CN108806830A - A kind of high performance solar cells electrocondution slurry and preparation method thereof - Google Patents

Abstract

The invention provides a high-performance conductive paste for solar cells and a preparation method thereof, which is prepared from the following raw materials in parts by weight: 60-80 parts of lauric acid modified conductive nano powder, 6-12 parts of glass powder, long oil 5-14 parts of alkyd resin, 7-15 parts of polystyrene resin, 3-6 parts of carboxylated nitrile rubber, 5-9 parts of propylene glycol methyl ether acetate, 3-8 parts of maleic acid rosin ester, methyl 6‑10 parts of dihydroxyethyl acrylate, 2‑5 parts of propylene glycol monobutyl ether, 1‑3 parts of trioctyl trimellitate, 2‑6 parts of zinc naphthenate, 1‑4 parts of lubricant, film forming 1-5 parts of auxiliary agent, 1-3 parts of thickener. In the present invention, by adjusting the content of each inorganic component and organic component, the prepared conductive paste is better applicable to the substrate, and has excellent electrical conductivity, contact performance, and connection performance. Therefore, the conductive paste of the present invention is used to prepare solar cell electrodes , can greatly improve the power generation efficiency of solar cells.

Description

A kind of conductive paste for high-performance solar cell and preparation method thereof

technical field

The invention relates to a conductive paste, in particular to a conductive paste for high-performance solar cells and a preparation method thereof.

Background technique

As a renewable and clean energy, solar energy is inexhaustible and inexhaustible, and almost no environmental pollution is generated during use. After 40 years of development, more research is now focused on how to apply solar cells, solar cars, and solar buildings to people's real life, so as to reduce the dependence on traditional energy sources. With the continuous deepening of solar cell research and development, solar cells have basically entered the stage of industrial application. At present, the solar cell materials on the market are mainly silicon-based solar cells, including crystalline silicon, crystalline silicon and polycrystalline silicon thin films, solar cells, and silicon-based thin-film solar cells. Batteries, etc., and some are non-silicon solar cells, such as multi-component solar cells, functional polymer solar cells, nanocrystalline solar cells, etc.

As an important part of the solar cell, the electrode mainly plays the role of collecting current, and at the same time has a decisive influence on the light-receiving area and series resistance of the cell. Therefore, the electrode is one of the important factors affecting the conversion efficiency of the solar cell. The composition of the electrode material is The key factor that determines the performance of the electrode. However, the existing electrode materials have poor comprehensive performance, such as poor adhesion and low conversion efficiency, which greatly restricts the improvement of solar cell performance.

Contents of the invention

In order to solve the above problems in the prior art, the object of the present invention is to provide a high-performance conductive paste for solar cells and a preparation method thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

A high-performance conductive paste for solar cells, prepared from the following raw materials in parts by weight: 60-80 parts of lauric acid modified conductive nano powder, 6-12 parts of glass powder, and 5-14 parts of long-oil alkyd resin , 7-15 parts of polystyrene resin, 3-6 parts of carboxylated nitrile rubber, 5-9 parts of propylene glycol methyl ether acetate, 3-8 parts of rosin maleate, 6-6 parts of dihydroxyethyl methacrylate 10 parts, 2-5 parts of propylene glycol monobutyl ether, 1-3 parts of trioctyl trimellitate, 2-6 parts of zinc naphthenate, 1-4 parts of lubricant, 1-5 parts of film-forming aid, Thickener 1-3 parts;

The lauric acid modified conductive nano powder is a mixture of lauric acid modified silver-coated copper nano powder and lauric acid modified graphene oxide;

The composition of the glass powder is: Al ₂ O ₃ , ZrO ₂ , TeO ₂ , MnO, SiO ₂ , and its mass ratio is (2-8):(5-12):(3-6):(6-15 ): (12-25).

