CN115274178B - High-concentration graphene conductive silver paste and preparation method thereof - Google Patents
High-concentration graphene conductive silver paste and preparation method thereof Download PDFInfo
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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Abstract
A high-concentration graphene conductive silver paste and a preparation method thereof relate to a conductive silver paste and a preparation method thereof. The invention aims to solve the problems that the graphene doped silver powder prepared by the existing method is uneven in silver powder particle and graphene doping, insecure in particle silver powder and graphene compounding, too harsh in reaction conditions and poor in conductivity of the conductive paste prepared from the silver powder particle and graphene. The high-concentration graphene conductive silver paste is prepared from 80-90 parts by weight of lamellar graphene @ lamellar silver, 2-5 parts by weight of glass powder and 8-16 parts by weight of organic carrier. The preparation method comprises the following steps: 1. weighing 80-90 parts of lamellar graphene @ lamellar silver, 2-5 parts of glass powder and 8-16 parts of organic carrier according to parts by weight; 2. mixing, rolling and sieving. The photoelectric conversion efficiency of the solar cell screen-printed by the high-concentration graphene conductive silver paste prepared by the method can reach 22.822%.
Description
Technical Field
The invention relates to conductive silver paste and a preparation method thereof.
Background
The conductive silver paste is a high-technology electronic functional material, is mainly used for manufacturing thick-film integrated circuits, resistors, resistor networks, capacitors, MLCCs, conductive ink, solar cell electrodes, LEDs, printed and high-resolution conductors, membrane switches/flexible circuits, conductive adhesives, sensitive components and other electronic components and the like, and the conductive characteristic of the conductive silver paste is realized by the main component of silver powder.
Adopt the silver powder that constitutes by single silver granule to make electrically conductive silver thick liquid among the prior art, its silver granule gathers easily and has a large amount of gaps, can add a certain amount of dispersant for solving the gathering, and the effective contact between the silver granule can be reduced in the gap simultaneously, and both can reduce the electric conductive property of silver thick liquid. Most of the silver powder prepared by the traditional reduction method is granular, and the particles are in point contact with each other, so that the conductivity cannot be reflected to the maximum extent.
Graphene is a new material with sp hybridized and connected carbon atoms tightly packed into a single-layer two-dimensional honeycomb lattice structure, has excellent optical, electrical and mechanical properties, has an important application prospect, and is considered to be a revolutionary material in the future. At present, related reports of graphene doped silver powder exist, wherein the phenomena that silver powder particles and graphene are not uniformly doped, the particle-shaped silver powder and the graphene are not firmly compounded, the reaction conditions are too harsh or the application is single and the like exist mostly, and therefore, the invention provides the high-concentration graphene conductive silver paste and the preparation method thereof.
Disclosure of Invention
The invention aims to solve the problems that the silver powder particles and graphene are not uniformly doped, the particle-shaped silver powder and the graphene are not firmly compounded, the reaction conditions are too harsh, and the conductivity of the conductive paste prepared from the silver powder particles and the graphene is poor in the graphene doped silver powder prepared by the existing method, and provides the high-concentration graphene conductive silver paste and the preparation method thereof.
The high-concentration graphene conductive silver paste is prepared from 80-90 parts by weight of lamellar graphene @ lamellar silver, 2-5 parts by weight of glass powder and 8-16 parts by weight of organic carrier;
the organic carrier is prepared from a solvent, a plasticizer, a binder, a thickening agent, a coupling agent, a surfactant and a defoaming agent;
the lamellar graphene @ lamellar silver is prepared from 0.5-7 mass percent of lamellar graphene solution and silver nitrate solution serving as raw materials.
A preparation method of high-concentration graphene conductive silver paste is completed according to the following steps:
1. weighing:
weighing 80-90 parts of lamellar graphene @ lamellar silver, 2-5 parts of glass powder and 8-16 parts of organic carrier according to parts by weight;
the organic carrier in the first step is prepared by the following steps:
(1) weighing a solvent, a plasticizer, a binder, a thickening agent, a coupling agent, a surfactant and a defoaming agent to obtain a reagent;
(2) stirring the reagent for 0.5 to 2h at the temperature of 55 to 85 ℃ and at the stirring speed of 800 to 1500r/min, filtering by using a 300-600 mesh screen, and cooling to room temperature to obtain an organic carrier;
2. mixing:
uniformly mixing the lamellar graphene @ lamellar silver, the glass powder and the organic carrier weighed in the step one, then rolling the mixture by using a three-roll mill, and filtering the mixture by using a 400-600-mesh screen to obtain the high-concentration graphene conductive silver paste.
