CN107658045B - Back electrode silver paste for lead-free PERC battery and preparation method - Google Patents
Back electrode silver paste for lead-free PERC battery and preparation method Download PDFInfo
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- CN107658045B CN107658045B CN201710760629.XA CN201710760629A CN107658045B CN 107658045 B CN107658045 B CN 107658045B CN 201710760629 A CN201710760629 A CN 201710760629A CN 107658045 B CN107658045 B CN 107658045B
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
Abstract
The invention discloses a back electrode silver paste for a lead-free PERC battery and a preparation method thereof. The back electrode silver paste comprises the following components in parts by mass: 50-60 parts of spherical silver powder with special requirements, 10-20 parts of superfine silver powder with special requirements, 1-5 parts of main glass, 0.1-0.5 part of auxiliary glass, 35-60 parts of organic binder and 1-5 parts of other auxiliary agents. The PERC back silver in the invention adopts a new technology, and 2 glass powders are selected: etching off SiNx on the surface of the auxiliary glass with low softening point corrosivity at 200-300 ℃; the high-softening-point main glass with the temperature of 400-600 ℃ provides welding tension. The nano silver powder is filled and matched with the monodisperse spherical silver powder to form a compact electrode surface layer. The solder-resisting additive effectively inhibits the corrosion of the soldering tin to the back electrode, and ensures the welding tension and the aging tension.
Description
Technical Field
The invention belongs to the field of battery back electrode silver paste, and relates to back electrode silver paste for a lead-free PERC battery and a preparation method thereof.
Background
The crystalline silicon solar cell is a cell device for converting solar energy into electric energy by utilizing photoelectric effect, and the electric energy is output by the front electrode and the back electrode through the internal current generated under the illumination condition. The PERC cell is characterized in that a passivation layer structure is added on the back of a crystalline silicon solar cell, so that the recombination of current carriers is reduced, and meanwhile, new requirements are provided for back materials, particularly back electrode silver paste.
With the continuous innovation of solar cell technology, the requirements on the electrode are higher and higher. Most of the conventional PERC back silver technology is adjusted on the conventional back silver, the back electrode has large damage to a passivation layer and high recombination rate, and the photoelectric conversion efficiency is greatly inhibited. Similar products on the market all have different degrees of blackening at the back electrode under the PL test, which indicates that the recombination exists.
The invention relates to a back electrode silver paste for a lead-free PERC battery, which is used as a back electrode of a crystalline silicon solar battery and mainly comprises a conductive functional phase, an organic carrier and an inorganic binder. Compared with similar products on the market, the PERC back silver has obvious improvement effect, and mainly aims to effectively reduce the recombination at the back electrode and brighten the back electrode under PL test. In addition, the damage of the sintered back electrode to the passivation layer is optimized by changing the non-base metal phase and the additive, and the photoelectric conversion efficiency of the PERC cell is improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a back electrode silver paste for a lead-free PERC battery and a preparation method thereof, aiming at the defects of the conventional PERC back silver technology.
The technical scheme adopted by the invention is as follows: the back electrode silver paste for the lead-free PERC battery comprises the following components in parts by mass: 50-60 parts of spherical silver powder with special requirements, 10-20 parts of superfine silver powder with special requirements, 1-5 parts of main glass, 0.1-0.5 part of auxiliary glass, 35-60 parts of organic binder and 1-5 parts of other auxiliary agents.
Furthermore, the spherical silver powder with special requirements needs low crystallinity and relatively high activity, is hollow silver powder, and has the particle size D50 of 0.7-1.8 μm and the specific surface area of 1.5m2/g～2.5m2/g。
Furthermore, the superfine silver powder with special requirements needs to have extremely high activity, the particle size of the superfine silver powder is 0.5-0.8 mu m in D50, and the specific surface area is 2.5-4.5 m2/g。
Further, the main glass is Bi-based and is made of Bi2O3、B2O3、SiO2、Al2O3、CuO、ZnO、TiO2、Cr2O3、NiO、Li2CO3、MnO2And several of TeO, the particle size D50 is controlled to be 0.5-2 mu m, and the softening point is controlled to be 400-600 ℃.
Further, the auxiliary glass is Pb series and is composed of PbO and B2O3、SiO2、Al2O3、ZnO、Li2CO3、Na2CO3、TeO2The particle size D50 is controlled to be 0.5-2 mu m, and the softening point is controlled to be 200-300 ℃.