Preferably, a high-performance solar cell conductive paste according to the present invention is prepared from the following raw materials in parts by weight: 70 parts of lauric acid modified conductive nano powder, 9 parts of glass powder, long oil alkyd resin 10 parts, 11 parts of polystyrene resin, 4.5 parts of carboxylated nitrile rubber, 7 parts of propylene glycol methyl ether acetate, 5.5 parts of rosin maleate, 8 parts of dihydroxyethyl methacrylate, 3.5 parts of propylene glycol monobutyl ether 2 parts, 2 parts of trioctyl trimellitate, 4 parts of zinc naphthenate, 2.5 parts of lubricant, 3 parts of film-forming aid, 2 parts of thickener;

The composition of the glass powder is: Al ₂ O ₃ , ZrO ₂ , TeO ₂ , MnO, and SiO ₂ , with a mass ratio of 5:9:5:10:18.

Preferably, the film-forming aid is pentaerythritol ester or polyvinyl alcohol.

Preferably, the lubricant is vinyl bisstearamide, lanolin or silicone oil.

Preferably, the thickener is one of sodium carboxymethylcellulose, hydroxypropylmethylcellulose or polyacrylamide.

The preparation method of high-performance conductive paste of the present invention, comprises the following steps:

(1) Preparation of glass powder: Weigh each raw material by weight, mix evenly in a porcelain crucible, melt in a muffle furnace, first raise the temperature to 600-700°C, keep it for 1 hour, and then raise the temperature to 1200-1300°C Melt for 1-2 hours, quench the melted glass with water to obtain coarse glass particles, and use ball milling to make the average particle size of the glass powder ≤ 10 μm;

(2) Add long-oil alkyd resin, polystyrene resin, carboxylated nitrile rubber, propylene glycol methyl ether acetate, rosin maleate, dihydroxyethyl methacrylate, and propylene glycol monobutyl ether according to the corresponding weight Mix parts, and heat to 100-130°C while stirring; after stirring for 1-2 hours, lower the temperature to 30-40°C, and then add zinc naphthenate, lubricant, film-forming aid, thickener, partial Trioctyl trimellitate, continue to stir for 1-2h, until the reaction system forms a homogeneous solution, and obtains an organic binder;

(3) Add lauric acid modified conductive nano-powder, glass powder, and organic binder into a vacuum mixer and stir for 2 hours to form a uniform mixture, then grind and disperse through a three-roll mill, grind into a homogeneous slurry, and control the fineness of the scraper ≤5μm, and then filtered through a 400-mesh screen to obtain a high-performance conductive paste for solar cells.

Further, the viscosity of the prepared conductive paste is 50-60 Pa·s.

Beneficial effects: the invention provides a high-performance solar cell conductive paste and its preparation method. According to the test results, the conductive paste prepared by the present invention has excellent performance, and has excellent electrical conductivity and conversion efficiency , the conductive nano-powder modified by lauric acid improves the biocompatibility of the conductive nano-powder in the system, improves the uniformity of the distribution of the conductive nano-powder in the system, and further improves the smoothness of the slurry on the substrate after brushing and excellent electrical conductivity. Moreover, the lauric acid-modified graphene oxide and the lauric acid-modified silver-coated copper nanopowder play a synergistic effect, which plays an important role in promoting the improvement of electrical conductivity. In the present invention, by adjusting the content of various inorganic components and organic components, the prepared conductive paste is better applicable to the substrate, and has excellent electrical conductivity, contact performance, and connection performance. Therefore, the conductive paste of the present invention is used to prepare solar cells. Electrodes can greatly improve the power generation efficiency of solar cells.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the examples are only exemplary and do not constitute any limitation to the scope of the present invention. Those skilled in the art should understand that the details and forms of the technical solutions of the present invention can be modified or replaced without departing from the spirit and scope of the present invention, but these modifications and replacements all fall within the protection scope of the present invention.