The glass powder used in the invention is commercial glass powder.
The invention has the advantages that:
1. the photoelectric conversion efficiency of the solar cell screen-printed by the high-concentration graphene conductive silver paste prepared by the method can reach 22.822%;
2. the high-concentration graphene conductive silver paste prepared by the method is printed on a monocrystalline silicon wafer, and the aspect ratio of the monocrystalline silicon wafer can reach 0.4111;
3. the flaky silver powder prepared by the invention can form surface-to-surface contact, and flaky particles are mutually overlapped in a fish scale shape at a certain thickness after printing, so that better conductivity is shown;
4. the graphene doped silver powder prepared by the prior art is prepared by independently preparing the graphene doped silver powder and the granular silver powder and then mixing the two silver powder, so that the phenomenon of uneven doping is easily caused, and the graphene is of a lamellar structure, so that the phenomenon of infirm compounding of the graphene and the granular silver powder is often caused by external conditions when the graphene and the granular silver powder are compounded; the prepared lamellar graphene @ lamellar silver is uniformly doped and firmly compounded;
5. the method can be completed at normal temperature and normal pressure, and the graphene doping is generally completed by a hydrothermal method and cannot be completed at normal temperature and normal pressure;
6. the lamellar graphene @ lamellar silver prepared by the invention not only can be used as an electronic functional material, but also can consider the value of the material in the aspects of medical use and the like.
Drawings
FIG. 1 is an SEM photograph of a 10 μm solution of 3% by mass lamellar graphene in step one (4) of example 1;
FIG. 2 is a SEM photograph of a 2 μm solution of 5% by mass lamellar graphene obtained in step one (4) of example 2;
FIG. 3 is a SEM photograph of a 2 μm solution of 7% by mass lamellar graphene obtained in step one (4) of example 3;
FIG. 4 is an SEM image of 10 μm of lamellar graphene @ lamellar silver prepared in step four of example 1;
FIG. 5 is an SEM image of 5 μm silver @ lamellar graphene prepared in step four of example 2;
FIG. 6 is an SEM image of 5 μm of sheet graphene @ sheet silver prepared in step four of example 3;
fig. 7 is a 3D microscopic image of glass frit dispersion during sintering of a high concentration graphene conductive silver paste screen printed solar cell made using the lamellar graphene @ lamellar silver prepared in example 1 with glass frit and organic vehicle in example 4;
fig. 8 is a 3D micrograph of glass frit dispersion during sintering for a high concentration graphene conductive silver paste screen printed solar cell of example 5 prepared using lamellar graphene @ lamellar silver prepared in example 2 with glass frit and organic vehicle;
fig. 9 is a 3D microscopic image of glass frit fly-away during sintering of a high concentration graphene conductive silver paste screen printed solar cell made using the lamellar graphene @ lamellar silver and glass frit, organic vehicle made in example 6, prepared in example 3;
fig. 10 is a 3D microscopic image of glass frit dispersion during sintering of a conductive silver paste screen printed solar cell prepared using commercial silver powder with glass frit and organic vehicle in example 7.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting thereof. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the high-concentration graphene conductive silver paste is prepared from 80-90 parts by weight of lamellar graphene @ lamellar silver, 2-5 parts by weight of glass powder and 8-16 parts by weight of organic carrier;
the organic carrier is prepared from a solvent, a plasticizer, a binder, a thickening agent, a coupling agent, a surfactant and a defoaming agent;
the lamellar graphene @ lamellar silver is prepared from a lamellar graphene solution and a silver nitrate solution which are 0.5-7% in mass percentage.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the high-concentration graphene conductive silver paste is prepared from 82 parts of lamellar graphene @ lamellar silver, 4 parts of glass powder and 14 parts of organic carrier in parts by weight. The other steps are the same as those in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the solvent is a mixture of terpineol and butyl carbitol acetate; the plasticizer is dibutyl phthalate; the binder is ethyl cellulose; the thickening agent is polyurethane thickening agent; the polyurethane thickener is polyurethane, bentonite or hydrogenated castor oil. The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is: the coupling agent is a silane coupling agent; the silane coupling agent is KH-550, KH-570 or isopropyl tri (dioctyl phosphate acyloxy) titanate; the surfactant is lecithin; the defoaming agent is methyl silicate. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and the first to the fourth embodiments is: the organic carrier is prepared from 64 parts of solvent, 8 parts of plasticizer, 7 parts of binder, 4 parts of thickener, 5 parts of coupling agent, 4.5 parts of surfactant and 7.5 parts of defoamer. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the preparation method of the lamellar graphene @ lamellar silver is completed according to the following steps:
1. preparing lamellar graphene solutions with different mass fractions:
(1) adding graphene into absolute ethyl alcohol to obtain a graphene premixed solution with the mass fraction of 0.5%;
(2) stirring the graphene premixed solution with the mass fraction of 0.5% under a sealed condition, then performing ultrasonic dispersion under an ice bath and the sealed condition, and adding absolute ethyl alcohol at intervals in the ultrasonic dispersion process to obtain a lamellar graphene solution with the mass fraction of 0.5%;
(3) firstly, adding graphene into a graphene solution with the mass fraction of 0.5%, stirring under a sealed condition, performing ultrasonic dispersion under an ice bath and the sealed condition, and adding absolute ethyl alcohol at intervals in the ultrasonic dispersion process to obtain a lamellar graphene solution with the mass fraction of 1%;
(4) circulating the step one (3) for 1-12 times to obtain a lamellar graphene solution with the mass fraction of 0.5-7%;
2. preparing a silver acid solution:
dissolving silver nitrate into deionized water, adding Arabic gum, and stirring uniformly at room temperature to obtain a silver nitrate solution;
3. preparing sol:
(1) dispersing polyvinyl alcohol into absolute ethyl alcohol, and stirring at room temperature to obtain sol;
(2) dripping a lamellar graphene solution with the mass fraction of 0.5-7% into the sol prepared in the step three (1) under the stirring condition, and carrying out ultrasonic treatment under the sealing condition to obtain a lamellar graphene sol;
4. preparing lamellar graphene @ lamellar silver:
dropwise adding a silver nitrate solution into the lamellar graphene sol under the condition of stirring, then adding sodium borohydride into the lamellar graphene sol for 10min to 30min in several times, stirring the mixture for reaction, and then adding polyethylene glycol and hydrazine hydrate into the mixture for 10min to 30min in several times to obtain a reaction system; adjusting the pH value of the reaction system to 6.5-9.5 by using ammonia water, and finally stirring and reacting at the reaction temperature of 10-40 ℃ to obtain a reaction product; and filtering, cleaning and vacuum drying the reaction product to obtain the lamellar graphene @ lamellar silver. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: adding absolute ethyl alcohol every 30min in the ultrasonic dispersion process in the step one (2); the stirring time in the step one (2) is 60min to 120min; the time of the ultrasonic dispersion in the step one (2) is from 3h to 15h; the mass of the graphene in the step one (3) is the same as that of the graphene in the step one (1); adding absolute ethyl alcohol every 30min in the ultrasonic dispersion process in the step one (3); stirring in the step one (3) for 60min to 120min; and (4) the time of ultrasonic dispersion in the step one (3) is from 3h to 15h. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the concentration of silver nitrate in the silver nitrate solution in the second step is 1-2 mol/L; the mass ratio of the gum arabic to the silver nitrate in the silver nitrate solution in the step two (0.5-1) is 1; the volume ratio of the mass of the polyvinyl alcohol to the volume of the absolute ethyl alcohol in the step three (1) is (0.2g to 0.8g) to (60mL to 140mL); stirring for 2h to 3h in the third step (1), wherein the stirring speed is 200r/min to 600r/min; the time of the ultrasonic treatment in the third step (2) is 2h to 8h, wherein evaporated absolute ethyl alcohol is added every 30 min; the volume ratio of the lamellar graphene solution to the sol in the third step (2) is (0.1-5): 1. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: in the fourth step, the stirring reaction is carried out at the reaction temperature of 10-40 ℃ for 3-24h; the mass fraction of the ammonia water in the step four is 3% -5%; the mass ratio of the sodium borohydride to the silver nitrate in the reaction system in the fourth step is (0.8-2.8) to 1; the mass ratio of the polyethylene glycol to the silver nitrate in the reaction system in the fourth step is (0.4 to 1.2) to 1; the mass ratio of hydrazine hydrate to silver nitrate in the reaction system in the fourth step is (0.5 to 2.5) to 1; the volume ratio of the silver nitrate solution to the lamellar graphene sol in the fourth step is (1 to 80) to (1 to 1200). The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is a preparation method of the high-concentration graphene conductive silver paste, which is completed according to the following steps:
1. weighing:
weighing 80-90 parts of lamellar graphene @ lamellar silver, 2-5 parts of glass powder and 8-16 parts of organic carrier according to parts by weight;
the organic carrier in the first step is prepared by the following steps:
(1) weighing a solvent, a plasticizer, a binder, a thickening agent, a coupling agent, a surfactant and a defoaming agent to obtain a reagent;
(2) stirring the reagent for 0.5h to 2h at the temperature of 55-85 ℃ and the stirring speed of 800-1500 r/min, filtering by using a 300-600 mesh screen, and cooling to room temperature to obtain an organic carrier;
2. mixing:
uniformly mixing the lamellar graphene @ lamellar silver, the glass powder and the organic carrier weighed in the step one, then rolling the mixture by using a three-roll mill, and filtering the mixture by using a 400-600-mesh screen to obtain the high-concentration graphene conductive silver paste.
The present invention will be described in detail with reference to examples.
Example 1: a method for preparing sol gel system lamellar graphene @ lamellar silver by taking graphene as a template method is specifically completed according to the following steps:
1. preparing lamellar graphene solutions with different mass fractions:
(1) adding graphene into absolute ethyl alcohol to obtain a graphene premixed solution with the mass fraction of 0.5%;
(2) stirring the graphene premixed solution with the mass fraction of 0.5% under a sealed condition, then performing ultrasonic dispersion under an ice bath and the sealed condition, and adding absolute ethyl alcohol at intervals in the ultrasonic dispersion process to obtain a laminar graphene solution with the mass fraction of 0.5%;
adding absolute ethyl alcohol every 30min in the ultrasonic dispersion process in the step one (2);
the stirring time in the step one (2) is 90min;
the ultrasonic dispersion time in the step one (2) is 8h;
(3) firstly, adding graphene into a graphene solution with the mass fraction of 0.5%, stirring under a sealed condition, performing ultrasonic dispersion under an ice bath and the sealed condition, and adding absolute ethyl alcohol at intervals in the ultrasonic dispersion process to obtain a lamellar graphene solution with the mass fraction of 1%;
the mass of the graphene in the step one (3) is the same as that of the graphene in the step one (1);
adding absolute ethyl alcohol every 30min in the ultrasonic dispersion process in the step one (3);
the stirring time in the step one (3) is 95min;
the ultrasonic dispersion time in the step one (3) is 8.5h;
(4) circulating the step one (3) for 4 times to obtain a 3% mass fraction lamellar graphene solution;
2. preparing a silver acid solution:
dissolving silver nitrate into deionized water, adding gum arabic, and uniformly stirring at room temperature to obtain a silver nitrate solution;
the concentration of silver nitrate in the silver nitrate solution in the second step is 1.55mol/L;
the mass ratio of the gum arabic to the silver nitrate in the silver nitrate solution in the second step is 0.75;
3. preparing sol:
(1) dispersing polyvinyl alcohol into absolute ethyl alcohol, and stirring at room temperature to obtain sol;
the volume ratio of the mass of the polyvinyl alcohol to the absolute ethyl alcohol in the step three (1) is 0.45g;
the stirring time in the step three (1) is 2.5h, and the stirring speed is 500r/min;
(2) dripping a 3% lamellar graphene solution into the sol prepared in the step three (1) under the stirring condition, and carrying out ultrasonic treatment under the sealing condition to obtain a lamellar graphene sol;
the ultrasonic treatment time in the step three (2) is 6h, wherein evaporated absolute ethyl alcohol is added every 30 min;
the volume ratio of the lamellar graphene solution to the sol in the step three (2) is 3.8;
4. preparing lamellar graphene @ lamellar silver:
dropwise adding a silver nitrate solution into the lamellar graphene sol under the stirring condition, then adding sodium borohydride for 25min in several times, stirring for reaction, and then adding polyethylene glycol and hydrazine hydrate for 28min in several times to obtain a reaction system; adjusting the pH value of the reaction system to 8 by using ammonia water, and finally stirring and reacting at the reaction temperature of 25 ℃ to obtain a reaction product; filtering the reaction product, washing with distilled water, and drying in vacuum to obtain lamellar graphene @ lamellar silver;
in the fourth step, the last stirring reaction time at the reaction temperature of 25 ℃ is 18h;
the mass fraction of the ammonia water in the step four is 3.5 percent;
the mass ratio of the sodium borohydride to the silver nitrate in the reaction system in the fourth step is 1.9;
the mass ratio of the polyethylene glycol to the silver nitrate in the reaction system in the step four is 0.85;
the mass ratio of hydrazine hydrate to silver nitrate in the reaction system in the fourth step is 1.8;
the volume ratio of the silver nitrate solution to the lamellar graphene sol in step four is 300.