Furthermore, the organic binder is composed of organic resin and organic solvent; the organic resin accounts for 10-30% of the organic adhesive by mass and is selected from one or more of ethyl cellulose and butyl acetate cellulose; the organic solvent accounts for 70-90% of the organic adhesive by mass and is selected from one or more of acetone, turpentine, alcohol ester dodeca, butyl carbitol acetate and glycerol.
Further, the other auxiliary agents comprise a surface dispersant and a thixotropic agent; the dispersing agent is one or more of stearic acid, stearic acid derivatives and unsaturated fatty acid; the thixotropic agent is selected from one or more of hydrogenated castor oil and polyamide wax.
A method for preparing the back electrode silver paste for the lead-free PERC battery comprises the following steps:
A. preparation of organic binder:
the organic binder consists of organic resin and an organic solvent; the organic resin accounts for 10-30% of the organic adhesive by mass and is selected from one or more of ethyl cellulose and butyl acetate cellulose; the organic solvent accounts for 70-90% of the organic adhesive by mass and is selected from one or more of acetone, turpentine, alcohol ester dodeca, butyl carbitol acetate and glycerol; weighing the mixed materials according to the formula proportion of the organic binder, and dissolving and dispersing for 1-3 hours at the temperature of 60-90 ℃ to obtain a transparent and uniform organic binder;
B. preparing lead-free glass powder:
the main body glass is made of Bi2O3、B2O3、SiO2、Al2O3、CuO、ZnO、TiO2、Cr2O3、NiO、Li2CO3、MnO2And several of TeO are melted, the mixed materials are weighed according to the formula and melted for 1 to 4 hours at 1200 ℃; melting auxiliary glass at 900 ℃ for 1-4 hours, then pouring molten glass material into deionized water for water quenching to obtain coarse material, using zirconium beads with two specifications of 0.5 mu m and 0.3 mu m for the coarse material according to the proportion of 1: 1-1: 3, and controlling the ball-to-material ratio to be 3: performing ball milling and drying at a ratio of 1-7: 1 to obtain a finished product of superfine glass powder with an average size of 0.5-2 mu m;
C. preparation of back electrode silver paste for lead-free PERC battery:
according to the formula proportion of the back lead-free conductive silver paste, the spherical silver powder, the superfine silver powder, the lead-free glass powder, the organic binder and other additives are uniformly mixed, and then the mixture is rolled for 6-8 times by using a three-roll grinding machine, so that the fineness is less than 8 mu m, and the viscosity is controlled to be 30-80 Pa.s, and the required back silver paste is obtained.
Has the advantages that: compared with the existing PERC back silver technology, the back electrode silver paste for the lead-free PERC battery has the following technical advantages:
(1) compared with the hollow silver powder, the high-activity hollow spherical silver powder with special requirements is used, the sintering activity is increased, and the conductivity is better; and a part of the superfine silver powder with special requirements is matched, so that the compactness of sintering is improved, and excellent aging tension is ensured.
(2) The invention uses the superfine Bi glass powder with special requirements, controls the softening point, and can ensure that the glass powder has certain embedding to the SiNx layer and does not damage Al2O3And (3) a layer.
(3) The invention uses the additives with special requirements to obviously modify the surface of the powder and effectively adjust the sintering degree of the metal phase.
(4) The PERC back silver in the invention adopts a new technology, and 2 glass powders are selected: etching off SiNx on the surface of the auxiliary glass with low softening point corrosivity at 200-300 ℃; the high-softening-point main glass with the temperature of 400-600 ℃ provides welding tension. The nano silver powder is filled and matched with the monodisperse spherical silver powder to form a compact electrode surface layer. The solder-resisting additive effectively inhibits the corrosion of the soldering tin to the back electrode, and ensures the welding tension and the aging tension.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Detailed Description
Detailed description of the preferred embodiment 1
(1) Preparation of organic Binders
60g of turpentine and 25g of butyl carbitol acetate are weighed and mixed, 15g of ethyl cellulose is added under stirring, the mixture is heated to 80 ℃, and the mixture is dissolved for 1.5 hours to obtain the organic binder A for later use.
(2) Preparation of PERC back silver paste
2g of a specific ultrafine lead-free Bi glass powder A (softening temperature: 480 ℃ C., D50: 1.5 μm) was weighed, and 50g of a glass powder having an average particle diameter of 1.5 μm and a specific surface area of 1.5m was weighed218g of a specific spherical silver powder having an average particle diameter of 0.6 μm and a specific surface area of 3.8m228g of special ultrafine silver powder, 28g of the organic binder A and 2g of other special additives are mixed and rolled until the fineness of the slurry is smallAnd obtaining the back silver paste at 8 microns and with the viscosity of 55 Pa.s.