The preparation method of the lauric acid modified conductive nano-powder described in the following examples and comparative examples is:

Add 5 g of copper (II) acetate hydrate to a solution of 2 mL of 20 wt % ammonia and 5 mL of water to form a blue solution, then add 0.5 mL of 10 M NaOH solution to form a light blue precipitated slurry; then add 3 mL of 50 wt % The hydrazine hydrate solution was added to the reaction system, and stirred vigorously in a nitrogen atmosphere at room temperature for 20 minutes to form a copper nanoparticle solution; silver nitrate was added to the copper nanoparticle solution to make the final concentration 10%, and then 1 -3mL of ascorbic acid solution with a mass fraction of 1%, stirred and reacted at room temperature for 1h, and removed the supernatant by centrifugation to collect the lower layer of silver-coated copper nanoparticles;

Add 1 g of lauric acid to 1 mL of methanol solution to form a mixture A, add the mixture A to silver-coated copper nanoparticles and 2 g of graphene to resuspend the particles, stir vigorously for 1 h under a nitrogen atmosphere, and remove the upper layer solution by centrifugation, Wash with deionized water for 2-3 times, and finally wash once with 10 mL of methanol, collect the precipitated particles by centrifugation, and then dry the collected precipitated particles in a vacuum environment to obtain lauric acid-modified conductive nanopowder.

Example 1

A high-performance conductive paste for solar cells, prepared from the following raw materials in parts by weight: 70 parts of lauric acid modified conductive nano powder, 9 parts of glass powder, 10 parts of long-oil alkyd resin, and 11 parts of polystyrene resin 4.5 parts of carboxylated nitrile rubber, 7 parts of propylene glycol methyl ether acetate, 5.5 parts of rosin maleate, 8 parts of dihydroxyethyl methacrylate, 3.5 parts of propylene glycol monobutyl ether, trioctyl trimellitate 2 parts of ester, 4 parts of zinc naphthenate, 2.5 parts of lubricant, 3 parts of coalescent, 2 parts of thickener;

The composition of the glass powder is: Al ₂ O ₃ , ZrO ₂ , TeO ₂ , MnO, and SiO ₂ , with a mass ratio of 5:9:5:10:18.

The film-forming aid is pentaerythritol fat.

Described lubricant is vinylbisstearamide.

The thickener is sodium carboxymethylcellulose.

The preparation method of high-performance conductive paste of the present invention, comprises the following steps:

(1) Preparation of glass powder: Weigh each raw material by weight, mix evenly in a porcelain crucible, melt in a muffle furnace, first heat up to 650°C, keep it warm for 1h, then heat up to 1200°C for 1.5h, Quenching the molten glass with water to obtain coarse glass particles, and using ball milling to make the average particle size of the glass powder ≤ 10 μm;

(2) Add long-oil alkyd resin, polystyrene resin, carboxylated nitrile rubber, propylene glycol methyl ether acetate, rosin maleate, dihydroxyethyl methacrylate, and propylene glycol monobutyl ether according to the corresponding weight Mix parts, heat to 115°C under stirring; after stirring for 1.5h, lower the temperature to 35°C, add zinc naphthenate, lubricant, film-forming aid, thickener, trioctyl trimellitate in sequence ester, continue to stir for 2h until the reaction system forms a homogeneous solution to obtain an organic binder;

(3) Add lauric acid modified conductive nano-powder, glass powder, and organic binder into a vacuum mixer and stir for 2 hours to form a uniform mixture, then grind and disperse through a three-roll mill, grind into a homogeneous slurry, and control the fineness of the scraper ≤5μm, and then filtered through a 400-mesh screen to obtain a high-performance conductive paste for solar cells.

Example 2

A high-performance conductive paste for solar cells, prepared from the following raw materials in parts by weight: 60 parts of lauric acid modified conductive nano powder, 6 parts of glass powder, 5 parts of long oil alkyd resin, 7 parts of polystyrene resin 3 parts of carboxylated nitrile rubber, 5 parts of propylene glycol methyl ether acetate, 3 parts of rosin maleate, 6 parts of dihydroxyethyl methacrylate, 2 parts of propylene glycol monobutyl ether, trioctyl trimellitate 1 part of ester, 2 parts of zinc naphthenate, 1 part of lubricant, 1 part of coalescent, 1 part of thickener;

The composition of the glass powder is: Al ₂ O ₃ , ZrO ₂ , TeO ₂ , MnO, SiO ₂ , and the mass ratio thereof is 2:5:3:6:12.