Example 2: the present example is different from example 1 in that: step one (3) and step one (4) are cycled for 8 times to obtain a lamellar graphene solution with the mass fraction of 5%; and step three (2), under the stirring condition, dripping the lamellar graphene solution with the mass fraction of 5% into the sol prepared in the step three (1), and carrying out ultrasonic treatment under the sealing condition to obtain the lamellar graphene sol. The other steps and parameters were the same as in example 1.
Example 3: the present embodiment is different from embodiment 1 in that: in the step one (4), the step one (3) is circulated for 12 times to obtain a 7% mass fraction lamellar graphene solution; and step three (2), under the stirring condition, dripping the lamellar graphene solution with the mass fraction of 7% into the sol prepared in the step three (1), and then carrying out ultrasonic treatment under the sealing condition to obtain the lamellar graphene sol. The other steps and parameters were the same as in example 1.
FIG. 1 is an SEM image of 10 μm solution of 3% by mass of lamellar graphene in step one (4) of example 1;
after the 3% mass fraction lamellar graphene solution is dried, the morphology of the solution is tested, and as can be seen from fig. 1: the graphene lamellar structure is clear and visible by adopting an ultrasonic dispersion method, but the small-multiple scanning morphology is not clear due to the relatively small content.
FIG. 2 is a SEM photograph of a 2 μm solution of 5% by mass lamellar graphene obtained in step one (4) of example 2;
after the lamellar graphene solution with the mass fraction of 5% is dried, the morphology of the solution is tested, and as can be seen from fig. 2: the graphene lamellar structure is clearly visible by adopting an ultrasonic dispersion method; the lamellar graphene solution with low mass fraction has no obvious effect or performance, the lamellar graphene solution with high mass fraction can cause inevitable impurities, the lamellar layer in the lamellar graphene solution with intrinsic mass fraction is more clear, and the small-multiple scanning morphology is also clear.
FIG. 3 is an SEM image of a 2 μm solution of 7% by mass of lamellar graphene in step one (4) of example 3;
after drying the 7% by mass of the lamellar graphene solution, testing the morphology of the solution, as shown in FIG. 3; the lamellar structure can be seen from fig. 3, but the content is not as well defined as 7% graphene lamellar since more graphene causes inevitable impurities.
FIG. 4 is an SEM image of 10 μm silver @ lamellar graphene prepared in step four of example 1;
the 3% lamellar graphene @ lamellar silver is tested for morphology, and the graphene is not well covered on the silver after the graphene with relatively low content is compounded with the silver powder, which shows that the compounding of the graphene with low content and the silver powder cannot achieve the optimal effect, and meanwhile, the small-multiple scanning morphology is not clear due to the low content of the graphene.
FIG. 5 is an SEM image of 5 μm silver @ lamellar graphene prepared in step four of example 2;
the morphology of the 5% lamellar graphene @ lamellar silver test can be seen: the structure is clear and visible; the effect of compounding the silver by using the lamellar graphene solution with low mass fraction is poor, inevitable mixing can be caused after the lamellar graphene solution with high mass fraction is compounded with the silver, the optimal effect is achieved by compounding the lamellar graphene solution with 5% mass fraction and the silver, and the small-multiple scanning morphology is clear.