Specific example 2
(1) Preparation of organic Binders
Weighing 20g of alcohol ester dodeca and 70g of butyl carbitol, mixing, adding 7g of ethyl cellulose and 3g of butyl acetate cellulose under stirring, heating to 70 ℃, and dissolving for 2 hours to obtain an organic binder B for later use.
(2) Preparation of PERC back silver paste
4g of a self-prepared lead-free Bi glass powder B (softening temperature 500 ℃ C., D50 1 μm) was weighed, 55g of a powder having an average particle diameter of 1 μm and a specific surface area of 2.2m2Specific spherical silver powder in an amount of 10g having an average particle diameter of 0.8 μm and a specific surface area of 2.6m2And mixing and rolling 30g of superfine spherical silver powder, 30g of the organic binder B and 1g of other special additives until the fineness of the slurry is less than 8 microns and the viscosity is 50Pa.s to obtain the back silver slurry.
Specific example 3
(1) Preparation of organic Binders
60g of turpentine and 25g of butyl carbitol acetate are weighed and mixed, 15g of ethyl cellulose is added under stirring, the mixture is heated to 80 ℃, and the mixture is dissolved for 1.5 hours to obtain the organic binder A for later use.
(2) Preparation of PERC back silver paste
Weighing 1.8g of self-made Bi system main body glass powder A1 (the softening temperature is 550 ℃, and the D50 is 1.5 mu m), 0.2g of self-made Pb system auxiliary glass powder A2 (the softening temperature is 220 ℃, and the D50 is 0.8 mu m), 50g of spherical silver powder with the average particle size of 1.1 mu m, 15g of nano silver powder with the average particle size of 0.6 mu m, 32g of the organic binder A and 1g of the welding resistant additive, mixing and rolling until the fineness of the slurry is less than 8 mu m and the viscosity is 55Pa.s, and obtaining the back silver slurry.
Specific example 4
(1) Preparation of organic Binders
Weighing 20g of alcohol ester dodeca and 70g of butyl carbitol, mixing, adding 7g of ethyl cellulose and 3g of butyl acetate cellulose under stirring, heating to 70 ℃, and dissolving for 2 hours to obtain an organic binder B for later use.
(2) Preparation of PERC back silver paste
Weighing 1g of self-made Bi glass powder B1 (the softening temperature is 480 ℃ and the D50 is 1 mu m), 0.5g of self-made Pb auxiliary glass powder B2 (the softening temperature is 280 ℃ and the D50 is 0.8 mu m), 60g of spherical silver powder with the average particle size of 0.9 mu m, 5g of nano silver powder with the average particle size of 0.4 mu m, 33g of the organic binder B and 0.5g of other special additives, mixing and rolling until the fineness of the slurry is less than 8 mu m and the viscosity is 50Pa.s, and obtaining the back silver slurry.
The back silver paste obtained in the above examples 1 to 4 was applied as follows:
and printing the PERC back silver paste on the solar PERC cell, drying, co-firing with the PERC aluminum paste and the PERC positive silver, and forming a back electrode at the peak temperature of 750-.
The photoelectric conversion efficiency is improved by more than 0.05 percent, the welding tension is 3-5N, and the test of each property is passed.
Compared with other similar products, the photoelectric conversion efficiency is improved by more than 0.05 percent, and the photoelectric conversion efficiency is verified by customers. The data are as follows:
the technical solutions in the embodiments of the present invention are clearly and completely described above, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the protection scope of the present invention is more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Claims (6)
1. The back electrode silver paste for the lead-free PERC battery is characterized in that: the back electrode silver paste comprises the following components in parts by mass: 50-60 parts of spherical silver powder, 10-20 parts of superfine silver powder, 1-5 parts of main glass, 0.1-0.5 part of auxiliary glass, 35-60 parts of organic binder and 1-5 parts of other additives;
the main glass is Bi system and is made of Bi2O3、B2O3、SiO2、Al2O3、CuO、ZnO、TiO2、Cr2O3、NiO、Li2CO3、MnO2And several of TeO are melted, the particle size D50 is controlled to be 0.5-2 mu m, and the softening point is controlled to be 400-600 ℃;
the auxiliary glass consists of B2O3、SiO2、Al2O3、ZnO、Li2CO3、Na2CO3、TeO2The particle size D50 is controlled to be 0.5-2 μm, and the softening point is controlled to be 200-300 ℃.