The film-forming aid is polyvinyl alcohol.

The lubricant is lanolin.

The thickener is hydroxypropyl methylcellulose.

The preparation method of high-performance conductive paste of the present invention, comprises the following steps:

(1) Preparation of glass powder: Weigh the raw materials by weight, mix them evenly in a porcelain crucible, and melt them in a muffle furnace. The molten glass is water-quenched to obtain coarse glass particles, and the average particle size of the glass powder is ≤10 μm by ball milling;

(2) Add long-oil alkyd resin, polystyrene resin, carboxylated nitrile rubber, propylene glycol methyl ether acetate, rosin maleate, dihydroxyethyl methacrylate, and propylene glycol monobutyl ether according to the corresponding weight Mix parts, heat to 100°C under stirring; after stirring for 1 hour, lower the temperature to 30°C, add zinc naphthenate, lubricant, film-forming aid, thickener, trioctyl trimellitate in sequence , and continue to stir for 1h until the reaction system forms a homogeneous solution to obtain an organic binder;

(3) Add lauric acid modified conductive nano-powder, glass powder, and organic binder into a vacuum mixer and stir for 2 hours to form a uniform mixture, then grind and disperse through a three-roll mill, grind into a homogeneous slurry, and control the fineness of the scraper ≤5μm, and then filtered through a 400-mesh screen to obtain a high-performance conductive paste for solar cells.

Example 3

A high-performance conductive paste for solar cells, prepared from the following raw materials in parts by weight: 65 parts of lauric acid modified conductive nano powder, 8 parts of glass powder, 7 parts of long oil alkyd resin, 10 parts of polystyrene resin 4 parts of carboxylated nitrile rubber, 6 parts of propylene glycol methyl ether acetate, 5 parts of rosin maleate, 7 parts of dihydroxyethyl methacrylate, 3 parts of propylene glycol monobutyl ether, and trioctyl trimellitate 1.5 parts of ester, 3 parts of zinc naphthenate, 2 parts of lubricant, 2 parts of coalescent, 1.5 parts of thickener;

The composition of the glass powder is: Al ₂ O ₃ , ZrO ₂ , TeO ₂ , MnO, and SiO ₂ , with a mass ratio of 3:7:4:8:15.

The film-forming aid is pentaerythritol fat.

The lubricant is silicone oil.

The thickener is polyacrylamide.

The preparation method of high-performance conductive paste of the present invention, comprises the following steps:

(1) Preparation of glass powder: Weigh each raw material by weight, mix evenly in a porcelain crucible, melt in a muffle furnace, first raise the temperature to 620°C, keep it warm for 1h, then raise the temperature to 1220°C for 1.2h, Quenching the molten glass with water to obtain coarse glass particles, and using ball milling to make the average particle size of the glass powder ≤ 10 μm;

(2) Add long-oil alkyd resin, polystyrene resin, carboxylated nitrile rubber, propylene glycol methyl ether acetate, rosin maleate, dihydroxyethyl methacrylate, and propylene glycol monobutyl ether according to the corresponding weight Mix parts, heat to 110°C under stirring; after stirring for 1.3h, lower the temperature to 32°C, add zinc naphthenate, lubricant, film-forming aid, thickener, trioctyl trimellitate in sequence ester, continue to stir for 1.2h until the reaction system forms a homogeneous solution to obtain an organic binder;

(3) Add lauric acid modified conductive nano-powder, glass powder, and organic binder into a vacuum mixer and stir for 2 hours to form a uniform mixture, then grind and disperse through a three-roll mill, grind into a homogeneous slurry, and control the fineness of the scraper ≤5μm, and then filtered through a 400-mesh screen to obtain a high-performance conductive paste for solar cells.