FIG. 6 is an SEM image of 5 μm of sheet graphene @ sheet silver prepared in step four of example 3;
the morphology of the 7% lamellar graphene @ lamellar silver test can be seen as follows: after the graphene with relatively high content is compounded with the silver, the graphene covers the silver too much, and graphene sheets cannot be seen clearly, which indicates that the compounding of the graphene with high content and the silver cannot achieve the optimal effect and can also reduce the performance of the composite material, and the appearance is not clear even in large-multiple scanning.
Example 4: the preparation method for preparing the high-concentration graphene conductive silver paste by using the lamellar graphene @ lamellar silver prepared in example 1, the glass powder and the organic carrier comprises the following steps:
1. weighing:
82 parts of lamellar graphene @ lamellar silver prepared in example 1, 4 parts of glass powder and 14 parts of organic carrier are weighed according to parts by weight;
the glass powder in the step one is purchased from a samsung SDI, and the particle size of the glass powder is as follows: d50:1.5 μm, D90:2.5 μm, softening point 430 ℃.
The organic carrier in the first step is prepared by the following steps:
(1) weighing 64 parts of solvent, 8 parts of plasticizer, 7 parts of binder, 4 parts of thickener, 5 parts of coupling agent, 4.5 parts of surfactant and 7.5 parts of defoamer to obtain a reagent;
the solvent is a mixture of terpineol and butyl carbitol acetate, wherein the mass ratio of the terpineol to the butyl carbitol acetate is 52; the plasticizer is dibutyl phthalate; the binder is ethyl cellulose; the thickening agent is polyurethane; the coupling agent is KH-550; the surfactant is lecithin; the defoaming agent is methyl silicate;
(2) stirring the reagent for 2 hours at the temperature of 80 ℃ and the stirring speed of 1200r/min, filtering by using a 400-mesh screen, and cooling to room temperature to obtain an organic carrier;
2. mixing:
uniformly mixing the lamellar graphene @ lamellar silver, the glass powder and the organic carrier weighed in the step one, then rolling the mixture by a three-roll mill, and filtering the mixture by using a 400-mesh screen to obtain the high-concentration graphene conductive silver paste.
Example 5: the present embodiment is different from embodiment 4 in that: 82 parts of lamellar graphene @ lamellar silver prepared in example 2, 4 parts of glass powder and 14 parts of organic carrier are weighed according to parts by weight. The other steps and parameters were the same as in example 1.
Example 6: the present embodiment is different from embodiment 4 in that: 82 parts of lamellar graphene @ lamellar silver prepared in example 3, 4 parts of glass powder and 14 parts of organic carrier are weighed in parts by weight. The other steps and parameters were the same as in example 1.
Example 7: the present embodiment is different from embodiment 4 in that: weighing 82 parts of commercial silver powder, 4 parts of glass powder and 14 parts of organic carrier according to parts by weight. The other steps and parameters were the same as in example 1.
The tap density of the commercial silver powder used in example 7 was 6.0g/cm 3 The particle diameter D50 was 1.3 μm and D90 was 2.0. Mu.m.
Printing the high-concentration graphene conductive silver paste prepared in the embodiments 4-6 and the conductive silver paste prepared in the embodiment 7 on a monocrystalline silicon slice by using a 500-mesh screen printing plate, sintering at the temperature of between 250 and 890 ℃ to obtain a monocrystalline silicon cell slice, and testing the electrical property of the cell slice, wherein the results are shown in table 1;
from table 1, it can be seen that: in example 5, the performance of the conductive silver paste prepared from the lamellar graphene @ lamellar silver prepared in example 2, the glass powder and the organic carrier is optimal, and the conductive silver paste is matched with commercial silver powder (the tap density is 6.0 g/cm) 3 The grain diameter D50 is 1.3 μm, and the grain diameter D90 is 2.0 μm) is compared, and the performance of the battery piece is remarkably improved.
