电子科技有限公司 | Improve the preparation method of the hygrometric state silver powder of slurry fineness |
| CN110444316B (en) * | 2019-08-07 | 2022-03-25 | 中山大学 | Low-temperature curing conductive silver paste with high conductivity and low silver content and preparation method thereof |
| CN114014972B (en) * | 2021-11-15 | 2022-11-08 | 上海银浆科技有限公司 | Ketone hydrazine crosslinking system for organic carrier in photovoltaic silver paste |
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| CN101279376A (en) * | 2008-05-15 | 2008-10-08 | 金川集团有限公司 | Preparation of high dispersed superfine spherical silver powder for conductive silver slurry |
| CN101289581A (en) * | 2008-06-16 | 2008-10-22 | 中南大学 | Method for preparing aluminum paste coated by polystyrene resin |
| CN101707062A (en) * | 2009-12-03 | 2010-05-12 | 北京有色金属研究总院 | Nano-silver powder, manufacturing method and application thereof |
| CN101716685A (en) * | 2009-12-14 | 2010-06-02 | 昆明理工大学 | Method for preparing spherical superfine silver powder by using chemical reduction method |
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| JP4789426B2 (en) * | 2004-04-26 | 2011-10-12 | 太陽ホールディングス株式会社 | Glass composition for silver paste, photosensitive silver paste and electrode pattern using the same |
| CN101816048A (en) * | 2007-10-18 | 2010-08-25 | E.I.内穆尔杜邦公司 | Conductive compositions and processes for use in the manufacture of semiconductor devices: multiple busbars |
| CN101708553B (en) * | 2009-12-11 | 2011-04-20 | 长沙奥特金属颜料有限公司 | Method for manufacturing high-metal-sense aluminum silver paste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101279376A (en) * | 2008-05-15 | 2008-10-08 | 金川集团有限公司 | Preparation of high dispersed superfine spherical silver powder for conductive silver slurry |
| CN101289581A (en) * | 2008-06-16 | 2008-10-22 | 中南大学 | Method for preparing aluminum paste coated by polystyrene resin |
| CN101707062A (en) * | 2009-12-03 | 2010-05-12 | 北京有色金属研究总院 | Nano-silver powder, manufacturing method and application thereof |
| CN101716685A (en) * | 2009-12-14 | 2010-06-02 | 昆明理工大学 | Method for preparing spherical superfine silver powder by using chemical reduction method |
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