2. The back electrode silver paste for a lead-free PERC cell of claim 1, wherein: the spherical silver powder needs low crystallinity and relatively high activity, is hollow silver powder, has the grain diameter D50 of 0.7-1.8 mu m and the specific surface area of 1.5m2/g～2.5m2/g。
3. The back electrode silver paste for a lead-free PERC cell of claim 1, wherein: the superfine silver powder needs to have extremely high activity, the particle size of the superfine silver powder is 0.5-0.8 mu m in D50, and the specific surface area is 2.5-4.5 m2/g。
4. The back electrode silver paste for a lead-free PERC cell of claim 1, wherein: the organic binder consists of organic resin and an organic solvent; the organic resin accounts for 10-30% of the organic adhesive by mass and is selected from one or more of ethyl cellulose and butyl acetate cellulose; the organic solvent accounts for 70-90% of the organic adhesive by mass and is selected from one or more of acetone, turpentine, alcohol ester dodeca, butyl carbitol acetate and glycerol.
5. The back electrode silver paste for a lead-free PERC cell of claim 1, wherein: the other auxiliary agents comprise a surface dispersant and a thixotropic agent; the dispersing agent is one or more of stearic acid, stearic acid derivatives and unsaturated fatty acid; the thixotropic agent is selected from one or more of hydrogenated castor oil and polyamide wax.
6. A method of preparing the back electrode silver paste for lead-free PERC battery according to any one of claims 1 to 5, wherein: the method comprises the following steps:
A. preparation of organic binder:
the organic binder consists of organic resin and an organic solvent; the organic resin accounts for 10-30% of the organic adhesive by mass and is selected from one or more of ethyl cellulose and butyl acetate cellulose; the organic solvent accounts for 70-90% of the organic adhesive by mass and is selected from one or more of acetone, turpentine, alcohol ester dodeca, butyl carbitol acetate and glycerol; weighing the mixed materials according to the formula proportion of the organic binder, and dissolving and dispersing for 1-3 hours at the temperature of 60-90 ℃ to obtain a transparent and uniform organic binder;
B. preparing lead-free glass powder:
the main body glass is made of Bi2O3、B2O3、SiO2、Al2O3、CuO、ZnO、TiO2、Cr2O3、NiO、Li2CO3、MnO2And several of TeO are melted, the mixed materials are weighed according to the formula and melted for 1 to 4 hours at 1200 ℃; melting auxiliary glass at 900 ℃ for 1-4 hours, then pouring molten glass material into deionized water for water quenching to obtain coarse material, using zirconium beads with two specifications of 0.5 mu m and 0.3 mu m for the coarse material according to the proportion of 1: 1-1: 3, and controlling the ball-to-material ratio to be 3: performing ball milling and drying at a ratio of 1-7: 1 to obtain a finished product of superfine glass powder with an average size of 0.5-2 mu m;
C. preparation of back electrode silver paste for lead-free PERC battery:
uniformly mixing spherical silver powder, superfine silver powder, lead-free glass powder, an organic binder and other additives, and then rolling the mixture for 6-8 times by using a three-roll grinder, wherein the fineness is less than 8 mu m, and the viscosity is controlled to be 30-80 Pa.s, so that the required back silver paste is obtained.
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| CN109524150B (en) * | 2018-07-06 | 2021-04-23 | 南通天盛新能源股份有限公司 | All-aluminum back surface field back silver paste and preparation method and application thereof |
| CN109473197B (en) * | 2018-11-14 | 2020-11-03 | 轻工业部南京电光源材料科学研究所 | High-resolution conductive silver paste containing silver-supermolecule organogel and preparation method thereof |
| CN110364286B (en) * | 2019-07-09 | 2021-02-12 | 湖南省国银新材料有限公司 | Single-crystal double-sided PERC battery back electrode silver paste and preparation method thereof |
| CN111091921A (en) * | 2019-12-27 | 2020-05-01 | 广东爱旭科技有限公司 | Positive silver auxiliary grid slurry of PERC battery and preparation method thereof |
| CN111403079B (en) * | 2020-03-30 | 2021-07-23 | 成都银盛新材料有限公司 | Conductive paste for back electrode of PERC crystalline silicon solar cell and preparation method thereof |
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