Printing a high-concentration graphene conductive silver slurry prepared by using the lamellar graphene @ lamellar silver prepared in example 1, glass powder and an organic carrier in example 4 on a monocrystalline silicon wafer by using a 500-mesh screen printing plate, sintering at the temperature of 250-890 ℃ to obtain a monocrystalline silicon battery wafer, wherein the aspect ratio 3D diagram of the tested battery wafer is shown in FIG. 7, and the data are listed in Table 2;
printing high-concentration graphene conductive silver slurry prepared by using the graphene @ sheet prepared in example 2, glass powder and an organic carrier in example 5 onto a monocrystalline silicon wafer by using a 500-mesh screen printing plate, sintering at the temperature of 250-890 ℃ to obtain a monocrystalline silicon battery piece, wherein the aspect ratio 3D diagram of the tested battery piece is shown in FIG. 8, and the data are listed in Table 3;
printing high-concentration graphene conductive silver slurry prepared by using the graphene @ sheet prepared in example 3, glass powder and an organic carrier in example 6 on a monocrystalline silicon wafer by using a 500-mesh screen printing plate, sintering at the temperature of 250-890 ℃ to obtain a monocrystalline silicon battery piece, wherein the aspect ratio 3D diagram of the tested battery piece is shown in FIG. 9, and the data are listed in Table 4;
as can be seen from fig. 7 to 9 and tables 2 to 4: the performances of the corresponding battery pieces with different contents of the graphene @ silver sheets are also obviously different, and the aspect ratio of the graphene @ silver sheets prepared by using the graphene sheet solution with the mass fraction of 5% in the example 2 to the battery pieces prepared by paste printing of the glass powder and the organic carrier is optimal.
Printing conductive silver slurry prepared by using commercial silver powder, glass powder and an organic carrier in example 7 on a monocrystalline silicon wafer by using a 500-mesh screen printing plate, sintering at the temperature of 250-890 ℃ to obtain a monocrystalline silicon battery piece, wherein the aspect ratio 3D diagram of the tested battery piece is shown in FIG. 10, and the data is listed in Table 5;
as can be seen from comparative experiments with commercial silver powders, the aspect ratio 3D plot of the cell prepared in example 7 is significantly less than that of the present invention.
Claims (9)
1. The high-concentration graphene conductive silver paste is characterized by being prepared from 80-90 parts by weight of lamellar graphene @ lamellar silver, 2-5 parts by weight of glass powder and 8-16 parts by weight of organic carrier;
the organic carrier is prepared from a solvent, a plasticizer, a binder, a thickening agent, a coupling agent, a surfactant and a defoaming agent;
the preparation method of the silver-coated graphene/silver flake comprises the following steps of:
1. preparing lamellar graphene solutions with different mass fractions:
(1) adding graphene into absolute ethyl alcohol to obtain a graphene premixed solution with the mass fraction of 0.5%;
(2) stirring the graphene premixed solution with the mass fraction of 0.5% under a sealed condition, then performing ultrasonic dispersion under an ice bath and the sealed condition, and adding absolute ethyl alcohol at intervals in the ultrasonic dispersion process to obtain a lamellar graphene solution with the mass fraction of 0.5%;
(3) firstly, adding graphene into a graphene solution with the mass fraction of 0.5%, stirring under a sealed condition, performing ultrasonic dispersion under an ice bath and the sealed condition, and adding absolute ethyl alcohol at intervals in the ultrasonic dispersion process to obtain a lamellar graphene solution with the mass fraction of 1%;
(4) 1-12 times of the first step (3) are circulated, and a lamellar graphene solution with the mass fraction of 0.5-7% is obtained;
2. preparing a silver acid solution:
dissolving silver nitrate into deionized water, adding Arabic gum, and stirring uniformly at room temperature to obtain a silver nitrate solution;
3. preparing sol:
(1) dispersing polyvinyl alcohol into absolute ethyl alcohol, and stirring at room temperature to obtain sol;
(2) dripping a lamellar graphene solution with the mass fraction of 0.5-7% into the sol prepared in the step three (1) under the stirring condition, and then carrying out ultrasonic treatment under the sealing condition to obtain a lamellar graphene sol;
4. preparing lamellar graphene @ lamellar silver:
dropwise adding a silver nitrate solution into the lamellar graphene sol under the condition of stirring, then adding sodium borohydride into the lamellar graphene sol for 10min to 30min in several times, stirring the mixture for reaction, and then adding polyethylene glycol and hydrazine hydrate into the mixture for 10min to 30min in several times to obtain a reaction system; adjusting the pH value of the reaction system to 6.5-9.5 by using ammonia water, and finally stirring and reacting at the reaction temperature of 10-40 ℃ to obtain a reaction product; and filtering, cleaning and vacuum drying the reaction product to obtain the lamellar graphene @ lamellar silver.