Example 4

A high-performance conductive paste for solar cells, prepared from the following raw materials in parts by weight: 80 parts of lauric acid modified conductive nano powder, 12 parts of glass powder, 14 parts of long oil alkyd resin, 15 parts of polystyrene resin 6 parts of carboxylated nitrile rubber, 9 parts of propylene glycol methyl ether acetate, 8 parts of rosin maleate, 10 parts of dihydroxyethyl methacrylate, 5 parts of propylene glycol monobutyl ether, and trioctyl trimellitate 3 parts of ester, 6 parts of zinc naphthenate, 4 parts of lubricant, 5 parts of coalescent, 3 parts of thickener;

The composition of the glass powder is: Al ₂ O ₃ , ZrO ₂ , TeO ₂ , MnO, and SiO ₂ , with a mass ratio of 8:12:6:15:25.

The film-forming aid is polyvinyl alcohol.

The lubricant is lanolin.

The thickener is hydroxypropyl methylcellulose.

The preparation method of high-performance conductive paste of the present invention, comprises the following steps:

(1) Preparation of glass powder: Weigh each raw material by weight, mix them evenly in a porcelain crucible, and melt them in a muffle furnace. The molten glass is water-quenched to obtain coarse glass particles, and the average particle size of the glass powder is ≤10 μm by ball milling;

(2) Add long-oil alkyd resin, polystyrene resin, carboxylated nitrile rubber, propylene glycol methyl ether acetate, rosin maleate, dihydroxyethyl methacrylate, and propylene glycol monobutyl ether according to the corresponding weight Mix parts, heat to 130°C under stirring; after stirring for 2 hours, lower the temperature to 40°C, add zinc naphthenate, lubricant, film-forming aid, thickener, trioctyl trimellitate in sequence , and continue to stir for 2h until the reaction system forms a homogeneous solution to obtain an organic binder;

(3) Add lauric acid modified conductive nano-powder, glass powder, and organic binder into a vacuum mixer and stir for 2 hours to form a uniform mixture, then grind and disperse through a three-roll mill, grind into a homogeneous slurry, and control the fineness of the scraper ≤5μm, and then filtered through a 400-mesh screen to obtain a high-performance conductive paste for solar cells.

Comparative example 1

The difference between Comparative Example 1 and Example 1 is that what is added in Comparative Example 1 is unmodified conductive nanopowder.

Comparative example 2

The difference between Comparative Example 2 and Example 1 is that no lauric acid-modified graphene oxide is added in Comparative Example 2.

The technical scheme of embodiment 1-4 and comparative example 1-2 is carried out following performance test, and test result is as shown in table 1:

Solderability: Print a 1cm x 1cm square area on a silicon wafer, after sintering, dip the surface with 2% rosin alcohol solution as flux, dip vertically into a Sn62Pb36Ag2 tin pot at 220°C for 1-3 seconds, measure the 1cm ² dip The tinned area accounts for more than 95% of the total area.

Solder resistance: Dip the 1cm ² solderability test piece after being dipped in alcohol rosin flux, then immerse it in a Sn62Pb36Ag2 tin pot at 220°C, and observe that the time for the sintered layer to be completely corroded is > 10 seconds.

Adhesion: Print the silver conductive paste on the front of the semi-finished crystalline silicon solar cell and burn it into the front silver electrode through the standard production process, use the standard tinned copper strip for automatic welding, and test the peeling force at a 45° angle with a tensile machine. The electrode adhesion (mean value) of slurry firing is >8.46N.

As can be seen from the results in Table 1, the conductive paste prepared by the present invention is excellent in various properties, and has excellent electrical conductivity and conversion efficiency. Therefore, the conductive paste of the present invention is used to prepare solar cell electrodes, which can greatly improve solar energy The power generation efficiency of the battery.