2. The high-concentration graphene conductive silver paste according to claim 1, wherein the high-concentration graphene conductive silver paste is prepared from 82 parts by weight of lamellar graphene @ lamellar silver, 4 parts by weight of glass powder and 14 parts by weight of organic vehicle.
3. The high-concentration graphene conductive silver paste according to claim 1 or 2, wherein the solvent is a mixture of terpineol and butyl carbitol acetate; the plasticizer is dibutyl phthalate; the binder is ethyl cellulose; the thickening agent is polyurethane thickening agent; the polyurethane thickener is polyurethane, bentonite or hydrogenated castor oil.
4. The high-concentration graphene conductive silver paste according to claim 1 or 2, wherein the coupling agent is a silane coupling agent; the silane coupling agent is KH-550, KH-570 or isopropyl tri (dioctyl phosphate acyloxy) titanate; the surfactant is lecithin; the defoaming agent is methyl silicate.
5. The high-concentration graphene conductive silver paste according to claim 1 or 2, wherein the organic carrier is prepared from 64 parts of a solvent, 8 parts of a plasticizer, 7 parts of a binder, 4 parts of a thickener, 5 parts of a coupling agent, 4.5 parts of a surfactant and 7.5 parts of a defoaming agent.
6. The high-concentration graphene conductive silver paste according to claim 1, wherein in the first step (2), absolute ethyl alcohol is added every 30min in the ultrasonic dispersion process; stirring in the step one (2) for 60min to 120min; the time of ultrasonic dispersion in the step one (2) is 3h to 15h; the mass of the graphene in the step one (3) is the same as that of the graphene in the step one (1); adding absolute ethyl alcohol every 30min in the ultrasonic dispersion process in the step one (3); the stirring time in the step one (3) is 60min to 120min; and (4) the time of ultrasonic dispersion in the step one (3) is from 3h to 15h.
7. The high-concentration graphene conductive silver paste according to claim 1, wherein the concentration of silver nitrate in the silver nitrate solution in the second step is 1-2 mol/L; the mass ratio of the gum arabic to the silver nitrate in the silver nitrate solution in the second step (0.5-1) is 1; the volume ratio of the mass of the polyvinyl alcohol to the absolute ethyl alcohol in the third step (1) is (0.2g to 0.8g): 60mL to 140mL; stirring for 2h to 3h in the third step (1), wherein the stirring speed is 200r/min to 600r/min; the time of the ultrasonic treatment in the third step (2) is 2h to 8h, wherein evaporated absolute ethyl alcohol is added every 30 min; the volume ratio of the lamellar graphene solution to the sol in the third step (2) is (0.1-5): 1.
8. The high-concentration graphene conductive silver paste as claimed in claim 1, wherein in the fourth step, the last stirring reaction is carried out at a reaction temperature of 10-40 ℃ for 3-24h; the mass fraction of the ammonia water in the step four is 3-5%; the mass ratio of the sodium borohydride to the silver nitrate in the reaction system in the fourth step is (0.8-2.8) to 1; the mass ratio of the polyethylene glycol to the silver nitrate in the reaction system in the fourth step is (0.4 to 1.2) to 1; the mass ratio of hydrazine hydrate to silver nitrate in the reaction system in the fourth step is (0.5 to 2.5) to 1; the volume ratio of the silver nitrate solution to the lamellar graphene sol in the fourth step is (1-80): 1-1200.
9. The method for preparing the high-concentration graphene conductive silver paste according to claim 1, wherein the method for preparing the high-concentration graphene conductive silver paste is completed according to the following steps:
1. weighing:
weighing 80-90 parts of lamellar graphene @ lamellar silver, 2-5 parts of glass powder and 8-16 parts of organic carrier according to parts by weight;
the organic carrier in the first step is prepared by the following steps:
(1) weighing a solvent, a plasticizer, a binder, a thickening agent, a coupling agent, a surfactant and a defoaming agent to obtain a reagent;
(2) stirring the reagent for 0.5h to 2h at the temperature of 55-85 ℃ and the stirring speed of 800-1500 r/min, filtering by using a 300-600 mesh screen, and cooling to room temperature to obtain an organic carrier;
2. mixing:
uniformly mixing the lamellar graphene @ lamellar silver, the glass powder and the organic carrier weighed in the step one, then rolling the mixture by using a three-roll mill, and filtering the mixture by using a 400-600-mesh screen to obtain the high-concentration graphene conductive silver paste.
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