Table 1

Claims (7)

1. a kind of high performance solar cells electrocondution slurry, which is characterized in that be prepared by the raw material of following parts by weight：Month 60-80 parts of cinnamic acid denatured conductive nano powder, 6-12 parts of glass powder, 5-14 parts of long oil alkyd, polystyrene resin 7-15 Part, 3-6 parts of carboxy nitrile rubber, 5-9 parts of propylene glycol methyl ether acetate, 3-8 parts of maleic acid rosin ester, methacrylic acid two 6-10 parts of hydroxy methacrylate, 2-5 parts of propylene glycol monobutyl ether, 1-3 parts of trioctyl trimellitate (TOTM), 2-6 parts of zinc naphthenate, lubricant 1-4 Part, 1-5 parts of coalescents, 1-3 parts of thickener；

The lauric acid denatured conductive nano powder is that lauric acid is modified wicker copper nano powder and lauric acid modified graphene oxide Mixture；

The group of the glass powder becomes：Al₂O₃、ZrO₂、TeO₂、MnO、SiO₂, mass ratio is（2-8）:（5-12）:（3-6）: （6-15）:（12-25）.

2. a kind of high performance solar cells electrocondution slurry according to claim 1, which is characterized in that by following weight The raw material of part is prepared：70 parts of lauric acid denatured conductive nano powder, 9 parts of glass powder, 10 parts of long oil alkyd, polyphenyl second 11 parts of olefine resin, 4.5 parts of carboxy nitrile rubber, 7 parts of propylene glycol methyl ether acetate, 5.5 parts of maleic acid rosin ester, methyl-prop 8 parts of olefin(e) acid dihydroxy ethyl ester, 3.5 parts of propylene glycol monobutyl ether, 2 parts of trioctyl trimellitate (TOTM), 4 parts of zinc naphthenate, lubricant 2.5 Part, 3 parts of coalescents, 2 parts of thickener；

The group of the glass powder becomes：Al₂O₃、ZrO₂、TeO₂、MnO、SiO₂, mass ratio 5:9:5:10:18.

3. a kind of high performance solar cells electrocondution slurry according to claim 1, which is characterized in that the film forming helps Agent is pentaerythritol resin or polyvinyl alcohol.

4. a kind of high performance solar cells electrocondution slurry according to claim 1, which is characterized in that the lubricant For vinyl bis-stearamides, lanolin or organic silicone oil.

5. a kind of high performance solar cells electrocondution slurry according to claim 1, which is characterized in that the thickener For one kind of sodium carboxymethylcellulose, hydroxypropyl methyl cellulose or polyacrylamide.

6. the preparation method of claim 1-5 any one of them high performance solar cells electrocondution slurries, which is characterized in that Include the following steps：

（1）The preparation of glass powder：Each raw material is weighed by weight, is uniformly mixed in porcelain crucible, is melted in Muffle furnace, first It is warming up to 600-700 DEG C, keeps the temperature 1h, 1200-1300 DEG C of melting 1-2h is then warming up to again, the glass water quenching after melting is obtained Glass grit is used in combination ball milling that glass powder average grain diameter is made to be≤10 μm；

（2）By long oil alkyd, polystyrene resin, carboxy nitrile rubber, propylene glycol methyl ether acetate, maleic acid Rosin ester, methacrylic acid dihydroxy ethyl ester, propylene glycol monobutyl ether are mixed according to corresponding parts by weight, in the state of stirring It is heated to 100-130 DEG C；Stirring 1-2h after cool the temperature to 30-40 DEG C, sequentially add zinc naphthenate, lubricant, coalescents, Thickener, trioctyl trimellitate (TOTM) continue to stir 1-2h, until reaction system forms homogeneous solution, organic bond is made；

（3）Lauric acid denatured conductive nano powder, glass powder, organic bond are added in de-airing mixer and stir 2h, is formed equal Even mixture, then through three-high mill grinding distribution, it is ground into homogeneous slurry, scraper plate fineness≤5 μm are controlled, then through 400 mesh silks Net filtration obtains high performance solar cells electrocondution slurry.

7. the preparation method of high performance solar cells electrocondution slurry according to claim 6, which is characterized in that be made Electrocondution slurry viscosity be 50-60Pas.